JP2009226860A - Hydraulic transfer sheet and hydraulic transfer method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic transfer sheet without causing any dullness in a pattern layer due to a hydraulic transfer even when the pattern layer is formed using water-based ink. <P>SOLUTION: In the hydraulic transfer sheet, at least a transparent filler layer (B), an image receiving layer (C), and a pattern layer (D) formed by a printing means in this order on one side of a water-soluble or water-swellable base sheet (A). The hydraulic transfer sheet is characterized in that the image receiving layer (C) is composed of a water-based resin layer, and the filler layer (B) is composed of a resin layer having low moisture permeability. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hydraulic transfer sheet used for transferring and printing a pattern layer on the surface of various molded articles by a hydraulic transfer method, and a hydraulic transfer method for transferring and printing the pattern layer to various molded articles by water pressure. .

  Conventionally, a hydraulic transfer sheet for forming a printed pattern by transfer printing on a surface of a molded body having a flat surface or a three-dimensional surface by unevenness, and a hydraulic transfer method as a means thereof are known (Patent Document 1, Patent). Literature 2, Patent Literature 3).

  On the other hand, in recent years, as a pattern formation, an ink-jet printing method that is easy to make full color and excellent in print quality is rapidly spreading. Ink-jet printing is usually performed by spraying organic solvent-diluted ink mainly as fine droplets from a nozzle onto a recording material. However, if the recording material has a very high water absorption like paper, the ink will bleed and a fine image cannot be obtained. On the other hand, if the recording material is a plastic film, the ink absorption Printing is difficult due to extremely low performance. Accordingly, it is desirable to use a water-soluble resin or a water-dispersible resin that prevents ink bleeding and has good ink absorbability for the recording material of the ink jet recording system.

  For this reason, when the pattern layer is formed by ink jet when performing hydraulic transfer, it is desirable to use the water-soluble resin or water-dispersible resin as an image receiving layer on which the pattern layer is formed. However, in the case of hydraulic transfer, since the support sheet is a water-soluble or water-swellable resin, when a water-soluble resin or a water-dispersible resin is used as the image receiving layer, the support sheet is transferred from the support sheet to the picture layer via the image receiving layer. Since moisture permeates, there is a problem in that the molded layer having the hydraulically transferred pattern layer is blurred in the pattern layer.

Japanese Examined Patent Publication No. 52-041683 Japanese Patent Publication No. 07-555999 Japanese Patent No. 2757346

In a hydraulic transfer sheet including at least a support sheet, a receiving layer, and a pattern layer, when the pattern layer is formed on the image receiving layer by an ink jet printing method, a receiving layer made of an aqueous resin having good ink absorbability is used. However, there is no known water pressure transfer sheet in which a white-brown blur does not occur in the pattern layer in the molded body having the water pressure transferred pattern layer.
The present invention provides a molded article having a pattern layer that has been hydraulically transferred even if a pattern layer is formed on the receptor layer by ink jet printing, using a receptor layer having good absorbability of water-based ink when performing hydraulic transfer. An object of the present invention is to provide an excellent water pressure transfer sheet which does not cause white browning.

As a result of earnest research on the solution of the above problems, the inventor of the present application has a low water permeability resin between the support sheet and the receiving layer in the hydraulic transfer sheet configured in the order of the support sheet, the receiving layer, and the pattern layer. It has been found that the above problems can be solved by providing a layer, and the present invention has been completed.
That is, the gist of the present invention is the invention described in the following (1) to (6).
(1) A pattern layer (D) formed by at least a transparent sealing layer (B), an image receiving layer (C), and printing means on one surface of a water-soluble or water-swellable support sheet (A). Are the hydraulic transfer sheets (E) formed in this order, wherein the image receiving layer (C) is made of an aqueous resin layer, and the sealing layer (B) is made of a resin layer having low moisture permeability. A hydraulic transfer sheet (hereinafter sometimes referred to as “first aspect”).
(2) The aqueous resin layer contains the water-soluble resin (S1), the water-dispersible resin (S2), or the water-soluble resin (S1) and the water-dispersible resin (S2). ) The hydraulic transfer sheet as described above.
(3) The hydraulic transfer sheet according to (2), wherein the water-dispersible resin (S2) is a layer formed from a urethane emulsion having a pH of 7.0 or more.
(4) The hydraulic transfer sheet according to (2), wherein the water-dispersible resin (S2) is a layer formed from a urethane emulsion having a pH of 7.5 to 9.0.
(5) One or more resins selected from the group consisting of acrylic resin, urethane resin, epoxy resin, alkyd resin, nitrified cotton, vinyl chloride resin, vinyl acetate resin, and polyvinyl butyral. The hydraulic transfer sheet according to any one of the above (1) to (4), comprising:
(6) A transparent sealing layer (B) and an image receiving layer (C) are formed in this order on at least a water-soluble or water-swellable support sheet (A), and a picture layer is further formed on the surface of the image receiving layer (C). A step of forming a hydraulic transfer sheet (E) obtained by drying (D) after printing (hydraulic transfer sheet forming step),
Next, after applying the activator to the surface of the pattern layer (D), the hydraulic transfer sheet (E) is suspended on the water surface so that the pattern layer (D) becomes the upper surface, and the hydraulic transfer sheet (E) is The substrate (F) to be transferred is pressed against the surface of the pattern layer (D) while being stretched, and the pattern layer (D) surface of the hydraulic transfer sheet (E) is brought into close contact with the required transfer portion of the substrate to be transferred (F) by water pressure. And then removing the support sheet (A) from the hydraulic transfer sheet portion by washing or dissolving with water to obtain a transfer target (G) (hydraulic transfer process)
A hydraulic transfer method comprising:
The image receiving layer (C) is composed of an aqueous resin layer, and the sealing layer (B) is composed of a resin layer having low moisture permeability.
This is a hydraulic transfer method (hereinafter sometimes referred to as “second aspect”).
(7) The hydraulic transfer method according to (6), wherein the pattern layer (D) is formed by ink jet printing.

In the hydraulic transfer sheet (E) of the present invention, the sealing layer (B) having a low water permeability is formed between the support sheet (A) and the receiving layer (C). Even if the pattern layer (D) is formed on the layer (C), the water pressure transfer sheet (E) is not blurred after the water pressure transfer, and the water pressure transfer sheet is excellent in transparency, appearance and the like. Yes.
Furthermore, when a printed pattern layer is formed by conventional electrostatic printing, there is a problem in color reproducibility because the photoreceptor and toner are unstable. However, if ink jet printing is used, color reproduction like electrostatic printing will occur. The color reproducibility is good and an excellent design can be imparted to the molded product.

As shown in FIG. 1, the hydraulic transfer sheet (E) of the present invention has a sealing layer (B) and an image receiving layer (C) on a support sheet (A) made of a water-soluble or water-swellable sheet. This is a hydraulic transfer sheet (E) on which a pattern layer (D) is formed by printing such as inkjet printing. The pattern layer (D) may be formed entirely on the surface of the image receiving layer (C) or may be partially formed.
FIG. 2 is a conceptual diagram showing an example of the water pressure transfer method of the present invention. As shown in FIG. 2, the hydraulic transfer sheet (E) is placed on the water surface (W) with the support sheet (A) side facing the water surface side and the pattern layer (D) side facing up. The substrate to be transferred (F) is pushed in from above the pattern layer (D) coated with the activator, and is stretched and brought into close contact with the surface of the substrate, and then the hydraulic transfer sheet (E The substrate to be transferred (F) is stretched and adhered to the substrate, and the support sheet portion is removed by a hot water shower or the like, followed by drying (to be transferred) G) is obtained.

[1] “Hydraulic transfer sheet” of the first aspect The “hydraulic transfer sheet” according to the first aspect has at least eyes on one surface of the water-soluble or water-swellable support sheet (A). A hydraulic transfer sheet in which a stop layer (B), a transparent image receiving layer (C), and a pattern layer (D) formed by printing means are formed in this order, and the image receiving layer (C) is at least an aqueous resin layer And the sealing layer (B) is made of a resin layer having low moisture permeability.

