JP5272587B2 - PRINTED PRODUCT AND METHOD FOR FORMING PRINTED PRODUCT - Google Patents

Description

The present invention relates to a printed matter and a method for forming a printed matter . More specifically, the present invention relates to a printed matter that can prevent cracks generated in a printed material when an image is formed on an aqueous image-receiving paper comprising a water-based intermediate layer and an aqueous receiving layer on a substrate, and a method for forming the printed material .

  Conventionally, an image such as a gradation image, a monotonous image such as a character, a symbol, or the like is formed using a thermal transfer method. As the thermal transfer system, a thermal sublimation transfer system and a thermal melt transfer system are widely used.

  Of these, the thermal sublimation transfer method uses a dye layer in which a sublimation dye used as a coloring material is dissolved or dispersed in a binder resin and a thermal transfer sheet carried on a base sheet, and this thermal transfer sheet is superposed on an image receiving sheet to perform thermal transfer. In this method, an energy corresponding to image information is applied by a heating device such as a head to transfer the sublimation dye contained in the dye layer on the thermal transfer sheet to the image receiving sheet to form an image.

  This heat-sensitive sublimation transfer method can control the amount of dye transfer in dot units according to the amount of energy applied to the thermal transfer sheet, and is therefore excellent in forming gradation images, and has the advantage of easy formation of characters, symbols, etc. Have.

  Images formed by the above heat-sensitive sublimation transfer method protect the images because the transferred dye is present on the surface of the transfer target, and also from the viewpoint of image protection such as light resistance and abrasion resistance. Many techniques for forming a protective layer are known (for example, Patent Documents 1 to 3).

However, an image formed on an aqueous image-receiving sheet (for example, an image-receiving sheet obtained by laminating a receiving layer similarly formed of an aqueous binder on an insulating layer formed by dispersing hollow particles in an aqueous binder) When a thermal transfer sheet with these protective layers is applied, the dimensional change is large under high-temperature and high-humidity storage, and the protective layer that cannot follow the dimensional change may crack, and the print design (quality) There was a problem of lowering.
Japanese Patent Laid-Open No. 7-276831 JP 2000-71626 A JP 2006-272672 A

  The present invention has been made in view of such problems, and when forming an image on an aqueous image-receiving paper, a protective layer thermal transfer sheet for forming a protective layer that does not crack even under high temperature and high humidity storage, and The main purpose is to provide a print using this.

The present invention for solving the above problems is a printed material, comprising a base material, an aqueous intermediate layer containing a water-based binder and hollow particles provided on the base material as main components, and the aqueous intermediate layer. An aqueous receptive layer provided on the adhesive layer, an adhesive layer provided so as to cover at least a part of the aqueous receptive layer, and a release layer provided on the adhesive layer, the adhesive layer, and the release layer Respectively, a resin obtained by copolymerizing methyl methacrylate and a reactive ultraviolet absorber in a proportion of 10 to 50% by weight of the reactive ultraviolet absorber as a main binder, and a proportion of 10 to 50% by weight with respect to the main binder component And, it is characterized by containing any one of an ultraviolet absorber, an antioxidant and a light stabilizer as an additive.

  The present invention for solving the above problems is a method for forming a printed product, wherein an aqueous intermediate layer containing a water-based binder and hollow particles as main components and a water-based receiving layer on a substrate in this order. And a protective layer transfer sheet in which a release layer and an adhesive layer are laminated in this order on the base sheet, and the protection on the receiving layer of the image receiving sheet. In the method for forming a printed matter for transferring and forming the adhesive layer of the layer transfer sheet and the release layer, the adhesive layer and the release layer of the protective layer transfer sheet are methyl methacrylate and a reactive ultraviolet absorber, respectively. Is a resin that is copolymerized in a proportion of 10 to 50% by weight of a reactive ultraviolet absorber, and a proportion of 10 to 50% by weight with respect to the main binder component as an additive, an ultraviolet absorber, an antioxidant, Gwangan Characterized in that it contains one of the agents.

  According to the present invention, as the binder resin constituting the adhesive layer of the protective layer thermal transfer sheet, a resin in which methyl methacrylate and a reactive ultraviolet absorbent are copolymerized at a reactive ultraviolet absorbent ratio of 10 to 50% by weight is mainly used. By using the binder as an additive at a ratio of 10 to 50% by weight based on the main binder component, the flexibility of the transferred protective layer can be improved.

  Therefore, even when the dimensions of the image receiving sheet are greatly changed by, for example, storing the printed matter with the protective layer transferred for a long time under high temperature and high humidity, the protective layer can follow the dimensional change of the image receiving sheet. It is possible to prevent the protective layer from cracking. Therefore, it is possible to prevent a decrease in designability (quality) of the printed matter.

  In the present invention, a release layer is further provided between the substrate sheet and the adhesive layer, and the release layer is composed of methyl methacrylate and a reactive ultraviolet absorber in a reactive ultraviolet absorber ratio of 10 to 50. The flexibility of the entire protective layer can be further improved by containing a main binder copolymerized in a proportion of wt% and an additive in a proportion of 10 to 50 wt% with respect to the main binder.

  Furthermore, according to the printed matter formed using the protective layer thermal transfer sheet having the above effects, cracks do not occur even when stored for a long time under high temperature and high humidity.

