JP2005001392A - Laminate for printing and printing method and print using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate for printing and a printing method and a print using the same which can prevent migration of a printed sublimable dyeing agent by forming, in an inner layer, a dye migration preventive colorable resin layer having affinity for a sublimable dyeing agent and capable of preventing migration of the dyeing agent. <P>SOLUTION: In this laminate for printing, a sublimable dyeing agent is penetrated into a resin layer by heating for coloration. In the laminate, a surface resin layer A (1) having low affinity for the sublimable dyeing agent and capable of permitting the dyeing agent to be passed therethrough, a colorable resin layer B1 (2) having affinity for the dyeing agent, and a dye migration preventive layer B2 (3) capable of preventing the migration of the dyeing agent are stacked on top of one another in that order from the surface. The dye migration preventive layer B2 (3) is formed of a biaxially oriented film which has been stretched by not less than 10% each in the direction of winding and in the direction of width and has a shrinkage of not more than 1.0% in the direction of winding of the film upon heating at 150°C for 30 min. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminate for printing used for sublimation dyeing in which a sublimable dyeing agent penetrates into a resin by heating, and a printing method and printed matter using the same. More specifically, the present invention relates to a printing laminate capable of preventing migration of a sublimable dyeing agent that occurs during dyeing or over time after dyeing, and a printing method and printed matter using the same.

Conventionally, when printing images and the like using a sublimable dye on a printing laminate, it is once printed on paper using an ink containing a sublimable dye, and the printed surface of the paper is laminated for printing. Apply to the surface of the body, use a vacuum thermocompression bonding machine or a heat roll, etc., to adhere the printed surface of the paper to the printing laminate, and heat-press to infiltrate the sublimation dye into the printing laminate. It was. As another method, the temporary display surface layer that accepts the ink provided on the surface of the printing laminate is printed with an ink containing a sublimable dyeing agent, and then heated to give inside the printing laminate. The intended printed image was obtained by diffusing and penetrating the dyeing agent. During printing, the dye sublimated to the molecular size penetrates into the resin and the colored resin layer prints an image, but the transfer temperature and transfer time are lower or shorter than the optimum conditions for transfer printing. If sufficient color density cannot be obtained, and if it exceeds the optimum conditions, sublimation dyeing can be applied to a layer continuous with the colored resin layer, such as a pressure-sensitive adhesive layer or adhesive layer provided for attaching a substrate. The agent permeates and spreads, resulting in a problem that the sharpness of the image is impaired or the outline of the image is blurred. Moreover, even if sublimation dyeing printing is performed under the optimum conditions, the dyeing agent moves successively over time to the layer continuous with the above-described coloring resin layer, and the dyeing agent to be held in the coloring resin layer is dispersed. As a result, problems such as occurrence of color fading and blurring of the image outline have occurred. As a conventional example, for example, as proposed in Patent Document 1 below, in producing a laminate for printing, a colored resin layer, a surface resin layer, and the like are sequentially laminated on a base film such as polyester, A laminate for printing was produced.
JP 2002-79751 A

  However, the technique of Patent Document 1 has a problem that the migration of the dye cannot be prevented if the polyester film used is unstretched. If a biaxially stretched polyester film is used, the biaxially stretched polyester film increases the crystallinity and intramolecular density of the resin by stretching. This is insufficient to maintain the sharpness of the image, and the contour of the printed image becomes unclear in a short time. In addition, if a biaxially stretched polyester film is used as the process substrate, the biaxially stretched polyester film shrinks due to heating during sublimation dyeing, and there is a problem that wrinkles and streaks are generated in the printing laminate. It was.

  In order to solve the above-mentioned conventional problems, the present invention provides a printing laminate capable of preventing migration of a sublimable dye, a printing method using the same, and a printed matter.

  The printing laminate of the present invention is a printing laminate in which a sublimable dye is infiltrated into the resin layer by heating to be colored, and in order from the surface, the affinity for the sublimable dye is weak, and As the surface resin layer (A) that allows the stain to pass through and the dye transfer-preventing color resin layer (B), the color resin layer (B1) that has an affinity for the stain and the migration of the stain. A dye transfer preventing layer (B2) to be prevented, and the dye transfer preventing layer (B2) is a biaxially stretched film stretched by 10% or more in the winding direction and the width direction, respectively, and 150 ° C. The film has a shrinkage in the winding direction of 30% when heated for 30 minutes at 1.0% or less.

  The printing method of the present invention is a method for printing the printing laminate, wherein the transfer paper is printed using an ink containing a sublimable dye, and the image forming surface of the transfer paper is the surface. The resin layer (A) is brought into contact, and then the heat treatment is performed to sublimate the sublimable dyeing agent to diffusely dye the coloring resin layer (B1).

  The printed matter of the present invention is printed using the printing method described above.

  The present invention prevents the migration of the printed sublimation dye by forming the coloring resin layer having an affinity for the sublimation dye in the inner layer and the dye transfer prevention layer for preventing the dye transfer. It is possible to provide a printing laminate that can be printed, a printing method using the same, and a printed matter.

  In the present invention, the surface resin layer (A) having weak affinity with the sublimable dye and allowing the dye to pass through, and dye transfer having affinity with the dye and preventing migration of the dye And a preventive coloring resin layer (B). Thus, by laminating the surface resin layer (A) on the upper layer of the dye transfer-preventing colored resin layer (B), the sublimation dye can be easily passed through the surface resin layer (A) by heating. The colorant resin layer (B) inside the laminate can be permeated, and the stain remaining on the colorant resin layer can be protected from ultraviolet rays, water, etc., and fading resistance can be improved. In addition, by making the coloring resin layer anti-dye transfer property, it is possible to prevent the dye from transferring to a layer that is not intended for coloring and preventing the image from fading or blurring of the image outline. Become.

  The dye transfer-preventing colorable resin layer (B) further comprises, in order from the surface, a colorant resin layer (B1) having an affinity for the dyeing agent and a dye transfer-preventing layer (B2) that prevents the dyeing agent from transferring. ) And may be formed separately. By providing a dye migration prevention layer below the coloring resin layer, it is possible to more effectively prevent the dye from migrating to an undesired lower layer and causing image discoloration and image outline blurring. Is possible.

  Further, when a biaxially stretched film is used for the dye transfer preventing colorable resin layer (B) or the dye transfer preventing layer (B2), the biaxially stretched by 10% or more in the winding direction and the width direction, respectively. It is a stretched film and preferably has a shrinkage in the winding direction of 1.0% or less when heated at 150 ° C. for 30 minutes. Thus, by using a biaxially stretched film having a low shrinkage rate in the dye transfer prevention layer, it becomes possible to prevent the generation of wrinkles and streaks during sublimation dyeing.

  Moreover, it is preferable that the said surface resin layer (A) is formed with the fluorine resin which consists of a fluoro olefin type copolymer soluble in a solvent. In this way, by using a fluoroolefin copolymer soluble in a solvent for the surface resin layer (A) of the printing laminate, the inside of the printing laminate can be colored efficiently by heating the sublimation dye. It can be permeated into the conductive resin layer, and the outdoor weather resistance can be further improved.

  The surface resin layer (A) may be formed of a silicon-modified acrylic resin. In this way, by using a silicon-modified acrylic resin for the surface resin layer (A) of the printing laminate, the sublimable dyeing agent is efficiently permeated into the coloring resin layer inside the printing laminate by heating. It is possible to further improve outdoor weather resistance.

  Moreover, it is preferable that the low-molecular weight compound having a molecular weight of about 1300 or less does not contain more than about 20% by weight in the dye transfer-preventing colored resin layer (B) or the colored resin layer (B1). By reducing the low molecular weight compound contained in the coloring resin layer in this way, the effect of preventing dye migration is increased.

  Further, a matting agent is added to the surface resin layer (A), and the surface resin layer has a 60-degree specular gloss (Method 3 (60-degree specular gloss) defined in JIS Z 8741 (Specular gloss measurement method)). Is preferably set to 70 or less, since it is possible to prevent reflection of a lighting fixture such as a fluorescent lamp.

 In addition, at least one of the surface resin layer (A), the dye migration-preventing colored resin layer (B), and the colored resin layer (B1) prevents image discoloration and improves the durability of the resin. Therefore, it is preferable to use at least one selected from ultraviolet absorbers, light stabilizers and antioxidants, but the ultraviolet absorbers, light stabilizers and antioxidants used at this time are preferably high molecular weight types. . In this way, UV absorbers, light stabilizers and antioxidants are made to have a high molecular weight type, so that the appearance of a phase due to phase separation from a transparent resin such as a surface layer, defects such as bleed out, and heating sublimation treatment Thus, it becomes possible to form a transparent resin that is stable over a long period of time, and to protect an image from ultraviolet rays or the like for a long period of time.

  Further, at least one of the surface resin layer (A), the dye transfer-preventing coloring resin layer (B), the dye transfer-preventing layer (B2), and each of the layers below these is a light diffusing fine particle. By adding a light diffusing function, it is possible to use it as a backlight film when illuminated from the back surface of the printing laminate.

  Further, a white layer is formed by using a white pigment in at least one of the dye transfer preventing colorable resin layer (B), the colorable resin layer (B1) and the dye transfer preventing layer (B2). If formed, the transmission density of the printed image can be improved.

 In addition, a layer containing high refractive glass beads is laminated below the dye transfer preventing colorable resin layer (B) or the dye transfer preventing layer (B2), and a metal below the layer containing the high refractive glass beads. If a retroreflective layer with a reflective film is formed, the laminate for printing is retroreflected by illumination by a headlight of a vehicle at night, thereby improving the visibility of printed matter at night and improving traffic safety and advertising. The advertising effect is greatly improved, which is preferable.

  Similarly, a fixing layer in which high refractive glass beads are fixed and a focus resin layer are sequentially laminated on the lower layer of the dye transfer preventing color resin layer (B) or the dye transfer prevention layer (B2), and further, a lower layer of the focus resin layer. It is preferable to provide a retroreflective layer having a metal reflective film deposited thereon because the same effect as described above can be obtained.

  Furthermore, a plurality of transparent spheres provided with a metal reflection film on a lower hemisphere, a support resin sheet holding the plurality of transparent spheres, and a surface of the support resin sheet are disposed to cover the plurality of transparent spheres. In the retroreflective sheet made of a transparent cover film and provided with a joining portion for holding the cover film on the support resin sheet, when the cover film is the laminate for printing, However, it is more preferable to obtain a laminate for printing that is much brighter and retroreflects.

In addition, the surface resin layer of the laminate for printing is [M ²⁺ _1-X M ³⁺ _X (OH) ₂ ] ^{X +} [A ^n- _{X / n} · mH ₂ O] ^X- (M ²⁺ is divalent) metal ion, M ³⁺ is a trivalent metal ion, a ^n-n-valent anion, X is greater than 0 0.33, 0 ≦ m ≦ 2) hydrotalcites and metal oxide represented by It is preferable to coat with a coating film-forming composition containing the fine particles, because a dirt substance does not adhere for a long time and a clear image can be displayed.

  Further, it is preferable that a release material such as a release film or release paper applied to the pressure-sensitive adhesive layer or the adhesive layer provided on the back surface of the printing laminate is subjected to an antistatic treatment. As described above, the antistatic treatment is applied to the release material such as the release film or release paper, and the static electricity generated when unwinding the sheet or the friction between the printing laminate and the printing press during printing by the ink jet printing press. It is possible to prevent the discharge direction of the ink discharged from the printing nozzle from being out of order due to static electricity and causing the printed image to be disturbed. That is, a precise image can be formed.

