WO2010061790A1 - Procédé de fabrication d'un film de transfert hydraulique - Google Patents

Procédé de fabrication d'un film de transfert hydraulique Download PDF

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Publication number
WO2010061790A1
WO2010061790A1 PCT/JP2009/069706 JP2009069706W WO2010061790A1 WO 2010061790 A1 WO2010061790 A1 WO 2010061790A1 JP 2009069706 W JP2009069706 W JP 2009069706W WO 2010061790 A1 WO2010061790 A1 WO 2010061790A1
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Prior art keywords
film
layer
water
hydraulic transfer
printing
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Ceased
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PCT/JP2009/069706
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English (en)
Japanese (ja)
Inventor
英晶 小田
孝徳 磯▲ざき▼
修 風藤
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2010502100A priority Critical patent/JP5290274B2/ja
Publication of WO2010061790A1 publication Critical patent/WO2010061790A1/fr
Anticipated expiration legal-status Critical
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    • 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

Definitions

  • the present invention relates to a method for producing a hydraulic transfer film.
  • a water-soluble polyvinyl alcohol film (hereinafter, polyvinyl alcohol film may be abbreviated as PVA film, and the raw material polyvinyl alcohol is PVA).
  • the water pressure transfer film obtained by printing on one side of the base film is floated on the water surface with the printing surface up, and the structure is pressed from above to utilize the water pressure.
  • a hydraulic transfer method for transferring a printing surface to a structure surface There is known a hydraulic transfer method for transferring a printing surface to a structure surface.
  • the PVA single-layer base film absorbs moisture in the atmosphere when printing the pattern and generates elongation, which may cause multicolor pattern shift. This phenomenon can be alleviated by lowering the temperature and humidity of the environment. However, when the temperature and humidity are lowered too much, another problem that the film becomes brittle and cuts is brought to the surface. Therefore, when a PVA single-layer base film is used, high-precision printing is difficult.
  • the use of ink containing water may be preferred for reasons such as having little influence on the environment.
  • the PVA single layer is formed by the water contained in the ink. Since the base film swells, the film is stretched before drying, resulting in the same problem (multicolor pattern misalignment) as when moisture in the atmosphere is absorbed. Further, in drying the ink after printing, it is necessary to dry at a low temperature in order to suppress the occurrence of elongation, and thus there is a problem that the printing speed cannot be increased.
  • a base film wound in a roll shape film roll
  • environmental moisture adheres to the end face of the film roll.
  • the base films are welded together (blocking), and the base film is cut when unwound.
  • a multilayer hydraulic transfer film in which a resin fine particle emulsion containing PVA as a dispersant is applied to a water-soluble PVA film and printed thereon is also known (Patent Document 1).
  • Patent Document 1 A multilayer hydraulic transfer film in which a resin fine particle emulsion containing PVA as a dispersant is applied to a water-soluble PVA film and printed thereon is also known.
  • Patent Document 1 A multilayer hydraulic transfer film in which a resin fine particle emulsion containing PVA as a dispersant is applied to a water-soluble PVA film and printed thereon is also known.
  • the present invention solves the above-mentioned problems of the prior art, and provides a method for producing a hydraulic transfer film capable of performing high-precision, high-definition printing at high speed on a base film using ink containing moisture.
  • the purpose is to do.
  • the present inventors have achieved the above object by using a multilayer base film for hydraulic transfer including a water-soluble PVA (X) layer and a moisture resistant resin (Y) layer.
  • a multilayer base film for hydraulic transfer including a water-soluble PVA (X) layer and a moisture resistant resin (Y) layer.
  • X water-soluble PVA
  • Y moisture resistant resin
  • the present invention prints on a water-soluble PVA (X) layer of a multilayer base film for hydraulic transfer including a water-soluble PVA (X) layer and a moisture-resistant resin (Y) layer using an ink containing moisture.
  • the present invention relates to a method for producing a hydraulic transfer film.
  • the water-soluble PVA (X) layer contains 0.01 to 3% by weight of a crosslinking agent.
  • the crosslinking agent is more preferably a boron compound.
  • the moisture resistant resin (Y) is preferably at least one resin selected from the group consisting of a polyester resin and a polyolefin resin.
  • the 90 ° interlayer adhesive strength (JIS K6854-3) between the water-soluble PVA (X) layer and the moisture-resistant resin (Y) layer at 20 ° C. and 65% RH is 0. It is preferably 001 to 0.1 N / cm.
  • the printing is preferably performed by an ink jet method.
  • the water content of the ink containing water is preferably 0.5 to 80% by weight.
  • the film stretches and talmi is not affected even when printed at high temperature and high humidity. Since there are few, there is no generation
  • the film has little stretch and tarnish, and has good dimensional stability, so there is no occurrence of misalignment of multiple colors and high-definition printing is possible. is there. Further, since blocking between the base films due to moisture hardly occurs, loss due to cutting of the base film at the time of unwinding is small, and long roll winding is also possible.
