WO2010082522A1 - Film de base à couches multiples pour transfert hydraulique - Google Patents

Film de base à couches multiples pour transfert hydraulique Download PDF

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Publication number
WO2010082522A1
WO2010082522A1 PCT/JP2010/050075 JP2010050075W WO2010082522A1 WO 2010082522 A1 WO2010082522 A1 WO 2010082522A1 JP 2010050075 W JP2010050075 W JP 2010050075W WO 2010082522 A1 WO2010082522 A1 WO 2010082522A1
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WO
WIPO (PCT)
Prior art keywords
layer
film
hydraulic transfer
water
mass
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PCT/JP2010/050075
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English (en)
Japanese (ja)
Inventor
英晶 小田
直祐 細田
修 風藤
Original Assignee
株式会社クラレ
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Priority to JP2010509054A priority Critical patent/JP5290278B2/ja
Publication of WO2010082522A1 publication Critical patent/WO2010082522A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/175—Transfer using solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability

Definitions

  • the present invention relates to a multilayer base film for hydraulic transfer and a hydraulic transfer film having a layer containing water-soluble polyvinyl alcohol.
  • a water-soluble polyvinyl alcohol film (hereinafter, polyvinyl alcohol film may be abbreviated as PVA film, and the raw material polyvinyl alcohol is PVA).
  • PVA film polyvinyl alcohol film
  • the raw material polyvinyl alcohol is PVA.
  • a transfer film on which one side is printed is floated on the water surface with the printing surface facing up and the structure is pressed from above to transfer the printing surface to the surface of the structure by hydraulic pressure.
  • the film absorbs water and expands, and curls so as to wind a printing surface that is relatively difficult to expand. There is a problem in that it cannot be used, and as a result, the yield decreases.
  • Hydraulic transfer film comprising a PVA film and a layer containing fine particles made of a resin having a solubility parameter of 7 to 11 such as styrene-methyl methacrylate copolymer and PVA as a binder.
  • a hydraulic transfer sheet printed on the hydraulic transfer film (base film) is already known (Patent Document 1).
  • Patent Document 1 When this water pressure transfer sheet is used for transfer, the transfer property to a molded body (transfer body) to be transferred is good, but the effect of preventing water surface curl is not sufficient as described later.
  • the present invention solves the above-described problems of the prior art, and has an object to provide a hydraulic transfer multilayer base film having good printability and a hydraulic transfer film that hardly causes curling when it floats on the water surface.
  • a multilayer base film for hydraulic transfer having an X layer selected from the following X1 layer to X3 layer and a Y layer containing water-soluble PVA (PY).
  • X1 layer a layer containing water-soluble PVA (PX1).
  • PX1 layer a layer containing water-soluble PVA (PX1).
  • the saponification degree and polymerization degree of the water-soluble PVA (PX1) are A mol% and B, respectively
  • the saponification degree and polymerization degree of the water-soluble PVA (PY) in the Y layer are C mol% and D, respectively.
  • the following expressions (1) to (6) are satisfied.
  • X2 layer a layer containing water-soluble PVA (PX2) and inorganic particles having an average particle diameter of 2 to 20 ⁇ m.
  • X3 layer a layer containing at least one water-soluble resin (X3) selected from the group consisting of polysaccharides and acrylic resins.
  • the X layer is an X1 layer and the swelling degrees of the X1 layer and the Y layer are E (%) and F (%), respectively, the following formula (7 ) To (9) are preferably satisfied.
  • the X layer is an X2 layer
  • the water-soluble polyvinyl alcohol (PX2) has a saponification degree and a polymerization degree of A mol% and B, respectively, and the water solubility in the Y layer.
  • the saponification degree and polymerization degree of polyvinyl alcohol (PY) are C mol% and D, respectively, it is preferable that the following formulas (1) to (6) are satisfied.
  • the X layer is preferably an X3 layer, and the water-soluble resin (X3) is preferably cellulose.
  • the X layer is preferably an X1 layer or an X3 layer, and the X layer further contains inorganic particles having an average particle diameter of 2 to 20 ⁇ m.
  • the X layer is disposed on at least one surface of the multilayer base film for hydraulic transfer, and the film surface roughness (Ra) of the X layer disposed on the surface is It is preferably 0.1 to 2 ⁇ m.
  • the multilayer base film for hydraulic transfer according to the present invention is characterized in that at least one of the water-soluble polyvinyl alcohol (PX1), the water-soluble polyvinyl alcohol (PX2), and the water-soluble polyvinyl alcohol (PY) is composed of two or more kinds of different polyvinyl alcohols. A blend is preferred.
  • the X layer and / or the Y layer preferably contains 0.01 to 3% by mass of a crosslinking agent.
  • the crosslinking agent is preferably a boron compound.
  • the X layer and / or the Y layer preferably contains 0.1 to 10% by mass of a surfactant.
  • the Y layer is preferably disposed on at least one surface of the multilayer base film for hydraulic transfer.
  • the above object is achieved by a hydraulic transfer film obtained by printing on one surface of the above-mentioned multilayer base film for hydraulic transfer.
  • the hydraulic transfer film of the present invention is preferably formed by printing on the Y layer surface.
  • the hydraulic transfer film of the present invention preferably has a maximum curl length in the width direction of 0.2 to 8 cm measured using a film having a length of 35 cm and a width of 25 cm.
  • the multilayer base film for hydraulic transfer of the present invention has good printability. Moreover, since the hydraulic transfer film of the present invention is less likely to curl when it floats on the water surface, the yield of the film is high and the printed surface is not easily deformed. For this reason, the hydraulic transfer film of this invention exhibits the performance outstanding as a hydraulic transfer film for curved surface printing especially used for transfer to a curved surface structure.
  • the multilayer base film for hydraulic transfer of the present invention has an X layer selected from the following X1 layer to X3 layer and a Y layer containing water-soluble PVA (PY).
  • X1 layer a layer containing water-soluble PVA (PX1).
  • PX1 layer a layer containing water-soluble PVA (PX1).
  • X2 layer a layer containing water-soluble PVA (PX2) and inorganic particles having an average particle diameter of 2 to 20 ⁇ m.
  • X3 layer a layer containing at least one water-soluble resin (X3) selected from the group consisting of polysaccharides and acrylic resins.
  • PVA PX1, PX2
  • PVA PY
  • water-soluble means that the complete dissolution time in 20 ° C. water is 800 seconds or less, preferably 500 seconds or less, more preferably 300 seconds or less, or the complete dissolution time in 30 ° C. water is 600 seconds.
  • it means preferably 500 seconds or shorter, more preferably 300 seconds or shorter.
  • limiting in particular about the minimum of the said complete dissolution time Preferably it is 1 second or more, More preferably, it is 2 second or more.
  • the complete dissolution time of PVA can be determined by the method described in Examples described later.
  • the water solubility of PVA can be adjusted by appropriately selecting the degree of saponification, the degree of polymerization, the degree of modification with a comonomer, and the like.
  • the saponification degrees of the PVA (PX1) and (PY) are A mol% and C mol%, respectively, and the PVA (PX1) and (PY)
  • the polymerization degrees are B and D, respectively, it is very important to satisfy the following formulas (1) to (6).
  • a hydraulic transfer with good printability is achieved by using a multilayer structure of X and Y layers, using different water-soluble PVA for both layers, and satisfying the above formulas (1) to (6).
  • a multilayer transfer base film can be obtained, and a hydraulic transfer film that hardly causes curling when floated on the water surface can be obtained.
  • the saponification degree A of the PVA (PX1) needs to be 80 to 99 mol%, preferably 85 to 98 mol%. is there.
  • the polymerization degree B needs to be 500 to 2500, and preferably 700 to 2400.
  • the saponification degree C of the PVA (PY) needs to be 75 to 99 mol%, and preferably 80 to 97 mol%.
  • the polymerization degree D needs to be 300 to 2500, and preferably 400 to 2400.
  • the saponification degrees A and C of the PVA (PX1) and (PY) must satisfy the following relational expression (1). It is preferable that the relational expression (1 ′) is satisfied. (1) 2 ⁇
  • the saponification degree C of PVA (PY) used for the Y layer is the saponification degree of PVA (PX1) used for the X layer. More preferably, it is smaller than A.
  • the polymerization degrees B and D of the PVA (PX1) and (PY) must satisfy the following relational expression (2). It is preferable that the relational expression (2 ′) is satisfied. (2) 0 ⁇
  • the saponification degrees of the PVA (PX2) and (PY) are A mol% and C mol%, respectively, and the PVA (PX2) and (PY)
  • the polymerization degrees are B and D, respectively.
  • the saponification degree A of PVA (PX2) used for the X2 layer is preferably 80 to 99 mol%, more preferably 85 to 97 mol. %.
