JP4332419B2 - Transfer sheet, card using the transfer sheet, and manufacturing method thereof - Google Patents

Description

  The present invention relates to a transfer sheet used for a card such as a magnetic card or an IC card, and in particular, a transfer sheet capable of forming an image by sublimation transfer printing, a method for using the transfer sheet, and a card using the transfer sheet. And its manufacturing method.

  In recent years, full-color printing of personal face photographs and other images on plastic cards such as credit cards, member cards, employee ID cards, etc. has been increasing for the purpose of preventing unauthorized use by persons other than the owner. ing. Since a face photograph or the like is personal information, it is generally provided by printing on the card surface after it has become a card shape.

  Sublimation transfer printing is small, has excellent maintainability and reliability, and is suitable when high resolution and high gradation are required as represented by facial photographs. Used for printing. The principle of sublimation transfer printing is printing with a heat-resistant film (hereinafter referred to as “ink ribbon”) provided with a dye layer containing a sublimation dye between a minute heating element (thermal head) and a platen roll. By running while pressing the sheet, the dye sublimates from the dye layer of the ink ribbon by instantaneous high-temperature heating by the thermal head, and the sublimated dye diffuses and dissolves in the sheet and is colored.

  In addition, a normal ink ribbon for sublimation transfer printing has a dye layer formed on one side of a heat-resistant substrate such as a polyester film, and polyacetal or the like is used as a binder resin for a paint layer. In general, a sheet or the like to be printed by a sublimation transfer printing method is required to have affinity with a dye and releasability from a dye layer of an ink ribbon after high-temperature pressing.

  By the way, in general, a card is printed on a white resin sheet called a core sheet, and then covered with a transparent resin sheet called an oversheet in order to protect the printed surface, and then subjected to hot pressing to form a laminate. Then, punching or the like is performed to form a card shape. Further, the card is embossed or printed as necessary. Due to its excellent printability and processability, polyvinyl chloride resin (hereinafter also referred to as “PVC”), amorphous polyester resin (hereinafter also referred to as “PETG”), polycarbonate resin (hereinafter referred to as “PET”). PC ”), acrylonitrile-butadiene-styrene copolymer resin (hereinafter also referred to as“ ABS ”), and the like are used as card materials such as core sheets and oversheets.

  When sublimation transfer printing is performed on the card surface, if the surface of the card substrate, for example, the oversheet is a vinyl chloride resin, it is printed directly on the surface of the card substrate with a sublimation transfer printer. In the case of resin, a sublimation transfer printing receiving layer was provided on the oversheet, and then printing was performed with a sublimation transfer printer. Since the sublimation transfer print image formed in this way exists on the surface of the card, “rubbing” occurs when the card is taken in and out from a card holder or a wallet, for example, a part of the printing part is peeled off, etc. The card has deteriorated. As a result, there is a problem that the card is deteriorated before the lifetime of the card base, the magnetic tape, the IC chip, etc. is exhausted, and the card life is remarkably shortened.

In order to prevent such deterioration of the printed part due to “rubbing”, Japanese Patent Application Laid-Open No. 62-238791 discloses that a protective layer and an image receiving layer are sequentially laminated on a sheet-like substrate, and sublimation is performed from the image receiving layer side. After transfer printing, the image-receiving surface of the image-receiving layer is attached to face an arbitrary article, and the image-receiving layer with a protective layer is transferred onto the article by peeling the sheet-like substrate after the attachment. A method is disclosed. Here, a synthetic resin having an ester bond, a urethane bond, an amide bond, a urea bond or the like dissolved in an organic solvent is applied onto a protective layer and dried to form an image receiving layer.
Therefore, there is a problem that the organic solvent evaporated during drying causes air pollution. In addition, there is a problem in that the dye layer and the image receiving layer of the ink ribbon are fused by instantaneous high temperature heating during sublimation transfer printing, and jamming occurs in the apparatus, making printing impossible.

JP-A-62-238791

  The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide release properties to the ink ribbon during sublimation transfer printing without causing environmental problems, and printing. Another object of the present invention is to provide a transfer sheet that can prevent the deterioration of the portion and a card using the transfer sheet.

  In order to solve the above problems, the transfer sheet of the present invention has a support having releasability, a protective layer, and a sublimation transfer printing receiving layer in this order, and the sublimation transfer printing receiving layer mainly includes an aqueous resin. It is a layer formed using a solution as a component.

  The transfer sheet of the present invention is the above transfer sheet having a support having a releasability, a protective layer, and a sublimation transfer print receiving layer in this order, and the transfer sheet is subjected to sublimation transfer printing to form an image. After the film is formed, it can be laminated on the transfer medium by heating and pressing.

  In the present invention, the aqueous resin is a mixed system of a main agent (A) and a curing agent (B), wherein the main agent (A) is an aqueous polyol, and the curing agent (B) is an aqueous polyisocyanate. it can.

Here, the aqueous polyol is preferably an aqueous polyurethane polyol.
The aqueous polyurethane polyol is an isocyanate group-terminated urethane prepolymer obtained from (a) a polyisocyanate compound, (b) a polymer polyol, and (c) a compound having a hydrophilic group and two or more active hydrogens. Hydroxyl group-containing aqueous solution obtained by using (d) at least one end-capping agent selected from the group consisting of a primary amine compound and a secondary amine compound having a hydroxyl group. A polyurethane polyol is preferred.

The (b) polymer polyol is preferably at least one polymer polyol selected from the group consisting of a polyester polyol, a polycarbonate polyol, and a polyether polyol.
Moreover, the gel fraction of the polyurethane resin after carrying out the crosslinking reaction of the said main ingredient (A) and a hardening | curing agent (B) can be 60% or more.

The card of the present invention is a laminate obtained by subjecting one of the transfer sheets to sublimation transfer printing to form an image, and then transferring the image to a card substrate by heating and pressing.
Here, a laminated structure from which the support having releasability is further removed may be used.

  The method for using the transfer sheet of the present invention includes a support having a releasability, a protective layer, and a transfer sheet having a sublimation transfer printing receiving layer formed in this order using a solution mainly composed of an aqueous resin. After sublimation transfer printing is performed on the surface of the sublimation transfer printing receiving layer, the sublimation transfer printing receiving layer is stacked on the transfer target, and then the support having the release property is removed. To do.

  In the card manufacturing method of the present invention, a protective layer is formed on a releasable support, and then a sublimation transfer printing receiving layer is formed using a solution containing an aqueous resin as a main component, and then sublimation. An image is formed on the sublimation transfer printing receiving layer by performing transfer printing, and then transferred to a card substrate by heating and pressurization, and then the support having releasability is peeled off.

The transfer sheet of the present invention has releasability from the ink ribbon during sublimation transfer printing, and is excellent in printability. Moreover, since the transfer sheet of the present invention can be produced without using an organic solvent, it is excellent in environmental properties.
Furthermore, since the transfer sheet of the present invention is provided with a protective layer so as to protect the sublimation transfer printing receiving layer, a card or the like formed using the transfer sheet of the present invention is placed on the outermost surface portion of the card or the like. Since the protective layer is disposed, it is possible to prevent the printing portion from being deteriorated due to “rubbing” or the like.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.
The transfer sheet of the present invention has a support having a releasability, a protective layer, and a sublimation transfer printing receiving layer in this order, and the sublimation transfer printing receiving layer is formed using a solution mainly composed of an aqueous resin. Layer. The sublimation transfer printing receiving layer and the support must be disposed on the outermost layer, respectively. For example, another layer may be included between the protective layer and the sublimation transfer printing receiving layer.