  • the hydraulic transfer film obtained by the production method of the present invention hardly causes curling when it floats on the water surface for transfer, so that there is little loss and deformation of the printing surface is small.
  • the multilayer base film for hydraulic transfer used in the present invention has a water-soluble PVA (X) layer (X layer) and a moisture-resistant resin (Y) layer (Y layer). Since this is particularly important, this point will be described first.
  • the PVA used for the X layer in the present invention is water-soluble.
  • water-soluble means that the complete dissolution time in water at 20 ° C. is 500 seconds or shorter, preferably 300 seconds or shorter.
  • the minimum of complete dissolution time Preferably it is 1 second or more, More preferably, it is 2 seconds 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 degree of saponification of the PVA used for the X layer is preferably 75 to 99 mol%, more preferably 80 to 97 mol%.
  • the degree of polymerization is preferably 300 to 2500, and more preferably 400 to 2400.
  • the saponification degree of PVA indicates the proportion of units that are actually saponified to vinyl alcohol units among the units that can be converted into vinyl alcohol units by saponification, and is measured according to JIS K6726.
  • the degree of polymerization (Po) is a value measured according to JIS K6726.
  • PVA can be produced by polymerizing a vinyl ester monomer and saponifying the resulting vinyl ester polymer.
  • 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.
  • 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.
  • Other monomers copolymerizable with such vinyl ester monomers include, for example, olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene; acrylic acid and salts thereof; methyl acrylate, Ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.
  • Methacrylic acid and its salts methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodemethacrylate
  • methacrylic acid esters such as octadecyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamidopropyldimethylamine and salts thereof, N-methylolacrylamide and derivatives thereof
  • Methacrylamide derivatives such as methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propyl dimethylamine and salts thereof, N-methylol methacrylamide and derivatives thereof;
  • copolymerizable monomers other than those described above include monomers represented by the following formula (II), N-vinyl-2-pyrrolidones, N-vinyl-2-caprolactams and the like. -Vinylamides.
  • 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.
  • 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, and an isopropyl group
  • the carbon represented by R 2 Examples of the alkyl group of 1 to 5 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group and the like.
  • Examples of the monomer represented by the formula (II) 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.
  • Further preferred other copolymerizable monomers include sulfonic acid group-containing monomers.
  • the sulfonic acid group-containing monomer one containing a sulfonic acid group or a salt thereof in the molecule and copolymerizable with a vinyl ester can be used.
  • 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 other 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.
  • PVA may be used alone or in combination of two or more.
  • blending a water-soluble resin other than PVA with the PVA used for the X layer in the present invention is preferable because it can improve the affinity with the ink and the clinging property during hydraulic transfer in addition to the adjustment of the dissolution behavior.
  • the water-soluble resin include polysaccharides such as starch and cellulose; and water-soluble acrylic resins.
  • 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.
  • 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.
  • water-soluble acrylic resin metal salts, such as polyacrylamide, polyacrylic acid, and its sodium salt, are mentioned.
  • polysaccharides, particularly cellulose is more preferable for achieving the object of the present invention.
  • the viscosity of aqueous solution should just be suitable for formation of the layer mentioned later. Specifically, a 1% by weight aqueous solution having a viscosity of 1 to 10,000 mPa ⁇ s when measured with a B-type viscometer at 20 ° C. is preferable.
  • the water-soluble PVA (X) layer contains a cross-linking agent because transferability can be improved and higher-definition printing can be performed.
  • the content of the crosslinking agent is preferably 0.01 to 3% by weight, and more preferably 0.03 to 2.5% by weight.
  • the content of the crosslinking agent is a value calculated by the following formula (III).
  • Content of crosslinking agent (% by weight) (weight of crosslinking agent in X layer / weight of X layer) ⁇ 100 (III)
  • the crosslinking agent is not particularly limited as long as it causes a crosslinking reaction with PVA, and among them, a boron compound is preferable.
  • a boron compound examples include boric acid; borate salts such as calcium salt, zinc salt, cobalt salt, ammonium salt, potassium salt, lithium salt, and borax. Among these, boric acid and borax are preferable.
  • the water-soluble PVA (X) layer also contains a plasticizer.
  • the high strength of the film is due to the strength of the film and the smoothness of the surface of the X layer and the provision of some flexibility. This is preferable from the viewpoint of enabling easy printing.
  • the plasticizer content is preferably 1 to 30% by weight, more preferably 2 to 25% by weight.
  • 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 water-soluble PVA (X) layer also contains a surfactant from the viewpoint of film-forming property, transferability, higher-definition printing, and control of water surface swelling during transfer. Is preferred.