  Furthermore, the laminate for printing provided with at least one peelable temporary display layer capable of printing display on the surface resin layer (A), the surface resin layer (A) of the temporary display layer and The non-contact surface side has the absorbability of ink containing a sublimable dye, and it is possible to sublimate the sublimable dye by heat treatment and diffusely dye it on the printing laminate. After the heat treatment, if the temporary display layer is provided on the surface resin layer of the printing laminate, the temporary display layer can be peeled from the surface resin layer of the printing laminate in a film state. It is preferable that a desired image or the like can be directly printed on the laminate for use by using a sublimable dyeing agent, and then a heat treatment is performed to easily obtain a clear image or the like having high weather resistance.

  In the printing method of the present invention, the transfer paper is printed using an ink containing a sublimable dye, and the image forming surface of the transfer paper is brought into contact with the surface resin layer (A) of the printing laminate. Then, heat treatment is performed to sublimate the sublimable dyeing agent, and the dye migration preventing coloring resin layer (B) or the coloring resin layer (B1) is diffusely dyed.

  In addition, by printing on at least one peelable temporary display layer capable of print display by a known and common method such as an ink jet printer, a thermal transfer printer, a laser printer, etc., it can be used as a temporary display laminate and becomes unnecessary. For example, when the temporary display layer is peeled off, the substrate to which the printed laminate of the present invention is attached is visually recognized, and can be used as a transparent protective film for the substrate.

  In addition, the temporary display layer is printed using an ink containing a sublimable dye, and then a heat treatment is performed to sublimate the sublimable dye to maintain a high weather resistance, etc. Is obtained.

  Further, the printing is more preferably an ink jet method using an ink jet printer capable of simple full color printing.

  Further, the heat treatment temperature after printing is 150 from the viewpoint of improving workability by sublimating the sublimable dyeing agent in a shorter time without giving large heat damage to the release film on the back surface of the printing laminate. It is preferably in the range of ~ 200 ° C.

  Furthermore, if the printing surface is dried before the heat treatment, the diffusibility of the sublimation dye during the heat treatment becomes uniform, which is more preferable.

  The printing laminate of the present invention will be described in detail below based on the embodiments.

  FIG. 2 is a configuration diagram of the printing laminate of the present invention. A release paper or a release film may be integrated under the printing laminate through an adhesive layer or an adhesive layer. As a material that can be used for the colorable resin layer, it is preferable to use a synthetic resin having an affinity for a staining agent in order to efficiently capture the dye that has been sublimated and diffused and to develop a high density of color. More preferably, a heat-resistant resin is used so that the heating temperature during sublimation dyeing does not remarkably soften or does not cause tackiness (so-called stickiness). Apply it. It is particularly preferable to use a resin that is cured by radiation. Useful forms of radiation include electron beams, ultraviolet radiation, nuclear radiation, ultra high frequency radiation, and heat, and materials that cure with such radiation are well known in the art. Moreover, it is dyeing | staining that the colored resin layer itself contains uniformly and contains the ultraviolet absorber of the grade which can cut an ultraviolet-ray 70% or more, Preferably it is 80% or more, More preferably, it is 90% or more. It is preferable for protecting the agent from ultraviolet rays and the like. Specifically, synthetic resins such as vinyl resins, acrylic resins, alkyd resins, polyester resins, urethane resins, and epoxy resins can be used as materials that satisfy such required characteristics.

  Furthermore, the low molecular weight compound in the resin causes a problem that the once fixed dye is gradually transferred, and as a result, the contour of the image becomes unclear. Therefore, it is preferable to leave low molecular weight compounds in the coloring resin layer or to use additives such as plasticizers as much as possible, and to reduce the low molecular weight compounds contained in the coloring resin layer as much as possible. This is an effective means for stably carrying an image. The aforementioned low molecular weight compound is a compound having a molecular weight of about 1300 or less, and its content is preferably about 20% by weight or less, preferably about 15% by weight or less, more preferably about 10% by weight or less. If a low molecular weight compound having a molecular weight of about 1300 or less is used in excess of about 20% by weight, the printed image tends to become unclear in a short time.

  Printed laminates colored by the sublimation dyeing method can be used by providing a layer of pressure-sensitive adhesive or adhesive on the back side of the colorable resin layer and affixing it to a substrate such as metal, wood, plastic, or glass. Also, use it sandwiched between plastics. However, at this time, the dye gradually diffuses and transfers from the colored resin layer to the pressure-sensitive adhesive, adhesive, sandwiched plastic, or the like. This causes problems such as blurring in the image, blurring of the edges of the image, and mixing of printed hues to make the image unclear.

  In order to solve this problem, the dye transfer that prevents the migration of the dye in the coloring resin layer is imparted or the dye transfer that prevents the dye from moving continuously in the color resin layer. It is effective to provide a prevention layer.

  One example of a dye transfer-preventing material or a preferable material for the dye transfer-preventing layer is a biaxially stretched film, and particularly a biaxially stretched film that has been crystallized and has an increased intermolecular density. In particular, a biaxially stretched polyester film that is stretched by 10% or more, preferably 50% or more, more preferably 100% or more, particularly preferably 200% or more in each of the winding direction and the width direction is suitable. If the stretching ratio is less than 10%, it is not sufficient to prevent migration of the sublimable dyeing agent. Furthermore, there is a problem that the biaxially stretched polyester film contracts due to heat generated when the resin is colored by infiltrating a sublimable dyeing agent into the resin, thereby causing wrinkles and streaks. In order to solve this problem, it is preferable to apply a biaxially stretched polyester film that has been biaxially stretched and then subjected to annealing at a temperature equal to or higher than the glass transition temperature by heating to a constant length or relaxing. It is preferable to apply a film having a shrinkage of 1.0% or less, preferably 0.8% or less, more preferably 0.6% or less in the film winding direction when heated for 30 minutes. If a biaxially stretched polyester film with a shrinkage ratio exceeding 1.0% is used, defects such as wrinkles, streaks, etc. will be caused by heat when the resin is colored by infiltrating a sublimation dye into the resin by heating. It is not desirable to occur. In the case of a biaxially stretched polyester film, the orientation of the polymer molecules proceeds and the crystallinity ratio increases by stretching, and the surfaces of the polymer molecules in contact with each other increase. As a result, it is considered that migration of the dye from the coloring resin layer can be effectively prevented by increasing the attractive force in the polymer molecule.

  Another effective form of the dye transfer preventing layer can prevent dye transfer by forming a metal thin film continuously with the colored resin layer or further with the dye transfer preventing layer. However, it is not preferable when a retroreflective layer is formed in the lower layer. Here, the metal layer can be formed of the following metals, and the thickness thereof varies depending on the metal used, but is 5 to 500 nm, preferably 10 to 400 nm, and more preferably 20 to 300 nm. When the thickness of the metal layer is less than 5 nm, the concealability of the metal layer is not sufficient, so that the purpose as a dye migration prevention layer cannot be achieved, and in addition, it is stretched when pasting the printing laminate on a curved surface or the like. For this reason, the metal film becomes thinner, which is not preferable. On the other hand, when the thickness exceeds 500 nm, the adhesion between the metal layer and the coloring resin layer or the dye migration preventing layer is lowered, the metal film is easily cracked, and the cost is increased. The method for providing the metal layer is not particularly limited, and a normal vapor deposition method, sputtering method, transfer method, plasma method, or the like can be used. In particular, a vapor deposition method or a sputtering method is preferably used from the viewpoint of workability. In forming such a metal layer, the metal used is not particularly limited, and examples thereof include metals such as aluminum, gold, silver, copper, nickel, chromium, magnesium, and zinc. Aluminum, chromium or nickel is particularly preferable in consideration of workability, ease of forming a metal layer, and the like. In addition, you may form the said metal layer with the alloy which consists of 2 or more types of metals.

  By providing a surface resin layer on the colorable resin layer of the laminate for printing of the present invention, the stain of the colorable resin layer can be protected from ultraviolet rays, water, etc., and sufficient outdoor durability can be maintained. It becomes possible. As materials satisfying such required characteristics, olefin resins, that is, polyethylene, polypropylene, vinyl alcohol resins, such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer resins, fluorine resins, silicon resins, or These mixtures etc. are mentioned.

  In particular, it is preferable to use a synthetic resin mainly composed of a fluorine-based resin or a silicon-modified acrylic resin which has high outdoor weather resistance and a high affinity with a staining agent. Synthetic resins mainly composed of fluororesin include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoro Fluorine resins such as alkyl vinyl ether copolymers, tetrafluoroethylene-ethylene copolymers, polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymers, polyvinylidene fluoride, polyvinyl fluoride and the like can be mentioned. In order to process these fluororesins, it is a general method to melt mainly by applying heat, process into a desired shape, and then cool and commercialize the product. However, since the film produced by such a method is stretched in the longitudinal direction and the transverse direction, it shows a tendency to shrink when the temperature is raised to a temperature of 150 to 200 ° C. at the time of thermal transfer, such as printing blur and blurring of the printed pattern. Defects are likely to occur. In order to prevent this occurrence, the surface resin layer is made of unstretched fluorine produced by processing a fluororesin composed of a fluoroolefin copolymer soluble in the above-mentioned solvent by a solution casting method (casting method) or the like. A fluoroolefin copolymer soluble in a solvent having a reactive functional group, and a curing agent and / or a curing catalyst that reacts with the reactive functional group. It is preferably formed by a reaction. Of these, the solubility in general-purpose solvents is good, and from the viewpoint of work in producing films, copolymer of fluoroolefins or copolymer of fluoroolefins and monomers other than fluoroolefins Polymers are particularly preferred (hereinafter, these are also referred to as “fluoroolefin copolymers”). Specific examples of the fluoroolefin used for preparing such a fluoroolefin copolymer include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and the like. Can be mentioned. By copolymerizing two or more of these fluoroolefins, a copolymer containing only fluoroolefins as monomer components can be obtained. In addition, a fluoroolefin copolymer soluble in a solvent can be prepared by copolymerization of the fluoroolefins and monomers copolymerizable therewith. Specific examples of vinyl monomers copolymerizable with these fluoroolefins include alkyl or cycloalkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, cyclopentyl vinyl ether, vinyl acetate, and vinyl propionate. , Vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl benzoate, vinyl pt-butyl benzoate, vinyl cyclohexanecarboxylate, isopropenyl acetate, 2-hydroxyethyl vinyl ether, 3- Monomers having a hydroxyl group such as hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl allyl ether, 2-hydroxyethyl (meth) acrylate , Monomers containing a carboxyl group such as acrylic acid and methacrylic acid, monomers having an amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl vinyl ether , Glycidyl vinyl ether, monomers having an epoxy group such as glycidyl (meth) acrylate, hydrolyzable silyl groups such as trimethoxyvinylsilane, triethoxyvinylsilane, 2-trimethoxyethylvinylether, γ-methacryloxypropyltrimethoxysilane Monomers, 2-trimethylsilyloxyethyl vinyl ether, vinyl monomers having a silyloxy group such as 4-trimethylsilyloxybutyl vinyl ether, trimethylsilyl (meth) acrylate, vinyl-5-trimethylsilyl Examples thereof include monomers having a silyloxycarbonyl group such as oxycarbonylpentanoate, ethylene, propylene, vinyl chloride, various alkyl (meth) acrylates, and the like. Among such monomers, it is particularly preferable to use vinyl esters and vinyl ethers having no functional group as essential components from the viewpoint of copolymerizability, coating film performance, etc. A monomer having such a reactive functional group may be copolymerized.