<Protective layer thermal transfer sheet>
(First embodiment)
Hereinafter, a first embodiment for carrying out the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic sectional view showing a protective layer thermal transfer sheet according to the first embodiment.

  As shown in FIG. 1, the protective layer thermal transfer sheet 10 of this embodiment is formed by laminating a base sheet 1 and an adhesive layer 2. Hereinafter, each layer will be described.

(1) Base sheet 1
The base material sheet 1 can be a base material sheet used in a conventional protective layer thermal transfer sheet.

  For example, thin paper such as glassine paper, condenser paper, paraffin paper, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ketone, polyether sulfone, etc., polyester, polypropylene, polycarbonate, cellulose acetate , Polyethylene derivatives, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polymethylpentene, ionomer and other plastic stretched or unstretched films, surface of these materials subjected to easy adhesion treatment, The thing which laminated | stacked these materials is mentioned.

  The thickness of the substrate sheet 1 can be appropriately selected according to the material so that the strength, heat resistance and the like are appropriate, but it is usually preferably about 1 to 100 μm.

(2) Adhesive layer 2
The adhesive layer 2 becomes an adhesive surface with an image receiving sheet on which an image is formed at the time of thermal transfer, and has a function of expressing good adhesion to various image receiving sheets and protecting the image.

  The adhesive layer 2 in the present invention uses, as a main binder, a resin obtained by copolymerizing methyl methacrylate and a reactive ultraviolet absorber at a reactive ultraviolet absorber ratio of 10 to 50% by weight, and 10 to 50% by weight with respect to the main binder. It is comprised by containing an additive in the ratio.

  Here, conventionally known salicylate series, benzophenone series, benzotriazole series, substituted acrylonitrile series, nickel chelate series, hindered amine series and the like can be widely used as reactive ultraviolet absorbers that can be copolymerized with methyl methacrylate.

  In a resin obtained by copolymerizing methyl methacrylate and a reactive ultraviolet absorbent, if the reactive ultraviolet absorbent ratio is lower than 10%, the print is cracked when stored under high temperature and high humidity, which is not preferable.

  In addition, in a resin obtained by copolymerizing methyl methacrylate and a reactive ultraviolet absorber, if the reactive ultraviolet absorber ratio is higher than 50%, Tg (glass transition temperature) of the copolymerized resin is lowered, and there is a problem in storage stability. Occurs.

  Further, the main binder is a case where 80% by weight or more is contained in the binder component, and any other resin in which a conventionally known pressure-sensitive adhesive, heat-sensitive adhesive or the like is blended can be used as the other binder component. However, it is also possible to use a thermoplastic resin having a glass transition temperature (Tg) of 50 to 80 ° C. in combination. Specific examples of such thermoplastic resins include polyester resins, vinyl chloride-vinyl acetate copolymer resins, acrylic resins, butyral resins, epoxy resins, polyamide resins, vinyl chloride resins, and the like.

  The adhesive layer in the present invention contains 10 to 50% by weight of additives such as an ultraviolet absorber, an antioxidant, and a fluorescent brightener with respect to these main binder components.

  If the blending ratio of the additive is less than 10% by weight with respect to the binder component, cracks occur when the printed product is stored under high temperature and high humidity, which is not preferable. When the blending ratio of the additive is more than 50% by weight with respect to the binder component, the scratch resistance of the printed matter is lowered, which is not preferable.

  The adhesive layer is an ordinary coating method such as a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, or an ink obtained by dissolving or dispersing the above-mentioned resin or other additives in a solvent such as water or an organic solvent. According to the above, it is formed by coating and drying.

  The thickness of the adhesive layer is usually about 0.1 to 10 μm, preferably about 0.5 to 5.0 μm.

(3) Release layer 3
In this invention, you may provide the peeling layer 3 between the base material sheet 1 and the said contact bonding layer 2 as needed.

  The release layer 3 is composed of a conventionally known binder resin. As the binder resin, known thermoplastic resins and thermosetting resins used in this field can be widely used.

  Examples of the thermoplastic resin include acrylic resins such as polymethacrylic acid, polymethacrylamide, polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate; polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl Examples thereof include vinyl resins such as alcohol and polyvinyl butyral; cellulose derivatives such as ethyl cellulose, nitrocellulose, and cellulose acetate.

  Examples of the thermosetting resin include unsaturated polyester resins, polyester resins, polyurethane resins, amino alkyd resins, and the like. These binder resins may be used alone or in combination of two or more. Among these binder resins, acrylic resins are preferable.

  Further, the release layer 3 may contain a wax. When the wax is contained, the scratch resistance and foil breakability of the release layer are improved.

  Examples of the wax include polyethylene wax, polyester wax, polystyrene powder, olefin powder, microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, wool wax, Examples include shellac wax, candelilla wax, petrolactam, partially modified wax, fatty acid ester, and fatty acid amide.

  Wax is usually contained in the release layer in an amount of about 0.1 to 30% by weight, preferably about 0.1 to 10% by weight.

  The release layer may contain an ultraviolet absorber. By blending the ultraviolet absorber, it is possible to improve the light resistance and weather resistance of the image of the transferred material covered with the protective layer after being transferred.

