JP2007152622A - Base film for transfer printing, manufacturing method thereof and transfer method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a base film for transfer printing which is a film of polyvinyl alcohol and little shows a dimensional change in printing, which is free from wrinkling or distortion of a pattern in swelling after it is put into water on the occasion of transfer and besides which enables high-precision transfer with an extension stress sharply reduced. <P>SOLUTION: The starting time of a break of the base film in 5°C water is 25-80 seconds. The film contains a polyvinyl alcohol resin (A) and a filler (B) and the content ratio between the polyvinyl alcohol resin (A) and the filler (B) is 60/40-85/15 in the weight ratio. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a transfer printing base film capable of smoothly giving a high-definition design to a transfer object having a three-dimensional surface such as a non-curved surface, a method for producing the same, and the transfer printing base film. It relates to the transfer method used.

  As a base film for transfer printing, for example, in Patent Documents 1 and 2, boric acid or its base material is added to a base film made of a polymer such as polyvinyl alcohol (PVA), starch, and polyacrylic amide to further improve the throwing power. It has been proposed to include a salt. However, in Patent Documents 1 and 2, although the throwing power has been improved, the stretch magnification is large, and the design printed on the base film and the adherend are transferred and printed with the recent high definition of the design. In some cases, the design has a different image. Further, when the crystallinity of the PVA is low, there is a problem that the film strength at the time of transfer is weak and the design property is lowered.

  In addition, for example, Patent Document 3 proposes a base film having a thickness of 35 μm or less, which has a composition containing two kinds of PVA resins at a specific weight ratio, and the film is formed into a thin film with a specific composition. Thus, it is disclosed that high-speed transfer is possible. However, since PVA with different polymerization degrees is mixed, swelling spots are likely to occur, and, as described above, transferred to the design printed on the base film and the adherend along with the recent high definition of the design. There was a problem that the printed design had a different image.

  Various studies have been made from the viewpoint of the composition of PVA and the types and contents of additives. For example, Patent Document 4 proposes a film made of a composition in which a natural gum mucilage is mixed with a PVA resin. However, since natural gum is used, there are problems such as a partial decrease in accuracy and low reproducibility in the printing surface. Patent Document 5 discloses a film capable of reliably transferring a high-definition design using modified PVA and a boron compound. Patent Document 6 discloses a film in which the temperature difference between two endothermic peaks measured by DSC is within 32 ° C. It is disclosed that a high design can be achieved by using. However, there are relatively many swelling wrinkles, and the design transferred and printed on the adherend may be different, so that the purpose has not been completely satisfied.

  Furthermore, Patent Documents 7 to 10 propose that a high design can be achieved by suppressing the extension of the film by defining the surfactant concentration in the transfer tank and the amount of the surfactant contained in the film. Further, in Patent Document 11, the moisture content of the base film is set to 1.5 to 4.0%, and the width shrinkage rate of the film is adjusted, thereby enabling high-definition transfer without shifting the printing pattern during printing. It is disclosed. However, in Patent Documents 7 to 10, although the spread of the film is suppressed and high-definition transfer is possible to some extent, the surfactant contained in the base film is always eluted in the transfer tank. It is difficult to maintain a constant surfactant concentration, and it is difficult to maintain a stable quality. In Japanese Patent Application Laid-Open No. H11-260260, although it can cope with high-definition printing from a base film, The design transferred and printed on the kimono may be different, and even this method has not completely satisfied the purpose.

JP-A-54-92406 JP 54-15028 A Japanese Patent Laid-Open No. 7-117327 Japanese Unexamined Patent Publication No. 7-117328 JP 2003-11590 A JP 2002-301899 A JP 2005-125717 A Japanese Patent Laying-Open No. 2005-1257178 JP 2005-145059 A JP 2005-153508 A JP 2005-60636 A

  The present invention has been made in view of the above-described technology, and is a PVA-based transfer printing base film that has little dimensional change during printing, and has a wrinkle pattern when swollen after landing on transfer. It is an object of the present invention to provide a base film for transfer printing that is capable of high-definition transfer without distortion of the stretching stress and with greatly reduced extension stress.

  However, as a result of intensive studies by the present inventors, in the prior art, when a large amount of filler was contained in the PVA resin, it was thought that the break start time of the film became extremely short and good transfer printing could not be performed. However, the inventors have found that the above object can be achieved by intentionally containing more filler than before and adjusting the film break start time to an appropriate range to form a film.

  That is, the break start time of the film in water at 5 ° C. is 25 to 80 seconds, the film contains the PVA resin (A) and the filler (B), and the PVA resin (A) and the filler (B ) Content ratio is 60/40 to 85/15 by weight, and relates to a base film for transfer printing.

