KR20100015962A - Base film for liquid pressure transfer printing, method for production of base film for liquid pressure transfer printing, and liquid pressure transfer method - Google Patents

Abstract

Disclosed is a base film for use in liquid pressure transfer printing, which has excellent suitability for printing and excellent transfer efficiency. Also disclosed is a liquid pressure transfer method using the base film. Specifically disclosed is a base film for use in liquid pressure transfer printing, which comprises a polyvinyl alcohol film and has a curl area ratio of 30% or less as measured 25 seconds after the film is floated on the surface of a liquid. The base film can be used in a continuous or batch-wise liquid pressure transfer method.

Description

BASE FILM FOR LIQUID PRESSURE TRANSFER PRINTING, METHOD FOR PRODUCTION OF BASE FILM FOR LIQUID PRESSURE TRANSFER PRINTING, AND LIQUID PRESSURE TRANSFER METHOD}

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a base film for hydraulic transfer printing, a method for producing the same, and a hydraulic transfer method using the same, which float on a liquid surface, particularly on the water surface, and which can transfer the design printed on the film surface to a transfer target smoothly.

Conventionally, the polyvinyl alcohol-type resin film which uses polyvinyl alcohol-type resin as a formation material is used as a base film for hydraulic transcription printing. And using the said polyvinyl alcohol-type resin film, it is provided to the water pressure transfer method as follows. That is, printing a desired design on the polyvinyl alcohol-based resin film surface, floating the surface of the design printing surface upward, pressing the transfer object onto the design printing surface from above the film, and transferring the design onto the transfer body, have.

In such a hydraulic transfer method, for example, the base film has a polyvinyl alcohol-based resin as a main component, has two endothermic peaks at 150 ° C or higher in an endothermic curve measured by a differential scanning calorimeter (DSC), and the peak temperature difference. It consists of polyvinyl alcohol of base film (refer patent document 1) which is less than 32 degreeC, polymerization degree 500-3000, saponification degree 80 mol%-99.9 mol%, moisture content is 1.5%-4.0%, and thickness is 20 By using the base film (refer patent document 2) whose width | variety shrinkage rate is 0.01%-1.5% when 1 micrometer-50 micrometers and the tension of 8.0 kg / m is applied at 50 degreeC in 50 degreeC in the longitudinal direction for 1 minute, It is disclosed that enabling transfer printing.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-301899

[Patent Document 2] Japanese Unexamined Patent Publication No. 2005-60636

Disclosure of Invention

Problems to be Solved by the Invention

However, in the conventional hydraulic transfer method using the polyvinyl alcohol-based resin films including Patent Documents 1 and 2, when the design-printed base film floats on the water surface, the base film stretches or curls. In some cases, there is a problem of transfer print aptitude that printing on an image is difficult. In addition, curling is also a problem in the productivity of the transfer printing of the chairman. In particular, in recent years, the printing of the design is multi-layer printing, or the printing ink with excellent durability is used, and a difference occurs in the absorptivity of the design printing surface and the non-printing surface of the film, and as a result, the occurrence of curl becomes more remarkable. It is a big problem.

This invention is made | formed in view of such a situation, and an object of this invention is to provide the base film for hydraulic transfer printing which is excellent in transfer printing aptitude, and excellent in transfer efficiency (productivity), its manufacturing method, and the hydraulic transfer method using the same.

Means for solving the problem

By the way, the present inventors have intensively studied to achieve the above object, and as a result, it has been found that the curl area ratio of the base film is important, and transfer printing aptitude is achieved by using a base film which can be lower than the conventional curl area ratio. The present invention was found to be excellent and excellent in transfer printing efficiency, thus completing the present invention.

This invention is achieved based on this knowledge, and the summary is as follows.

[1] A base film for hydraulic transfer printing, comprising a polyvinyl alcohol-based film, wherein the curl area ratio after 25 seconds after floating the base film on a liquid level is 30% or less.

[2] The base film for hydraulic transfer printing according to [1], wherein the flatness after 30 seconds after floating the base film on the liquid surface is 30% or less.

[3] The base film for hydraulic transfer printing according to [1] or [2], wherein the polyvinyl alcohol-based film has a water content in the range of 2% by weight to 6% by weight.

[4] The hydraulic transfer printing according to any one of [1] to [3], wherein the polyvinyl alcohol-based film is formed of a film forming material containing a polyvinyl alcohol-based resin (A) and a crosslinking agent (B). Base film.

[5] The hydraulic transfer printing according to any one of [1] to [4], wherein the polyvinyl alcohol-based film is formed of a film forming material containing a polyvinyl alcohol-based resin (A) and a filler (C). Base film.

[6] The hydraulic transfer printing according to any one of [1] to [5], wherein the polyvinyl alcohol-based film is formed of a film forming material containing a polyvinyl alcohol-based resin (A) and a plasticizer (D). Base film.

[7] The average viscosity of the 4% by weight aqueous solution of the polyvinyl alcohol-based resin (A) is 10 mPa · s to 70 mPa-s at 20 ° C, and the average saponification degree of the polyvinyl alcohol-based resin (A) It is 70 mol%-98 mol%, The base film for hydraulic transfer printing in any one of [4]-[6] characterized by the above-mentioned.

[8] The base film for hydraulic transfer printing according to any one of [1] to [7], wherein the polyvinyl alcohol-based film has a thickness of 20 µm to 50 µm.

