TWI565592B - Hydraulic transfer film - Google Patents

Description

Hydraulic transfer film

The present invention relates to a multilayer base film for water pressure transfer and a hydraulic transfer film having a layer containing a water-soluble polyvinyl alcohol.

As a method of printing characters or patterns on a structure having a three-dimensional surface or a curved surface having irregularities, there is a method of printing on a water-soluble polyvinyl alcohol film (hereinafter, a polyvinyl alcohol film is also referred to as a PVA film, and a polyethylene material thereof is also used. The alcohol is a PVA) single-sided transfer film, and the printing surface is floated on the water surface, and the printing surface is hydraulically transferred onto the surface of the structure by pressing the structure from above. However, when the PVA single-layer hydraulic transfer film floats on the water surface, the film swells and swells, and is curled into a printing surface which is less likely to expand, so that the end portion of the water-pressure transfer film cannot be used, and as a result, There is a problem of reduced yield.

It is known, for example, to apply a water pressure composed of a layer composed of a resin containing a solubility parameter of 7 to 11 such as a styrene-methyl methacrylate copolymer and a layer of PVA as a binder on a PVA film. A transfer film (base film) or a water-pressure transfer sheet printed on the film for water-pressure transfer (base film) (Patent Document 1). However, when the hydraulic transfer sheet is used for the transfer, the transfer property to the transferred molded body (transferd body) is good, but the water surface curl is prevented as will be described later. The effect is not sufficient.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-18776

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-261694

The present invention has been made in an effort to solve the above problems of the prior art, and an object of the invention is to provide a multilayer base film for water pressure transfer which is excellent in printability, and a water pressure transfer film which is less likely to be curled when floating on a water surface.

The above object can be attained by a multilayer film for water pressure transfer having an X layer selected from the following X1 layer to X3 layer and a Y layer containing a water-soluble PVA (PY).

X1 layer: a layer containing water-soluble PVA (PX1); however, the degree of saponification and degree of polymerization of the water-soluble PVA (PX1) are respectively set to A mole % and B, and the water-soluble PVA in the above Y layer ( When the degree of saponification and the degree of polymerization of PY) are respectively set to C mol % and D, the following formulas (1) to (6), (1) 2 ≦ | AC | ≦ 20 are satisfied.

(2)0≦|B-D|≦2000

(3) 80≦A≦99

(4)500≦B≦2500

(5)75≦C≦99

(6) 300≦D≦2500.

X2 layer: a layer containing water-soluble PVA (PX2) and inorganic particles having an average particle diameter of 2 to 20 μm.

X3 layer: a layer containing at least one water-soluble resin (X3) selected from the group consisting of a polysaccharide and an acrylic resin.

In the multilayer base film for water pressure transfer according to the present invention, the X layer is an X1 layer, and when the degree of swelling of the X1 layer and the Y layer is E (%) and F (%), respectively, the following formula is satisfied ( 7)~(9) is better, (7)0.1≦|EF|≦29.5

(8)0.5≦E≦20

(9) 0.6≦F≦30.

In the multilayer base film for hydraulic transfer according to the present invention, the X layer is an X2 layer, and the saponification degree and polymerization degree of the water-soluble polyvinyl alcohol (PX2) are respectively A and M, and B is in the Y layer. When the degree of saponification and the degree of polymerization of the water-soluble polyvinyl alcohol (PY) are respectively set to C mol% and D, it is preferable to satisfy the following formulas (1) to (6), and (1) 2≦|AC|≦ 20

(2)0≦|B-D|≦2000

(3) 80≦A≦99

(4)500≦B≦2500

(5)75≦C≦99

(6) 300≦D≦2500.

In the multilayer base film for hydraulic transfer according to the present invention, the X layer is an X3 layer, and the water-soluble resin (X3) is cellulose.

In the multilayer base film for hydraulic transfer according to the present invention, the X layer is an X1 layer or an X3 layer, and the X layer further contains an average particle diameter of 2~. 20 μm of inorganic particles are preferred.

In the multilayer base film for water pressure transfer according to the present invention, the X layer is disposed on at least one surface of the multilayer base film for hydraulic transfer, and the surface roughness (Ra) of the X layer disposed on the surface is 0.1~2μm is preferred.

The multilayer base film for hydraulic pressure transfer according to the present invention is at least one of water-soluble polyvinyl alcohol (PX1), water-soluble polyvinyl alcohol (PX2), and water-soluble polyvinyl alcohol (PY). A blend of heteropolyvinyl alcohol is preferred.

In the multilayer base film for hydraulic transfer according to the present invention, it is preferred that the X layer and/or the Y layer contain 0.01 to 3% by mass of a crosslinking agent. Among them, the crosslinking agent is preferably a boron compound.

In the multilayer base film for hydraulic transfer according to the present invention, it is preferred that the X layer and/or the Y layer contain 0.1 to 10% by mass of a surfactant.

In the multilayer base film for hydraulic pressure transfer according to the present invention, it is preferred that the Y layer be disposed on at least one surface of the multilayer base film for hydraulic transfer.

In addition, the above object is achieved by applying a printed base film for water pressure transfer on one surface of the multilayer base film for water pressure transfer.

The hydraulic transfer film of the present invention is preferably printed on the Y layer.

The water pressure transfer film of the present invention has a maximum curl length of 0.2 in the width direction measured by using a film having a length of 35 cm and a width of 25 cm. ~8cm is better.

The multilayer base film for hydraulic transfer of the present invention has good printability. Further, since the water pressure transfer film of the present invention is less likely to be curled when floating on the surface of the water, the yield of the film is high, and the printed surface is less likely to be deformed. Therefore, the hydraulic transfer film of the present invention exhibits excellent performance particularly in the case of a water-pressure transfer film which is used for the transfer of a curved surface structure.

[Formation of the Invention]

The invention is further described in detail below.

The multilayer base film for hydraulic pressure transfer according to the present invention has an X layer selected from the following X1 layer to the X3 layer, and a Y layer containing a water-soluble PVA (PY).

X1 layer: a layer containing water-soluble PVA (PX1); however, the degree of saponification and degree of polymerization of the water-soluble PVA (PX1) are respectively set to A mole % and B, and the water-soluble PVA in the above Y layer ( When the degree of saponification and the degree of polymerization of PY) are respectively set to C mol % and D, the following formulas (1) to (6), (1) 2 ≦ | AC | ≦ 20 are satisfied.

(2)0≦|B-D|≦2000

(3) 80≦A≦99

(4)500≦B≦2500

(5)75≦C≦99

(6) 300≦D≦2500.

X2 layer: a layer containing water-soluble PVA (PX2) and inorganic particles having an average particle diameter of 2 to 20 μm.

X3 layer: a layer containing at least one water-soluble resin (X3) selected from the group consisting of a polysaccharide and an acrylic resin.

In the present invention, it is important that the PVA (PX1, PX2) and PVA (PY) used in the X layer and the Y layer are water-soluble. Here, the water-soluble, the complete melting time in water at 20 ° C is 800 seconds or less, preferably 500 seconds or less, more preferably 300 seconds or less, or the complete melting time in water at 30 ° C is 600 seconds or less, preferably. It is 500 seconds or less, more preferably 300 seconds or less. The lower limit of the above complete melting time is not particularly limited, but is preferably 1 second or longer, more preferably 2 seconds or longer. The complete melting time of PVA can be specifically determined by the method described in the examples below. The water solubility of PVA can be adjusted by appropriately selecting the degree of saponification, degree of polymerization, degree of denaturation by comonomer, and the like.

In the case where the multilayer base film for water pressure transfer of the present invention has the X1 layer, the saponification degrees of the PVA (PX1) and (PY) are respectively A and M%, and the PVA (PX1) and When the degree of polymerization of (PY) is set to B and D, it is very important to satisfy the following formulas (1) to (6).

(1) 2≦|A-C|≦20

(2)0≦|B-D|≦2000

(3) 80≦A≦99

(4)500≦B≦2500

(5)75≦C≦99

(6)300≦D≦2500

In this way, the multilayer structure of the X layer and the Y layer is set, and the water-soluble PVA different from each other is used in the two layers, and the water pressure transfer printing having good printability is obtained by satisfying the above formulas (1) to (6). A multi-layer base film, and a water-pressure transfer film which is less likely to be curled when floating on the surface of the water is obtained.

In the case where the multilayer base film for hydraulic transfer of the present invention has the X1 layer, the saponification degree A of the PVA (PX1) must be 80 to 99 mol%, preferably 85 to 98 mol%. Further, the degree of polymerization B must be 500 to 2,500, preferably 700 to 2,400. On the other hand, the saponification degree C of the above PVA (PY) must be 75 to 99 mol%, preferably 80 to 97 mol%. Further, the degree of polymerization D must be from 300 to 2,500, preferably from 400 to 2,400. When the degree of saponification of PVA (PX) and (PY) exceeds a predetermined value, the solubility of PVA in water is lowered, the stretchability of the film at the time of transfer is lowered, and the adhesiveness is deteriorated. On the other hand, if the degree of saponification is less than a predetermined value, swelling and dissolution occur in a short period of time, and there is a problem that the pattern is distorted and there is no adjustment time in the process. In addition, when the degree of polymerization of PVA (PX1) and (PY) exceeds a predetermined value, the stretchability at the time of transfer is lowered, and the adhesiveness is deteriorated. On the other hand, if the degree of polymerization is lower than a predetermined value, pattern distortion is caused, and the film strength is lowered, and it is easy to cut at the time of printing.

Further, in the case where the multilayer base film for hydraulic transfer of the present invention has the X1 layer, the saponification degrees A and C of the PVA (PX1) and (PY) must satisfy the following relationship (1), and satisfy the relationship (1). ') is better.

(1) 2≦|A-C|≦20

(1')3≦|A-C|≦15

When A-C| is less than 2, the curl of the water surface becomes large. Also, |A-C| When the temperature exceeds 20, the difference in solubility between the layers becomes large, and fine wrinkles due to the difference in film stretching occur during transfer, and wrinkles are likely to remain on the pattern. Further, as will be described later, the Y layer is suitable as a surface to be printed. Therefore, the saponification degree C of PVA (PY) used for the Y layer is more preferably smaller than the saponification degree A of PVA (PX1) used for the X layer.

Further, in the case where the multilayer base film for hydraulic transfer of the present invention has the X1 layer, the polymerization degrees B and D of the PVA (PX1) and (PY) must satisfy the following relationship (2), and satisfy the relationship (2). ') is better.

(2)0≦|B-D|≦2000

(2')0≦|B-D|≦1500

When B-D| exceeds 2,000, the difference in solubility between layers becomes large, and fine wrinkles due to the difference in film stretching occur during transfer, and wrinkles are likely to remain on the pattern.