  • the polymerization degree B is preferably 500 to 2500, and more preferably 600 to 2200.
  • the saponification degree C of PVA (PY) used for the Y layer is preferably 75 to 99 mol%, more preferably 80 to 97. Mol%.
  • the polymerization degree D is preferably 300 to 2500, and more preferably 500 to 2200.
  • the saponification degrees A and C of the PVA (PX2) and (PY) preferably satisfy the following relational expression (1). More preferably, the relational expression (1 ′) is satisfied. (1) 2 ⁇
  • the saponification degree C of PVA (PY) used for the Y layer is more than the saponification degree A of PVA (PX2) used for the X2 layer. Is preferably smaller.
  • the multilayer base film for hydraulic transfer of the present invention has an X2 layer
  • the polymerization degrees B and D of the PVA (PX2) and (PY) satisfy the following relational expression (2). More preferably, the relational expression (2 ′) is satisfied. (2) 0 ⁇
  • the saponification degree of PVA (PY) used for the Y layer is preferably 75 to 99 mol%, more preferably 80 to 97 mol%. It is.
  • the polymerization degree of PVA (PY) is preferably 300 to 2500, and more preferably 400 to 2400.
  • the degree of saponification of PVA indicates the proportion of units that are actually saponified to vinyl alcohol units among the units that can be converted to vinyl alcohol units by saponification, according to JIS K6726. Measured accordingly.
  • the degree of polymerization is a value measured according to JIS K6726.
  • PVA PX1, PX2
  • PVA PY
  • PVA PVA
  • PX1 or PX2 contains one type of PVA
  • PVA (PY) is a blend of two or more different types of PVA It is a thing.
  • PVA (PX1 or PX2) is a blend of two or more different types of PVA
  • PVA (PY) is one type Contains PVA.
  • both PVA (PX1 or PX2) and PVA (PY) are blends of two or more different types of PVA.
  • PVA (PY) is a blend of two or more different types of PVA.
  • PVA (PX1, PX2) and / or PVA (PY) a PVA having a saponification degree of 90 mol% or more and a polymerization degree of 1500 or more is used. Mixing 5 to 30% by mass of the total mass is preferable from the viewpoint of improving the strength and transferability of the film.
  • PVA PX1, PX2, and PY
  • vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like. Of these, vinyl acetate is preferred.
  • the vinyl ester monomer When the vinyl ester monomer is polymerized, if necessary, another copolymerizable monomer can be copolymerized within a range not impairing the effects of the invention.
  • the monomer copolymerizable with the vinyl ester monomer include olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene; acrylic acid and salts thereof; methyl acrylate and acrylic acid.
  • Acrylics such as ethyl, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.
  • Acid esters methacrylic acid and salts thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, methacrylic acid 2-ethylhexyl, dodecyl methacrylate Methacrylic acid esters such as octadecyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidopropyldimethylamine and salts thereof, N-methylolacrylamide and derivatives thereof, etc.
  • methacrylamide derivatives such as methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropyldimethylamine and salts thereof, N-methylolmethacrylamide and derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl Vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl Vinyl ethers such as ether, dodecyl vinyl ether and stearyl vinyl ether; Nitriles such as acrylonitrile and methacrylonitrile; Halogenated vinyls such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; Allyl such as allyl acetate and allyl chloride Compounds; maleic acid and salts thereof or esters thereof; itaconic acid and salts or esters thereof; vinylsilyl
  • suitable copolymerizable monomers include monomers represented by the following formula (I), N-vinylamides such as N-vinyl-2-pyrrolidones and N-vinyl-2-caprolactams. kind.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Table above formula (I) the alkyl group having 1 to 3 carbon atoms represented by R 1, for example, there may be mentioned a methyl group, an ethyl group, a propyl group, an isopropyl group, and in R 2
  • Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, and isopentyl group.
  • Examples of the monomer represented by the above formula (I) include N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide and the like.
  • Examples of N-vinyl-2-pyrrolidones include N-vinyl-2-pyrrolidone, N-vinyl-3-propyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, and N-vinyl. Examples include -3,5-dimethyl-2-pyrrolidone and the like.
  • a more preferable copolymerizable monomer includes a sulfonic acid group-containing monomer.
  • the sulfonic acid group-containing monomer can be used as long as it contains a sulfonic acid group or a salt thereof in the molecule and can be copolymerized with a vinyl ester.
  • Specific examples include 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid and alkali metal salts thereof; ethylenesulfonic acid, allyl Examples thereof include olefin sulfonic acids such as sulfonic acid and methacryl sulfonic acid, and alkali metal salts thereof.
  • 2-acrylamido-2-methylpropanesulfonic acid and alkali metal salts thereof are preferable from the viewpoints of reactivity when copolymerized with vinyl ester and stability during saponification.
  • alkali metal include Na, K, and Li.
  • the copolymerization ratio of these copolymerizable monomers is preferably 15 mol% or less, and more preferably 10 mol% or less. About a lower limit, it is 0.01 mol% or more suitably, and is 0.05 mol% or more more suitably.
  • the X2 layer described above contains the PVA (PX2) and inorganic particles having an average particle diameter of 2 to 20 ⁇ m.
  • PX2 PVA
  • the film rolls adhere to each other due to moisture absorption and softening during storage and transfer of film rolls at high temperatures and high humidity, and the roll ends of the film adhere to moisture. There was a problem that it melts and sticks due to, etc., and cuts when unwinding.
  • the above-described hydraulic transfer sheet of Patent Document 1 has not been sufficiently effective in preventing adhesion and cutting, in addition to not being sufficiently effective in preventing water surface curl.
  • Patent Document 2 a PVA film having a ratio of storage elastic modulus under 20 ° C., dry atmosphere condition and storage elastic modulus under 20 ° C., 80% RH condition of 10 or less as a film for hydraulic transfer.
  • Patent Document 2 it is disclosed that two types of PVA having different saponification degrees are blended and further an inorganic powder is blended. Even when used in a film for hydraulic transfer, it could not be expected to satisfy all the effects of adhesion prevention, cutting prevention and water surface curl prevention.
  • printing is achieved by having an X2 layer and a Y layer containing water-soluble PVA (PX2) and inorganic particles having an average particle diameter of 2 to 20 ⁇ m.
  • PX2 water-soluble PVA
  • a multilayer base film for hydraulic transfer with good aptitude can be obtained, curling is suppressed when floating on the water surface, there is no adhesion between films, and there is no cutting due to sticking of the roll end of the film
  • a hydraulic transfer film having excellent peelability can be obtained.
  • the inorganic substance constituting the inorganic particle is not particularly limited as long as it does not adversely affect other physical properties.
  • silicon compounds such as silicon dioxide, diatomaceous earth, silicon balloon, glass beads, glass fiber, etc .
  • calcium carbonate Inorganic carbonates such as magnesium carbonate
  • inorganic sulfates such as calcium sulfate, barium sulfate, sodium sulfate, potassium sulfate, zinc sulfate, copper sulfate, iron sulfate, magnesium sulfate, and aluminum sulfate
  • 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 and calcium chloride
  • the average particle size of the inorganic particles needs to be 2 to 20 ⁇ m, preferably 3 to 15 ⁇ m, and more preferably 4.5 to 12 ⁇ m.
  • the average particle diameter of the inorganic particles is less than 2 ⁇ m, the obtained film is easily adhered.
  • the average particle diameter of the inorganic particles exceeds 20 ⁇ m, when the X layer is wound into a roll shape and the surface of the X layer contacts the opposite surface, the convex portions of the inorganic particles are transferred to the surface, or the printing is lost. May occur.
  • the average particle diameter of the inorganic particles is determined by observing the range of the cross section of 100 ⁇ m 2 of the layer containing the inorganic particles with an electron microscope and observing all particles having a particle diameter of 0.2 ⁇ m or more.
  • the particle diameter of each particle was obtained, and the same operation was repeated by changing the observation point, and the particle diameters of all particles having a particle diameter of 0.2 ⁇ m or more, which were observed at a total of 10 observation points, were obtained and obtained. It is possible to calculate by simply averaging the particle sizes of the individual particles for 10 points.
  • the particle diameter of each particle is obtained by obtaining the observed longest diameter and shortest diameter with an accuracy of 0.1 ⁇ m and simply averaging both.
  • the inorganic particles are preferably contained in the X2 layer in an amount of 0.1 to 8% by mass, and more preferably 0.5 to 5% by mass. If 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 exceeds 8% by mass, the film becomes hard and easy to cut, or when the X2 layer comes into contact with the surface on the opposite side when wound in a roll shape, There is a risk that the convex portion may be transferred to the surface of the convex portion, or printing may be lost.
