DE2918639A1 - METHOD OF TRANSFERRING A PATTERN PRINTED ON A THIN FILM MADE OF A POLYVINYL ALCOHOL RESIN TO A SURFACE OF AN OBJECTIVE. OBJECTS - Google Patents

Description

The invention relates to a method for transferring a pattern printed on a thin film of a polyvinyl alcohol resin to a surface of an object, in which the object or object is attached to the thin ones floating on the surface of water with the printed surface facing up Pressing the film and immersing the object or the object in the water, taking care that boric acid or salts thereof is contained in the thin film or in the water, whereby a clear _r sharp and precise pattern on the object or the object can be transferred even if it has an uneven surface; The invention relates in particular to a transfer printing method for applying a beautiful print to uneven objects or »objects with grooves, protrusions, a curved surface and the like.

From US Pat. No. 4,010,057 a © printing device is known,

in which a thin film on which a pattern has been printed floats on the surface of a liquid and the pattern is transferred to the surface of an object or object to be printed with the pattern using the liquid pressure by immersing the object or object in the liquid while the object or object is in contact with the thin film is pressed (see. The abstract of this patent). It is stated therein that it is most preferred than thin Film to use a farinaceous or farinaceous film and that the materials of the thin film are also sodium polyacrylic acid, Polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, Polyethylene oxide, polyvinylpyrrolidone and acrylic acid amide as synthetic high-molecular substances; Glue, gelatine, Casein and polypeptide among the high molecular substances, starch, cellulose, dextrin, albumin, soybean protein, gum arabic and gum tragacanth among the vegetable high molecular substances; and seaweed glue, Japan gelatin and alginic acid sodium act among the high molecular weight seaweed substances.

However, the thin film produced from the above-mentioned materials does not have sufficient strength and elongation for multi-color printing, no good swellability, in particular no good extensibility on the surface of the masser, as explained in more detail below, and no great flexibility and no good softening properties, see Sect It is difficult to firmly bond the thin film to an uneven surface of an object or object to be printed. Among the large number of materials listed above, the only material that can be used in practice is polyvinyl alcohol resin.

-47 / 0684-

- ORIGINAL INSPECTED

. " I ₀ 1318639

However, a thin film made of a polyvinyl alcohol resin also exhibits has the following shortcomings: since the thin film dissolves heavily 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 identify a pattern printed on the thin film to be transferred to the object or object. Because the time it takes to press an object to be printed or object to the thin film is short, mistransfer tends to occur. It can also be used in case of oppression an object with a complicated curved surface, a pointed part, or a concave one Part, a spherical object or object or a longitudinally elongated object or object There is a slit, interference, or overlap in the printed pattern.

The aim of the present invention is therefore to provide a method for accurately and clearly transferring a printed matter

Pattern from the surface of a thin film onto the surface of an object or object to be printed by control the elongation of the thin film floating on the surface of the water. Another object of the invention is therein to provide a method of transferring a printed pattern in which the allowable period of time for treatment and the transfer process can be easily performed Another object of the invention is to provide a method of transferring a printed pattern onto an object or «to specify an object with a complicated curved surface in which there is no slit, no disturbance and no overlap of the

909847 / 96.81

ORIGINAL

-} 2918633

Pattern occurs.

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

Figures 1 and 2 are graphs showing the elongation curves of thin films explain.

It has now been found that the above objects according to the invention can be achieved by in a process for transferring one to a thin film of a polyvinyl alcohol resin printed pattern on a surface of an object by pressing the object against the with the printed surface facing up on the surface of water floating thin film and immersing the object or object in the water,

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

ORIGINAL INSPECTED

"g": 318639

The term "boric acid or a salt thereof" used here is _{to be understood as boric acid of the formula H 3} BO ₃ , borax of the formula Na ₂ B ₄ O ₇ JOH ₂ O and anhydrous borax of the formula Na ₉ BO ₇ , and other borates can also be used can be used as sodium borate according to the invention.