  As a suitable copolymer of the fluoroolefin and the monomer other than the fluoroolefin used in the present invention, about 15 to 70% by weight of the fluoroolefin and about 0 of the vinyl monomer containing a reactive functional group. -30% by weight and about 5 to 85% by weight of other monomers copolymerizable therewith. More preferable copolymers include about 20 to 65% by weight of a fluoroolefin, about 5 to 25% by weight of a vinyl monomer containing a reactive functional group, and other monomers copolymerizable therewith. About 10 to 75% by weight is copolymerized. When the amount of fluoroolefin used is less than about 15% by weight, the durability and antifouling effect and the permeability of the sublimation dye are insufficient, and when it exceeds about 70% by weight, the solubility in general-purpose solvents decreases. This is not preferable because workability is deteriorated. The weight average molecular weight of the copolymer used is preferably in the range of about 5000 to 400,000, more preferably about 7000 to 300,000, from the viewpoint of workability and film durability.

  The fluororesin which is the surface resin layer of the laminate for printing of the present invention can be prepared from a fluoroolefin copolymer and an acrylic polymer as described above. The acrylic polymer here is a homopolymer or copolymer having an acrylic ester or methacrylic ester as an essential component, and any of those having and having no reactive functional group described above is used. Is possible. Various known acrylic polymers can be used, but those having a weight average molecular weight of about 5,000 to 400,000, more preferably about 7,000 to 300,000 are particularly preferred from the viewpoint of durability and workability.

  When the above-mentioned fluoroolefin copolymer and acrylic polymer are used in combination as the resin for the surface resin layer, the ratio of the former to the latter is about 30:70 to about 98: 2, more preferably, by weight. It is desirable to be in the range of about 40:60 to about 95: 5. If the amount of the acrylic polymer used is less than about 2%, the characteristics of the acrylic polymer to be imparted will not be exhibited, and if it exceeds about 70% by weight, the durability and antifouling effect and the permeability of the sublimation dye will be poor. This is not preferable because it is sufficient.

  When forming the surface resin layer of the printing laminate of the present invention, the fluoroolefin copolymer and the acrylic polymer are used in a form dissolved in an organic solvent. When the fluoroolefin copolymer or the acrylic polymer to be blended has a reactive functional group as described above, a curing agent having a functional group that reacts with the reactive functional group can be blended. . In the case of having a hydrolyzable silyl group as a reactive functional group, curing catalysts for acids, bases, or various organic tin compounds can be blended. Further, as described above, also when a curing agent is blended, a catalyst suitable for accelerating the curing reaction can be added. When the reactive functional group of the fluoroolefin copolymer is a hydroxyl group or a silyloxy group, polyisocyanate, block polyisocyanate, amino resin, metal alkoxide, metal chelate compound, or the like is blended. Moreover, when a reactive functional group is an epoxy group, a polycarboxy compound, a polysilyloxycarbonyl compound, a polyamine compound, etc. are mix | blended. Further, when the reactive functional group is a carboxyl group or a silyloxycarbonyl group, a polyepoxy compound, an epoxysilane compound, a metal chelate compound, or the like is blended. Further, when the reactive functional group is an amino group, a polyepoxy compound or an epoxysilane compound is blended as a curing agent. When an amino resin is blended as a curing agent in a fluoroolefin copolymer or a blend of a fluoroolefin copolymer and an acrylic copolymer, the amino resin is added to about 100 parts by weight of the base resin component. 5 to 100 parts by weight, preferably about 10 to 60 parts by weight may be blended.

  When a curing agent other than an amino resin is blended, the functionality in the curing agent is equivalent to 1 equivalent of the reactive functional group in the fluoroolefin copolymer or fluoroolefin copolymer and acrylic polymer blend. What is necessary is just to mix | blend a hardening | curing agent so that group may exist in the range of about 0.2-2.5 equivalent, More preferably, about 0.5-1.5 equivalent.

  Fine particles such as silica, calcium carbonate, aluminum hydroxide, acrylic resin, organic silicone resin, polystyrene, urea resin, formaldehyde condensate as matting agent in the composition used to form the surface resin layer described above Is added to lower the 60 ° gloss of the surface to 70 or less, it is possible to prevent reflection of lighting equipment such as a fluorescent lamp on the surface layer. Preferably, an acrylic resin is used because the compatibility with the fluoroolefin copolymer is good.

  The composition used for forming the above-described surface resin layer and the above-described dye transfer-preventing coloring resin layer or the composition used for forming the coloring resin layer include an ultraviolet absorber, light stability Long-term durability can be further improved by adding an agent and an antioxidant individually or in combination, and adding them. As such ultraviolet absorbers, known ones can be used, and representative ones include benzophenone series, benzotriazole series, cyanoacrylate series, salicylate series and oxalic acid anilide series, and hindered amine series as light stabilizers. Known compounds such as hindered phenolic compounds, amine-based antioxidants and sulfur-based antioxidants can be used as the antioxidants such as compounds. However, if low molecular weight compound UV absorbers, light stabilizers, and antioxidants are used, the appearance of phases due to phase separation from transparent resins, bleeding out, and sublimation dyes will penetrate inside the laminate for printing. Therefore, it is preferable to use a high molecular weight ultraviolet absorber, a light stabilizer, and an antioxidant.

  Examples of the ultraviolet absorber used in the present invention include salicylic acid type compounds such as phenyl salicylate, p-di-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxybenzophenone, 2 -Hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy- Benzophenone compounds such as 4-methoxy-5-sulfobenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole , 2- (2 ' Hydroxy-3′-tert-butyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 Benzotriazoles such as '-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3 Cyanoacrylates such as 3,3'-diphenylacrylate, metal oxides such as titanium oxide, zinc oxide, cerium oxide, anilide oxalate, triazine, dibenzoylmethane, benzylidene, etc. .

  As the ultraviolet absorber, there is a so-called high molecular weight type ultraviolet absorber in which the ultraviolet absorber is introduced into a part of the polymer.

  As the high molecular weight type ultraviolet absorber, known ones can be used. For example, [2-hydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (Methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyl oxide decyloxy) ) Benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2,2′-dihydroxy-4- (methacryloyloxyethoxy) benzophenone ] -Methyl methacrylate copolymer, [2,2'- Hydroxy-4- (methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2,2′-dihydroxy-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2,2 ′ -Dihydroxy-4- (methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2,2-dihydroxy-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2,2 ', 4-Trihydroxy-4'-(methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2,2 ', 4-trihydroxy-4'-(methacryloyloxymethoxy) benzophenone] -methyl methacrylate Copolymer, [2,2 ′, 4-trihydroxy-4 ′-(methacrylo Ruoxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2,2 ′, 4-trihydroxy-4 ′-(methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2,2 ′ , 4-Trihydroxy-4 ′-(methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4 ′-(methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [4 -Hydroxy-4 '-(methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4'-(methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy- 4 ′-(methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate Polymer, [4-hydroxy-4 ′-(methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4′-methyl-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate Copolymer, [2-hydroxy-4′-methyl-4- (methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4′-methyl-4- (methacryloyloxyoctoxy) benzophenone ] -Methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- (methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- ( Methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2- (2′- Droxy-4′-methacryloyloxyethoxy) benzotriazole] -methyl methacrylate copolymer, [2- (2′-hydroxy-4′-methacryloyloxyethoxy) -5-chlorobenzotriazole] -methyl methacrylate copolymer Etc. Furthermore, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] and other high molecular weight ultraviolet absorbers having a molecular weight of 500 or more Agents are also suitable.

  The light stabilizer efficiently captures (bonds) radicals generated by ultraviolet rays, inactivates them, and prevents the deterioration of the dye by blocking the chain reaction. 4-benzoyloxy-2,2,6, 6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2- (3 5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,2,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6- Various hindered amines such as tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,4-di-tert-butylphenyl-3,5-di-tert Hindered phenols such as butyl-hydroxybenzoate, [2,2′-thiobis- (4-tert-butylphenolate)]-tert-butylamine nickel (II), [2,2′-thiobis- (4-tert -Butyl phenolate)] nickel complexes of nickel such as 2-ethylhexylamine nickel (II), nickel of phosphate esters such as nickel salt of 3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethyl ester Examples thereof include salts.

  In particular, N, N, N ′, N ′,-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine- 2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6 tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl- 4-piperidyl) imino}], dimethyl succinate and 4 It hindered amine light stabilizer having a molecular weight of 1000 or more high molecular weight type polymer such as hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol is more preferable.

  There are two types of antioxidants, a radical acceptor type which stabilizes the generated radical peroxide by giving a proton, and a peroxide separated type which converts hydroperoxide into a stable alcohol. As the former, phenolic compounds and amine compounds are representative, but as phenolic compounds, compounds such as hydroquinone and gallate, 2,6-di-tert-butyl-p-cresol, stearyl-β -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6- tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-4-hydroxybenzyl) benzene, tris (3 Hindered phenolic compounds such as 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [methylene-3 (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, Examples of the amine compounds include N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, phenyl-α-naphthylamine, N, N′-β-naphthyl-p-phenylenediamine, N, Examples include N′-diphenylethylenediamine, phenothiazine, N, N′-di-sec-butyl-p-phenylenediamine, 4,4′-tetramethyl-diaminodiphenylmethane, and the like.

  Further, as the latter, sulfur compounds and phosphorus compounds are representative, but as sulfur compounds, dilauryl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dithiol. Examples include myristyl thiodipropionate, distearyl-β, β′-thiodibutyrate, 2-mercaptobenzimidazole, dilauryl sulfide and the like, and phosphorus compounds include triphenyl phosphite, trioctadecyl phosphite, tri Examples include decyl phosphite, trilauryl trithiophosphite, diphenylisodecyl phosphite, trinonylphenyl phosphite, distearyl pentaerythritol phosphite. The quencher is a compound that absorbs ultraviolet light to remove excitation energy from the excited molecule and suppresses the reaction of the excited molecule, and includes various known metal complexes. Of these antioxidants and quenchers, hindered phenol compounds having a molecular weight of 1000 or more are particularly suitable.

  Further, conventionally known organic solvents can be used, specifically, ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate, and aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene. , Hexane, heptane, octane, cyclohexane, ethylcyclohexane and other aliphatic or alicyclic hydrocarbons, methanol, ethanol, isopropanol, n-butanol, isobutanol and other alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Such ketone solvents are mentioned. Among these, when a polyisocyanate compound is used as a curing agent, the use of an alcohol solvent must be avoided. This is because the isocyanate group reacts with the alcohol.

If only specific representative examples of the silicone-modified acrylic resin are shown, the following can be mentioned.
(1) A cured film obtained by adding a hydrolysis catalyst to a vinyl copolymer obtained by copolymerizing a vinyl monomer having a hydrolyzable silyl group.
(2) A compound having both an epoxy group and a hydrolyzable silyl group in one molecule is added to a vinyl copolymer obtained by copolymerizing a vinyl monomer having an amino group and / or a carboxyl group, and a cured film and What you did.
(3) A cured film obtained by adding a polyisocyanate compound to a vinyl copolymer having a hydroxyl group obtained by graft polymerization of a silicone resin.
(4) A cured film obtained by adding a hydrolysis catalyst to a vinyl copolymer having a hydrolyzable silyl group obtained by graft polymerization of a silicone resin.