(1) Support sheet (A)
As the support sheet (A), any sheet having water-solubility or water-swellability can be used without particular limitation. Specific materials that can be used for the support sheet (A) include polyvinyl alcohol resin (including saponified products), dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylic acid amide, and polyacrylic acid. Soda, polyvinyl methyl ether, copolymer of methyl vinyl ether and maleic anhydride, copolymer of vinyl acetate and itaconic acid, polyvinyl pyrrolidone, acetyl cellulose, acetyl butyl cellulose, carboxyl methyl cellulose, methyl cellulose, hydroxyl ethyl cellulose, sodium alginate, etc. Is mentioned. And a support body sheet | seat will be obtained if one type selected from these, or a 2 or more types of mixture is formed into a film.
Preferred as the support sheet (A) is saponified polyvinyl alcohol. The thickness of the support sheet (A) is preferably about 10 to 100 μm.

(2) Sealing layer (B)
The sealing layer (B) is an essential layer for the hydraulic transfer sheet (E) of the present invention, and is provided between the support sheet (A) and the image receiving layer (C). In addition, it has a function of preventing the support sheet (A) from being water-soluble or swollen by water as a main solvent at the time of forming an image-receiving layer (C) made of an aqueous resin. When the sheet is floated on the surface of the water, it has an effect of preventing moisture from permeating from the support sheet (A) to the image receiving layer (C), and further, the transfer target (G) after the hydraulic transfer is performed. A surface layer is formed. Therefore, the resin layer forming the sealing layer (B) needs to be a resin having low moisture permeability and excellent appearance and weather resistance in order to exert the above-described action.
The method for forming the filler layer (B) on the support sheet (A) includes inkjet printing, intaglio printing method, planographic printing method, relief printing method, screen printing method, brush coating, spatula coating, and spray coating. Etc. Among these, inkjet printing is preferable. The sealing layer (B) is a solution obtained by dissolving a resin having low moisture permeability in an organic solvent (sealing layer forming coating solution), and is applied on the support sheet (A) to a desired thickness and then dried. It is formed.
1-10 micrometers is preferable and, as for the film thickness after drying of a sealing layer (B), 1-2 micrometers is more preferable.

When transferring the hydraulic pressure transfer sheet (E) while floating on the water surface, it is necessary that the sealing layer (B) has a physical property that appropriately extends following the extension of the support sheet (A). In order to impart appropriate stretchability and followability to the sealing layer (B) in this case, it is preferable to form the sealing layer (B) with an appropriate thickness as described above.
Therefore, as the resin used for forming the sealing layer (B), the water permeability is low, the adhesiveness with the image receiving layer (C) is good, and the surface layer is formed after the water pressure transfer. It is required to have excellent properties, appearance, wear resistance, weather resistance and the like. In addition, since a support body sheet | seat (A) is melt | dissolved in water or removed by water washing after water pressure transfer, the high adhesiveness between a sealing layer (B) and a support body sheet | seat (A) is not required.

From the above-mentioned purpose and effect required for the sealing layer (B), the sealing layer (B) is an acrylic resin, a urethane resin, an epoxy resin, an alkyd resin (including a modified resin) described below, It is preferably formed from one or more resins selected from nitrified cotton, vinyl chloride resin, vinyl acetate resin, and polyvinyl butyral.
(I) Acrylic resin Examples of the acrylic resin include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer. And acrylic resins such as (meth) methyl acrylate-styrene copolymer. Here, (meth) acryl means acryl or methacryl.

(Ii) Urethane resin Examples of the urethane resin include a two-component curable urethane resin, a one-component curable (moisture curable) urethane resin, and a thermoplastic urethane resin. The two-component curable urethane resin is a urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent). As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like are used. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanate such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4′-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. And aliphatic (or alicyclic) isocyanates. Further, adducts or multimers of the above various isocyanates can also be used. For example, adducts of tolylene diisocyanate, tolylene diisocyanate trimers and the like can be mentioned. In addition, since aliphatic (or alicyclic) isocyanate such as hexamethylene diisocyanate is excellent in weather resistance and heat-resistant yellowing, it can be suitably used.

  The one-component curable urethane resin is a composition containing a prepolymer having an isocyanate group at the molecular end as an essential component. The prepolymer is usually a prepolymer having at least one isocyanate group at both molecular ends, specifically, a polyisocyanate prepolymer having a polycarbonate skeleton, a polyurethane skeleton, a polybutadiene skeleton, a polyester skeleton, or the like as a skeleton. is there. When such a one-component curable urethane resin is used, isocyanate groups react with each other by moisture in the air to cause a chain extension reaction, resulting in a reaction product having a urea bond in the molecular chain. Then, an isocyanate group at the molecular end further reacts with the urea bond to cause a biuret bond to branch and crosslink, thereby forming a sealing layer (B).

(Iii) Epoxy resin Examples of the epoxy resin include a vinyl-modified epoxy ester resin obtained by graft polymerization of a carboxyl group-containing vinyl monomer to a so-called epoxy ester obtained by reacting an epoxy resin with a fatty acid, and neutralizing water dispersion.
(Iv) Alkyd Resin The alkyd resin is a resin obtained by a condensation reaction of a polyhydric alcohol and a polybasic acid. In the present invention, the alkyd resin includes a modified alkyd resin such as an amino alkyd resin. The amino alkyd resin is a resin in which an amino resin and an alkyd resin are blended. An amino resin is a resin obtained by reacting formaldehyde with the amino group of an amino group-containing compound such as urea, melamine, graanamin, aniline, sulfoamide, or an amino group-containing acrylic resin. In the case of urea, urea resin, melamine Is called melamine resin, guanamine is called guanamine resin, and aniline is called aniline resin. The alkyd resin is typically, for example, an ester of a dibasic acid such as phthalic anhydride and a polyhydric alcohol such as glycerin or pentaerythritol, which is further modified with various oils or fatty acids such as castor oil. However, there are also rosin-modified alkyd resins modified with rosin or phenol, modified alkyd resins such as phenol-modified alkyd resins, and the like.
Of the above-mentioned resins, it is preferable to contain an alkyd resin and nitrified cotton.

(Iv) Solvent The solvent used in the sealing layer-forming coating solution is not particularly limited. For example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, A water-insoluble organic solvent such as ethylene glycol monoethyl ether or a mixture of two or more thereof is preferably used.

(3) Image receiving layer (C)
The image receiving layer (C) comprises at least an aqueous resin layer (S). In the present invention, the image receiving layer (C) is a layer composed of the aqueous resin layer (S). When the pattern layer (D) is formed by inkjet, the pattern layer (D) is placed thereon. This is because the image receiving layer (C) is preferably an aqueous resin layer which is a layer mainly composed of an aqueous resin (S) which prevents ink bleeding and has good ink absorbability.
Since the aqueous resin (S) constituting the aqueous resin layer is classified into a water-soluble resin (S1) and a water-dispersible resin (S2), the aqueous resin layer is composed of a water-soluble resin (S1) and a water-dispersible resin (S2). It is preferable that S2), or water-soluble resin (S1) and water-dispersible resin (S2) are the main components.
The aqueous resin layer can be formed only from the aqueous resin (S), but an aqueous resin composition (hereinafter, referred to as an aqueous resin composition) containing other additives that will be practically described later. .).
The aqueous resin (S) is roughly classified into a water-soluble resin (S1) having a property of being dissolved in water, the main solvent being water, and a water-dispersible resin (S2) being a resin having a property of being dispersed in water. The The water-dispersible resin (S2) usually uses an emulsifier to disperse the resin in water, and has a hydrophilic group in the molecule.

