DE2918639C2 - - Google Patents

Description

The invention relates to a method for transferring one to one thin film of a pattern printed on a polyvinyl alcohol resin on a surface of an object or object in which one the object or the object on the with the printed surface thin floating upward on the surface of water Presses the film and dips the object into the water, taking care that boric acid or salts thereof in the thin film or in the water is (are), whereby a clear, sharp and precise pattern on the object can be transferred even if the surface is uneven having; the invention particularly relates to a transfer printing process to apply a nice print on uneven Objects or objects with grooves, protrusions, a curved one Surface and the like

DD-PS 1 897 describes the production of decals and sliding pictures described in order to accelerate the dissolution of polyvinyl alcohol an alkaline salt such as borax is added in water. It is believed, that this acceleration of dissolution is due to a salt effect which increases the degree of dispersion of the polyvinyl alcohol powder. A Dimensional stabilizing effect of boric acid or its salts on polyvinyl alcohol films against water is not in this patent described.

A printing device is known from US Pat. No. 40 10 057,  which is a thin film on which a pattern has been printed is floating on the surface of a liquid and the pattern on the surface of an object to be printed with the pattern or object is transferred using the liquid pressure by immersing the object or object in the liquid, while the object or the object to the thin film is pressed (see the abstract of this patent). It indicates that it is most preferred to be thin Film to use a floury or floury film, and that the thin film materials are also polyacrylic acid sodium, Polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, Polyethylene oxide, polyvinyl pyrrolidone and acrylic acid amide as synthetic high molecular substances, glue, gelatin, Casein and polypeptide among the high molecular substances, Starch, cellulose, dextrin, albumin, soybean protein, gum arabic and tragacanth among the vegetable high molecular weight Substances, and seaweed glue, Japan gelatin and alginic acid sodium can act among the high molecular weight seaweed substances.

The thin film made from the above materials however, does not have sufficient strength for multi-color printing and stretch, not good swellability, especially not good Stretchability on the surface of the water, as detailed below explained, and no great flexibility and no good softening properties on so that it is difficult to thin the film solid with an uneven surface of an object to be printed or object to connect. Under the large number of the materials listed above is the only one in the Practical material is a polyvinyl alcohol resin.  

However, a thin film made of a polyvinyl alcohol resin also has the following shortcomings: since the thin film stretches a lot and often partially dissolves in water so that it tears and spreads when it floats on the surface of the water, it is difficult to accurately match a pattern printed on the thin film to transfer to the object. Because the period of time, those for pressing on an object to be printed or object to the thin film is short, occurs easily mistransference. In addition, in the case of printing of an object with a complicated curved surface, a pointed part or a concave Part, a spherical object or an object longitudinal (elongated) object Slot, a malfunction, or an overlap of the printed one Pattern occur.

The aim of the present invention is therefore to provide a method for exact and clear or sharp transfer of a printed Pattern from the surface of a thin film to the surface of an object to be printed or object by checking the stretch of the floating on the surface of the water specify thin film. Another object of the invention is therein a method of transferring a printed pattern specify the period of time allowed for treatment is long and the transfer process can be carried out easily can. Another object of the invention is a method for transferring a printed pattern to an object or to indicate an object with a complicated curved surface, where there is no slot, no interference and no overlap of the  Pattern occurs.

These and other objects, features and advantages of the invention go from the following description in conjunction with the enclosed Drawing. Show:

Fig. 1 and 2 are diagrams which illustrate the strain curves of thin films.

According to the invention, the above-mentioned goals can be achieved by that in a process of the type mentioned a polyvinyl alcohol resin with an average degree of polymerization of 300 to 3000 and an average degree of hydrolysis of 65 to 97 mol% and boric acid or a salt thereof to the thin film in an amount of 0.02 to 10 wt .-%, based on the polyvinyl alcohol resin, or the water incorporated in a concentration of 0.002 to 0.5% by weight.

This means, According to the invention, (i) a thin film made of a polyvinyl alcohol resin is left, of 0.02 to 10% by weight, preferably 0.1 to 2% by weight Boric acid or a salt thereof, based on the polyvinyl alcohol resin, contains, float on the surface of the water and performs transfer printing by (hereinafter referred to as "embodiment X"), or (ii) a thin film of polyvinyl alcohol resin is left float on the surface of the water, the 0.002 to 0.5 wt .-% Contains boric acid or a salt thereof, and carries out the transfer printing by (hereinafter referred to as "embodiment Y" designated).  