  As the ultraviolet absorber, conventionally known organic ultraviolet absorbers such as salicylate, benzophenone, benzotriazole, substituted acrylonitrile, nickel chelate, hindered amine and the like can be widely used. Also, for example, addition polymerizable double bonds such as vinyl groups, acryloyl groups, and methacryloyl groups, or functional groups such as alcoholic hydroxyl groups, amino groups, carboxyl groups, epoxy groups, and isocyanate groups are introduced into these ultraviolet absorbers. An ultraviolet absorbing resin may be contained in the release layer.

  Furthermore, you may contain various additives, such as antioxidant and a fluorescent whitening agent, in the said peeling layer.

  The release layer 3 is a gravure printing method, screen printing, or the like obtained by adding a necessary additive such as wax to the binder resin and dissolving or dispersing in water, an organic solvent or the like on the binder resin. It is formed by applying and drying according to a normal coating method such as a reverse roll coating method using a gravure plate.

  The thickness of the release layer 3 is usually about 0.1 to 10 μm, particularly preferably about 0.5 to 5 μm.

  Here, in the protective layer thermal transfer sheet of the present invention, the release layer is made of a resin obtained by copolymerizing methyl methacrylate and a reactive ultraviolet absorbent at a reactive ultraviolet absorbent ratio of 10 to 50% by weight, as in the above adhesive layer. It is particularly preferable that the main binder is constituted by containing an additive in a proportion of 10 to 50% by weight with respect to the main binder.

  As described above, the main binder is a resin obtained by copolymerizing methyl methacrylate and a reactive ultraviolet absorber at a reactive ultraviolet absorber ratio of 10 to 50% by weight in both the release layer and the adhesive layer, and 10 to 50 with respect to the main binder. By containing the additive at a ratio of% by weight, cracks, storage stability and scratch resistance as a protective layer (including a release layer and an adhesive layer) transferred onto the printed matter are further improved.

(4) Back layer 4
It is preferable to form a back layer made of the following materials on the back surface (the side opposite to the side on which the adhesive layer is formed) of the base material of the protective layer thermal transfer sheet.

  Examples of the resin constituting the back layer 4 include cellulose resins such as ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, and nitrocellulose; polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal Vinyl resins such as polyvinylpyrrolidone; acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, and acrylonitrile-styrene copolymers; polyamide resins; polyvinyl toluene resins; coumarone indene resins; polyester resins; Polyurethane resin; natural or synthetic resin such as silicone-modified or fluorine-modified urethane can be used.

  These resins are used singly or in combination of two or more.

  From the viewpoint of further improving the heat resistance of the back layer 4, among the above resins, a resin having a reactive group such as a hydroxyl group (for example, butyral resin, acetal resin, etc.) is used, and a polyisocyanate is used as a crosslinking agent. Etc. are preferably used together to form a crosslinked resin layer.

Furthermore, for the purpose of imparting slidability with the thermal head, a solid or liquid release agent or lubricant may be blended in the back layer.
Examples of release agents or lubricants include various waxes such as polyethylene wax and paraffin wax; higher aliphatic alcohols, organopolysiloxanes, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants Examples thereof include various surfactants such as an activator and a fluorosurfactant; fine particles of inorganic compounds such as organic carboxylic acids and derivatives thereof, fluororesins, silicone resins, talc, and silica.

  The amount of the lubricant contained in the back layer 4 is usually about 5 to 50% by weight, preferably about 10 to 30% by weight in the back layer.

  The back layer 4 is a reverse roll coating using a gravure printing method, a screen printing method, and a gravure plate, which is obtained by dissolving or dispersing the above resin and other additives in a solvent such as water or an organic solvent on a base sheet. It is formed by applying and drying in accordance with a normal coating method such as a method.

  The thickness of the back layer 4 is usually about 0.1 to 10 μm, preferably about 0.5 to 5 μm.

(Second embodiment)
FIG. 2 is a schematic cross-sectional view showing a protective layer thermal transfer sheet according to the second embodiment.

  As shown in FIG. 2, the protective layer thermal transfer sheet 20 according to the present embodiment is obtained by sequentially providing an adhesive layer 14 and a dye layer 17 on a base sheet 11.

  The adhesive layer 14 is the adhesive layer described in the first embodiment, and description thereof is omitted here.

  The dye layer 17 is composed of dye layers 17Y, 17M, 17C, and 17BK having hues of yellow, magenta, cyan, and black. Such a dye layer 17 (17Y, 17M, 17C, 17BK) contains at least a dye and a binder resin.

  As the dye to be used, any dyes such as azo, azomethine, methine, anthraquinone, quinophthalone, and naphthoquinone that are used in the conventional heat-sensitive sublimation transfer type protective layer thermal transfer sheet can be used. There is no. In addition, a dye having an arbitrary hue such as black can be prepared by combining the above various dyes.

  As the binder resin for supporting the dye in the dye layer 17, any conventionally known binder resin can be used. For example, cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, Examples include polyvinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, polyacrylamide, and polyester. Among these, cellulose, acetal, butyral, and polyester are heat-resistant, dyes It is preferable from the viewpoint of the transferability.