Here, as a support having releasability, a polyethylene film, a polypropylene film, a styrene film (especially a syndiotactic styrene film), a fluorine film, a polyester film coated with a silicone resin on the surface (as polyester) Examples thereof include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN)). Moreover, the paper etc. by which the mold release process was given to the surface may be sufficient.
The thickness of the support having releasability is generally 10 μm to 250 μm, preferably 15 μm to 150 μm, particularly preferably 25 μm to 100 μm in view of handling properties and economy.

  The protective layer constituting the transfer sheet of the present invention can be formed by applying and curing on the surface of the support by a solution coating method or the like. The protective layer is preferably made of a material excellent in scratch resistance and contamination resistance in consideration of contact with the thermal head and contact with the card holder and other objects. For example, the protective layer is preferably formed using an ultraviolet curable resin, an electron beam curable resin, a thermosetting resin, or the like. In particular, ultraviolet curable resins and electron beam curable resins are preferred. For example, various acrylate monomers, other additives, etc. are appropriately mixed with those mainly composed of oligomers such as urethane acrylates and epoxy acrylates. What adjusted the property, sclerosis | hardenability, etc. can be used. Moreover, when forming a protective layer using an ultraviolet curable resin, it is preferable to carry out curing polymerization by adding a suitable amount of a photopolymerization initiator such as benzoin, acetophenone, thioxanthone, or peroxide.

  The thickness of the protective layer is preferably designed as appropriate according to the type of resin material forming the protective layer, etc., but is generally preferably in the range of 0.5 μm to 20 μm, more preferably 2 μm to It is in the range of 10 μm. If the protective layer is thinner than 0.5 μm, a sufficient protective effect may not be obtained, while if it is thicker than 20 μm, it may cause curling.

  A card or the like formed using the transfer sheet of the present invention sees an image formed on the sublimation transfer printing receiving layer through the protective layer, and therefore the protective layer is preferably substantially transparent. For example, the total light transmittance of 0.1 mm thickness measured based on JIS K-7105 (1981 version) is preferably 80% or more, and more preferably 90% or more.

  The sublimation transfer printing receiving layer constituting the transfer sheet of the present invention is, for example, a layer formed on the surface of the protective layer using a solution containing an aqueous resin as a main component. For example, a solution containing an aqueous resin as a main component is used as a protective layer. It can be applied to the surface or cured after application.

  In the present invention, “aqueous” means aqueous dispersion or water-soluble. The aqueous resin is preferably a mixed system of the main agent (A) and the curing agent (B). In particular, the main agent (A) is an aqueous polyol and the curing agent (B) is an aqueous polyisocyanate. preferable.

  In the present invention, the aqueous polyol used as the main agent (A) includes polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol; polyethylene adipate (terephthalate), polypropylene adipate (terephthalate), poly Polyester polyols such as butylene adipate (terephthalate), polyhexylene adipate (terephthalate), polycaprolactone; glycols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol and dimethyl carbonate; Polycarbonate polyol obtained by reaction with diethyl carbonate, ethylene carbonate, diphenyl carbonate, phosgene And, these aqueous polyurethane polyol obtained by reacting an isocyanate compound. Among these, polyester polyol or aqueous polyurethane polyol is preferable from the viewpoint of affinity of the dye.

  In the present invention, the aqueous polyurethane polyol can be obtained by a conventionally known method. For example, an isocyanate obtained from (a) a polyisocyanate compound, (b) a polymer polyol, and (c) a compound having a hydrophilic group and two or more active hydrogens (hydrogen atoms capable of reacting with an isocyanate group). After the chain end urethane prepolymer neutralized product is chain-extended in water as necessary, at least one kind selected from (d) a primary amine compound having a hydroxyl group and a secondary amine compound having a hydroxyl group It is preferably an aqueous polyurethane polyol having a hydroxyl group, obtained by reacting with a terminal blocking agent.

(A) Although there is no restriction | limiting in particular in a polyisocyanate compound, When a typical thing is illustrated, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 3,3'-dimethyl-4 , 4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, naphthalene diisocyanate, tetrahydronaphthalene diisocyanate and the like; tetramethylene diisocyanate, pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, Aliphatic diisocyanates such as dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate Cyclohexylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate (sometimes referred to as “hydrogenated xylylene diisocyanate”), dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4 ′ -Cycloaliphatic diisocyanates such as dicyclohexylmethane diisocyanate. Among these, aliphatic diisocyanates and alicyclic diisocyanates can be preferably used, and isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and 1,6-hexamethylene diisocyanate can be particularly preferably used.
These polyisocyanate compounds can be used alone or in combination of two or more.

  (B) The polymer polyol preferably has a weight average molecular weight of 300 to 10,000, and more preferably a weight average molecular weight of 500 to 5,000. Examples of such (b) polymer polyols include polyester polyols, polycarbonate polyols, polyether polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols, polythioether polyols, and the like. Among these, polyester polyol, polycarbonate polyol, and polyether polyol can be preferably used. These polymer polyols can be used alone or in combination of two or more.

  Examples of the polyester polyol include a polyester polyol obtained by a dehydration condensation reaction between a glycol component and an acid component. Here, examples of the glycol component include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, Examples include 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone, and alkylene oxide adducts thereof. Acid components include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid , Phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′- Dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, ester-forming derivatives of these hydroxycarboxylic acids, and the like It is done.

  In addition to these, polyester polyols obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, and copolymerized polyester polyols thereof can be mentioned. These polyester polyols can be used alone or in combination of two or more.

Polyether polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, sorbitol, bisphenol A, hydrogenated bisphenol A, sucrose, aconite sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, One or more of compounds having at least two active hydrogen atoms such as dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propanetrithiol, etc. As a reaction starting point, one or two or more monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran (THF), cyclohexylene, or the like, or a monomer obtained by addition polymerization in the usual manner Examples thereof include those obtained by ring-opening polymerization using a cationic catalyst, a protonic acid, a Lewis acid or the like as a catalyst.
The polyether polyol obtained by addition polymerization, ring-opening polymerization or the like may be a homopolymer using one of the above monomers, or a block polymer or a random polymer using two or more of the monomers. It may be.

  Furthermore, it is also possible to use a polyether polyester polyol having an ether bond and an ester bond. Moreover, in this invention, 1 type of the said polyether polyol can be used individually or in combination of 2 or more types as a polyether polyol.

  Polycarbonate polyol is obtained by reacting glycols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and diethylene glycol with dimethyl carbonate, diethyl carbonate, ethylene carbonate, diphenyl carbonate, and phosgene. The compound which can be mentioned is mentioned. These polycarbonate polyols can be used alone or in combination of two or more.

  (C) As a compound having a hydrophilic group and two or more active hydrogens, the hydrophilic group is preferably a carboxyl group, and examples thereof include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutane. Examples include acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and the like. In addition, as the component (c), a polyester polyol having a pendant carboxyl group obtained by reacting a diol having a carboxyl group with a dicarboxylic acid such as an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid. Can also be used. In the reaction, a diol component having no carboxyl group may be added to the diol having a carboxyl group. These (c) compounds having a hydrophilic group and two or more active hydrogens can be used singly or in combination of two or more.