  The dye for sublimation ink used in the present invention is preferably a dye that sublimates or evaporates at 70 to 260 ° C. under atmospheric pressure. For example, there are dyes such as azo, anthraquinone, quinophthalone, styryl, diphenylmethane, triphenylmethane, oxazine, triazine, xanthene, methine, azomethine, acridine, diazine, etc. Among these, 1,4-dimethylaminoanthraquinone, brominated or Chlorinated 1,5-dihydroxy-4,8-diamino-anthraquinone, 1,4-diamino-2,3-dichloro-anthraquinone, 1-amino-4-hydroxyanthraquinone, 1-amino-4-hydroxy-2- ( β-methoxyethoxy) anthraquinone, 1-amino-4-hydroxy-2-phenoxyanthraquinone, 1,4-diaminoanthraquinone-2-carboxylic acid methyl, ethyl, propyl, butyl ester, 1,4-diamino-2-methoxy Anthraquinone 1-amino-4-anilinoanthraquinone, 1-amino-2-cyano-4-anilino (or cyclohexylamino) anthraquinone, 1-hydroxy-2- (p-acetaminophenylazo) -4-methylbenzene, 3- Examples include methyl-4- (nitrophenylazo) pyrazolone and 3-hydroxyquinophthalone. Further, malachite green, methyl violet, or the like can be used as a basic dye, and it is preferable to use a dye modified with sodium acetate, sodium ethylate, sodium methylate, or the like.

Using sublimation-type inks that use these dyes, printing processing is performed on transfer paper and temporary ink display surface layers provided on the surface of laminates for printing by electrophotography, electrostatic recording, ink jet, thermal transfer, etc. In the case of transfer paper, the printing surface of the paper is applied to the surface of the laminate for printing, and when it is printed on the temporary ink display surface layer, the vacuum heating / crimping machine, oven dryer, far-infrared heating device is used as it is. The sublimable dyeing agent is sublimated by heating at about 100 to about 200 ° C. for several tens of seconds to several minutes using a material, and the printed image is diffusely dyed inside the colored resin layer. In addition, the printing method at this time can be a printing method by a publicly known method such as thermal transfer, electrostatic printing, gravure printing, ink jet method, etc., but particularly, an ink jet printer capable of simple full color printing is used. In particular, the on-demand type is economical and preferable from the viewpoint of ink use efficiency.
In addition, the heat treatment temperature after printing is such that the sublimation dye can be sublimated in a shorter time and workability is improved without causing significant thermal damage to the release film on the back of the printing laminate. Is preferably in the range of 150 to 200 ° C., and further, if the printing surface is dried to the touch-drying level before the heat treatment, the diffusibility of the sublimable dyeing agent during the heat treatment becomes uniform and more suitable. Become. The transfer paper used at this time may be a commercially available inkjet printing paper, and it is preferable to use a hydrophilic resin for the temporary ink display surface layer. The hydrophilic resin used to form the temporary display surface layer includes polyurethane resin, acrylic resin, fluorine resin, unmodified and modified polyvinyl alcohol, polyester, acrylic urethane, vinyl acetate, and maleic anhydride. Polymer, sodium salt of alkyl ester, gelatin, albumin, casein, starch, SBR latex, NBR latex, cellulose resin, amide resin, melamine resin, polyacrylamide, polyvinylpyrrolidone, those obtained by cationic modification, It is also possible to use one or more of those having a hydrophilic group added.

  Further, fillers such as silica, clay, talc, diatomaceous earth, zeolite, calcium carbonate, alumina, zinc oxide and titanium may be added.

  FIG. 1 is a cross-sectional view of a laminate for printing in a reference example of the present invention, the surface resin layer (A) 1 having a weak affinity with a sublimable dye in order from the surface and allowing the dye to pass through, It is composed of a dye transfer-inhibiting coloring resin layer (B) 12 that has an affinity for a dye and prevents the dye from transferring.

  FIG. 2 is a cross-sectional view of the printing laminate in one embodiment of the present invention, in which the surface resin layer (A) 1 and the coloring resin layer (B1) 2 having an affinity for the dyeing agent are sequentially formed from the surface. , And a dye transfer preventing layer (B2) 3 for preventing transfer of the dyeing agent.

  FIG. 3 is a cross-sectional view of a laminate for printing in another reference example of the present invention. The surface resin layer (A) 1, the coloring resin layer (B 1) 2, and the dye transfer prevention layer (B 2) in order from the surface. 3) and a flexible resin layer (C) 4 having a higher elongation rate than the dye transfer prevention layer (B2) 3.

  FIG. 4 is a cross-sectional view of a laminate for printing in still another reference example of the present invention, in which the surface resin layer (A) 1, the dye transfer-inhibiting coloring resin layer (B) 12, and the dye are sequentially formed from the surface. The back surface of the migration-preventing coloring resin layer (B) 12 is further provided with a pressure-sensitive adhesive layer 5 and a release material 6 below the pressure-sensitive adhesive layer 5, and the pressure-sensitive adhesive layer 5 or the release material 6 is subjected to antistatic treatment.

FIG. 5 is a cross-sectional view of a laminate for printing in still another reference example of the present invention. The surface resin layer (A) 1, the coloring resin layer (B 1) 2, and the dye transfer prevention layer ( B2) 3, flexible resin layer (C) 4 having a higher elongation than dye transfer prevention layer (B2) 3, and adhesive layer 5 on the back surface of flexible resin layer (C) 4 A release material 6 is provided on the lower side, and the pressure-sensitive adhesive layer 5 or the release material 6 is subjected to antistatic treatment.
1 to 3, the pressure-sensitive adhesive layer 5 and the release material 6 may be formed, and the pressure-sensitive adhesive layer 5 or the release material 6 may be subjected to an antistatic treatment.

  In the first step, the laminate for printing shown in FIG. 1 has a dry film thickness of about 0.5 to about 300 μm, preferably about 2 to about 200 μm, on a support film such as a polyethylene terephthalate film or process paper. Preferably, the surface resin layer 1 is coated so as to have a thickness of about 3 to about 100 μm, and dried by normal temperature or heating. Next, in the second step, the coating material for the dye transfer-inhibiting coloring resin layer 12 following the surface resin layer 1 is dried to a thickness of about 1 to about 500 μm, preferably about 2 to about 400 μm, more preferably about 3 to 3. It is applied so as to have a thickness of about 300 μm, and is dried at room temperature or by heating.

  In the first step, the laminate for printing shown in FIG. 3 has a dry film thickness of about 0.5 to about 300 μm, preferably about 2 to about 200 μm, on a support film such as a polyethylene terephthalate film or process paper. Preferably, the surface resin layer 1 is coated so as to have a thickness of about 3 to about 100 μm, and dried by normal temperature or heating. Next, in the second step, the paint for the coloring resin layer 2 following the surface resin layer 1 has a dry film thickness of about 1 to about 500 μm, preferably about 2 to about 400 μm, more preferably about 3 to about 300 μm. Then, it is formed by drying at room temperature or by heating.

  In the third step, the coating material for the dye migration preventing layer 3 subsequent to the colored resin layer 2 is dried to a thickness of about 1 to about 500 μm, preferably about 2 to about 400 μm, more preferably about 3 to about 300 μm. And dried and laminated at room temperature or by heating. In the fourth step, the coating of the flexible resin layer 4 following the dye transfer prevention layer 3 is dried to a thickness of about 1 μm to about 100 μm, preferably about 3 μm to about 80 μm, more preferably about 5 μm to about 60 μm. It is applied and dried by normal temperature or heating.

  In this step, the paint for the flexible resin layer 4 is used in the first step, the paint for the dye transfer prevention layer 3 is used in the second step, and the paint for the coloring resin layer 2 is used in the third step. It is also possible to produce the coating material for the coloring resin layer 2 by applying the coating material for the surface resin layer 1 in the fourth step. Moreover, the process which removed the said flexible resin layer 4 is also possible as needed. After these steps are completed, a support film such as a polyethylene terephthalate film or process paper is peeled off from the laminate, and if necessary, a pressure-sensitive adhesive layer or a back surface of the laminate, that is, a layer on the opposite side of the surface resin layer. An adhesive layer may be formed, and a release material such as a release paper or a release film may be bonded to the pressure-sensitive adhesive layer or the adhesive layer to complete a printed laminate. However, when a biaxially stretched polyester film is used for the dye transfer preventing layer 3, the above-described support film and the dye transfer preventing layer 3 are used in common, so the step of peeling and removing the support film from the laminate is omitted. That is, in the present invention, the paint for the colored resin layer 2 is applied on a biaxially stretched film such as a polyethylene terephthalate film in the first step, and the paint for the surface resin layer 1 is applied in the second step. Can be manufactured. In addition, the drying conditions after coating in the first, second, third, and fourth steps are as follows: the type of base resin used as a coating material, the type of functional group in the base resin, and the reactivity in the base resin. It is determined appropriately according to the type of functional group, the type of curing agent, and the type of solvent. Application of the paint in each of the above steps may be performed by spray coating, or may be performed using a commonly used coating apparatus such as a knife coater, comma coater, roll coater, reverse roll coater, or flow coater.

  In addition, by using a clear paint containing no pigment as a paint used for forming each layer of the printing laminate of the present invention, a printing laminate without coloring can be obtained. A colored laminate for printing can also be obtained by using a colored paint containing a pigment as a paint for forming the lower layer. Examples of pigments used in obtaining such colored paints include organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone red, or hansa yellow, iron oxide red, iron oxide yellow, titanium white, cobalt blue, and carbon. Known pigments such as inorganic pigments such as black are suitable. Furthermore, the pigment itself has a five-layer structure, and the incident light generates an interference wavelength due to the spectral effect in which about 50% of the incident light is reflected by the surface layer and the remaining 50% is reflected by the opaque reflector metal. If the chroma flare pigment (manufactured by Flex Products) is used, different colors can be visualized, and it is possible to obtain a laminate for printing excellent in design. A similar effect can be obtained with “VARIOCROM” (trade name, manufactured by BASF) in which the surface of an aluminum flake pigment is coated with iron oxide.

  A light diffusing layer in which light diffusing fine particles are blended in at least one of the surface resin layer 1, the dye transfer preventing colorable resin layer 12, the dye transfer preventing layer 3 and each of the lower layers is prepared. Then, the laminate for printing of the present invention can be used as an internally-illuminated film (backlight film), which is preferable. In this case, it is more preferable to mix light diffusing fine particles on the lower layer side of the colored layer without impairing the sharpness and color development of the image.

  Examples of the light diffusing fine particles constituting the light diffusion layer include silica, calcium carbonate, titanium dioxide, aluminum hydroxide, acrylic resin, organic silicone resin, polystyrene, urea resin, and formaldehyde condensate. One or more of them may be selected, and is not particularly limited.

  The light transmissive resin that serves as a binder for the light diffusing layer in which light diffusing fine particles are dispersed and blended includes acrylic resins, polyurethane resins, polyester resins, polyvinyl chloride resins, polyvinyl acetate resins, and cellulose resins. Resin, polyamide resin, fluorine resin, polypropylene resin, polystyrene resin alone or a mixture thereof is suitable, or each resin is used by using a curing agent such as melamine resin, isocyanate resin, epoxy resin, etc. It is more suitable to apply a resin composition that has been three-dimensionally cured with the above functional group, but it is not particularly limited. The refractive index difference between the light transmissive resin and the light diffusing fine particles is generally good when it is about 0.02 or more. Further, the Tg (glass transition point) of the light-transmitting resin is preferably 50 ° C. or higher. If the Tg is less than 50 ° C., when the light diffusion layer comes into contact with another member, there is a problem in storage stability due to blocking. It is not preferable because it occurs.

  Among them, acrylic resins, polyurethane resins, polyester resins, polyvinyl chloride resins, polyvinyl acetates are excellent in dispersion suitability (wetting properties) of light diffusing fine particles and control suitability of refractive index difference. A single resin or a mixture of resin is preferable, but a resin composition in which each resin is three-dimensionally cured with a functional group of the resin using a curing agent such as a melamine resin, an isocyanate resin, or an epoxy resin is more preferable. It is.