  Further, the dye layer 17 can contain any conventionally known release agent in order to prevent thermal fusion of the dye layer, the binder and the receiving layer resin during printing. Specifically, various waxes such as polyethylene wax and paraffin wax, higher aliphatic alcohols, organopolysiloxanes, various surfactants, various phosphate esters, fluorine-based resins, silicone-based resins, and the like can be used.

  The dye layer 17 is prepared by applying an ink prepared by dissolving or dispersing a sublimable dye as described above and a binder resin added with a necessary additive in an appropriate solvent by a known method. It is formed by drying. The thickness of the dye layer 17 can be set in the range of 0.2 to 5 μm, preferably 0.4 to 2 μm, and the ratio of the sublimable dye in the dye layer 17 is 5 to 90% by weight, preferably 10 to 70% by weight. It is a range.

  In the protective layer thermal transfer sheet 20 described above, the order is 17Y → 17M → 17C → 17BK → adhesive layer 14, but is not limited thereto. Further, the black dye layer 17BK may be omitted. Further, a part or all of the dye layer 17 (17Y, 17M, 17C, 17BK) may have a two-layer structure in which a functional intermediate layer is provided between the substrate and the dye layer.

  The protective layer thermal transfer sheet of the present invention is not limited to the above-described embodiment, and can be arbitrarily set according to the purpose of use. In particular, by using a composite type protective layer thermal transfer sheet, it is possible to simultaneously perform image formation by the thermal transfer method and transfer of the adhesive layer to the printed material.

<Printed matter>
Next, the printed matter of the present invention will be described.

  FIG. 3 is a schematic cross-sectional view showing the printed material of the present invention. As shown in FIG. 3, the print 30 includes a water-based intermediate layer 22 containing a water-based binder and hollow particles as main components and a water-based receptive layer 23 on a base sheet 21, and the water-based receptive layer 23 is thermally sublimated. It has an image 24 recorded by the transfer method, and a protective layer (including an adhesive layer and a release layer) 25 provided to cover the image 24. The image 24 includes a full-color image 24a composed of three colors of yellow, magenta, and cyan, or four colors added with black as necessary, and a monotonous image 24b of characters, symbols, and the like.

  In the printed matter 30 shown in FIG. 3 described above, the entire image 24 is covered with the protective layer 25, but it is sufficient that at least a part of the image 24 is covered.

  Such a printed matter can be created by forming a thermal transfer image on an image receiving sheet shown below using, for example, the protective layer thermal transfer sheet according to the second embodiment.

<Image receiving sheet>
It is a laminate of a water-based intermediate layer containing at least a water-based binder and hollow particles, a water-based binder and a water-based receptive layer mainly composed of a release material on the base material. It is also possible to interpose a second functional intermediate layer between the intermediate layer and the aqueous intermediate layer and the aqueous receiving layer.

(Base material)
There is no restriction | limiting in particular as a base material of an image receiving sheet, According to the intended purpose etc., the thing of a various material, layer structure, and a size can be selected and used suitably. For example, various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or a composite material obtained by laminating them with paper), a vinyl chloride resin sheet, an ABS resin sheet, a polyethylene terephthalate (PET) base film, Polybutylene terephthalate base film, polyethylene naphthalate (PEN) base film, polyarylate base film, polycarbonate base film, polyether ether ketone base film, polysulfone base film, polyether sulfone base film, polyetherimide base film, polyimide base film Or various plastic films or sheets in which they are laminated in two or more layers, films or sheets formed of various metals, various ceramics It can be mentioned composite materials were appropriately combined laminate from those formed by the class film or sheet or the forth, or the like.

(Aqueous intermediate layer)
Examples of the hollow particles contained in the aqueous intermediate layer formed on the substrate include thermally expandable hollow particles and capsule-shaped hollow polymers as the hollow particles constituting the aqueous intermediate layer. Thermally expandable hollow particles are hollow particles whose wall material is a thermoplastic material such as vinylidene chloride-acrylonitrile copolymer, and a material containing a thermally expandable gas such as propane, n-butane, isobutane, etc. inside the particles. is there. The capsule-like hollow polymer is a hollow polymer having a wall material made of a resin such as styrene-acrylic resin or melamine resin. The hollow particles as described above generally have a particle size of about 0.1 to 100 μm, but in the present invention, hollow particles having a particle size of about 0.1 to 50 μm are preferably used. If the thickness is less than 0.1 μm, a sufficient heat insulating effect as a hollow particle cannot be obtained, and if it exceeds 50 μm, the smoothness is significantly lowered.

  Examples of water-based binders used in the water-based intermediate layer include polyester resins, polyacrylate resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, and the like; polyurethane resins having amide bonds; amide bonds As a thing which has a polyamide resin (nylon); As a thing which has a urea bond, a urea resin; Furthermore, as another thing which has a highly polar bond, a polycaprolactone resin, a polystyrene resin, a polyvinyl chloride, a polyacrylonitrile resin, etc. Can also be used, or can be used as a copolymer mainly composed of one or more of the structural units of the resin, for example, vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, etc. Furthermore, the above resins are used alone or in combination of two or more. Door can be.