  The tensile elongation at break of the transfer printing base film in a humidity controlled environment at 23 ° C. and 50% RH is preferably 40 to 230%.

In the intrinsic infrared absorption spectrum of the film surface measured by a Fourier transform infrared spectrophotometer of the base film for transfer printing, an absorption band of 1425 cm ^{−1 of} an absorption band intensity of at least one of the film surfaces of 1140 cm ⁻¹ It is preferable that the strength ratio to the strength is 0.7 or more.

  The viscosity of a 4% by weight aqueous solution of the polyvinyl alcohol-based resin (A) in the transfer printing base film is preferably 10 to 70 mPa · s at 20 ° C., and the average degree of saponification is preferably 70 to 98 mol%.

  The transfer printing base film preferably has a thickness of 30 to 60 μm.

  The filler (B) in the transfer printing base film is preferably a polysaccharide and / or an inorganic substance.

  The base film for transfer printing preferably contains 0.01 to 10% by weight of a crosslinking agent with respect to 100 parts by weight of the total of the polyvinyl alcohol resin (A) and the filler (B).

  It is preferable that the moisture content of the base film for transfer printing is 3.0 to 6.5% by weight.

  Further, the present invention provides a base film for transfer printing, wherein one or more heat treatment rolls having a surface temperature of 50 to 120 ° C. are passed through after being peeled off from the film forming belt or the first film forming drum. Regarding the method.

  Furthermore, the present invention includes (a) a step of printing a design on the transfer printing base film and applying an activator capable of being reactivated on the printing surface, and (b) a width with respect to the flow direction of the transfer printing base film. Set a regulation of 1.25 times or less in the direction, float on the water surface with the printing surface of the base film for transfer printing coated with the activator upward, and continuously press the object to be transferred from above the base film The present invention relates to a transfer method including a hydraulic transfer process.

  (A) a step of printing a design on the transfer printing base film and applying an activator capable of reactivation on the printing surface; and (b) 1.25 times or less of the transfer printing base film. It includes a step of providing vertical and horizontal restrictions, floating on the water surface with the printing surface of the base film for transfer printing coated with the activator facing upward, and pressing the transfer target from above the base film in a batch manner to perform hydraulic transfer. And a transfer method characterized by the above.

  The base film for transfer printing containing the polyvinyl alcohol resin (A) and the filler (B) has a break start time in 5 ° C. water of 25 to 80 seconds, and the polyvinyl alcohol resin (A) and the filler (B). By making the content ratio 60/40 to 85/15 by weight, there is little dimensional change during printing, no wrinkles or pattern distortion occurs during swelling after landing on transfer, and uniform throughout the entire surface Thus, it is possible to provide a base film for transfer printing capable of high-definition transfer.

  The base film for transfer printing of the present invention comprises polyvinyl alcohol (PVA) resin (A) and filler (B), has a break start time in water at 5 ° C. of 25 to 80 seconds, and PVA resin The content ratio of (A) and filler (B) is 60/40 to 85/15 in weight ratio.

  The PVA-based resin (A) used in the present invention may be unmodified or modified. In the case of modification, for example, 10 mol% or less, as long as the effect of the present invention is not inhibited in the main chain. In the range of preferably 7 mol% or less, other monomers can be copolymerized. Examples of such monomers include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, and the like. Unsaturated acids or salts thereof, mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid, or Its salts, alkyl vinyl ethers, polyoxyethylene (meth) allyl ether, polyoxyalkylene (meth) allyl ether such as polyoxypropylene (meth) allyl ether, polyoxyethylene (meth) acrylate, Polyoxyalkylene (meth) acrylates such as reoxypropylene (meth) acrylate, polyoxyethylene (meth) acrylamide, polyoxyalkylene (meth) acrylamides such as polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meta ) Acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, diacrylacetone amide, N -Acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethyldiallylammonium chloride, Methyl allyl vinyl ketone, N- vinylpyrrolidone, vinyl chloride, vinylidene chloride and the like. These other monomers may be used alone or in combination.

  Moreover, you may mix and use 2 or more types of PVA-type resin (A) as needed.

  The average viscosity at 20 ° C. of a 4% by weight aqueous solution of the PVA resin (A) is preferably 10 to 70 mPa · s, and more preferably 15 to 60 mPa · s. When the average viscosity of the 4% by weight aqueous solution is less than the lower limit value, the film strength when printing the design (pattern, pattern) on the base film of the present invention is insufficient, and printing spots tend to occur, In addition to facilitating dissolution of the base film, the transfer time is shortened, and the pattern printed on the film when it floats on water is not stable, and the throwing power tends to be lowered. When the average viscosity exceeds the upper limit, the adhesion between the transferred material and the transfer printing film (base film on which the design is printed) decreases during transfer to the transferred material, and wrinkles and peeling tend to occur. In addition, it is possible to suppress the extension of the film on the surface of the water, but in addition to delaying the transfer time, the viscosity tends to be high and film formation tends to be difficult. The viscosity is measured according to JIS K 6726.

