JP6093793B2 - Base film for hydraulic transfer - Google Patents

Description

  The present invention relates to a base film for hydraulic transfer used for hydraulic transfer printing.

  The film for water pressure transfer is a target on which the printing surface is transferred in a state where a film surface made of a water-soluble resin such as polyvinyl alcohol or a water-swellable resin is preliminarily printed and floated on the water surface. It is known as a film for transferring a transfer object by pressing it from above.

And as described in Patent Document 1, as a film for such use, there is a multilayer base film for hydraulic transfer composed of at least three layers of polyvinyl alcohol layers and at least one layer of polysaccharide and acrylic resin, It is known that various surfactants can be blended in these layers as optional components.
However, since the multilayer base film for hydraulic transfer consists of at least four layers, it exhibits a predetermined effect for the first time, and the surfactant is not described in the examples. The agent is not essential.

International Publication No. 2010/082522

  The present invention makes it possible to form a high-quality print layer even in high-speed printing while having a simpler structure as a base film for hydraulic transfer, and to accurately transfer the formed print layer. It is a problem to transfer the image.

1. A base film for hydraulic transfer, wherein the surface resistivity of the printed surface is 9.9 × 10 ¹³ Ω or less, and the contact angle with the wet surface tension test liquid mixture of 73.0 mN / m is 15 to 50 °.
2. 2. The base film for hydraulic transfer according to 1, which contains a nonionic surfactant and / or an anionic surfactant.
3. The base film for hydraulic transfer according to 1 or 2, comprising 0.1 to 5.0 parts by weight of a nonionic surfactant and / or an anionic surfactant with respect to 100 parts by weight of the water-soluble resin.
4). 4. The base film for hydraulic transfer according to any one of 1 to 3, wherein the tensile modulus is 6000 MPa or less.
5. The base film for hydraulic transfer according to any one of 1 to 4, which does not contain a crosslinking agent.

  By using the hydraulic transfer base film of the present invention, it is possible to obtain a high-quality print layer free from dot omission or dot bleeding, and by using this, transfer of a high-quality print layer to a transfer medium can be realized. .

The material which comprises the base film for hydraulic transfer of this invention is demonstrated below.
It is preferable to use a water-soluble or water-swellable resin for the hydraulic transfer base film of the present invention, and it can be selected from resins conventionally used as a hydraulic transfer base film. .

(resin)
Examples of such water-soluble or water-swellable resins include polyvinyl alcohol, dextrin, gelatin, glue, casein, shellac, gum arabic, protein, polyacrylic amide, sodium polyacrylate, polyvinyl methyl ether, methyl vinyl ether. And a copolymer of vinyl acetate and maleic anhydride, a copolymer of vinyl acetate and itaconic acid, polyvinylpyrrolidone, acetylcellulose, acetylbutylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate and the like.
These resins may be used alone or in combination of two or more.
In addition, rubber components such as mannan, xanthan gum and guar gum may be added to the water-soluble or water-swellable resin. Polyvinyl alcohol used may be unmodified polyvinyl alcohol, or olefins such as ethylene and propylene, acrylic acid esters, methacrylic acid esters, maleic acid and salts or esters thereof in the main chain of polyvinyl alcohol, The modified polyvinyl alcohol in which one or two or more monomers are copolymerized may be used.
Of these materials, polyvinyl alcohol is preferable from the viewpoints of production stability, solubility in water and economy, and the amount of the other resin is 20 parts by weight or less to 100 parts by weight of the polyvinyl alcohol. You may blend.