Using these procedures, the following can be achieved excellent effects can be achieved in transfer printing on an industrial scale:

1.) Since the thin film used in the present invention has a tensile strength of not less than 1.0 kg / cm and an elongation of not more than 200 % at ordinary temperature and humidity (20 C, 65 % RH) and no curling and good Has dimenion resistance, the present invention is suitable for performing multicolor printing;

2.) the thin film printed with the pattern spreads out smoothly the surface of the water / without rolling up, and the allowable period of time for treatment or processing is long and the implementation of the transfer is easy;

3.) the thin film has good stretchability (good expansibility) and high surface softness of water, a pattern printed on the thin film will appear on an object with an uneven surface Transferred surface without incurring slit, interference and pattern overlap;

ORIGINAL INSPECTED

4.) because the expansion of a thin film on the surface of the Water is appropriately controlled, there is no ambiguity (blurring) of a printed pattern due to over- «Moderate expansion of the pattern to;

5 ·) the thin film that adheres to the surface of a printable item Object adhering can be easily removed from the surface by washing with water after transfer printing will·

According to the invention, a beautiful, clear or sharp print can be used are applied to objects or objects, not only to those that have a smooth (flat) surface, but also to those with complicated curved surfaces

The polyvinyl alcohol resins used according to the invention are they are those with an average degree of polymerization of 300 to 3000 and an average degree of hydrolysis of 65 to 97 mole yS. When the average degree of polymerization is less than 300, the film strength, particularly the film strength on the surface of the water, is very poor, so that the film tears and the transferred pattern is disturbed. If the average degree of polymerization is more than 3000, If the film strength is too high and the film lacks the necessary conformability, under the term "conformability" the The property of film is to be understood as precisely following every surface of an object or object and on this surface to adhere without tearing and wrinkling at the time of pressing the object to the film and dipping

• 051 ^ 7/1684

__—— ORIGINAL INSPECTED

40 2918839

the same in the water · When the average degree of hydrolysis less than 65 mol /? cheats, the film lacks the necessary Extensibility, the required flexibility and the required adaptability. On the other hand, if the average If the degree of hydrolysis is more than 97 Mol-jS, the film lacks the necessary adaptability during transfer, since the film is to the When swimming on the surface of the water rolls up and it also lacks the necessary expansion capacity and flexibility on the surface of the water, and moreover, it becomes difficult to remove the film by washing with water after the transfer.

The polyvinyl alcohol resins can be used singly or in admixture. When using two or more kinds of polyvinyl alcohol resins, the average degrees of polymerization and hydrolysis of a mixture thereof should be within the areas mentioned above are

According to the invention, modified polyvinyl alcohol resins can also be used the above average degrees of polymerization and hydrolysis can be used. Examples of modified polyvinyl alcohol resins which can be used according to the invention are hydrolyzed ones Copolymers of a vinyl ester with an unsaturated carboxylic acid or an ester or a salt thereof, an unsaturated one Sulfonic acid or a salt thereof, an α-01efin with 2 to 20 Carbon atoms, an unsaturated amide, an unsaturated nitrile, a vinyl ether or vinyl chloride and polyvinyl alcohol resins, which are subsequently produced by acetalization, urethanization, esterification, etherification or graft polymerization

909147/0604

have been modified.

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

Component (B.) 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 of the polyvinyl alcohol resin and the component (B.) improves the elongation and the printability of the thin film. In addition, the component (B.) contributes to reducing the expansion rate and improving the adaptability. However, by using more than 50 Gev *% of the component (Bj), the thin film becomes brittle and the strength of the thin film is markedly lowered, and therefore a thin film having sufficient strength for printing a pattern thereon cannot be obtained.