  The content of the carboxyl group can be expressed as an acid value (hereinafter sometimes referred to as “AV”) in the solid content of the aqueous polyurethane polyol, and is preferably 3 to 65 mgKOH / g, and preferably 6 to 40 mgKOH / g. More preferably, it is g. If the AV is less than 3 mg KOH / g, emulsification may be difficult, or the emulsion stability may be insufficient. When AV exceeds 65 mgKOH / g, the water resistance of the polyurethane after the crosslinking reaction with the curing agent (B) may be lowered.

  In the production of the neutralized isocyanate group-terminated urethane prepolymer in the present invention, in addition to the components (a), (b), and (c), (e) low molecular weight active hydrogen as a chain extender. Containing compounds may be used.

  The (e) low molecular weight active hydrogen-containing compound used as a chain extender is a compound having two or more hydrogen atoms in the molecule capable of reacting with an isocyanate group and having a molecular weight of 300 or less. For example, glycol components listed as raw materials for polyester polyols; low molecular weight polyols such as polyhydroxy compounds such as glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol; ethylenediamine, 1,2-propanediamine, 1,6- Hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2- Examples include low molecular weight polyamines such as cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazines, acid hydrazides, diethylenetriamine, and triethylenetetramine. Door can be. These low molecular weight active hydrogen-containing compounds can be used singly or in combination of two or more.

  In order to obtain an aqueous polyurethane polyol, first, the above-mentioned (a) polyisocyanate compound, (b) polymer polyol, (c) a compound having a hydrophilic group and two or more active hydrogens, and if necessary ( e) A low molecular weight active hydrogen-containing compound is reacted to produce an isocyanate group-terminated urethane prepolymer.

  The isocyanate group-terminated urethane prepolymer can be produced, for example, by a conventionally known one-shot method (one-stage type) or multi-stage isocyanate polyaddition reaction method. The reaction temperature in the production is preferably about 40 to 150 ° C. In the reaction, if necessary, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine alone or 2 More than one species can be added in combination. Moreover, you may add the organic solvent which does not react with an isocyanate group in the reaction stage or after completion | finish of reaction. Examples of such an organic solvent include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, and the like.

  In the present invention, “isocyanate group-terminated urethane prepolymer neutralized product” is obtained by neutralizing the hydrophilic group (carboxyl group) of component (c) and then reacting the components, or After reacting the above components to synthesize an isocyanate group-terminated urethane prepolymer, the hydrophilic group (carboxyl group) of component (c) is neutralized. Here, a base is used for neutralizing the carboxyl group. Examples of the base used include non-volatile bases such as sodium hydroxide and potassium hydroxide, trimethylamine, triethylamine, tri-N-propylamine, and tributylamine. , Tertiary amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine, and volatile bases such as ammonia.

  Next, the obtained isocyanate group-terminated urethane prepolymer neutralized product is at least one selected from the group consisting of (d) a primary amine compound having a hydroxyl group and a secondary amine compound having a hydroxyl group in water. An aqueous polyurethane polyol having a hydroxyl group at the terminal can be obtained by blocking the terminal isocyanate group using the terminal blocking agent. In addition, the isocyanate group-terminated urethane prepolymer neutralized product can be chain-extended in water as necessary. In this case, the isocyanate group-terminated urethane prepolymer neutralized product is used as the (f) chain extender. After the chain extension reaction in water or simultaneously with the chain extension reaction, the terminal isocyanate group is blocked using the component (d).

  When an organic solvent is used in producing the isocyanate group-terminated urethane prepolymer, it is preferable to remove the organic solvent by a method such as distillation under reduced pressure after blocking the terminal isocyanate group. When removing the organic solvent, surfactants such as higher fatty acids, resinates, long chain fatty alcohol sulfates, higher alkyl sulfonates, alkylaryl sulfonates, sulfonated castor oil, sulfosuccinates, etc. It is preferable to maintain the emulsifiability by using a nonionic surfactant such as an anionic surfactant, a reaction product of ethylene oxide and a long-chain fatty alcohol or phenol.

  Examples of the primary amine compound having a hydroxyl group used as the component (d) include hydroxylamine, monoethanolamine, 3-amino-1-propanol, 2-amino-2-hydroxymethylpropane-1, 3-diol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, N, N-di-2-hydroxyethylethylenediamine, N, N-di-2-hydroxypropylethylenediamine, N, N-di-2-hydroxy And propylpropylenediamine.

  Examples of the secondary amine compound having a hydroxyl group used as the component (d) include N-methylethanolamine, diethanolamine, N, N′-di-2-hydroxyethylethylenediamine, N, N′-di- Examples include 2-hydroxypropylethylenediamine, N, N′-di-2-hydroxypropylpropylenediamine, and the like.

  Among the enumerated above, monoethanolamine and diethanolamine can be particularly preferably used as the primary amine compound or secondary amine compound having a hydroxyl group. These compounds can be used individually by 1 type or in combination of 2 or more types.

  (F) As the chain extender, water-soluble polyamine, hydrazine and derivatives thereof can be used, for example, ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine. And amidoamines derived from triethylenetetramine, hydrazine, diprimary amines and monocarboxylic acids, monoketimines of diprimary amines, and the like. These chain extenders can be used individually by 1 type or in combination of 2 or more types.

  When the aqueous polyol used as the main agent (A) is an aqueous polyurethane polyol, the content of hydroxyl groups in the aqueous polyurethane polyol, that is, (d) a primary amine compound having a hydroxyl group and / or a hydroxyl group. The hydroxyl group content derived from the secondary amine compound can be expressed as a hydroxyl value (hereinafter sometimes referred to as “OHV”) in the aqueous polyurethane polyol solid content, and OHV is 1 to 90 mgKOH / g. It is preferable that it is 20-60 mgKOH / g. If the OHV is less than 1 mg KOH / g, the crosslinking density is insufficient during the crosslinking reaction with the curing agent (B), and the resulting polyurethane coating film may have insufficient heat resistance. When OHV exceeds 90 mgKOH / g, the liquid stability after mixing with the curing agent (B) is lowered, which may make it difficult to use.

  In the present invention, as the aqueous polyisocyanate used as the curing agent (B), as a first aspect, by introducing a hydrophilic group into the hydrophobic polyisocyanate, it is water-soluble or self-emulsifiable (without the addition of an emulsifier). , Having a performance capable of being emulsified and dispersed by itself).

  Examples of the hydrophobic polyisocyanate include isocyanurate type polyisocyanate, uretdione type polyisocyanate, allophanate type polyisocyanate obtained by using diisocyanate as a constituent element, and adduct type polyisocyanate obtained by reaction of diisocyanate with bifunctional or higher functional polyol. An isocyanate etc. can be mentioned. In the present invention, it is preferable to use an isocyanurate type polyisocyanate and / or an adduct type polyisocyanate which can easily increase the degree of crosslinking.

  Here, as the diisocyanate, aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate; aliphatics such as tetramethylene diisocyanate, pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate Diisocyanates; cyclophoric diisocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate (hydrogenated xylylene diisocyanate), 4,4′-dicyclohexylmethane diisocyanate, and the like.