  It is preferable that the average saponification degree of PVA-type resin (A) is 70-98 mol%, More preferably, it is 75-96 mol%. When the average saponification degree of the PVA resin (A) is less than the lower limit value, it tends to take a long time to dissolve the base film after transfer. When the upper limit value is exceeded, the dissolution time of the base film is delayed, Since the film strength is high, there is a tendency that creases occur during transfer or even if transfer is completed, the film removal is poor. The average saponification degree is measured according to JIS K 6726.

  Examples of the filler (B) include polysaccharides and / or inorganics. Among the polysaccharides, starch is preferable. Physically modified starch (α-starch, fractionated amylose, wet heat-treated starch, etc.); Enzyme-modified starch (hydrolyzed dextrin, enzyme-degraded dextrin, amylose, etc.); Chemically-modified modified starch (acid-treated starch , Hypochlorite oxidized starch, dialdehyde starch, etc.); chemically modified starch derivatives (esterified starch, etherified starch, cationized starch, crosslinked starch, etc.) and the like are used. Among the chemically modified starch derivatives, esterified starch includes acetate esterified starch, succinate esterified starch, nitrate esterified starch, phosphate esterified starch, urea phosphate esterified starch, xanthate esterified starch, acetate As the etherified starch such as acetate esterified starch, allyl etherified starch, methyl etherified starch, carboxymethyl etherified starch, hydroxyethyl etherified starch, hydroxypropyl etherified starch, etc. as cationized starch, starch and 2 -Crosslinked starch such as a reaction product of diethylaminoethyl chloride, a reaction product of starch and 2,3-epoxypropyltrimethylammonium chloride, such as formaldehyde crosslinked starch, epichlorohydrin crosslinked starch, phosphate crosslinked starch, acrolein crosslinked starch, etc. The Among them, raw starch is preferably used from the viewpoint of easy availability and economical efficiency.

  Examples of inorganic substances include talc, clay, silica, diatomaceous earth, kaolin, mica, asbestos, gypsum, graphite, glass balloon, glass beads, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, calcium carbonate, whisker-like Examples thereof include 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, and copper powder.

  These fillers (B) may be used alone or in combination of two or more.

  The content ratio of the PVA resin (A) and the filler (B) is 60/40 to 85/15, more preferably 65/35 to 80/20, by weight. When the content ratio of the PVA-based resin (A) is less than the lower limit, the film strength is greatly reduced, and there is a tendency to cause difficulty in production, printing, and transfer of a base film for transfer printing. In addition, the film strength is lowered, which causes a transfer failure. Further, when the PVA-based resin (A) exceeds the upper limit value, when transferring, when the film swells after landing, wrinkles greatly enter, and further when it extends within a regulation range of 1.25 times or less In addition, since the extension stress increases and wrinkles and creases occur, the transferable range is narrowed and not only the design is distorted but also the transfer magnification tends to be increased.

  The average particle size of the filler (B) in the base film for transfer printing of the present invention is preferably 0.1 to 30 μm, and more preferably 0.3 to 25 μm. If the average particle size is less than the lower limit value, powder formation becomes severe in the base film manufacturing process, which tends to hinder the work.If the average particle size exceeds the upper limit value, the film strength of the base film is greatly reduced, and during transfer In addition, the film tends to be easily broken during the base film manufacturing process and printing.

The crosslinking agent blended in the PVA resin (A) is not particularly limited as long as it causes a crosslinking reaction with the PVA resin (A). For example, K ₃ C ₆ H ₅ O ₇ (tripotassium citrate) ), Boric acid, calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum borate / potassium borate (ammonium metaborate, ammonium tetraborate, pentaborate) Ammonium phosphate, ammonium octaborate, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, octaborate) Potassium oxide, etc.), silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate, copper metaborate, copper tetraborate, etc.), Sodium oxalate (sodium metaborate, sodium diborate, 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.), boron Bismuth acid, magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, etc.), manganese borate (manganese borate, manganese metaborate, tetraborate) Manganese oxide), lithium borate (lithium metaborate, lithium tetraborate) , Pentaborate and lithium) other such as borax, car Knight, In'yoaito, island stone, Suian stone include boron compounds such as borate minerals such Zaiberi stone. These crosslinking agents are used alone or in combination of two or more. Among the above crosslinking agents, borax and boric acid are preferably used.