Polyvinyl alcohol is necessary when forming a printing layer for transfer on a hydraulic transfer base film by changing the polymerization degree, saponification degree, modified species, and the amount of other resins such as rubber. The mechanical strength, moisture resistance during handling, the speed of softening by water absorption after floating on the water surface, the time required for spreading or spreading in water, the ease of deformation in the transfer process, etc. can be adjusted as appropriate. it can.
Among them, in the present invention, the polymerization degree of polyvinyl alcohol is preferably 1000 to 4000. When the degree of polymerization is less than 1000, the film dissolves quickly during hydraulic transfer, and sufficient throwing power may not be obtained, and the original function of hydraulic transfer may not be sufficiently exhibited. On the other hand, when the degree of polymerization exceeds 4000, dissolution of the film is slow, and an economical hydraulic transfer speed may not be obtained.

Moreover, the preferable saponification degree of polyvinyl alcohol is 70-99 mol%, More preferably, it is 74-90 mol%. When the saponification degree of polyvinyl alcohol is less than 70 mol%, the solubility in water is lowered or insolubilized, and the workability of the hydraulic transfer process is significantly lowered.
The thickness of the base film for hydraulic transfer is preferably 15 to 100 μm, more preferably 20 to 75 μm, and further preferably 25 to 50 μm. If the thickness is less than 15 μm, the film is poor and the handling may be hindered. On the other hand, if it is thicker than 100 μm, it may take time to swell the hydraulic transfer base film, which may cause a problem that the hydraulic transfer workability deteriorates.
And the surface specific resistance value of the printing surface of the base film for hydraulic transfer needs to be 9.9 × 10 ¹³ Ω or less, and if it exceeds 9.9 × 10 ¹³ Ω, the ink formed on the printing surface May not be stably fixed on the surface. The surface resistivity is preferably 5.0 × 10 ¹³ Ω or less, and more preferably 9.9 × 10 ¹² Ω or less.
Furthermore, the contact angle between the printed surface and the wet tension test mixture 73.0 mN / m needs to be 15 to 50 °, preferably 20 to 45 °, more preferably 20 to 35 °. .
The tensile modulus of the base film for hydraulic transfer is 6000 MPa or less, preferably 5000 MPa or less, more preferably 4000 MPa or less.
Moreover, as a moisture content of the base film for hydraulic transfer, 1.0-10.0 weight% is preferable, More preferably, it is 2.2-10.0 weight%, More preferably, it is 2.2-8.0 weight%. Most preferably, it is 2.2 to 5.0% by weight.

(Nonionic surfactant and / or anionic surfactant)
Nonionic surfactants blended in the base film for hydraulic transfer include, for example, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene alkyl Examples include amines, polyoxyalkylene alkylamides, polypropylene glycol ethers, acetylene glycols, and allyl phenyl ethers. These are used alone or in combination of two or more.
Examples of the anionic surfactant blended in the hydraulic transfer base film include carboxylic acid types such as potassium laurate; sulfate ester types such as octyl sulfate; sulfonic acid types such as dodecylbenzenesulfonate and sodium alkylbenzenesulfonate; Polyoxyethylene lauryl ether phosphate monoethanolamine salt, octyl phosphate potassium salt, lauryl phosphate potassium salt, stearyl phosphate potassium salt, octyl ether phosphate potassium salt, dodecyl phosphate sodium salt, tetradecyl Phosphate ester sodium salt, dioctyl phosphate sodium salt, trioctyl phosphate sodium salt, polyoxyethylene arylphenyl ether phosphate potassium Unsalted, polyoxyethylene aryl phenyl ether phosphate amine salts.
These surfactants are also used alone or in combination of two or more, and the anionic surfactant and / or nonionic surfactant is added in an amount of 0. The amount is preferably 1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight. In addition, when the anionic surfactant is used, the amount thereof is preferably 0.1 to 7.0 parts by weight, more preferably 0.1 to 100 parts by weight of the water-soluble or water-swellable resin. It is -5.0 weight part, More preferably, it is 0.3-1.0 weight part.