[9] The film-forming material containing the polyvinyl alcohol-based resin (A) is flow-cast on a film forming belt or a film forming drum, dried to prepare a film, and then contacted with a film forming belt or a film forming drum. A method for producing a base film for hydraulic transfer printing, characterized by performing heat treatment on a surface that is opposite to the surface.

[10] The film-forming material containing the polyvinyl alcohol-based resin (A) is flow casted on a film forming belt or a film forming drum, dried to form a film, and then opposite to a surface in contact with the film forming belt or the film forming drum. The surface is heat-treated, The manufacturing method of the base film for hydraulic-transfer printing in any one of [1]-[8] characterized by the above-mentioned.

[11] A step of printing a predetermined design on the surface of the base film for hydraulic transfer printing according to any one of [1] to [8], a step of coating an ink activator on the surface of the design printing, and flow of the base film for hydraulic transfer printing. A step of 1.5 times or less is provided in the width direction with respect to the direction, and the base film for hydraulic transfer printing is floated on the liquid surface with the design printing surface upward, and the base to be pressed is pressed from above the base film for hydraulic transfer printing. And a step of transferring the design printed on the film surface to the transfer target body.

[12] a step of printing a predetermined design on the surface of the base film for hydraulic transfer printing according to any one of [1] to [8], a step of coating an ink activator on the surface of the design printing, and the base film for hydraulic transfer printing A vertical and horizontal regulation of 1.5 times or less is provided in each of the vertical and horizontal directions, and the transfer member is pressed from the upper side of the hydraulic transfer printing base film in the stop state and the process of floating the hydraulic transfer printing base film on the liquid surface with the design printing surface upward. And a step of transferring the design printed on the base film surface to the transfer target body.

Effect of the Invention

The base film for hydraulic transfer printing of the present invention includes a polyvinyl alcohol-based film, and since the curl area ratio after 25 seconds after floating the base film on the liquid surface is 30% or less, transfer printing aptitude is excellent, and transfer printing The efficiency is excellent.

<Best Mode for Carrying Out the Invention>

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The base film for hydraulic transfer printing of the present invention (hereinafter referred to as "base film") is a base film for hydraulic transfer printing containing a polyvinyl alcohol-based film, and the curl area ratio after 25 seconds after floating the base film on the liquid surface is 30%. It is a base film which is the following.

Here, "the polyvinyl alcohol-type film is included" means also including the case where another layer (film, a coating film, etc.) is laminated other than a polyvinyl alcohol-type film. However, usually only a polyvinyl alcohol-type film is used as a base film in many cases.

In addition, although "polyvinyl alcohol system" means the unmodified polyvinyl alcohol, modified polyvinyl alcohol, etc., it is usually polyvinyl alcohol.

The polyvinyl alcohol-based film contains, for example, polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) -based resin (A) as a main component, preferably a crosslinking agent (B), a filler (C) and a plasticizer (D). It is formed in a film form using the film forming material which contains at least 1 of further), and is an unstretched film normally. In addition, in this invention, said "making it main component" is a main component in solid components other than solvents, such as water, and it is the meaning which also includes the case where a film forming material consists only of a main component, The content is 50 weight% normally 100 weight%, Preferably it is 70 weight%-100 weight%, More preferably, they are 80 weight%-100 weight%.

The PVA-based resins may be used alone or in combination of two or more PVA-based resins having different saponification degrees or 4% by weight aqueous solution viscosity.

The PVA resin may be unmodified or modified, and in the case of denaturation, other monomers may be used in the range of not impairing the effect of the present invention in the main chain, for example, in the range of 10 mol% or less, preferably 7 mol% or less. Can be copolymerized. Examples of the other monomers include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene and α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, and ita. Unsaturated acids such as cholic acid or salts thereof, mono or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, ethylene sulfonic acid, allyl sulfonic acid and metaallyl sulfonic acid Polyoxyalkylene (meth) allyl ethers such as olefinsulfonic acid or salts thereof, alkyl vinyl ethers, polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether, polyoxyethylene (meth) acrylate, Poly, such as polyoxyalkylene (meth) acrylate, such as polyoxypropylene (meth) acrylate, polyoxyethylene (meth) acrylamide, and polyoxypropylene (meth) acrylamide Cyalkylene (meth) acrylamide, polyoxyethylene [1- (meth) acrylamide-1,1-dimethylpropyl] ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene Allylamine, polyoxyethylenevinylamine, polyoxypropylenevinylamine, diacrylacetoneamide, N-acrylamidemethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethyldiallylammonium chloride, dimethylallylvinylketone, N-vinylpyrroli Toner, vinyl chloride, vinylidene chloride, etc. are mentioned. It is also preferable to use PVA resin having a 1,2-glycol bond in the side chain as the PVA resin, and PVA resin having a 1,2-glycol bond in the side chain is, for example, (1) vinyl acetate; A method of saponifying a copolymer of 3,4-diacetoxy-1-butene, (2) A method of saponifying and decarbonizing a copolymer of vinyl acetate and vinyl ethylene carbonate, (3) A vinyl and 2,2-di And saponifying and deketalizing the copolymer of alkyl-4-vinyl-1,3-dioxolane, (4) saponifying the copolymer of vinyl acetate and glycerin monoallyl ether, and the like. These other monomers may be used alone or in combination of two or more.