  • 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 inorganic particles having an average particle diameter of 2 to 20 ⁇ m as described above. It is preferable because adhesion can be prevented and slipperiness during processing can be improved. Such an embodiment is particularly preferable when the X layer is disposed on the surface of the multilayer base film for hydraulic transfer and is not the 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, the effect of adding the inorganic particles may not be obtained. On the other hand, when the content of the inorganic particles exceeds 8% by mass, the film becomes hard and easy to cut, or when wound into a roll and the X1 layer or X3 layer contacts the opposite surface, There is a possibility that the convex portions of the inorganic particles may be transferred to the surface of the inorganic particles or may cause printing failure.
  • the present invention it can be expected that by blending the same inorganic particles in the Y layer, the hardness and strength of the film are improved, and the printability and the cohesiveness of the film at the time of transfer are improved.
  • Such an embodiment is particularly preferable when the Y layer is disposed on the surface and is not a printing surface.
  • the water-soluble resin (X3) used for the X3 layer described above is selected from the group consisting of polysaccharides and acrylic resins.
  • the polysaccharide include starch and cellulose.
  • starch natural starch such as corn starch and potato starch; etherified starch, esterified starch, cross-linked starch, grafted starch, baked dextrin, enzyme-modified dextrin, pregelatinized starch, oxidized starch and the like are preferable
  • the cellulose metal salts such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, nitrocellulose, cationized cellulose, and sodium salts thereof are preferable.
  • examples of the acrylic resin include metal salts such as polyacrylamide, polyacrylic acid, and a sodium salt thereof.
  • these resins one kind may be used alone, or two or more kinds may be mixed and used.
  • polysaccharides, particularly cellulose is more preferable for achieving the object of the present invention.
  • the viscosity of the aqueous solution of the water-soluble resin (X3) is not particularly limited as long as it is suitable for forming a layer. Specifically, a 1% by mass aqueous solution having a viscosity of 1 to 10,000 Pa ⁇ s when measured with a B-type viscometer at 20 ° C. is preferable.
  • the water-soluble resin (X3) used in the X3 layer described above has a complete dissolution time in water at 20 ° C. of 2000 seconds or less, preferably 500 seconds or less.
  • a complete dissolution time of the water-soluble resin (X3) can be determined by the method described in Examples described later.
  • the water solubility of the water-soluble resin (X3) can be adjusted by appropriately selecting the modified species, the modification degree, the polymerization degree, and the like of the resin used as a raw material.
  • a multi-layer base for hydraulic transfer with good printability as will be apparent from the examples described later, by having an X3 layer and a Y layer containing the water-soluble resin (X3). Hydraulic transfer that can obtain films, has no adhesion between films, does not cut due to sticking of film roll ends, has a wide transferable time range after floating on the water surface, and is less likely to curl A film can be obtained.
  • the multilayer base film for hydraulic transfer of the present invention has an X layer selected from the X1 layer to the X3 layer and a Y layer containing water-soluble PVA (PY).
  • the layer structure include a two-layer structure of X layer / Y layer, a three-layer structure of X layer / Y layer / X layer, a three-layer structure of Y layer / X layer / Y layer, or a multilayer structure having more layers. Is mentioned.
  • the multilayer base film for hydraulic transfer of the present invention may consist of only the X layer and the Y layer, but other water-soluble layers other than the X layer and the Y layer are within the range in which the object of the present invention is not hindered. It may be provided.
  • the Y layer is suitable as a surface to be printed, the Y layer is disposed on at least one surface of the multilayer base film for hydraulic transfer.
  • the two-layer configuration of X layer / Y layer is more preferable from the viewpoint of productivity.
  • the X layer is also preferably disposed on at least one surface of the multilayer base film for hydraulic transfer.
  • the film surface roughness (Ra) measured by JIS B0601 of the X layer disposed on the surface is preferably 0.1 to 2 ⁇ m, and more preferably 0.4 to 2 ⁇ m. .
  • the film surface roughness (Ra) of the X layer is less than 0.1 ⁇ m, the obtained film may be easily adhered.
  • the film surface roughness (Ra) of the X layer exceeds 2 ⁇ m, the convex portions of the inorganic particles are transferred to the surface when the X layer is wound into a roll and the X layer contacts the opposite surface.
  • the film surface roughness of the X layer should be appropriately adjusted depending on, for example, the average particle diameter, the amount added, and the film forming conditions, stretching conditions, heating / heat treatment conditions described below, when inorganic particles are used. Can do.
  • the X1 layer may consist of only water-soluble PVA (PX1), but may contain other components other than PVA (PX1) as long as the effects of the present invention are not impaired.
  • the content of water-soluble PVA (PX1) in the X1 layer is preferably 50% by mass or more, more preferably 70% by mass or more, and may be 90% by mass or more.
  • X2 layer may consist only of water-soluble PVA (PX2) and said inorganic substance particle, as long as the effect of this invention is not inhibited, other than PVA (PX2) and said inorganic substance fine particle Ingredients may be included.
  • 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 may be 90% by mass or more.
  • X3 layer may consist only of said water-soluble resin (X3), unless the effect of this invention is inhibited, other components other than said water-soluble resin (X3) are included. May be.
  • 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 may be 90% by mass or more.
  • the Y layer may be composed only of water-soluble PVA (PY), but may contain other components other than PVA (PY) as long as the effects of the present invention are not impaired.
  • the content of water-soluble PVA (PY) in the Y layer is preferably 50% by mass or more, more preferably 70% by mass or more, and may be 90% by mass or more.
  • the X layer and / or the Y layer contain a crosslinking agent from the viewpoint of improving the transferability, and further from the viewpoints of printability and expansion of the appropriate transfer time.
  • the content of the crosslinking agent is preferably 0.01 to 3% by mass, more preferably 0.03 to 2.5% by mass, and more preferably 0.03 to 2% by mass.
  • the content of the crosslinking agent is a value calculated by the following formula.
  • Crosslinker content (mass%) (mass of crosslinker in layer / mass of layer) ⁇ 100
  • the crosslinking agent is not particularly limited as long as it causes a crosslinking reaction with PVA (PX1, PX2 or PY) or water-soluble resin (X3).
  • PVA PX1, PX2 or PY
  • X3 water-soluble resin
  • boric acid calcium borate, cobalt borate, zinc borate , Potassium aluminum borate, ammonium borate, cadmium borate, potassium borate, copper borate, lead borate, nickel borate, barium borate, bismuth borate, magnesium borate, manganese borate, lithium borate, Boron compounds such as borax, carnite, inyoite, agate stone, suian stone, zyberite, etc .; tripotassium citrate and the like.
  • boron compounds are preferable, and boric acid and borax are more preferable.
  • the X layer and / or the Y layer contain a plasticizer from the viewpoint of film strength and cutting prevention.
  • the plasticizer content is preferably 1 to 30% by mass, and more preferably 2 to 25% by mass.
  • the plasticizer is preferably a polyhydric alcohol, and examples thereof include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like, one or two of these. A mixture of seeds or more can be used. Among these, ethylene glycol, glycerin and diglycerin are preferable.
  • the X layer and / or the Y layer contain a surfactant from the viewpoint of film forming property and transferability.
  • the content of the surfactant is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, further preferably 0.1% by mass or more, and 0.2% by mass. % Or more is particularly preferable.
  • the content of the surfactant is preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less.
  • the content of the surfactant is a value calculated by the following formula.
  • Surfactant content (mass%) (mass of surfactant in layer / mass of layer) ⁇ 100
  • the surfactant examples include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
  • the anionic surfactant include carboxylic acid types such as potassium laurate; sulfate ester types such as octyl sulfate; sulfonic acid types such as dodecylbenzenesulfonate and sodium alkylbenzenesulfonate; polyoxyethylene lauryl ether phosphate mono Ethanolamine salt, octyl phosphate potassium salt, lauryl phosphate potassium salt, stearyl phosphate potassium salt, octyl ether phosphate potassium salt, dodecyl phosphate sodium salt, tetradecyl phosphate sodium salt, dioctyl phosphate Ester sodium salt, Trioctyl phosphate sodium salt, Polyoxyethylene aryl phenyl ether phosphate potassium salt, Polyoxy
  • nonionic surfactants include alkyl ether types such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; alkyl ester types such as polyoxyethylene laurate.
  • An alkylamine type such as polyoxyethylene lauryl amino ether; an alkylamide type such as polyoxyethylene lauric acid amide; a polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; an alkanolamide type such as oleic acid diethanolamide; Examples include allyl phenyl ether type such as oxyalkylene allyl phenyl ether.
  • Examples of the cationic surfactant include amines such as laurylamine hydrochloride; quaternary ammonium salts such as lauryltrimethylammonium chloride; and pyridinium salts such as laurylpyridinium chloride.