(Plasticizer)
This hydraulic transfer base film can contain a plasticizer for the purpose of imparting the flexibility of the film. The type of plasticizer to be used is not particularly limited, but it may be a polyhydric alcohol plasticizer such as glycerin, diglycerin, triethylene glycol, diethylene glycol, trimethylolpropane, or polyethylene glycol, or a saccharide such as sorbitol, glucose, or xylitol. May be. Of these, glycerin is preferable. The addition amount of the plasticizer is preferably 0 to 10 parts by weight, more preferably 0.5 to 5.0 parts by weight, and still more preferably 1.0 to 4.0 parts by weight with respect to 100 parts by weight of polyvinyl alcohol. is there. If the amount of the plasticizer added is more than 30 parts by weight, the plasticizer bleeds and sticks from the ink receiving layer, which is not preferable.

In addition, for the purpose of preventing blocking between base films for hydraulic transfer, fillers such as silica and starch may be added as an anti-blocking agent as long as the smoothness of the film surface is not impaired, and the dispersibility of these additives is improved. For this purpose, a surfactant or the like may be used as appropriate. Moreover, you may employ | adopt the dryer which has an unevenness | corrugation on the surface for the purpose of blocking prevention. In addition, an uneven pattern may be formed on the film surface by embossing.
Moreover, a crosslinking agent can be added to the base film for hydraulic transfer. At this time, it is not particularly limited as long as the resin is cross-linked, and known cross-linking agents such as tripotassium citrate, boric acid and various borates can be used. However, it is necessary to add while paying attention to the possibility that the extensibility during hydraulic transfer and the throwing power of the film may deteriorate.
However, in the present invention, extensibility and throwing power to a transfer target having a complicated surface shape can be realized without adding a crosslinking agent.

(Base material layer)
When the hydraulic transfer base film of the present invention is stored or printed, it is not particularly necessary to laminate a base material layer on the hydraulic transfer base film in order to support the hydraulic transfer base film. The hydraulic transfer base film of the present invention has sufficient strength to enable storage, printing and hydraulic transfer without having such a base material layer. However, a coating film can be laminated on both sides or one side in order to prevent contamination during storage.

(Manufacturing method of hydraulic transfer base film)
As a method for producing the hydraulic transfer base film of the present invention, a method for forming an ordinary hydraulic transfer base film can be basically employed, and is not particularly limited.
Among them, a method of adopting polyvinyl alcohol as a water-soluble resin and casting an aqueous solution containing this water-soluble resin is preferable, and a film can be formed regardless of the degree of polymerization of polyvinyl alcohol. For example, a solvent casting method (solution casting) in which a raw material solution for a hydraulic transfer base film dissolved in a solvent (water) is cast onto a metal band or a metal or coating drum, and the solvent is removed by drying. Method). At this time, if a band or drum having a concavo-convex pattern is used, a film having a concavo-convex pattern on one side can be easily obtained. The printing surface of the hydraulic transfer base film thus obtained is a smooth surface on the opposite side, not the uneven side. On the other hand, in the base film composition for hydraulic transfer in which a filler such as silica or starch is added as an antiblocking agent, a smooth surface on the band or drum surface side is formed by forming a film by a solution casting method using a smooth band or drum. Becomes the printing surface.

(Used ink)
The hydraulic transfer base film of the present invention is used for hydraulic transfer after a printing layer is formed on the surface thereof. As the ink used for the printing, a known ink can be selected and used. it can.
Such an ink may be a solvent type ink or an ultraviolet ray curable or electron beam curable energy ray curable ink.