  In order to introduce a hydrophilic group into a hydrophobic polyisocyanate, for example, a hydrophilic compound such as an ethylene oxide adduct of alcohol or fatty acid or a random or block adduct of ethylene oxide and propylene oxide is reacted with the hydrophobic polyisocyanate. Let The amount of the hydrophilic group to be introduced (ethylene oxide adduct) is preferably 2 to 50% by mass in the aqueous polyisocyanate. If the amount of the hydrophilic group in the aqueous polyisocyanate is less than 2% by mass, the effect of lowering the interfacial tension may not be sufficient, and emulsification of the aqueous polyisocyanate may be insufficient. On the other hand, when the amount of the hydrophilic group exceeds 50% by mass, the reactivity of the isocyanate group of the aqueous polyisocyanate with respect to water may be too high.

  As such an aqueous polyisocyanate, for example, an adduct modified product of hexamethylene diisocyanate (trade name “DURANATE WB40-100” manufactured by Asahi Kasei Kogyo Co., Ltd.), an isocyanurate modified product of hexamethylene diisocyanate (Nippon Polyurethane Industry Co., Ltd.) Commercially available product names “Aquanate 100”, “Aquanate 200”, a product name “NK Assist IS-100N” manufactured by Nikka Chemical Co., Ltd.) and the like can be obtained commercially.

Moreover, as aqueous polyisocyanate, the water dispersion which disperse | distributed polyisocyanates, such as the said hydrophobic polyisocyanate, in water as a 2nd aspect can also be used. For the preparation of the aqueous dispersion, it is preferable to use one or more compounds selected from existing various nonionic surfactants and anionic surfactants as an emulsifier.
In addition, there is no restriction | limiting in particular in the usage-amount of an emulsifier, What is necessary is just to adjust suitably according to the emulsification state of polyisocyanate.

  Typical nonionic surfactants include linear or branched polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene propylene alkyl phenyl ether, polyoxyethylene alkyl ether, Examples thereof include ethylene distyryl phenyl ether, polyoxyethylene propylene distyryl phenyl ether, polyoxyethylene tristyryl phenyl ether, polyoxyethylene propylene tristyryl phenyl ether, and a pluronic-type nonionic surfactant.

Illustrative examples of anionic surfactants include sulfate esters and phosphate esters of the nonionic surfactants, higher fatty acid salts such as sodium oleate, alkylbenzene sulfonates, alkyl naphthalene sulfonates, and naphthalenes. Examples thereof include sulfonate formalin polycondensate, melamine sulfonate formalin polycondensate, polyoxyethylene alkylsulfosuccinic acid di-salt, sulfated oil and the like.
The term “salt” as used herein refers to a salt of an alkali metal hydroxide, or a salt of a volatile base such as ammonia or triethylamine.

  In the present invention, the aqueous resin which is a mixed system of the main agent (A) and the curing agent (B) has a gel fraction of the polyurethane resin after the crosslinking reaction between the main agent (A) and the curing agent (B) is 60. % Or more is preferable, and 70% or more is more preferable. Moreover, it is preferable that the gel fraction of a polyurethane is less than 95%. When the gel fraction is less than 60%, when sublimation transfer printing is performed, fusion may occur due to the heat of the thermal head, or printability may deteriorate. Further, the water-based resin constituting the receiving layer also has a function as an adhesive with the card substrate, but if the gel fraction exceeds 95%, this adhesion may be lowered.

  Even if the mixing ratio of the aqueous polyisocyanate and the aqueous polyol is the same, the gel fraction varies depending on the main agent. For example, the equivalent ratio (NCO / OH) of isocyanate group (NCO) to hydroxyl group (OH) is Within the range of 0.5 to 3.0, more preferably within the range of 1.3 to 2.0, the aqueous polyisocyanate and the aqueous polyol are mixed and used so that the gel fraction is appropriate. Is preferred. When NCO / OH is less than 0.5, the crosslinking density is insufficient and sufficient performance may not be exhibited. Moreover, when NCO / OH is larger than 3.0, it is uneconomical.

  In the present invention, as the aqueous resin, an aqueous acrylic resin, an aqueous ethylene-vinyl acetate copolymer resin, or the like can be used instead of the mixed system of the main agent (A) and the curing agent (B).

  Examples of aqueous acrylic resins include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid glycidyl, and (meth) acrylic acid. Examples include hydroxypropyl and (meth) acrylic acid-2-hydroxyethyl. Moreover, the ultraviolet curable resin which has as a main component what consists of prepolymers, such as a polyurethane acrylate, polyester acrylate, and an epoxy acrylate, and mixed suitably the additives, such as various acrylate monomers and other polymerization initiators, to this is mentioned. Among these, from the viewpoint of preventing tackiness of the ink ribbon, it is preferable to use an ultraviolet curable type. A trade name “Dicure Excel Coat W EXP-11219” manufactured by Dainippon Ink and Chemicals, Inc. can be obtained commercially.

  The aqueous ethylene-vinyl acetate copolymer preferably has an ethylene ratio of 50% by mass or more from the viewpoint of peelability from the decorative plate after pressing, and preferably 80% by mass or less from the viewpoint of dyeability. As an aqueous ethylene-vinyl acetate copolymer preferably used in the present invention, for example, trade name “DW871” manufactured by Nogawa Chemical Co., Ltd. can be obtained commercially.

In order to improve the releasability from the ink ribbon at the time of printing, various substances (sliding substances) for adjusting the slipperiness can be further added to the aqueous resin. Examples of the slipping material preferably used include a fluorine-based resin, a silicon-based resin, an organic sulfonic acid chloride, and an organic carboxylic acid compound.
In addition, an inorganic filler can be added in order to improve releasability from the ink ribbon at the time of printing. Examples of inorganic fillers preferably used include silica, talc, calcium carbonate and the like.

The sublimation transfer printing receiving layer in the present invention can be formed by mixing and stirring a solution containing an aqueous resin, applying the solution on the protective layer, and drying. In the present invention, a dilution solvent may be added to the aqueous resin to form a coating solution, and water, isopropyl alcohol, ethanol, glycol ether, etc. are preferably used as the dilution solvent. The coating solution preferably has a solid content of 10 to 40% by mass and a viscosity of 50 to 1,000 cps. In the present invention, the solid content may be adjusted using a diluting solvent. By adjusting the coating solution in this manner, an image receiving layer having a uniform film thickness can be formed.
As a coating method of the coating solution, a normal method can be used. For example, it is preferable to apply and dry using a gravure coater because a uniform film thickness can be obtained.

  The thickness of the sublimation transfer printing receiving layer is not particularly limited, and it is preferable to design appropriately according to the type of resin constituting the receiving layer, but generally it is in the range of 1 to 20 μm. Is preferable, and more preferably in the range of 2 to 10 μm. If the film thickness is less than 1 μm, sufficient dyeability may not be obtained, and sufficient adhesion to the card substrate may not be obtained. On the other hand, if it is thicker than 20 μm, it may cause curling of the transfer sheet, or decrease the drying speed in the coating process, leading to a reduction in the line speed, which tends to increase costs.

  In general, a card is composed of, for example, a core sheet used as a middle layer of the card, an oversheet disposed on the surface of the card, and a magnetic stripe tape or an IC chip for recording information as necessary. . An oversheet is overlaid on the core sheet, and the sheets are fused together by hot pressing or the like, and then punched into a card shape. In the present invention, the term “card base material” refers to a sheet as a base material used for card manufacture, including a sheet such as a core sheet and an oversheet, a sheet having a laminated structure in which an oversheet is laminated on a core sheet, and the like. Shall be. That is, in the present invention, the card base material is not limited to the thickness and type as long as it is a base material used for card manufacturing, but in the following, it is a thick layer in which a core sheet and an oversheet are laminated. A type of card substrate will be described as an example.