  • examples of the amphoteric surfactant include N-alkyl-N, N-dimethylammonium betaine. Surfactant can be used 1 type or in combination of 2 or more types.
  • the X layer and / or the Y layer may be mixed with hardly soluble particles represented by raw starch and various modified starches. By blending these, it is possible to improve the hardness, strength, printability, and clinging property of the film during transfer.
  • the inorganic fine particles, the crosslinking agent, the plasticizer, the surfactant and the like described above are used when the X layer and / or the Y layer are manufactured, or when the coating liquid containing PVA and / or the water-soluble resin (X3) is manufactured. And can be used in combination.
  • the multilayer base film for hydraulic transfer of the present invention has an X1 layer
  • the swelling degrees of the X1 layer and the Y layer are E (%) and F (%), respectively
  • the following formulas (7) to (9 ) Is preferably satisfied.
  • ⁇ 29.5 (8) 0.5 ⁇ E ⁇ 20 (9) 0.6 ⁇ F ⁇ 30
  • the swelling degree E of the X1 layer is preferably 0.5 to 20%, more preferably 0.7 to 15%.
  • the swelling degree F of the Y layer is preferably 0.6-30%, more preferably 0.8-20%. If the swelling degree 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 below a predetermined value, the extensibility is insufficient and the clinging property may be deteriorated.
  • E and F preferably satisfy the following relational expression (7), and more preferably satisfy the relational expression (7 ′). (7) 0.1 ⁇
  • is less than 0.1, there is a possibility that curling on the water surface may become severe as in the case of a single layer film.
  • is always 29.5 or less.
  • the degree of swelling of the X1 layer and the Y layer is determined by the method described in the examples described later, 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 transfer of the present invention is not particularly limited, and is a method of laminating a pre-formed X layer and a Y layer, and the PVA (PY used for the Y layer is formed on the formed X layer. ), A coating solution containing PVA (PX1) used for the X1 layer, a coating solution containing PVA (PX2) and inorganic particles used for the X2 layer. Or a method of coating a coating solution containing a water-soluble resin (X3) used for the X3 layer, a method of co-extruding the X layer and the Y layer, and the like.
  • the coating liquid containing PVA (PX1) used for the X1 layer, the coating liquid containing PVA (PX2) and inorganic particles used for the X2 layer, or the X3 layer is used for the formed Y layer.
  • a method of coating a coating liquid containing the water-soluble resin (X3) to be formed is preferable.
  • a melt extrusion film forming method in which PVA (PX1, PX2, or PY) or a water-soluble resin (X3) containing a plasticizer and, if necessary, inorganic fine particles and a solvent described later is melted.
  • the casting film forming method, the solution coating method, and the melt extrusion film forming method are preferable.
  • PY a coating solution containing PVA
  • PX1 a pre-formed Y layer with PVA
  • the concentration of PVA is 1 to 40% by mass (more preferably 2 to 20% by mass). So that it is dissolved in a solvent, and if necessary, inorganic particles and other additives are blended, and this is applied to ordinary coating methods such as gravure roll coating, Meyer bar coating, reverse roll coating, air knife coating, spray coating, etc. The method of coating by is mentioned.
  • the coating process and conditions are not particularly limited, but coating is performed on a roll or belt during film formation of the first layer (layer coated with a coating solution), and then hot air drying, hot roll drying, far infrared drying, etc. And a method of drying or solidifying by a known means, a method of forming a first layer once, coating in a subsequent step, and then drying or solidifying. At that time, in order not to impair the physical properties of the layer formed in advance, it is important to adjust the temperature, amount, drying or solidification temperature, timing and the like of the coating solution. As drying conditions, a temperature of 30 to 120 ° C. and a time of 3 to 200 seconds are preferable.
  • a typical solvent for PVA is water, but organic solvents such as methanol, ethanol, propanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone can also be used. When using these organic solvents, it is preferable to use together with water. In particular, when coating, mixing methanol, ethanol, and propanol is preferable because drying time can be shortened and deterioration of the film before coating can be reduced.
  • the concentration of the water-soluble resin (X3) is adjusted to 1 to 30% by mass.
  • a method of coating it by a usual coating method such as gravure roll coating, Mayer bar coating, reverse roll coating, air knife coating, spray coating and the like.
  • the solvent of the water-soluble resin (X3) include water; alcohols such as methanol, ethanol and propanol; dimethyl sulfoxide, water / alcohol mixed liquid and the like. Among these, a water / alcohol mixed solution is preferable because the drying time can be shortened.
  • the coating process and conditions are not particularly limited, but coating with a coating solution containing a water-soluble resin (X3) is performed on the roll or belt during the formation of the Y layer, followed by hot air drying, hot roll drying, far infrared drying. And a method of drying or solidifying by a known means such as a method of forming a Y layer once, coating with a coating solution containing a water-soluble resin (X3) in a subsequent step, and then drying or solidifying. At that 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 of drying or solidification, the timing, and the like. As drying conditions, a temperature of 30 to 120 ° C. and a time of 3 to 400 seconds are preferable.
  • the multilayer film thus obtained can be uniaxially or biaxially stretched before and after the drying step, if necessary.
  • stretching conditions a temperature of 20 to 120 ° C. and a stretching ratio of 1.05 to 5 times are preferable, and 1.1 to 3 times are more preferable.
  • the residual stress can be reduced by heat fixing the film after stretching.
  • each of the X layer and Y layer is preferably 10 to 90 ⁇ m, more preferably 15 to 80 ⁇ m, further preferably 20 to 80 ⁇ m, more preferably 20 to 80 ⁇ m from the viewpoint of water solubility when each is a film (not a coat layer).
  • 50 ⁇ m is particularly preferable, and may be 25 to 50 ⁇ m.
  • the thickness is preferably 0.05 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, and even more preferably 0.1 to 5 ⁇ m.
  • the total thickness of the hydraulic transfer multilayer base film is preferably 10 to 100 ⁇ m, more preferably 20 to 45 ⁇ m.
  • the moisture content of the entire X-layer, Y-layer, and hydraulic transfer multilayer base film is preferably 1 to 10% by mass, more preferably 1 to 8% by mass, from the viewpoint of the strength of the film. If the moisture content of each layer or the entire multilayer base film for hydraulic transfer is less than 1% by mass, the layer may become brittle or the film may be easily torn. On the other hand, if the moisture content of each layer or the entire multilayer base film for hydraulic transfer exceeds 10% by mass, the film may be stretched during printing, and the printed pattern may be displaced or the multicolor pattern may be lost.
  • the moisture content of each layer can be determined by appropriately adjusting the amount of solvent (water, etc.) in producing the X layer and Y layer or the aforementioned PVA coating solution, the drying conditions after film formation or coating, and the like. it can.
  • either the X layer or the Y layer may be a printed surface, but when the X layer is an X1 layer, the PVA used has a low degree of saponification. Is preferable from the viewpoint of reducing the occurrence of curling, which will be described later, and facilitating cleaning of the subject after transfer, and the Y layer is preferably the printing surface. Even when the X layer is an X2 layer or an X3 layer, the Y layer is preferably the printing surface from the viewpoints of reducing the occurrence of curling, which will be described later, and facilitating cleaning of the transfer target.
  • the printing surface is embossed or a slip agent such as starch or silica is previously contained in the layer.
  • a slip agent such as starch or silica
  • an embossing method for example, a hydraulic transfer between a rubber roll having a general hardness of A10 to 100 (JIS K 6301) and a metal roll having an embossed surface and a surface temperature set to 10 to 150 ° C.
  • the multilayer base film may be processed by traveling at a speed of 5 to 50 m / min.
  • the content of the slip agent is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to each layer. Either the embossing method or the slip agent-containing method may be employed, or both may be used in combination.
  • the hydraulic transfer multilayer base film of the present invention thus obtained can be made into a hydraulic transfer film by printing on one surface thereof, for example, non-coated on the X layer or Y layer (preferably Y layer) surface.
  • a hydraulic transfer film can be obtained by printing a picture pattern or characters with water-soluble ink or the like. This hydraulic transfer film floats on the water surface with the printing layer up, sprays the ink activator on the printing surface as necessary, presses the transferred material from above, and sufficiently adheres the printed layer to the surface of the transferred material
  • the X layer and the Y layer are removed with water or the like, dried, and then coated with a protective film such as an acrylic resin to obtain a product printed on the surface.
  • Printing methods include gravure printing, screen printing, offset printing, roll coating, and the like.
  • the printing may be performed directly on the multilayer base film for hydraulic transfer, or may be once printed on another film and re-transferred to the multilayer base film for hydraulic transfer.
  • Examples of the material to be transferred include a structure having a flat surface and a structure having a curved surface (curved surface structure).