It is preferable that content of such PVA system resin (A) is 50 weight%-100 weight% with respect to a PVA film, Furthermore, it is preferable that they are 70 weight%-100 weight%, Especially 80 weight%-100 weight%. Do.

Moreover, it is preferable that the average viscosity in 20 degreeC of the 4 weight% aqueous solution of the said PVA-type resin (A) is the range of 10 mPa * s-70 mPa * s, and 15 mPa * s-60 mPa * It is more preferable that it is the range of s. When the average viscosity of 4 weight% aqueous solution is too low, there exists a tendency for the film strength at the time of printing a design (pattern, a pattern, etc.) to a base film, or the tendency which print unevenness can generate | occur | produce. Moreover, the tendency that the dissolution of a base film is accelerated | stimulated and transfer time is reduced, or the design printed on the film when it floats in water is not stabilized, and adhesiveness falls. On the other hand, if the average viscosity of the 4 wt% aqueous solution is too high, the dissolution of the base film is slow when transferring the printed design onto the transfer object, and it is hard for a predetermined transfer time, whereby wrinkles tend to occur, Moreover, although extension | stretching of the film | membrane in water surface can be suppressed, it is seen that the film formation becomes difficult because a viscosity is high besides the transfer time delayed.

In addition, the average viscosity in 20 degreeC of the said 4 weight% aqueous solution is measured according to JISK6726.

Moreover, it is preferable that the average saponification degree of the said PVA-type resin (A) is the range of 70 mol%-98 mol%, More preferably, it is the range of 75 mol%-96 mol%. If the average saponification degree of the PVA-based resin (A) is too low, a tendency to take a long time to dissolve the base film after the transfer can be seen, and if too high, the dissolution time of the base film is delayed, and the film strength at the time of transfer is increased. Because of the high folds, there is a tendency for wrinkles to be generated during transfer or a film removal defect even if transfer is performed.

In addition, the said saponification degree is measured according to JISK6726.

Moreover, in this invention, mix | blending a crosslinking agent (B) with PVA system resin (A) is also preferable at the point which does not deform | transform a pattern at the time of transfer printing, and the point that adhesiveness is good.

As such a crosslinking agent (B), if it crosslinks reaction with PVA system resin (A), it will not specifically limit, A boron compound, an inorganic salt, etc. are mentioned.

As such a boron compound, for example, boric acid, calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum borate, potassium borate, ammonium borate (ammonium metaborate, ammonium tetraborate, ammonium pentaborate, octaborate) Ammonium, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, potassium octaborate, etc.), silver borate (silver metaborate, 4 Silver borate, etc.), copper borate (copper borate, copper metaborate, copper tetraborate, etc.), sodium borate (sodium metaborate, sodium biborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate, etc. ), Lead borate (lead metaborate, lead hexaborate, etc.), nickel borate (nickel orthoborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.), barium borate (barium orthoborate, barium metaborate, barium diborate) , Barium tetraborate etc.), bismuth borate, magnesium borate (magnesium orthoborate, magnesium diborate, metaborate Magnesium, trimagnesium tetraborate, 5 magnesium tetraborate, etc.), manganese borate (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, etc.) And borate minerals such as borax, cornite, inyoite, kotoite, suanite, and szibelyite.

As inorganic salts, for example, (NH ₄ ) ₂ SO ₄ , Na ₂ SO ₄ , K ₂ SO ₄ , ZuSO ₄ , CuSO ₄ , FeSO ₄ , MgSO ₄ , Al ₂ (SO ₄ ) ₃ , KAl (SO ₄ ) ₂ , NH ₄ NO ₃ , NaNO ₃ , KNO ₃ , Al (NO ₃ ) ₃ , NH ₄ Cl, NaCl, KCl, MgCl ₂ , CaCl ₂ , Na ₃ PO ₄ , K ₂ CrO ₄ , K ₃ C ₆ H ₅ O ₇ etc. are mentioned.

The said crosslinking agent (B) can be used individually or in combination, Especially, boric acid or its salts, especially borax are used suitably.

It is preferable that content of such a crosslinking agent (B) is 0.1 weight part-5 weight part with respect to 100 weight part of PVA-type resin (A), Furthermore, it is 0.1 weight part-4 weight part, Especially 0.3 weight part-3 weight part It is preferable. If the content is too small, there is a tendency that pattern deformation occurs or the adhesiveness decreases during transfer printing. On the contrary, if the content is excessively large, the base film on which the adherend and the design are printed is hard during transfer printing to the adherend. Because of this, wrinkles tend to occur.

In this invention, it is also preferable to mix | blend filler (C) further as a film formation material from a blocking-resistant viewpoint, and as such a filler (C), at least one among polysaccharides and an inorganic compound is mentioned especially.