Component (B ^) 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 (B ") is in an amount of not more than 50 wt - used% and by the use of more than 50% by weight of component (Bg), the film strength is lowered, and the thin film thus obtained has a poor printability. and transferability to

The component (A) is used in an amount of not less than 50 wt -.%

909847/0684

-for-

used. If the amount of component (A) less than 50 wt -. Betrögt%, the film strength is too low and the thin film is poor not only in -Bezug on printability, but also in relation to its Ausdehnungsvermö'gen while floating on Surface of the water.

The functions of components (B.) and (B ") are up to one different from one another to a certain extent. The component (B-i) is used controlling the rigidity and elasticity of the thin film and improving printability and transferability. The component (B ~) serves to increase the adhesion of the thin Films and the improvement of the adaptation in the transfer process. However, the function of each component is not as accurate delimited as indicated above and the components combine organically with each other and thus result in the desired functions for the thin film for transfer printing.

When using component (A) in combination with component (B ₁ ) and / or component (B «), these components are used in amounts within the ranges given below:

Component (A) 98-50

Component (B ^) 0 - 50)

_v , fr, \ λ rn) a total of 2-50 components (Β «; 0 - 50 < ^a

If at least one of the components (B) and (B ^) in an amount of not less than 2 wt -.% Is present, the elongation of the film is sufficiently controlled (controlled) so that the

909847/0884

Printability, in particular the printability for multicolor printing, is improved and, moreover, the adaptation of the film to an object or an object is improved. Particularly preferred results are obtained when three components (A), (B ₁ ), (Βλ) are used in amounts within the ranges given below:

Weight - 7S

Component (A) 98.8-50

Component (B ^) 1 - 49.5)

w χ ^ d ^ η c An ) a total of 1.5 - 50 component \ Β ~) 0.5-49 ί

Particularly preferred results are obtained when the three components (A), (B.) and (B ") are used in amounts within the following Areas' are used:

Component (A) 96-50

Component (B.) 3 to 30)

Component (B _£ ) 1 to 30> ^ins S ^ amt 4 - 50

However, in practical use, one thin film is two Components, for example from components (A) and (B.), Are sufficient easily applied to an object or an object with very complex curved surfaces or uneven parts.

In addition to the above components (A), (Β,) and (B ^), which build up the film substrate can, depending on requirements, also contain other water-soluble polymeric materials, plasticizers for the Polyvinyl alcohol resin component (Α), such as polyhydroxy alcohols,

Polysaccharides, surfactants, lubricants, pH control agents, such as acids, alkalis and salts, and fillers are used.

The thin film is generally made by pouring an aqueous solution of the above components, but it is an extrusion method also applicable. When boric acid or a salt thereof is incorporated into the film, it becomes the film-forming one Composition added.

It is desirable that the surface of the thin film be smooth because a pattern is printed thereon on one or both sides of the thin film can also be subjected to 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 poor strength on and thereby not only its printability is impaired, but the thin film also dissolves in water within a short time in a transmission stage, so that the time that is available for the transmission is in a narrow range is limited and, moreover, the film tears easily. On the other hand, if the thickness is more than 0.1 mm, the difference becomes with respect to the water content between both sides of the thin film floating on the surface of the water, that the film curls up on the surface of the water and transfer printing cannot be performed. According to the invention

909847/8684

For example, a laminated film in which two or more sheets of film are laminated into one sheet can also be used.

Printing the pattern on the thin film can be done using any known printing process can be performed.

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 typical expansion behavior a thin film floating on the surface of the water.

Under the term used here and in Figs "Expansion rate" is understood to mean the rate (speed) of increase in the length of a film when the film is on the surface of the water on which the film stretches in all directions, and it is calculated from the following equation:

(Length of the expanded movie) - (length of the original movie) - _ _x

(Length of the original film)

The film expands in all directions when it is on the surface of the water floats. It expands quickly between points 0 and K and rather slowly between points L and M and it expands very quickly after passing the point N, dissolving or dispersing. In the step between the No reproducible transmission can be carried out at points 0 and K because the film has not yet swelled and softened sufficiently. Even in the stage after passing the point N, it is impossible to

.909967 / 0384

to carry out the transfer without tearing because the film strength becomes poor. The transfer printing can be started in any stage after the point K has been passed, 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 transfer. An area extending from the point K to the point M, in particular from the point L to the point M, is hereinafter referred to as a "transmission area". Therefore, the transfer operation is all the easier the longer the time period from the point L to the point M. For example, the transfer area can be more than 20 seconds when using a thin film that contains boric acid or a salt thereof, a period of time which is sufficient for the transfer of a pattern.