  • the compounding amount of the surfactant is preferably 0.01 to 7% by weight, more preferably 0.02 to 5% by weight with respect to PVA as a raw material for the X layer.
  • 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.
  • cationic surfactant examples include amines such as laurylamine hydrochloride; quaternary ammonium salts such as lauryltrimethylammonium chloride; and pyridinium salts such as laurylpyridinium chloride.
  • amphoteric surfactant examples include N-alkyl-N, N-dimethylammonium betaine. Surfactant can be used 1 type or in combination of 2 or more types.
  • a water-soluble PVA (X) layer contains a slip agent such as starch or silica.
  • the addition amount of the slip agent is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the weight of the X layer.
  • cross-linking agent plasticizer, surfactant and the like can be mixed and used in advance when the PVA film (X layer) is manufactured or when the PVA coating solution is manufactured.
  • the moisture-resistant resin used for the Y layer is left in a film state in an atmosphere of 20 ° C. and 60% RH for 24 hours and in an atmosphere of 60 ° C. and 90% RH for 24 hours. It is important that the rate of change of the vertical and horizontal lengths is 5% or less, preferably 3% or less. Specifically, the rate of change in the length of the moisture-resistant resin can be determined by the method described in Examples described later.
  • moisture resistant resins examples include polyester resins, polyolefin resins, polyamide resins, acrylic resins (polyacrylic acid esters, polymethacrylic acid esters, etc.), halogen resins (polyvinyl chloride, polyvinylidene chloride, etc.), and the like.
  • a polyester resin and a polyolefin resin are preferable, and a polyester resin is more preferable.
  • the polyester resin include polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate. Among these, polyethylene terephthalate is preferable.
  • polystyrene resin examples include polypropylene, polyethylene, ethylene copolymers (ethylene-propylene copolymer, ionomer, etc.), and among these, polypropylene is preferable. These resins are blocked, grafted or grafted to prevent thermal deterioration during film formation, to prevent the occurrence of unmelted materials, to improve water resistance, to improve fracture resistance, to improve slip properties, to improve strength, and to improve stretchability. It is also preferable to use random copolymers or to add additives such as plasticizers, antioxidants, crystallization agents, slip agents, etc. to these resins.
  • the Y layer may be an unstretched film, but a stretched film is preferable from the viewpoint of water resistance, and a biaxially stretched film is more preferable.
  • a biaxial stretching method either sequential biaxial stretching or simultaneous biaxial stretching can be employed.
  • a draw ratio changes with kinds of resin, in the case of a polyester resin, it is preferable to extend about 3 times in a vertical direction and a horizontal direction, respectively.
  • the multi-layer base film for hydraulic transfer used in the present invention has a multilayer structure including a water-soluble PVA (X) layer and a moisture-resistant resin (Y) layer, so that even in printing under high temperature and high humidity, printing including moisture is performed.
  • the multilayer structure means a two-layer structure of X layer / Y layer, a three-layer structure of X layer / Z layer / Y layer, or a multilayer structure of more than that.
  • the ratio of the total thickness of the X layer and the Y layer to the total thickness of the multilayer base film for hydraulic transfer is preferably 80% or more.
  • examples of the Z layer include a water-soluble PVA (X) layer, a water-soluble resin layer other than PVA, a hardly soluble PVA layer (the aforementioned complete dissolution time exceeds 500 seconds), and a moisture-resistant resin. (Y) layer etc. are mentioned.
  • X water-soluble PVA
  • Y moisture-resistant resin
  • an adhesive layer may exist between the respective layers.
  • a two-layer structure of X layer / Y layer is preferable from the viewpoint of productivity.
  • the interlayer adhesion between the X layer and the Y layer is 0.001 to 0.00 as the 90 ° interlayer adhesion measured by the 90 ° peeling method (JIS K 6854-3) in an atmosphere of 20 ° C. and 65% RH. It is preferably 1 N / cm, more preferably 0.005 to 0.05 N / cm.
  • the interlayer adhesion is less than 0.001 N / cm, there is a possibility that delamination may occur during printing due to printing tension or moisture absorption. Further, when the interlayer adhesive strength exceeds 0.1 N / cm, it may be difficult to peel off the X layer during hydraulic transfer.
  • an adhesive may be used between the X layer and the Y layer.
  • a water-soluble adhesive that is easily dissolved in water after hydraulic transfer is preferable because the appearance after transfer is good.
  • a PVA-based adhesive, a starch-based adhesive, and those obtained by adding 0.5 to 40 parts by weight of an inorganic substance such as silica for controlling the adhesive force are preferably used.
  • the interlayer adhesive force between the X layer and the Y layer is a water-soluble layer including the X layer and a moisture-resistant layer including the Y layer. It means the interlaminar adhesion strength with the layer.
  • each of the X layer and the Y layer is preferably 10 to 90 ⁇ m, more preferably 15 to 80 ⁇ m, and even more preferably 20 to 50 ⁇ m when each is a film.
