JPH0232160B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a printing method for transferring a printed pattern onto an object having an uneven or curved surface using water pressure.

(Prior art) It is already known to apply a printed pattern to a water-soluble film, float it on the surface of water, and then push the object to be transferred from above to transfer the printed pattern.
No. 14682). According to this method, it is possible to apply a constant and desired print pattern along the shape of transfer objects of various shapes, which is impossible with suminagashi. However, in this method, in order to perform the transfer, the printed pattern must be used after it has been printed but before it has dried, and therefore printing is performed each time the transfer is performed, which not only reduces printing efficiency but also reduces the ink. Since it cannot be dried, multicolor printing cannot be performed.

On the other hand, any pattern can be printed on a water-soluble base,
Furthermore, a method is also known in which an adhesive is applied, the pattern is floated on water, the water-soluble base is dissolved, the pattern remains on the water surface, and the object to be transferred is pressed against it from above (Japanese Patent Publication No. 57-50547). However, in this method, once the water-soluble base of the support is dissolved, it is difficult to maintain the shape of the pattern, and the transferred pattern inevitably suffers from distortion. Furthermore, as an invention by the same applicant as the present invention, there is a method in which a thin film with multicolor printing is coated with a liquid containing a solvent that swells the ink, the film is floated on water, and an object to be transferred is pressed from above. (No. 33115, 1973). This method uses a film printed in multiple colors and allows transfer without distortion of the pattern, but the efficiency of floating the film coated with liquid on water is not good, and the thin film does not change after floating on water. When spreading after water absorption and swelling, the spreading is not uniform due to the thickness and unevenness of the film and variations in the amount of ink applied to each part of the printed pattern, which may cause overlapping wrinkles in areas where spreading is slow. The pattern may become unsightly after being transferred.

In addition, different from the above method, there is also a method in which a patterned water-soluble support is floated on water, and then immediately before transfer, thinner is applied using a sprayer, and the transfer target is pressed against the support from above. (Unexamined Japanese Patent Publication No. 58-191187
issue). However, in this method, when thinner is sprayed, the water-soluble support suddenly stretches with strong force, which tends to cause overlapping wrinkles. It is difficult to print on such a film, and since the transfer is performed immediately after spraying the thinner, thinner is used to instantly activate the printed pattern. As a component, a solvent with a strong ability to dissolve ink must be used, which limits the range of solvents to choose from.Furthermore, the thin water-soluble support after spraying thinner is thin as mentioned above, so after spreading suddenly, The time it takes for the torn to pieces to disappear (diffusion) is short, and the transfer must be performed in an extremely short period of time, making it difficult to accurately transfer down to the finest details of the object to be transferred.

(Objective of the Invention) That is, it is desired to solve the following problems in this type of transfer using a water-soluble support and water pressure.

(b) The support must be thick enough to allow stable printing; (b) When the support is floated on water, it absorbs water and becomes flexible, but by the time transfer is complete, (c) The timing of spraying the liquid capable of dissolving the ink must be between the time the water-soluble support is floated in water and the time before the water-soluble support spreads; (d) The liquid that can be transferred It's a long time.

The present invention solves the above-mentioned drawbacks of the prior art,
It was designed to meet the requirements, and after printing on one side of a water-soluble film, it is dried to form a printed film, and then the printed film is floated on the water surface with the printed side facing up. , then,
An activating liquid that can reactivate the printed pattern is applied to the printing surface of the printing film, and after application, transfer is performed by pushing in part or all of the object to be transferred from above the printing film. A hydraulic transfer method comprising removing a water-soluble film, characterized in that application of the activating liquid is performed between time Tc and time Tb, and transfer is performed between time Te and time Tb. A hydraulic transfer method.

[In the above, times Tb, Tc, and Te are all times measured based on the time when the printed film was floated on the water surface, and Tb is the time when the printed film is coated with an activating liquid in advance. Tc is the time at which the printed film floating on the water surface with its surface facing up starts to spread, and Tc is the time when the printed film floating on the water surface with its coated side facing up starts to spread. Te is the time at which the printed film is spread to about 1.2 to 1.3 times its original size, and if the activating solution is applied between Tc and Tb after the printed film is floated on the water surface, the printed film is placed on the water surface with the coated side facing up. Each refers to the time at which the spreading of the floating printed film is prevented by the spreading barrier. ].