When the ink contains an organic solvent as a solvent, the solvent used is aliphatic carbon such as pentane, hexane, heptane, octane, etc., or a mixture thereof such as gasoline, petroleum, benzine, mineral spirit, petroleum naphtha, etc. Hydrogen: aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, ethylbenzene; halogenated hydrocarbons such as trichloroethylene, perchlorethylene, chloroform, carbon tetrachloride; methyl alcohol, ethyl alcohol, n-propyl alcohol , Monohydric alcohols such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, amyl alcohol, benzyl alcohol, diacetone alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cyclohexanone, isophorone; ethyl ether, isopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Ethers such as diethylene glycol dibutyl ether and propylene glycol monobutyl ether; ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Ether acetate, acetic acid esters such as diethylene glycol monobutyl ether acetate, esters, such as butyrate; cellosolve; nitro hydrocarbons; nitriles; amines; Other acetals; acids; furans, and the like. Among these, in consideration of the environment, it is preferable not to use aromatic hydrocarbons such as benzene, toluene, xylene, etc., and ethyl acetate, propyl acetate, butyl acetate, cellosolve, cyclohexanone, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, Methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monobutyl ether, propylene glycol, and the like are preferably used from the viewpoint of solubility in the activator composition. In addition, these solvents can be used individually by 1 type or in mixture of 2 or more types.
When the ink is an ink having a water-based solvent, water alone or a mixed solvent obtained by selecting and mixing water and a water-soluble organic solvent agent among the above solvents can be used.
However, among the above inks, an ink using an aqueous solvent may be used. However, an organic solvent-based ink is preferable for hydraulic transfer because it is excellent in water resistance.

  As the colorant contained in the ink, water-insoluble ones can be used. For example, titanium white, antimony white, lead white, iron black, yellow lead, titanium yellow, vermilion, cadmium red, ultramarine, cobalt blue, pearl pigment Inorganic pigments such as silver pigments such as aluminum paste; organic pigments such as carbon black (black ink), benzidine yellow, isoindolinone yellow, polyazo red, quinacridone red, indanthrene blue, phthalocyanine blue, etc. can be used.

  As the vehicle contained in the ink, known ones can be used, for example, various oils such as linseed oil, soybean oil, synthetic drying oil; natural resins such as rosin, hardened rosin, rosin ester, polymerized rosin; phenol resin, Synthetic resins such as rosin-modified phenolic resin, maleic acid resin, alkyd resin, petroleum resin, vinyl resin, acrylic resin, polyamide resin, epoxy resin, aminoalkyd resin, fluorine resin; nitrocellulose, cellulose acetate butyrate resin And cellulose derivatives; rubber derivatives such as chlorinated rubber and cyclized rubber; and other caseins, dextrins and zeins.

In consideration of stability during use after hydraulic transfer, etc., various necessary additives can be added to the ink in advance. Therefore, it is preferable to add an ultraviolet absorber or a light stabilizer, and the weather resistance of the printing layer transferred to the transfer surface of the transfer target can be improved.
Examples of the ultraviolet absorber include organic compounds such as benzotriazole, benzophenone, and salicylic acid ester, and inorganic compounds such as fine particle zinc oxide and cerium oxide having a particle size of 0.2 μm or less. Examples thereof include hindered amine radical scavengers such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and radical scavengers such as piperidine radical scavengers.
In addition, content of these ultraviolet absorbers and light stabilizers is about 0.5-10 mass%, respectively.
In the case of an energy ray curable ink, an ink containing a monomer, an oligomer, or the like that optionally contains a colorant such as a pigment and has a property of being cured by irradiation with energy rays can be used.

(Print layer formation)
As a means for forming a printing layer using the above-mentioned ink, printing methods conventionally employed in hydraulic transfer such as offset printing, letterpress printing, and gravure printing may be used. Printing is also acceptable.
Examples of the printing pattern include an arbitrary pattern such as a wood grain pattern, a marble pattern, a geometric pattern, an elephant pattern, an abstract pattern, and a character.