In the case where the multilayer base film for hydraulic transfer of the present invention has an X2 layer, the saponification degrees of the PVA (PX2) and (PY) are set to A mole % and C mole %, respectively, and the PVA (PX2) is used. When the degree of polymerization of (PY) is set to B and D, respectively, it is preferable to satisfy the following formulas (1) to (6).

(1) 2≦|A-C|≦20

(2)0≦|B-D|≦2000

(3) 80≦A≦99

(4)500≦B≦2500

(5)75≦C≦99

(6)300≦D≦2500

In the case where the multilayer base film for hydraulic transfer of the present invention has the X2 layer, the saponification degree A of the PVA (PX2) used in the X2 layer is preferably It is 80 to 99% by mole, more preferably 85 to 97% by mole. Further, the degree of polymerization B is preferably from 500 to 2,500, more preferably from 600 to 2,200. On the other hand, in the case where the multilayer base film for hydraulic transfer of the present invention has the X2 layer, the saponification degree C of the PVA (PY) used for the Y layer is preferably 75 to 99 mol%, more preferably 80. ~97 moles %. Further, the degree of polymerization D is preferably from 300 to 2,500, more preferably from 500 to 2,200.

Further, in the case where the multilayer base film for hydraulic transfer of the present invention has the X2 layer, the saponification degrees A and C of the PVA (PX2) and (PY) satisfy the following relationship (1), and the relationship is satisfied. (1') is better.

(1) 2≦|A-C|≦20

(1')3≦|A-C|≦15

As will be described later, the Y layer is suitable as a surface to be printed. Therefore, the saponification degree C of PVA (PY) used in the Y layer is more preferably smaller than the saponification degree A of PVA (PX2) used in the X2 layer.

Further, in the case where the multilayer base film for hydraulic transfer of the present invention has the X2 layer, the polymerization degrees B and D of the PVA (PX2) and (PY) satisfy the following relationship (2), and the relationship is satisfied. (2') is better.

(2)0≦|B-D|≦2000

(2')0≦|B-D|≦1500

In the case where the multilayer base film for hydraulic transfer of the present invention has an X3 layer, the saponification degree of PVA (PY) used in the Y layer is preferably from 75 to 99 mol%, more preferably from 80 to 97 mol%. . Further, the degree of polymerization of PVA (PY) is preferably from 300 to 2,500, more preferably from 400 to 2,400.

In the present specification, the degree of saponification of PVA (PX1, PX2, and PY) means a unit obtained by converting saponification into a vinyl alcohol unit. The ratio of the actual saponification to the unit of the vinyl alcohol unit, which is measured in accordance with JIS K6726. Further, the degree of polymerization (Po) is a limit viscosity [η] (unit: deciliter/g) measured from water at 30 ° C after re-saponification and purification of PVA according to the value measured in JIS K6726. It is obtained by the following formula.

Po=([η]×10 ³ /8.29) ^(1/0.62)

In the present invention, at least one of the PVA (PX1, PX2) and PVA (PY) is a blend of two or more kinds of heterogeneous PVA, which is also one of preferable embodiments. Specific examples are as follows.

<1> In the case where the multilayer base film for hydraulic transfer of the present invention has an X1 layer or an X2 layer, PVA (PX1 or PX2) is a blend of two kinds of PVA and one or more kinds of PVA (PY). Things.

<2> When the multilayer base film for hydraulic transfer of the present invention has an X1 layer or an X2 layer, PVA (PX1 or PX2) is a blend of two or more kinds of heterogeneous PVA, and PVA (PY) includes one type. PVA.

<3> When the multilayer base film for hydraulic transfer of the present invention has an X1 layer or an X2 layer, both PVA (PX1 or PX2) and PVA (PY) are a blend of two or more kinds of heterogeneous PVA.

<4> In the case where the multilayer base film for hydraulic transfer of the present invention has an X3 layer, PVA (PY) is a blend of two or more kinds of heterogeneous PVA.

When PVA (PX1, PX2) and/or PVA (PY) are used in combination with two or more kinds of PVA, a PVA having a degree of saponification of 90 mol% or more and a polymerization degree of 1500 or more is mixed in a layer containing the same. In the case of 5 to 30% by mass of the total mass of the PVA, it is preferred from the viewpoint of improving the strength and transferability of the film.

PVA (PX1, PX2, and PY) is a vinylated monomer, and the obtained vinyl ester polymer can be produced by a saponification method. Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, and vinyl pivalate. And alkanoic acid vinyl ester, etc., among which vinyl acetate is also preferred.

When the vinyl ester monomer is polymerized, it is necessary to copolymerize other monomers copolymerizable without departing from the effects of the invention. Examples of the monomer copolymerizable with the vinyl ester monomer include olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene; acrylic acid and salts thereof; methyl acrylate and acrylic acid. Ethyl ester, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, acrylic acid Acrylates such as octaalkyl ester; methacrylic acid and its salts; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate Ester, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, etc. Benzene amide, N-methyl acrylamide, N-ethyl acrylamide, N,N-dimethyl decylamine, diacetone acrylamide, acrylamidopropyl dimethylamine and Acrylamide derivatives such as salts, N-methylol acrylamide and its derivatives; methacrylamide, N-methylmethacrylamide, N-ethyl Methyl acrylamide derivatives such as acrylamide, methacrylamine dimethylamine and salts thereof, N-methylol methacrylamine and derivatives thereof; methyl vinyl ether, ethyl vinyl ether , n-propyl vinyl ether, i-propyl vinyl ether, Vinyl ethers such as n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; chlorine a halogenated ethylene such as ethylene, vinylidene chloride, fluorinated ethylene or vinylidene fluoride; an allyl compound such as allyl acetate or chloropropene; maleic acid and its salt or its ester; itaconic acid and its salt or Ethyl vinyl sulfonyl compound such as vinyl trimethoxy decane; isopropenyl acetate; dihydroxy butene derivative; ethylene carbonate; 3,4-diethoxycarbonyl-1-butene, 3,4 - Diethoxy-1-butene and the like.

Further, examples of the monomer which can be copolymerized in addition to the above are the monomeric N-vinyl-2-pyrrolidone represented by the following formula (I), and N-vinyl-2-caprolactam. N-vinylamines.

CH ₂ =CH-N(R ¹ )-C(=O)-R ² (I)

(wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

In the above formula (I), examples of the alkyl group having 1 to 3 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like, and the carbon number represented by R ² is 1 Examples of the alkyl group of ~5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group and the like. As the monomer represented by the above formula (I), N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N- can be exemplified. Vinyl acetamide and the like. Further, examples of the N-vinyl-2-pyrrolidone include N-vinyl-2-pyrrolidone, N-vinyl-3-propyl-2-pyrrolidone, and N-vinyl-5,5-dimethyl group. -2-pyrrolidone, N-vinyl-3,5-dimethyl-2-pyrrolidone, and the like.

As a further preferred copolymerizable monomer, it can be mentioned A monomer containing a sulfonic acid group. The single-system molecule containing a sulfonic acid group contains a sulfonic acid group or a salt thereof, and can be used as long as it can be copolymerized with a vinyl ester. Specific examples include 2-propenylamine-2-methylpropanesulfonic acid, 2-propenylamine-1-methylpropanesulfonic acid, and 2-methylpropenylamine-2-methylpropanesulfonic acid. And the alkali metal salt; an olefin sulfonic acid such as ethyl disulfonic acid, allyl sulfonic acid or methacryl sulfonic acid; and the alkali metal salt. Among these, 2-propenylamine-2-methylpropanesulfonic acid and an alkali metal salt thereof are preferred from the viewpoints of reactivity at the time of copolymerization with a vinyl ester or stability at the time of saponification. Among them, examples of the alkali metal include Na, K, and Li.

The copolymerization ratio of the copolymerizable monomers is preferably 15 mol% or less, more preferably 10 mol% or less. The lower limit is preferably 0.01 mol% or more, more preferably 0.05 mol% or more.

The X2 layer is mainly composed of the inorganic particles containing the PVA (PX2) and the average particle diameter of 2 to 20 μm. The conventional PVA single-layer hydraulic transfer film is used in the storage of a film roll at a high temperature or under a lot of humidity or during a transfer operation, because the film adheres to each other due to moisture absorption or softening, and the roll end of the film is hydrated. It is dissolved, glued, and cut off when it is rolled out. Further, in the hydraulic transfer sheet of Patent Document 1, in addition to preventing insufficient water surface curling effect, prevention of adhesion and prevention of cutting effect are insufficient. Further, a PVA-based film having a storage elastic modulus at a temperature of 20 ° C and a dry environment and a storage elastic modulus at 20 ° C and 80% RH is preferably 10 or less, and is used in a film for hydraulic transfer. In order to satisfy the above conditions, the proposal (Patent Document 2) discloses a method in which two types of PVA having different degrees of saponification are blended, and an inorganic powder is further added, even if such a PVA film is used for a film for hydraulic transfer, Looking forward to fully satisfying the prevention of adhesion, Prevents cutting and prevents the surface from curling. On the other hand, the structure of the X2 layer and the Y layer containing the water-soluble PVA (PX2) and the inorganic particles having an average particle diameter of 2 to 20 μm can be understood from the examples described later, and the water pressure transfer excellent in printability can be obtained. A multi-layer base film is printed, and a water-pressure transfer film which is capable of suppressing curling when floating on a water surface and which does not adhere to each other, which is not cut by the end of the roll, and which is excellent in further peelability, can be obtained. .

The inorganic material constituting the inorganic particles is not particularly limited as long as it does not adversely affect other physical properties, and examples thereof include cerium compounds such as cerium oxide, diatomaceous earth, helium balloon, glass beads, and glass fibers; and calcium carbonate. Inorganic carbonates such as magnesium carbonate; calcium sulfate, barium sulfate, sodium sulfate, potassium sulfate, zinc sulfate, copper sulfate, iron sulfate, magnesium sulfate, aluminum sulfate and the like; inorganic sulfites such as calcium sulfite; ammonium nitrate, Inorganic nitrates such as sodium nitrate and potassium nitrate; inorganic chlorides such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride; sodium phosphate, potassium chromate, talc, clay, kaolin, mica, bentonite, montmorillonite, gypsum , dawsonite, dolomite, titanium oxide, carbon black, and the like. Among these, ruthenium compounds, talc, and clay are preferred, and ruthenium compounds are preferred.

In the X2 layer, the average particle diameter of the inorganic particles must be 2 to 20 μm, preferably 3 to 15 μm, more preferably 4.5 to 12 μm. When the average particle diameter of the inorganic particles is less than 2 μm, the obtained film becomes easily adhered. On the other hand, when the average particle diameter of the inorganic particles exceeds 20 μm, the film is wound into a roll, and when the X layer is in contact with the surface on the opposite side, the convex portion of the inorganic particles is transferred to the surface or the printing is peeled off. Hey.