First, in the present invention, one side of a water-soluble film is printed and then dried to produce a printed film.

The most preferred example of the printed film is a polyvinyl alcohol resin film printed by a gravure printing method and dried. By changing various conditions such as the degree of polymerization, degree of saponification, and blending of additives such as starch, polyvinyl alcohol resin film can be improved in terms of mechanical strength required for printing, moisture resistance during handling, and ability to float on water. It is possible to control the speed of softening due to water absorption, the time required for spreading or diffusion, and the ease of deformation during transfer. In addition, by using the gravure printing method, the ink vehicle is selected in consideration of its adhesion to the transfer target during transfer, and the ink can be air-dried or set by slightly heated air without the need for heating. Printing ink can be dried and fixed by air drying.

An example of a more preferable film containing polyvinyl alcohol (PVA) resin as its main component is JP-A-Sho.
It has a composition of 80% PVA resin, 15 parts starch, and 5 parts starch, as described in No. 54-92406, and has an equilibrium moisture content of about 3%.

In addition to polyvinyl alcohol resin films, printing films can in principle be used as long as they are water-soluble (including water-swellable films), and examples include the following: dextrin, gelatin, glue, casein,
Shellac, gum arabic, starch, protein, polyacrylic acid amide, sodium polyacrylate, polyvinyl methyl ether, copolymer of methyl vinyl ether and maleic anhydride, copolymer of vinyl acetate and itaconic acid, polyvinylpyrrolidone, or cellulose, Films of cellulose derivatives such as acetyl cellulose, acetyl butyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and single or mixed resins such as sodium alginate. These films, including the polyvinyl alcohol resin film, have a thickness of 10 to 100 μm, preferably 20 to 60 μm.

Note that the above film may be laminated with a water-permeable base material such as paper, non-woven fabric, cloth, etc., but if it is laminated in this way, it must be separated when floating on water, or it may be difficult to use water. It is preferable that the structure is such that the separation is performed at

As for the printing method, a known printing method other than the above-mentioned gravure printing method can be adopted, and a known printing ink can also be used. Examples of ink vehicles include: Various oils and fats such as linseed oil, soybean oil, and synthetic drying oils; Cellulose derivatives such as ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, nitrocellulose, and cellulose acetate. , styrene resins and styrene copolymer resins such as polystyrene and poly-α-methylstyrene, acrylic or methacrylic resins alone or copolymer resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate, and rosin. , rosin-modified maleic acid resin, rosin-modified phenolic resin, rosin ester resin such as polymerized rosin, polyvinyl acetate resin,
Coumaron resin, vinyl toluene resin, vinyl chloride resin, polyester resin, polyurethane resin, butyral resin, polyamide resin, vinyl chloride-vinyl acetate copolymer resin, polyvinylidene chloride resin,
Melamine resin, silicone resin, chlorinated rubber, rubber derivatives of cyclized rubber, glue, casein, dextrin, zein, etc.

Two or more of the above resins may be used if necessary.

Printed film can be stored by winding it up or cutting it to the required size if necessary, but since it is a water-soluble film, it is relatively easy to absorb water, so take measures to prevent it from moisture until it is used. It is a good idea to take this lesson.

The desiccant printed film is then floated on the surface of the water, printed side up. When floating, you can cut the film one by one and float it, but
As shown in No. 33115, a continuous sheet may be floated using a water stream (without applying an activating liquid). If air bubbles form between the film and the water surface when floating on water, the film above the air bubbles will be inhibited from absorbing water and will be less likely to deform during transfer, so care must be taken to prevent air bubbles from intervening.

The water in which the printed film is floated may be appropriately heated. Also, the water-soluble film dissolves in water and its concentration gradually increases, but in pure water, the time it takes for the water-soluble film to diffuse is short, and as the concentration increases through repeated transfers, the time it takes to diffuse increases. stretches. When using polyvinyl alcohol film as a water-soluble film, keep the polyvinyl alcohol resin concentration in water at around 3000 ppm. Even if the concentration increases, the time for diffusion has already reached saturation, so transfer can be repeated in the same water. Therefore, it is advisable to adjust the concentration to about 3000 ppm in advance.

At a predetermined time, an activating liquid that can reactivate the printed pattern is applied to the printed film floating on the water surface with the printed side facing up. The application timing of this activation liquid is determined as follows.