  The amount of the crosslinking agent is preferably 0.01 to 10 parts by weight and preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total of the PVA resin (A) and the filler (B). More preferred. If the amount of the cross-linking agent is less than the lower limit value, the film stretching speed at the time of transfer is increased, the transferable time is shortened, and the throwing power tends to be reduced. There is a tendency for the design to be distorted because wrinkles at the time of lowering or swelling are increased.

  Thus, a PVA-based resin (A) and a filler (B), preferably a resin composition further containing a crosslinking agent, is formed into a base film for transfer printing. It is not particularly limited, and after the resin composition is made into an aqueous solution, it is cast on a smooth metal surface such as a roll, drum, endless belt or the like, and water or a plasticizer described later is appropriately added to the resin composition. In addition, a polyvinyl alcohol film serving as a base film can be obtained by a melt molding method or the like such as an extrusion method.

  Further, at the time of production, a plasticizer is added to the resin or the aqueous solution as necessary. Examples of such plasticizers include glycerin, diglycerin, triethylene glycol, polyethylene glycol, polypropylene glycol, dipropylene glycol, and the like, and one or more of them are used in combination.

  Although it does not specifically limit about content of this plasticizer, It is preferable that it is 0.01-10 weight part with respect to a total of 100 weight part of PVA-type resin (A) and a filler (B), 0.05- More preferably, it is 8 parts by weight. If the content is less than the lower limit, the plasticizing effect is low and causes breakage. If the content exceeds the upper limit, the dimensional stability during printing tends to be poor, and high-definition printing tends to be difficult.

  Furthermore, the base film for transfer printing of the present invention may contain a surfactant for the purpose of improving the peelability between the metal surface such as a drum or belt of a film forming apparatus and the formed film. The surfactant is not particularly limited. For example, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl nonyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene Polyoxyethylene such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyalkylene alkyl ether phosphate monoethanolamine salt, polyoxyethylene laurylamine, polyoxyethylene stearylamine An alkylamine etc. are mentioned, It uses 1 type or in combination of 2 or more types. Among them, polyoxyalkylene alkyl ether phosphate monoethanolamine salt, polyoxyethylene alkylamine, and polyoxyethylene sorbitan monolaurate are preferable in terms of peelability.

  The content of the surfactant is not particularly limited, but is preferably 0.01 to 5.0 parts by weight with respect to 100 parts by weight in total of the PVA resin (A) and the filler (B). It is more preferable that it is 03-4.5 weight part. If the content is less than the lower limit, the peelability between the metal surface of the film forming apparatus, such as a drum or belt, and the film formed is difficult to produce, and if the content exceeds the upper limit, the film layer is bleed to form a printed layer. There is a tendency to drop out.

  In addition, antioxidants (phenolic, amine-based, etc.), stabilizers (phosphate esters, etc.), coloring agents, fragrances, extenders, anti-packaging agents, rust inhibitors, An ultraviolet absorber, inorganic powder, and other water-soluble polymers (polyacrylic acid soda, polyethylene oxide, polyvinylpyrrolidone, dextrin, chitosan, chitin, methylcellulose, hydroxyethylcellulose) may be added.

  The base film for transfer printing preferably has a break start time in water at 5 ° C. of 25 to 80 seconds, more preferably 30 to 75 seconds, and still more preferably 35 to 70 seconds. When the fracture start time is less than the lower limit, the shape of the base film itself can be maintained when floating and transferring to water at 30 ° C. within a regulation range of 1.25 times or less. ) Is pushed from the top of the film, the film (film) is easily cut and the pattern cannot be accurately transferred. When the break start time exceeds the upper limit value, when the floating film is transferred to water at 30 ° C. within the regulation range of 1.25 times or less, the base film is hard, and therefore when the object to be transferred (specific adherend) is pushed in. Folding occurs, and in extreme cases, the film is cut. For this reason, the time for dropping the transfer object must be greatly delayed, and the production efficiency is lowered.

  Here, the break start time in water at 5 ° C. means that the base film is fixed by sandwiching the base film between the mounts (outer dimensions: 50 mm × 50 mm, inner dimensions: 23 mm × 35 mm), 1000 ml of cold water at 5 ° C. in a 1000 ml beaker. The time until the base film swells and at least a part of the film starts to break (begins to break) under non-stirring conditions is gently immersed so as to become horizontal inside (depth from the water surface is 20 mm). .