The image-receiving layer (C) is a sealing layer (B) as a solution in which the aqueous resin (S) (or further containing an additive) is dissolved or dispersed in water (hereinafter sometimes referred to as an image-receiving layer-forming coating solution). ) It is formed by applying a desired thickness and then drying.
The image-receiving layer (C) is not sticky when formed by coating and drying on the sealing layer (B) and is required to have an appropriate drying property. Further, after drying, it is necessary to be transparent and have good penetration of the pigment in the pattern layer and to have excellent adhesion to the transfer target (G). Furthermore, when the hydraulic transfer sheet (E) is suspended on the surface of the water, the image receiving layer (C) and the image receiving layer (C) have a physical property that moderately follows the extension of the support sheet (A). Is needed. In order to impart appropriate extensibility and followability to the image receiving layer (C) in this case, it is preferable to form the image receiving layer (C) with an appropriate thickness as described later.
Below, water-soluble resin (S1) and water-dispersible resin (S2) are demonstrated.

(I) Water-soluble resin (S1)
The water-soluble resin (S1) that can be used in the present invention is not particularly limited in structure and production method. Specific examples include polyvinyl alcohol (PVA), polyvinyl pyrrolidone, polyvinyl acetal, methyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose and other cellulose derivatives, polyethyleneimine, polyamide, various quaternary ammoniums. Examples include base-containing water-soluble resins, starch, and derivatives thereof.
The water-soluble resin (S1) is about 10,000 to 2,000,000 in terms of physical properties required for the receiving layer (C), for example, the strength of the film and the viscosity of the image-receiving layer forming coating solution suitable for coating. Is preferred.

Among the water-soluble resins (S1), PVA and its derivatives are preferable because they have characteristics such as transparency, film strength, and excellent pigment absorbability, and have a wide range of applicable applications. PVA is generally obtained by saponification of a vinyl acetate polymer.
As the PVA used in the aqueous resin composition of the present invention, those having appropriate saponification degree and polymerization degree can be appropriately used according to the required physical properties of the aqueous resin composition. Commercially available PVA includes PVA having various saponification ratios (saponification degrees) and polymerization degrees, and these can be used. For example, when the aqueous resin composition is applied to a barrier coat, the saponification degree is preferably 90% or more and the polymerization degree is preferably 500 or more from the viewpoint of barrier properties against water, various solvents and gases.

Moreover, modified PVA into which various modifying groups are introduced can be used as the PVA derivative. Examples of such a modifying group include an acetoacetyl group, a silyl group, a quaternary ammonium base, a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid group, a ketone group, a mercapto group, and an amino group. Any of these can be used depending on the required physical properties. The water-soluble resin (S1) used in the present invention can be used alone or in combination of two or more.

(Ii) Water dispersible resin (S2)
The water-dispersible resin (S2) of the present invention refers to a resin that cannot take a form in which the resin is completely dissolved in water but can take a form dispersed in water. The water dispersible resin (S2) is not particularly limited in its structure and production method. Specific examples of the water-dispersible resin (S2) include urethane resins; synthetic rubbers such as styrene-butadiene and acrylonitrile-butadiene; emulsions such as acrylic resins and vinyl acetate resins. In general, the water-dispersible resin (S2) can be easily solidified more easily than the water-soluble resin (S1). Therefore, when both are used in combination, the solid content of the image-receiving layer-forming coating solution can be increased. The amount of water that is can be reduced. For this reason, there are effects such as improvement in processability of the image-receiving layer-forming coating solution, for example, shortening of the drying time after coating, and ease of adjusting the coating thickness. Further, the water-dispersible resin (S2) can improve physical properties that are insufficient with the water-soluble resin (S1) alone.

  The water-dispersible resin (S2) is roughly classified into one type selected from an emulsifier-containing type in which the resin is dispersed in water using an emulsifier, and an anionic group, a cationic group, a nonionic group, and an amphoteric group described later in the resin. There is a self-dispersing type in which the above hydrophilic group is introduced and the resin is dispersed in water by the action of the hydrophilic group. Of these, the self-dispersing type is preferred from the viewpoint of good water resistance of the product obtained.

Examples of the anionic group include an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group; and an acid such as a carboxylic acid group, a sulfonic acid group, and a phosphate group obtained by neutralizing these acid groups. Mention may be made of neutralized salts of groups. Of these, neutralized salts of acid groups are preferred because the stability of the water-dispersible resin becomes better. Examples of neutralizing agents for these acid groups include non-volatile bases such as sodium hydroxide and potassium hydroxide, and tertiary amines such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, and triethanolamine; volatilization of ammonia and the like Can be mentioned.
Examples of the cationic group include a tertiary amino group, a tertiary amine salt obtained by neutralizing the tertiary amino group, and a quaternary ammonium base. Among these, a tertiary amine salt and a quaternary ammonium base are preferable because the stability of the water-dispersible resin becomes better. Examples of the tertiary amino group neutralizing agent include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and lactic acid.
Examples of the nonionic group include a group composed of ethylene oxide repeating units, a group composed of ethylene oxide repeating units and other alkylene oxide repeating units. Examples of amphoteric groups include betaine groups. The molecular weight of the water-dispersible resin (S2) is preferably 10,000 or more on a weight average from the viewpoint of the durability of the image-receiving layer-forming coating solution of the present invention. Various water-dispersible resins (S2) can be used according to the required physical properties of the image-receiving layer-forming coating solution of the present invention, but importance is attached to toughness, durability, water resistance, and adhesion to various substrates. In this case, it is preferable to use a urethane resin as the water dispersible resin (S2).

(Ii-1) Urethane resin Examples of the method for producing an aqueous dispersion of a urethane resin include the following methods (a) to (c).
(A) Neutralizing, if necessary, an organic solvent solution or an organic solvent dispersion of a urethane resin having a hydrophilic group obtained by reacting an active hydrogen-containing compound, a compound having a hydrophilic group, and a polyisocyanate. A method for obtaining an aqueous dispersion by mixing an aqueous solution containing an agent.
(B) Whether the active hydrogen-containing compound, the compound having a hydrophilic group, and the terminal isocyanate group-containing urethane prepolymer having a hydrophilic group obtained by reacting the polyisocyanate are mixed with an aqueous solution containing a neutralizing agent. Alternatively, a method of obtaining a water dispersion by adding a neutralizing agent to a prepolymer in advance, mixing water and dispersing in water, and then reacting with polyamine.
(C) Mixing an active hydrogen-containing compound, a compound having a hydrophilic group, and a terminal isocyanate group-containing urethane prepolymer having a hydrophilic group obtained by reacting a polyisocyanate with an aqueous solution containing a neutralizing agent and a polyamine. Or a method in which a neutralizing agent is added to the prepolymer in advance, and then an aqueous solution containing a polyamine is added and mixed to obtain an aqueous dispersion.

  Examples of the polyisocyanate used in the production of the urethane resin include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phphenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2 , 4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'- Dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate Nate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, and the like. Of these polyisocyanates, aliphatic diisocyanates or alicyclic diisocyanates are preferred from the viewpoint of light resistance. Further, a polyisocyanate having a valence of 3 or more can be used in combination as long as the effects of the present invention are not impaired.

  In the urethane resin, the weight ratio of components other than the polyisocyanate to the polyisocyanate is preferably 50% by weight or less, and within such a range, the stability as a self-dispersing urethane resin is excellent. The active hydrogen-containing compound has a weight average molecular weight of preferably 300 to 10,000, more preferably 500 to 5,000, and a low molecular weight compound having a molecular weight of 300 or less. Divided into types. Examples of the high molecular weight compound include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols, polythioether polyols, polybutadiene-based polyolefin polyols, and the like. Two or more of these high molecular weight compounds can be used in combination. Known polyester polyols can be used.