  In addition, vinyl polymers such as water-soluble polyvinyl alcohol, polyvinyl pyrrolidone, cation-modified polyvinyl alcohol and derivatives thereof, polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, polyacrylic acid or salts thereof, acrylic acid-methacrylic acid copolymer Combined or salt thereof, polymethacrylic acid or salt thereof, acrylic group-containing polymer such as acrylic acid-vinyl alcohol copolymer or salt thereof, starch, oxidized starch, starch acetate, carboxyl starch, dialdehyde starch, cationic starch, dextrin , Natural alginate such as sodium alginate, gum arabic, casein, pullulan, dextran, or derivatives thereof, maleic acid-vinyl acetate copolymer, maleic acid-N-vinylpyrrolidone copolymer , Maleic acid chromatography alkyl vinyl copolymer, synthetic polymers such as polyethylene imine, can be also used.

  If necessary, a color pigment, a white pigment, etc. can be used for the aqueous intermediate layer. Specific examples of the white pigment include barium sulfate, titanium dioxide (rutile type and anatase type), zinc sulfide, calcium carbonate, Examples thereof include magnesium oxide, various silicates, aluminum oxide, titanium phosphate, satin white, talc, and clay. In particular, from the viewpoint of high whiteness, barium sulfate, titanium dioxide, calcium carbonate and the like are preferably used. Further, an antistatic agent, a fluorescent brightening agent, a wetting agent, an antifoaming agent, a dispersing agent, an ultraviolet absorber, a light stabilizer and the like may be added as necessary.

  The aqueous intermediate layer is prepared by dispersing or dissolving an aqueous binder, hollow particles, and other additives that are added as necessary in water or an aqueous solution to prepare an aqueous coating solution, and applying the aqueous coating solution to the surface of the support. -It can be manufactured by a drying coating method.

  When preparing an aqueous coating solution, it is desirable to dissolve or disperse the resin in water according to the solubility or dispersibility of the aqueous binder in water. Moreover, depending on the case, you may use together the alcohol solvent which mixes with water, acetone, a dioxane, etc. in the ratio of 20 weight% or less with respect to 100 weight% of water.

  The aqueous intermediate layer-forming coating solution prepared as described above is applied and dried on the substrate using a known coating method such as extrusion coating, wire bar coating, or roll coating. The thickness of the aqueous intermediate layer comprising the above components can be appropriately provided in the range of 20 to 80 μm.

(Water receptive layer)
As an aqueous receptive layer binder used for an aqueous receptive layer mainly composed of an aqueous binder and a release material, it has a dyeing property with respect to a heat-diffusible dye, and the preparation of an aqueous receptive layer forming coating liquid described later. Therefore, those having good solubility or dispersibility in water are preferable.

  Examples of such binders include polyvinyl chloride resins, copolymer resins of vinyl chloride and other monomers (isobutyl vinyl ether, vinyl propionate, etc.), polyester resins, poly (meth) acrylic acid, poly (meth) acrylic acid. Esters, polyvinyl pyrrolidone, polyvinyl acetal resins, polyvinyl alcohol, polycarbonate, cellulose triacetate, polystyrene, copolymers of styrene and other monomers (acrylic ester, acrylonitrile, ethylene chloride, etc.), ethylene and other monomers (acetic acid Vinyl, acrylate ester, etc.), vinyl toluene acrylate resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, phenoxy resin, polycaprolactone resin, polyacrylonitrile resin, methyl Cellulose resins such as cellulose, may be mentioned gelatin, starch, casein and a modified product thereof.

  Among the above-mentioned resins, polyvinyl chloride resin, copolymers of vinyl chloride and other monomers, polyvinyl acetal resins, copolymers of styrene and other monomers, polyester resins, and epoxy resins are preferable.

  These resins can be used alone or in combination of two or more.

  The release agent used in combination with the binder includes silicone oil (including those called silicone resins); solid waxes such as polyethylene wax, amide wax, Teflon (registered trademark) powder; fluorine-based, phosphate ester-based In particular, silicone oil is preferable. This silicone oil is classified into a type that is simply added and a type that is cured or reacted.

  As a type to be simply added, modified silicone oil (polyester-modified silicone oil, urethane-modified silicone oil, acrylic-modified silicone oil, alcohol-modified silicone oil, amide-modified silicone oil, etc.) in order to improve compatibility with the above-mentioned resin Is preferably used.

  The amount of these silicone oils to be added varies depending on the type and cannot be determined uniformly, but is generally 0.1 to 50% by weight based on the binder for the receiving layer. It is preferably 0.5 to 20% by weight.

  Examples of the curing reaction type silicone oil include reaction curing type (such as those obtained by reaction curing of amino-modified silicone oil and epoxy-modified silicone oil), photo-curing type, and catalyst-curing type.

  The addition amount of these curable silicone oils is preferably 0.5 to 30% by weight of the receptor layer binder.

  The aqueous receiving layer is prepared by dispersing or dissolving a resin, a release material, and other additives that are added as necessary in water or an aqueous solution to prepare an aqueous coating solution. When preparing an aqueous coating solution, it is desirable to dissolve or disperse the resin in water according to the solubility or dispersibility of the receptor layer binder in water. Moreover, depending on the case, you may use together the alcohol solvent which mixes with water, acetone, a dioxane, etc. in the ratio of 20 weight% or less with respect to 100 weight% of water.