Among the polysaccharides, starch is particularly preferable, and for example, raw starch (corn starch, potato starch, sweet potato starch, wheat starch, cassava starch, sago starch, tapioca starch, sorghum starch, rice starch, soybean starch, boiled starch , Fern starch, lotus starch, dried starch, etc.); Physically modified starch (α-starch, fractionated amylose, wet heat treated starch, etc.); Enzyme-modified starch (hydrolysis dextrin, enzyme degrading dextrin, amylose and the like); Chemically denatured starch (acid treated starch, hypochlorite oxidized starch, dialdehyde starch, etc.); Chemically modified starch derivatives (esterified starch, etherified starch, cationic starch, crosslinked starch, etc.) are used. Among the chemically modified starch derivatives, esterified starch includes acetic acid esterified starch, succinic acid esterified starch, nitrate esterified starch, phosphate esterified starch, urea phosphate esterified starch, xanthic acid esterified starch, acetic acid esterified starch and the like. As etherified starch, starch and 2-diethylaminoethyl as cationic starches, such as allyl ether starch, methyl ether starch, carboxymethyl ether starch, hydroxyethyl ether starch, hydroxypropyl ether starch, etc. Examples of the crosslinked starch such as the reactant of the chloride, the reactant of the starch and 2,3-epoxypropyltrimethylammonium chloride, and the like may include formaldehyde crosslinked starch, epicrohydrin crosslinked starch, phosphoric acid crosslinked starch, acrolein crosslinked starch and the like. Among them, raw starch is suitably used in view of availability and economical efficiency.

Examples of the inorganic materials include talc, cray, silica, diatomaceous earth, kaolin, mica, asbestos, gypsum, graphite, glass balloons, glass beads, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, calcium carbonate, whisker calcium carbonate, Magnesium carbonate, dosonite, dolomite, potassium titanate, carbon black, glass fiber, alumina fiber, boron fiber, processed mineral fiber, carbon fiber, carbon hollow sphere, bentonite, montmorillonite, copper powder, and the like.

These fillers (C) may be used independently and may be used in combination of 2 or more type.

About content of such a filler (C), it is preferable that it is 0.1 weight part-15 weight part normally with respect to 100 weight part of PVA-type resin (A), Especially 0.3 weight part-13 weight part, Furthermore, 0.5 weight part- It is preferable that it is 10 weight part. If the content is too small, the adhesiveness of the film increases, which tends to cause difficulty in the production, printing, and transfer of the base film for transfer printing. If the content is excessively large, the swelling after the film is under water during transfer printing. There exists a tendency which becomes a cause of a dot defect by entering a lot of fine wrinkles.

It is preferable that it is 0.1 micrometer-30 micrometers normally, and, as for the average particle diameter in the said filler (C), it is more preferable that it is 0.3 micrometer-25 micrometers. When the average particle diameter is too small, the blowing of the powder becomes severe in the base film manufacturing process, and it tends to cause trouble in the work. When too large, the film strength of the base film is greatly reduced, and not only during the transfer printing, but also in the base film manufacturing process. It also tends to break easily during printing.

Moreover, in this invention, further mix | blending a plasticizer (D) is also preferable at the point which makes a film flexible, As such a plasticizer (D), glycerin, triethylene glycol, such as glycerin, diglycerol, and triglycerol, Alkylene glycols, such as polyethyleneglycol, polypropylene glycol, and dipropylene glycol, trimethylol propane, etc. are mentioned.

These may be used alone or in combination of two or more.

It is preferable that it is 10 weight part or less with respect to 100 weight part of PVA-type resins (A), and, as for content of the said plasticizer (D), it is more preferable that it is 0.1 weight part-5 weight part. When the content of the plasticizer (D) is too small, the plasticizing effect is low, which tends to cause breakage of the obtained base film. When the content is too large, the dimensional stability when printing the design on the base film surface is low. The tendency of printing with high definition is difficult to see.

Various additives can be mix | blended with the said film forming material other than the said PVA system resin (A), a crosslinking agent (B), a filler (C), and a plasticizer (D) as needed.

For example, surfactant can be mix | blended for the purpose of the peelability of the metal surface, such as a drum and a belt which are a film forming apparatus of a base film, and the film formed into a film.

It does not specifically limit as said surfactant, For example, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl nonyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate , Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyalkylene alkyl ether phosphoric acid ester monoethanolamine salt, polyoxyethylene laurylamine, polyoxy Polyoxyethylene alkylamine, such as ethylene stearylamine, etc. are mentioned. These may be used alone or in combination of two or more. Especially, it is suitable to use polyoxyalkylene alkyl ether phosphate ester monoethanolamine salt, polyoxyethylene alkylamine, and polyoxyethylene sorbitan monolaurate from a peelable point.

Although it does not specifically limit about content of the said surfactant, It is preferable that it is 0.01 weight part-5 weight part with respect to a total of 100 weight part of PVA system resin (A) and a plasticizer (D), and it is 0.03 weight part-4.5 weight part More preferred. When the content of the surfactant is too small, the peelability of the film formed by the metal surface of the film forming apparatus, such as a drum or a belt, may be reduced, and the production tends to be difficult. On the contrary, when the content of the surfactant is excessively large, the film surface is bleeded. It can be seen that the design print layer tends to fall off.

In addition, antioxidants (phenols, amines, etc.), stabilizers (phosphate esters, etc.), coloring agents, flavoring agents, extenders, antifoaming agents, rust inhibitors, ultraviolet absorbers, organic powders (polymethyl) Methacrylate, etc.), and other water-soluble high molecular compounds (sodium polyacrylate, polyethylene oxide, polyvinylpyrrolidone, dextrin, chitosan, chitin, methyl cellulose, hydroxyethyl cellulose, etc.) may be added. .

The PVA system film which comprises the base film of this invention is manufactured as follows, for example.

First, each raw material, such as said PVA-type resin (A), Preferably a crosslinking agent (B), a filler (C), a plasticizer (D), surfactant, etc. is further mix | blended in a predetermined compounding quantity, and a film forming material is prepared. Next, a film forming material is cast from the T die onto the film forming belt or the film forming drum and dried to form a film, preferably by further heat treatment.