Under the term "boric acid or a salt thereof" used here is boric acid of the formula H₃BO₃, borax of the formula Na₂B₄O₇ · 10 H₂O and to understand anhydrous borax of the formula Na₂B₄O₇, and it Borates other than sodium borate can also be used according to the invention will.

By using these methods, the following can be given excellent effects when transfer printing in an industrial Scales to be achieved:

• 1. Because the thin film used in the present invention has tensile strength of not less than 1.0 kg / cm and an elongation of no more than 200% at ordinary temperature and ordinary humidity (20 ° C, 65% relative humidity) and no tendency to roll up and a good one Dimensional stability, the present is suitable Invention for performing multi-color printing;
• 2. The thin film printed with the pattern spreads smoothly the surface of the water without rolling up, and the allowable time for treatment or processing long, and the transfer is easy;
• 3. the thin film has good extensibility (good expansion capacity) and high softness on the surface of water, a pattern printed on the thin film is on an object or an object with an uneven one Surface transferred without a slit, a glitch and pattern overlap occurs;  
• 4. since the expansion of a thin film on the surface of the Water is controlled in a suitable manner, no occurs Uncertainty (blurring) of a printed pattern due to excessive Expansion of the pattern on;
• 5. the thin film that sticks to the surface of a printable Object or object sticks, can be washed with water slightly removed from the surface after transfer printing will.

According to the invention, a beautiful, clear or sharp imprint not just be applied to items that have a smooth possess (flat) surface, but also on those with complicated curved surfaces.

The polyvinyl alcohol resins used according to the invention are those with an average degree of polymerization from 300 to 3000 and an average degree of hydrolysis of 65 to 97 mol%. If the average degree of polymerization is less than 300, the film strength, especially that Film strength on the surface of the water, very low, so that the film breaks and the transferred pattern is disturbed. If the average degree of polymerization is more than 3000, the film strength is too high and the film lacks the required Adaptability, under the term "adaptability" the Property of the film is to be understood at the time of pressing an object to the film and immersing it in the water to follow exactly the surface of the object and on this surface to stick without tearing and wrinkling.  

If the average degree of hydrolysis is less than 65 mole%, the film lacks what is required Expansion, the flexibility and the required Adaptability. On the other hand, if the average If the degree of hydrolysis is more than 97 mol%, the film lacks the required Adaptability when transferring, as the film turns into Time of swimming rolls up on the surface of the water and also the necessary expansion and the necessary Lack of flexibility on the surface of the water, and In addition, the film is removed by washing with Water difficult after transfer.

The polyvinyl alcohol resins can be used individually or in the form of a mixture be used. When using two or more types of polyvinyl alcohol resins, the average polymerization and degrees of hydrolysis of a mixture thereof within the above ranges.

According to the invention, modified polyvinyl alcohol resins with the above average degrees of polymerization and hydrolysis can also be used. Examples of modified polyvinyl alcohol resins which can be used according to the invention are hydrolyzed copolymers of a vinyl ester with an unsaturated carboxylic acid or an ester or a salt thereof, an unsaturated sulfonic acid or a salt thereof, an α- olefin having 2 to 20 carbon atoms, an unsaturated amide, an unsaturated nitrile, a Vinyl ether or vinyl chloride and polyvinyl alcohol resins which have been subsequently modified by acetalization, urethanization, esterification, etherification or graft polymerization.

The thin film is made by using the above Polyvinyl alcohol resin (A) alone or preferably in combination with the component (B₁) and / or the component specified below (B₂).

The component (B₁) is selected from starches, such as starch, modified Starches, dextrin and enzyme-treated starches, Alginic acid salts such as sodium alginate and xanthan gum. The combination improved from the polyvinyl alcohol resin and component (B₁) the stretch and printability of the thin film. Furthermore carries component (B₁) to reduce the rate of expansion and improve adaptability. By using of more than 50 wt .-% of component (B₁), however, the thin Film becomes brittle and the strength of the thin film becomes clear reduced, and therefore no thin film with one for that Print a pattern on it to obtain sufficient strength will.

The component (B₂) is selected from polyacrylamide, polyethylene oxide and methyl cellulose. Copolymers of acrylamide and an acrylic acid salt are preferred over the homopolymer of acrylamide. Component (B₂) is used in an amount of not more than 50% by weight used. By using more than 50% by weight the component (B₂) the film strength is reduced, and the the thin film obtained has poor printability and portability to.