  In the above methods (a) to (c), an emulsifier can be further used as long as the effects of the present invention are not impaired. Examples of such emulsifiers include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene sorbitol tetraoleate; fatty acid salts such as sodium oleate, alkyl Anionic emulsifiers such as sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates; polyoxyethylene alkyl sulfates, polyoxyethylene alkylphenyl sulfates Nonionic anionic emulsifiers such as

In order to improve the stability of the emulsion, a urethane emulsion having a pH of 7.0 or higher, more preferably 7.5 to 9.0 is preferable.
In carrying out the present invention, a commercially available aqueous dispersion of a self-dispersing urethane resin can be used. Examples of such commercially available products include those manufactured by Dainippon Ink and Chemicals, Inc., trade names: “PARACOAL RSI-001”, “Bondic”, and “Hydran”, manufactured by Bayer, Inc. Can be mentioned. The average particle size of the aqueous dispersion of the self-dispersing urethane resin used in the present invention is preferably 3.0 μm or less from the viewpoint of the stability of the urethane resin particles and the water resistance and gloss of the ink jet receiving layer.

(Ii-2) Synthetic rubber latex Synthetic rubber can be used as the water-dispersible resin (S2). The synthetic rubber aqueous dispersion (synthetic rubber latex) can be produced, for example, by emulsion polymerization of an aliphatic conjugated diene monomer and another copolymerizable monomer. Examples of the aliphatic conjugated diene monomer used here include 1,2-butadiene, 1,3-butadiene, isoprene, chloroprene and the like.
Examples of other polymerizable monomers that can be copolymerized include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) arylate, and (meth) acrylic. (Meth) acrylic acid ester monomers such as hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, octadecyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid and anhydrous , Α-methyl, unsaturated bond-containing monomer having a carboxyl group, such as carboxylic acid, fumaric acid, itaconic acid, unsaturated dicarboxylic acid monoalkyl ester (eg, monomethyl maleate, monoethyl fumarate, mononormal butyl itaconate) Ethylenic unsaturation such as styrene, vinyltoluene, chlorostyrene, 2,4-dibromostyrene Aromatic monomers; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; vinylidene halides such as vinylidene chloride and vinylidene bromide; 2-hydroxyethyl (meth) acrylate; Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids such as (meth) acrylic acid-2-hydroxypropyl; glycidyl esters of ethylenically unsaturated carboxylic acids such as (meth) acrylic acid glycidyl; (meth) acrylamide, N-methylol (meth) Examples include acrylamide, butoxymethyl (meth) acrylamide, and diacetone acrylimide.

The synthetic rubber latex that can be used as the water-dispersible resin (S2) can be obtained by emulsion polymerization of the above monomer in an aqueous medium in the presence of an emulsifier, a free radical generating catalyst, and the like. In this case, a two-stage polymerization method can also be employed. As an emulsifier, various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used.
Examples of the anionic surfactant include sulfates of higher alcohols, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, etc., and examples of nonionic surfactants include polyoxyethylene alkyls. Examples include ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, and the like. Examples of the cationic surfactant include alkyl ammonium chloride (Arcard 12-50 manufactured by Lion Corporation). Furthermore, examples of the amphoteric surfactant include polyoxyethylene alkyl sulfate, polyoxyethylene alkyl phenyl sulfate, and the like, and one or a mixture of two or more thereof can be used.

(Ii-3) Acrylic resin When the image-receiving layer (C) is required to have light resistance, it is preferable to use an acrylic resin as the water-dispersible resin (S2). A method for producing an aqueous dispersion of an acrylic resin (hereinafter sometimes referred to as an acrylic resin emulsion) includes a (meth) acrylic acid ester monomer in the presence of a polymerization initiator, if necessary, an emulsifier and a dispersion stabilizer. Can be obtained by copolymerizing a mixture of other polymerizable monomers copolymerizable with these monomers as necessary.

  Examples of the polymerizable monomer that can be used in the production of the acrylic resin emulsion include the following. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) arylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, ( Octadecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylic acid ester monomers such as (meth) acrylic acid dicyclopentanyl, phenyl (meth) acrylate, benzyl (meth) acrylate; acrylic acid, methacrylic acid, β-carboxyethyl (meth) acrylate , 2- (meth) acryloylpropionic acid, crotonic acid, itako Unsaturated bond-containing monomers having a carboxyl group such as acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride; glycidyl (meth) acrylate, allyl glycidyl ether, etc. Glycidyl group-containing polymerizable monomers; hydroxyl group-containing polymerizable monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and glycerol mono (meth) acrylate Ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate Rate, polypropylene glycol di (meth) acrylate, diallyl phthalate, divinylbenzene, allyl (meth) acrylate, and the like.

  As the emulsifier used in the production of the acrylic resin emulsion, the above emulsifiers can be used. In addition, the aqueous medium for producing the acrylic resin emulsion is not particularly limited, but only water may be used, or a mixed solvent of water and a water-soluble solvent may be used. . Examples of the water-soluble solvent used here include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone. A mixture of two or more can be used.

A known radical polymerization initiator is used as the polymerization initiator used when producing the acrylic resin emulsion. Moreover, when it is necessary to adjust the molecular weight of the polymer of an acrylic resin emulsion, you may add the compound which has chain transfer ability as a molecular weight modifier. Examples of such molecular weight regulators include mercaptans such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, thioglycerin, or α-methylstyrene dimer. Is mentioned.
In addition, the polymerization temperature when producing the acrylic resin emulsion varies depending on the type of monomer used, the type of polymerization initiator, etc., but when polymerizing in an aqueous medium, it is usually performed in the range of 30 to 90 ° C. Is preferred.
The water-dispersible resin (S2) used in the present invention may be used alone or in combination of two or more, and can be appropriately selected and used according to the required physical properties.
Of the resins described above, a urethane emulsion is preferable, a urethane emulsion having a pH of 7.0 or higher is more preferable, and a urethane emulsion having a pH of 7.5 to 9.0 is most preferable.

(Iii) Image-receiving layer-forming coating solution In the image-receiving layer-forming coating solution of the present invention, either or both of the water-soluble resin (S1) and the water-dispersible resin (S2) contain a quaternary ammonium base. It is preferable that Quaternary ammonium bases are cationic, so they are electrostatically bonded to the colorant of inkjet inks, that is, anionic groups in dyes and pigments, improving the water resistance of printed images and preventing bleeding. can do. Examples of the water-soluble resin containing a quaternary ammonium base include epichlorohydrin polyamide resin, amine epichlorohydrin resin, polyethyleneimine salt-containing resin, polyvinylamine salt-containing resin, polyvinylamidine resin, and polyallylamine salt-containing resin.

The water-dispersible resin (S2) containing a quaternary ammonium base has an acrylic resin as its main skeleton; a synthetic rubber such as styrene-butadiene or acrylonitrile-butadiene; a skeleton such as urethane resin or vinyl acetate resin. What has it is mentioned.
As the production method, for example, a method of copolymerizing a monomer or polyol having a quaternary ammonium base, a monomer or polyol having a tertiary amino group is copolymerized, and then the tertiary amino group portion is alkyl halide, Examples thereof include a method of quaternary ammonium chloride using a so-called quaternizing agent such as dialkyl sulfuric acid and alkyl p-toluenesulfonate.

In the image-receiving layer-forming coating solution of the present invention, it is preferable to use PVA and / or a derivative thereof as the water-soluble resin (S1) because the ink-jet ink has good absorbability. As the saponification degree and polymerization degree of PVA, those having a saponification degree of 75 to 99% and a polymerization degree of 300 to 5000 are preferable from the viewpoint of absorbability of the inkjet ink. More preferably, the saponification degree is 80 to 95% and the polymerization degree is 500 to 3500. Further, it is preferable that the water-soluble resin (S1) is a PVA having an acetoacetyl group, since the water resistance is particularly good and the printability of pigment ink is good.
In the image-receiving layer-forming coating solution of the present invention, when a self-dispersing urethane resin is used as the water-dispersible resin (S2), the color density of the printed image is improved, the pigment ink printability is imparted, and the adhesion to the substrate is improved. It is preferable from the point of having the effect of.