Such a drying process and a heat processing process are also useful as adjustment of the moisture content of the PVA system film mentioned later.

The method of heat treatment is not particularly limited, and examples thereof include hot rolls (including calendar rolls), hot air, far infrared rays, and dielectric heating. The surface to be heat-treated is preferably the surface (β surface) opposite to the surface (α surface) in contact with the film forming belt or the film forming drum, but may be nipped. Moreover, it is preferable that the water content of the film which heat-processes is about 4 weight%-8 weight% normally. Moreover, it is preferable that the water content of the film after heat processing is 3 weight%-7 weight% normally.

In more detail, after peeling from the film forming 1st drum of the said film forming belt or a film forming drum, until it winds up, it carries out 1 or more heat processing rolls of surface temperature 50 degreeC-120 degreeC, Preferably it is 1-10 pieces. It is preferable to pass. Here, the said film forming belt has an endless belt which runs across a pair of rolls, and casts and forms the film forming material which flowed out from a T die on an endless belt. It is preferable that the said endless belt consists of stainless steel, for example, and the outer peripheral surface is mirror-finished.

In addition, the said film forming 1st drum is a drum type roll located in the most upstream side in the film forming machine which casts and dries the film forming material which flowed out from T-die on one or more rotating drum-type rolls.

And after peeling from a film forming belt or a film forming 1st drum, until it winds up, the film forming material discharged from a T die etc. is dried on a film forming belt or a film forming 1st drum, and becomes a film form. The process of peeling from the first drum, preferably passing through the heat treatment machine, and winding up by the winding machine is shown.

It is preferable to perform heat processing by the said heat processing machine at 50 degreeC-120 degreeC, More preferably, it is 60 degreeC-110 degreeC. That is, if the temperature of the heat treatment is too low, when the base film floats on the surface during transfer, the curl of the surface (α plane) in contact with the film forming belt or the film forming first drum is strong, which tends to be a problem in the transfer process. If the temperature of the heat treatment is too high, the solubility of the base film during transfer is lowered, or the film is elongated in the longitudinal direction and the flatness is increased, so that the pattern at the time of transfer may be distorted.

The time required for the heat treatment depends on the surface temperature of the heat treatment roll, but is usually 0.5 seconds to 60 seconds, particularly 0.5 seconds to 30 seconds, still more preferably 0.5 seconds to 15 seconds. If the time is too short, the heat treatment tends to be insufficient. If the time is too long, the heat treatment is excessively excessive and the productivity tends to decrease. The heat treatment is usually performed by a dry roll treatment for film drying, followed by a separate heat treatment roll.

Moreover, as a moisture content of the said PVA system film, it is preferable that it is the range of 2 weight%-6 weight%, More preferably, it is 3 weight%-5 weight%. In other words, when the moisture content is too small, breakage tends to occur during the printing of the design, or the degree of curling of the PVA film itself is large. On the contrary, when the moisture content is too large, the curling becomes small, but the expected accuracy in the design printing is high. It can be seen that there is a tendency to cause problems such as deterioration.

In addition, the moisture content of a PVA system film can be measured, for example using a Culfischer moisture meter ("MKS-210" by Kyoto Denshi Kogyo Co., Ltd.).

As an adjustment method of the moisture content of the said PVA system film, the method shown below is mentioned, for example. That is, according to the adjustment method of the moisture content shown below, it becomes possible to set to the moisture content of the PVA system film in the said range.

(1) The moisture content is adjusted by the method of humidifying and dehumidifying a PVA system film by adjusting the dryer temperature at the time of drying and forming a dope which melt | dissolved PVA system resin (A) up and down. Since the temperature of dope influences drying efficiency according to the temperature, it adjusts within the range of 70 degreeC-98 degreeC. In addition, at the time of drying, Preferably it is between 1 degreeC-12 minutes in at least 2 or more hot air dryers which have a temperature gradient between 50 degreeC-150 degreeC, More preferably, between 60 degreeC-145 degreeC Preferably, drying for 1 to 11 minutes is preferable from the viewpoint of moisture adjustment.

If the inclination range of the drying temperature is too large or the drying time is too long, the drying tends to be excessive. On the contrary, if the inclination range of the drying temperature is too small or the drying time is too short, the drying tendency becomes insufficient. There is this.

The said temperature inclination changes a drying temperature stepwise between 50 degreeC-150 degreeC, Usually, the highest drying of the drying temperature range set once until the predetermined water content is gradually raised up from a drying start until it reaches predetermined water content It is effective to attain the desired water content finally by reaching the temperature and then gradually lowering the drying temperature. This is done to control crystallinity, peelability, productivity, etc., for example, 120 ° C-130 ° C-115 ° C-100 ° C, 130 ° C-120 ° C-110 ° C, 115 ° C-120 ° C-110 ° C-90 Temperature gradient settings, such as ° C, can be mentioned, and appropriately selected and carried out.

(2) Humidification and dehumidification of a PVA system film are performed by passing through a humidity control tank before winding up a PVA system film, and a moisture content is adjusted.

(3) The PVA-based film is dehumidified by carrying out the heat treatment before or after the PVA-based film is wound up to adjust the moisture content.

Thus, when the PVA system film obtained by forming into a film is considered the use as hydraulic transfer printing, it is preferable that the thickness of a PVA system film is 20 micrometers-50 micrometers, More preferably, it is 25 micrometers-45 micrometers.