  That is, in order to prepare this aqueous coating solution, a water-soluble resin in which the binder is well dissolved in water (water-soluble polyvinyl acetal resin, water-soluble polyester, polyvinyl alcohol, starch, casein, gelatin, polyacrylic acid, etc.) If so, if it is an emulsion resin (polyvinyl chloride resin, styrene-butadiene copolymer, etc.) formed by solution polymerization using water or a solvent as a binder, the binder is suitably used. Suspension resin (epoxy resin, copolymer of vinyl chloride and other monomers, etc.) dispersed in water by suspending in water or aqueous solution together with surfactant or by using a dispersant as the binder If this is the case, use a dispersing agent to remove water or an aqueous solution using a known dispersing machine such as an attritor, ball mill, or sand grinder. It is dispersed desirably.

  These coating liquids can be used together as appropriate, and emulsion resins and dispersion resins are commercially available suspensions (vinyl chloride latex, styrene-butadiene latex, ethylene-vinyl acetate latex from the beginning). , Water-dispersed polymer polyester, etc.) or a dispersion.

  The aqueous receptive layer-forming coating solution prepared as described above is applied and dried on the aqueous intermediate layer using a known coating method, such as an extrusion coating method, a wire bar coating method, or a roll coating method. .

The thickness of the water-based receiving layer comprising the above components can be appropriately provided in the range of 0.5 to 10 μm.

  Hereinafter, the present invention will be described by way of examples. In the examples, “parts” or “%” are based on weight unless otherwise specified.

[Example 1]
On a 6 μm thick polyethylene terephthalate film (an easy-adhesive product manufactured by Toray Industries, Inc.), a back layer ink having the following composition was applied by a gravure coating method (coating amount 1.0 g / m ² (during drying)) and dried. Thereafter, a curing process was performed to form a back layer.
Next, an adhesive layer ink having the following composition was applied to the surface opposite to the surface on which the back layer was formed by a gravure coating method and dried to form an adhesive layer having a thickness of 0.6 μm. A protective layer thermal transfer sheet was produced.
(Back layer ink)
Polyvinyl butyral (Sekisui Chemical Co., Ltd. ESREC BX-1) 15 parts Polyisocyanate (Dainippon Ink Chemical Co., Ltd. Barnock D450) 35 parts Phosphate ester surfactant (Daiichi Kogyo Seiyaku Co., Ltd. Prisurf) A208S) 10 parts Talc (Nihon Talc Co., Ltd. Microace P-3) 3 parts (Adhesive layer ink 1)
-Main binder Methyl methacrylate and benzotriazole (reactive ultraviolet absorber) copolymer (Shin-Nakamura Chemical Co., Ltd. vanaresin UVA-73A solid content (42%)) 18 parts Reactive ultraviolet absorption in the above copolymer Agent ratio = 20%
・ Additives (UV absorbers)
(Tinubin 928 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts Additive (ultraviolet absorber) ratio to main binder component (solid content) = 20%
・ Solvent 9 parts methyl acetate

[Example 2]
A protective layer thermal transfer sheet of Example 2 was produced in the same manner as in Example 1 except that the adhesive layer ink was changed to the following.
(Adhesive layer ink 2)
Main binder Methyl methacrylate and benzophenone (reactive UV absorber) copolymer (BASF Japan UVA635L solid content (42%)) 18 parts Reactive UV absorber ratio in the above copolymer = 50%
・ Additives (UV absorbers)
(Cinubin 928 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts UV absorber ratio to main binder component (solid content) = 20%
・ Solvent 9 parts methyl acetate

[Example 3]
The protective layer of Example 3 was prepared by the same method as in Example 1 except that a release layer ink having the following composition was applied between the base sheet and the adhesive layer by a gravure coating method and dried to form a release layer. A thermal transfer sheet was produced.
(Ink for release layer)
-Main binder Methyl methacrylate and benzotriazole (reactive ultraviolet absorber) copolymer (Shin-Nakamura Chemical Co., Ltd. vanaresin UVA-73A solid content (42%)) 18 parts Reactive ultraviolet absorption in the above copolymer Agent ratio = 20%
・ Additives (UV absorber + light stabilizer + antioxidant)
UV absorber (Ciba Specialty Chemicals Co., Ltd. Tinuvin 928) 0.5 part Light stabilizer (Ciba Specialty Chemicals Co., Ltd. chinuvin 770) 0.5 part Antioxidant (Ciba Specialty Chemicals ( Ciba Iruganox 1076) 0.5 part Additive ratio to main binder component (solid content) = 20%
・ Solvent 9 parts methyl acetate

[Comparative Example 1]
A protective layer thermal transfer sheet of Comparative Example 1 was produced in the same manner as in Example 1 except that the adhesive layer ink was changed as follows.
(Adhesive layer ink 3)
-Main binder Methyl methacrylate and benzotriazole (reactive UV absorber) copolymer (Shin Nakamura Chemical Co., Ltd. Vanaresin UVA-73A based on the ratio of reactive UV absorber is changed and synthesized solids (42 %)) 18 parts Reactive UV absorber ratio in the above copolymer = 5%
・ Additives (UV absorbers)
(Cinubin 928 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts UV absorber ratio to main binder component (solid content) = 20%
・ Solvent 9 parts methyl acetate