(Active agent)
If necessary, the activator is applied to the surface of the base film for hydraulic transfer so as to appropriately dissolve or swell and soften (activate) at least a part of the printed portion. This state can be maintained until the printing layer is transferred. The application to the surface may be performed after the hydraulic transfer base film is floated on the water surface, or may be performed before it is floated.
When the printing surface is activated by applying the activator after the hydraulic transfer base film is floated on the water surface, means for spraying the activator on the hydraulic transfer base film can be adopted. When the activator is applied before floating on the water surface, it can be applied by a known means such as a roll coater or spray while feeding the film from a roller around which a hydraulic transfer base film is wound.
The activator used in the present invention comprises alcohols, ketones, plasticizers and esters having a boiling point of 170 ° C. or higher.

  Alcohols include ethyl alcohol (boiling point 78 ° C.), isopropyl alcohol (boiling point 82 ° C.), tert-butyl alcohol (boiling point 84 ° C.), n-propyl alcohol (boiling point 97 ° C.), 2-butyl alcohol (boiling point 99 ° C.). Examples include low-boiling alcohols having a boiling point of 70 to 100 ° C., high-boiling alcohols having a boiling point of more than 100 to 130 ° C. such as isobutyl alcohol (boiling point 108 ° C.), n-butyl alcohol (boiling point 117 ° C.), and the like. , Or a combination of two or more. Of these, isopropyl alcohol and isobutyl alcohol are preferred. Further, it is preferable to use a low-boiling alcohol and a high-boiling alcohol in combination, and a combination of isopropyl alcohol and isobutyl alcohol is particularly preferable, and a mass ratio of the blend is preferably 1: 7 to 1: 1, and 1: 6. 5 to 1: 2 is more preferable.

  Examples of the ketones preferably include those having a boiling point of 200 ° C. or less such as methyl ethyl ketone (boiling point 80 ° C.), methyl isobutyl ketone (boiling point 116 ° C.), dibutyl ketone (boiling point 187 ° C.), and diisobutyl ketone (boiling point 168 ° C.). Of these, diisobutyl ketone is preferred.

Preferred examples of the plasticizer include phthalate esters. The plasticizer is for imparting a function of softening the ink of the printing layer to the active agent.
Preferred examples of the phthalic acid ester include phthalic acid diesters such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, and diisooctyl phthalate. Of these, dimethyl phthalate and dibutyl phthalate are more preferable, and among them, dimethyl phthalate is preferable because it stabilizes the active state and appropriately evaporates with other solvents.

  Examples of esters having a boiling point of 170 ° C. or higher include acetate esters such as dibutyl oxalate (boiling point 246 ° C.) and methoxybutyl acetate (boiling point 172 ° C.), and glycol ether acetates such as butyl carbitol acetate (boiling point 247 ° C.). Series esters and the like. Of these, dibutyl oxalate is preferred.

  60-90 mass% is preferable and, as for content of alcohol of the activator used when using the base film for hydraulic transfer of this invention, 65-80 mass% is more preferable. 0-15 mass% is preferable and, as for content of ester, 5-12 mass% is more preferable. 1-20 mass% is preferable and, as for content of ketones, 5-12 mass% is more preferable. Further, the content of the plasticizer is 1 to 20% by mass, there is no problem that a part of the ink is dissolved too quickly, and printed characters and patterns do not flow or distort. -18 mass% is preferable.

The activator used in the present invention can contain aliphatic hydrocarbons and ethers.
Examples of the aliphatic hydrocarbon include heptane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, octane, and isooctane. Among these, heptane is preferable.
Examples of ethers include butyl cellosolve and isoamyl cellosolve, and among these, butyl cellosolve is preferable.