  As a method for producing the light diffusion layer, a general coating method such as a roll obtained by dissolving or dispersing a light transmitting resin and one or more kinds of light diffusing fine particles in a suitable organic solvent (or water) is used. Apply using a coating method, knife coating method, etc., then dry and evaporate the organic solvent (or water), and further proceed the curing reaction between the resin and the curing agent as necessary. The coating method may be appropriately selected in consideration of the viscosity of the diffusion resin composition, the target film thickness, and the like. The addition amount of the light diffusing fine particles is preferably 1 to 40% by weight with respect to the light transmissive resin, and may be dispersed and blended according to the required characteristics. The coating thickness of the light diffusion layer is generally preferably about 3 to 50 μm, but is not limited thereto.

  When the illumination light is incident from the back side opposite to the surface resin layer, the printing laminate having the light diffusion layer function is uniformly diffused by the light diffusion film, such as a fluorescent light source of a backlight. It becomes a bright surface illuminator and also prevents reflection on the surface of a fluorescent lamp on the back surface. At this time, light also passes through the color coloring layer printed by sublimation dyeing on the coloring resin layer, and the function as an internally illuminated signboard is exhibited. However, since sublimation dyes are very transparent, it is necessary to print a large amount of ink in order to increase the transmission density to a desired density, so that the printing workability is lowered and there is a problem with the drying property after printing. Occurred. In order to solve this problem, it has been found that the transmission density of a printed image is improved by using a white pigment in the sublimation dyed layer to form a white layer.

In this case, a white pigment is used in at least one of the dye transfer preventing colorable resin layer 12, the colorable resin layer 2 and the dye transfer preventing layer 3 in order to improve the sharpness. It has been found that the transmission density of a printed image is improved if a white layer is formed. At this time, the dye-transfer-preventing colored resin layer is further divided, and when the upper layer is a transparent resin layer, the lower layer is a white layer, and when the colorable resin layer and the dye-transfer-preventing layer are configured, the colorable resin layer is Further, if the upper layer is a transparent resin layer and the lower layer is a white layer, the transmission density is improved while maintaining the sharpness of the image. In this case, the white pigment used for whitening may be any pigment that is usually used for coloring a synthetic resin white. Specifically, titanium oxide, zinc white, lead white, barium sulfate, zinc sulfide, and antimony oxide are used. , MTiO ₃ (M is one or more elements selected from the group consisting of Mg, Ca, Sr, and Ba). The amount of white pigment used at this time is such that the transmission density V of the white layer (manufactured by Noritz Koki Co., Ltd., using a concentration measuring device DM-201) is 0.10 to 1.70, preferably 0.15 to 1.65. More preferably, it is suitable to be 0.20 to 1.40. If the transmission density V of the white layer is less than 0.10, it is not sufficient to increase the transmission density of the image, and if it exceeds 1.70, the light transmission is insufficient and the characteristics of the internally illuminated signboard are lowered. It is not preferable.

  If a retroreflective structure described below is formed on the lower layer continuous to the dye transfer preventing colorable resin layer 12, the lower layer continuous to the dye transfer preventing layer 3, or the lower layer of the flexible resin layer 4, the night time The vehicle headlights and other lights also accurately return the light in the direction of the light source, and a full-color image similar to daytime is visible to the driver of the vehicle, making it suitable for various advertising signs including road signs It is. Furthermore, since it is possible to print an image by an on-demand system, it is not necessary to prepare a plate for each image as in the case of silk screen printing conventionally applied to a retroreflective sheet, which is extremely useful for cost reduction.

Examples of the production methods (1) to (3) of the retroreflective sheet will be described below.
(1) As shown in FIG. 6, after applying the focus resin composition in which the high refractive glass beads 102 are blended in the lower layer of each resin layer described above as the focus layer film 101 so as to obtain an optimum dry film thickness, Dried by normal drying or heating. Here, the optimum dry film thickness of the focal layer varies depending on the particle size of the glass beads, but is generally about 10 to 70 μm. Next, a reflective layer made of the metal reflective film 103 is formed. Suitable as the focus resin composition paint used at this time are those having a base polymer component such as polyurethane resin, polyvinyl acetal resin, acrylic resin, alkyd resin, polyester resin, etc., and these are non-crosslinked types It can also be used as a thermosetting type by blending a curing agent such as amino resin, epoxy resin, polyisocyanate or block polyisocyanate.

  In addition, the drying conditions after the application of the focus resin composition paint in the above are appropriately determined according to the type of base resin used as a coating material, the type of reactive functional group in the base resin, the type of curing agent, and the type of solvent. It is determined.

  The glass beads used preferably have a refractive index of 1.90 to 2.40, more preferably 2.10 to 2.30. The particle diameter is preferably 5 to 300 μm, more preferably 20 to 100 μm. When the particle size of the beads is less than 5 μm, the required focal layer thickness is extremely thin, and it becomes difficult to control the thickness. On the other hand, when the thickness exceeds 300 μm, the required focal layer thickness becomes extremely large, and due to the flow of the resin in the heating process at the time of molding, the resin is molded concentrically with the spherical diameter of the glass beads. Have difficulty. If the refractive index is less than 1.9, the required focal layer thickness becomes extremely large, and it is difficult to mold the resin concentrically with the spherical diameter of the glass beads. Further, when producing beads having a refractive index exceeding 2.4, it is extremely difficult to prevent the crystallization and to industrially produce transparent glass beads with high accuracy.

The method for providing the metal reflective film 103 is not particularly limited, and a normal vapor deposition method, sputtering method, transfer method, plasma method, or the like can be used. In particular, vapor deposition and sputtering are preferably used from the viewpoint of workability. The metal used in forming the metal layer is not particularly limited, and examples thereof include metals such as aluminum, gold, silver, copper, nickel, chromium, magnesium, and zinc. Among these, In consideration of workability, ease of forming a metal reflection film, durability of light reflection efficiency, and the like, aluminum, chromium, or nickel is particularly preferable. The metal reflective film may be formed of an alloy composed of two or more metals. The thickness varies depending on the metal used, but is 5 to 200 nm, preferably 10 to 100 nm. If the thickness of the metal reflection film is less than 5 nm, the concealment property of the metal reflection film is insufficient and the purpose of the reflection layer cannot be achieved. Conversely, if it exceeds 200 nm, the metal reflection film is cracked. This is not preferable because it easily enters and the cost is increased.
(2) As shown in FIG. 7, in the lower layer of each resin layer, the glass bead fixing layer 201 has a dry film thickness of 10% of the glass bead particle diameter to be used, preferably 100 μm. The glass bead fixing layer forming coating is applied so that the thickness becomes 20 μm from 20% of the bead particle diameter, and then the solvent is evaporated by drying at room temperature or by heating, and then the highly refractive glass beads 202 are embedded. . Typical paints used for forming the glass bead fixing layer include fluoroolefin copolymers containing reactive functional groups, polyester resins, alkyd resins, polyurethane resins, and reactive functional groups. Examples thereof include those in which an acrylic polymer is used as a base resin component and a curing agent such as an amino resin, an epoxy resin, a polyisocyanate, or a block polyisocyanate and / or a curing catalyst is blended. Here, each above-mentioned base resin component may be used independently, and can also be used as a 2 or more types of mixture. As the paint form, any of a solution type, a non-aqueous dispersion type, a water-soluble type, and a water dispersion type can be used, but the solution type is particularly preferable.

  Next, the focus resin composition paint described in (1) above is applied as the focus layer film 203 so as to obtain an optimal dry film thickness, and then dried by normal drying or heating.

  Application of the coating material in each step described above may be performed by spray coating, or may be performed using a coating apparatus such as a knife coater, comma coater, roll coater, reverse roll coater, or flow coater.

  Further, by using a clear coating material that does not contain a pigment as a coating material used for forming each layer of each retroreflective sheet of the present invention, a retroreflective sheet having no coloring can be obtained. It is also possible to obtain a colored retroreflective sheet by using a colored paint containing a pigment as a paint for forming each layer in the figure. Examples of pigments used in obtaining such colored paints include organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone red, and hansa yellow, and inorganic pigments such as iron oxide red, iron oxide yellow, titanium yellow, and cobalt blue. Known and conventional ones are used.

In the retroreflective sheet of the present invention thus obtained, after the metal reflective film 204 is formed as described above, a pressure-sensitive adhesive layer or an adhesive layer is formed on the metal reflective film, and further required. Accordingly, a release material such as a release paper or a release film can be bonded to the pressure-sensitive adhesive layer or the like to obtain a final product.
(3) As shown in FIG. 8A, transparent glass balls 302 are embedded in a plurality of planes on the surface of the polyethylene glass ball temporary fixing layer 307 laminated on the polyester film 308. The polyethylene laminated film (the glass sphere temporary fixing layer 307 and the polyester film 308) is heated to soften the polyethylene, and the glass sphere 302 is embedded. The glass sphere 302 is a fine particle having a particle diameter of about 5 to 300 μm and a refractive index of about 1.8 to 2.1. Particularly preferred as glass spheres have a refractive index of about 1.9 to 1.95 (particularly preferred is 1.92 to 1.93) and a particle size of about 20 to 90 μm (particularly preferred is 40 to 80 μm).

  Next, a metal reflective film 303 is formed on the hemispherical surface of the glass sphere 302 exposed from the surface of the glass sphere temporary fixing layer 307 by vapor deposition. This vapor deposition is performed on the entire surface of the glass ball temporary fixing layer 307. Then, the metal reflective film 303 deposited on the surface of the glass sphere temporary fixing layer 307, which will be described later, is deposited on the surface of the glass sphere temporary fixed layer 307 as it is, and the other metal reflective film 303 is supported together with the glass sphere 302. It moves to the resin sheet 304 (FIG. 8E). The metal reflective film 303 is preferably an aluminum reflective film, and can be implemented even if it is formed of another metal such as gold, silver, copper, nickel, or chromium.

As the next step, there is a method for producing a retroreflective sheet having the following two types of structures.
(A) Type with primer layer 305 (B) Type without primer layer In the case of (A) above, an adhesive is laminated on the back surface of the primer layer 305, and in the case of (B), an adhesive is laminated on the back surface of the support resin sheet 304. . In order to adjust the glass bead transfer performance of the support resin film on which the glass beads of the glass sphere temporary fixing layer are transferred and embedded, a polymer or low molecular plasticizer may be used for the support resin sheet. These plasticizers and the like move to the interface between the pressure-sensitive adhesive and the supporting resin sheet or the pressure-sensitive adhesive layer over time, and deteriorate the performance of the pressure-sensitive adhesive. That is, the interface adhesive force between the pressure-sensitive adhesive and the supporting resin sheet is reduced, and the adhesive performance of the pressure-sensitive adhesive to the substrate is reduced. In order to eliminate this problem, that is, in order to prevent migration of a plasticizer or the like from the support resin sheet to the pressure-sensitive adhesive layer, a primer layer may be laminated.

  The type having the primer layer 305 of (A) includes a resin resin having the above-described functional groups, or a supporting resin sheet among those resins and a curing agent having a functional group that reacts with the functional groups of those resins. A resin having excellent interlayer adhesion is selected as the resin for the primer layer 305. Then, a resin solution selected for the primer layer 305 is coated on a separately prepared polyester film 306 and dried using a hot air dryer. The film thickness of the primer layer 305 at this time is preferably 3 μm to 100 μm, preferably 6 μm to 50 μm. If it is less than 3 μm, the effect of preventing the migration of plasticizer or the like is lowered, and if it exceeds 100 μm, it is not preferred. This is not preferable because workability such as sticking is reduced.

  Next, a supporting resin sheet 304 having a constant thickness of about 10 to 300 μm, preferably about 30 to 100 μm, is prepared above the primer layer 305 created above (FIG. 8B). The resin that can be used for the supporting resin sheet 304 is preferably a resin having the functional group described above.