In addition, the average particle diameter of the inorganic particles in the present specification is a range of 100 μm ² in the cross section of the layer containing the inorganic particles, and is observed by an electron microscope, and the observed particles having a particle diameter of 0.2 μm or more are individually obtained. The particle size of the particles is further changed. The same operation is repeated for the observation point. For the observation point of 10 points in total, the particle diameter of the observed particle having a particle diameter of 0.2 μm or more is obtained, and the obtained observation point is 10 points. The particle diameter of each particle was calculated simply on average. Here, the particle diameter of each particle is obtained by obtaining the longest diameter and the shortest diameter to be observed with an accuracy of 0.1 μm, and the two are simply averaged.

The inorganic particles are preferably contained in the X2 layer in an amount of 0.1 to 8% by mass, more preferably 0.5 to 5% by mass. When the content of the inorganic particles is less than 0.1% by mass, the effect of adding the inorganic particles may not be obtained. On the other hand, when the content of the inorganic particles is more than 8% by mass, the film becomes hard and is easily cut, or is wound into a roll, and when the X2 layer is brought into contact with the surface on the opposite side, the convex portion of the inorganic particles is Transfer to the surface, or create a flaw in the print off. Here, the content of the inorganic particles is calculated according to the following formula.

Content of inorganic particles (% by mass) = (mass of inorganic particles in X2 layer / mass of X2 layer) × 100

In the case where the X layer constituting the multilayer base film for hydraulic transfer of the present invention is an X1 layer or an X3 layer, the X layer contains the inorganic particles having an average particle diameter of 2 to 20 μm, thereby preventing the film from being adhered, and It is preferable to improve the slidability at the time of processing. Such a pattern is particularly preferable when the surface of the multilayer base film for water pressure transfer is provided with an X layer and a non-printing surface.

The inorganic particles are preferably contained in the X1 layer or the X3 layer in an amount of 0.5 to 8% by mass. If the content of the inorganic particles is less than 0.5% by mass, then There is no way to obtain the effect of adding inorganic particles. On the other hand, when the content of the inorganic particles is more than 8% by mass, the film becomes hard and is easily cut, or is wound into a roll such that the X1 layer or the X3 layer contacts the surface on the opposite side, and inorganic particles are present. The convex portion is transferred to the surface or the print is peeled off. Here, the content of the inorganic particles is calculated according to the following formula.

Content of inorganic particles (% by mass) = (mass of inorganic particles in X1 layer or X3 layer / mass of X1 layer or X3 layer) × 100

Further, in the present invention, by adding the same inorganic particles to the Y layer, it is expected to improve the hardness and strength of the film, and to improve the printability and the adhesion of the film during transfer. This aspect is particularly preferred when the Y layer is disposed on the surface and is not printed.

It is important that the water-soluble resin (X3) used in the above X3 layer is selected from the group consisting of polysaccharides and acrylic resins. Examples of the polysaccharide include starch, cellulose, and the like. As the starch, natural starch such as corn starch and potato starch; etherified starch, esterified starch, crosslinked starch, grafted starch, burned dextrin, enzyme modified dextrin, gelatinized starch, oxidized starch and the like modified starch are preferred. As the cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose is preferred. A metal salt such as hydroxypropylcellulose, nitrocellulose, cationized cellulose, or a sodium salt thereof; and examples of the acrylic resin include metal salts such as polyacrylamide, polyacrylic acid, and sodium salts thereof. One type of these resins may be used alone or two or more types may be used in combination. Among these, in order to achieve the object of the present invention, polysaccharides, particularly cellulose, are more preferred. Water soluble resin (X3) The viscosity of the aqueous solution is not particularly limited as long as it is suitable for the formation of a layer. Specifically, the viscosity of the 1% by mass aqueous solution measured at 20 ° C using a B-type viscosity meter is 1 to 10000 Pa. s is better.

It is important that the water-soluble resin (X3) used in the above X3 layer has a complete dissolution time in water at 20 ° C of 2000 seconds or less, preferably 500 seconds or less. The lower limit of the above complete melting time is not particularly limited, but is preferably 1 second or longer, more preferably 2 seconds or longer. The complete melting time of the water-soluble resin (X3) can be specifically determined by the method described in the examples below. The water solubility of the water-soluble resin (X3) can be adjusted by appropriately selecting the denatured species, the degree of modification, the degree of polymerization, and the like of the resin used as the raw material.

In recent years, when the size of the transfer-receiving body is increased, or the small-sized parts are being multi-headed, the expansion of the transferable time range from the surface of the water has become a major issue. In the conventional PVA single-layer hydraulic transfer film, since the transferable time range is limited, improvements such as control of PVA molecular structure, change in composition, and mixing of resins having different solubility have been reviewed, but they are not damaged. Within the scope of other physical properties, the extended transferable time range is limited. Moreover, even in the hydraulic transfer sheet of the above-mentioned Patent Document 1, in addition to the fact that it is not expected to have a sufficient curl preventing effect, the transfer time range cannot be said to be sufficiently large. On the other hand, by having the configuration of the X3 layer and the Y layer containing the water-soluble resin (X3), it is also possible to obtain a multilayer base film for water pressure transfer which is excellent in printability, and can be obtained from the examples described later. It was found that the films were not in close contact with each other, and the film was not cut by the end portion of the roll, and the water transfer transfer film which was large in the transferable time from the surface of the water and which was less likely to be curled.

The multilayer base film for hydraulic transfer according to the present invention has the X layer selected from the group consisting of X1 layer to X3 and the Y layer containing water-soluble PVA (PY) as described above. The specific layer structure includes a two-layer structure of an X layer/Y layer, a three-layer structure of an X layer/Y layer/X layer, a three-layer structure of a Y layer/X layer/Y layer, or a multilayer structure of the above. . Further, the multilayer base film for hydraulic transfer of the present invention may be composed only of the X layer and the Y layer. However, other water-soluble layers other than the X layer and the Y layer may be provided within the range not inhibiting the object of the present invention. Floor. In the multilayer base film for water pressure transfer of the present invention, as described later, the Y layer is suitable as a surface on which printing is performed. Therefore, it is preferable that the Y layer is disposed on at least one surface of the multilayer base film for hydraulic transfer. Sexually, the two layers of the X layer/Y layer are more preferably constructed.

In the multilayer base film for water pressure transfer of the present invention, it is preferable that the X layer is disposed on at least one surface of the multilayer underlayer film for water pressure transfer. In this case, the surface roughness (Ra) of the film measured in accordance with JIS B0601 of the X layer disposed on the surface is preferably 0.1 to 2 μm, more preferably 0.4 to 2 μm. If the film surface roughness (Ra) of the X layer is less than 0.1 μm, the obtained film has a tendency to be easily adhered. On the other hand, when the surface roughness (Ra) of the film of the X layer is more than 2 μm, when the X layer is wound into a roll-like contact on the surface on the opposite side, the convex portion of the inorganic particles is transferred to the surface, and the film is produced. Printing off the shackles. The surface roughness of the film of the X layer can be, for example, the average particle diameter, the amount of addition, and the film forming conditions, elongation conditions, and heating of the film described later. The heat treatment conditions, etc., are appropriately adjusted.

In the present invention, the X1 layer may be composed only of water-soluble PVA (PX1), and may contain PVA (PX1) as long as it does not inhibit the effects of the present invention. Other ingredients outside. The water-soluble PVA (PX1) content in the X1 layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more.

Further, in the present invention, the X2 layer may be composed only of the water-soluble PVA (PX2) and the inorganic particles, and may contain PVA (PX2) and other components other than the inorganic fine particles as long as the effects of the present invention are not inhibited. The total content of the water-soluble PVA (PX2) and the inorganic fine particles in the X2 layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more.

Further, in the present invention, the X3 layer may be composed only of the water-soluble resin (X3), and may contain other components than the water-soluble resin (X3) as long as the effects of the present invention are not inhibited. The content of the water-soluble resin (X3) in the X3 layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more.

Further, in the present invention, the Y layer may be composed only of water-soluble PVA (PY), and may contain other components than PVA (PY) as long as the effects of the present invention are not inhibited. The content of the water-soluble PVA (PY) in the Y layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more.

In the present invention, the X layer and/or the Y layer contain a crosslinking agent, and it is preferable from the viewpoint of improving transferability, further expanding printability, and accommodating transfer time. In the printing described later, it is preferred to perform printing on the layer containing the crosslinking agent. The content of the crosslinking agent is preferably 0.01 to 3% by mass, more preferably 0.03 to 2.5% by mass, more preferably 0.03 to 2% by mass. Here, the content of the crosslinking agent is a value calculated by the following formula.

Crosslinker content (% by mass) = (mass of crosslinker in layer / mass of layer) × 100

The crosslinking agent is not particularly limited as long as it can be crosslinked with PVA (PX1, PX2 or PY) or the water-soluble resin (X3), and examples thereof include boric acid, calcium borate, cobalt borate, and zinc borate. , potassium aluminum borate, ammonium borate, cadmium borate, boron potassium, copper borate, lead borate, nickel borate, barium borate, barium borate, magnesium borate, manganese borate, lithium borate, borax, arsenite, borosilicate Boron compounds such as Xiaotengshi, Pan'an and Boraxite; Among these, boron compounds are preferred, and boric acid and borax are more preferred.

Further, in the present invention, the X layer and/or the Y layer contains a plasticizer, and is also preferable from the viewpoint of the strength of the film or the prevention of cutting. The content of the plasticizer is preferably from 1 to 30% by mass, more preferably from 2 to 25% by mass, and the content of the plasticizer is a value calculated by the following formula.

Plasticizer content (% by mass) = (mass of plasticizer in layer / mass of layer) × 100

The polyvalent alcohol is preferable as the plasticizer, and examples thereof include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethylolpropane. These may be used in combination of one type or two or more types. Among them, ethylene glycol, glycerin and diglycerin are preferred.

The X layer and/or the Y layer contain a surfactant, and are also suitable from the viewpoints of film formability and transfer suitability. The content of the surfactant is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. Further, the content of the surfactant is preferably 10% by mass or less, more preferably 7% by mass or less, and still more preferably 5% by mass or less. Here, the content of the surfactant is a value calculated by the following formula.

Surfactant content (% by mass) = (mass of surfactant in layer / mass of layer) × 100

Examples of the type of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.

Examples of the anionic surfactant include a carboxylic acid type such as potassium laurate; a sulfate type such as zinc sulfate; a sulfonic acid type such as dodecylbenzenesulfonic acid or sodium alkylbenzenesulfonate; and a polyoxyethylene laurel Ethyl ether phosphate monoethanolamine salt, octyl phosphate potassium salt, lauryl phosphate potassium salt, stearyl phosphate potassium salt, octyl ether phosphate potassium salt, sodium lauryl phosphate sodium salt, fourteen Alkyl phosphate sodium salt, dioctyl phosphate sodium salt, trioctyl phosphate sodium salt, polyoxyethylene aryl phenyl ether phosphate potassium salt, polyoxyethylene aryl phenyl ether phosphate ammonium salt, and the like.