The expansion curve of the thin film 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 component (B. ) and (B ") _; and the temperature of the water.

According to the invention, the rate of expansion can be kept low. For example, in the case of a thin film containing boric acid or a salt thereof, the rate of expansion is at most about 60 %. Excessively large expansion of a thin film makes a printed pattern unclear and imprecise *

889347/0604

The adaptation test is explained in more detail below.

When an uneven object or object to be printed is attached to the printed surface of a with a pattern of printed thin film floating on the surface of water and when in the transfer area is immersed in water, the thin film adheres firmly to the object along the uneven surface of the Object or object as a result of the fluid pressure.

As a simple method of assessing this property, namely adaptability, the following test method applied: a mug with a frustoconical shape with a bottom and a groove (namely, with a diameter at the base of 65 mm, a top 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 used. The bottom of the cup is pressed against a thin film that floats on the surface of water, and with it a speed of 20 cm / min, immersed in the water after the thin film spreads over the point K to the point L has expanded. The adaptation . a thin film can easily be determined by a vertical distance from the bottom up to a point that causes a defect such as tearing, wrinkling, up to a conformance blocking point. The transferability to a very uneven surface, a curved surface with a small curvature or a narrow one Groove can also be determined by the condition of a thin film on the slit portion of the cup in this test.

909847/0684

According to the invention, the thin film adheres uniformly to the whole Surface of the cup, also at the slit part, and a good fit of a thin film can be achieved. The vertical one Distance from the floor to the adaptation blocking point is not less than 80 mm, especially 100 mm, and this shows that a thin film is sufficiently firmly attached to an object to be printed with a complicated in practical use uneven surface adheres.

In embodiment X, the thin film is composed of component (A) alone or of a mixture of component (A) and at least one of components (B 1) and (B ") to which boric acid or a salt thereof has been incorporated is used in transfer printing.

The amount of the boric acid or a salt thereof is selected within the range of from 0.02 to 10 wt .- / 5, preferably from 0.1 to 2 wt .-% based on the polyvinyl alcohol resin component (A), and in the case of Salt hydrates, the amount is calculated excluding the water of crystallization. When the amount of boric acid or a salt thereof is less than 0.02 wt -.% Is, the transmission range is narrow, and the expansion rate is also such that a transmitted on an object pattern is not clear (blurred). On the other hand, when the amount of boric acid or a salt thereof is more than 10 wt .- /? sufficient flexibility is not obtained, so that the matching is deteriorated and an overlap of a printed pattern occurs due to wrinkling.

In embodiment X, the boric acid or a salt thereof can be prepared using either of the two methods X described below

909847/068 *

and X «are incorporated into a thin film.

In the method X, the boric acid or a salt thereof is added to a film-forming composition and it becomes a thin film made. If necessary, the pH value can be a film-forming composition can be adjusted by using an alkali or an acid. For example, in the case of Use of boric acid or one. Salt thereof within the lower range is an alkali of a film-forming composition may be added, and in the case of use within the upper range, an acid may be added.

Another method X ~ is a solution of boric acid or a salt thereof on one or both sides of a polyvinyl alcoholic resin thin film or a thin film composed mainly of the polyvinyl alcohol resin is applied. The one with the Solution coated thin film is practically the same as the thin film according to the method X ,, since the applied boric acid or a salt thereof penetrates inside the thin film. The application the solution on the surface of the thin film is carried out by roller coating, brushing, spraying, dipping, Coating by means of 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 one organic solvents. After applying the solution to the thin film, drying is generally carried out for the transfer however, an undried or semi-dried thin film can also be used.