  • the thickness of the X layer is preferably 10 to 70 ⁇ m, more preferably 15 to 50 ⁇ m, and even more preferably 20 to 40 ⁇ m.
  • the total thickness of the hydraulic transfer multilayer base film is preferably 10 to 120 ⁇ m, more preferably 30 to 45 ⁇ m.
  • the surface roughness (Ra) measured by JIS B0601 on the outer surface of the X layer, which is the printing surface is preferably 0.1 to 5.0. 2 to 3.0 is more preferable. If the surface roughness (Ra) is less than 0.1, the slipperiness is poor and a problem may occur due to friction during printing. When surface roughness (Ra) exceeds 5.0, the unevenness
  • the moisture content of the X layer is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight from the viewpoint of the strength and flexibility of the film. If the moisture content of the X layer is less than 0.5% by weight, the film may be easily torn, whereas if it exceeds 10% by weight, the film may be stretched during printing and the multicolor pattern may be lost.
  • the moisture content of the X layer can be determined by appropriately adjusting the amount of water at the time of producing a PVA film or PVA coating liquid described later, the drying conditions after film formation or coating, and the like.
  • the method for producing the hydraulic transfer multilayer base film used in the present invention and a method of laminating the water-soluble PVA (X) film and the moisture-resistant resin (Y) film separately, and moisture resistance.
  • examples thereof include a method of coating a resin (Y) film with a water-soluble PVA (X) coating solution, a method of co-extruding the X layer and the Y layer, and the like.
  • a method of coating a moisture-resistant resin (Y) film with a water-soluble PVA (X) coating solution is preferable from the viewpoint of cost and performance.
  • the method of laminating after forming the films separately is effective when the thickness and quality of each layer are controlled and high quality is pursued.
  • the PVA concentration is dissolved in a solvent so as to be 5 to 40% by weight, and this is dissolved in a usual coating method, for example, Coating by gravure roll coating, Meyer bar coating, reverse roll coating, air knife coating, spray coating, etc., or extruding from a die in the same way as a general melt extrusion method while keeping the coating solution at a high viscosity Etc.
  • the coating process and conditions are not particularly limited, but the moisture-resistant resin (Y) film roll is continuously fed out from the feeding device, guided onto the belt or roll, and then coated by the method exemplified above, and thereafter And a method of drying or solidifying by known means such as hot air drying, hot roll drying, and far infrared drying. At that time, in order not to impair the physical properties of the moisture-resistant resin (Y) film, it is important to adjust the temperature, amount, drying or solidifying temperature, timing and the like of the coating liquid. As drying conditions, a temperature of 30 to 120 ° C. and a time of 3 to 500 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 water with methanol, ethanol and / or propanol is preferable because drying time can be shortened and deterioration of the film before coating can be reduced.
  • organic solvents such as methanol, ethanol, propanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone
  • a generally used method can be adopted. For example, a normal film laminator is used and a heat roll is heated to 110 ° C. The film can be bonded by processing at a speed of 40 m / min, with the tension on the film being 5 kg / m. If the tension on the film is too large, residual stress is generated after bonding, and printability may be deteriorated.
  • the water content is preferably 2 to 5% by weight by humidifying the water-soluble PVA (X) film before bonding.
  • the interlayer adhesion may be insufficient.
  • the moisture content exceeds 5% by weight, there is a risk that tarmi may occur in the film.
  • a method for producing a water-soluble PVA (X) film as a pre-lamination step for example, using a PVA solution, a casting film forming method, a solution coating method, a wet film forming method (discharging into a poor solvent) Method), a gel film forming method (a method in which an aqueous solution of PVA is once cooled and gelled, and then a solvent is extracted and removed), a method using a combination thereof, a melt extrusion film forming method in which PVA containing a plasticizer is melted, Can be mentioned.
  • the casting film forming method, the solution coating method, and the melt extrusion film forming method are preferable.
  • the PVA solvent those mentioned above can be used.
  • the multilayer film thus obtained can be used as it is as a multilayer base film for hydraulic transfer, or, if necessary, can be uniaxially or biaxially stretched before and after the drying step to form a multilayer base film for hydraulic transfer.
  • the temperature is preferably 20 to 120 ° C.
  • the stretching ratio is preferably 1.05 to 5 times, more preferably 1.1 to 3 times.
  • the residual stress can be reduced by heat fixing the film after stretching.
  • the X layer of the above-mentioned multilayer base film for hydraulic transfer is embossed as necessary, and after drying, water-insoluble (80% by mass or more of the total amount of ink (after drying) does not dissolve within 3 minutes on the water surface)
  • a hydraulic transfer film can be manufactured by printing a picture pattern, a character, etc. using the ink which becomes. Examples of the printing method include inkjet printing, gravure printing, screen printing, offset printing, roll coating, and the like.