Examples of the nonionic surfactant include an alkyl ether type such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether; an alkylphenyl ether type such as polyoxyethylene octylphenyl ether; and polyoxyethylene. Alkyl ester type such as laurate; alkylamine type such as polyoxyethylene lauryl amino ether; alkyl guanamine type such as polyoxyethylene laurylamine; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; oleic acid An alkane oxime type such as diethanol decylamine; an allyl phenyl ether type such as a polyoxyalkylene allyl phenyl ether; and the like.

Examples of the cationic surfactant include amines such as laurylamine hydrochloride; quaternary ammonium salts such as lauryl trimethylammonium chloride; and pyridinium salts such as lauryl pyridinium chloride compound.

Further, examples of the amphoteric surfactant include N-alkyl-N,N-dimethylbetaine ammonium salts.

The surfactant may be used in combination of one type or two or more types.

Further, in the X layer and/or the Y layer, poorly soluble particles typified by raw starch and various modified starches may be added. By adding these methods, the hardness, strength, printability, and adhesion of the film during transfer can be improved.

The inorganic fine particles, the crosslinking agent, the plasticizer, the surfactant, and the like may be used in advance when the X layer and/or the Y layer are produced or when the coating liquid containing the PVA and/or the water-soluble resin (X3) is produced.

When the multilayer base film for hydraulic transfer of the present invention has an X1 layer, when the degree of swelling of the X1 layer and the Y layer is E (%) and F (%), respectively, the following formula (7) to (() is satisfied. 9) is better.

(7)0.1≦|E-F|≦29.5

(8)0.5≦E≦20

(9)0.6≦F≦30

The degree of swelling E of the X1 layer is preferably from 0.5 to 20%, more preferably from 0.7 to 15%. Further, the swelling degree F of the Y layer is preferably from 0.6 to 30%, more preferably from 0.8 to 20%. If the degree of swelling of the X1 layer and the Y layer exceeds a predetermined value, the printed pattern may be distorted due to expansion. On the other hand, if the degree of swelling is less than a predetermined value, the stretchability is insufficient and the adhesiveness is deteriorated.

Further, it is preferable that the above E and F satisfy the following relational expression (7), and it is more preferable to satisfy the relational expression (7').

(7)0.1≦|E-F|≦29.5

(7')0.2≦|E-F|≦20

When E-F| is less than 0.1, the single-layer film will have a more intense curl on the water surface. In addition, E and F satisfy the above relations (8) and (9) In the case where |E-F| is often maintained at 29.5 or less, in order to suppress the difference in interlayer swellability, the curl generated on the water surface is small, and |E-F| is preferably 20 or less. The degree of swelling of the X1 layer and the Y layer is determined by the method described in the examples below, and can be adjusted by selecting the water temperature of the transfer tank, the moisture content of the film before transfer, and the like.

The method for producing the multilayer base film for hydraulic pressure transfer according to the present invention is not particularly limited, and a method of laminating the X layer and the Y layer obtained by previously forming a film, and coating the X layer and the Y layer including the film formation are used. A method of coating a coating liquid of PVA (PY), coating a coating liquid containing a film formed Y layer, PVA (PX1) used in the X1 layer, and coating a coating liquid containing PVA (PX2) and inorganic particles used in the X2 layer. Or a method of applying a coating liquid containing a water-soluble resin (X3) used for the X3 layer, a method of pressing the X layer and the Y layer together, and the like. In these, it is preferred to apply a coating liquid containing PVA (PX1) used for forming the Y layer and the X1 layer, apply a coating liquid containing PVA (PX2) and inorganic particles used in the X2 layer, or apply a coating solution. A method of applying a coating liquid of a water-soluble resin (X3) used for the X3 layer.

As a method of forming a film of the X layer or the Y layer in advance, for example, a solution containing PVA (PX1, PX2 or PY) or a water-soluble resin (X3) and further containing inorganic particles as needed, a cast film forming method or a wet method is used. Membrane method (method of discharging into a weak solvent), gel film forming method (method of extracting and removing solvent after cooling and gelatinization of PVA aqueous solution), and a combination of these methods, containing a plasticizer and requiring The inorganic fine particles or a PVA (PX1, PX2, or PY) or a water-soluble resin (X3) of a solvent described later is melted and melted and formed into a film forming method. Among these, a casting film forming method, a solution coating method, and a melt extrusion film forming method are preferred.

a method of applying a coating liquid containing PVA (PY) used in a previously formed X layer or a Y layer, or a coating liquid containing PVA (PX1) used in a Y layer or an X1 layer which has been previously formed, or The method of containing the PVA (PX2) and the coating liquid of the inorganic particles used in the X2 layer is to dissolve the PVA into a solvent at a concentration of 1 to 40% by mass (more preferably 2 to 20% by mass), and if necessary, add inorganic particles or Other additives may be applied by, for example, gravure roll coating, Meyer bar coating, reverse roll coating, air knife coating, spray coating, or the like by a usual coating method. The steps and conditions for the coating are not particularly limited, but coating is carried out on a roll or a belt in the film formation of the first layer (layer coated by the coating liquid), followed by hot air drying and hot roll drying. A method of drying or solidifying by well-known means such as far-infrared drying; once the initial layer is formed, and then coating is carried out in a subsequent step, followed by drying or curing. In this case, in order not to impair the physical properties of the layer to be formed in advance, it is important to adjust the temperature and amount of the coating liquid, the temperature and timing of drying or curing, and the timing. As the drying conditions, the temperature is preferably 30 to 120 ° C and the time is 3 to 200 seconds.

The solvent of PVA is typically water, but an organic solvent such as methanol, ethanol, propanol, dimethyl hydrazine, dimethylformamide, dimethylacetamide or N-methylpyrrolidone can also be used. In the case of using these organic solvents, it is preferred to use them in combination with water. In particular, in the case of coating, the drying time can be shortened by mixing methanol, ethanol, or propanol, and it is preferable to reduce the deterioration of the film before coating.

Further, as a method of applying a coating liquid containing a water-soluble resin (X3) used for a Y layer or an X3 layer which has been previously formed, a water-soluble resin (X3) is dissolved in a solvent at a concentration of 1 to 30% by mass. Use it again Typical coating methods include, for example, gravure roll coating, Meyer bar coating, reverse roll coating, air knife coating, spray coating, and the like. In addition, examples of the solvent of the water-soluble resin (X3) include water, alcohols such as methanol, ethanol, and propanol, and a mixture of dimethyl hydrazine and a water/alcohol. Among these, a water/alcohol mixture is preferred because the drying time can be shortened. The step and conditions of the coating are not particularly limited, but in the film formation of the Y layer, coating of a coating liquid containing a water-soluble resin (X3) is carried out on a roll or a belt, followed by drying by hot air, and a hot roll. Drying or curing by a well-known means such as drying or far-infrared drying; once the Y layer is formed, the coating liquid containing the water-soluble resin (X3) is applied in a subsequent step, followed by drying or curing. At this time, in order not to impair the physical properties of the Y layer, it is important to adjust the temperature and amount of the coating liquid, the temperature and timing of drying or solidification, and the like. As the drying conditions, the temperature is preferably 30 to 120 ° C and the time is 3 to 400 seconds.

The multilayer film thus obtained may also be extended in one or two axes before and after the drying step as needed. The extension conditions are a temperature of 20 to 120 ° C, a stretching ratio of 1.05 to 5 times, preferably 1.1 to 3 times. Further, when necessary, the film can be thermally fixed after stretching to reduce residual stress.

When the thicknesses of the X layer and the Y layer are each a film (in the case of a non-coating layer), from the viewpoint of water solubility, each is preferably 10 to 90 μm, more preferably 15 to 80 μm, and more preferably 20 to 80 μm, and 20 to 50 μm. Very good, 25~50μm. When each is a coating layer, the thickness thereof is preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm, and even more preferably 0.1 to 5 μm. Further, the thickness of the entire multilayer film for hydraulic transfer is preferably 10 to 100 μm, more preferably 20 to 45 μm.

The moisture content of the entire layer of the X layer, the Y layer, and the multilayer base film for water pressure transfer is preferably from 1 to 10% by mass, and more preferably from 1 to 8% by mass, from the viewpoint of film strength. When the water content of the entire layer or the multilayer base film for hydraulic transfer is less than 1% by mass, the layer becomes brittle or the film is easily cleaved. On the other hand, when the water content of the entire layer or the multilayer base film for hydraulic transfer is more than 10% by mass, the film may be stretched during printing to cause the printed pattern to be shifted or the multicolor pattern to fall off. The moisture content of each layer can be determined by appropriately adjusting the amount of the solvent (water or the like) in the X layer and the Y layer or the above-mentioned PVA coating liquid, the drying conditions after film formation or coating, and the like.

In the multilayer base film for water pressure transfer of the present invention, any of the X layer and the Y layer may be used as a printing surface. However, when the X layer is the X1 layer, the layer having a low degree of saponification of the PVA used is used as a printing surface, which will be described later. It is preferable from the viewpoint of reducing the occurrence of curl and easily washing the transferred image, and the Y layer is preferably used as the printing surface. When the X layer is the X2 layer or the X3 layer, it is preferable to use the Y layer as the printing surface from the viewpoint of reducing curl generation and easily washing the transferred image after printing.

This printing surface is suitable for the purpose of improving the printability and reducing the friction with the printing apparatus, and is preferably embossed and previously contained a lubricant such as starch or cerium oxide in the layer. Examples of the embossing method include a rubber roller having a general hardness of A10 to 100 (JIS K 6301) and a metal roller having a surface temperature of 10 to 150 ° C having an embossed surface. A method of printing a multilayer base film at a speed of 5 to 50 m/min. Further, when the lubricant is contained, the content of the lubricant is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, for each layer. Any one of a method of performing embossing and a method of containing a lubricant may be employed. Can also be used together.

The multilayer base film for hydraulic transfer of the present invention thus obtained can be printed as a hydraulic transfer film by printing on one surface thereof, for example, on the X layer or the Y layer (preferably the Y layer). A water-pressure transfer film is printed by printing a pattern or a character or the like with a water-insoluble ink or the like. The printed layer of the hydraulic transfer film is floated on the water surface as the upper surface, and the active agent for spraying the ink on the printing surface is required to press the transfer body from above, so that the printed layer is sufficiently fixed on the surface of the transferred body. Then, the X layer and the Y layer are removed by water or the like, dried, and then coated with a protective film such as an acrylic resin to obtain a surface-printed product.

Examples of the printing method include gravure printing, screen printing, offset printing, roll coating, and the like. The printing system can be directly printed on a multilayer base film for hydraulic transfer, and once printed on another film, it can be retransferred to a multilayer base film for hydraulic transfer.