  • the hydraulic transfer film of the present invention is extremely useful for transferring a curved structure.
  • the hydraulic transfer film obtained by using the multilayer base film for hydraulic transfer having the X3 layer is particularly useful for transferring a curved structure requiring a wide range of transferable time.
  • the curved surface means a spherical surface, an undulating surface, a three-dimensional surface with unevenness, or the like.
  • wood base materials such as wood board, plywood and particle board; various plastic molded products; cement products such as pulp cement, slate board, glass fiber reinforced cement and concrete board; gypsum board and calcium silicate board And inorganic products such as magnesium silicate; metal products such as iron, steel, copper, aluminum and alloys, and glass products.
  • the water pressure transfer film of the present invention is excellent in the property of clinging to the transfer material without being broken by the film softened by water absorption on the surface of the water.
  • the clinging property is evaluated by the method described in Examples described later, and is preferably 8 cm or more, more preferably 10 cm or more.
  • the hydraulic transfer film of the present invention has little dimensional change and little curl when it floats on the water surface.
  • the maximum curl length (the maximum curl length in the width direction measured using a film having a length of 35 cm and a width of 25 cm) determined by the method described in Examples described later is preferably used. 0.2 to 8 cm, and more preferably 0.4 to 6 cm.
  • the maximum curl length is equal to or less than the above upper limit, loss due to a decrease in the transfer effective area is reduced.
  • the maximum curl length is equal to or more than the above lower limit because the film edge is prevented from expanding due to slight curl of the film floating on the water surface, and printing blur is reduced.
  • the maximum curl length can be adjusted by satisfying the above formulas (1) to (6), or by appropriately selecting the stretching conditions, the drying conditions, etc. during the production of the above-mentioned multilayer base film for hydraulic transfer. .
  • the effective width of the print pattern that can be used for hydraulic transfer is reduced by curling the hydraulic transfer film, and further, the curl of the printed pattern at the end is distorted by the curl, so it is smaller than the part that is not actually curled.
  • the effective width of the hydraulic transfer film varies depending on the width of the film to be used, but the effective width determined by the method described in the examples described later is preferably 60% or more, more preferably 70% or more. It is.
  • the transfer start time is the time when the hydraulic transfer film absorbs water on the surface of the water and is sufficiently softened.
  • the transfer is normally carried out by pressing the transfer target to a height of 8 cm from the bottom. For example, in the case of a film having a thickness of 30 ⁇ m, in many cases, it is about 40 seconds at a water temperature of 30 ° C. If the time for floating the hydraulic transfer film on the surface of the water is shorter than this, water absorption of the film is insufficient, and it tends to remain hard and difficult to stretch.
  • the hydraulic transfer film of the present invention is a multilayer film having an X layer and a Y layer, it is easy to adjust the solubility without impairing other physical properties as compared with the case of a single layer film.
  • an X layer containing PVA (PX1), PVA (PX2), or a water-soluble resin (X3) having lower solubility than PVA (PY) constituting the Y layer is laminated on the Y layer.
  • PX1 PVA
  • PX2 PVA
  • X3 water-soluble resin
  • the omission of printing was determined according to the following criteria. There is a 1mm 2 or more print missing without There is no 1mm 2 or more print missing in ⁇ 50cm ⁇ 50cm in ⁇ 50cm ⁇ 50cm in
  • the printed circular film is floated in a water tank and waited for 1 minute, 26 parts by mass of butyl cellosolve acetate, 26 parts by mass of butyl carbitol acetate, 8 parts by mass of butyl methacrylate polymer, 20 parts by mass of butyl phthalate and 20 parts by mass of barium sulfate.
  • the ink activator consisting of the above mixture was sprayed at 10 to 15 g per 1 m 2 of the film, and the transfer was carried out with the bottom of the cylinder of the transfer body down and submerged at the center of the film at a speed of 20 cm / min. The point at which printing was interrupted as the film dissolved or was cut was observed, and the distance from the bottom of the cup to that point was measured. The same measurement was performed 5 times, and the average value was taken.
  • the film was floated on water, and the film was curled. After 10 seconds, before the film began to swell, the width of the most curled portion at the center of the film was measured. The same measurement was performed 5 times, the average value was taken, and the value was subtracted from the original film width of 25 cm to obtain the maximum curl length (maximum curl length in the width direction measured using a film of length 35 cm ⁇ width 25 cm). ).
  • Width effective rate (W / 25) ⁇ 100
  • Transferable time (start time and limit time)
  • start time and limit time The above-mentioned clinging ability is measured by changing the time from when the film is floated to the water tank until it is transferred, and the pattern is accurately transferred from the bottom of the cup to a height of 8 cm without wrinkling or tearing the film. This time was defined as the transfer start time.
  • the time when the clinging property becomes 8 cm is set as the limit time for transfer.
  • Example 1 An aqueous solution (liquid Y) containing 15 parts by mass of PVA and 0.65 parts by mass of glycerin having a saponification degree of 88 mol%, a degree of polymerization of 1700, and a complete dissolution time of 24 seconds in water at 20 ° C., on a conveyor belt. And dried for 5 minutes while applying hot air at 120 ° C. on the belt to obtain a film (Y layer) having a thickness of 30.2 ⁇ m, a width of 60 cm, and a length of 1050 m. The moisture content of this film was 3.0% by mass, and the glycerin content was 4.0% by mass.
  • a gravure roll having a gravure width of 54 cm is prepared by using, as a coating liquid (solution X), an aqueous solution having a saponification degree of 94 mol%, a polymerization degree of 2000, and PVA having a complete dissolution time of 51 seconds in 20 ° C.
  • the above film was coated at a rate of 15 m / min using 1 and immediately dried with hot air at 100 ° C. for 30 seconds to obtain a multilayer film having a coating layer (layer X) having a thickness of 1.9 ⁇ m.
  • the moisture content of this multilayer film was 3.1% by mass.
  • Both ends of this multilayer film are cut off by 5 cm each with a slitting device so as to have a width of 50 cm and a length of 1000 m, and a winding tension of 15 kg / m is wound on a cylindrical paper tube having an outer diameter of 88.2 mm whose surface is processed with polyethylene.
  • the film was continuously wound up under conditions of a take-up speed of 40 m / min and a touch roll pressure of 3 kg / m 2 to obtain a roll-shaped multilayer base film for hydraulic transfer.
  • Example 2 The thickness of the PVA used in the coating liquid (liquid X) was 2 in the same manner as in Example 1 except that PVA having a saponification degree of 96 mol%, a polymerization degree of 1000, and a complete dissolution time of 450 seconds in water at 20 ° C. was used. A multilayer film having a coating layer (X layer) of 1 ⁇ m was obtained. The moisture content of this multilayer film was 3.2% by mass. Moreover, when the swelling degree was calculated
  • Example 3 A thickness of 32.6 ⁇ m, a width of 60 cm, and a length of 1050 m were obtained in the same manner as in Example 1, except that boric acid was added to the Y liquid of Example 1 so that the concentration was 0.15% by mass. Film (Y layer) was obtained. The moisture content of this film was 3.2% by mass, the glycerin content was 4.0% by mass, and the boric acid content was 0.9% by mass.
  • Example 2 a multilayer film having a coat layer (X layer) having a thickness of 2.4 ⁇ m was obtained.
  • the moisture content of this multilayer film was 3.4% by mass.
  • the swelling degree of X layer was 8% and the swelling degree of Y layer was 12%.
  • Example 4 As a coating solution (solution X), a solution obtained by adding silica having an average particle diameter of 6.6 ⁇ m (“NIPGEL0063” manufactured by Tosoh) to 0.4 mass% to the solution X in Example 1 Obtained a multilayer film having a coating layer (X layer) having a thickness of 2.8 ⁇ m in the same manner as in Example 1.
  • the charged amount (content) of silica with respect to the total solid content of the coating liquid (liquid X) was 3.1% by mass.
  • the moisture content of this multilayer film was 3.2% by mass.
  • Example 5 As the coating liquid (X liquid), a thickness of 2. was obtained in the same manner as in Example 3, except that boric acid was added to the X liquid of Example 3 so that the concentration was 0.15% by mass. A multilayer film having a 6 ⁇ m coat layer (X layer) was obtained. The amount (content) of boric acid charged relative to the total solid content of the coating liquid (liquid X) was 1.2% by mass. The moisture content of this multilayer film was 3.3% by mass. Moreover, when the swelling degree was calculated
  • Example 1 instead of the multilayer film, the film (Y layer) obtained in Example 1 was used as a single layer. In the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from this film (Y layer) and subjected to various evaluations by the methods described above. The results are shown in Tables 1 and 2.