Component (A) is used in an amount of not less than 50% by weight.  used. If the amount of component (A) is less than 50% by weight the film strength is too low and the thin film is bad not only in terms of printability, but also in in terms of its expansibility when swimming on the surface of the water.

The functions of components (B₁) and (B₂) are up to one to some extent different from each other. The component (B₁) is used the control (control) of the stiffness and elasticity of the thin Films and improving printability and portability. The component (B₂) serves to increase the adhesion of the thin Films and the improvement of the adaptation during the transfer process. However, the function of each component is not as precise delimited as indicated above, and the components connect organic with each other and thus result in the desired functions for the thin film for transfer printing.

When using component (A) in combination with the component (B₁) and / or the component (B₂) these components in Quantities used within the ranges given below:

If at least one of the components (B₁) and (B₂) in an amount of not less than 2% by weight, the elongation of the Films are controlled (controlled) to a sufficient extent so that the  Printability, especially the printability for multi-color printing, and also the adaptation of the film are improved on the subject. Favorable results are obtained when three components (A), (B₁), (B₂) in amounts within the following Areas are used:

Particularly favorable results are obtained if the three Components (A), (B₁) and (B₂) in amounts within the following Areas are used:

In practical use, however, a thin film is made of two Components, for example from components (A) and (B₁) sufficient good on an object with very complicated curved surfaces or uneven parts can be applied.

In addition to the above components (A), (B₁) and (B₂), that build up the film substrate can also, if necessary other water soluble polymeric materials, plasticizers for the Polyvinyl alcohol resin component (A), such as. B. polyhydroxy alcohols,  Polysaccharides, surfactants, lubricants, pH control agents, such as acids, alkalis and salts, and fillers be used.

The thin film is generally made by potting an aqueous solution of the above components, but it is an extrusion process can also be used. If the boric acid or a Salt is incorporated into the film, it becomes the film-maker Composition added.

It is desirable that the surface of the thin film be smooth because a pattern is printed on one or both sides of the thin film can also be a surface treatment, for example a satin treatment or an embossing treatment, be subjected.

The thickness of the thin film is within the range of 0.01 to 0.1 mm, preferably from 0.015 to 0.07 mm. The thin film with a thickness of less than 0.01 mm has a low strength and not only does it affect its printability, but the thin film also dissolves in water within one short time so that the time that is available for transmission is limited; moreover, the film tears easily. On the other hand if the thickness is more than 0.1 mm, the difference in terms of water content between both sides of the thin film floating on the surface of the water so big that the film curls on the surface of the water and no Transfer printing can be done more. According to the invention  can also be a laminated film in which two or more film foils laminated to a film can be used.

The pattern can be printed on the thin film using known printing processes are carried out.

The following is the expansion curve of a film with reference explained in more detail on the accompanying drawings.

Curve 1 in FIG. 1 shows a typical expansion behavior of a thin film floating on the surface of the water.

The term "stretch" used here and in Figs. 1 and 2 means the increase in the length of a film when the film floats on the surface of the water on which the film extends in all directions, and it becomes off calculated from the following equation:

The film expands in all directions when it floats on the surface of the water. It expands quickly between points O and K and rather slowly between points L and M , and expands very quickly after passing point N , dissolving or dissipating. A reproducible transfer cannot be carried out in the step between points O and K since the film has not yet swollen and softened enough. Even in the step after passing the point N , it is impossible to carry out the transfer without tearing because the film strength becomes poor. The transfer printing can be started at any stage after passing the point K , preferably in the stage between the point L at a certain distance from the point K and the point M. The thin film with a wide step between points L and M allows sufficient time for treatment (handling) and contributes to accurate and reproducible transmission. An area which extends from the point K to the point M , in particular from the point L to the point M , is referred to below as the "transmission area". Therefore, the longer the time from point L to point M , the easier the transmission process. For example, the transmission range may be more than 20 seconds using a thin film containing boric acid or a salt thereof, a period of time sufficient to transfer a pattern.

The thin film expansion curve varies depending on the type and amount of boric acid or its salt, the film thickness, the type of the polyvinyl alcohol resin component (A), the presence of a polymeric material other than component (A), such as. B. of the components (B₁) and (B₂), and the temperature of the water.

According to the invention, the expansion rate can be kept low. For example, in the case of a thin film, boric acid or a salt thereof, the extent at most about 60%. An excessively large expansion of a thin film can printed pattern unclear (out of focus) and inaccurate.  

The following is the test to determine adaptability explained in more detail.