The structure to be transferred is a structure having a flat surface and a structure having a curved surface (curved surface structure). However, the hydraulic transfer film of the present invention is extremely suitable for transfer of a curved structure. Further, the water pressure transfer film obtained by using the multilayer base film for water pressure transfer having the X3 layer is particularly suitable for transfer of a curved structure which is required to have a wide transfer time range. Among them, the curved surface refers to a spherical surface, a undulating surface, a three-dimensional surface having irregularities, and the like. Specific examples of the structure include wood substrates such as wood boards, plywoods, and hard fiberboards; various plastic molded articles; cement products such as pulp cement, slate, glass fiber reinforced cement, and concrete slab; gypsum board, calcium silicate board, Inorganic products such as magnesium citrate; metal products such as iron, steel, copper, aluminum, alloy, glass products, etc.

The hydraulic transfer film of the present invention is excellent in "adhesiveness" in that the film which is softened by water absorption on the water surface is not broken and adheres to the transfer target. The adhesion is preferably 8 cm or more, more preferably 10 cm or more, as measured by the method described in the examples below.

Further, the water pressure transfer film of the present invention has a small dimensional change, and has less curl when floating on the water surface. Specifically, the maximum curl length (the maximum curl length in the width direction measured by using a film having a length of 35 cm and a width of 25 cm) determined by the method described in the examples below is preferably 0.2 to 8 cm, more preferably 0.4~6cm. The loss due to the reduction in the effective area of the transfer is reduced by the method in which the maximum curl length is equal to or less than the above upper limit. Further, by setting the maximum curl length to be equal to or higher than the above lower limit, it is preferable to use a slight curl of the film floating on the water surface to suppress the expansion of the film end portion and to reduce the printing blur. The maximum curl length can be adjusted by satisfying the above formulas (1) to (6), or appropriately selecting the stretching conditions, drying conditions, and the like at the time of production of the multilayer base film for water pressure transfer.

On the other hand, the effective width of the printing pattern for water pressure transfer can be made smaller because the water pressure transfer film is curled, and because the curling causes the printed pattern of the end portion to be distorted, actually becomes more than the non-curled portion. small. The effective width of the hydraulic transfer film varies depending on the width of the film to be used. However, the width determined by the method described in the examples below is effective, and is preferably 60% or more, and more preferably 70% or more.

When the water pressure transfer is performed, the transferable time range is a period in which the hydraulic transfer film is sufficiently softened and maintains a certain degree of viscosity. The start time of the transfer is when the water pressure transfer film absorbs water on the water surface and softens sufficiently, usually by pressing the transferred body from the bottom to a height of 8 cm. It can be normally transferred to a qualified target. For example, when a film having a thickness of 30 μm is used, in many cases, the water temperature is 30 ° C and 40 seconds before and after. When the time during which the water pressure transfer film floats on the water surface is shorter than the above-described case, the film is insufficient in water absorption, and it tends to become hard and difficult to stretch. As a result, when the object to be transferred is pressed, the film is wrinkled, and the printed pattern is transferred under the folding and deposition, and wrinkles or distortion are likely to occur in the pattern. Further, when the transfer target is pressed against the film, the film is broken, and the pattern on the transfer target is peeled off.

On the other hand, when the time required for the water pressure transfer film to float on the water surface is longer than the above time, water absorption and dissolution progress, and the film viscosity is lowered. Finally, when the pressed body is pressed, the film is broken, and after all, it cannot be transferred. This limit time is, for example, when the film is 30 μm thick, and the water temperature is usually 30 ° C for about 2 minutes.

Since the hydraulic transfer film of the present invention has a multilayer film of an X layer and a Y layer, it is easier to adjust the solubility without deteriorating other physical properties than in the case of a single layer film. For example, in the case of the Y layer, the PVA (PX1), PVA (PX2), or the X layer containing the water-soluble resin (X3) having a lower PVA (PY) constituting the Y layer can be greatly formed. Expand the transferable time range.

[Examples]

The present invention will be specifically described below by way of examples, but the invention is not limited by the examples.

Further, the water-soluble PVA and the water-soluble resin (X3) used in the following examples and comparative examples were completely dissolved in water at 20 ° C or 30 ° C, the swelling degree of the X layer and the Y layer, printing suitability, and transfer. Each measurement or evaluation method of sex is shown below.

[Measurement method of complete melting time of water-soluble PVA and water-soluble resin (X3) in water at 20 ° C or 30 ° C]

325 ml of ion-exchanged water was injected into a 500 ml glass beaker to maintain the water temperature at 20 ° C (30 ° C if the complete melting time in water at 30 ° C was measured). A water-soluble PVA film having a thickness of about 30 μm as a sample (to measure the complete melting time of the water-soluble resin (X3), a water-soluble resin (X3) film having a thickness of about 10 μm) at 20 ° C (to measure 30) After the complete dissolution time in the water of °C was 30 ° C), the temperature was adjusted by 65% RH, and the size was 3.5 cm × 4 cm, and it was clamped in a sliding seat having a window frame size of 2.3 cm × 3.4 cm. Using a magnetic stirrer, the glass of the glass beaker was stirred at a speed of 280 rotations/min using a magnetic stirrer, and the film sandwiched between the centers of the beakers was quickly immersed and observed. The film immersed in water passes through the sliding seat and dissolves or ruptures over time, and then detaches from the sliding seat, and gradually dissolves while floating in the water, and becomes invisible to the naked eye. The time until the naked eye is invisible after the impregnation of the film is measured, that is, its complete dissolution time.

[Measurement method of moisture content of PVA layer or multilayer film]

The moisture content H of the PVA layer or the multilayer film is obtained by using a vacuum dryer DP33 manufactured by Yamato Scientific Co., Ltd. and a vacuum pump VR16LP manufactured by Hitachi Koki Co., Ltd., and the sample is subjected to a reduced pressure of 1 Pa or less at 50 ° C, 4 After drying for an hour, the mass M0 before drying of the film and the mass Md after drying were calculated by the following formula.

H (% by mass) = [(M0-Md) / M0] × 100

[Measurement method of swelling degree of X layer and Y layer]

In the following examples and comparative examples, each of the X layers and the Y layer is separately prepared. A single-layer film of the same composition of 30±3 μm was conditioned at 20° C. and 65% RH, and then cut out to a size of 25 cm×25 cm. After drawing a frame of 10 cm×10 cm with an oil-based pen at the center, the oil-painted pen was drawn. As the top surface, the ion-exchanged water floating at 30 ° C is not fixed on the four sides, and the longitudinal and transverse lengths (L1, L2) of the square drawn by the oil-based pen after 10 seconds are measured with a ruler (unit: cm) The swelling degree S was calculated according to the following formula. This measurement was repeated 5 times and averaged as the degree of swelling of each layer.

S(%)=[{(L1+L2)/2-10}/10]×100

[Printability evaluation method]

. Spacing deviation

With respect to the obtained printed matter, the deviation between the colors was determined based on the following criteria.

Very small... the deviation of each color is less than 0.1mm

Small...the deviation of each color is 0.1mm or more and less than 0.3mm

Large...the deviation of each color is 0.3mm or more

. Printing off

With respect to the obtained printed matter, the print off was judged based on the following criteria.

No... no printing of 1mm ² or more in 50cm × 50cm

There is a printing loss of 1mm ² or more in 50cm × 50cm

. Number of cuts

In the printing step, the number of times between the printed film and the printed film of 1000 m, which is caused by the adhesion of the film, particularly the end face of the film (the film is cut without considering mechanical changes), is taken as the number of times of cutting.

. Printing peeling (adhesion)

The roll of the printed matter (hydraulic transfer film) was released and kept at 40 ° C and 80% RH for one week. Then, when the film was taken out from the roll, the state in which the ink on the printing surface migrated to the adjacent film surface and peeled off was observed, and it was judged based on the following criteria.

No... no peeling at all

Small... the area ratio of the peeling part to the whole is less than 5%

The area ratio of the peeling part to the whole is 5% or more and less than 20%.

The area ratio of the large peeling part to the whole is 20% or more

[Transferability evaluation method]

. Adhesive

The obtained printed matter was cut into a circle having a diameter of 20 cm, and humidity-conditioned at 20 ° C and 65% RH for 24 hours. On the other hand, 35 L of ion-exchanged water (water depth: about 22 cm) was injected into a rectangular parallelepiped having a rectangular shape of 45 cm × 35 cm and a depth of 25 cm, and the film 53 g was dissolved in advance in order to eliminate the influence of PVA eluted during transfer. Adjust to 40 ± 2 °C. As the transfer body, a PET film having a thickness of 50 μm was wound around a cylindrical paper tube having a diameter of 7 cm and a length of 23 cm. The printed circular film was floated in a water tank and waited for 1 minute, and 26 parts by mass of butyl cellulose acetate, 26 parts by mass of butyl carbitol acetate, and 8 parts by mass of butyl methyl propionate polymer, An active agent of an ink composed of a mixture of 20 parts by mass of butyl phthalate and 20 parts by mass of barium sulphate is sprayed 10 to 15 g per 1 m ^{2 of the} film, and the bottom surface of the transfer body is regarded as below, at 20 cm/min. The speed is sunk into the center of the film for transfer. Observe the film break, cut or print break point and measure the distance from the bottom of the cup to the point. The same measurement was performed 5 times to obtain an average value, and the result was used as adhesion.

. Maximum curl length

A rectangular test piece having a film forming direction of 43 cm and a width direction of 25 cm (the center of the original film and the center of the cut test piece were aligned) was cut out from the printed matter adjusted to moisture at 30 ° C and 80% RH to prepare a film. Each of the two ends of the short side (25 cm side) was folded into the printing surface side to form a slender cylindrical portion, and an iron rod having a diameter of 2 mm was inserted therein, and wrapped in a folded portion of the film, and fixed with a paper tape. On the other hand, in a container of 35 cm × 50 cm × 5.5 cm, two pairs of iron rod-embedded depressions are provided in the abyss on the long side of the container so that the iron rods 2 can be fixed at intervals of 35 cm. 5 L of ion-exchanged water was injected into the container, and the temperature was adjusted to 30 ± 1 ° C on a hot plate. Next, the printed surface of the film was used as the upper surface, and one of the iron bars inserted into the film of the iron bar was inserted into the recess of the container, and the other iron bar was inserted into the other recess to bring the film into contact with the water surface. At this time, it is noted that the film is prevented from biting the bubble and the end of the film is sunk into the water. The film was floated on the surface of the water to cause curling. After 10 seconds, the width of the portion where the central portion of the film was most curled was measured before the film began to swell. The same measurement was performed 5 times and the average value was obtained, and the value was subtracted from the original film width of 25 cm as the maximum crimp length (the maximum curl length in the width direction measured using a film having a length of 35 cm × a width of 25 cm).