  Moreover, about the activator used by this invention, the following resin can be added about 1-20 mass% with respect to a solvent, for example. Examples of this resin include vinyl halide polymers such as polyvinyl chloride and polyvinylidene chloride; styrene polymers such as polystyrene and polystyrene derivatives; vinyl ester polymers such as polyvinyl acetate; (meth) acrylic acid, itacon Polymers of ester derivatives of unsaturated carboxylic acids such as acid, crotonic acid, maleic acid or fumaric acid; polymers of nitrile derivatives or acid amide derivatives; N-methylol derivatives of acid amide derivatives of the above unsaturated carboxylic acids And the same N-alkylmethylol ether derivatives, glycidyl (meth) acrylate, allyl glycidyl ether, vinyl isocyanate, allyl isocyanate, 2-hydroxyethyl- (meth) acrylate, 2-hydroxypropyl- (meth) acrylate, ethylene glycol-mono ( A) Thermoplastic resins composed of monomers such as acrylates or copolymers; polyamide resins; polyester resins; phenol resins; melamine resins; urea resins; epoxy resins; diallyl phthalate resins Silicon resin; thermosetting resin such as polyurethane resin, modified resin or initial condensate thereof, natural resin, rosin and derivatives thereof, natural or synthetic rubber, petroleum resin, cellulose acetate butyrate (CAB), nitrified cotton Cellulosic resins such as (nitrocellulose), alkyd resins, and the like.

(Water pressure transfer process)
The hydraulic transfer base film of the present invention can use a widely used hydraulic transfer device, and the transfer target may be an object on which a pattern or the like is formed by hydraulic transfer, and is the same as the conventional one. Any solid shape may be used. The material of the transfer object is not particularly limited, and may be any material such as resin, metal, and wood.
The water surface activated when the hydraulic transfer base film floats on the water surface so that the printed layer of the hydraulic transfer base film on which the image has been printed is on top and the water transfer base film contains sufficient moisture and swells and becomes soft. The upper hydraulic pressure transfer base film is pushed down into the water by the transfer target.
As a result, the dissolved and / or swollen hydraulic transfer base film is brought into close contact with the transfer medium while being wound around by the hydraulic pressure, and the printing layer is transferred. By washing away the transfer object taken out from the water with a large amount of water, the hydraulic transfer base film remaining on the surface is removed, and the transfer of the printing layer onto the transfer object is completed.
Furthermore, after drying the surface of the transfer object, a topcoat layer can be formed by means such as spraying as necessary.

(Effects of the present invention)
The surface specific resistance value of the printing surface of the present invention is 9.9 × 10 ¹³ Ω or less, and the contact angle with the wet surface tension test liquid mixture of 73.0 mN / m is 15 to 50 ° for hydraulic transfer. When the base film is used, it is possible to form a print layer without dot missing or bleeding. Further, by including a nonionic surfactant and / or an anionic surfactant, it is easy to make the surface specific resistance and the contact angle within appropriate ranges, and further it is possible to prevent the occurrence of missing dots. In addition, when a hydraulic transfer base film having a tensile elastic modulus of 6000 Mpa or less is used, a printed layer with no missing dots can be formed by optimizing the film hardness.
Therefore, by using a hydraulic transfer base film that satisfies these requirements, a high-quality print layer free from dot omission or dot bleeding can be obtained, and by using this, a high-quality print layer can be transferred to a transfer target. realizable.