In this invention, it is necessary for the base film comprised from the above-mentioned PVA system film to have a curl area ratio of 30% or less after 25 seconds after floating the said film on a liquid surface. If the curl area ratio exceeds 30%, the printed pattern may be distorted or the magnification may be enlarged during hydraulic transfer. The preferable range of such curl area ratio is 25% or less, More preferably, it is 20% or less, Especially preferably, it is 15% or less.

In this invention, a curl area ratio is a ratio of the area of the part which became non-contact with the liquid surface by curling the edge part of a film, when the film floats uniformly on the liquid surface with respect to a film area. Specifically, the curl area ratio is measured as follows.

That is, after filling 10 liters of water in the container of 420 mm x 320 mm x 160 mm in height, and adjusting it to 30 degreeC, the base film (size: 200 mm x 200 mm) is made into the (beta) film (film forming belt or the base film) of a film. Surface on the opposite side to the film forming drum) comes into contact with water and floats in water. Then, the film floated on the surface of the water, but if narrowing of the area floating curl, starting offset to the film, and then measuring the area (Amm ²⁾ floating after 25 seconds, and calculates the local area ratio (%) by the following equation.

Curled area ratio (%) = [1-A / (200 × 200)] × 100

In addition, when the edge part of a film curls, it usually curls upward with respect to a liquid level.

The area Amm ² is measured by camera-taking the operation and performing image processing with a computer.

In addition, the curl area ratio at the time of printing a design with respect to the said base film is measured as follows, It is preferable that such a curl area ratio is 30% or less, Especially 25% or less, Furthermore, 20% or less It is preferable to become.

That is, the gravure printing on the base film, the ink activator is further coated with a wire bar coater (# 10), and after 2 minutes, the ink activator coated surface is turned upward and floated on the water surface, as described above. Measure by

If the curl area ratio is more than 30%, the printed pattern may be distorted or the magnification may be enlarged during hydraulic transfer.

As a method of adjusting the curl area ratio of the said base film to the said range, the above heat processing is strongly performed on the surface (evaporation surface) ((beta) surface) which becomes a side opposite to the surface which contact | connects a film forming belt or a film forming drum with a calendar roll, for example. The method or the method of performing the above heat treatment only on the surface (evaporation surface) (β surface) which is opposite to the surface in contact with the film forming belt or the film forming drum in the heat treatment, and in particular, the film forming belt or film forming in such heat treatment It is preferable to perform only on the surface (evaporation surface) ((beta) surface) which becomes a side opposite to the surface which contact | connects a drum on the above heat processing conditions.

Moreover, in this invention, in the base film obtained above, it is preferable that the flatness after 30 second after making the said film float on the water surface is 30% or less, It is especially preferable that it is 25% or less, Furthermore, 20% or less. If the flatness is too high, the distortion of the printed pattern after the temple tends to increase.

About the measuring method of a flat rate, it is as follows in detail.

That is, after filling 10 liters of water in the container of 420 mm x 320 mm x 160 mm in height, and adjusting it to 30 degreeC, the base film (size: 200 mm x 200 mm) is made into the (beta) film (film forming belt or the base film) of a film. Surface on the opposite side to the film forming drum) comes into contact with water and floats on the surface of the water. Then, the base film swells and starts to expand after being floated, but the dot-to-dot distance (length direction (A) of 50 mm intervals in which the flatness percentage (%) 30 seconds after the film was started to float was drawn near the center with a water-based pen. ) And the widthwise direction B] are calculated by the following equation.

Flatness rate (%) = [1- (A / 50) / (B / 50)] × 100

In addition, the flatness at the time of printing a design with respect to the said base film is measured as follows, It is preferable that such a flatness is 30% or less, It is especially preferable that it is 25% or less, Furthermore, it is 20% or less.

That is, a gravure printing is carried out on the base film, and the ink activator is further coated with a wire bar coater (# 10), and after 2 minutes, the ink activator coated surface is placed upward and floated on the water surface, and measured as described above.

If the flatness is too high, the distortion of the printed pattern after the temple tends to increase.

As a method of adjusting the flatness ratio of the said film to the said range, for example, the method of reducing the weight at the time of peeling a film from a film forming belt or a film forming drum, or the temperature of the heat roll after peeling from a film forming belt or a film forming drum is more than necessary. And the method of not raising too much, the method of not lifting too much tension more than necessary by peeling from a film forming belt or a film forming drum, and winding up.

In addition, the film of this invention is a film which melt | dissolves in 30 degreeC water within 2 minutes. "Film which melt | dissolves in 30 degreeC water within 2 minutes" is sampled in the size of 3 cm x 3 cm, 30-degree water in 1 liter beaker etc. by fixing such a sample to a jig | tool, etc. It is immersed in (1 liter) and stirred with a stirrer or the like, and the time until the sample dissolves is within 2 minutes. Here, dissolution refers to the fact that such a sample is not recognized and recognized, but at this time is 1 mm or less in diameter. In the case of insoluble fine particles dispersed therein, the present invention is included in the meaning of dissolution.

The base film (disk film) obtained by this invention is subjected to a conventionally well-known moisture-proof packaging process, for example so that a change may not occur in the various physical property mentioned above, and to preserve | maintain it in the state suspended in the air in 10 degreeC-25 degreeC atmosphere. desirable.