If an uneven object, the to be printed on the printed surface with a a pattern of printed thin film is pressed on the Surface of water floats, and when it is in the transmission area when immersed in water, the thin film adheres firmly the object along the uneven surface of the Object as a result of fluid pressure.

As a simple method of assessing adaptability, the following test procedure is used: a frusto-conical cup with a bottom and a groove (namely, with a diameter at the base of 65 mm, an upper diameter of 90 mm, a height of 250 mm and with a 2 mm wide and 1 mm deep slot in the position 50 mm from the floor) is used as the standard item. The bottom of the cup is pressed against a thin film floating on the surface of water and immersed in the water at a speed of 20 cm / min after the thin film has extended beyond point K to point L. The adaptability of the thin film can easily be determined by the vertical distance from the floor to the point where a defect occurs, such as e.g. B. a tear, a wrinkle, so the adjustment blocking point. The transferability to a very uneven surface, a curved surface with a small curvature or a narrow groove can also be determined by the condition of the thin film on the slot part of the cup in this test.

According to the invention, the thin film adheres uniformly to the whole Surface of the cup, also on the slot part, and there can be a good adaptability of the thin film can be achieved. The vertical Distance from the ground to the adjustment blocking point is not less than 80 mm, especially 100 mm what shows that the thin film is sufficient in practical use firmly on an object to be printed with a complicated uneven surface adheres.

In embodiment X , the thin film of component (A) alone or a mixture of component (A) and at least one of components (B₁) and (B₂) to which boric acid or a salt thereof has been incorporated is used in transfer printing used.

The amount of boric acid or a salt thereof is selected within the range from 0.02 to 10% by weight, preferably from 0.1 to 2% by weight, based on the polyvinyl alcohol resin component (A), and im In the case of salt hydrates, the amount is calculated under exclusion of crystal water. If the amount of boric acid or a salt of which is less than 0.02% by weight, is the transmission range narrow, and the rate of expansion also becomes so great that one on one Object transferred pattern is unclear (out of focus). If on the other hand the amount of boric acid or a salt thereof more than 10% by weight is not sufficient flexibility, so that the adjustment worsens and an overlap of one printed pattern occurs due to wrinkling.

In embodiment X , the boric acid or a salt thereof can be incorporated into the thin film using one of the methods X 1 and X 2 described below.

In the process X ₁ the boric acid or a salt thereof is added to the film-forming composition. A thin film is made from this. If necessary, the pH of the film-forming composition can be adjusted by using an alkali or an acid. For example, in the case of using boric acid or a salt thereof, an alkali can be added within the lower range of the film-forming composition; if used within the upper range, an acid can be added.

In the other method X ₂, a solution of boric acid or a salt thereof is applied to one or both sides of the thin polyvinyl alcohol resin film or a thin film mainly composed of the polyvinyl alcohol resin. The thin film coated with the solution is practically the same as the thin film according to the method X ₁, since the boric acid applied or a salt thereof penetrates into the interior of the thin film. The solution is applied to the surface of the thin film by roller coating, brushing, spraying, dipping, coating with a doctor blade or in any other known manner. The application is carried out using a solution of boric acid or a salt thereof in water, an organic solvent or a mixed solvent of water and an organic solvent. After the solution has been applied to the thin film, drying is generally carried out, but an undried or semi-dried thin film can also be used for the transfer.

In the further embodiment Y , transfer printing is carried out by floating the thin polyvinyl alcohol resin film or a thin film mainly composed of the polyvinyl alcohol resin on the surface of water containing 0.002 to 0.5% by weight of boric acid or a salt thereof contains, and then presses the object to be printed on the thin film and immerses the object in the water. Fig. 2 shows the expansion behavior of a thin film with a thickness of 25 microns made of polyvinyl alcohol with an average degree of polymerization of 1400 and an average degree of hydrolysis of 86.5 mol% when the thin film on the surface of an aqueous solution of boric acid or Borax in varying concentrations floats at 25 ° C, in which case the solid lines show the expandability on an aqueous boric acid solution, the dashed lines show the expandability on an aqueous borax solution and the dash-dotted line show the expandability on water.

The concentration of boric acid or its salt in the aqueous Solution is selected within the range of 0.002 to 0.5% by weight. When using boric acid, the concentration becomes particularly selected within the range of 0.02 to 0.5 wt%, and at Using borax, the concentration is selected within in the range of 0.002 to 0.1% by weight. Too low a concentration does not lead to improvement, while on the other hand it does high concentration swelling and softening of the thin film impaired so that the desired adjustment is not achieved can be.