  In the present invention, the timing for pushing the transfer object (adhered body) is not particularly limited. However, in consideration of the transfer start time and the film break start time, the film is allowed to land, and once wrinkles enter. There is no wrinkle and it becomes smooth. Thereafter, the film gradually swells and dissolves and can be transferred. This transferable time is preferably 40 to 180 seconds later, since a clear design transfer can be obtained. Note that the timing of pressing the transfer target, that is, the transfer start time may be any time as long as the base film is in a fluid state and the strength of the film is maintained. Specifically, the transfer target having a complicated shape is used. Although it is the timing at which wrinkles due to stress or the like do not occur even when the body is pressed, it is not limited, but normally, about 40 to 180 seconds after the water is put in the water tank is optimal.

  Moreover, it is preferable that the tensile breaking elongation in a 23 degreeC x 50% RH humidity control environment is 40 to 230%, More preferably, it is 45 to 220%. If the tensile elongation at break is less than the lower limit, the swelling wrinkle at the time of transfer is small, but there is a tendency to cause difficulty in the production, printing, and transfer of the base film. When floating and transferring to water, there is a tendency that the running performance is lowered and it is difficult to cope with a transfer object having a complicated shape. On the other hand, when the upper limit is exceeded, there are many wrinkles at the time of swelling, and when floating and transferring to water at 30 ° C. within the regulation range of 1.25 times or less, the extension stress is strong, and wrinkles (breaks) occur by the transfer time. There is a tendency to occur.

Further, the crystallinity index of the base film for transfer printing of the present invention is at least one of the film surfaces in the intrinsic infrared absorption spectrum of the film surface measured by a Fourier transform infrared spectrophotometer (FT-IR). Measured by the intensity ratio of the absorption band intensity of 1140 cm ^{-1 to} the absorption band intensity of 1425 cm ^{-1 on} the surface, the crystallinity index of at least one surface is preferably 0.7 or more, more preferably 0.75 or more It is. If the crystallinity index is less than the lower limit, the crystallinity of the film is low, so the solubility is high and the handle is cracked, and the film strength is greatly reduced, so that there is a tendency to cause poor wear-in. The upper limit of the crystallinity index is usually 1.4. When the upper limit is exceeded, the fracture start time is delayed, the productivity is deteriorated, and the throwing power tends to be inferior even at the time of transfer. .

  The intrinsic infrared absorption spectrum of the film surface is measured by the ATR method, which is an amount corresponding to the crystallinity in the region from the film surface to a depth of several μm.

  Although the film thickness of the base film for transfer printing of this invention is not specifically limited, It is preferable that it is 30-60 micrometers, More preferably, it is 32-50 micrometers. If the film thickness of the base film is less than the lower limit, there is a tendency that the film strength when printing the design on the base film is insufficient and print spots tend to occur.If the thickness of the base film exceeds the upper limit, the extension stress is increased. There is a tendency that wrinkles (breaks) are likely to occur within a large regulation range of 1.25 times or less. In addition, as the film thickness increases, the base film becomes stiff and creases occur when the transferred object is pushed in. In extreme cases, the film is cut off, so the time for dropping the transferred object is greatly delayed. Production efficiency tends to decrease.

  The water content of the transfer printing base film of the present invention is preferably 3.0 to 6.5% by weight, more preferably 3.3 to 6.3% by weight, and still more preferably 3.5 to 6.%. 0% by weight. If the moisture content is less than the lower limit, the film strength is greatly reduced, and there is a tendency to cause breakage during the production, printing, and transfer of the base film. If the moisture content exceeds the upper limit, the base wound in a roll shape Winding may occur while the film is packaged and left unattended, and there may be a problem in registration accuracy during printing.

  The base film for transfer printing of the present invention is subjected to heat treatment after the selection of the PVA resin, the types and blending amounts of fillers and plasticizers, the types and amounts of crosslinking agents used, and the molded film is dried. Thus, the crystallinity index can be achieved. There is no restriction | limiting in particular as the method of heat processing, For example, it is possible to heat-process by methods, such as a hot roll (a calender roll is included), a hot air, a far infrared ray, and dielectric heating. The surface to be heat-treated is preferably opposite to the surface in contact with the film-forming belt or the film-forming first drum. The water content of the film to be heat-treated is usually desirably about 4 to 8% by weight.