  The type (B) without the primer layer 305 can be carried out by omitting the primer layer preparation step in the above-described method for producing a retroreflective sheet. Next, as shown in FIG. 8C, the support resin sheet 304 as described above is placed along the surface of the glass ball temporary fixing layer 307. Then, as shown in FIG. 8D, the supporting resin sheet 304 is pressed against the surface of the glass ball temporary fixing layer 307. This pressing is performed so that the hemispherical surface on which the metal reflective film 303 of the glass sphere 302 is deposited is embedded in the support resin sheet 304. At this time, in order to increase the fixing force of the glass sphere 302 of the support resin sheet 304, it is more effective to add a coupling agent or the like to the support resin sheet 304. Then, as shown in FIG. 8E, the glass ball temporary fixing layer 307 is peeled off together with the polyester film 308 from the surface of the support resin sheet 304. At this time, as shown in FIG. 8E, the glass sphere 302 remains on the support resin sheet 304 and is held in a state where the hemisphere is buried by the support resin sheet 304. Then, when applying a cured form (for example, isocyanate curing etc.) in which the reaction proceeds at room temperature to the primer layer and / or the supporting resin sheet, the variation in the performance of the bonded portion at the time of thermoforming in the next step is eliminated, In order to stabilize the subsequent free-standing form, it is preferable to perform the aging treatment in an environment of 30 to 40 ° C. to substantially terminate the reaction. Further, a heat treatment step at 120 to 150 ° C. is also effective in order to improve the adhesion between the glass sphere and the supporting resin sheet.

  Next, the surface of the supporting resin sheet formed in the state shown in FIG. 8F is covered with the dye transfer-preventing colored resin layer 12 or the dye transfer-preventing layer 3 or the flexible resin layer 4 of the printing laminate. . From the back polyester film side 306 of the supporting resin sheet 304 on which the resin layer is disposed, thermocompression molding is performed with a patterned embossing roll 309 (FIG. 8G). As a means for this thermocompression bonding, it is preferable to pass a heating roll having a roll surface temperature of 150 to 240 ° C., preferably 170 to 220 ° C. A support resin sheet that can be heat-molded at a temperature of less than 150 ° C. and exhibits adhesiveness with the surface film is not preferable because it cannot maintain the self-standing form of the sheet for a long period of time. In addition, a support resin sheet capable of being heat-molded at a temperature exceeding 240 ° C. is not preferable because a polyester film used as a protective film is melted when a heat-molding process is performed, causing a decrease in workability during heat-molding.

  After the heat forming process, the back polyester film 306 is peeled off to produce a recursive high-intensity reflective sheet original. Thus, an embossed groove 310 having a width of 200 to 800 μm and a depth of 100 to 150 μm is formed on the back surface side of the support resin sheet 304, for example.

  A pressure-sensitive adhesive layer or an adhesive layer may be formed so as to embed the embossed groove, and a release material such as release paper or a release film may be bonded to the pressure-sensitive adhesive layer or the like as necessary to obtain a final product. it can.

  As the retroreflective sheet positioned in the lower layer of the printing laminate of the present invention, various known retroreflective sheets can be applied in addition to the above-described retroreflective sheet original.

  The laminate for printing according to the present invention obtained through the above steps is the dye transfer preventing layer 3 or the flexible resin layer 4 or metal vapor deposition on the side opposite to the surface side in the structure other than the retroreflective sheet. After the film is formed, a pressure-sensitive adhesive layer or an adhesive layer is formed on these layers as necessary, and a release material such as a release paper or a release film is formed on the pressure-sensitive adhesive layer or the adhesive layer. Can be bonded together to make a finished product of a printed laminate. At this time, an antistatic agent is added by a kneading method or an antistatic agent is applied to the surface of the release material in order to reduce the electrical resistance on the surface of the release material and prevent the generation of static electricity. In other words, the discharge direction of the ink discharged from the printing nozzles is distorted by static electricity generated when the sheet is unwound or static electricity generated by friction between the printing laminate and the printing machine during printing by the ink jet printer. This is preferable because it is possible to prevent the printed image from being disturbed. Examples of the antistatic agent used at this time include various surfactants, inorganic salts, polyhydric alcohols, metal compounds, and carbon. Examples of surfactants include anionic antistatic agents such as alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfate esters, alkyl ethoxy sulfate esters, and alkyl phosphate ester salts, alkyl trimethyl ammonium salts, and acyloyl amides. Cationic antistatic agents such as propyltrimethylammonium methosulfate, alkylbenzyldimethylammonium salt, acylcholine chloride, amphoteric antistatic agents such as alkylbetaine type, alkylimidazoline type, alkylalanine type, fatty acid alkylolamide, di- ( 2-hydroxyethyl) alkylamine, polyoxyethylene alkylamine, glycerin fatty acid ester, polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxysol Fatty acid ester, polyoxyethylene alkyl phenyl ethers, various surfactants of the nonionic antistatic agent of polyoxyethylene alkyl ether, and the like. When the release material 6 is polyethylene terephthalate, for example, about 5% by weight of polyethylene glycol can be copolymerized at the time of polymer synthesis.

  In addition, it is preferable to apply the biaxially stretched polyester film that has been annealed by heating as the base material film as the release material, and when heated at 150 ° C. for 30 minutes, the film release direction is 1.0% or less. It is preferable to apply a biaxially stretched polyester film having a shrinkage of 0.8% or less, more preferably 0.6% or less as a base film. A release material having a shrinkage rate exceeding 1.0% is not preferable because the laminate is curled on the release material side when the printing laminate of the present invention is heated and sublimated.

If necessary, the surface resin layer 1 may be [M ²⁺ _1-X M ³⁺ _X (OH) ₂ ] ^{X +} [A ^n- _{X / n} · mH ₂ O] ^X- (M ²⁺ is divalent). metal ion, M ³⁺ is a trivalent metal ion, a ^n-n-valent anion, X is greater than 0 0.33, 0 ≦ m ≦ 2) hydrotalcites and metal oxide represented by When a coating film-forming composition containing the fine particles is applied and dried, a hydrophilic film is formed, resulting in a strong surface having a sufficiently small contact angle with water, thereby preventing contamination due to hydrophilicity. In addition, since it is possible to prevent adhesion of water droplets due to condensation that inhibits the retroreflective effect, it is possible to secure sufficient retroreflective at night, so it is preferable to apply it to various advertising signs such as road signs. Further, the composition exhibits a sufficient hydrophilic performance with a film thickness of 1 μm or less, and maintains a long-term hydrophilic performance outdoors, and further, a sublimation dye from the surface resin layer is heated inside the laminate for printing. In the case of permeation, it is very suitable without impeding permeation of the staining agent. As the metal oxide fine particles, titanium oxide particles, particularly a slurry solution of titanium oxide, is most preferable. Instead of titanium oxide, transition metal oxides such as zirconium oxide, strontium titanate, tungsten oxide, iron oxide, and others It is also possible to use metal oxides such as zinc oxide, bismuth oxide, tin oxide, alumina, magnesia, strontium oxide, and the like. The average particle diameter is preferably in the range of 0.001 to 0.5 μm, and particularly preferably 0.01 to 0.1 μm.

  Moreover, it is also possible to laminate | stack a peelable temporary display surface layer on the surface side of the said printing laminated body as needed. At this time, the temporary display surface layer is produced by using the coating apparatus described above for the resin for the temporary display surface layer so that the dry film thickness is about 1 μm to about 100 μm, preferably about 3 μm to about 80 μm, more preferably about 5 μm to What is necessary is just to adjust so that it may be set to about 60 micrometers. Further, if necessary, the temporary display surface layer can be produced as a laminated film of two or more layers. At that time, the temporary display surface layer is produced by laminating the upper layer sequentially from the lower layer. In this case, the uppermost layer side of the temporary display surface layer has absorptivity of ink containing a sublimable dyeing agent, and the surface side in contact with the surface resin layer (A) has the sublimation property. It is more preferable that the dye is formed of a resin having no affinity.

  In particular, the laminate for printing of the present invention in which a temporary display surface layer is laminated on the surface side can be directly printed on the temporary display surface layer of the laminate for printing by using an inkjet printer with an image taken with a commercially available digital camera, Thereafter, if heat treatment is performed at 150 to 200 ° C. for several minutes, the sublimable dyeing agent printed on the temporary display surface layer is diffused and penetrated into the printing laminate to easily form an image. This image has a resolution as high as that of a conventional silver salt photograph, and after a 1000 hour test using a sunshine carbon type accelerated weathering tester described in JIS Z 9117 (outdoor south surface vertical exposure 5 years) In this case, no abnormality occurred in the image, and the durability was so high that the fading was hardly visible. Replacing this with indoor storage resulted in a storage stability that greatly exceeded 100 years, and was larger than conventional silver halide photographs and water-based inkjets that are widely used for business and home use. Images can be produced at a lower cost than before, and the developer disposal process required for silver salt photography is not required, so it is extremely environmentally friendly, and is extremely sharp and highly durable with high storage stability. Excellent photographic images can be obtained.

  Examples of a method for performing the heat diffusion printing at this time include an indirect heating method and a direct heating method. Indirect methods include heating with hot air and heating with far-infrared radiation, and direct heating includes methods such as bringing the printing laminate into direct contact with a heating plate or wrapping around a hot roll. Either of these heating methods may be selected or used in combination. Although high temperature heating at 150 to 200 ° C. is required for diffusion dyeing, if the temperature of the printing laminate itself is rapidly raised to the above-described high temperature, rapid thermal expansion of the sheet occurs, and the sheet This is not preferable because of abnormal appearance of wrinkles. As a result of intensive studies by the inventor to solve this problem, initial heating is 70 to 130 ° C., followed by 120 to 150 ° C., and further heating is performed in the order of 140 to 200 ° C. 150 ° C, 70-130 ° C, normal temperature, and gradually increase the temperature gradient, heat at a constant temperature, and perform diffusion printing in a cycle of temperature decrease, the thermal expansion and shrinkage due to the temperature decrease can be mitigated, and the sheet has an appearance such as wrinkles It is preferable that no abnormality occurs. Furthermore, it is preferable that the initial heating is 10 to 60% of the entire heating time, the heating at a constant temperature is 20 to 80% of the entire heating time, and the temperature drop is 10 to 40% of the entire heating time, more preferably It is more preferable that the initial temperature raising heating is 15 to 35% of the whole heating time, heating at a constant temperature is 30 to 70% of the whole heating time, and temperature lowering is 15 to 35% of the whole heating time. In the case of roll heating, if a crown roll having a thicker central part than both ends at the time of temperature reduction is used, wrinkles generated due to sheet shrinkage due to temperature reduction can be prevented, which is preferable. The gradient of the crown roll at this time is more preferably such that the difference in diameter between the both end portions and the central portion per width of 1000 mm is 0.5 to 10 mm, preferably 1 to 5 mm. In addition, in the case of indirect heating, the sheet is sandwiched between two upper and lower rolls at the entrance to the heater, and the sheet is conveyed by the lower support guide roll that is sequentially driven. It is more preferable to provide an upper pressing roll so as to assist proper conveyance so as to sandwich the sheet. As described above, indirect heating is preferable because a necessary quantity can be heat-treated without losing the printing laminate. When a single plate is heat-treated, the sheet may be left on a heating plate heated to the required temperature. However, when continuous treatment is performed with a hot roll, in addition to the above-described conditions, the winding tension is set to If the width is 5 to 40 kg / m, preferably 10 to 30 kg / m, wrinkles generated on the sheet can be prevented. If it is less than 5 kg / m width, wrinkles are generated when the sheet is wound, and if it exceeds 40 kg / m width, unnecessary elongation is undesirably applied to the sheet.