  Further, the image-receiving layer-forming coating solution of the present invention can further contain other additives as long as the effects of the present invention are not impaired. Examples of additives include nonionic, cationic, anionic and amphoteric surfactants, pigment dispersants, silicone, fluorine and acetylenic diol leveling agents, ultraviolet absorbers, and oxidation agents. Examples thereof include an inhibitor and an antistatic agent. The amount of these additives to be used is not particularly limited as long as the effects of the present invention are not impaired. Usually, the range of 0.01 to 5% by weight in terms of solid content in the image-receiving layer-forming coating solution is preferable. In addition, a water-soluble metal salt such as magnesium chloride, calcium chloride, or aluminum chloride may be added to the image-receiving layer-forming coating solution of the present invention in order to further improve the pigment ink printability. The addition amount of these water-soluble metal salts is preferably in the range of 1 to 20% by weight in terms of solid content in the image-receiving layer forming coating solution.

Moreover, various porous pigments, such as a silica, clay, an alumina, a calcium carbonate, can also be added to the image receiving layer forming coating liquid of this invention. By adding such a porous pigment, an ink receiving layer may be provided with an appropriate whiteness and ink absorbency may be improved. The addition amount of the porous pigment is preferably in the range of 10 to 90% by weight in terms of solid content in the image-receiving layer forming coating solution.
For flame retardancy, organic flame retardants can be used, and these components include known chlorine, bromine, phosphorus, silicone, nitrogen, phosphorus and halogen, phosphorus and nitrogen, etc. Preferably, chlorine-based, bromine-based, phosphorus-based and silicone-based organic flame retardants are used. These preferable blending amounts can be appropriately determined in consideration of ink transferability, image reproducibility, density of printed matter, and the like.

  A leveling agent, a slip agent and a dispersant can be added to the image receiving layer (C) of the present invention. Examples of leveling agents include metal soaps, polyamides, acrylics, vinyls, and silicones. Examples of slip agents include aluminum stearate, calcium stearate, silicone, polyethylene wax, and dispersants. Examples thereof include polymer dispersants such as polyester, acrylic, and urethane, and aluminum chelates. A preferable addition amount of these leveling agents and slip agents is an amount of 0.01 to 3.0% by mass in the receiving layer (C).

(Iv) Coating method and thickness after drying As the coating method of the image-receiving layer forming coating solution when forming the image-receiving layer (C), a gravure coater (such as a gravure direct coater or a gravure reverse roll coater), a reverse roll coater, Known methods such as a bar coater, a blade coater, an air knife coater, a spray coater, and a curtain coater can be used.
The coating amount of the image-receiving layer-forming coating solution on the filler layer (B) is not particularly limited, but is preferably about 1 to 10 g / m ^{2, and} is dried by evaporating the solvent by a known drying method after coating. To do.
The film thickness of the image receiving layer (C) after drying is preferably 1 to 40 μm. If the film thickness of the image receiving layer (C) exceeds 40 μm, it may be difficult to control the extension of the support sheet to about 1.1 to 1.5 times.

(4) Pattern layer (D)
The means for forming the pattern layer (D) on the surface of the image receiving layer (C) is not particularly limited, but ink jet printing, intaglio printing method, planographic printing method, relief printing method, screen printing method, brush coating, spatula coating, spray coating Etc. to form a picture layer (D). Among these, inkjet printing is particularly preferable.
In particular, in the case of ink-jet printing, when printing a small lot, it is extremely effective to form a printed pattern layer by on-demand printing that is widely used in commercial printing or the like. This on-demand printing is not a method using electrostatic printing (copying), but is performed using inkjet printing. As an apparatus used for ink jet printing, an ink jet printer, an electronic computer for controlling the printing machine and receiving image information processing, a scanner device for reading a document image and performing AD conversion, a storage device for storing image information, an image display device, etc. Consists of Using these devices, the image data is taken in, the customer's request is taken into the image, and the image is displayed on an image display device such as a CRT to adjust the color tone on the desktop, image correction (removal of unnecessary portions, etc.) ), Combination with other image data, image breeding, endless image processing, and the like are performed, and this is ink-jet printed on the surface of the image receiving layer (C) to form the pattern layer (D).

The pattern of the pattern layer formed by inkjet printing is not particularly limited, and may be formed in an arbitrary shape such as a grain pattern, a stone pattern, a cloth pattern, a character, a figure, a symbol, or a pattern. The pattern layer (D) may be formed entirely on the surface of the image receiving layer (C) or may be partially formed. The thickness of the pattern layer (D) is usually about 1 to 10 μm.
Inkjet printing is a method of printing by ejecting ink in the form of particles (droplets) from a thin nozzle. Depending on the type of ink ejection method and ink particle control method, charge control type, Hertz type, electric field There are methods such as a control type and a pressure control type (on-demand type).

Hereinafter, a pigment in which an inorganic pigment and / or an organic pigment are dispersed in a non-aqueous vehicle (fixing resin), which is a component of inkjet ink mainly used in inkjet printing, and a solvent used in the pigment will be described.
As the inkjet ink, a pigment type non-aqueous inkjet ink in which inorganic and / or organic pigments are dispersed in a non-aqueous vehicle that can withstand outdoor use performance can be used, and a pigment type containing a glycol ether as a main solvent. Inkjet inks are preferred. Examples of the glycol ethers include di- or triethylene glycol monobutyl ether, propylene glycol monobutyl ether, monoethyl ether, monopropyl ether or monomethyl ether, dipropylene glycol monobutyl ether, and diethylene glycol monohexyl ether. Examples include ethers, esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and mixtures thereof. In addition, as the inkjet ink, a water-based inkjet ink using a known dye type can also be used.

As the non-aqueous ink vehicle (resins), any known inkjet ink vehicle that can be mixed and dispersed in an ink medium containing the glycol ethers can be used. Examples of the vehicle (resin) include acrylic resins, styrene-acrylic copolymers, rosin-modified phenolic resins, terpene resins, polyamide resins, epoxy resins, polyester resins, vinyl chloride-vinyl acetate copolymers, and fiber-based resins. Etc. These resins include known plasticizers, dispersants, waxes, surfactants, antistatic agents, viscosity modifiers, antifoaming agents, antioxidants, ultraviolet absorbers, light stabilizers and the like as necessary. Additives can be added.

  Examples of the pigment used in the inkjet ink include inorganic pigments such as carbon black, titanium oxide, ultramarine blue, bitumen, iron oxide, zinc white, and petal, insoluble azo pigments such as arylide and pyrazolone, and copper phthalocyanine blue. And organic pigments such as quinacridone, thioindigo, industrone, anthraquinone, perylene, and quinophthalone. The recording material of the present invention can also be applied to dye-type inkjet inks other than the above-mentioned pigments, depending on the intended use. Examples of the dye include azo dyes, quinoline dyes, indigo dyes, naphthoquinone dyes, nitro dyes, and metal complex dyes.

When the pigment-type non-aqueous inkjet ink is used for forming the pattern layer (D) of the present invention as described above, the weather resistance, print density and image reproducibility are excellent.
As ink used for inkjet printing, water-based (aqueous solution or water-dispersed emulsion) ink can also be used from the viewpoint of preventing nozzle clogging, fire prevention (explosion-proof) for organic solvents, and avoiding complicated hygiene management. . One preferred form is that it is water-based during printing and water-insoluble and non-water-swellable after printing. As a specific example of such a form, a water-based ink is formed from a polyol and a blocked isocyanate, and ink-jet printing is performed to form a picture layer (D). After printing (before floating on the water surface), the picture layer (D) Is heated to release the block, and the polyol and isocyanate are cross-linked to make the pattern layer (D) water-insoluble and water-swellable.
The printing conditions for forming the pattern layer (D) are not particularly limited, and printing can be performed at a normal printing speed and resolution, for example, at a resolution of 720 dpi using an ordinary inkjet printer.