  It is preferable to pass one or more heat treatment rolls having a surface temperature of 50 to 120 ° C. until the film is wound after being peeled off from the film forming belt or the film forming first drum. Here, the film-forming belt has an endless belt that runs across a pair of rollers, and the stock solution flowing out from the die is cast on the belt and dried. The belt is preferably made of stainless steel, for example, and its outer peripheral surface is preferably mirror-finished. The film-forming first drum is a drum-type roll located on the most upstream side in a film-forming machine for casting and drying the stock solution flowing out from the die onto one or more rotating drum-type rolls, Until the film is peeled off from the belt or the film-forming first drum and then wound up, the stock solution discharged from the T-die or the like is dried on the film-forming belt or the film-forming first drum to form a film. The process from peeling from the film first drum, passing through a heat treatment machine, and being wound up by a winder is shown. It is preferable to perform heat processing at 50-120 degreeC, More preferably, it is 60-110 degreeC. When the temperature of the heat treatment is less than the lower limit value, the curling of the surface contacting the film forming belt or the first drum is strong and tends to cause problems in the printing and transfer process. There is a tendency that the water solubility after transfer is lowered due to excessive crystallinity. The heat treatment time is preferably 0.5 to 15 seconds, although it depends on the surface temperature of the heat treatment roll. Such heat treatment is usually performed by a separate heat treatment roll following the drying roll treatment for drying the film.

  Further, the present invention includes (a) a step of applying a reactive activator to the printed surface of the transfer printing base film, and (b) a printing surface of the transfer printing base film coated with the activator. Is a transfer method using a base film for transfer printing, which includes a step of floating on the surface of the water and pressing the transfer target from above the base film to perform hydraulic transfer, and when transferring continuously, The present invention relates to a transfer method using a base film for transfer printing, wherein transfer is performed with a restriction of 1.25 times or less in the width direction with respect to the flow direction.

  The present invention also relates to a transfer method using a base film for transfer printing, which is characterized in that, in the case of a batch method, transfer is performed with a vertical and horizontal restriction of 1.25 times or less applied to the film.

  A design (pattern, pattern) for transfer is printed on the surface of the base film for transfer printing of the present invention, and is practically used as a film for transfer printing. Examples of such designs include arbitrary patterns such as leopard patterns, wood grain patterns, marble patterns, geometric patterns, hieroglyphics, abstract patterns, characters, and the like. These designs (patterns, patterns) are preferably formed by printing ink formed by adding a colorant such as a dye or a pigment to a water-insoluble resin binder. Examples of the water-insoluble resin include a mixture of nitrified cotton and alkyd resin.

  (A) In the step of applying the activator, the activator can be applied by a gravure roll or spray. The activator is not particularly limited, but a solvent in which a resin can be added to a solvent that can reactivate a printed pattern is used. In addition, an extender pigment, a plasticizer, a curing agent, and the like may be appropriately added. For example, a mixture of butyl methacrylate / pigment / plasticizer / butyl cellosolve acetate / butyl carbitol acetate can be used.

  Subsequent to the step (a), the transfer printing film is floated on the water surface, and the adherend is pressed from above to perform the water pressure transfer (b) step. At that time, the range of regulation is 1.25 times or less so that the film does not stretch and the design is not blurred after water absorption. For example, in a continuous transfer device, the width direction with respect to the feed direction is the distance of the transport chain, and batch transfer In that case, it is better to limit the film periphery with a regulation frame of 1.25 times or less. The regulation range is preferably 1.25 times or less, and more preferably 1.20 times or less. When the regulation range exceeds 1.25 times, not only the design is blurred, but the throwing power tends to decrease.

  The material of the adherend is not particularly limited, and for example, a plastic molding, a metal molding, a wood molding, glass, an inorganic molding, or the like can be used. Further, the shape of the adherend may be flat or solid.

  The transfer printing base film of the present invention floats in water with the printing surface of the base film facing up, and after applying an activator that can be reactivated, presses the transferred object from above the base film to You may use by the method of transferring.

  EXAMPLES 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 the examples, “parts” and “%” mean weight basis unless otherwise specified.

Examples 1-4, Comparative Examples 1-3
[Preparation of base film]
After dissolving polyoxyethylene sorbitan monolaurate in water as a PVA resin (A), filler (B), cross-linking agent, plasticizer and release agent shown in Table 1, an aqueous solution of 18% was prepared. The film is formed by a casting film forming method using a belt film forming machine equipped with an endless belt, dried at a temperature of 95 ° C., then brought into contact with one hot roll at 85 ° C. for 7 seconds, and a PVA film (base film) ) In Example 4, no heat treatment was performed. In Table 1, filler (B1) is corn starch having an average particle size of 20 μm, DPG used as a plasticizer is dipropylene glycol, and Gly is glycerin.

  The following evaluation was performed about the obtained base film.

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

[Moisture content]
The water content of the obtained base film was measured using a Karl Fischer moisture meter (MKS-210, manufactured by Kyoto Electronics Industry Co., Ltd.).