-If-

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

The concentration of the boric acid or its salt in the aqueous solution is selected within the range from 0.002 to 0.5% by weight . When using boric acid, the concentration is selected in particular within the range from 0.02 to 0.5% by weight , and when using borax, the concentration is selected within the range from 0.002 to 0.1% by weight . Too low a concentration leads to no improvement, while, on the other hand, too high a concentration adversely affects the swelling and softening of the thin film, so that the desired adjustment cannot be achieved.

The above-described embodiments X and Y can be used with each other be combined. In this case the amount of '

9Ö9847 / Ö68 *

Boric acid or salt thereof, which is present inside the thin film or inside the water, is less to some extent compared with the case of using only one embodiment.

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

After finishing the transfer process, the rest of the thin one will be Remove film from an object by washing it with water in any way, such as through Immersing the object or object in water or running water, by blowing up dark water, by sprinkling with it Water or by lightly brushing, washing it with water

9098A7 / 0634

brings in contact. If necessary, the wash water can also Acids, alkalis, surface active agents, enzymes or coagulants or gelling agents for polyvinyl alcohol resins can be added. In this way, the film remaining on the surface of the object can be easily removed, so that only that printed pattern remains on the surface of the object or object. After transfer printing is completed, a further surface treatment can be carried out by applying a top coat to the surface of the object or object, to which the pattern has been transferred to protect the surface.

The invention is explained in more detail below using examples, but without being limited to it. All percentages and parts given therein relate unless otherwise stated is on weight. The amount of borax is also given in parts by weight, calculated excluding the water of crystallization.

909847/0684

- 20 -

So

Example 1 2918639

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

Strength (Β _χ ) 10 parts

Borax 0.7 parts

Dipropylene glycol 4 parts

The above three components were dissolved in water to form a 20% aqueous solution of the same and using the drum casting method, a thin film was formed at a drum temperature of 95 ° C made with a thickness of 0.035 mm. The thin film was printed on using a copper gravure printing process (Rotogravure process) a wood grain pattern is printed.

After applying a prescribed amount of butyl cellosolve to the printed surface, the thin film printed with the pattern was floated on the surface by water of 30 ° C with the printed surface facing up, and the rate of expansion of the film was determined. The expansion curve obtained is curve 1 of FIG. 1. The time between points L and. M, which is the optimum range for starting the transmission, was 55 seconds, and the expansion time up to 30 % of the expansion rate was 30 seconds.

Another sheet of the thin one printed with a pattern The film was floated on the surface of the water and the conformance test was carried out. as

- 21 -ftt <

the expansion rate was 30%, the standard item, namely a frustoconical cup with a Diameter of 65 mm at the base, a top diameter of 90 mm and a height of 250 mm with a bottom and a 2 mm wide and 1 mm deep slot in a position 50 mm from the floor, against that on the surface of the water floating thin film pressed with the soil in contact with the film, and with a Speed of 20 cm / min, immersed in the water. The grain pattern was transferred to the entire base and side of the mug and there was no overlap of the thin film.

After the conformance test, that adhered to the cup became thin film dissolved and easily removed by spraying water of ordinary temperature on the beaker, so that only the grain pattern remained on the entire base and side of the mug. The results in relation on the film formation properties, the printability for the color printing and the transferability are given in Table I below.

Example 2

The procedure of Example 1 was repeated except that component (B.) was not used this time. The received Results are given in Table I below.

Comparative example 1

From a 20% aqueous solution of polyvinyl alcohol

909δ /, 7/0684

with an average degree of polymerization of 1400 and an average degree of hydrolysis of 88.5 mol% a thin film 0.035 mm thick was formed. A wood grain pattern was printed on the film, however, the change in elongation at the time of printing was large and therefore it could be in register Application in multi-color printing (four-color printing) difficult to perform and distortion (shear) occurred in printing.