(5) Hydraulic transfer sheet (E)
Since the image receiving layer (C) in the hydraulic transfer sheet (E) of the first aspect is composed of an aqueous resin layer, ink jet printing using aqueous ink is possible and obtained when the pattern layer (D) is formed. The image can be easily made full color and has excellent print quality. Further, since the sealing layer (B) having a low water permeability is provided between the support sheet (A) and the image receiving layer (C), the moisture content from the support sheet (A) to the image receiving layer (C) is reduced. As a result of the suppression of the transmission, no white-brown blur occurs in the pattern layer (D), which is excellent as a hydraulic transfer sheet.

[2] “Hydraulic transfer method” according to the second aspect The “hydraulic transfer method” according to the second aspect of the present invention is a method of carrying out transparent sealing on at least a water-soluble or water-swellable support sheet (A). Forming a hydraulic transfer sheet (E) obtained by forming a layer (B) and an image receiving layer (C), printing a pattern layer (D) on the surface of the image receiving layer (C), and then drying (hydraulic transfer) Sheet forming process),
Next, after applying the activator to the surface of the pattern layer (D), the hydraulic transfer sheet (E) is suspended on the water surface so that the pattern layer (D) becomes the upper surface, and the hydraulic transfer sheet (E) is The substrate (F) to be transferred is pressed against the surface of the pattern layer (D) while being stretched, and the pattern layer (D) surface of the hydraulic transfer sheet (E) is brought into close contact with the required transfer portion of the substrate to be transferred (F) by water pressure. Removing the support sheet (A) from the sheet portion for hydraulic transfer after drying by washing or dissolving with water to obtain a transfer target (G) (hydraulic transfer process)
A hydraulic transfer method comprising:
The image receiving layer (C) is composed of an aqueous resin layer, and the sealing layer (B) is composed of a resin layer having low moisture permeability.
It is characterized by that.

The support sheet (A), sealing layer (B), image receiving layer (C), and pattern layer (D) used in the second mode are basically the same as those described in the first mode. It is.
The “water pressure transfer sheet forming process” and the “water pressure transfer process” will be described below.
(1) Hydrostatic transfer sheet forming process The "hydraulic transfer sheet forming process" is a transparent transparent sealing layer (B) and image receiving layer (C) on a water-soluble or water-swellable support sheet (A). And a hydraulic transfer sheet (E) obtained by drying after printing the pattern layer (D) on the surface of the image receiving layer (C). In the following description of the “hydraulic transfer sheet forming method”, the description of the same parts as described in the “hydraulic transfer sheet” section of the first aspect may be omitted.

(I) Formation of sealing layer (B) and image receiving layer (C) on support sheet (A) About supporting sheet (A), sealing layer (B) and image receiving layer (C) on This is the same as described in the “hydraulic transfer sheet” in the first embodiment. In addition, the sealing layer forming coating solution, the image receiving layer forming coating solution, and the coating method used for forming the sealing layer (B) and the image receiving layer (C), respectively, are also referred to as “for hydraulic transfer”. This is the same as described in “Sheet”.

(Ii) Formation of the image layer (D) on the image receiving layer (C) surface The means for forming the image layer (D) on the image receiving layer (C) surface is not particularly limited, but inkjet printing, intaglio printing method, lithographic printing method The pattern layer is formed by letterpress printing, screen printing, brush coating, spatula coating, spray coating, or the like. Among these, inkjet printing is particularly preferable.
In particular, in the case of ink-jet printing, when printing a small lot, it is extremely effective to form a printed pattern layer by on-demand printing that is widely used in commercial printing or the like. This on-demand printing is not performed by applying electrostatic printing (copying), but is performed using ink jet printing. As an apparatus used for ink jet printing, an ink jet printer, an electronic computer for controlling the printing machine and receiving image information processing, a scanner device for reading a document image and performing AD conversion, a storage device for storing image information, an image display device, etc. Consists of Using these devices, the image data is taken in, the customer's request is taken into the image, and the image is displayed on an image display device such as a CRT to adjust the color tone on the desktop, image correction (removal of unnecessary portions, etc.) ), Combination with other image data, image breeding, endless image processing, and the like are performed, and this is ink-jet printed on the surface of the image receiving layer (C) to form the pattern layer (D).

The pattern of the pattern layer formed by inkjet printing is not particularly limited, and may be formed in an arbitrary shape such as a grain pattern, a stone pattern, a cloth pattern, a character, a figure, a symbol, or a pattern. The pattern layer (D) may be formed entirely on the surface of the image receiving layer (C) or may be partially formed. The thickness of the pattern layer (D) is usually about 1 to 10 μm.
The ink generally used for ink jet printing is the same as that described in the “hydraulic transfer sheet” of the first embodiment.

(2) Water pressure transfer process In the “water pressure transfer process”, after applying the activator to the surface of the pattern layer (D), the sheet for water pressure transfer is floated on the surface of the water so that the pattern layer (D) becomes the upper surface. The hydraulic transfer sheet is extended and the substrate to be transferred (F) is pressed against the surface of the pattern layer (D), and the hydraulic layer is applied to the transfer portion of the substrate to be transferred (F) by the hydraulic pressure. Are adhered, and after drying, the support sheet (A) is removed from the hydraulic transfer sheet portion by washing or dissolving with water to obtain a transferred object (G).
(A) Transfer target substrate (F)
In the method of the present invention, various products can be used as the substrate to be transferred (F). For example, resin moldings such as ABS resin, polystyrene, polyolefin resin, polyvinyl chloride and phenol resin, metal moldings such as iron, aluminum and copper, wood moldings, glass, ceramics, and other various inorganic moldings Those formed in a three-dimensional shape can be optimally used.
In addition, the transfer surface of the transfer substrate (F) is subjected to an easy-adhesion treatment for improving the adhesion with the pattern layer (D) or the image receiving layer (C) of the hydraulic transfer sheet (E). I can leave. The easy adhesion treatment includes formation of an easy adhesion layer or corona discharge treatment. For example, when the transfer target is a (G) polystyrene resin molded body, the easy adhesion layer is formed by applying a coating composition using a urethane or acrylic resin.

(B) Hydraulic transfer step (i) Application of activator When the pattern layer (D) of the hydraulic transfer sheet (E) is activated, a part of the pattern layer (D) dissolves or swells, An adhesive force is imparted so as to easily adhere to the transfer target (G). As such an activator, what contains the solvent which can melt | dissolve or swell the binder component of a pattern layer (D) is used. The solvent used as the activator can be appropriately selected from those exemplified as the solvent for the image receiving layer (C) according to the binder component of the picture layer (D).
The activator may be composed of only the above solvent, but the process of transferring the pattern layer (D) of the hydraulic transfer sheet (E) to the transfer surface of the transfer substrate (F) is completed on the water surface. It is preferable that the material does not evaporate until the surface of the substrate (F) to be transferred does not erode. As such an activator, a swollen liquid obtained by adding the following resin to about 5 to 60% by mass of the solvent in the solvent for activating the above-described pattern layer (D) is used. it can. The swelling liquid has the advantage that the viscosity of the active agent can be easily adjusted, the application means of the coating liquid can be widely used, and stable adhesiveness can be obtained even when the transfer process takes time. There is.

  Examples of the resin added to the swelling liquid include vinyl halide polymers such as polyvinyl chloride and polyvinylidene chloride; polymers obtained from polystyrene and styrene derivatives; vinyl ester polymers such as polyvinyl acetate; Polymers obtained from ester derivatives of unsaturated carboxylic acids such as acrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid; nitrile derivatives such as unsaturated carboxylic acids; heavy polymers obtained from acid amide derivatives such as the acids N-methylol derivative of the acid amide derivative of the unsaturated carboxylic acid and the N-alkylmethylol ether derivative; glycidyl (meth) acrylate, acrylic glycidyl ether, vinyl isocyanate, allyl isocyanate, 2-hydroxyethyl- (meth) acrylate 2-hydroxypropyl- (meth) a Relates, thermoplastic resins such as ethylene, ethylene glycol-mono (meth) acrylate monomers or copolymers; initial condensates, natural resins, rosin and derivatives thereof, cellulose derivatives, natural or synthetic rubbers, Examples thereof include resins such as petroleum resins. Incidentally, (meth) acrylate means acrylate or methacrylate.