. Width efficient

The same operation as the measurement of the maximum curl length described above was carried out, and the width W (cm) of the substantially untwisted portion of the printed pattern was measured for the film which was floated on the water surface for 20 seconds. The same measurement was performed five times to obtain an average value, and the width efficiency was calculated by the following formula using this value.

Width effective rate (%) = (W / 25) × 100

. Transferable time (start time and limit time)

The time at which the film floated in the water tank to the transfer was changed, and the above adhesiveness was measured, and the bottom surface of the cup was raised to a height of 8 cm, and no wrinkles or film breakage occurred and the pattern was correctly transferred for the shortest time as the start time of transfer. On the other hand, the longer the time until the transfer is, the shorter the adhesiveness is. Therefore, the time when the adhesiveness is 8 cm is taken as the limit time for transfer.

[Example 1]

An aqueous solution (Y liquid) having a saponification degree of 88 mol%, a polymerization degree of 1700, a water having a complete melting time of 24 seconds, a PVA concentration of 15% by weight, and a propylene glycol 0.65 part by mass of a PVA concentration of 15% by mass (Y liquid). The film was cast on top, and hot air of 120 ° C was applied to the belt and dried for 5 minutes to obtain a film (Y layer) having a thickness of 30.2 μm, a width of 60 cm, and a length of 1050 m. The film had a water content of 3.0% by mass and a glycerin content of 4.0% by mass.

Next, an aqueous solution containing a PVA concentration of 12% by mass of PVA having a saponification degree of 94 mol%, a degree of polymerization of 2000 and 20 ° C for 51 seconds in a water having a complete melting time of 51 ° C was used as a coating liquid (X liquid), and a gravure having a gravure width of 54 cm was used. The roll was applied to the film at a rate of 15 m/min, and immediately dried by hot air at 100 ° C for 30 seconds to obtain a multilayer film having a coating layer (X layer) having a thickness of 1.9 μm. The moisture content of the multilayer film was 3.1% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 8%, and the degree of swelling of the Y layer was 21%. These results are shown in Table 1.

After the two ends of the multilayer film were cut into 5 cm, the width was 50 cm, and the length was 1000 m by a cutting device, a cylindrical paper tube having an outer diameter of 88.2 mm processed by polyethylene on the surface was wound at a tension of 15 kg/m. A coiling speed of 40 m/min and a contact roll pressure of 3 kg/m ² were continuously taken up to obtain a roll of a multilayer base film for water pressure transfer.

Using a coloring ink of building materials consisting of a mixture of a dye and a barium sulfate of 70% by mass and a mixture of an alkyd resin and a nitrocellulose of 30% by mass, the texture is gravure printed at 20 ° C and 65% RH. The Y layer side of the multilayer base film for water pressure transfer described above. The thickness of the printed layer was 2 μm each, the unwinding tension was 1 kg/m, and the printing speed was 50 m/min. After printing, the multilayer film was dried in a drying zone of 1 m after being heated by hot air at 60 ° C, and wound up at a take-up tension of 5 kg/m. The obtained printed matter (hydraulic transfer film) was provided in various evaluations by the above method. The results are shown in Table 2.

[Embodiment 2]

In the same manner as in Example 1, except that the PVA used in the coating liquid (X liquid) was a PVA having a degree of saponification of 96 mol % and a degree of polymerization of 1000 and 20 ° C in a complete melting time of 450 seconds, the thickness was obtained in the same manner as in Example 1. A multilayer film of a coating layer (X layer) of 2.1 μm. The moisture content of the multilayer film was 3.2% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 5%, and the degree of swelling of the Y layer was 21%. These results are shown in Table 1.

Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2.

[Example 3]

A thickness of 32.6 μm was obtained in the same manner as in Example 1 except that boric acid was added to the Y solution of Example 1 to have a concentration of 0.15% by mass. A film (Y layer) having a width of 60 cm and a length of 1050 m. The film had a water content of 3.2% by mass, a glycerin content of 4.0% by mass, and a boric acid content of 0.9% by mass.

Next, in the same manner as in Example 1, a multilayer film having a coating layer (X layer) having a thickness of 2.4 μm was obtained. The moisture content of the multilayer film was 3.4% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 8%, and the degree of swelling of the Y layer was 12%. These results are shown in Table 1.

Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2.

[Example 4]

In the same manner as in Example 1, except that the coating liquid (X liquid) was added to the X liquid having the average particle diameter of 6.6 μm (the "NIPGEL0063" manufactured by Tosoh Corporation) in the X liquid of Example 1 to be 0.4% by mass. A multilayer film having a coating layer (X layer) having a thickness of 2.8 μm was obtained. The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.1% by mass. The moisture content of the multilayer film was 3.2% by mass. Further, when a single layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 6%, and the degree of swelling of the Y layer was 21%. These results are shown in Table 1.

Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2.

[Example 5]

In the coating liquid (X liquid), a coating layer (X layer) having a thickness of 2.6 μm was obtained in the same manner as in Example 3 except that boric acid was added to the X liquid of Example 3 to have a concentration of 0.15% by mass. film. The addition amount (content) of boric acid to the total solid content of the coating liquid (X liquid) was 1.2% by mass. The moisture content of the multilayer film was 3.3% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 3%, and the degree of swelling of the Y layer was 12%. These results are shown in Table 1.

Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2.

[Comparative Example 1]

Instead of the multilayer film, a single layer of the film (Y layer) obtained in Example 1 was used. In the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the film (Y layer), and various evaluations were provided by the above method. The results are shown in Tables 1 and 2.

[Comparative Example 2]

Instead of the multilayer film, a single layer of the film (Y layer) obtained in Example 3 was used. In the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the film (Y layer), and various evaluations were provided by the above method. The results are shown in Tables 1 and 2.

[Comparative Example 3]

In the same manner as in the production of the film (Y layer) of Example 1, except that the coating liquid (Y liquid) of Example 1 was used instead of the aqueous solution (Y liquid) of Example 1, a thickness of 31.9 μm, a width of 60 cm, and a length of 1050 m were obtained. Film (Y layer). The moisture content of the film was 2.9% by mass.

Next, in place of the multilayer film, a film (yellow layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was obtained from the film (Y layer) in the same manner as in Example 1. The method is provided in various evaluations. The results are shown in Tables 1 and 2.

[Comparative Example 4]

In the same manner as in the production of the film (Y layer) of Example 1, except that the coating liquid (Y liquid) of Example 2 was used instead of the aqueous solution (Y liquid) of Example 1, a thickness of 33.1 μm, a width of 60 cm, and a length were obtained. 1050m film (Y layer). The moisture content of the film was 3.4% by mass.

Next, in place of the multilayer film, a film (yellow layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was obtained from the film (Y layer) in the same manner as in Example 1. The method is provided in various evaluations. The results are shown in Tables 1 and 2.

[Comparative Example 5]

The thickness of 30.7 μm, the width of 60 cm, and the length were obtained in the same manner as in the production of the film (Y layer) of Example 1 except that the aqueous solution (Y liquid) of Example 1 was used instead of the coating liquid (X liquid) of Example 4. 1050m film (Y layer). The film had a moisture content of 2.9% by mass and a cerium oxide content of 3.1% by mass.

Next, in place of the multilayer film, a film (yellow layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was obtained from the film (Y layer) in the same manner as in Example 1. The method is provided in various evaluations. The results are shown in Tables 1 and 2.

[Comparative Example 6]

In addition to being used as a coating liquid (X liquid), a styrene-methyl methacrylate copolymer (styrene/methyl methacrylate=50/50, mass ratio) having an average particle diameter of 0.8 μm was used as a dispersoid, and saponification was used. A resin latex having a degree of 88 mol% and a polymerization degree of 1700 as a dispersing agent (concentration of styrene-methyl methacrylate copolymer of 1% by mass, saponification degree of 88 mol% as a binder, and PVA of a polymerization degree of 1750) A multilayer film having a coating layer (X layer) having a thickness of 1.8 μm was obtained in the same manner as in Example 1 except that the concentration was 1% by mass and the solid content concentration was 2% by mass in total. The moisture content of the multilayer film was 3.3% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 16%, and the degree of swelling of the Y layer was 21%. These results are shown in Table 1.

Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2.

[Comparative Example 7]

In addition to using an aqueous solution (Y liquid) having a saponification degree of 70 mol %, a polymerization degree of 1700, a water having a complete melting time of 35 seconds, a PVA concentration of 35 seconds, and a propylene glycol 0.65 mass part of a PVA concentration of 15 mass% (Y liquid), In the same manner as in Example 1, a film (Y layer) having a thickness of 31.2 μm, a width of 60 cm, and a length of 1050 m was obtained. The film had a moisture content of 2.8% by mass and a glycerin content of 4.1% by mass.

Next, in the same manner as in Example 1, a multilayer film having a coating layer (X layer) having a thickness of 2.2 μm was obtained. The moisture content of the multilayer film was 3.0% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 8%, and the swelling of the Y layer was carried out. The degree of moisture is 28%. These results are shown in Table 1.

Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2.

[Comparative Example 8]

In addition to using an aqueous solution (Y liquid) having a saponification degree of 88% by mol, a polymerization degree of 100, a partial melting time of 20 seconds of PVA in a water having a degree of polymerization of 20° C., and a PVA concentration of 15% by mass of 0.65 parts by mass of glycerin. In the same manner as in Example 1, a film (Y layer) having a thickness of 25.7 μm, a width of 60 cm, and a length of 1050 m was obtained. The film had a moisture content of 2.7% by mass and a glycerin content of 4.1% by mass.

Next, in the same manner as in Example 2, a multilayer film having a coating layer (X layer) having a thickness of 2.4 μm was obtained. The moisture content of the multilayer film was 3.1% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 5%, and the degree of swelling of the Y layer was 36%. The results are shown in Table 1.

Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2.

[Comparative Example 9]

In the same manner as in Example 1, except that the PVA used in the coating liquid (X liquid) was a PVA having a degree of saponification of 94 mol % and a degree of polymerization of 3000 and 20 ° C in a complete melting time of 105 seconds, the thickness was obtained in the same manner as in Example 1. A multilayer film of a coating layer (X layer) of 2.6 μm. The moisture content of the multilayer film was 3.5% by mass. In addition, a separately produced single layer film of the X layer and the Y layer is used. When the degree of swelling was determined by the above method, the degree of swelling of the X layer was 6%, and the degree of swelling of the layer of Y was 21%. The results are shown in Table 1.

Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2.

[Embodiment 6]

An aqueous solution (Y liquid) containing 15 parts by volume of a saponification degree of 88 mol%, a degree of polymerization of 2000, 30 ° C, a complete dissolution time of 29 seconds, and a PVA concentration of 15 mass % of glycerin (15 parts by mass) (Y liquid) on a conveyor belt The upper casting was applied with a hot air of 120 ° C and dried for 5 minutes to obtain a film (Y layer) having a thickness of 30.4 μm, a width of 60 cm, and a length of 1050 m. The film had a water content of 3.1% by mass and a glycerin content of 4.0% by mass.