[Starting time of 5 ° C cold water break of base film]
Place the base film in the mount (outside dimension: 50 mm x 50 mm, inside dimension: 23 mm x 35 mm), fix the base film, and gently dip it in 1000 ml of 5 ° C cold water in a 1000 ml beaker (from the water surface) The depth (20 mm) was measured under non-stirring conditions until the base film swelled and started to break (seconds).

  The portion protruding from the mount is cut before measurement, and the portion in contact with water is the same as the inner size (23 mm × 35 mm) of the mount.

[Tensile breaking elongation]
A base film that has been conditioned for 30 hours in a 23 ° C. × 50% RH humidity control environment is cut into a size of 150 mm (longitudinal direction) × 15 mm in the same environment, and this film is adjusted to 23 ° C. × 50% RH control. The breaking displacement was measured using an autograph (Autograph AGS-H, manufactured by Shimadzu Corporation) in a wet environment (tensile speed: 200 mm / min. Distance between chucks: 50 mm), and the breaking elongation was determined by the following equation. .
Breaking elongation (%) = (breaking displacement / 50 mm) × 100

[Crystallinity index of base film surface]
The surface of the base film was measured by the ATR method using a Fourier transform infrared spectrophotometer (Nicolet AVATAR360 manufactured by THERMOELECTRON) under a humidity control environment of 23 ° C. × 50% RH. The single reflection type ATR attachment used was Thunderdome (ATR crystal is Ge, the contact surface with the sample is a three-dimensional curved surface, and the incident angle of infrared rays is 45 degrees) manufactured by SPECTRA TECH. Other measurement conditions are: 256 sample scans (256 background scans per measurement), 4.00 resolution, 4.0 sample gain, 0.6329 mirror speed, 100.00 aperture, The detector is DTGS KBr, the beam splitter is KBr, and the light source is IR. The ATR correction is performed using the OMNIC ver. 7 was done.

In the infrared absorption spectrum of the base film, an intensity ratio of an absorption band intensity of 1140 cm ⁻¹ , which is known as a crystallization band, to an absorption band intensity of 1425 cm ⁻¹ was defined as a crystallinity index. However, the base line of the band when calculating the intensity of each band was drawn as shown in FIG.

[Print base film]
The base film is cut to a size of 150 mm x 150 mm and the building material ink [mixture of red dye and barium sulfate (70%), alkyd resin and nitrocellulose (30%)] is cast into the film After the film was coated uniformly on the belt surface side with a bar coater (dry thickness of the ink layer 2 μm), as shown in FIG. 2, marks (dots) at intervals of 40 mm with a black water-based pen 75 mm (center) (Near) and 15 mm from the end (near the end), and the activator (butyl methacrylate / pigment / plasticizer / butyl cellosolve acetate / butyl carbitol acetate = 8/20/20/26/26 parts by weight) Was applied to produce a transfer printing film.

[Correction during transfer]
One side is 1.1 times (inner dimensions: 165 mm x 165 mm) or 1.2 times (inner dimensions: 180 mm x 180 mm) of the size of the film for transfer printing (150 mm x 150 mm). Float in a tank. Next, the transfer printing film coated with printing and activator is gently floated with the printing surface facing up in the frame where the film is floated first. The film once wrinkles the entire film after landing, and then stretched uniformly and gradually stretches. However, the extension is stopped by the frame, and no further extension is possible. At that time, if the force to stretch the base film is large, wrinkles will gradually occur due to stress, and not only the entire surface of the film can be used without waste, but also the printed pattern may be distorted and the stretch magnification may be increased. . For this reason, once the film has landed, wrinkles once enter the entire film, and after that, the film is stretched homogeneously and then gradually extended. It is necessary that the stress habits caused by extension regulations do not occur without breaking down. The proper transfer time is 50 to 180 seconds after the base film has landed.
○: No wrinkle on the film even at the proper transfer time ×: Wrinkle on the film before the proper transfer time

[Around]
Gently transfer the above printing and transfer printing film (150 mm x 150 mm) coated with an activator with the printing surface up in the frame of the above described 1.1-fold frame and 1.2-fold frame floating in the water tank. Float. Then, after the film stretches and completely reaches the frame, a vinyl chloride cylinder (diameter: 30 mm) is pushed at a speed of 200 mm / min vertically from the top of the film, and the printed pattern is transferred to the cylinder surface. The height from the landing point to the part where the handle was cut was measured. The time to push the tube is between 50 and 180 seconds, the film will not be bent hard when the tube is inserted, and the optimum time for the pattern to be transferred to the cylinder without cutting deeply. To do.