(a) First, an activating liquid is applied to the printed surface of a printed film, and the film is floated on the water surface with the coated side facing up. The floating printed film absorbs water from the lower surface and swells, but at this point the printed film does not substantially change in size. Thereafter, the printed film begins to increase (expand) in the vertical and horizontal dimensions. In the case of polyvinyl alcohol film (manufactured by Nichigo Film Co., Ltd., Hi-Selon C-300, thickness 40 μm) used in the examples described later (the same applies below)
The time Ta when the size begins to increase is based on when the printed film is floated on the water surface (the same applies below)
After about 30 seconds.

(b) Next, after applying the activating liquid in (a), the printed film floating on the water surface increases in size almost linearly after time Ta, but after a certain time Tb, there appears to be no spreading. The speed increases rapidly, and at the same time, the printed film is torn into strips and disappears (in this sense, it will be referred to as "spreading").
Time Tb is, for example, 120 seconds later.

(c) On the other hand, when placing the printed film coated with the activating liquid on the water surface, a spreading barrier is placed in advance on the water surface so that the printed film is centered within the barrier. For example, if the spreading barrier and the printed film are square, and the vertical and horizontal dimensions of the spreading barrier are about 1.3 times the vertical and horizontal dimensions of the printed film, then the time Tc at which the printed film spreads and is prevented from spreading by the spreading barrier is Determined. In this case
Tc is, for example, after 75 seconds.

(d) Tests were conducted for each of the above times Ta, Tb, and Tc, and it was found that if the activating liquid was applied to the printing film floating on the water surface after time Ta but before time Tc, it would not overlap. This is not preferable because it tends to cause wrinkles, and it is better to apply the activation liquid after time Tc. However, if the activation liquid is applied late after Tc, the maximum transferable time will be shortened to Tb, so the activation liquid application time Td will be from Tc to
It is preferable that the time is before about the midpoint between Tb, and the time Td is about 80 seconds later.

Next, the timing of transcription is determined as follows.

(e) The printed film on the water surface was coated with the activating liquid at the timing of Td. The water-soluble film as the base material had already absorbed water and swelled, but its spreading was prevented by the solidified printed pattern. As the printed pattern is activated and softened by the application of the activating liquid, it begins to spread, and the dimensions of the printed film gradually expand, but eventually the spreading barrier stops the spreading and the dimensions of the printed film become constant. . Under the conditions of the dimensions of the printed film and the spreading barrier described above, the time Te at which spreading is inhibited is 85 seconds.

Therefore, the transferable time is after Te,
And the time is equivalent to less than Tb. In the above example, it is about 35 seconds from 85 seconds to 120 seconds.

In the present invention, it is not clear why if the activating liquid is applied to the printed surface of the printed film floating on the water surface after time Tc, no overlap and wrinkles will occur during spreading, but if the activating liquid is applied before time Tc,
The spreading force of the printed film, that is, the force that tries to spread it, is strong, and when there is a difference in the spreading force locally due to the thickness of the film, etc., uneven spreading occurs and overlapping wrinkles are likely to occur. On the other hand, time
This is thought to be because after Tc, the force that tries to spread the printed film is weak, and even if there is a difference in the force that tries to spread partially, there is no longer enough force to cause overlapping wrinkles.

The activating liquid used in the present invention is capable of reactivating the pattern printed on the printing film, and in this sense, if the solvent in the printing ink is used,
However, as will be described later, if it dries and is lost within the time required for transfer, it is not preferable because the reactivated state cannot be maintained. Examples of solvents that can be adopted from this point of view are as follows. Examples of such solvents include known solvents such as pentane, hexane, heptane, octane, etc., and aliphatic hydrocarbons such as gasoline, petroleum, benzine, mineral spirits, petroleum naphtha, etc.; , aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and ethylbenzene, halogenated hydrocarbons such as trichlorethylene, perchlorethylene, chloroform, and carbon tetrachloride, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, Monohydric alcohols such as amyl alcohol, benzyl alcohol, diacetone alcohol, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone, ethyl Ethers such as ether, isopropyl ether, ethylene glycol mono-methyl ether, ethylene glycol mono-ethyl ether, diethylene glycol mono-methyl ether, diethylene glycol mono-ethyl ether, diethylene glycol mono-butyl ether, diethylene glycol di-butyl ether, etc. , ethylene glycol mono-methyl ether acetate, ethylene glycol mono-ethyl ether acetate, diethylene glycol mono-methyl acetate, diethylene glycol mono-ethyl ether acetate, diethylene glycol mono-butyl ether acetate, and other acetic acid esters; Esters such as butyrate esters, nitrohydrocarbons,
Nitriles, amines, other acetals, acids, furans, etc. can be used alone or as a mixed solvent.