  • ink jet printing printing by an ink jet method
  • Ink-jet printing makes it possible to directly print a pattern created by a computer or the like without producing a plate, which is advantageous in terms of cost in the production of a hydraulic transfer film and greatly shortens the production period. it can.
  • the ink used in the above printing contains moisture.
  • the moisture content of the ink is not necessarily limited, it is preferably 0.5 to 80% by weight and more preferably 1 to 75% by weight because the effects of the present invention are more remarkable. preferable. If the moisture content of the ink exceeds 80% by weight, the degree of curling that occurs when the moisture-resistant resin (Y) layer is peeled off from the hydraulic transfer film for transfer and then floats on the water surface increases, and the printed surface is deformed. There is a tendency to increase the possibility.
  • the printing environment is preferably normal temperature (eg, 5 to 40 ° C.) and humidity of 20 to 90% RH, more preferably 30 to 80% RH, and even more preferably 40 to 75% RH.
  • the drying temperature is preferably 30 to 100 ° C., more preferably 50 to 90 ° C.
  • the dimensional change of the hydraulic transfer film due to the tension in the printing process and the heat in the drying process is reduced, and the hydraulic transfer film using the conventional PVA single layer base film Compared with, water resistance is significantly improved. For this reason, it is possible to greatly increase the printing speed without causing multicolor pattern misalignment during printing. Ink that needs to be dried at a high temperature can also be used.
  • conventional PVA single-layer base films often experience film elongation, tarmi, and blocking due to moisture absorption and temperature rise, requiring careful attention to temperature and humidity control during storage, transportation, and printing processes.
  • this problem is greatly improved, and the management range can be greatly relaxed.
  • the printed layer is floated on the water surface, the ink activator is sprayed on the printed surface, and the transferred object is pressed from above, and the printed layer Is sufficiently fixed to the surface of the transfer object, then the water-soluble PVA (X) layer is 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. .
  • the ink activator may be sprayed or coated before the moisture resistant resin (Y) layer is peeled off.
  • the water-soluble PVA (X) layer of the hydraulic transfer film is dried without applying tension on the moisture-resistant resin (Y) layer when the ink is dried, so that the moisture-resistant resin (Y) layer is peeled off.
  • the water-soluble PVA (X) layer after undergoing little dimensional change has little curl when it floats on the water surface.
  • the maximum curl length determined by the method described in Examples described later is preferably 0.2 to 9 cm, more preferably 0.4 to 8 cm, and even more preferably 0.5. ⁇ 8cm.
  • the maximum curl length does not exceed the above upper limit, the effective transfer area is not reduced and lost, and when it is not less than the above lower limit, the surrounding film is suppressed by slight curling of the floated film. This is preferable because printing blur is reduced.
  • it is preferable that the above-mentioned maximum curl length is also satisfied for the multilayer base film for hydraulic transfer before printing.
  • 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 obtained by the production method of the present invention is capable of high-definition printing. It is extremely useful for required transfer, especially for transfer of curved structures.
  • the curved surface means a spherical surface, an undulating surface, a three-dimensional surface with unevenness, or the like.
  • Specific examples of structures include wood base materials such as wood plates, plywood and particle boards, various plastic molded products, pulp cement, slate boards, cement products such as glass fiber reinforced cement, concrete boards, gypsum boards, calcium silicate boards, Examples include inorganic products such as magnesium silicate, metal products such as iron, steel, copper, aluminum, and alloys, and glass products.
  • the film immersed in water dissolves on the slide mount over time or tears, then comes off the slide mount, gradually dissolves while floating in water, and becomes invisible to the naked eye.
  • the time from immediately after immersing the film until it disappears with the naked eye is measured, and this is defined as the complete dissolution time.
  • a multilayer base film for hydraulic transfer having a PET film width of 100 cm, a coat width of 96 cm, and a length of 1000 m was obtained.
  • the complete dissolution time of the water-soluble PVA (X) layer peeled from the multilayer base film was 24 seconds, and the thickness measured with an Anritsu contact-type continuous thickness meter was 30 ⁇ m.
  • the water content of the water-soluble PVA (X) layer was measured by a 90 ° peeling method (JIS K 6854-3) at 3.1% by weight, glycerin content at 4.0% by weight, 20 ° C. and 65% RH.
  • the interlayer adhesion (90 ° interlayer adhesion) between the water-soluble PVA (X) layer and the PET (Y) layer is 0.024 N / cm, and the surface of the outer surface of the water-soluble PVA (X) layer measured according to JIS B0601 The roughness (Ra) was 0.5.
  • ink for building materials consisting of 70% by weight of a mixture of dye and barium sulfate and 30% by weight of a mixture of alkyd resin and nitrocellulose, and the above-mentioned multilayer for hydraulic transfer in an atmosphere of 20 ° C. and 72% RH Gravure printing was performed on the water-soluble PVA (X) layer of the base film.