[Comparative Example 2]
A protective layer thermal transfer sheet of Comparative Example 2 was produced in the same manner as in Example 1 except that the adhesive layer ink was changed to the following.
(Adhesive layer ink 4)
-Main binder Methyl methacrylate and benzotriazole (reactive UV absorber) copolymer (Shin Nakamura Chemical Co., Ltd. Vanaresin UVA-73A based on the ratio of reactive UV absorber is changed and synthesized solids (42 %)) 18 parts Reactive UV absorber ratio in the above copolymer = 60%
・ Additives (UV absorbers)
(Cinubin 928 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts UV absorber ratio to main binder component (solid content) = 20%
・ Solvent 9 parts methyl acetate

[Comparative Example 3]
A protective layer thermal transfer sheet of Comparative Example 3 was produced in the same manner as in Example 1 except that the adhesive layer ink was changed to the following.
(Adhesive layer ink 5)
-Main binder Methyl methacrylate and benzotriazole (reactive ultraviolet absorber) copolymer (Shin-Nakamura Chemical Co., Ltd. vanaresin UVA-73A solid content (42%)) 18 parts Reactive ultraviolet absorption in the above copolymer Agent ratio = 20%
・ Additives (UV absorbers)
(Cinubin 928 manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.3 part UV absorber ratio to main binder component (solid content) = 5%
・ Solvent Methyl acetate 8.5 parts

[Comparative Example 4]
A protective layer thermal transfer sheet of Comparative Example 4 was produced in the same manner as in Example 1 except that the adhesive layer ink was changed to the following.
(Adhesive layer ink 6)
-Main binder Methyl methacrylate and benzotriazole (reactive ultraviolet absorber) copolymer (Shin-Nakamura Chemical Co., Ltd. vanaresin UVA-73A solid content (42%)) 18 parts Reactive ultraviolet absorption in the above copolymer Agent ratio = 20%
・ Additives (UV absorbers)
(Cinubin 928 manufactured by Ciba Specialty Chemicals Co., Ltd.) 3.7 parts UV absorber ratio to main binder component (solid content) = 51%
・ Solvent 10 parts methyl acetate

  Next, each protective layer thermal transfer sheet of Examples and Comparative Examples was printed on a water-based image-receiving sheet prepared as described below with a thermal printer head under the same printing conditions as described below to form an image and evaluated for cracks. Then, storage stability evaluation, gloss evaluation and scratch resistance evaluation were performed.

Aqueous image-receiving sheet RC paper (STF-150, manufactured by Mitsubishi Paper Industries Co., Ltd.) is used as a base sheet, and a porous layer forming coating solution and a receiving layer forming coating solution having the following compositions are heated to 50 ° C., respectively. Using a slide coating, the thickness when dried is 30 μm and 5 μm, respectively, cooled and gelled at 5 ° C. for 1 minute, dried at 50 ° C. for 5 minutes, and a thermal transfer image receiving sheet (image receiving paper) )

<Porous layer forming coating solution>
・ Hollow particles (HP-91 Rohm and Haas) (as solid content) 70 parts ・ Gelatin (RR Nitta Gelatin Co., Ltd.) (as solid content) 30 parts ・ Interface slip material (Surfinol 440 Nissin Chemical Industry) 0.15 parts

<Coating liquid for forming receiving layer>
・ Emulsion (as solids) 70 parts ・ Resin filler (VB900) (as solids) 15 parts ・ Gelatin (RR Nitta Gelatin Co., Ltd.) (as solids) 15 parts ・ Silicone mold release agent (Surfinol 440) Shin-Etsu Chemical Co., Ltd.) 10 parts ・ Interface slip material (Surfinol 440 Nissin Chemical Industry Co., Ltd.) 1 part

  For the synthesis of the emulsion of the coating solution for forming the receiving layer, in a 500 mL Erlenmeyer flask, 103 g of styrene, 54 g of ethyl acrylate, 41 g of lauryl acrylate, 2 g of acrylic acid, emulsifier (AQUALON HS-10 Daiichi Kogyo Seiyaku Co., Ltd.) 1 .9 g was added and stirred and mixed (hereinafter referred to as monomer A). In a 1 L three-necked flask, 200 g of distilled water was added and heated to 80 ° C., and about 20% of the total amount of monomer A was added and stirred for 10 minutes. Thereafter, 0.2 g of ammonium persulfate dissolved in 20 g of pure water was added and stirred for 10 minutes, and then the remaining 80% of the monomer A was dropped with a dropping funnel over 3 hours and further stirred for 3 hours. Thereafter, the mixture was cooled to room temperature and filtered through # 150 mesh (Japanese fabric) to obtain an emulsion. Molecular weight 242273, Tg 50 ° C. Further, from the molecular weight of styrene, ethyl acrylate and lauryl acrylate and the amount used for the reaction, the respective molar ratios are 58%, 32% and 10%.

  As the resin filler, a vinyl chloride-ethyl acrylate copolymer (monomer blending ratio is 90% vinyl chloride, 10% ethyl acrylate) and Tg 70 ° C. (VB900 Nissin Chemical Industry Co., Ltd.) was used.