Moreover, a resin that dissolves in the above solvent can be added to the above solvent.

That is, known materials such as vinyl chloride,
Vinyl halide monomers such as vinylidene chloride, styrene and its derivatives, vinyl ester monomers such as vinyl acetate, allyl alcohol and allyl esters, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid. unsaturated carboxylic acids such as, ester derivatives, nitrile derivatives or amide derivatives of the above unsaturated carboxylic acids, N-methylol derivatives and N-methylol ether derivatives of the acid amide derivatives of the above unsaturated carboxylic acids, glycidyl acrylate,
Glycidyl methacrylate, allyl glycidyl ether, vinyl isocyanate, allyl isocyanate, 2-hydroxyethyl-acrylate or -methacrylate, 2-hydroxypropyl-
Acrylate or -methacrylate, ethylene glycol monoacrylate or -monomethacrylate, ethylene glycol diacrylate or -dimethacrylate, maleic anhydride, itaconic anhydride, methyl vinyl ketone, butadiene, ethylene, propylene, dimethylaminoethyl methacrylate, vinylpyridine , tert-butylaminoethyl methacrylate, monoallyl ether of polyhydric alcohol, etc., thermoplastic resins such as homopolymers or copolymers of monomers, polyamide resins, polyester resins, phenolic resins, melamine resins. Thermosetting resins such as resins, urea resins, epoxy resins, diallyl phthalate resins, silicone resins, polyurethane resins, modified resins or initial condensates thereof, other natural resins, rosin and its derivatives, cellulose By using a swelling liquid containing 5 to 60% by weight of a resin such as a derivative, natural or synthetic rubber, or petroleum resin, the viscosity can be easily adjusted, regardless of the application method, the ink retention time is long, and the transfer time is short. Effects such as long-lasting hair can be obtained.

In addition to the solvent and resin, the activation liquid also contains extender pigments,
Plasticizers, curing agents, etc. can also be added as appropriate. When an extender pigment is added, the solvent in the activating solution can be easily removed during washing with water after transfer. Addition of a plasticizer improves the extensibility of the activation liquid and improves deep drawing properties. Further, when a curing agent (eg, isocyanate) is added, the adhesion between the printed pattern and the substrate after transfer is improved.

Since the above-mentioned activating liquid is applied to the film on the water surface, it must not apply local force to the printed film, causing wrinkles or causing water droplets on the printed film. From this point of view, a preferred method for applying the activation liquid is a method using an airless gun, which has the advantage that there is no jet flow, the printing film does not move, and it can be applied over a wide area in a short time. Another method that can be used is to apply ultrasonic waves to the activating solution in a container and let it air at room temperature. However, in this case, only the solvent in the activating solution is vaporized, so essentially only the solvent is used. Suitable for activating liquids.

The coating amount of the activator is about 5 to 30 g/m ² (at the time of coating).

A transfer object is pushed from above at a predetermined time into a printing film that is floating on the water surface and coated with an activating liquid. The transferable time is as described above.

Further, in the above, it is preferable that the size of the barrier to prevent the printed film from spreading is about 1.2 to 1.3 times the size of the printed film, but depending on the printed film, it may be outside this range. It's okay. Even if the barrier is in the form of a frame, other forms such as 〓-shaped ones are arranged in succession (Japanese Patent Laid-Open No. 54
-33115) or the tank itself containing water.

By pushing a transfer object onto the printing film on the water surface for the time range mentioned above, the printing film deforms according to the shape of the transfer object, and the water pressure brings the printing film into close contact with the transfer object and activates it. The printed pattern is transferred to the transferred object.

Thereafter, the water-soluble film adhering to the surface of the transfer object is removed by washing with water or the like, and after drying to remove moisture, painting is performed as necessary. Here, washing with water may be carried out by once pulling up the transferred object and transferring it to another water tank, but it is also possible to continue dissolving the transferred object by keeping it in the water in the water tank used for transfer, or This may also be done by removing it from the water and showering or spraying it with water or warm water.