  • the thickness of the printing layer was 2 ⁇ m each, the unwinding tension was 1 kg / m, and the printing speed was 40 m / min.
  • the multilayer film was dried in a 1 m drying zone heated with hot air at 60 ° C. and wound up at a winding tension of 5 kg / m.
  • the moisture content in the ink remaining in the pan under the gravure roll was measured with a Karl Fischer moisture meter and found to be 2.3% by weight.
  • the obtained printed matter was subjected to various evaluations shown below.
  • Printing failure The printing failure of the above printed matter 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
  • Number of cuttings The number of times of film cutting (not considering film cutting due to machine fluctuations) generated by the adhesion of the film, particularly the film end face, during the 1000 m printing of the film in the above printing process was defined as the number of cuttings.
  • the printed water-soluble PVA (X) layer is peeled off, and both ends of the short side (22 cm side) of the water-soluble PVA (X) film are folded by 1 cm each on the printing surface side to form an elongated cylinder.
  • a 2 mm diameter iron rod was inserted into the shape, wrapped in the folded portion of the film, and fixed with paper tape.
  • 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 22 cm to obtain the maximum curl length.
  • Example 2 A printed matter (hydraulic transfer film) was obtained in the same manner as in Example 1 except that the printing speed was 80 m / min and the drying temperature after printing was 90 ° C., and subjected to various evaluations. The results are shown in Tables 1-3.
  • Example 3 From the hydraulic transfer multilayer base film obtained in Example 1, a rectangular multilayer film of 43 cm in the film forming direction and 22 cm in the width direction (the center of the original film coincides with the center of the film to be cut out) was cut out. Using a Canon inkjet printer PIXUS MX850, a similar pattern produced via a computer was printed on the cut multilayer film. Within 10 seconds after printing, it was dried with hot air at 60 ° C. for 10 seconds. No abnormalities in the appearance such as film elongation and tarmi were observed.
  • Example 4 The solution X used in Example 1 was cast on a conveyor belt and dried for 5 minutes while applying hot air of 120 ° C. on the belt to obtain a water-soluble PVA (X) film having a thickness of 31 ⁇ m, a width of 97 cm, and a length of 1050 m. Obtained.
  • the water-soluble PVA (X) film had a complete dissolution time of 21 seconds, a moisture content of 2.9% by weight, and a glycerin content of 4.0% by weight.
  • Example 2 Under an atmosphere of 20 ° C. and 45% RH, the water-soluble PVA (X) film and the PET film used in Example 1 were stacked so that the water-soluble PVA (X) film was in contact with the corona-treated surface of the PET film.
  • a multilayer base film for hydraulic transfer was obtained by passing between a metal roll and a rubber roll heated to 80 ° C. at a speed of 40 m / min.
  • the interlayer adhesion (90 ° interlayer adhesion) between the water-soluble PVA (X) layer and the PET (Y) layer was 0.009 N / cm, and the water-soluble PVA (X) layer
  • the surface roughness (Ra) of the outer surface was 0.4.
  • Example 5 A multilayer base film for hydraulic transfer was obtained in the same manner as in Example 1 except that 0.15 part by weight of boric acid was added to 100 parts by weight of the X solution of Example 1.
  • the complete dissolution time of the water-soluble PVA (X) layer was 28 seconds
  • the thickness was 29 ⁇ m
  • the moisture content was 3.0% by weight
  • the glycerin content was 4.0% by weight
  • the interlayer adhesive strength (90 ° interlayer adhesive strength) between the water-soluble PVA (X) layer and the PET (Y) layer is 0.031 N / cm
  • the surface roughness (Ra) of the outer surface of the water-soluble PVA (X) layer is 0. 6.
  • Example 6 Example 1 except that silica having an average particle size of 6.6 ⁇ m (“NIPGEL0063” manufactured by Tosoh Corporation) was added to the solution X of Example 1 so that the concentration was 0.3% by weight. In the same manner as above, a multilayer base film for hydraulic transfer was obtained.
  • silica having an average particle size of 6.6 ⁇ m (“NIPGEL0063” manufactured by Tosoh Corporation) was added to the solution X of Example 1 so that the concentration was 0.3% by weight.
  • Example 7 Instead of the biaxially stretched PET film, a biaxially stretched polypropylene film (PP film OP U-1, manufactured by Tosero Co., Ltd., thickness 20 ⁇ m, width 100 cm, single-sided corona treatment, rate of change in length in the longitudinal direction and width direction when opened, and A multi-layer base film for hydraulic transfer was obtained in the same manner as in Example 1 except that the rate of change under load was 1% or less.
  • PP film OP U-1 manufactured by Tosero Co., Ltd.