  This will be described more specifically with reference to examples. In the following examples, “parts” represents parts by weight. “%” Means% by weight.

(Example 1, reference example)
In preparing the resin composition for the surface resin layer 1 shown in FIG. 1, hexafluoropropylene / ethyl vinyl ether / veova 9 / monovinyl adipate having a weight average molecular weight of about 45,000 as a fluororesin = 50/15/20/15. (Weight ratio) Copolymer solution ("Beova 9": Japan Epoxy Resin brand name, vinyl ester of branched fatty acid, solvent is toluene / n-butanol = 70/30 weight ratio mixed solvent, nonvolatile content about 50 %) Is approximately 7.4 parts of sorbitol polyglycidyl ether having an epoxy equivalent of 170, approximately 0.6 parts of diazabicyclooctane, Tinuvin 900 (manufactured by Ciba Specialty Chemicals, benzotriazole UV absorber) ) About 1 part, Tinuvin 292 (Ciba Specialty Chemicals, Hinder) A resin composition containing about 1 part of an amine-based light stabilizer) is applied on a polyester film so that the dry film thickness is about 20 μm, and is heated and dried at about 140 ° C. for about 10 minutes to form the surface resin layer 1. Obtained. Subsequently, about 100 parts of the vinyl polymer (a-1) synthesized in Reference Example 1 described above on the surface resin layer 1 produced as described above, Vernock DN-950 (Dainippon Ink & Chemicals, Inc.) as a curing agent. Apply about 25 parts of polyisocyanate prepolymer (non-volatile content: about 75%) and apply the resin composition to a dry film thickness of about 30μm, and dry at about 140 ° C for about 10 minutes to prevent dye migration. The colorable resin layer 12 was produced. As shown in FIG. 4, about 100 parts of acrylic pressure-sensitive adhesive fine tack SPS-1016 (manufactured by Dainippon Ink & Chemicals, Inc.) Apply a mixed solution of about 2 parts of the crosslinker Finetac TA-101-K (Dainippon Ink Chemical Co., Ltd., adhesive curing agent chelate type), heat dry at about 100 ° C. for about 5 minutes, thickness About 35 μm of the pressure-sensitive adhesive layer 5 was formed. Further, a release film obtained by subjecting this adhesive layer 5 to an antistatic process and an annealing process on the opposite side of the 50 μm thick biaxially stretched polyester release film coated with silicon on one side. 6 (manufactured by Teijin DuPont Films, trade name A-31, shrinkage in the winding direction of the film when heated at 150 ° C. for 30 minutes) is bonded, and then the polyester film as the support film is peeled off The final product.

Next, an image was printed on a transfer paper (Gradess S-coat Paper) by a piezo printer (RJ-6000 manufactured by Muto Kogyo Co., Ltd.), which is a type of inkjet method separately prepared. As the sublimation ink-jet ink, an ink-jet ink (6-color set of cyan, magenta, yellow, black, light cyan and light magenta) manufactured by Kiwa Chemical Industry Co., Ltd. containing a sublimable dye was used. The print surface of the transfer paper is applied to the surface resin layer 1 of the printing laminate produced above, and the degree of vacuum is 3.99 × 10 ³ Pa (30 mmHg) using a heat vacuum applicator (VACUSeal 4468 manufactured by HUNT EUROPE). ) At about a set temperature of about 170 ° C. for about 7 minutes, and by heating the printing laminate and the transfer paper together, the image printed on the transfer paper is diffused and dyed on the printing laminate. The image was transferred to the dye transfer-preventing colored resin layer 12.

(Example 2, reference example)
In preparing the resin composition for the surface resin layer 1 shown in FIG. 2, fluorinate K-703 (manufactured by Dainippon Ink & Chemicals, Inc., weight average molecular weight 40000, solid content hydroxyl value 72, non-volatile content approx. 60%), Bernock DN-950 as a curing agent, Tinuvin 900 as an ultraviolet absorber, and Tinuvin 292 as an antioxidant. The blending ratio of the resin composition for the surface resin layer 1 in Example 2 is about 100 parts for fluorinate K-703, about 25 parts for Bernock DN-950, about 1 part for Tinuvin 900, and about 1 part for Tinuvin 292. is there. And the said composition was apply | coated so that the dry film thickness might be set to about 20 micrometers on a polyester film, and it heat-dried at about 140 degreeC for about 10 minutes, and obtained the surface resin layer 1. FIG. Subsequently, a polycarbonate non-yellowing urethane resin NY-331 (manufactured by Dainippon Ink & Chemicals, Inc., nonvolatile content of about 25%, solvent DMF, 100% modulus of about 55 kg / cm ² ) is applied on the surface resin layer 1 produced above. It was used so that the dry film thickness was about 20 μm, and was heated and dried at about 140 ° C. for about 10 minutes to produce a colored resin layer 2. Subsequently, about 100 parts of the vinyl polymer (a-2) synthesized in Reference Example 2 described above and about 50 parts of Bernock DN-950 as a curing agent were blended on the colored resin layer 2. Was applied on the colorable resin layer 2 so that the dry film thickness was about 15 μm, and dried at about 140 ° C. for about 10 minutes to prepare the dye migration prevention layer 3. Subsequently, about 100 parts of Acrydic 49-394-IM (manufactured by Dainippon Ink & Chemicals, Inc., non-volatile content: about 50%) as an acrylic resin on the dye migration prevention layer 3, about 15 parts of Bernock DN-950, The blended resin composition was applied so as to have a dry film thickness of about 20 μm, and dried at about 140 ° C. for about 10 minutes to produce a flexible resin layer 4.

  As shown in FIG. 5, the pressure-sensitive adhesive layer 5 and the release film 6 were formed on the surface of the flexible resin layer 4 of the printing laminate thus obtained in the same manner as in Example 1 to obtain a final product.

  Next, in the same manner as in Example 1, the printing surface of the transfer paper was applied to the surface resin layer 1 to transfer the image to the coloring resin layer 2.

(Example 3, reference example)
The structure, dimensions, manufacturing method, and the like are the same as in Example 2 except that the resin composition mixture liquid of the surface resin layer 1 and the color resin layer 2 liquid mixture are changed as follows. The compounding example of the resin composition for the surface resin layer 1 in this example is Fluonate K-700 (manufactured by Dainippon Ink & Chemicals, Inc., weight average molecular weight of about 70000, solid content hydroxyl value of 48, nonvolatile content of about 50%). About 100 parts, about 15 parts Sumimar M-100C (Methylated melamine resin manufactured by Sumitomo Chemical Co., Ltd., 100% nonvolatile content) as a curing agent, Neicure 3525 (made by KING INDUSTRIES, dinonylnaphthalenedisulfonic acid) as a curing catalyst Is about 1.3 parts, Tinuvin 900 is about 1 part, and Tinuvin 292 is about 1 part.

  The formulation example of the resin composition for the coloring resin layer 2 is about 100 parts of Bernock D6-439 (Dainippon Ink & Chemicals, Inc., alkyd resin, solid content hydroxyl value 140, non-volatile content 80%), and Vernock as a curing agent. About 82 parts of DN-980 (a polyisocyanate prepolymer manufactured by Dainippon Ink and Chemicals, non-volatile content: 75%).

(Example 4, reference example)
The structure, dimensions, manufacturing method, and the like are the same as in Example 2 except that the resin composition for the surface resin layer 1 is changed as follows. In this example, the compounding example of the resin composition for the surface resin layer 1 is about 100 parts of Acrydic A-9521 (Dainippon Ink & Chemicals, Silicon acrylic resin, solid content 50%), and Acrydic as a curing agent. About 22 parts of HZ-1018 (Dainippon Ink & Chemicals, Inc. epoxy group-containing silicon compound, solid content 55%).

(Example 5, reference example)
The structure, dimensions, manufacturing method, and the like are the same as those in Example 2 except that a peelable temporary display surface layer capable of printing display is laminated on the surface of the printing laminate. On the surface resin layer 1 of the printing laminate produced in Example 2, a dry film thickness of about 15 μm was obtained using Fluorate FEM-600 (solid content 45%) manufactured by Dainippon Ink & Chemicals, Inc. as an aqueous fluororesin. It was applied so that it was heated and dried at about 110 ° C. for about 5 minutes. Subsequently, MZ-100 (manufactured by Takamatsu Yushi Co., Ltd., a mixture of amorphous silicon dioxide, polyurethane and vinyl resin, solid content 15%, solid content so that the dry film thickness is about 30 μm on the dry film. The porous pigment content was about 56%, and the mixture was dried by heating at about 110 ° C. for about 5 minutes. An image was printed on the temporary display surface layer thus produced by the same method as in Example 1. Thereafter, a hot air dryer (Fine Oven DF6L manufactured by Yamato Kagaku Co., Ltd.) is set at about 170 ° C., and heat treatment is performed for about 7 minutes to diffuse and infiltrate the sublimation dye, and the colored resin layer 2 on the printing laminate side. An image was printed on the film, and then the temporary display surface layer was peeled off in a film state.

(Example 6)
As the dye transfer prevention layer 3 shown in FIG. 2, an annealed biaxially stretched polyester film (trade name MX534, manufactured by Teijin DuPont Films, Ltd. has a shrinkage of 0 in the winding direction of the film when heated at 150 ° C. for 30 minutes. 3% and a film thickness of 97 μm), a resin composition for the colored resin layer 2 having the same composition as in Example 2 was applied so that the dry film thickness was about 20 μm, and about 10 at about 140 ° C. Heat-drying was performed for a minute, and the coloring resin layer 2 was produced.

  Subsequently, the resin composition for the surface resin layer 1 described in Example 2 is applied on the colored resin layer 2 so that the dry film thickness is about 20 μm, and is heated and dried at about 140 ° C. for about 10 minutes. The surface resin layer 1 was obtained. The pressure-sensitive adhesive layer 5 and the release film 6 are formed on the back surface of the biaxially stretched polyester film, which is the dye transfer preventing layer of the printing laminate thus obtained, in the same manner as in Example 1, and the final product did. Next, in the same manner as in Example 1, the printing surface of the transfer paper was applied to the surface resin layer 1 to transfer the image to the coloring resin layer 2.

(Comparative Example 1)
The structure, dimensions, manufacturing method, and the like are the same as those in Example 2 except that the step of the dye transfer prevention layer 3 is omitted.

(Comparative Example 2)
Except for omitting the steps of the dye transfer preventing layer 3 and the flexible resin layer 4, the structure, dimensions, manufacturing method, and the like are the same as those in the second embodiment.

(Comparative Example 3)
The structure, dimensions, manufacturing method, etc., except that the resin composition mixture liquid, the color resin layer 2, and the dye migration prevention layer 3 are changed as follows and the flexible resin layer 4 is omitted. Is the same as in the second embodiment.

Polyurethane-based resin solution Burnock L7-920 (Dainippon Ink Chemical Co., Ltd., non-volatile component) on a biaxially stretched polyester support film (no annealing treatment, used as dye transfer prevention layer 3) subjected to double-sided easy adhesion treatment 25 ± 1%, solvent toluene, sec-butanol) was applied so as to have a dry film thickness of 20 μm, and heat treatment was performed at about 140 ° C. for about 10 minutes to prepare a colored resin layer 2. Subsequently, a vinyl chloride resin paint having the following composition is applied on the colored resin layer 2 so that the dry film thickness is about 20 μm, and is heated and dried at about 140 ° C. for about 10 minutes to form the surface resin layer 1. did.
(1) 100 parts of vinyl chloride resin
(2) 25 parts of ethylene / vinyl ester resin
(3) Polyester plasticizer 10 parts As the above-mentioned vinyl chloride resin, Nikavinyl SG-1100N (manufactured by Nippon Carbide Industries Co., Ltd.) and as the ethylene / vinyl ester resin, Elvalloy (manufactured by Mitsui DuPont Polychemical Co., Ltd., trade name) As the polyester plasticizer, a polyester plasticizer having a number average molecular weight (Mn) of about 3000 synthesized from a mixed dihydric alcohol composed of propylene glycol, butanediol, and hexanediol and adipic acid was used.