  • Example 2 instead of the multilayer film, the film (Y layer) obtained in Example 3 was used as a single layer. In the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from this film (Y layer) and subjected to various evaluations by the methods described above. The results are shown in Tables 1 and 2.
  • Example 3 Similar to the production of the film (Y layer) in Example 1 except that the coating liquid (X liquid) of Example 1 was used instead of the aqueous solution (Y liquid) of Example 1, the thickness was 31.9 ⁇ m, the width A film (Y layer) having a length of 60 cm and a length of 1050 m was obtained. The moisture content of this film was 2.9% by mass. Subsequently, instead of the multilayer film, the film (Y layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was produced from this film (Y layer) in the same manner as in Example 1. Obtained and subjected to various evaluations by the methods described above. The results are shown in Tables 1 and 2.
  • Example 4 Similar to the production of the film (Y layer) in Example 1, except that the coating liquid (X liquid) of Example 2 was used instead of the aqueous solution (Y liquid) of Example 1, the thickness was 33.1 ⁇ m, the width A film (Y layer) having a length of 60 cm and a length of 1050 m was obtained. The moisture content of this film was 3.4% by mass. Subsequently, instead of the multilayer film, the film (Y layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was produced from this film (Y layer) in the same manner as in Example 1. Obtained and subjected to various evaluations by the methods described above. The results are shown in Tables 1 and 2.
  • Example 5 Similar to the production of the film (Y layer) in Example 1, except that the coating liquid (X liquid) of Example 4 was used instead of the aqueous solution (Y liquid) of Example 1, the thickness was 30.7 ⁇ m, the width A film (Y layer) having a length of 60 cm and a length of 1050 m was obtained. The moisture content of this film was 2.9% by mass, and the silica content was 3.1% by mass. Subsequently, instead of the multilayer film, the film (Y layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was produced from this film (Y layer) in the same manner as in Example 1. Obtained and subjected to various evaluations by the methods described above. The results are shown in Tables 1 and 2.
  • Resin emulsion containing 1700 PVA as a dispersant concentration of styrene-methyl methacrylate copolymer 1 mass%, saponification degree 88 mol% as binder, PVA density 1750 mass%, total solid content 2 (Mass%) was used in the same manner as in Example 1 to obtain a multilayer film having a coating layer (X layer) having a thickness of 1.8 ⁇ m.
  • the moisture content of this multilayer film was 3.3% by mass.
  • Example 7 A PVA concentration of 15 mass% aqueous solution (Y liquid) containing 70 mass% of saponification, polymerization degree of 1700, PVA of 15 parts by mass in water of 20 ° C. and a dissolution time of 35 seconds and 0.65 parts by mass of glycerin was used.
  • Example 2 a multilayer film having a coat layer (X layer) having a thickness of 2.2 ⁇ m was obtained.
  • the moisture content of this multilayer film was 3.0% by mass.
  • the swelling degree of X layer was 8% and the swelling degree of Y layer was 28%.
  • Example 8 A PVA concentration of 15% by mass aqueous solution (Y liquid) containing PVA of 15 parts by mass with a saponification degree of 88 mol%, a degree of polymerization of 100, and a complete dissolution time of 20 seconds in water at 20 ° C. and 0.65 part by mass of glycerin.
  • Example 2 a multilayer film having a coat layer (X layer) having a thickness of 2.4 ⁇ m was obtained.
  • the moisture content of this multilayer film was 3.1% by mass.
  • the swelling degree of X layer was 5% and the swelling degree of Y layer was 36%.
  • Example 9 The thickness of the PVA used in the coating liquid (X liquid) was the same as in Example 1 except that PVA having a saponification degree of 94 mol%, a polymerization degree of 3000, and a complete dissolution time of 105 seconds in water at 20 ° C. was used. A multilayer film having a coating layer (X layer) of 6 ⁇ m was obtained. The moisture content of this multilayer film was 3.5% by mass. Moreover, when the swelling degree was calculated
  • Example 6 An aqueous solution (Y liquid) containing 15 parts by mass of PVA having a saponification degree of 88 mol%, a degree of polymerization of 2000, and a complete dissolution time of 29 seconds in water at 30 ° C. and 0.65 parts by mass of glycerin, having a PVA concentration of 15% by mass on the conveyor belt. And dried for 5 minutes while applying hot air of 120 ° C. on the belt to obtain a film (Y layer) having a thickness of 30.4 ⁇ m, a width of 60 cm, and a length of 1050 m. The moisture content of this film was 3.1 mass%, and glycerin content was 4.0 mass%.
  • the range of 100 ⁇ m 2 in cross section of the coating layer (X layer) of this multilayer film is observed with an electron microscope, the longest diameter and the shortest diameter of one silica particle are determined with an accuracy of 0.1 ⁇ m, both are simply averaged, The particle diameter was taken. Similarly, the particle diameter was determined for all particles observed, and the same operation was repeated while changing the observation point, and the particle diameters of all particles observed at a total of 10 observation points were determined. Of these, the average particle size was calculated by simply averaging the particles having a particle size of 0.2 ⁇ m or more, and it was 6.2 ⁇ m. Further, the surface roughness (Ra) of the coat layer (X layer) measured by JIS B0601 was 1.2 ⁇ m. Furthermore, the moisture content of the multilayer film was 3.3% by mass. These results are shown in Table 3.
  • Both ends of this multilayer film are cut off by 5 cm each with a slitting device so as to have a width of 50 cm and a length of 1000 m, and a winding tension of 15 kg / m is wound on a cylindrical paper tube having an outer diameter of 88.2 mm whose surface is processed with polyethylene.
  • the film was continuously wound up under conditions of a take-up speed of 40 m / min and a touch roll pressure of 3 kg / m 2 to obtain a roll-shaped multilayer base film for hydraulic transfer.
  • Example 7 An aqueous solution having a PVA concentration of 15% by mass, containing 15 parts by mass of PVA having a saponification degree of 96 mol%, a polymerization degree of 1700, a complete dissolution time of 63 seconds in water at 30 ° C., and 0.65 parts by mass of glycerin as the coating liquid (X liquid)
  • silica having an average particle diameter of 6.6 ⁇ m (“NIPGEL0063” manufactured by Tosoh Corporation) was added so as to be 0.53% by mass, a thickness of 1.9 ⁇ m was used.
  • a multilayer film having a coat layer (X layer) was obtained.
  • the charged amount (content) of silica with respect to the total solid content of the coating liquid (liquid X) was 3.3% by mass.
  • the average particle size of silica in the coat layer (X layer) and the surface roughness (Ra) of the coat layer (X layer) were measured in the same manner as in Example 6, the average particle size was 6.0 ⁇ m.
  • the surface roughness was 0.9 ⁇ m.
  • the moisture content of this multilayer film was 2.8 mass%.
  • Example 8 A mixture of PVA having a saponification degree of 88 mol% and a polymerization degree of 2000, and PVA having a saponification degree of 96 mol% and a polymerization degree of 1700 in a mass ratio of 90/10 instead of the aqueous solution (Y liquid) of Example 6 ( The film in Example 6 (Y layer), except that an aqueous solution (Y liquid) having a PVA concentration of 15% by mass containing 15 parts by mass and 0.65 parts by mass of glycerin was used. ) To obtain a film (Y layer) having a thickness of 31.1 ⁇ m, a width of 60 cm, and a length of 1050 m. The moisture content of this film was 2.9% by mass, and the glycerin content was 4.3% by mass.
  • a coating solution (solution X)
  • a PVA concentration of 15% by mass containing 88 parts by mole of saponification 15 parts by weight of PVA having a complete dissolution time of 24 seconds in water at a polymerization degree of 1700 and 30 ° C., and 0.65 parts by weight of glycerin.
  • silica having an average particle size of 6.6 ⁇ m (“NIPGEL0063” manufactured by Tosoh Corporation) was added to the aqueous solution in an amount of 0.53% by mass was used.
  • NIPGEL0063 manufactured by Tosoh Corporation
  • the charged amount (content) of silica with respect to the total solid content of the coating liquid (liquid X) was 3.3% by mass.
  • the average particle diameter of silica in the coat layer (X layer) and the surface roughness (Ra) of the coat layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 5.8 ⁇ m.
  • the surface roughness was 1.7 ⁇ m.
  • the moisture content of this multilayer film was 3.3 mass%.
  • Example 9 The thickness was 30.4 ⁇ m, the width was 60 cm, and the length was 1050 m, except that the Y solution of Example 6 was added with boric acid added to a concentration of 0.05% by mass. Film (Y layer) was obtained. The moisture content of this film was 2.7% by mass, the glycerin content was 3.8% by mass, and the boric acid content was 0.3% by mass.