  The card of the present invention can be produced by laminating an oversheet on at least one surface of the core sheet. For example, the surface of the white core sheet is printed by silk screen printing, offset printing, etc., and the formed printing surface is covered with an oversheet, and if necessary, the other surface of the core sheet is also covered with an oversheet. After pasting, it is sandwiched between decorative plates and hot pressed to form a card substrate. Then, the sheet | seat for cards can be formed by overlapping and pressing the transfer sheet which gave sublimation transfer printing. The obtained card sheet can be punched into a card shape with a punching blade. Alternatively, the card substrate and the transfer sheet may be cut into a card shape and then pressed to form a card.

  Oversheet is excellent in processability such as printing, punching, embossing, etc., so polyvinyl chloride resin (PVC), amorphous polyester resin, polycarbonate resin (PC), acrylonitrile-butadiene-styrene copolymer resin (Hereinafter referred to as ABS) or the like is preferable. The amorphous polyester-based resin is preferably a substantially amorphous aromatic polyester resin in which about 30 mol% of ethylene glycol in polyethylene terephthalate is replaced with 1,4-cyclohexanedimethanol. For example, Eastman Chemical The trade name “PETG” manufactured by the company is commercially available.

  As the core sheet, a sheet containing an amorphous polyester resin as a main component can be used, but any sheet can be used without particular limitation as long as it can be integrated with the oversheet. However, from the viewpoint of environmental protection, a resin other than PVC is preferable.

  In the case of an IC card, the core sheet is preferably a material that can absorb irregularities such as an antenna coil and an IC chip, and is preferably one that can be deformed by heating and pressing. For example, a thermoplastic resin that is deformed by heating, pressing, or the like is preferably used. Examples of the thermoplastic resin preferably used include general-purpose plastics such as polyolefin resin, amorphous polyester resin, crystalline polyester resin, acrylic resin, ABS resin, AS resin, and PC resin. In the present invention, as the core sheet, a film or sheet mainly composed of one or more of these thermoplastic resins is preferably used.

  In addition, an engineering plastic having good heat resistance can be used as a material for the core sheet. Examples of the engineering plastic include polyphenylene sulfide, polyether imide, polyimide, polyether ether ketone, and the like, and films and sheets mainly composed of one or more of these are preferably used. However, if the glass transition temperature (Tg), melting temperature, etc. are too high, it is assumed that the reversible recording layer, IC chip, etc. will be deteriorated or destroyed during heat press processing. Thus, it is preferable to select a material having an appropriate glass transition temperature.

Moreover, a thermosetting resin can also be used as a material for the core sheet. In this case, the sheet on which the IC chip or the like is placed and the oversheet or the like are overlapped with each other while the thermosetting resin is soft at room temperature, and heated and pressed to be cured. In this way, an IC card can be manufactured. Examples of the thermosetting resin used here include an epoxy resin, a phenol resin, and a melamine resin.
From the viewpoint of material design such as fusion and heat resistance during hot pressing, it is desirable to use the same resin as the main component resin constituting the thermocompression bonding substrate.

  In the present invention, the method for integrating the oversheet and the core sheet is not particularly limited, and examples thereof include a method using thermal fusion, an adhesive, and the like. In this invention, it is preferable to integrate by heat sealing | fusion. In addition, you may stick a magnetic tape on an oversheet beforehand.

  The transfer sheet of the present invention is obtained by sequentially laminating a protective layer and a sublimation transfer printing receiving layer on a support. The sublimation transfer printing receiving layer is printed with an arbitrary image using a sublimation transfer printing printer, and then the transfer sheet is attached to the surface of the card substrate (oversheet) by heating and pressing, and then the support is peeled off. By doing so, the sublimation transfer printing receiving layer with a protective layer can be transferred onto the surface of the card substrate. Since the card thus obtained has a protective layer on the surface of the sublimation transfer printing receiving layer, it is possible to prevent the printing portion from being deteriorated due to “rubbing” or the like.

Further, the transfer sheet of the present invention may be half-cut into an arbitrary shape after performing sublimation transfer printing. By half-cutting, only the protective layer and the sublimation transfer printing receiving layer can be cut without cutting the support having releasability. If the transfer sheet thus half-cut is transferred to the surface of the card substrate, a protective layer is formed only on the transferred portion. Therefore, other processing (for example, printing, thermal transfer, etc.) can be easily performed on the obtained card.

Examples of the present invention will be described below and will be described in more detail. However, the present invention is not limited to these examples, and various applications are possible without departing from the technical idea of the present invention.
In the examples and comparative examples, each measured value was determined by the following method.

(Solid content)
The residual weight percentage after the sample was dried at 105 ° C. for 3 hours was calculated and used as the solid content.

(Gel fraction)
The coating solution for the receiving layer was dried at 80 ° C. for 1 minute to form a polyurethane resin coating film having a thickness of 3 μm. 0.5 g of this polyurethane resin coating film was immersed in a THF solution at 23 ° C. for 24 hours to dissolve uncrosslinked components. Thereafter, the mixture was filtered to remove the residue (crosslinked resin). First, preliminary drying was performed at 23 ° C. for 48 hours, followed by drying at 80 ° C. for 30 minutes, and the weight was measured. The gel fraction was determined based on the following formula. That is, a value obtained by dividing the weight of the resin for the cross-linked portion by the original resin weight (0.5 g) before dissolution was displayed as a 100 fraction, which was defined as a gel fraction.

Gel fraction (%) = (resin weight of crosslinked part / 0.5) × 100

Synthesis Example 1 (Synthesis of aqueous polyurethane polyol A)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 149.1 g of polyhexamethylene adipate isophthalate diol (weight average molecular weight 1,800), 4.6 g of ethylene glycol, 2,2- 17.8 g of dimethylolpropionic acid, 0.001 g of dibutyltin dilaurate and 120 g of methyl ethyl ketone were added and mixed uniformly. Next, 108.5 g of 2,2′-dicyclohexylmethane diisocyanate was added thereto and reacted at 80 ° C. for 5 hours to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer. This urethane prepolymer had a free isocyanate group content of 3.7% by mass relative to the solid content.

The obtained methyl ethyl ketone solution of urethane prepolymer was cooled to 30 ° C. and neutralized by adding 13.4 g of triethylamine, and then 520 g of water was gradually added and emulsified and dispersed. To this emulsified dispersion, 18.6 g of a 20% by mass aqueous solution of ethylenediamine was added and stirred for 0.5 hours, and then 13.1 g of diethanolamine was further added and stirred for 2 hours. The solvent was removed while raising the temperature to 50 ° C. over 2 hours under reduced pressure to obtain an aqueous polyurethane polyol A.
The solid content of the aqueous polyurethane polyol A was 36% by mass. The acid value (AV) derived from 2,2-dimethylolpropionic acid in the solid content was 25 mgKOH / g, and the hydroxyl value (OHV) in the solid content was 47 mgKOH / g.
Table 1 shows the composition ratio and the various functional group contents in this synthesis example.