  The results after image transfer and the test methods for the above Examples and Comparative Examples are summarized in Tables 1 to 4 below.

(Note 1) South surface 45 ° outdoor exposure test (test location: Wakayama Prefecture) The test period is one year. ○ (Keeps clear)> △ (There is a slight blur in the image)> × (Image is blurred and unclear)
(Note 2) Yubucon (made by US Atlas Co., Ltd.) accelerated weathering test 1 cycle: UV irradiation 60 ° C. × 4 hours / condensation 40 ° C. × 4 hours Test time: 1000 hours ○ (Keep clear)> △ (Slightly on image Blurred)> × (Image is blurred and unclear)
(Note 3) Based on the conditions of the sunshine carbon type accelerated weather resistance test described in JIS Z 9117, the test time is 1000 hours.

○ (preserves sharpness)> △ (the image has a slight blur)> × (the image is blurred and unclear)
(Note 4) Eriksen testing machine (manufactured by Toyo Seiki Seisakusho)
Affixed substrate: An aluminum plate with a thickness of 1 mm and an A50502P hardness H24 specified in JIS H 4000.
Test method: A printing laminate is attached to a substrate, left at room temperature for 48 hours, a punch having a radius of 10 mm is pressed from the rear surface of the substrate, and a curved surface is formed by pressing 6 mm. Thereafter, the Ayumukon accelerated weathering test (Note 2) is conducted for 1000 hours.
○: No appearance abnormality.
(Triangle | delta): A crack generate | occur | produces on the peak of the extruded curved surface.
X: The whole sheet floats from the substrate.
(Note 5) Using a heat vacuum applicator (VACUSeal 4468 manufactured by HUNT EUROPE), heat press-bonding is performed at a set temperature of about 170 ° C. for about 7 minutes at a vacuum degree of 3.99 × 10 ³ Pa (30 mmHg). A state of the film after the printing laminate and the transfer paper are both heated to diffuse and dye the image printed on the transfer paper on the printing laminate to transfer the image.
○: No appearance abnormality.
X: Wrinkles occur on the entire sheet.
(Note 6) The test method is the same as (Note 3). The color difference ΔE was measured by the stimulus value direct reading method defined in JIS Z 8722, and was obtained using the color difference formula defined in “JIS Z 8730 color difference display method 6”.
(Note 7) The test method is the same as (Note 1). The color difference ΔE was determined in the same manner as (Note 6).

  As shown in Tables 1 to 4 above, Example 1 did not have a flexible resin layer, so that the three-dimensional curved surface sticking ability was not good, but it had excellent image sharpness retention, and a sheet after heat transfer. The condition was also good. Examples 2 to 5 were also suitable for three-dimensional curved surface sticking, were excellent in image sharpness retention, and were in good condition after heating and transfer. In Example 6, although the three-dimensional curved surface sticking ability is poor, the biaxially stretched polyester film annealed to the dye transfer prevention layer is used, so that the image sharpness retention power is excellent, and the sheet after heat transfer No wrinkles were observed. In Comparative Examples 1 and 2, since the dye migration preventing layer 3 was not formed, image bleeding or the like occurred, and the image sharpness retention was inferior. In Comparative Example 3, since a biaxially stretched polyester film was used for the dye transfer prevention layer, the suitability for 3D curved surface sticking was poor, and wrinkles were generated on the sheet after heat transfer. Further, since a vinyl chloride resin was used for the surface resin layer 1, the image sharpness retaining ability was low and the image fading resistance was also poor. Therefore, the printing laminate of the present invention in which the dye migration preventing layer 3 is formed can maintain the sharpness of the image without causing blurring or blurring of the image even under long-term standing conditions. Highly weather-resistant printed laminates with extremely excellent properties could be realized. In addition, when biaxially stretched polyester is used, generation of wrinkles due to heating can be prevented by using an annealed film. Moreover, when using for curved surface sticking, if the flexible resin layer 4 was formed in the lower part of the dye transfer prevention layer 3, it turned out that it can fully respond.

It is sectional drawing of the laminated body for printing in the reference example of this invention. It is sectional drawing of the laminated body for printing in one Embodiment of this invention. It is sectional drawing of the laminated body for printing in another reference example of this invention. It is sectional drawing of the laminated body for printing in another reference example of this invention. It is sectional drawing of the laminated body for printing in another reference example of this invention. It is sectional drawing of the laminated body for printing in another reference example of this invention. It is sectional drawing of the laminated body for printing in another reference example of this invention. A is a process diagram showing still another embodiment of the present invention, in which a glass ball temporary fixing layer is formed on a polyester film, transparent glass balls are embedded on a plurality of planes on the surface, and a metal reflective film is formed. , B is a schematic cross-sectional view of a portion where a primer layer is formed on a polyester film and a support resin sheet is formed thereon, and C is the same, and the support resin sheet is formed on the surface of the glass ball temporary fixing layer. Schematic cross-sectional view of a portion along which the support resin sheet is pressed against the surface of the glass ball temporary fixing layer, E is a glass ball temporary fixing layer together with the polyester film from the surface of the support resin sheet. , F is the same, and F is the same as the cross section of the support resin sheet surface covered with the printing laminate of the present invention, and the part is subjected to thermocompression molding with a patterned embossing roll, and G is the same. , It is a cross-sectional schematic view of the portion subjected to thermocompression bonding molded at Nbosuroru.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Surface resin layer 2 Colorable resin layer 3 Dye transfer prevention layer 4 Flexible resin layer 5 Adhesive layer 6 Release material 12 Dye transfer prevention color resin layer 101 Focal layer film 102 High refractive glass bead 103 Metal reflecting film 201 Glass bead fixing layer 202 High refractive glass bead 203 Focal layer film 204 Metal reflecting film 302 Glass sphere 303 Metal reflecting film 304 Supporting resin sheet 305 Primer layer 306 Polyester film 307 Temporary glass ball fixing layer 308 Polyester film 309 Embossed roll with handle 310 Embossed groove

Claims (22)

A laminate for printing in which a sublimable dyeing agent is infiltrated into the resin layer by heating and colored, and in order from the surface,
A coloring resin having an affinity for the dyeing agent as a surface resin layer (A) having a weak affinity with the sublimation dyeing agent and allowing the dyeing agent to pass therethrough and a dye-transfer-preventing coloring resin layer (B) A layer (B1) and a dye migration preventing layer (B2) for preventing migration of the staining agent are laminated,
The dye transfer prevention layer (B2) is a biaxially stretched film stretched by 10% or more in the winding direction and the width direction, respectively, and has a shrinkage rate in the winding direction of the film when heated at 150 ° C. for 30 minutes. A laminate for printing, which is 1.0% or less.   The laminate for printing according to claim 1, wherein the surface resin layer (A) is formed of a fluorine resin made of a fluoroolefin copolymer soluble in a solvent.   The laminate for printing according to claim 1, wherein the surface resin layer (A) is formed of a silicon-modified acrylic resin.   The laminate for printing according to any one of claims 1 to 3, wherein the coloring resin layer (B1) is a resin containing 20% by weight or less of a low molecular weight compound having a molecular weight of 1300 or less.   The printing laminate according to any one of claims 1 to 4, wherein a matting agent is added to the surface resin layer (A) to make the surface layer have a 60 ° gloss of 70 or less.   At least one of the surface resin layer (A) and the colored resin layer (B1) includes a high molecular weight type ultraviolet absorber, a high molecular weight type hindered amine light stabilizer, and a high molecular weight type hindered phenol type. The laminate for printing according to any one of claims 1 to 5, comprising at least one selected from antioxidants.   A light diffusing function is added by adding light diffusing fine particles to at least one of the surface resin layer (A), the dye migration preventing layer (B2), and each lower layer thereof. Item 7. The laminate for printing according to any one of Items 1 to 6.   The white density layer is formed by using a white pigment in at least one of the coloring resin layer (B1) and the dye transfer prevention layer (B2) to improve the transmission density of a printed image. The laminated body for printing in any one of -7.   The laminate for printing according to any one of claims 1 to 8, wherein a metal layer is formed in a lower layer of the coloring resin layer (B1) or the dye migration prevention layer (B2).   A retroreflective layer in which a layer containing a high refractive glass bead is laminated under the dye transfer prevention layer (B2) and a metal reflective film is further formed under the layer containing the high refractive glass bead. Item 10. A laminate for printing according to any one of Items 1 to 8.   A retroreflective layer in which a fixed layer having a high refractive glass bead fixed to the lower layer of the dye transfer preventing layer (B2) and a focus resin layer are sequentially laminated, and a metal reflective film is formed on the lower layer of the focus resin layer. The laminated body for printing according to any one of claims 1 to 8.   A plurality of transparent spheres provided with a metal reflection film on a lower hemisphere, a support resin sheet holding the plurality of transparent spheres, and a transparent cover that covers the plurality of transparent spheres by being disposed on the surface side of the support resin sheet The printing according to any one of claims 1 to 8, wherein the cover film is a laminate for printing in a retroreflective sheet made of a film and provided with a joining portion for holding the cover film on the support resin sheet. Laminated body. The surface resin layer (A) is composed of [M ²⁺ _1-X M ³⁺ _X (OH) ₂ ] ^{X +} [A ^n- _{X / n} · mH ₂ O] ^X- (where M ²⁺ is divalent) metal ion, M ³⁺ is a trivalent metal ion, a ^n-n-valent anion, X is greater than 0 0.33 or less, the 0 ≦ m ≦ 2 hydrotalcites represented by) and metal oxides The laminate for printing according to any one of claims 1 to 12, which is coated with a coating film-forming composition containing fine particles.   The back surface of the laminate for printing is further provided with a pressure-sensitive adhesive layer and a release material on the outside thereof, and the pressure-sensitive adhesive layer or the release material is subjected to antistatic treatment. Laminate for printing.   At least one peelable temporary display layer capable of printing and displaying is further provided on the surface resin layer (A), and the surface side of the temporary display layer not in contact with the surface resin layer (A) is sublimable dyeing. The ink containing an agent has an absorptivity, and it is possible to sublimate the sublimable dyeing agent by heat treatment to diffusely dye the printing laminate, and after the heat treatment, the temporary display layer is The laminate for printing according to any one of claims 1 to 14, which can be peeled off from the surface resin layer (A) of the laminate for printing in a film state. A method for printing the printing laminate according to claim 1, comprising:
The transfer paper is printed using an ink containing a sublimable dye, and the image forming surface of the transfer paper is brought into contact with the surface resin layer (A), followed by heat treatment, and the sublimable dye. A printing method, wherein the coloring resin layer (B1) is dyed by diffusion dyeing. A method for printing the printing laminate according to claim 15, comprising:
A printing method, wherein printing is performed using an ink containing a sublimable dye on the temporary display layer. A method for printing the printing laminate according to claim 15, comprising:
Printing on the temporary display layer using an ink containing a sublimable dyeing agent, followed by heat treatment to sublimate the sublimable dyeing agent to diffusely dye the coloring resin layer (B1). A printing method characterized by the above.   The printing method according to claim 16, wherein the printing is printing by an inkjet method.   The printing method according to claim 16 or 18, wherein the heat treatment temperature is in a range of 150 to 200 ° C.   The printing method according to claim 16 or 18, further comprising a step of drying printing ink between the printing and the heat treatment. A printed matter printed using the printing method according to claim 16.

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