The embodiments X and Y described above can be combined with one another. In this case, the amount of boric acid or salt thereof that is inside the thin film or inside the water may be to some extent less than when only one embodiment is used.

Transfer printing is carried out according to embodiment X or Y by letting a pattern-printed thin film float on the surface of water with the printed surface up and then an object to be printed, presses against the printed surface and immerses the object or the object in the water when the thin film is within the transmission range. The thin film adheres firmly to the surface of the object, and the pattern printed on the thin film is transferred to the surface of the object by liquid pressure. The thin film printed with the pattern can be used as is, or if an ink layer of the thin film printed with the pattern is hard, it can be floated on the surface of the water after a solvent is printed on the water Surface applied to achieve the flexibility required for the transfer.

After the transfer process is complete, the rest of the thin Removed film from an object by clicking it on washes with water in any way, for example by Immersing the object or object in water or flowing Water, by blowing up atomized water, by sprinkling with Water or by light brushing, taking it with water  brings in contact. If necessary, the wash water can also Acids, alkalis, surfactants, enzymes or coagulants or gelling agents for polyvinyl alcohol resins can be added. In this way, the surface of the object remaining film can be easily removed, leaving only that printed patterns on the surface of the object remains. After the transfer printing is finished, a further surface treatment can be carried out using a Top coat on the surface of the object, onto which the pattern has been transferred applies to the surface to protect.

The invention is explained in more detail below with the aid of examples, without being limited to it. All specified in it Percentages and parts relate unless otherwise stated is on weight. The amount of borax is also given in parts by weight, calculated excluding crystal water.  

example 1

Polyvinyl alcohol with an average degree of polymerization of 1400 and
an average degree of hydrolysis of 88.5 mol% (A) 100 parts starch (B₁) 10 parts borax 0.7 parts dipropylene glycol 4 parts

The above three components were in water to form a 20% aqueous solution thereof solved. Using the drum casting process a thin film at a drum temperature of 95 ° C made with a thickness of 0.035 mm. On the thin one Film was made using a rotogravure process (Rotogravür process) printed a wood grain pattern.

After applying a prescribed amount of butyl cellosolve to the printed surface, the patterned thin film was floated on the surface of water at 30 ° C with the printed surface facing upward, and the extent of the film was determined. The expansion curve thus obtained is curve 1 of FIG. 1. The time between points L and M , which represents the optimal area for the start of the transmission, was 55 seconds, and the expansion time up to 30% of the expansion rate was 30 seconds.

Another sheet of the thin printed with a pattern Films were floated on the surface of water and performed the adaptation test. As  the expansion rate was 30%, became the standard item, a frustoconical cup with one Diameter of 65 mm at the base, an upper diameter of 90 mm and a height of 250 mm with a bottom and a 2 mm wide and 1 mm deep slot in one Position 50 mm from the ground, against the on the Water surface floating thin film pressed, being the floor came into contact with the film, and with one Speed of 20 cm / min immersed in the water. The grain pattern was based on the entire base and the Side of the cup transferred. There was no overlap of the thin film.

After the adjustment test, the one sticking to the cup became thin film by spraying water of ordinary temperature dissolved on the cup and easily removed, so that only the grain pattern on the entire base and the Side of the cup remained. The results related on film formation properties, printability for multi-color printing and transferability are in the Table I given below.

Example 2

The procedure of Example 1 was repeated, this time the component (B₁) was not used. The received Results are in the table below I specified.

Comparative Example 1

From a 20% aqueous solution of polyvinyl alcohol  with an average degree of polymerization of 1400 and an average degree of hydrolysis of 88.5 mol% a thin film with a thickness of 0.035 mm was produced. A wood grain pattern was printed on the film, the change in elongation at the time of printing was large, however, and therefore could be a perfect fit Application in multi-color printing (four-color printing) difficult to carry out, so when printing Distortion (shear) occurred.

After the pattern was printed, the determination of expansion, the matching test and the washing with water were carried out in the same manner as in Example 1. The film's expansion curve is curve 2 of Figure 1. The time between points L and M was approximately 15 seconds. In the fitting test, tearing was observed at the position 45 mm from the bottom of the cup, and the grain pattern expanded considerably at the position near 30 mm due to the large expansion, so that an accurate transfer of the pattern was not obtained. The film adhering to the cup was easily removed by washing with water. The results obtained are given in Table I below.