Synthesis Example 2 (Synthesis of aqueous polyurethane polyol B)
In the same reactor as used in Synthesis Example 1, 206.2 g of polybutylene terephthalate diol (weight average molecular weight 2,000), 16.1 g of 2,2-dimethylolpropionic acid, 0.001 g of dibutyltin dilaurate, and Then, 120 g of methyl ethyl ketone was added and mixed uniformly. Next, 57.7 g of hexamethylene diisocyanate was added thereto and reacted at 80 ° C. for 5 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer. This urethane prepolymer had a free isocyanate group content of 3.6% by mass based on the solid content.

The obtained methyl ethyl ketone solution of urethane prepolymer was cooled to 30 ° C., neutralized by adding 12.2 g of triethylamine, and then 510 g of water was gradually added to emulsify and disperse. To this emulsified dispersion, 21.7 g of a 20% by mass aqueous solution of ethylenediamine was added and stirred for 0.5 hour, and then 10.1 g of diethanolamine was further added and stirred for 2 hours. The solvent was removed while the temperature was raised to 50 ° C. over 2 hours under reduced pressure to obtain an aqueous polyurethane polyol B.
The solid content of the aqueous polyurethane polyol B was 36% by mass. The acid value (AV) derived from 2,2-dimethylolpropionic acid in the solid content was 22 mgKOH / g, and the hydroxyl value (OHV) in the solid content was 37 mgKOH / g.
In addition, Table 1 shows the composition ratio and the above-mentioned various functional group contents in this synthesis example.

Synthesis Example 3 (Synthesis of aqueous polyurethane polyol C)
In a reaction apparatus similar to that used in Synthesis Example 1, 156.4 g of poly-ε-caprolactone diol (weight average molecular weight 2,000), 4.4 g of ethylene glycol, 16.8 g of 2,2-dimethylolpropionic acid, 0.001 g of dibutyltin dilaurate and 120 g of methyl ethyl ketone were added and mixed uniformly. Next, 102.5 g of 2,2′-dicyclohexylmethane diisocyanate was added thereto and reacted at 80 ° C. for 5 hours to obtain a methyl ethyl ketone solution of urethane prepolymer. This urethane prepolymer had a free isocyanate group content of 3.5% by mass relative to the solid content.

The obtained methyl ethyl ketone solution of urethane prepolymer was cooled to 30 ° C. and neutralized by adding 12.6 g of triethylamine, and then 520 g of water was gradually added and emulsified and dispersed. To this emulsified dispersion, 17.6 g of a 20% by mass aqueous solution of ethylenediamine was added and stirred for 0.5 hour, and then 12.3 g of diethanolamine was further added and stirred for 2 hours. The solvent was removed while raising the temperature to 50 ° C. over 2 hours under reduced pressure, to obtain an aqueous polyurethane polyol C.
The solid content of the aqueous polyurethane polyol C was 36% by mass. The acid value (AV) derived from 2,2-dimethylolpropionic acid in the solid content was 24 mgKOH / g, and the hydroxyl value (OHV) in the solid content was 44 mgKOH / g.
In addition, Table 1 shows the composition ratio and the above-mentioned various functional group contents in this synthesis example.

Synthesis Example 4 (Synthesis of aqueous polyurethane polyol D)
In the same reactor as used in Synthesis Example 1, 162.6 g of polytetramethylene glycol (weight average molecular weight 2,000), 6.7 g of 1,4-butanediol, 2,2-dimethylolpropionic acid 13 0.9 g, dibutyltin dilaurate 0.001 g and methyl ethyl ketone 120 g were added and mixed uniformly. Next, 96.8 g of 2,2′-dicyclohexylmethane diisocyanate was added thereto and reacted at 80 ° C. for 5 hours to obtain a methyl ethyl ketone solution of a prepolymer. In this urethane prepolymer, the content of free isocyanate groups relative to the solid content was 3.3% by mass.

The methyl ethyl ketone solution of the obtained prepolymer was cooled to 30 ° C. and neutralized by adding 10.5 g of triethylamine, and then 510 g of water was gradually added to emulsify and disperse. To this emulsified dispersion, 18.3 g of a 20% by mass aqueous solution of ethylenediamine was added and stirred for 0.5 hour, and then 10.5 g of diethanolamine was further added and stirred for 2 hours. The solvent was removed while raising the temperature to 50 ° C. over 2 hours under reduced pressure, to obtain an aqueous polyurethane polyol D.
The solid content of the aqueous polyurethane polyol D was 36% by mass. The acid value (AV) derived from 2,2-dimethylolpropionic acid in the solid content was 20 mgKOH / g, and the hydroxyl value (OHV) in the solid content was 38 mgKOH / g.
In addition, Table 1 shows the composition ratio and the above-mentioned various functional group contents in this synthesis example.

Synthesis Example 5 (Synthesis of aqueous polyurethane polyol E)
In the same reactor as used in Synthesis Example 1, 163.4 g of polyhexamethylene carbonate diol (weight average molecular weight 2,000), 6.6 g of 1,4-butanediol, 2,2-dimethylolbutanoic acid 19.3 g, 0.001 g of dibutyltin dilaurate and 120 g of methyl ethyl ketone were added and mixed uniformly. Next, 90.7 g of isophorone diisocyanate was added thereto and reacted at 80 ° C. for 5 hours to obtain a methyl ethyl ketone solution of a prepolymer. In this urethane prepolymer, the content of free isocyanate groups relative to the solid content was 3.3% by mass.

The methyl ethyl ketone solution of the obtained prepolymer was cooled to 30 ° C., neutralized by adding 13.2 g of triethylamine, and then 530 g of water was gradually added to effect emulsification and dispersion. To this emulsified dispersion, 5.6 g of a 60% by mass aqueous solution of hydrazine hydrate was added and stirred for 0.5 hour, and then 11.6 g of diethanolamine was further added and stirred for 2 hours. The solvent was removed while raising the temperature to 50 ° C. over 2 hours under reduced pressure, and an aqueous polyurethane polyol E was obtained.
The solid content of the aqueous polyurethane polyol E was 36% by mass. The acid value (AV) derived from 2,2-dimethylolbutanoic acid in the solid content was 25 mgKOH / g, and the hydroxyl value (OHV) in the solid content was 42 mgKOH / g.
In addition, Table 1 shows the composition ratio and the above-mentioned various functional group contents in this synthesis example.

Synthesis Example 6 (Synthesis of aqueous polyisocyanate A)
A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube was charged with an isocyanurate of hexamethylene diisocyanate (manufactured by Rhodia Japan, trade name “Tronate HDT-LV2”, NCO content 23. 02.6%), polyoxyethylene alkylaryl phosphate ester (Rhodia Japan Co., Ltd., trade name “Rodafac PA / 19”) 10.4 g, polyoxyethylene tristyrylphenyl ether phosphate (Rhodia) -7.0 g made by Japan Co., Ltd., trade name “SOPROFOL 3D 33” was added and mixed uniformly to obtain an aqueous dispersion of isocyanurate type polyisocyanate. The NCO content was 19.0% by mass. This is designated as aqueous polyisocyanate A.

Production Example 1 (Preparation of aqueous coating solution 1 for receiving layer)
100 g of the aqueous polyurethane polyol A obtained in Synthesis Example 1 was mixed as the main agent (A), and 2.0 g of the aqueous polyisocyanate A obtained in Synthesis Example 6 was mixed as the curing agent (B) and stirred until uniform. Thus, an aqueous coating solution 1 was prepared. In addition, the equivalent ratio (NCO / OH) of the isocyanate group in the curing agent (B) and the hydroxyl group in the main agent (A) is 0.3, and the gel fraction of the polyurethane resin after the crosslinking reaction is 49%. there were. The composition ratio and gel fraction in this production example are shown in Table 2.