As a coating means on the pattern layer (D) of the activator, gravure offset coat, gravure coat, roll coat, bar coat, spray coat, ultrasonic coat, etc. can be used. preferably 1 to 30 g / m ^2, and more preferably about 1 to 10 g / m ^2. As a method for applying the activator to the decorative layer surface side of the hydraulic transfer sheet, there are typically the following two methods, and either can be selected.
(I-1) First, after the activator is applied to the decorative layer surface side of the hydraulic transfer sheet, the hydraulic transfer sheet is floated on the water surface with the support sheet side facing the water surface side (i-2) ) First, the hydraulic transfer sheet is floated on the water surface with the support sheet side facing the water surface side, and then the activator is applied to the decorative layer surface side of the hydraulic transfer sheet

(Ii) Water surface transfer of water pressure transfer sheet (E), water pressure transfer The means for floating the water pressure transfer sheet (E) on the water surface (W) can float one sheet of water pressure transfer sheet one by one, A continuous belt-shaped water pressure transfer sheet is continuously supplied and floated on the surface of water flowing from one direction.
When the hydraulic transfer sheet (E) is suspended on the water surface (W), the extension of the support sheet (A) is preferably controlled to be about 1.2 to 1.5 times. Such control means can be easily performed by physical means such as fixing the end of the support sheet (A).
In the water pressure transfer, the substrate for transfer (F) is pressed from above against the water pressure transfer sheet (E) on the water surface after the activator is applied, and the water pressure transfer sheet (E) is applied by water pressure. ) In close contact with the substrate to be transferred (F), and the pattern layer (D) in close contact with the surface to be transferred of the substrate to be transferred (F). FIG. 2 is an explanatory view conceptually showing this step. That is, in the hydraulic transfer, the transfer substrate (F) is lowered from the hydraulic transfer sheet (E) suspended on the water surface (W) with the transfer surface to be decorated facing down. Then, by pushing the substrate to be transferred (F) into the water, the hydraulic transfer sheet (E) is stretched and deformed along the shape of the surface to be transferred, and the transfer of the substrate to be transferred (F) by water pressure is performed. The hydraulic transfer sheet (E) is brought into close contact with the transfer surface.

When the hydraulic transfer sheet (E) floats on the water surface (W) and the support sheet (A) comes into contact with water, the support sheet swells if it is water-swellable, and is water-soluble. Is at least partially dissolved.
The water for transferring the hydraulic transfer sheet (E) by floating water pressure is the type of the support sheet (A) in the hydraulic transfer sheet (E) (for example, difference in water solubility or water swellability) It is desirable to adjust the water temperature accordingly. For example, when the support sheet (A) is a starch-based sheet, the water temperature is preferably 40 to 50 ° C. Moreover, you may add the additive which accelerates | stimulates removal of a support body sheet | seat (A), for example, in the case of a starch-type sheet | seat, it is preferable to add amylase etc.

(Iii) Dewatering with water washing After the above-mentioned hydraulic transfer, a film removal process is appropriately performed. In this film removal process, the support sheet (A) is pressed against the transfer surface of the transfer substrate (F) together with the image receiving layer (C) and the pattern layer (D) in the above-described hydraulic transfer process. When the substrate (F) is in close contact, the support sheet (A) is removed by dissolution or washing, and the image receiving layer (C) and the pattern layer (D) are left on the substrate (F) to be transferred. It is a process. Therefore, when the substrate to be transferred (F) is pushed into water and transferred by hydraulic pressure, the support sheet (A) is completely dissolved in water and only the image receiving layer (C) and the picture layer (D) are floated on the water surface. In this case, this film removal step may be unnecessary. In the film removal step, when at least a part of the support sheet (A) of the hydraulic transfer sheet (E) remains undissolved on the transfer substrate (F), the transfer substrate ( After the pattern layer (D) is sufficiently adhered to the transfer surface of F), the support sheet (A) is removed.
The support sheet (A) is removed by, for example, shower cleaning using water. The support sheet (A) adhering to the transfer surface is completely removed by the film removal step. In addition, although the conditions of shower washing differ with kinds etc. of a support body sheet | seat (A), the water temperature of 15-60 degreeC and the washing | cleaning time of 10 second-5 minutes are preferable normally. Then, after the film removal process or when the film removal process is omitted, after the water pressure transfer process or at the end of the water pressure transfer process, the transfer target (G) is sufficiently dried to evaporate the water. A transfer article provided with a desired design is obtained by the pattern layer (D) transferred to the transfer surface of the transfer body (G).

(3) Transfer object (G) having a hydraulically transferred pattern layer
The transferred body (G) having the hydraulically transferred pattern layer (D) obtained in this way has the pattern layer (D) in which the blur of the pattern layer (D) does not occur covered with the image receiving layer (C). There exists a sealing layer (B) that forms a surface layer on the top, and is excellent in scratch resistance. Further, since the pattern layer (D) has little extension, the color density of the printed pattern can be accurately reproduced.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. The raw materials and evaluation items used in this example are described below.
1. Raw Material (1) Support Sheet A polyvinyl alcohol resin having a thickness of 40 μm (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: trade name Hi-Selon C-300) was used as the support sheet.
(2) Sealing Layer Forming Coating Liquid As a method for forming the sealing layer, a printing pattern layer is formed by a gravure coating method using printing ink (trade name: KLCF, manufactured by The Inktec Co., Ltd.) as a coating liquid. Formed.
In this ink, 17% by mass of an inorganic pigment composed of calcium carbonate and silica and 4% by mass of a binder resin (a binder resin composed of cellulose acetate and an alkyd resin) have a solid content of 33.5% by mass. It is dissolved. As a solvent for the printing ink, a mixed solvent composed of isopropyl alcohol, toluene, and ethyl acetate is used.

(3) Image-receiving layer-forming coating solution An image-receiving layer-forming coating solution containing the following water-dispersible resin was used as the coating solution ink for forming the image-receiving layer.
It is a self-dispersing type in which a cationic group is introduced into the resin, and contains a urethane resin whose pH is maintained at 7.5 to 9.0 (trade name: Paracor RSI- manufactured by Dainippon Ink Co., Ltd.) 001) was used.
In addition, solid content concentration is 35 mass%, and a solvent is water / methanol (weight ratio): 1/1.
(4) Ink A water-based ink that can be used for inkjet printing, manufactured by Roland DG, Ecosol MAX ink, product number: MAX-ESL3 series was used.
(5) Activator As the activator, CPA-H (component: phthalic acid alkyd (resin), microsilica (pigment), DBP (additive), solvent) manufactured by Ohashi Chemical Co., Ltd.) was used.
(6) Substrate to be transferred An ABS molded body was used.

2. Evaluation Item (a) Evaluation of Formability of Image Receiving Layer An image receiving layer was formed on a support sheet by inkjet printing, and the following items were evaluated.
(I) Printability of image-receiving layer: Coating unevenness and transferability were evaluated. The evaluation criteria were as follows.
A: Coating unevenness and transferability are not observed at all.
○: Although coating unevenness and dispersibility were faintly observed by observation with a magnifying glass, it was at a level where there was no practical problem.
X: Coating unevenness and / or transferability is observed.
(Ii) Transparency of the image receiving layer: The presence or absence of cloudiness was evaluated. The evaluation criteria were as follows.
○: No cloudiness is observed.
X: A cloudiness feeling is observed.
(B) Evaluation of printability of pattern layer on image-receiving layer Inkjet printing was performed on the image-receiving layer, and gradation and printability of the pattern were evaluated as printability in the receiving layer.
(I) Gradation: Ink swim (unevenness) and transferability were evaluated. The evaluation criteria were as follows.
A: There is no ink swimming and there is no transferability.
○: Although ink swimming is slightly observed, the transferability is at a level that does not cause any practical problems.
X: The ink has swimming and has transferability.
(Ii) Printability of pattern: Evaluation was made on ink swimming and transferability. The evaluation criteria were as follows.
A: There is no ink swimming and there is no transferability.
○: Although there is some ink swimming, the transferability is at a level where there is no practical problem.
X: The ink has swimming and has transferability.
(Iii) Crack after image-receiving layer printing: One day after the hydraulic transfer, the presence or absence of cracking of the image-receiving layer was visually inspected. The evaluation criteria were as follows.
A: No cracks are observed.
○: Although very few cracks were observed, it was at a level causing no practical problems.
X: Cracks are observed.