Comparative Example 2

Polyvinyl alcohol with an average degree of polymerization of 1400 and
an average degree of hydrolysis of 88.5 mol% (A) 100 parts of starch (B₁) 10 parts

The above two components were dissolved in water to form a 20% aqueous solution thereof. In the same manner as in Example 1, a thin film 0.035 mm thick was made therefrom and printed with a wood grain pattern. The expansion, the adaptability and the removability by washing with water of the film printed with the pattern were determined in the same manner as in Example 1. The expansion curve is curve 3 of FIG. 1. The time between points L and M was approximately 20 seconds. In the fitting test, tearing by dissolution was observed at the position 60 mm from the bottom of the cup, and the grain pattern expanded considerably at the position near 30 mm due to the large expansion, so that an accurate transfer of the pattern was not obtained . The removability of the film by washing with water was good. The results obtained are given in Table I below.

Example 3

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 88.2 mol% (A) 100 parts glycerin (plasticizer for the film) 10 parts boric acid 0.5 parts non-ionic surfactant 0.2 parts

The above three components were in water to form a 20% aqueous solution thereof solved. In the same way as in Example 1 produced a thin film with a thickness of 0.035 mm and printed with a wood grain pattern.

The thin film printed with the pattern was floated on the surface of water at 30 ° C, and the expansion of the film was determined. The expansion curve obtained is curve 4 of FIG. 1.

Another sheet of the thin printed with the pattern Films were floated on the water surface and, when the expansion had reached 35%, the adjustment test in the same way as in Example 1. The grain pattern was based on the entire surface of the cup transferred without overlap, and after Only the film was finished by sprinkling the test Mug easily dissolved and removed with water. The one there Results obtained are as follows Table I given.

Example 4

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 88.2 mol% 80 parts of polyvinyl alcohol with an average degree of polymerization of 1200 and
an average degree of hydrolysis of 96.5 mol% 20 parts borax 0.5 parts diglycerin 3 parts

The above components were used to manufacture a 70% aqueous solution of the same dissolved in water. In the same way as in Example 1 a thin film with a thickness of 0.035 mm was produced therefrom and printed with a wood grain pattern.

The thin film printed with the pattern was floated on the water surface at 30 ° C with the printed surface facing upward, and the expansion of the film was determined. The expansion curve obtained in this way is curve 5 in FIG. 1. The time between points L and M was 90 seconds and the time until the expansion rate had reached 30% was 50 seconds.

The fitting test was done in the same way as in Example 1 performed. The grain pattern was based on the transfer the entire surface of the cup without overlap. The removability of the film by washing with water was also easy. The results obtained are in Table I given below.

Comparative Example 3

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 88.2 mol% 65 parts of polyvinyl alcohol with an average degree of polymerization of 1200 and
an average degree of hydrolysis of 96.5 mol% 35 parts

The above components were in water dissolved to form a 20% aqueous solution thereof. A thin film with a thickness of 0.035 mm became made from it and with a wood grain pattern printed.

The expansion, conformability, and removability of the film adhering to the surface of the article by washing with water were determined in the same manner as in Example 1. The expansion curve of the film is curve 6 of Fig. 1. The time between points L and M was relatively long, but in the fitting test, wrinkled overlaps of the film were observed at the portion above 30 mm from the bottom of the cup, and the film was observed also torn in position 80 mm from the bottom of the cup due to lack of stretch. The removability of the film by washing with water was good, but there was a marked overlap and peeling of the pattern on the above overlap part and the part above about 40 mm from the bottom where the film printed with the pattern did not adhere firmly to the cup. detected. The results obtained are given in Table I below.

The expansion curves of the films obtained in the above examples and comparative examples are shown in FIG. 1:

Curve 1: Thin film of Example 1
Curve 2: Thin film of Comparative Example 1
Curve 3: Thin film of Comparative Example 2
Curve 4: Thin film of example 3
Curve 5: Thin film of example 4
Curve 6: Thin film of Comparative Example 3

Table I

Examples 5 to 8

There was an aqueous solution of the following Components to form a film-forming composition made of 6% dipropylene glycol and 0.4% a non-ionic surfactant as a plasticizer and as a modifier based on the resin, were added. The composition became a thin one Film made with a thickness of 0.035 mm and on its Surface printed with a marble pattern. To Apply the prescribed amount of butyl cellosolve acetate the adaptation test was carried out on the printed surface carried out in the manner indicated in Example 1. The results obtained are as follows Table II given.