  • a coating solution (solution X)
  • a PVA concentration of 15% by mass containing 94 parts by mass of PVA having a saponification degree of 94 mol%, a polymerization degree of 2000, and a complete dissolution time of 51 seconds in water at 30 ° C. and 0.65 parts by mass of glycerin.
  • silica having an average particle size of 6.6 ⁇ m (“NIPGEL0063” manufactured by Tosoh Corporation) was added to the aqueous solution in an amount of 0.53% by mass was used.
  • NIPGEL0063 manufactured by Tosoh Corporation
  • the charged amount (content) of silica with respect to the total solid content of the coating liquid (liquid X) was 3.3% by mass.
  • the average particle diameter of silica in the coat layer (X layer) and the surface roughness (Ra) of the coat layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 6.1 ⁇ m.
  • the surface roughness was 1.1 ⁇ m.
  • the moisture content of this multilayer film was 2.8 mass%.
  • Example 10 The same procedure as in Example 6 was used except that the Y liquid of Example 6 was used by adding silica having an average particle size of 6.6 ⁇ m (“NIPGEL0063” manufactured by Tosoh Corporation) to a concentration of 0.3 mass%. Thus, a film (Y layer) having a thickness of 30.4 ⁇ m, a width of 60 cm, and a length of 1050 m was obtained. The moisture content of this film was 3.3% by mass, the glycerin content was 4.1% by mass, and the silica content was 1.9% by mass.
  • silica having an average particle size of 6.6 ⁇ m (“NIPGEL0063” manufactured by Tosoh Corporation)
  • Example 8 a multilayer film having a coat layer (X layer) having a thickness of 2.0 ⁇ m was obtained.
  • the average particle diameter of silica in the coat layer (X layer) and the surface roughness (Ra) of the coat layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 5.7 ⁇ m.
  • the surface roughness was 0.7 ⁇ m.
  • the moisture content of this multilayer film was 3.1 mass%.
  • Example 11 In the same manner as in Example 6 except that polyoxyethylene polyoxypropylene ether was added as a surfactant to the Y liquid of Example 6 so as to have a concentration of 0.4% by mass, the thickness was 29. A film (Y layer) having a thickness of 1 ⁇ m, a width of 60 cm, and a length of 1050 m was obtained. The moisture content of this film was 3.0% by mass, the glycerin content was 4.0% by mass, and the surfactant content was 2.5% by mass.
  • Example 6 the coating liquid (X liquid) was added to the X liquid of Example 6 with a polyoxyethylene polyoxypropylene ether added as a surfactant to a concentration of 0.4% by mass.
  • a multilayer film having a coat layer (X layer) having a thickness of 2.2 ⁇ m was obtained.
  • the amount (content) of silica charged with respect to the total solid content of the coating liquid (solution X) was 3.2% by mass, and the amount (content) of surfactant was 2.4% by mass.
  • Example 12 In the coating solution (solution X), a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 6 except that talc (“P-4” manufactured by Nippon Talc Co., Ltd.) having an average particle size of 4.5 ⁇ m was added instead of silica. A multilayer film having a coating layer (X layer) was obtained. The amount of talc charged (content) with respect to the total solid content of the coating liquid (liquid X) was 3.3% by mass. With respect to this multilayer film, the average particle size of talc in the coat layer (X layer) and the surface roughness (Ra) of the coat layer (X layer) were measured in the same manner as in Example 6. As a result, the average particle size was 4.5 ⁇ m.
  • Example 10 instead of the multilayer film, the film (Y layer) obtained in Example 6 was used as a single layer. With respect to this film, the surface roughness (Ra) was measured in the same manner as in Example 6. As a result, it was 0.08 ⁇ m. These results are shown in Table 3. Subsequently, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from this film (Y layer) and subjected to various evaluations by the above-described methods. The results are shown in Table 4.
  • Resin emulsion containing 1700 PVA as a dispersant concentration of styrene-methyl methacrylate copolymer 1 mass%, saponification degree 88 mol% as binder, PVA density 1750 mass%, total solid content 2
  • a multilayer film having a coating layer (X layer) having a thickness of 2.8 ⁇ m was obtained in the same manner as in Example 6 except that (mass%) was used.
  • the surface roughness (Ra) of the coating layer (X layer) was measured in the same manner as in Example 6. As a result, it was 2.2 ⁇ m.
  • the moisture content of this multilayer film was 3.2 mass%.
  • Example 12 Similar to the production of the film (Y layer) in Example 6, except that the coating liquid (X liquid) of Example 6 was used instead of the aqueous solution (Y liquid) of Example 6, the thickness was 29.0 ⁇ m, the width A film (Y layer) having a length of 60 cm and a length of 1050 m was obtained. The moisture content of this film was 2.7% by mass, and the glycerin content was 3.9% by mass. Moreover, when the average particle diameter and surface roughness (Ra) of the silica were measured in the same manner as in Example 6, the average particle diameter was 6.0 ⁇ m and the surface roughness was 1.0 ⁇ m. These results are shown in Table 3.
  • Example 13 A PVA concentration of 15 mass% aqueous solution (liquid Y) containing 70 mass% of saponification, polymerization degree of 1700, 15 mass parts of PVA with a complete dissolution time of 35 seconds in water at 30 ° C., and 0.65 mass parts of glycerin was used.
  • Example 6 except that the above-mentioned film was used as the Y layer, and glass powder having an average particle size of 21.8 ⁇ m (“N powder” manufactured by Nissho Material) was added instead of silica in the coating liquid (X liquid).
  • glass powder having an average particle size of 21.8 ⁇ m (“N powder” manufactured by Nissho Material) was added instead of silica in the coating liquid (X liquid).
  • a multilayer film having a coat layer (X layer) having a thickness of 4.5 ⁇ m was obtained.
  • the charged amount (content) of the glass powder with respect to the total solid content of the coating liquid (liquid X) was 3.3% by mass.
  • the average particle diameter of the glass powder in the coat layer (X layer) and the surface roughness (Ra) of the coat layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 21.
  • pulverized bentonite “Super Clay” manufactured by Hojun Co., Ltd. average particle size 1.2 ⁇ m, measured by HORIBA particle size analyzer LA920
  • a multilayer film having a coating layer (X layer) having a thickness of 2.8 ⁇ m was obtained.
  • the amount (content) of bentonite with respect to the total solid content of the coating liquid (liquid X) was 3.3% by mass.
  • the average particle diameter of bentonite in the coat layer (X layer) and the surface roughness (Ra) of the coat layer (X layer) were measured in the same manner as in Example 6.
  • Example 13 An aqueous solution (Y liquid) having a PVA concentration of 15% by mass and containing 15 parts by mass of PVA having a saponification degree of 88 mol%, a polymerization degree of 1700, and a complete dissolution time of 22 seconds in water at 20 ° C. and 0.65 parts by mass of glycerin on a conveyor belt. And dried for 5 minutes while applying hot air at 120 ° C. on the belt to obtain a film (Y layer) having a thickness of 30.2 ⁇ m, a width of 60 cm, and a length of 1050 m. The moisture content of this film was 3.0% by mass, and the glycerin content was 4.0% by mass.
  • aqueous solution having a concentration of 7% by mass of water-soluble cellulose “CMC (carboxymethylcellulose) Daicel 1160” manufactured by Daicel Chemical Industries, Ltd. with a complete dissolution time of 80 seconds in water at 20 ° C. is used as a coating solution (solution X).
  • the film was coated at a rate of 15 m / min using a gravure roll having a width of 54 cm, and immediately dried with hot air at 100 ° C. for 30 seconds to obtain a multilayer film.
  • the average thickness of the coat layer (X layer) was 2.1 ⁇ m.
  • the surface roughness (Ra) of the coat layer (X layer) measured by JIS B0601 was 1.4 ⁇ m.
  • the moisture content of this multilayer film was 3.0 mass%.
  • Both ends of this multilayer film are cut off by 5 cm each with a slitting device so as to have a width of 50 cm and a length of 1000 m, and a winding tension of 15 kg / m is wound on a cylindrical paper tube having an outer diameter of 88.2 mm whose surface is processed with polyethylene.
  • the film was continuously wound up under conditions of a take-up speed of 40 m / min and a touch roll pressure of 3 kg / m 2 to obtain a roll-shaped multilayer base film for hydraulic transfer.
  • Example 14 As a water-soluble cellulose used in the coating liquid (liquid X), a water-soluble cellulose “Metroses 6-SH-50” (hydroxypropylmethylcellulose, HPMC) manufactured by Shin-Etsu Chemical Co., Ltd. with a complete dissolution time of 70 seconds in water at 20 ° C. is used.