Then, in an aqueous solution having the same composition as the aqueous solution (Y liquid), cerium oxide having an average particle diameter of 6.6 μm ("NIPGEL0063" manufactured by Tosoh Corp.) was added to obtain a coating liquid (X liquid) of 0.53 mass%, and a gravure width was used. A 54 mm-thick, full-length gravure roll having a depth of 30 μm was applied at a speed of 15 m/min, and immediately dried by hot air at 100 ° C for 30 seconds to obtain a multilayer film having a coating layer (X layer) having a thickness of 2.1 μm. . The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.3% by mass.

The cross section of the coating layer (X layer) of the multilayer film was observed by an electron microscope to a range of 100 μm ² , and the longest diameter and the shortest diameter of one cerium oxide particle were determined with an accuracy of 0.1 μm, and the two were simply averaged as the particles. path. Similarly, the particle diameters of all the particles observed were determined, and the same operation was repeated by changing the observation point, and the particle diameters of all the particles observed at the observation point of 10 points in total were obtained. In particular, when the particles having a particle diameter of 0.2 μm or more were simply averaged to calculate an average particle diameter, the particles were 6.2 μm. Moreover, the surface roughness (Ra) of the coating layer (X layer) measured according to JIS B0601 was 1.2 μm. Further, the moisture content of the multilayer film was 3.3% by mass. These results are shown in Table 3.

After the two ends of the multilayer film were cut into 5 cm, the width was 50 cm, and the length was 1000 m by a cutting device, a cylindrical paper tube having an outer diameter of 88.2 mm processed by polyethylene on the surface was wound at a tension of 15 kg/m. A coiling speed of 40 m/min and a contact roll pressure of 3 kg/m ² were continuously taken up to obtain a roll of a multilayer base film for water pressure transfer.

Using a coloring ink of building materials consisting of a mixture of a dye and a barium sulfate of 70% by mass and a mixture of an alkyd resin and a nitrocellulose of 30% by mass, the texture is gravure printed at 20 ° C and 65% RH. The Y layer side of the multilayer base film for water pressure transfer described above. The thickness of the printed layer was 2 μm each, the unwinding tension was 1 kg/m, and the printing speed was 50 m/min. After printing, the multilayer film was dried in a drying zone of 1 m after being heated by hot air at 60 ° C, and wound up at a take-up tension of 5 kg/m. The obtained printed matter (hydraulic transfer film) was subjected to various evaluations by the above method. The results are shown in Table 4.

[Embodiment 7]

In addition to the coating liquid (X liquid), 15 parts by mass of PVA having a complete melting time of 63 seconds in water containing a degree of saponification of 96 mol%, a degree of polymerization of 1700, and 30 ° C, and a PVA concentration of 15 parts by mass of glycerin 0.65 parts by mass were used. A coating layer (X layer) having a thickness of 1.9 μm was obtained in the same manner as in Example 6 except that cerium oxide having an average particle diameter of 6.6 μm ("NIPGEL0063" manufactured by Tosoh Corporation) was added in an amount of 0.53 mass%. Multilayer film. The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, when the average particle diameter of cerium oxide in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 6.0 μm. The surface roughness was 0.9 μm. Further, the moisture content of the multilayer film was 2.8% by mass. These results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4.

[Embodiment 8]

The aqueous solution (Y liquid) of Example 6 was used instead of the PVA having a saponification degree of 88 mol%, a polymerization degree of 2000, and a PVA having a degree of polymerization of 96 mol% and a polymerization degree of 1,700 in a mass ratio of 90/10 (30 ° C). In the same manner as in the production of the film (Y layer) of Example 6, except that the total melting time in water was 36 seconds), 15 parts by mass, and propylene glycol (0.65 parts by mass) of an aqueous solution (Y liquid) having a PVA concentration of 15% by mass. A film (Y layer) having a thickness of 31.1 μm, a width of 60 cm, and a length of 1050 m. The film had a moisture content of 2.9% by mass and a glycerin content of 4.3% by mass.

Next, as a coating liquid (X liquid), in addition to using soap a degree of polymerization of 88% by mole, a degree of polymerization of 1700, a complete dissolution time of water of 30 ° C for 15 seconds, 15 parts by mass of PVA, glycerol of 0.65 parts by mass of a PVA concentration of 15% by mass, and an addition of an average particle diameter of 6.6 μm. A multilayer film having a coating layer (X layer) having a thickness of 2.2 μm was obtained in the same manner as in Example 6 except that the product was changed to 0.53 mass% (manufactured by Tosoh Corporation). The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, when the average particle diameter of cerium oxide in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 5.8 μm. The surface roughness was 1.7 μm. Further, the moisture content of the multilayer film was 3.3% by mass. These results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4.

[Embodiment 9]

A film (Y layer) having a thickness of 30.4 μm, a width of 60 cm, and a length of 1050 m was obtained in the same manner as in Example 6 except that boric acid was added to the Y solution of Example 6 to a concentration of 0.05% by mass. The film had a water content of 2.7% by mass, a glycerin content of 3.8% by mass, and a boric acid content of 0.3% by mass.

Next, in addition to the coating liquid (X liquid), 15 parts by mass of PVA having a complete melting time of 51 seconds containing water having a degree of saponification of 94 mol%, a degree of polymerization of 2000, and 30 ° C, and a PVA concentration of 0.65 parts by mass of glycerin were used. 15% by mass of an aqueous solution, and an amount of 6.6 μm of cerium oxide ("NIPGEL0063" manufactured by Tosoh Corp.) was added to make it 0.53 mass%. Example 6 Similarly, a multilayer film having a coating layer (X layer) having a thickness of 2.4 μm was obtained. The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, when the average particle diameter of cerium oxide in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 6.1 μm. The surface roughness was 1.1 μm. Further, the moisture content of the multilayer film was 2.8% by mass. These results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4.

[Embodiment 10]

A thickness of 30.4 μm and a width were obtained in the same manner as in Example 6 except that cerium oxide ("NIPGEL0063" manufactured by Tosoh Corporation) having an average particle diameter of 6.6 μm was added to the Y liquid of Example 6 to a concentration of 0.3% by mass. Film of 60 cm in length and 1050 m in length (Y layer). The film had a water content of 3.3% by mass, a glycerin content of 4.1% by mass, and a cerium oxide content of 1.9% by mass.

Next, in the same manner as in Example 8, a multilayer film having a coating layer (X layer) having a thickness of 2.0 μm was obtained. With respect to the multilayer film, when the average particle diameter of cerium oxide in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 5.7 μm. The surface roughness was 0.7 μm. Further, the moisture content of the multilayer film was 3.1% by mass. These results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4.

[Example 11]

A thickness of 29.1 μm, a width of 60 cm, and a length of 1050 m were obtained in the same manner as in Example 6 except that the polyoxyethylene polyoxypropylene ether as a surfactant was added to the liquid Y of Example 6 to have a concentration of 0.4% by mass. Film (Y layer). The film had a water content of 3.0% by mass, a glycerin content of 4.0% by mass, and a surfactant content of 2.5% by mass.

In the same manner as in Example 6, except that the polyoxyethylene polyoxypropylene ether as a surfactant was added to the X liquid of Example 6 and the concentration was 0.4% by mass. A multilayer film having a coating layer (X layer) having a thickness of 2.2 μm was obtained. The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.2% by mass, and the amount (content) of the surfactant added was 2.4% by mass. With respect to the multilayer film, when the average particle diameter of cerium oxide in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 6.3 μm. The surface roughness was 1.5 μm. Further, the moisture content of the multilayer film was 3.1% by mass. These results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4.

[Embodiment 12]

In the coating liquid (X liquid), a talc having an average particle diameter of 4.5 μm ("P-4" manufactured by Talc Co., Ltd., Japan) was added instead of cerium oxide, and a thickness of 2.5 μm was obtained in the same manner as in Example 6. A multilayer film of a coating layer (X layer). The addition amount (content) of the total solid content of the talc to the coating liquid (X liquid) was 3.3% by mass. This multilayer film was produced in the same manner as in Example 6. When the average particle diameter of the talc in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured, the average particle diameter was 4.5 μm, and the surface roughness was 1.0 μm. Further, the moisture content of the multilayer film was 2.9% by mass. These results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4.

[Comparative Example 10]

Instead of the multilayer film, a single layer of the film (Y layer) obtained in Example 6 was used. The film was measured to have a surface roughness (Ra) of 0.08 μm in the same manner as in Example 6. These results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the film (Y layer), and various evaluations were provided by the above method. The results are shown in Table 4.

[Comparative Example 11]

In addition to being used as a coating liquid (X liquid), a styrene-methyl methacrylate copolymer (styrene/methyl methacrylate=50/50, mass ratio) having an average particle diameter of 0.8 μm was used as a dispersoid, and saponification was used. A resin latex having a degree of 88 mol% and a polymerization degree of 1700 as a dispersing agent (concentration of styrene-methyl methacrylate copolymer of 1% by mass, saponification degree of 88 mol% as a binder, and PVA of a polymerization degree of 1750) A multilayer film having a coating layer (X layer) having a thickness of 2.8 μm was obtained in the same manner as in Example 6 except that the concentration was 1% by mass and the solid content concentration was 2% by mass. The multilayer film was measured to have a surface roughness (Ra) of the coating layer (X layer) of 2.2 μm in the same manner as in Example 6. Further, the moisture content of the multilayer film was 3.2% by mass. These The results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4.

[Comparative Example 12]

In the same manner as in the production of the film (Y layer) of Example 6, except that the coating liquid (X liquid) of Example 6 was used instead of the aqueous solution (Y liquid) of Example 6, a thickness of 29.0 μm, a width of 60 cm, and a length were obtained. 1050m film (Y layer). The film had a moisture content of 2.7% by mass and a glycerin content of 3.9% by mass. Further, in the film, when the average particle diameter and surface roughness (Ra) of cerium oxide were measured in the same manner as in Example 6, the average particle diameter was 6.0 μm, and the surface roughness was 1.0 μm. These results are shown in Table 3.

Next, in place of the multilayer film, a film (water layer) obtained from the film (Y layer) was obtained in the same manner as in Example 6 except that the film (Y layer) obtained by the above method was used alone. Available in various evaluations. The results are shown in Table 4.

[Comparative Example 13]

In addition to using an aqueous solution (Y liquid) having a PVA concentration of 15% by mass of a saponification degree of 70% by mol, a degree of polymerization of 1,700, and a temperature of 1700, 30 ° C for 35 seconds, and a PVA concentration of 15 mass % of glycerin (0.65 parts by mass) In the same manner as in Example 6, a film (Y layer) having a thickness of 25.0 μm, a width of 60 cm, and a length of 1050 m was obtained. The film had a moisture content of 3.0% by mass and a glycerin content of 4.3% by mass.