Components for example 5

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 77.8 mol% (A) 95 parts of polyethylene oxide with a molecular weight of 4,000,000 (B₂) 5 parts of borax 0.5 parts

Components for example 6

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 88.2 mol% (A) 75 parts of white dextrin (B₁) 20 parts of methyl cellulose (B₂) 5 parts of borax 1 part

Components for example 7

Polyvinyl alcohol with an average degree of polymerization of 700 and
an average degree of hydrolysis of 92.0 mol% (A) 100 parts of boric acid 1 part

Components for example 8

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 88.2 mol% 90 parts of polyacrylamide with an average molecular weight of 2,000,000 (B₂) 10 parts of borax 0.3 parts

Table II

Example 9

From a 20% aqueous solution of polyvinyl alcohol with an average degree of polymerization of 1400 and an average degree of hydrolysis of 86.5 mol% was made using a drum casting process at a Drum temperature of 95 ° C a thin film with a Made of thickness 0.045 mm and on its surface using a rotogravure process printed a wood grain pattern.

The thin film printed with the pattern was on the surface a 0.02% aqueous solution of borax at 25 ° C floated with the printed surface facing up and the adaptation test performed by the bottom of the standard cup after 140 seconds (expansion of the film 45%) pressed against the thin film and the cup at a speed of 20 cm / min Solution immersed. The grain pattern was on the whole Transfer the base and side of the cup and none Overlap of the film observed.

After completing the adjustment test, the on the cup adhesive film by spraying water of a usual Temperature dissolved on the cup and easily removed so that only the grain pattern remained. The one there Results obtained are in the table below III specified.

Comparative Example 4

The adjustment test of Example 9 was repeated  but this time with pressing and dipping the Cup after 25 seconds (film expansion 5%) was started. It was torn apart by the dissolution of the Film in the position 45 mm above the bottom of the cup observed, and the grain pattern expanded on the Position close to 30 mm because of the high expansion clearly out, so that an accurate transfer of the pattern was not received. Removability of the film by washing with water was good. The results obtained are given in Table III below.

Example 10

The thin film of Example 9 printed with the pattern became on the surface of a 0.03% aqueous solution of anhydrous Borax floated at 25 ° C and after 120 seconds (40% stretch of the film) the standard cups pressed to the film and immersed in the solution. The the results obtained are shown in Table III.

Example 11

The thin film of Example 1 printed with the pattern became on the surface of a 0.1% solution of boric acid from Floated 25 ° C and after 80 seconds (expansion of the film 100%) the standard cup is pressed onto the film and immersed in the solution. The results are in given in Table III.  

Table III

Example 12

The one obtained in Comparative Example 2 with a sample printed thin film with a thickness of 0.035 mm was applied the surface of a 0.005% aqueous solution of borax floated from 25 ° C and transfer printing then carried out in the same manner as in Example 9. The results obtained are as follows Table IV given.

Comparative Example 5

The procedure of Example 12 was repeated, this time however, the thin film printed with the pattern on the Surface of the water was floated. The results are given in Table IV below.

Example 13

The procedure of Example 12 was repeated, this time the thin film printed with the pattern on the surface a 0.05% aqueous solution of borax at 30 ° C was floated. The results obtained are in given in Table IV.

Example 14

The procedure of Example 12 was repeated, this time the thin film printed with the pattern on the surface a 0.5% aqueous solution of boric acid at 30 ° C. was floated. The results obtained are in given in Table IV.  

Table IV

Example 15

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 88.2 mol% 80 parts of polyvinyl alcohol with an average degree of polymerization of 1200 and
an average degree of hydrolysis of 96.5 mol% 20 parts

The above components were submerged in water Formation of a 17% aqueous solution of the same dissolved. Using a drum casting process, a Drum temperature of 95 ° C a thin film with a Thickness of 0.035 mm made from it and using it a known printing device with a wood grain pattern printed. The thin one printed with the pattern Film was coated on the surface of a 0.01% aqueous solution Borax solution floated at 25 ° C, and transfer printing was then done in the same way as in Example 9 performed. The results obtained are given in Table V below.

Comparative Example 6

The procedure of Example 15 was repeated, this time the thin film printed with the pattern on the surface of the water was floated. The results are given in Table V.