After the pattern was printed, the determination of the expansion rate, the conformance test. and washing carried out with water in the same manner as in Example 1. The expansion curve of the film is curve 2 of the Figure 1. The time between points L and M was about 15 seconds. In the adaptation test was in the position Tearing was observed 45 mm from the bottom of the cup and the grain pattern elongated considerably out at the position near 30mm because of the high expansion rate, so that no accurate transmission of the Pattern was obtained. The film adhered to the beaker was easily removed by washing with water. The one with it The results obtained are shown 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

Strength (B ₁ ) 10 parts

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Sb -

The above two components were dissolved in water to form a 20% aqueous solution of the same and in the same manner as in Example 1, a thin film having a thickness of 0.035 mm was prepared therefrom and printed with a wood grain pattern. The expansion rate the adaptability · and the removability by washing with water the film printed with the pattern were obtained in the same manner as in Example 1 certainly. The expansion curve is curve 3 in FIG. 1. The time between points L and M was about 20 Seconds. In the conformance test, tearing was caused at the position 60 mm from the bottom of the cup Dissolution was observed, and the grain pattern expanded considerably at the position near 30 mm because of a high rate of expansion, so that no accurate transfer of the pattern was obtained. The removability the film by washing with water was good. The results obtained are in the table below I stated.

Example 3

Polyvinyl alcohol with an average degree of polymerization of 1700 and an average Degree of hydrolysis of 88.2 mol-7 »(A) 100 parts

Glycerin (plasticizer for the film) 10 parts

Boric acid 0.5 parts

Non-ionic surfactant 0.2 parts

909847/0684

- ZM -

The above three components were dissolved in water to form a 20% aqueous solution of the same and in the same manner as in Example 1, a thin film having a thickness of 0.035 mm was prepared and printed with a wood grain pattern.

The thin film printed with the pattern was allowed to float on the surface of water at 30 ° C, and the The rate of expansion of the film Xiurde was determined. The received The expansion curve is curve 4 in FIG. 1.

Another sheet of the thin film printed with the pattern was floated on the surface of the water, and when the expansion rate reached 35 % , the fit test: in the same manner as in Example 1 was carried out. The grain pattern was transferred to the whole of the cup without overlap and after the test was complete, only the film was slightly dissolved and removed by sprinkling the cup with water. The results obtained are given in Table I below.

Example 4

Polyvinyl alcohol with an average degree of polymerization of 1700 and an average Degree of hydrolysis of 88.2 mol% 80 parts

Polyvinyl alcohol with an average degree of polymerization of 1200 and an average Degree of hydrolysis of 96.5 mol% 20 parts

909847/0634

Diglycerin 3 parts

The above components were dissolved in water to prepare a 70% aqueous solution of the same and in the same manner as in Example 1, a thin film having a thickness of 0.035 mm was prepared therefrom and printed with a wood grain pattern.

The thin film printed with the pattern was on the surface of the water at 30 ° C with the printed surface floated upward and the rate of expansion of the film was determined. The resulting expansion curve is curve 5 in Figure 1. The time between the Points L and M was 90 seconds, and the time until the expansion rate reached 30% was 50 seconds.

The adaptation test “was carried out in the same way as in Example 1 carried out. The grain pattern was transferred to the entire surface of the cup with no overlap. The removability of the film by washing with water was likewise easily. The results obtained are given in Table I below.

Comparative example 3

Polyvinyl alcohol with an average degree of polymerisation of 1700 and an average Degree of hydrolysis of 88.2 mol% 65 parts

Polyvinyl alcohol with an average degree of polymerization of 1200 and an average Degree of hydrolysis of 96.5 mol% 35 parts

903647/0684

The above components were dissolved in water to form a 20% aqueous solution of the same and a thin film 0.035 mm thick and having a wood grain pattern was made therefrom printed.