The following Examples 1 to 10 and Comparative Examples 1 to 6 were performed, and the results are shown in Table 1.
<Example 1>
100 parts by weight of partially saponified polyvinyl alcohol having a polymerization degree of 2400 and an average saponification degree of 88 mol%, 3.5 parts by weight of glycerin as a plasticizer, 0.5 parts by weight of polyoxyethylene oleyl ether as a surfactant, and water In addition, an aqueous solution of the resin composition was obtained.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 30 μm and a moisture content of 3.4% by weight.
<Example 2>
100 parts by weight of partially saponified polyvinyl alcohol having a degree of polymerization of 1800 and an average degree of saponification of 90 mol%, 2.5 parts by weight of glycerin as a plasticizer, and 0.1 parts by weight of polyoxyethylene lauryl ether phosphate as a surfactant, And water were added to obtain an aqueous solution of the resin composition.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 35 μm and a water content of 3.5% by weight.
<Example 3>
An aqueous solution was obtained in the same manner as in Example 2 except that the content of polyoxyethylene lauryl ether phosphate as the surfactant was 0.3 parts by weight.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 35 μm and a water content of 3.3% by weight.
<Example 4>
An aqueous solution was obtained in the same manner as in Example 2 except that the content of polyoxyethylene lauryl ether phosphate as the surfactant was 0.5 part by weight.
This aqueous solution was molded on a drum having a concavo-convex pattern by a solution casting method to obtain a base film for hydraulic transfer having a thickness of 35 μm and a moisture content of 3.4% by weight.
<Example 5>
An aqueous solution was obtained in the same manner as in Example 2 except that the content of polyoxyethylene lauryl ether phosphate as a surfactant was 1.0 part by weight.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 35 μm and a water content of 3.5% by weight.
<Example 6>
An aqueous solution was obtained in the same manner as in Example 2 except that the content of polyoxyethylene lauryl ether phosphate as the surfactant was 5.0 parts by weight.
This aqueous solution was molded on a drum having a concavo-convex pattern by a solution casting method to obtain a base film for hydraulic transfer having a thickness of 35 μm and a moisture content of 3.4% by weight.

<Example 7>
A hydraulic transfer base film was obtained in the same manner as in Example 4 except that the hydraulic transfer base film had a water content of 2.5% by weight.
<Example 8>
A base film for hydraulic transfer was obtained in the same manner as in Example 4 except that the base film for hydraulic transfer had a water content of 7.2% by weight.
<Example 9>
100 parts by weight of partially saponified polyvinyl alcohol having a degree of polymerization of 2000 and an average degree of saponification of 88 mol%, 2.5 parts by weight of glycerin as a plasticizer, 0.3 parts by weight of polyoxyethylene oleyl ether as a surfactant, diethylhexylsulfosuccinate 0.1 parts by weight of acid and water were added to obtain an aqueous solution of the resin composition.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 30 μm and a moisture content of 3.4% by weight.
<Example 10>
100 parts by weight of partially saponified polyvinyl alcohol having a polymerization degree of 2400 and an average saponification degree of 88 mol%, 1.3 parts by weight of glycerin as a plasticizer, 0.6 parts by weight of polyoxyethylene oleyl ether as a surfactant, polyoxyethylene 0.3 parts by weight of lauryl ether phosphate and water were added to obtain an aqueous solution of the resin composition.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 37 μm and a moisture content of 3.6% by weight.

<Comparative Example 1>
An aqueous solution was obtained in the same manner as in Example 1 except that 2.5 parts by weight of glycerin as a plasticizer and 0.5 parts by weight of oleylamine acetate as a surfactant were used.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 35 μm and a water content of 3.3% by weight.
<Comparative example 2>
An aqueous solution was obtained in the same manner as in Example 1 except that 2.5 parts by weight of glycerin as a plasticizer and 0.5 parts by weight of lauryl betaine as a surfactant were used.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 35 μm and a water content of 3.3% by weight.
<Comparative Example 3>
An aqueous solution was obtained in the same manner as in Example 2 except that the content of polyoxyethylene lauryl ether phosphate as the surfactant was 0.05 part by weight.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 35 μm and a water content of 3.6% by weight.
<Comparative example 4>
An aqueous solution was obtained in the same manner as in Example 2 except that the content of polyoxyethylene lauryl ether phosphate as the surfactant was 8.0 parts by weight.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a hydraulic transfer base film having a thickness of 35 μm and a water content of 3.5% by weight.
<Comparative Example 5>
An aqueous solution was obtained in the same manner as in Example 2 except that no plasticizer was added and the content of polyoxyethylene lauryl ether phosphate was 0.05 parts by weight as the surfactant.
This aqueous solution was molded on a concavo-convex pattern drum by a solution casting method to obtain a hydraulic transfer base film having a thickness of 35 μm and a water content of 3.3% by weight.