Production Examples 2 to 5 (Preparation of aqueous coating solutions 2 to 5)
Aqueous coating solutions 2 to 5 were prepared in the same manner as in Production Example 1 except that the amount of aqueous polyisocyanate A used in Production Example 1 was changed as shown in Table 2. The composition ratio and gel fraction of each aqueous coating solution are shown in Table 2.

Production Example 6 (Preparation of aqueous coating solution 6)
100 g of the aqueous polyurethane polyol B obtained in Synthesis Example 2 was mixed as the main agent (A), and 9.5 g of the aqueous polyisocyanate A obtained in Synthesis Example 6 was mixed as the curing agent (B) and stirred until uniform. Thus, an aqueous coating solution 6 was prepared. The equivalent ratio (NCO / OH) of the isocyanate group in the curing agent (B) and the hydroxyl group in the main agent (A) is 1.8, and the gel fraction of the polyurethane resin after the crosslinking reaction is 79%. Met. The composition ratio and gel fraction in this production example are shown in Table 2.

Production Example 7 (Preparation of aqueous coating solution 7)
100 g of the aqueous polyurethane polyol C obtained in Synthesis Example 3 was mixed as the main agent (A), and 11.2 g of the aqueous polyisocyanate A obtained in Synthesis Example 6 was mixed as the curing agent (B) and stirred until uniform. Thus, an aqueous coating solution 7 was prepared. In addition, the equivalent ratio (NCO / OH) of the isocyanate group in the curing agent (B) and the hydroxyl group in the main agent (A) is 1.8, and the gel fraction of the polyurethane resin after the crosslinking reaction is 80%. there were. In addition, Table 2 shows the composition ratio and the gel fraction in this coating solution production example.

Production Example 8 (Preparation of aqueous coating solution 8)
100 g of the aqueous polyurethane polyol D obtained in Synthesis Example 4 was mixed as the main agent (A), and 9.7 g of the aqueous polyisocyanate A obtained in Synthesis Example 6 was mixed as the curing agent (B) and stirred until uniform. Thus, an aqueous coating solution 8 was prepared. The equivalent ratio (NCO / OH) of the isocyanate group in the curing agent (B) and the hydroxyl group in the main agent (A) is 1.8, and the gel fraction in the image receiving layer after drying is 79%. there were. The composition ratio and gel fraction in this production example are shown in Table 2.

Production Example 9 (Preparation of aqueous coating solution 9)
100 g of the aqueous polyurethane polyol E obtained in Synthesis Example 5 was mixed as the main agent (A), and 10.7 g of the aqueous polyisocyanate A obtained in Synthesis Example 6 was mixed as the curing agent (B) and stirred until uniform. Thus, an aqueous coating solution 9 was prepared. In addition, the equivalent ratio (NCO / OH) of the isocyanate group in the curing agent and the hydroxyl group in the main agent (A) was 1.8, and the gel fraction of the polyurethane resin after the crosslinking reaction was 80%. The composition ratio and gel fraction in this production example are shown in Table 2.

Production Example 10 (Preparation of aqueous coating solution 10)
As the main agent (A), 100 g of the aqueous polyurethane polyol A obtained in Synthesis Example 1, and as the curing agent (B), aqueous polyisocyanate B (manufactured by Nikka Chemical Co., Ltd., trade name “NK Assist IS-100N”, Aqueous coating solution 10 was prepared by mixing 13.3 g of isocyanate content (17.2 mass%) and stirring until uniform. In addition, the equivalent ratio (NCO / OH) of the isocyanate group in the curing agent (B) and the hydroxyl group in the main agent (A) is 1.8, and the gel fraction of the polyurethane resin after the crosslinking reaction is 80%. there were. The composition ratio and gel fraction in this production example are shown in Table 2.

Production Example 11 (Preparation of aqueous coating solution 11)
As the main agent (A), 100 g of the aqueous polyurethane polyol A obtained in Synthesis Example 1, and as the curing agent (B), aqueous polyisocyanate B (manufactured by Nikka Chemical Co., Ltd., trade name “NK Assist IS-100N”, Aqueous coating solution 11 was prepared by mixing 2.2 g of isocyanate content (17.2 mass%) and stirring until uniform. The equivalent ratio (NCO / OH) of the isocyanate group in the curing agent (B) and the hydroxyl group in the main agent (A) is 0.3, and the gel fraction of the polyurethane resin after the crosslinking reaction is 48%. there were. The composition ratio and gel fraction in this production example are shown in Table 2.

Production Example 12 (Preparation of aqueous coating solution 12)
As the main agent (A), aqueous polyurethane polyol F (trade name “Evaphanol HO-18”, manufactured by Nikka Chemical Co., Ltd.) and aqueous polyisocyanate B (manufactured by Nikka Chemical Co., Ltd., product name “NK Assist IS-”) 100N "and an isocyanate content of 17.2% by mass) were mixed so that NCO / OH was 1.8 to prepare an aqueous coating solution 12. The gel fraction of the polyurethane resin after the crosslinking reaction was 60%.

Production Example 13 (Preparation of aqueous coating solution 13)
In Production Example 12, an aqueous coating solution 13 was prepared in the same manner as in Production Example 12 except that NCO / OH was changed to 1.2. The gel fraction of the polyurethane resin after the crosslinking reaction was 50%.

Example 1
(Preparation of card substrate)
As an oversheet, a PETG sheet (trade name “Diafix PG-CHI”, manufactured by Mitsubishi Plastics, Inc., thickness 100 μm) is used, and as a core sheet, a PETG sheet (trade name “Diafix PG-WHI”, Mitsubishi Plastics Co., Ltd., thickness 560 μm) was used.
Each sheet was cut into a size of 300 mm × 300 mm and overlaid in the order of an oversheet, a core sheet, and an oversheet. Next, each sheet is sandwiched between chrome-plated plates so as not to be displaced, heated and pressed for 20 minutes under conditions of a temperature of 120 ° C. and a pressure of 20 kg / cm ² , and then cooled and cooled to form a card substrate. Obtained. This card substrate was punched into a card shape to produce a card-shaped card substrate made of PETG.

(Preparation of transfer sheet)
A releasable PET film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., “Diafoil MRX-38”) was used as a support, and the following ultraviolet curable resin paint was applied to the surface of this film using a bar coater. After coating, 160 W / cm ultraviolet rays were irradiated at 10 m / min to cure, and a protective layer having a thickness of 3 μm was formed.
Composition of UV curable resin paint:
UV curable resin (KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.) 50 parts by weight Photopolymerization initiator (Irgacure 184, manufactured by Chivas Hessical Chemicals) 3 parts by weight Solvent (2-propanol) 50 parts by weight

  Next, the aqueous coating solution 1 obtained in Production Example 1 was coated on the protective layer using a bar coater and dried at 100 ° C. for 10 minutes using a hot air dryer. A transfer sheet having a sublimation transfer printing receiving layer having a thickness of 5 μm was prepared. The transfer sheet had a card-shaped half cut of 300 mm × 300 mm.

(Card production)
The sublimation transfer printing receiving layer of the obtained transfer sheet was printed with a sublimation transfer printing printer. Next, taking the half-cut into consideration, the receiving layer was superposed on the card substrate and transferred by pressing at a temperature of 120 ° C. and a pressure of 10 kg / cm ² for 5 minutes. Thereafter, the support was peeled off to produce a card having a receiving layer and a protective layer in this order on the card substrate.