The rate of expansion, adaptability and removable The ability of the film adhered to the surface of the object by washing with water was checked determined in the same manner as in Example 1. The expansion curve of the film is curve 6 of Figure 1. The time between the points L and M was relatively long, but in the fit test there were wrinkled overlaps of the film was observed at the portion above 30 mm from the bottom of the cup, and the film was also torn in the position 80 mm from the bottom of the cup due to lack of stretch. The removability of the film through Washing with water was good, but there became noticeable overlapping and peeling of the ester at the above overlapping part and at the portion above about 40mm from the floor where the pattern printed film does not adhere to the cup adhered, established. The results obtained are shown in Table I below.

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

Curve 1: Thin film of Example 1

Ö098O / 068 *

- τη - 30

Curve 2: Thin film of Comparative Example 1.

Curve 3: Thin film of Comparative Example 2

Curve 4: thinner. Example 3 movie

Curve 5: Thin film of Example 4

Curve 6: Thin film of Comparative Example 3

Table I.

Film formation

Printable for multi-ply printing Off time

Transferability

Time expansion occurrence rate of adjustment of disturbances

Removability

frr "TZ / et: S / fh, 4- ^{to time} - Sen, such as blocking * (poss arrival elongation (sec) _(° F transmitted _via _ _(Hoh f..

number of n- «*,« «». »«., t- r ■ ser

number of colors)

rate

(X)

Example 1 slightly 4 or more

If

SgI.

«Ice. 1 "

JEisp. 2 "

Jeisp. 3 "

Example 4 "

See.

Example 3 "

4 or more 2

4 or more

4 or more 4 or more 4 or more

27 30 40 30 32

28.

25 25 25 20

30th

45 30

xn "Starts of the lapping of the Bo transfer and defenses in mm)
sen

(55)

35> 80

(45)

40— ^ 55 (15)

30—> 50 (20) ._

(60)

50 5> 140

(90)

40 »70

(30)

early
Tear

size
strain

overlap
and tearing

180

150

• 45

60

~~
"> 200

30 ^ - 50

easy

Il

• I • I

Il

Il

• I

OD CT)

Examples 5 to 8

- ys -

An aqueous solution of the components listed below was prepared to produce a film-forming composition to which 6 "L dipropylene glycol and 0.4% of a nonionic surfactant were added as plasticizers and modifiers, based on the resin. The composition was made A thin film 0.035 mm thick was prepared and a marble pattern was printed on its surface After applying a prescribed amount of butyl cellosolve acetate to the printed surface, the adaptation test - - - was carried out in the same manner as in Example are given in Table II below.

Components for example 5

Polyvinyl alcohol with an average degree of polymerization of 1700 and an average Degree of hydrolysis of 77.8 Μο1 · *% (Α) 95 parts

Polyäthylenojd-d with a molecular weight

from 4,000,000 (B ₂ ) 5 "

Borax 0.5 "

Components for example 6

Polyvinyl alcohol with an average degree of polymerization of 1700 and an average Degree of hydrolysis of 88.2 Mo1 -% (A) 75 parts

white dextrin (B.) 20 "

Methyl cellulose (B ₃ ) x 5 "

Borax 1 "

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Components for example 7 29l8o39

Polyvinyl alcohol with an average degree of polymerization of 700 and an average Degree of hydrolysis of 92.0 mol% (A) 100 parts

Boric acid I 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% (A) 90 parts

Polyacrylamide with an average molecular weight of 2,000,000 (B ₂ ) '10 parts

Borax 0.3 parts

Table II

Film formation

Transferability

Printable

Point K time, expansion occurrence adjustment

\ t -L · γ -u a Z —ΓΓ L — 5> M ning rate of disturbances _TT .. .. _TT

Multi-color off time ^& “... __ _n . Washing with water

J ₁ J ₁ . ζ «ι \ / γ ·, -. . at the time, like blocking printing deh- (sec.) (transmission,., τ. * ^ ι *. / ττ-ι. ^ser