  • thickness 20 ⁇ m thickness 20 ⁇ m, width 100 cm
  • single-sided corona treatment rate of change in length in the longitudinal direction and width direction when opened
  • a multi-layer base film for hydraulic transfer was obtained in the same manner as in Example 1 except that the rate of change under load was 1% or less.
  • Example 8 A multilayer base film for hydraulic transfer was obtained in the same manner as in Example 1 except that PVA (B) having a saponification degree of 91 mol% and a polymerization degree of 1700 was used instead of PVA (A).
  • PVA (B) having a saponification degree of 91 mol% and a polymerization degree of 1700 was used instead of PVA (A).
  • the complete dissolution time of the water-soluble PVA (X) layer was 43 seconds
  • the thickness was 28 ⁇ m
  • the moisture content was 3.4% by weight
  • the glycerin content was 4.0% by weight
  • the interlayer adhesive strength (90 ° interlayer adhesive strength) between the water-soluble PVA (X) layer and the PET (Y) layer is 0.018 N / cm
  • the surface roughness (Ra) of the outer surface of the water-soluble PVA (X) layer is 0. 0. 4.
  • Example 9 The ink cartridge used in Example 3 was opened, and each ink was taken out. After adding 100 parts by weight of deionized water to 100 parts by weight of each ink and stirring well, the ink cartridge was returned to the ink cartridge, taking care not to overflow. A printed matter (hydraulic transfer film) was obtained in the same manner as in Example 3 except that this ink cartridge was used, and was subjected to various evaluations. After printing, the moisture content in the ink remaining in the ink cartridge was measured with a Karl Fischer moisture meter, and it was in the range of 81 to 84% by weight, although it was different for each of the four types of ink. The results are shown in Tables 1-3.
  • Example 1 A printed matter (hydraulic transfer film) was obtained in the same manner as in Example 1 except that the water-soluble PVA (X) film obtained in the same manner as in Example 4 was used as a single layer, and was subjected to various evaluations. The film absorbed moisture, and stretched in the direction of the apparatus during drying after printing, resulting in severe pattern displacement. Moreover, moisture adhered to the roll end face and blocked, and cutting occurred frequently during feeding. The results are shown in Tables 1-3.
  • Comparative Example 2 A printed matter (hydraulic transfer film) was obtained in the same manner as in Comparative Example 1 except that the humidity during printing was 46% RH, and subjected to various evaluations. Although the elongation of the film has been greatly improved, there is still some pattern misalignment, which is a problem level in applications where high definition is required. The results are shown in Tables 1-3.
  • Comparative Example 3 A printed matter (hydraulic transfer film) was obtained in the same manner as in Comparative Example 1 except that the printing speed was 80 m / min and the drying temperature after printing was 90 ° C., and subjected to various evaluations. The film absorbed moisture, and stretched in the direction of the apparatus during drying after printing, resulting in severe pattern displacement. The results are shown in Tables 1-3.
  • [Reference Example 1] Enclose the gravure roll and the pan under the gravure roll with a plastic film so as not to contact the hydraulic transfer base film during printing, and supply dry air from the gas cylinder at a flow rate that does not cause the hydraulic transfer base film to vibrate.
  • a printed matter (hydraulic transfer film) was obtained in the same manner as in Comparative Example 1 except that the moisture absorption of the ink during printing was suppressed, and was subjected to various evaluations. After printing, the moisture content in the ink remaining on the pan under the gravure roll was measured with a Karl Fischer moisture meter and found to be 0.2% by weight. The results are shown in Tables 1-3.
  • Example 10 Instead of using a water-soluble PVA (X) film in a single layer, a printed material (hydraulic transfer film) was used in the same manner as in Reference Example 1 except that a multilayer base film for hydraulic transfer obtained in the same manner as in Example 1 was used. And obtained for various evaluations. After printing, the moisture content in the ink remaining on the pan under the gravure roll was measured with a Karl Fischer moisture meter and found to be 0.2% by weight. The results are shown in Tables 1-3.
  • a hydraulic transfer film with little film elongation and sagging and no occurrence of multicolor pattern displacement can be obtained.
  • the hydraulic transfer film is useful for transfer that requires high-precision and high-definition printing, particularly for transfer of curved structures.

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  • Laminated Bodies (AREA)
  • Decoration By Transfer Pictures (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un film de transfert hydraulique dans lequel un imprimé très précis et fin peut être rapidement préparé sur un film de base en utilisant une encre contenant de l'eau. L'invention concerne spécifiquement un procédé de fabrication d'un film de transfert hydraulique dans lequel un imprimé est préparé en utilisant une encre contenant de l'eau sur une couche d'alcool polyvinylique soluble dans l'eau (X) d'un film de base multicouche pour transfert hydraulique, ledit film de base multicouche comprenant la couche d'alcool polyvinylique soluble dans l'eau (X) et une couche de résine résistant à l'humidité (Y). Cette couche de résine (Y) est de préférence composée d'au moins une résine choisie dans le groupe constitué par les résines de polyester et les résines de polyoléfines.