[Dot spacing]
Transfer printing film (150mm x 150mm) coated with the above-mentioned printing / activator is gently placed with the printing surface facing up in the frame with the 1.1-fold frame and the 1.2-fold frame floating above the water tank. Float. Then, after the film stretches and completely reaches the frame, the vinyl chloride plate of the same size as the frame floats horizontally around the center of the film with the same size of the vinyl chloride plate in the frame as described above. Transfer to a vinyl chloride plate and measure the distance between the dots of the previously drawn water-based pen.

  From the results of Tables 1 and 2, Examples 1 to 3 were a combination of a specific PVA and a compounding agent, and the molded film was heat-treated after drying and manufactured. It turns out that it becomes moderate. In addition, Example 4 is not heat-treated, but it can be seen that a film having a certain level of break start time can be obtained by selecting and combining specific PVA and a compounding agent.

  On the other hand, in Comparative Example 1, since the content ratio of the filler is high, the strength as a base film and the elongation at break are low, and there is a concern about paper breakage during printing, and the dispersibility of the base film is enhanced during transfer. It can be seen that the handle cracks on the surface of the water, and that there is little PVA-based resin, so that there is a large decrease in throwing power.

  In Comparative Example 2, since the content ratio of the filler is low, the strength as the base film is high, but there is a concern that the transfer time is delayed because the break start time is long, and further, when the film is extended within the specified range, It can be seen that the stress is strong and stress wrinkles are generated, which causes the pattern to be distorted and the area that can be transferred to be narrowed.

  In Comparative Example 3, it can be seen that even if the content ratio of the PVA-based resin and the filler is good, the break start time is short, so that the throwing power is greatly reduced during the transfer, and the pattern cracks on the water surface also occur.

  The base film for transfer printing of the present invention can be widely applied to transfer printing on automobile interior and exterior products, mobile phones, electrical appliances, building materials, household and household items.

2 is an infrared absorption spectrum of the base film obtained in Example 1. It is a figure which shows the dot position of the water-based pen drawn on a film in the case of printing.

Claims (11)

The break start time of the film in water at 5 ° C. is 25 to 80 seconds, and the film contains the polyvinyl alcohol resin (A) and the filler (B), and the polyvinyl alcohol resin (A) and the filler (B ) Content ratio of 60/40 to 85/15 in weight ratio. 2. The base film for transfer printing according to claim 1, wherein the tensile elongation at break in a humidity controlled environment at 23 [deg.] C. and 50% RH is 40 to 230%. In the intrinsic infrared absorption spectrum of the film surface measured with a Fourier transform infrared spectrophotometer, the intensity ratio of the absorption band intensity of 1140 cm ⁻¹ of at least one of the film surfaces to the absorption band intensity of 1425 cm ⁻¹ is 0. The base film for transfer printing according to claim 1 or 2, wherein the base film is 7 or more. The 4% by weight aqueous solution viscosity of the polyvinyl alcohol-based resin (A) is 10 to 70 mPa · s at 20 ° C, and the average saponification degree is 70 to 98 mol%. A base film for transfer printing according to 1. The base film for transfer printing according to claim 1, wherein the film thickness is 30 to 60 μm. The base film for transfer printing according to any one of claims 1 to 5, wherein the filler (B) is a polysaccharide and / or an inorganic substance. The transfer printing according to any one of claims 1 to 6, further comprising 0.01 to 10 parts by weight of a crosslinking agent with respect to 100 parts by weight of the total of the polyvinyl alcohol resin (A) and the filler (B). Base film. The base film for transfer printing according to any one of claims 1 to 7, wherein the moisture content of the film is 3.0 to 6.5% by weight. The transfer printing according to any one of claims 1 to 8, wherein at least one heat treatment roll having a surface temperature of 50 to 120 ° C is passed between the film forming belt and the film forming first drum after being peeled off and wound up. Method for manufacturing a base film. (A) The process which prints a design on the base film for transfer printing in any one of Claims 1-8, and apply | coats the activator which can be reactivated on the printing surface, and (b) The flow of the base film for transfer printing The width of the base film for transfer printing coated with the activator is floated on the water surface with the regulation of 1.25 times or less in the width direction with respect to the direction, and continuously transferred from above the base film. A transfer method comprising the step of hydraulically transferring by pressing. (A) The process which prints a design on the base film for transfer printing in any one of Claims 1-8, and apply | coats the activator which can be reactivated on a printing surface, and (b) With respect to the base film for transfer printing In each case, the vertical and horizontal restrictions of 1.25 times or less are set, the printing surface of the transfer printing base film coated with the activator is floated on the water surface, and the transfer target is pressed from above the base film in a batch mode. And a hydraulic transfer process.

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