In addition to using the above film as the Y layer, and in the coating liquid (X liquid), a glass powder having an average particle diameter of 21.8 μm is added instead of the cerium oxide. A multilayer film having a coating layer (X layer) having a thickness of 4.5 μm was obtained in the same manner as in Example 6 except for the end of the "N powder". The amount (content) of the total solid content of the glass powder with respect to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, when the average particle diameter of the glass powder in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 21.8 μm. The surface roughness was 23 μm. Further, the moisture content of the multilayer film was 2.7% by mass. These results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4.

[Comparative Example 14]

In addition to the pulverizer of the "Super clay" of Hojun Co., Ltd. (average particle diameter: 1.2 μm, measured by HORIBA particle size analyzer LA920), the coating liquid (X liquid) was replaced with the cerium oxide. Also, a multilayer film having a coating layer (X layer) having a thickness of 2.8 μm was obtained. The addition amount (content) of the total solid content of the bentonite to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, when the average particle diameter of the bentonite in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 1.2 μm, and the surface was rough. The degree is 0.07 μm. Further, the moisture content of the multilayer film was 3.2% by mass. These results are shown in Table 3.

Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4.

[Example 13]

An aqueous solution (Y liquid) containing 15 parts by weight of a saponification degree of 88 mol %, a polymerization degree of 1700, 20 ° C in a complete melting time of 22 seconds, and a PVA concentration of 15 mass % of glycerin (15 parts by mass) in a conveyor belt The upper casting was carried out by applying hot air at 120 ° C for 5 minutes to obtain a film (Y layer) having a thickness of 30.2 μm, a width of 60 cm, and a length of 1050 m. The film had a water content of 3.0% by mass and a glycerin content of 4.0% by mass.

Next, an aqueous solution having a concentration of 7 mass% of water-soluble cellulose "CMC (carboxymethyl cellulose) DAICEL 1160" manufactured by DAICEL Chemical Industry Co., Ltd., which was completely dissolved in water at 20 ° C for 80 seconds, was used as a coating liquid (X). The liquid was applied to the above film at a speed of 15 m/min using a gravure roll having a gravure width of 54 cm, and immediately dried by hot air at 100 ° C for 30 seconds to obtain a multilayer film. When the cross section of the multilayer film was observed under a microscope, the coating layer (X layer) had an average thickness of 2.1 μm. Further, the surface roughness (Ra) of the coating layer (X layer) measured in accordance with JIS B0601 was 1.4 μm. Further, the moisture content of the multilayer film was 3.0% by mass. These results are shown in Table 5.

After the two ends of the multilayer film were cut into 5 cm, the width was 50 cm, and the length was 1000 m by a cutting device, a cylindrical paper tube having an outer diameter of 88.2 mm processed by polyethylene on the surface was wound at a tension of 15 kg/m. A coiling speed of 40 m/min and a contact roll pressure of 3 kg/m ² were continuously taken up to obtain a roll of a multilayer base film for water pressure transfer.

Using a coloring ink of building materials consisting of a mixture of a dye and a barium sulfate of 70% by mass and a mixture of an alkyd resin and a nitrocellulose of 30% by mass, the texture is gravure printed at 20 ° C and 65% RH. The Y layer side of the multilayer base film for water pressure transfer described above. The thickness of the printed layer was 2 μm each, the unwinding tension was 1 kg/m, and the printing speed was 50 m/min. After printing, the multilayer film was dried in a drying zone of 1 m after being heated by hot air at 60 ° C, and wound up at a take-up tension of 5 kg/m. The obtained printed matter (hydraulic transfer film) was subjected to various evaluations by the above method. The results are shown in Table 6.

[Embodiment 14]

In addition to the water-soluble cellulose used in the coating liquid (X liquid), the water-soluble cellulose "METOLOSE 6-SH-50" manufactured by Shin-Etsu Chemical Co., Ltd., which has a complete melting time of 20 seconds in water at 20 ° C, is used. A multilayer film was obtained in the same manner as in Example 13 except for carboxypropylmethylcellulose and HPMC. When the cross section of the multilayer film was observed under a microscope, the coating layer (X layer) had an average thickness of 1.9 μm. Further, the surface roughness (Ra) of the coating layer (X layer) measured in accordance with JIS B0601 was 0.9 μm. Further, the moisture content of the multilayer film was 3.1% by mass. These results are shown in Table 5.

Next, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. will The results are shown in Table 6.

[Example 15]

A film (Y layer) having a thickness of 32.6 μm, a width of 60 cm, and a length of 1050 m was obtained in the same manner as in Example 13 except that boric acid was added to the liquid Y of Example 13 to a concentration of 0.15% by mass. The film had a water content of 3.2% by mass, a glycerin content of 4.0% by mass, and a boric acid content of 0.9% by mass.

Next, in the same manner as in Example 13, a multilayer film was obtained. When the cross section of the multilayer film was observed under a microscope, the coating layer (X layer) had an average thickness of 2.4 μm. Further, the surface roughness (Ra) of the coating layer (X layer) measured in accordance with JIS B0601 was 1.3 μm. The moisture content of the multilayer film was 3.4% by mass. These results are shown in Table 5.

Next, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 6.

[Example 16]

A multilayer film was obtained in the same manner as in Example 13 except that cerium oxide ("NIPGEL0063" manufactured by Tosoh Corporation) having an average particle diameter of 6.6 μm was added to the X liquid of Example 13 to have a concentration of 0.4% by mass. . The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 5.2% by mass.

The cross section of the coating layer (X layer) of the multilayer film was observed by an electron microscope to a range of 100 μm ² , and the longest diameter and the shortest diameter of one cerium oxide particle were determined with an accuracy of 0.1 μm, and the two were simply averaged as the particles. path. Similarly, the particle diameters of all the particles observed were determined, and the same operation was repeated by changing the observation point, and the particle diameters of all the particles observed at the observation point of 10 points in total were obtained. In particular, when the particles having a particle diameter of 0.2 μm or more were simply averaged to calculate an average particle diameter, it was 6.1 μm. Further, when the cross section of the multilayer film was observed under a microscope, the average thickness of the coating layer (X layer) was 3.1 μm, and the surface roughness (Ra) of the coating layer (X layer) measured according to JIS B0601 was 1.5 μm. Further, the moisture content of the multilayer film was 3.2% by mass. These results are shown in Table 5.

Next, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 6.

[Comparative Example 15]

Instead of the multilayer film, a single layer of the film (Y layer) obtained in Example 13 was used. The surface roughness (Ra) of the film measured according to JIS B0601 was 0.08 μm. These results are shown in Table 5.

Next, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the film, and various evaluations were provided by the above method. The results are shown in Table 6.

[Comparative Example 16]

In the same manner as in the production of the film (Y layer) of Example 13, except that the coating liquid (Y liquid) of Example 13 was used instead of the aqueous solution (Y liquid) of Example 13, a thickness of 29.4 μm, a width of 60 cm, and a length were obtained. 1050m film (Y layer). The moisture content of the film was 2.4% by mass. Further, the surface roughness (Ra) of the film measured in accordance with JIS B0601 was 1.2 μm. These results are shown in Table 5.

Next, instead of the multilayer film, a single layer is used by the above method. In the obtained film (Y layer), a printed matter (hydraulic transfer film) was obtained from the film (Y layer) in the same manner as in Example 13, and various evaluations were provided by the above method. The film is easily broken at the time of printing and is difficult to use. Further, even at the time of transfer, it was not sufficiently dissolved in 1 minute, and it was necessary to maintain it for a long time in order to obtain adhesiveness. The results are shown in Table 6.

[Comparative Example 17]

In the same manner as in the production of the film (Y layer) of Example 13, except that the coating liquid (Y liquid) of Example 14 was used instead of the aqueous solution (Y liquid) of Example 13, a thickness of 27.8 μm, a width of 60 cm, and a length were obtained. 1050m film (Y layer). The moisture content of the film was 2.8% by mass. Further, the surface roughness (Ra) of the film measured in accordance with JIS B0601 was 1.4 μm. These results are shown in Table 5.

Then, in place of the multilayer film, a film (yellow layer) obtained by the above method was used in the same manner as in Example 13, and a printed matter (hydraulic transfer film) was obtained from the film (Y layer). The method is provided in various evaluations. The film is easily broken at the time of printing and is difficult to use. Further, even at the time of transfer, it was not sufficiently dissolved in 1 minute, and it was necessary to maintain it for a long time in order to obtain adhesiveness. The results are shown in Table 6.

[Comparative Example 18]

Instead of the multilayer film, a single layer of the film (Y layer) obtained in Example 15 was used. The surface roughness (Ra) of the film measured according to JIS B0601 was 0.1 μm. These results are shown in Table 5.

Next, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the film, and various evaluations were provided by the above method. The results are shown in Table 6.

[Comparative Example 19]

As the multilayer film, the multilayer film obtained in Comparative Example 6 was used. The surface roughness (Ra) of the coating layer (X layer) measured according to JIS B0601 of the multilayer film was 1.3 μm. The results are shown in Table 5.

Next, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 6.

[Industrial availability]

The multilayer base film for water pressure transfer and the hydraulic transfer film of the present invention are excellent in printability and are less likely to be curled when floating on a water surface, and therefore are particularly suitable for transfer of a curved structure.

Claims (9)

A hydraulic transfer film comprising a X3 layer and a Y layer containing a water-soluble polyvinyl alcohol (PY), a multilayer film for water pressure transfer, which is at least a multilayer film for water pressure transfer. a water-pressure transfer film in which the Y layer of the Y-layer water-pressure transfer multilayer base film is printed on the surface of one side, and the X3 layer contains a material selected from the group consisting of polysaccharides and acrylic resins. A layer of at least one water-soluble resin (X3) in the group. The water pressure transfer film of claim 1, wherein the water-soluble resin (X3) is cellulose. The water pressure transfer film of claim 1 or 2, wherein the X3 layer further contains inorganic particles having an average particle diameter of 2 to 20 μm. The water pressure transfer film according to claim 1 or 2, wherein the X3 layer is disposed on at least one surface of the multilayer base film for hydraulic transfer, and the surface roughness of the X layer disposed on the surface (Ra) ) is 0.1~2 pieces m. The water pressure transfer film according to claim 1 or 2, wherein the water-soluble polyvinyl alcohol (PY) is a blend of two or more kinds of different polyvinyl alcohols. The water pressure transfer film of claim 1 or 2, wherein the X3 layer and/or the Y layer contains 0.01 to 3% by mass of a crosslinking agent. The water pressure transfer film of claim 6, wherein the crosslinking agent is a boron compound. The water pressure transfer film of claim 1 or 2, wherein the X3 layer and/or the Y layer contains 0.1 to 10% by mass of a surfactant. The water-pressure transfer film of claim 1 or 2, wherein the maximum curl length in the width direction measured by using a film having a length of 35 cm × a width of 25 cm is 0.2 to 8 cm.