  • a multilayer film was obtained in the same manner as in Example 13 except that it was used. When the cross section of this multilayer film was observed with a microscope, the average thickness of the coat layer (X layer) was 1.9 ⁇ m. Further, the surface roughness (Ra) of the coat layer (X layer) measured by JIS B0601 was 0.9 ⁇ m. Furthermore, the moisture content of this multilayer film was 3.1 mass%. These results are shown in Table 5. Subsequently, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from this multilayer film, and subjected to various evaluations by the above-described methods. The results are shown in Table 6.
  • Example 15 A thickness of 32.6 ⁇ m, a width of 60 cm, and a length of 1050 m were obtained in the same manner as in Example 13 except that boric acid was added to the Y solution of Example 13 to a concentration of 0.15% by mass. Film (Y layer) was obtained. The moisture content of this film was 3.2% by mass, the glycerin content was 4.0% by mass, and the boric acid content was 0.9% by mass.
  • Example 13 a multilayer film was obtained in the same manner as in Example 13.
  • the average thickness of the coating layer (X layer) was 2.4 ⁇ m.
  • the surface roughness (Ra) of the coat layer (X layer) measured by JIS B0601 was 1.3 ⁇ m.
  • the moisture content of this multilayer film was 3.4% by mass.
  • Example 16 Example 13 except that silica having an average particle size of 6.6 ⁇ m (“NIPGEL0063” manufactured by Tosoh Corporation) was added to the X solution of Example 13 so that the concentration was 0.4% by mass. In the same manner, a multilayer film was obtained. The charged amount (content) of silica with respect to the total solid content of the coating liquid (liquid X) was 5.2% by mass.
  • the range of 100 ⁇ m 2 in cross section of the coating layer (X layer) of this multilayer film is observed with an electron microscope, the longest diameter and the shortest diameter of one silica particle are determined with an accuracy of 0.1 ⁇ m, both are simply averaged, The particle diameter was taken. Similarly, the particle diameter was determined for all particles observed, and the same operation was repeated while changing the observation point, and the particle diameters of all particles observed at a total of 10 observation points were determined. Of these, the average particle size was calculated by simply averaging the particles having a particle size of 0.2 ⁇ m or more, and it was 6.1 ⁇ m.
  • Example 15 instead of the multilayer film, the film (Y layer) obtained in Example 13 was used as a single layer.
  • a printed material hydroaulic transfer film was obtained from this film and subjected to various evaluations by the methods described above. The results are shown in Table 6.
  • the film (Y layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was obtained from this film (Y layer) in the same manner as in Example 13. Obtained and subjected to various evaluations by the methods described above. This film was easily broken during printing and was difficult to handle. Also, in transfer, dissolution was insufficient in 1 minute, and it was necessary to hold for a long time in order to obtain cohesion. The results are shown in Table 6.
  • Example 17 Similar to the production of the film (Y layer) in Example 13, except that the coating liquid (Liquid X) in Example 14 was used instead of the aqueous solution (Y liquid) in Example 13, the thickness was 27.8 ⁇ m, the width A film (Y layer) having a length of 60 cm and a length of 1050 m was obtained. The moisture content of this film was 2.8% by mass. Moreover, the surface roughness (Ra) of this film measured by JIS B0601 was 1.4 micrometers. These results are shown in Table 5.
  • the film (Y layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was obtained from this film (Y layer) in the same manner as in Example 13. Obtained and subjected to various evaluations by the methods described above. This film was easily broken during printing and was difficult to handle. Also, in transfer, dissolution was insufficient in 1 minute, and it was necessary to hold for a long time in order to obtain cohesion. The results are shown in Table 6.
  • Example 18 instead of the multilayer film, the film (Y layer) obtained in Example 15 was used as a single layer.
  • the multilayer base film for hydraulic transfer and the hydraulic transfer film of the present invention have good printability and are less likely to curl when floated on the water surface, and are particularly useful for transferring curved structures.

Landscapes

  • Decoration By Transfer Pictures (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte à un film de base à couches multiples pour transfert hydraulique, qui présente une bonne imprimabilité. L'invention se rapporte également à un film de transfert hydraulique qui ne se gondole pas facilement lorsqu'il flotte sur l'eau. L'invention se rapporte de manière spécifique à un film de base à couches multiples pour transfert hydraulique, qui comprend une couche X sélectionnée parmi les couches X1-X3 spécifiées ci-dessous, et une couche Y contenant un alcool polyvinylique soluble dans l'eau (PY). L'invention se rapporte également de manière spécifique à un film de transfert hydraulique obtenu par la réalisation d'une impression sur une surface du film de base à couches multiples pour transfert hydraulique. Couche X1 : une couche contenant un alcool polyvinylique soluble dans l'eau (PX1), à condition que le degré de saponification et le degré de polymérisation de l'alcool polyvinylique soluble dans l'eau (PX1) et le degré de saponification et le degré de polymérisation de l'alcool polyvinylique soluble dans l'eau (PY) dans la couche Y répondent à une relation spécifique. Couche X2 : une couche contenant un alcool polyvinylique soluble dans l'eau (PX2) et des particules inorganiques ayant un diamètre de particule moyen de 2 à 20 μm. Couche X3 : une couche contenant au moins une résine soluble dans l'eau (X3) sélectionnée dans un groupe constitué par des polysaccharides et des résines acryliques.
PCT/JP2010/050075 2009-01-13 2010-01-07 Film de base à couches multiples pour transfert hydraulique WO2010082522A1 (fr)

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JP2012139846A (ja) * 2010-12-28 2012-07-26 Nippon Synthetic Chem Ind Co Ltd:The 転写印刷用積層体
CN104999822A (zh) * 2015-07-02 2015-10-28 嘉善宏瑞包装材料有限公司 Pva水转印膜的制备方法
CN105038054A (zh) * 2015-07-02 2015-11-11 嘉善宏瑞包装材料有限公司 水转印膜
WO2016204133A1 (fr) * 2015-06-15 2016-12-22 株式会社クラレ Film de base pour transfert hydraulique
WO2020138445A1 (fr) 2018-12-28 2020-07-02 株式会社クラレ Film de base de transfert hydraulique et film d'impression par transfert hydraulique

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US20160107427A1 (en) * 2014-10-21 2016-04-21 American Hydrographics Film for printed hydrographics and methods of making and using the same

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JP2003011590A (ja) * 2001-07-04 2003-01-15 Nippon Synthetic Chem Ind Co Ltd:The 転写印刷用ベースフィルム
JP2003094895A (ja) * 2001-09-26 2003-04-03 Kuraray Co Ltd 水圧転写用フィルムおよび水圧転写用印刷フィルムの製造法
JP2009001009A (ja) * 2007-05-22 2009-01-08 Nippon Synthetic Chem Ind Co Ltd:The 液圧転写印刷用ベースフィルム、液圧転写印刷用ベースフィルムの製造方法および液圧転写方法

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JP2003011590A (ja) * 2001-07-04 2003-01-15 Nippon Synthetic Chem Ind Co Ltd:The 転写印刷用ベースフィルム
JP2003094895A (ja) * 2001-09-26 2003-04-03 Kuraray Co Ltd 水圧転写用フィルムおよび水圧転写用印刷フィルムの製造法
JP2009001009A (ja) * 2007-05-22 2009-01-08 Nippon Synthetic Chem Ind Co Ltd:The 液圧転写印刷用ベースフィルム、液圧転写印刷用ベースフィルムの製造方法および液圧転写方法

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JP2012139846A (ja) * 2010-12-28 2012-07-26 Nippon Synthetic Chem Ind Co Ltd:The 転写印刷用積層体
WO2016204133A1 (fr) * 2015-06-15 2016-12-22 株式会社クラレ Film de base pour transfert hydraulique
CN107635791A (zh) * 2015-06-15 2018-01-26 株式会社可乐丽 液压转印用基膜
JPWO2016204133A1 (ja) * 2015-06-15 2018-04-05 株式会社クラレ 液圧転写用ベースフィルム
US10576777B2 (en) 2015-06-15 2020-03-03 Kuraray Co., Ltd. Hydraulic transfer printing base film
CN104999822A (zh) * 2015-07-02 2015-10-28 嘉善宏瑞包装材料有限公司 Pva水转印膜的制备方法
CN105038054A (zh) * 2015-07-02 2015-11-11 嘉善宏瑞包装材料有限公司 水转印膜
CN104999822B (zh) * 2015-07-02 2017-03-08 嘉善宏瑞包装材料有限公司 Pva水转印膜的制备方法
WO2020138445A1 (fr) 2018-12-28 2020-07-02 株式会社クラレ Film de base de transfert hydraulique et film d'impression par transfert hydraulique

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TWI472431B (zh) 2015-02-11
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TW201437020A (zh) 2014-10-01
JP5442878B2 (ja) 2014-03-12

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