Examples 2-13
In Example 1, a transfer sheet was prepared in the same manner as in Example 1 except that the aqueous coating solutions 2 to 13 were used instead of the aqueous coating solution 1. Next, sublimation transfer printing was performed in the same manner as in Example 1 to produce a card.

Comparative Example 1
Sublimation transfer printing using a solvent-based coating solution (trade name “Evergrip P-71”, manufactured by Aron Evergrip Limited) in which an ethylene-vinyl acetate polymer is dissolved in a mixed solvent of toluene and methylethylketone. A transfer sheet was produced in the same manner as in Example 1 except that the receiving layer was formed. Moreover, it printed similarly to Example 1 and produced the card | curd. However, in the drying process after coating, toluene and methyl ethyl ketone evaporated and a solvent odor was generated.

Comparative Example 2
Transfer sheet in the same manner as in Example 1 except that “Byron UR-8200” (manufactured by Toyobo Co., Ltd.) using toluene and methyl isobutyl ketone as a solvent was used as a coating solution and dried after coating to form a sublimation transfer printing receiving layer. Was made. Next, when this transfer sheet was printed by a sublimation transfer printing printer, the ink ribbon was fused, and printing could not be performed.
In addition, due to drying after coating, toluene and methyl isobutyl ketone evaporated and a solvent odor was generated.

About the transfer sheet obtained in Examples 1-13 and Comparative Examples 1-2, printability and environmental property were evaluated by the following method. The results are shown in Table 3.
Evaluation methods:
(1) Printability Sublimation transfer printing of a pattern was performed on a sublimation transfer printing receiving layer of a transfer sheet using a card color printer “PR5300” manufactured by Nisca Corporation. At this time, whether or not the ink ribbon was stuck was visually observed to evaluate printability. The symbol “○” indicates that there was no sticking and the printability was good, and it can be used without any problem in practice. However, the symbol “△” indicates that a sticking sound with the ink ribbon has occurred, and sticking is recognized. Those in which jamming occurred are indicated by a symbol “x”.

(2) Environmental properties The odor of vapor generated by drying after application of the solution for the receiving layer was confirmed.

(3) Comprehensive evaluation Symbols “◯” indicate that the printability and environmental properties are good, symbol “Δ” indicates that the product is practically usable, and symbol “×” indicates that it cannot be used.

As is apparent from Table 3, the transfer sheets obtained in Examples 1 to 13 all show excellent printability, have no solvent odor, and are excellent in environmental properties. The aqueous coating solutions of Examples 1 to 4 and Examples 6 to 13 have a long pot life and excellent workability. The aqueous coating solution of Example 5 had a short pot life.
In addition, the transfer sheets of Examples 1 to 13 are advantageous because the sublimation transfer printing receiving layer also functions as an adhesive for the card base material, which reduces the number of processes compared to the case where an adhesive layer is newly provided.
Furthermore, the coating liquid for sublimation transfer printing receiving layers of Examples 1 to 13 is not a solvent system but an aqueous solution, so that it does not erode the base (object to be coated). Therefore, problems such as shrinkage and swelling of the support and the protective layer did not occur during transfer sheet preparation.

  In Comparative Examples 1 and 2, after applying the coating liquid for the sublimation transfer printing receiving layer, a solvent odor was generated when drying, resulting in poor environmental properties. In Comparative Example 2, when sublimation transfer printing was performed on the transfer sheet, fusing with the ink ribbon occurred, so printing could not be continued, and printability was extremely inferior.

Claims (8)

An aqueous resin having a support having a releasability, a protective layer, and a sublimation transfer printing receiving layer in this order, wherein the sublimation transfer printing receiving layer is a mixed system of the main agent (A) and the curing agent (B). layer der formed using a solution composed mainly of is,
In the isocyanate group-terminated urethane prepolymer obtained when the main agent (A) is obtained from (a) a polyisocyanate compound, (b) a polymer polyol, and (c) a compound having a hydrophilic group and two or more active hydrogens. A water-based polyurethane polyol containing a hydroxyl group, obtained by using (d) at least one end-capping agent selected from the group consisting of a primary amine compound and a secondary amine compound having a hydroxyl group. And
A transfer sheet, wherein the curing agent (B) is an aqueous polyisocyanate . 2. The transfer sheet according to claim 1 , wherein the (b) polymer polyol is at least one polymer polyol selected from the group consisting of a polyester polyol, a polycarbonate polyol, and a polyether polyol. The transfer according to claim 1 or 2 , wherein the gel fraction of the polyurethane resin after the crosslinking reaction between the main agent (A) and the curing agent (B) is 60% or more. Sheet. A transfer sheet having a support having a releasability, a protective layer, and a sublimation transfer printing receiving layer in this order. After the transfer sheet is subjected to sublimation transfer printing to form an image, it is heated and pressed to apply the transfer sheet. The transfer sheet according to claim 1 , wherein the transfer sheet can be laminated on a transfer body. A card, which is a laminate obtained by subjecting the transfer sheet according to any one of claims 1 to 4 to sublimation transfer printing to form an image, and then transferring the image to a card substrate by heating and pressing. . 6. The card according to claim 5 , further comprising a laminated structure from which the support having releasability is removed. A support having a releasing property, protective layer, and a transfer sheet having a sublimation transfer printing receiving layer in this order,該昇Hua transfer printing receiving layer in a mixed system of the base material (A) and the curing agent (B) Ri layer der formed using a solution composed mainly of certain aqueous resin, the base resin (a), (a) a polyisocyanate compound, (b) a polymer polyol, and, (c) a hydrophilic group and a 2 A neutralized isocyanate group-terminated urethane prepolymer obtained from a compound having at least one active hydrogen, (d) at least selected from the group consisting of a primary amine compound and a secondary amine compound having a hydroxyl group A method for using the transfer sheet, which is an aqueous polyurethane polyol containing a hydroxyl group, obtained using one type of end-capping agent, and the curing agent (B) is an aqueous polyisocyanate.
After sublimation transfer printing is performed on the surface of the sublimation transfer printing receiving layer, the sublimation transfer printing receiving layer is stacked on the transfer target, and then the support having the releasability is removed. How to use the transfer sheet. Forming a protective layer on a releasable support;
Forming a sublimation transfer printing receiving layer on the protective layer ;
Applying sublimation transfer printing to form an image on the sublimation transfer printing receiving layer;
Transferring the sublimation transfer printing receiving layer on which the image is formed to the card substrate by heating and pressing ; and
Comprising a step of peeling the support having releasability ,
And in the step of forming the sublimation transfer printing receiving layer, the sublimation transfer printing receiving layer is formed using a solution mainly composed of an aqueous resin which is a mixed system of the main agent (A) and the curing agent (B), In the isocyanate group-terminated urethane prepolymer obtained when the main agent (A) is obtained from (a) a polyisocyanate compound, (b) a polymer polyol, and (c) a compound having a hydrophilic group and two or more active hydrogens. A water-based polyurethane polyol containing a hydroxyl group, obtained by using (d) at least one end-capping agent selected from the group consisting of a primary amine compound and a secondary amine compound having a hydroxyl group. And the curing agent (B) is an aqueous polyisocyanate,
A card manufacturing method characterized by the above.