Next, the hydraulic transfer printing method using the base film of the present invention will be described.

Examples of the hydraulic transfer printing method include a hydraulic transfer printing method according to a continuous method and a hydraulic transfer printing method according to a batch method.

First, the hydraulic transfer printing method according to the continuous method will be described.

That is, a predetermined design is printed on the base film surface obtained as mentioned above. Thereafter, an ink activator is coated on the design printing surface. Then, the base film is stretched after absorption, and a restriction of 1.5 times or less, preferably 1.4 times or less, is provided in the width direction with respect to the flow direction of the base film so that the design is not blurred. The base film is floated on the liquid surface and moved upward. Hydraulic transfer printing is performed by pressing a to-be-transferred body from above the said moving base film, and transferring the design printed on the base film surface to the to-be-transferred body. And after sticking, the target product is obtained by fully drying the to-be-transferred body which removed the base film and transferred the design.

On the other hand, the hydraulic transfer printing method according to the arrangement method will be described.

That is, a predetermined design is printed on the base film surface obtained as mentioned above. Thereafter, an ink activator is coated on the design printing surface. Then, in the same manner as the continuous method, the base film is stretched after the absorption, and the vertical film is provided 1.5 times or less, preferably 1.4 times or less, in each of the longitudinal and transverse directions with respect to the base film so that the design is not blurred. The base film is floated on the liquid surface with the design printing surface on which the activator is applied upwards. Then, hydraulic transfer printing is performed by pressing the transfer target from above the base film in a stationary state and transferring the design printed on the base film surface onto the transfer target and sufficiently fixing the transfer target. After fixing, the target product is obtained by sufficiently removing the base film and transferring the transferred object.

According to the hydraulic transfer printing method via such a process, the design printed on the base film surface can be transferred to the transfer object. Moreover, as a design printed on the said base film surface, it is not specifically limited, Any thing may be used as long as it is printable, such as wood grain, various patterns, an image, and the like.

The ink activator to be coated on the design printing surface is not particularly limited, and an addition of a resin to a solvent capable of reactivating the design printed on the base film surface is used, and further, a extender pigment, a plasticizer, a curing agent, and the like. Can be added as appropriate. For example, what mixed a pigment, a plasticizer, a butyl cellosolve acetate, and a butyl carbitol acetate with butyl methacrylate is used. Moreover, the coating method using a gravure roll or a spray is mentioned as a coating method of the said ink active agent.

Further, the step of applying the ink activator to the design printing surface may be either before the base film is floated on the liquid surface, or after the float on the liquid surface, and is particularly limited as long as the design is pressed before the transfer object from above the printed base film. none.

As a material of the to-be-transferred body in the hydraulic transfer printing method of this invention, it does not specifically limit, For example, a plastic molded object, a metal molded object, a wooden molded object, inorganic molded objects, such as glass, etc. can be used. In addition, the shape thereof is not particularly limited, and may be flat or have various three-dimensional shapes.

<Example>

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.

In addition, "%" in an example means a basis of weight unless there is particular notice.

Examples 1-5, Comparative Examples 1-2

[Production of base film]

After dissolving polyoxyethylene sorbitan monolaurate in water as PVA resin (A), crosslinking agent (B), filler (C), plasticizer (D) and surfactant (release agent) shown in Table 1, The aqueous solution was formed into a belt film forming machine equipped with a stainless endless belt according to the casting film forming method, and dried for 2 minutes at a temperature of 95 ° C., followed by heat treatment under the heat treatment conditions shown in Table 1, followed by a PVA system. A film (base film) was obtained. In Comparative Example 1, no heat treatment was performed. In Table 1, the filler is corn starch with an average particle size of 20 μm.

About the obtained base film, each physical property was measured as follows.

Each evaluation result is shown in Table 1 and Table 2.

[Printing base film]

The obtained base film was cut into a size of 200 mm x 200 mm, and the ink for a building material (a mixture of a mixture of red dye and barium sulfate (70%) and a mixture of alkyd resin and nitrocellulose (30%)) was filmed. Was uniformly applied to the α surface (belt surface) side at the time of casting film formation by gravure printing (dry thickness of the ink layer 2 µm). Thereafter, a black aqueous pen was used to draw a mark (dot) at 50 mm intervals in the longitudinal direction and the width direction in the center portion, and on the ink activator [butyl methacrylate / pigment / plasticizer / butyl cellosolve acetate / butyl carbitol Acetate = 8/20/20/26/26 (parts by weight)] was coated with a wire bar coater (# 10) to prepare a transfer printing film.

The following evaluation was performed about the obtained base film and the film for transfer printing.

The evaluation results are shown in Table 2.

[Moisture Content of Base Film (PVA Film)]

The moisture content of the obtained base film (PVA film) was measured using the Culfischer moisture meter (MKS-210 by Kyoto Denshi Kogyo KK).

[Curve Area]

(1) curl area ratio of base film

After filling 10 liters of water in the container of 420 mm x 320 mm x 160 mm in height, and adjusting it to 30 degreeC, the base film (size: 200 mm x 200 mm) was made into the (beta) film (film forming belt or film forming drum) of a film. The surface opposite to the surface facing to the surface) was brought into contact with water and floated in water. And the floating area (Amm <^2> ) after 25 second after starting to float a film was measured, and the curl area ratio (%) was computed by following Formula.

Curled area ratio (%) = [1-A / (200 × 200)] × 100

With respect to the measurement area, and the above operation, the camera and image processing by a computer, to measure the film area (Amm ^2).