(C) Evaluation of water pressure transferability (i) Wrinkle generation on the water surface: Evaluation of the presence or absence of wrinkle generation due to the extension of the receptor layer on the water surface (in Table 1, the evaluation item is described as "water surface") Did). The evaluation criteria were as follows.
A: Wrinkles were not observed in the receiving layer.
○: Slight wrinkles in the receptive layer were observed, but at a level causing no practical problems.
X: Wrinkles were observed in the receiving layer.
(Ii) Extensibility: The elongation of the image receiving layer and the extensibility of the support sheet were evaluated on the water surface. The evaluation criteria were as follows.
(Double-circle): A film stretches moderately on the water surface, and is fully extended to a base material.
○: The film stretches moderately on the water surface and is stretched on the substrate.
X: The film is not easily stretched on the surface of the water or excessively stretched, so that the film is not sufficiently stretched on the substrate.
(Iii) Rolling-around property: The rolling property of the receiving layer was evaluated on the support sheet. The evaluation criteria were as follows.
(Double-circle): A film adheres to a base material (adhesion) is enough.
A: The film is attached to the base material with little adhesion (adhesion), but at a level that does not cause any problems in practice.
X: A film is not attached to the substrate (adhesion) is insufficient.
(Iv) Occurrence of white-brown in the pattern layer: The occurrence of white-brown was observed after the transferred material obtained by drying after hydraulic transfer was left for 1 day.
A: White brown was not observed at all.
○: Slight browning was observed, but there was no practical problem.
X: White brown was clearly observed visually.

[Example 1]
(1) Manufacture of a hydraulic transfer sheet (i) Formation of a sealing layer and an image receiving layer on a support sheet A coating layer forming coating solution is applied onto the support sheet by a gravure coating method at a coating amount of 2 g / m. ^{2 was} applied and dried to form a printed pattern layer. Next, using an inkjet printing machine (Soljet SC-545EXW, manufactured by Roland DG), a coating solution for forming an image receiving layer containing a water-dispersible resin is applied on the filler layer at a coating amount of 4 g / m ^2. And dried to form an image receiving layer.
(Ii) Formation of pattern layer Using an ink jet printer (Roland DG, Soljet SC-545EXW) and the ink, printing was performed on the image receiving layer at a resolution of 720 dpi to prepare a hydraulic transfer sheet.
The obtained hydraulic transfer sheet was evaluated for (i) printability of the image-receiving layer, (ii) transparency of the image-receiving layer, and (iii) printability (gradation, person (or wood grain), crack after printing of the image-receiving layer). The results are shown in Table 1.

(2) Hydraulic transfer (i) Application of activator on printed pattern layer The above-mentioned activator is applied at 3 g / m ² on the printed pattern layer of the hydraulic transfer sheet obtained by the production of the hydraulic transfer sheet. Dried under.
(Ii) Water pressure transfer The water pressure transfer sheet obtained by applying the activator was floated on the water surface with the support sheet side of the transfer sheet facing the water surface at a water temperature of 30 ° C. for 1 minute. Thereafter, in a state where the support sheet was swollen, the substrate to be transferred was pushed in from above the hydraulic transfer sheet, and spread and adhered to the surface of the molded body. Subsequently, the substrate to be transferred, on which the hydraulic transfer sheet was spread and adhered to the surface, was drawn out of the water. Table 1 shows the average values of the extended hydraulic pressure transfer sheet in the vertical and horizontal directions after swelling.
(Iii) Removal and drying of support sheet After the transfer sheet is spread and adhered to the surface, the transfer substrate is showered with warm water at 40 ° C. for 30 minutes and then showered with clean water to transfer the polyvinyl alcohol of the transfer sheet. And a support sheet made of starch were removed, followed by drying to obtain a polystyrene resin molded body on which a printed pattern was formed.
In water pressure transfer, (i) transferability, (ii) throwing power, (iii) extensibility, and (iv) occurrence of white-brownness were evaluated.
The evaluation results are summarized in Table 1.

[Comparative Example 1]
A hydraulic transfer sheet was produced in the same manner as described in Example 1 except that the sealing layer was not formed, and hydraulic transfer was performed using the obtained hydraulic transfer sheet to obtain a transfer target.
The same evaluation as described in Example 1 was performed for these hydraulic transfer sheets and the transfer target. The evaluation results are summarized in Table 1.

It is a schematic sectional drawing of the sheet | seat for hydraulic transfer used for the hydraulic transfer method of this invention. It is a conceptual diagram which shows an example of the hydraulic transfer method of this invention.

Explanation of symbols

A Support sheet B Sealing layer C Image receiving layer D Picture layer E Hydraulic transfer sheet F Transfer target substrate

Claims (7)

  On one surface of the water-soluble or water-swellable support sheet (A), at least a transparent sealing layer (B), an image receiving layer (C), and a pattern layer (D) formed by printing means are arranged in this order. A water pressure transfer sheet (E) formed, wherein the image receiving layer (C) is composed of an aqueous resin layer, and the sealing layer (B) is composed of a resin layer having low moisture permeability. Transfer sheet.   The water-based resin layer contains the water-soluble resin (S1), the water-dispersible resin (S2), or the water-soluble resin (S1) and the water-dispersible resin (S2). Hydraulic transfer sheet.   The hydraulic transfer sheet according to claim 1 or 2, wherein the water dispersible resin (S2) is formed from a urethane emulsion having a pH of 7.0 or more.   The hydraulic transfer sheet according to any one of claims 1 to 3, wherein the water-dispersible resin (S2) is formed from a urethane emulsion having a pH of 7.5 to 9.0.   The said sealing layer (B) consists of 1 type, or 2 or more types of resin selected from an acrylic resin, a urethane resin, an epoxy resin, an alkyd resin, nitrified cotton, a vinyl chloride resin, a vinyl acetate resin, and polyvinyl butyral The hydraulic transfer sheet according to any one of claims 1 to 4, wherein: A transparent sealing layer (B) and an image receiving layer (C) are formed in this order on at least a water-soluble or water-swellable support sheet (A), and a pattern layer (D) is further formed on the surface of the image receiving layer (C). A step of forming a hydraulic transfer sheet (E) obtained by drying after printing (hydraulic transfer sheet forming step),
Next, after applying the activator to the surface of the pattern layer (D), the hydraulic transfer sheet (E) is suspended on the water surface so that the pattern layer (D) becomes the upper surface, and the hydraulic transfer sheet (E) is The substrate (F) to be transferred is pressed against the surface of the pattern layer (D) while being stretched, and the pattern layer (D) surface of the hydraulic transfer sheet (E) is brought into close contact with the required transfer portion of the substrate to be transferred (F) by water pressure. And then removing the support sheet (A) from the hydraulic transfer sheet portion by washing or dissolving with water to obtain a transfer target (G) (hydraulic transfer process)
A hydraulic transfer method comprising:
A hydraulic transfer method, wherein the image receiving layer (C) comprises an aqueous resin layer, and the sealing layer (B) comprises a resin layer having low moisture permeability.   The hydraulic transfer method according to claim 6, wherein the pattern layer (D) is formed by ink jet printing.

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