Examples 16 to 18

It became an aqueous solution of the components listed below  made to form a film-forming composition, the 6% dipropylene glycol and 0.4% one non-ionic surfactants as plasticizers and modifiers based on the resin are added has been. The composition became a thin film made of a thickness of 0.035 mm and on its surface printed with a marble pattern. After applying a prescribed amount of a solvent with a Affinity for a printer color on the printed surface the film was immediately used in transfer printing.

Components for example 16

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 77.8 mol% (A) 95 parts of polyethylene oxide with a molecular weight of 4,000,000 (B₂) 5 parts

Components for example 17

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 88.2 mol% (A) 75 parts sodium alginate (B₁) 20 parts methyl cellulose (B₂) 5 parts

Components for example 18

Polyvinyl alcohol with an average degree of polymerization of 1700 and
an average degree of hydrolysis of 88.2 mol% (A) 90 parts of xanthan gum (B₂) 10 parts

Transfer printing was done by floating of the film on the surface of a 0.01% aqueous solution Solution of borax from 25 ° C, pressing on the standard beaker the film and immersing it in the solution. The one there Results obtained are shown in Table V below.  

Table V

Example 19

A 0.5% solution of borax in a water / methanol (Weight ratio 1: 1) solvent mixture was in Form a layer on the back of the one obtained in Example 9, applied with a pattern printed thin film and dried by leaving the film. The The amount of borax applied was 0.5%, based on the polyvinyl alcohol.

The thin film was then on the surface of water from 25 ° C with the printed surface facing up relaxed and after 50 seconds (extension of the Films 30%) of the adjustment test by pressing the Base of the standard cup to the thin film and immersing the Mug carried into the water. The grain pattern was on the entire base and side of the Bechers transferred. There was no overlap of the film on.

After completing the adjustment test, the on the cup adhesive film by spraying atomized water ordinary temperature dissolved on the cup and easily removed, so that only the grain pattern remained on it. The results obtained are in the table VI specified.

Example 20

The procedure of Example 19 was repeated, this time a 1.0% solution of boric acid in a water /  Methanol (weight ratio 1: 1) solvent mixture in the form of a layer on the one obtained in Example 12, with a pattern printed thin film in an amount of 6%, based on the polyvinyl alcohol, was applied. The results obtained are given in Table VI.

Examples 21 to 23

The procedure of Example 19 was repeated, with this time a 0.3% aqueous borax solution in the form of a Layer on each of those obtained in Examples 15, 17 and 18, patterned thin films in one Amount of 3%, based on the polyvinyl alcohol, applied and dried using hot air at 80 ° C has been. The results obtained are as follows Table VI given.  

Table VI

Claims (8)

1. A method of transferring a pattern printed on a thin film of a polyvinyl alcohol resin to a surface of an object by pressing the object onto the thin film floating on the surface of water with the printed surface and immersing the object in the water, characterized reacting a polyvinyl alcohol resin having an average polymerization degree of 300 to 3000 and an average degree of hydrolysis from 65 to 97 mol% is used, and boric acid or a salt thereof of the thin film in an amount of 0.02 to 10 wt .-%, based on the polyvinyl alcohol resin, or the water in a concentration of 0.002 to 0.5 wt .-% incorporated. 2. The method according to claim 1, characterized in that one Boric acid or a salt thereof, the thin film made of a polyvinyl alcohol resin incorporated by mixing the boric acid or a salt thereof with the mixes the film-forming composition and from the resultant Mix creates the thin film. 3. The method according to claim 1, characterized in that the Boric acid or its salt in the thin film made of a polyvinyl alcohol resin incorporated by using a solution of boric acid or a salt thereof on at least one side of the thin film. 4. The method according to any one of claims 1 to 3, characterized in that a thin film with a thickness of 0.01 to 0.1 mm is used.   5. The method according to any one of claims 1 to 4, characterized in that a thin film made of a polyvinyl alcohol resin is used, 98 to 50% by weight of a polyvinyl alcohol resin component (A) and 2 up to 50% by weight of at least one component (B₁) and / or component (B₂) contains, as component (B₁) at least one of starch, alginic acid salt and xanthan gum, and as component (B₂) at least one from polyacrylamide, polyethylene oxide and methyl cellulose. 6. The method according to claim 5, characterized in that one thin film of a polyvinyl alcohol resin used, both at least 1 wt .-% of component (B₁) and at least 0.5 wt .-% of Component (B₂) contains. 7. The method according to any one of claims 1 to 6, characterized in that that one uses borax as boric acid salt. 8. The method according to claim 1, characterized in that the thin film 0.1 to 2 wt .-% boric acid or a salt thereof incorporated.