Printing condition thermal head: KGT-217-12MPL20 (manufactured by Kyocera Corporation)
Heating element average resistance: 2994 (Ω)
Main scanning direction printing density; 300 dpi
Sub-scanning direction print density; 300 dpi
Applied power: 0.10 (w / dot)
1 line cycle: 5 (msec.)
Printing start temperature; 40 (° C)
Applied pulse (gradation control method); using a multi-pulse test printer that can vary the number of divided pulses from 0 to 255 in one line period and having a pulse length obtained by equally dividing one line period into 256 The duty ratio of the divided pulses was fixed to 70%, and the number of pulses per line period was divided into 15 from 0 to 255. Thereby, different energy can be given to 15 steps.

  This time, only the largest energy of 15 different energy levels was used for printing.

Printing pattern: black solid And the image printed on the water-based image-receiving sheet was subjected to crack evaluation, storage stability evaluation, light resistance evaluation, and scratch resistance evaluation. The results are also shown in Table 1. In Table 1, the standards for crack evaluation, storage stability evaluation, light resistance evaluation, and scratch resistance evaluation were as follows.

<Evaluation>
-Cracks An evaluation pattern was printed and stored in an atmosphere of 40 ° C and 90%. The surface condition after storage for 100 hours was visually observed.
When there was a crack, it evaluated as x, and when there was no crack, it evaluated as (circle).
-Storage property The evaluation pattern was printed and stored in an atmosphere of 40 ° C and 90%. The surface condition after storage for 100 hours was visually observed.
If the print pattern was blurred, it was evaluated as x. If the print pattern was not blurred, it was evaluated as o.
-Light resistance Light resistance measurement condition The light resistance test was done with the following xenon fade meter.
Irradiation tester: Atlas Ci4000
Light source: Xenon lamp black Panel temperature: 45 ° C
Inner filter: CIRA
Outer filter: Soda lime irradiance: 1.2 (W / m ² ) ... Measured value at 420 nm Irradiation energy: 200 (kJ / m ² ) ... Integrated value at 420 nm Optical before irradiation For a step with a reflection density near 1.0, the change in optical density before and after irradiation was measured, and the residual density ratio was calculated by the following formula to evaluate the light resistance.
Density residual ratio (%) = (optical reflection density after irradiation / optical reflection density before irradiation) × 100
A sample having a concentration residual ratio of 80% or more was evaluated as ◎, and a sample having 70 to 80% was evaluated as ○.
-Scratch resistance Using the Taber test, the surface of the printed material was polished under conditions of a wear wheel CS-10 and a load of 500 gf. The surface condition was visually observed after polishing.
Those markedly deteriorated were evaluated as x, and others were evaluated as o.

<Results and discussion>
As shown in Table 1, in Examples 1 and 2, good results were obtained in all of cracking, storage stability, light resistance, and scratch resistance. In Example 3, even if the release layer was formed, good results were obtained in all of cracking, storage stability, light resistance, and scratch resistance.

  On the other hand, in Comparative Examples 1 and 2, since the reactive ultraviolet absorber ratio of the adhesive layer is not copolymerized at a ratio of 10 to 50% by weight with respect to the examples, it was evaluated for cracking or storage. The result marked with ×. In Comparative Examples 3 and 4, since the proportion of the additive is not contained in the proportion of 10 to 50% by weight with respect to the main binder component, the evaluation for cracking or scratch resistance is × As a result.

It is a section schematic diagram of a protection layer thermal transfer sheet concerning a first embodiment. It is a section schematic diagram of a protection layer thermal transfer sheet concerning a second embodiment. 1 is a schematic cross-sectional view of a printed material according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 11 ... Base material sheet 2, 14 ... Adhesive layer 3 ... Release layer 4 ... Back layer 25 ... Protective layer 17 ... Dyeing layer 21 ... Base material 22 ...・ Aqueous intermediate layer 23 ... Aqueous receiving layer 24 ... Image 10, 20 ... Protective layer thermal transfer sheet 30 ... Print

Claims (2)

A base, a water-based intermediate layer containing water-based binder and hollow particles as main components provided on the base, a water-based receptive layer provided on the water- based intermediate layer, and at least a part of the water-based receptive layer An adhesive layer provided so as to cover , and a release layer provided on the adhesive layer ,
Each of the adhesive layer and the release layer has, as a main binder component, a resin obtained by copolymerizing methyl methacrylate and a reactive ultraviolet absorber at a reactive ultraviolet absorbent ratio of 10 to 50% by weight. A printed matter comprising 10 to 50% by weight of an ultraviolet absorber, an antioxidant, or a light stabilizer as an additive. An image receiving sheet in which a water-based intermediate layer containing a water-based binder and hollow particles as main components on a substrate, and a water-based receiving layer are laminated in this order, and a release layer and an adhesive layer in this order on the substrate sheet. In the method for forming a printed matter, the protective layer transfer sheet laminated in step 1 is used to transfer and form the adhesive layer and the release layer of the protective layer transfer sheet on the receiving layer of the image receiving sheet. ,
Each of the adhesive layer and the release layer of the protective layer transfer sheet has, as a main binder, a resin in which methyl methacrylate and a reactive ultraviolet absorbent are copolymerized at a reactive ultraviolet absorbent ratio of 10 to 50% by weight. A method for forming a printed matter, which comprises a UV absorber, an antioxidant or a light stabilizer as an additive in a proportion of 10 to 50% by weight based on the main binder component.