<Comparative Example 6>
An aqueous solution was obtained in the same manner as in Example 2 except that the surfactant was not added.
This aqueous solution was formed on a drum having a concavo-convex pattern by a solution casting method to obtain a base film for hydraulic transfer having a thickness of 35 μm and a moisture content of 3.4% by weight.

<Water content of film>
The moisture content of the hydraulic transfer base film was measured using a Karl Fischer moisture measuring device (manufactured by Hiranuma Sangyo Co., Ltd .: AQV-2200S).
<Surface specific resistance>
The printing surface of the base film for hydraulic transfer was measured using an ULTRA HIGH RESISTANCE METER (manufactured by ADC Corporation: 8340A) and a resiliency chamber (manufactured by ADC Corporation: 12702A).
Breakdown voltage: 1.5 kV, 1 minute Surface resistivity = {π (D + d) ÷ (D−d)} × Rs
π: Circumference ratio = 3.14
D: Guard electrode inner diameter = 7 cm * Conforms to JIS-K6911 d: Main electrode diameter = 5 cm * Conforms to JIS-K6911 Rs: Surface resistance measured value <Contact angle>
The printing surface of the base film for hydraulic transfer was measured by a droplet method using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .: DM-501).
Test liquid: Wet tension test liquid mixture 73.0 mN / m
Liquid volume: 2 μl
Measurement timing: 1 second after landing <Tension modulus>
The base film for hydraulic transfer was measured using a tensile tester (manufactured by Shimadzu Corporation: AGS-1kN).
Test piece: width 15mm x length 150mm
Distance between chucks: 100mm
Tensile speed: 300 mm / min

<Gravure printing conditions>
The ink used was Sapiria ink manufactured by Sakata Inx Corporation, ethyl acetate was used as a solvent, and a Zahn cup having an orifice diameter of 3 m and a viscosity of 20 seconds was used.
As the gravure plate, one having a plate depth of 28 μm and a line number of 175 lines was used and printing was performed at a printing density of 30%.
The printing conditions were a printing speed of 50 m / min, a drying temperature of 45 ° C., and a printing pressure of 200 kg.
<Ink dot stability>
The number of ink dot missing or dot bleeding within 50 mm × 50 mm on the printing surface of the hydraulic transfer base film was counted.
When the number of missing dots or blurred dots is 0 to 49 ... ◎
When the number of missing dots or blurred dots is 50 to 299 ...
When the number of missing dots or blurred dots is 300 to 999 ...
When the number of missing dots or blurred dots is 1000 or more ... ×
◎, ○ means excellent printing stability.

As is clear from Examples 1 to 10 shown in Table 1 above, according to the hydraulic transfer base film according to the present invention, there was no or little ink missing or bleeding from the printing layer. . Particularly good results were obtained according to Examples 3-5 and 10.
On the other hand, when the base films of Comparative Examples 1 to 6 that were not the hydraulic transfer base film of the present invention were used, ink loss or bleeding of the printing layer occurred.

Claims (4)

It contains nonionic and / or anionic surfactant, and contains 0.5 to 5 parts by weight of a plasticizer, the surface resistivity of the printed surface is 9.9 × 10 ¹³ Ω or less, and the printed surface is wet. It is a polyvinyl alcohol film having a contact angle with a mixed liquid for tension test of 73.0 mN / m of 15 to 50 °, a polymerization degree of 1000 to 4000, a saponification degree of 70 to 99 mol% and a thickness of 15 to 100 μm. , hydraulic transfer base film for being more printed gravure printing without laminating the substrate layer. Base film for hydraulic transfer of claim 1 containing 0.1 to 5.0 parts by weight of A anion-based surfactant per 100 parts by weight of a water-soluble resin. The base film for hydraulic transfer according to claim 1 or 2 , wherein the tensile elastic modulus is 6000 MPa or less. The base film for hydraulic transfer according to any one of claims 1 to 3, wherein a crosslinking agent is not blended.