PCT/JP2009/069706 2008-11-28 2009-11-20 Procédé de fabrication d'un film de transfert hydraulique Ceased WO2010061790A1 (fr)

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Cited By (10)

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JP2013000896A (ja) * 2011-06-10 2013-01-07 Dainippon Printing Co Ltd 水圧転写シート製造用転写箔、水圧転写シート及び加飾成形品並びにそれらの製造方法
WO2013094424A1 (fr) * 2011-12-21 2013-06-27 アイセロ化学株式会社 Film pour transfert hydraulique
JP2013216063A (ja) * 2012-04-12 2013-10-24 Sharp Corp 印刷装置および印刷方法
JP2014080009A (ja) * 2012-09-28 2014-05-08 Toppan Printing Co Ltd インクジェット用記録シート
KR101402130B1 (ko) 2012-05-10 2014-06-11 신애순 홀로그램 수압 전사 필름 및 홀로그램 수압 전사 필름에 따른 홀로그램 수압 전사물의 제조공정
DE102013102915A1 (de) * 2013-03-21 2014-10-09 Knauf Gips Kg Verfahren zur Herstellung einer mit einem Dekor ausgerüsteten Trägerplatte
JP2016036943A (ja) * 2014-08-06 2016-03-22 日東電工株式会社 積層体の製造方法
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
CN115058045A (zh) * 2022-07-21 2022-09-16 石狮市锦源体育用品有限公司 一种稳定型镭射pva水转印膜
US12420538B2 (en) 2020-08-28 2025-09-23 O-Well Corporation Transfer sheet for forming recessed and projecting shape, method of producing transfer sheet for forming recessed and projecting shape, and method of forming recessed and projecting shape

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DE102022104164A1 (de) * 2022-02-22 2023-08-24 Forever Gmbh Transferfolie, Beschichtungssystem und Verfahren zum Übertragen von Abbildungen auf Substrate

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JP2003094894A (ja) * 2001-09-26 2003-04-03 Kuraray Co Ltd 水圧転写用フィルム
JP2005212340A (ja) * 2004-01-30 2005-08-11 Dainippon Ink & Chem Inc 艶消し調水圧転写体の製造方法

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JP4302361B2 (ja) * 2002-06-19 2009-07-22 株式会社クラレ 水圧転写方法

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JP2003094894A (ja) * 2001-09-26 2003-04-03 Kuraray Co Ltd 水圧転写用フィルム
JP2005212340A (ja) * 2004-01-30 2005-08-11 Dainippon Ink & Chem Inc 艶消し調水圧転写体の製造方法

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013000896A (ja) * 2011-06-10 2013-01-07 Dainippon Printing Co Ltd 水圧転写シート製造用転写箔、水圧転写シート及び加飾成形品並びにそれらの製造方法
US8865276B2 (en) 2011-12-21 2014-10-21 Aicello Corporation Water-pressure transfer printing film
WO2013094424A1 (fr) * 2011-12-21 2013-06-27 アイセロ化学株式会社 Film pour transfert hydraulique
KR101385825B1 (ko) 2011-12-21 2014-04-16 가부시키가이샤 아이세로 수압 전사용 필름
JP2013216063A (ja) * 2012-04-12 2013-10-24 Sharp Corp 印刷装置および印刷方法
KR101402130B1 (ko) 2012-05-10 2014-06-11 신애순 홀로그램 수압 전사 필름 및 홀로그램 수압 전사 필름에 따른 홀로그램 수압 전사물의 제조공정
JP2014080009A (ja) * 2012-09-28 2014-05-08 Toppan Printing Co Ltd インクジェット用記録シート
DE102013102915A1 (de) * 2013-03-21 2014-10-09 Knauf Gips Kg Verfahren zur Herstellung einer mit einem Dekor ausgerüsteten Trägerplatte
JP2016036943A (ja) * 2014-08-06 2016-03-22 日東電工株式会社 積層体の製造方法
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
JPWO2020138445A1 (ja) * 2018-12-28 2021-11-11 株式会社クラレ 水圧転写用ベースフィルムおよび水圧転写用印刷フィルム
JP7240423B2 (ja) 2018-12-28 2023-03-15 株式会社クラレ 水圧転写用ベースフィルムおよび水圧転写用印刷フィルム
US12420538B2 (en) 2020-08-28 2025-09-23 O-Well Corporation Transfer sheet for forming recessed and projecting shape, method of producing transfer sheet for forming recessed and projecting shape, and method of forming recessed and projecting shape
CN115058045A (zh) * 2022-07-21 2022-09-16 石狮市锦源体育用品有限公司 一种稳定型镭射pva水转印膜

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