(2) curl area ratio of film for transfer printing

As described above, the transfer printing film 2 minutes after the design and the ink activator was applied was floated on the water with the ink activator coated surface upward, and the floating area (Amm ² ) after 25 seconds was measured, Calculated by

[Flatness]

(1) flatness of base film

After filling 10 liters of water in the container of 420 mm x 320 mm x 160 mm in height, and adjusting it to 30 degreeC, the base film (size: 200 mm x 200 mm) was made into the (beta) film (film forming belt or film forming drum) of a film. Surface which is opposite to the surface facing the surface) is in contact with water, and floated on the surface of the water. Then, the distance between dots (length direction (A), width direction (B)) of dots at 50 mm intervals drawn in a flatness ratio (%) 30 seconds after the start of film release in the vicinity of the center with an aqueous pen was measured. It calculated by the following formula.

Flatness rate (%) = [1- (A / 50) / (B / 50)] × 100

(2) Flatness ratio of film for transfer printing

As described above, the transfer printing film 2 minutes after the design and the ink activator was applied was floated on the water with the ink activator coated surface side upward, and the flatness (%) after 30 seconds was calculated in the same manner as above.

[Transfer Printing Aptitude]

2 minutes after the design and the ink activator was applied, the transfer printing film was floated on the water with the ink activator coated surface side upward, and after 1 minute, a pressure-transfer printing was performed on the ABS resin molded article (flat plate). It was evaluated in five steps together.

5... The pattern is clear and no distortion.

4… Slightly distorted pattern is recognized, the chair is clear.

3... Distortion is acknowledged and the chair tends to be blurred.

2… The distortion of the pattern was large.

One… Could not transfer printing.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on the JP Patent application (patent application 2007-134866) of an application on May 22, 2007, The content is taken in here as a reference.

The base film for hydraulic transfer printing of the present invention can be widely applied to hydraulic transfer printing applications for exteriors of automobiles, exteriors of mobile phones, various telephone products, building materials, home and household goods, and the like.

Claims (12)

A base film for hydraulic transfer printing comprising a polyvinyl alcohol-based film, wherein a base area of curl after 25 seconds after floating the base film on a liquid surface is 30% or less. The base film for hydraulic transfer printing according to claim 1, wherein the flatness after 30 seconds after floating the base film on the liquid surface is 30% or less. The moisture content of a polyvinyl alcohol-type film exists in the range of 2 weight%-6 weight%, The base film for hydraulic transfer printing of Claim 1 or 2 characterized by the above-mentioned. The base for hydraulic transfer printing according to any one of claims 1 to 3, wherein the polyvinyl alcohol-based film is formed of a film forming material containing a polyvinyl alcohol-based resin (A) and a crosslinking agent (B). film. The base for hydraulic transfer printing according to any one of claims 1 to 4, wherein the polyvinyl alcohol-based film is formed of a film forming material containing a polyvinyl alcohol-based resin (A) and a filler (C). film. The base for hydraulic transfer printing according to any one of claims 1 to 5, wherein the polyvinyl alcohol-based film is formed of a film forming material containing a polyvinyl alcohol-based resin (A) and a plasticizer (D). film. The average viscosity of the 4 weight% aqueous solution of polyvinyl alcohol-type resin (A) is 10 mPa * s-70 mPa * s at 20 degreeC, Furthermore, polyvinyl The average saponification degree of alcohol-type resin (A) is 70 mol%-98 mol%, The base film for hydraulic transfer printing characterized by the above-mentioned. The thickness of a polyvinyl alcohol-type film is 20 micrometers-50 micrometers, The base film for hydraulic transcription printing of any one of Claims 1-7 characterized by the above-mentioned. The film-forming material containing the polyvinyl alcohol-based resin (A) is flow-cast on a film forming belt or a film forming drum, dried to prepare a film, and then opposite to the surface contacting the film forming belt or the film forming drum. Heat-processing is performed on the surface used, The manufacturing method of the base film for hydraulic transcription printing. The film-forming material containing the polyvinyl alcohol-based resin (A) is flow casted on a film forming belt or a film forming drum, dried to prepare a film, and then heat-treated on the surface opposite to the surface contacting the film forming belt or the film forming drum. The manufacturing method of the base film for hydraulic-transfer printing as described in any one of Claims 1-8 characterized by the above-mentioned. A process of printing a predetermined design on the surface of the hydraulic transfer printing base film according to any one of claims 1 to 8, a process of coating an ink activator on the design printing surface, and a flow direction of the base film for hydraulic transfer printing. And a step of 1.5 times or less in the width direction relative to the width direction, the process of floating the base film for hydraulic transfer printing on the liquid surface with the design printing surface upward, and pressing the transfer member from above the base film for hydraulic transfer printing to press the base film surface. And a step of transferring the design printed on the transfer onto the transfer target body. A process of printing a predetermined design on the base film surface for hydraulic transfer printing according to any one of claims 1 to 8, a step of coating an ink activator on the design printing surface, and vertical and horizontal respectively for the base film for hydraulic transfer printing. The vertical film of 1.5 times or less is provided in the direction of, and the base film is pressed by pressing the transfer object from above the base film for hydraulic transfer printing in the stop state and the process of floating the base film for hydraulic transfer printing on the liquid surface. And a step of transferring the design printed on the surface to the transfer target body.