(Effects of the Invention) The method of the present invention has the following advantages compared to a method in which an activating liquid is applied in advance and then floated on the water surface, and a method in which the printed film is simply floated on the water surface and then an activating liquid is applied. have That is, when the activating liquid is applied to a printed film, the printed pattern that had previously been prevented from spreading softens and immediately begins to spread, but in the present invention, the spreading force of the printed film is extremely small, and almost no spreading occurs. After time Tc, when it became steady, it rapidly spread,
Since the activating liquid is applied until the time Tb disappears, the spreading force is weak and the spreading speed is low.This is due to the unevenness of the thickness of the water-soluble film and the degree of activation of the printed pattern layer. The occurrence of wrinkles due to the spreading speed distribution can be prevented. In addition, a thick water-soluble film can be used since the generation of wrinkles can be prevented, and a thick water-soluble film is advantageous in terms of mechanical strength and deterioration due to moisture absorption. In addition, the method of the present invention allows sufficient time from application of the activating solution to transfer, as well as the time required for transfer, so there is no need to use a solvent with particularly high dissolving power in the activating solution. There is a wide range of selection. Moreover, the method of the present invention has the advantage that it can be applied to either method, whether the printed film is used in the form of a roll or in the form of individual sheets.

Example Polyvinyl alcohol resin film (manufactured by Nichigo Film Co., Ltd., Hi-Selon C-300, thickness 40 μm)
A rosewood pattern was printed in two colors using a gravure printing method using nitrocellulose resin ink (Moroboshi Ink Co., Ltd., KLCF) in the reverse order of the usual printing order.

Cut the printed film obtained above into a square of 800 mm x 800 mm, and place the cut printed film in a water tank filled with water at a temperature of 27°C (inner size: 950 mm x 950 mm).
A square) was floated in the center of the water surface with the printed side facing up.

After 80 seconds from the time the printed film was floated on the water surface, an activating solution having the composition shown below was applied using an airless gun in an amount of 10 g/m ² .

Activation liquid composition Acrylic resin 15% by weight Xylene 10 〃 Methyl isobutyl ketone 30 〃 Butyl cellosolve 45 〃 Next, a furniture handle made of ARS resin was applied from above the printing film coated with the activating liquid, and the printing film was floated on the water surface. After 100 seconds of measurement, the handle was pushed in and transferred, then removed from the water, washed with water in the shower, and dried to obtain a furniture handle with a three-dimensionally transferred rosewood pattern.

Furthermore, polyurethane resin paint (manufactured by Fujikura Kasei, Retsukura Tsuku 110) was applied to the transferred furniture handle.
was applied at 10g/m ² (when dry) to form a protective layer.

Claims (1)

[Claims] 1. After printing on one side of a water-soluble film, it is dried to form a printed film, and then the printed film is floated on a water surface with the printed side facing up,
After that, an activating liquid that can reactivate the printed pattern is applied to the printed surface of the printing film, and after application,
This is a hydraulic transfer method that involves pushing part or all of the transfer target from above the printing film to perform the transfer, and after the transfer, removing the water-soluble film from the transfer target, and the activation liquid is applied at time Tc. to time Tb, and the transcription is performed from time Te to time Tb.
A hydraulic transfer method characterized in that it is performed during Tb. [In the above, times Tb, Tc, and Te are all times measured based on the time when the printed film was floated on the water surface, and Tb is the time measured based on the time when the printed film was coated with the activation liquid in advance. Tc is the time at which the printed film floating on the water surface with its surface facing up starts to spread, and Tc is the time when the printed film floating on the water surface with its coated side facing up starts to spread. Te is the time at which the printed film is spread to about 1.2 to 1.3 times its original size, and if the activating solution is applied between Tc and Tb after the printed film is floated on the water surface, the printed film is placed on the water surface with the coated side facing up. Each refers to the time at which the spreading of the floating printed film is prevented by the spreading barrier. ] 2 The spreading barrier is 1.2 to 1.2 of the original size of the water-soluble film.
The hydraulic transfer method according to claim 1, wherein the hydraulic transfer method is installed so that the size is 1.3 times larger.