/..,.,-... .. point of e.g. over- point (high

(possible down payment * ^ Z ^ .Starts of the lapping of the

Transfer and indentation in mm) tear

for that

g ^ g of colors) rate

Example 5 easy ^{4 or more} ₂₈

Example 6 "4 or more ₂ 5

4 or more -3

4 or more 27

Example 7 "
Example 8 "

26th

35 40 25

40> 120

(80)

(55)

50 »100

(50)

35> 7S

(40)

> 200 180 160 130

easy

Il

cn co co

- 32 -

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% a thin film with a Thickness of 0.045 mm and was made on ssma.surface using a copper gravure printing process (rotogravure process) a wood grain pattern printed on it.

The thin film printed with the pattern was on the surface of a 0.02% aqueous solution of borax at 25.degree floated with the printed surface facing up, and the conformance test was performed by pressed the bottom of the standard cup to the thin film after 140 seconds (expansion rate of the film 45%) and dipped the beaker into the solution at a speed of 20 cm / min. The grain pattern was on the entire The base and side of the cup transferred and no overlap of the film was observed.

After termination of the adjustment test, the adhering to the cup film was dissolved and removed easily by spraying water of a normal temperature to the cup, ■ eo that only the grain pattern was back. The results obtained are given in Table III below.

Comparative example 4

The adaptation test. ■ of example 9 was repeated,

9098Ä7 / 0684

this time, however, with the pressing and immersion of the cup after 25 seconds (expansion rate of the film 5%) started. There was a tear by dissolving the film at the position 45 mm above the bottom of the beaker observed and the grain pattern expanded significantly at the position near 30mm because of the high expansion rate, 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 III below.

Example 10

The pattern-printed thin film of Example 9 was deposited on the surface of a 0.03% aqueous solution of water Float free Bprax of 25 C and after 120 seconds (Expansion rate of the film 40%) the standard beaker was pressed against the film and immersed in the solution. the The results obtained are shown in Table III.

Example 11

The printed with the pattern thin film of Example 1 was on the surface of a 0.1% solution of boric acid from Let it float at 25 ° C. and after 80 seconds (expansion rate of the film 100%) the standard beaker was pressed against the film and immersed in the solution. The results are given in Table III.

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Table III

Ex. 9 time to See. to start ex. 4th the over bearing Ex. 10 (Sec.) co Ex. 11 co 130 CD 25th & cn 120 80

Expansion rate Adjustment at the time of the blocking start of the excess point (height of bearing (%) the soil in tritn) Reproducibility of the pattern

The film can be removed by washing with water

45

40 100

140

30-45

135 143 good
bad

Well
Well

Well
Well

Well
Well

CX) CD CO

Example 12

The one obtained in Comparative Example 2 with a pattern Printed thin film with a thickness of 0.035 mm was on the surface of a 0.005% aqueous solution of borax of 25 ° C, and transfer printing was then carried out in the same manner as in Example 9. The results obtained are given in Table IV below.

Comparative example · 5

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

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Table IV

12th time to to start the over 5 bearing 13th (Sec.) coExample
ο 40 «T * 14th "See. 25th «^ Ex. _e Ex. 60 β » 50 ••• Ex.

Expansion rate adjustment _p reproducibility at the time of the blockability of the start of the over-point (height of the pattern support (%) 'the floor in mm)

65

40

90 70

Well

something bad

Well

Well

Removability of the
Films by washing
with water

Well

ti

Il

Example 15

Polyvinyl alcohol with an average degree of polymerization of 1700 and an average Degree of hydrolysis of 88.2 mol% 80 parts

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 dissolved in water to form a 17% aqueous solution thereof and using a drum casting method, a thin film with a Thickness of 0.035 mm made therefrom and using a known printing device with a wood grain pattern printed. The thin film printed with the pattern was applied to the surface of a 0.01% aqueous · Solution of borax at 25 C was floated and the transfer was then printed in the same manner as in FIG Example 9 carried out. The results obtained are given in Table V below.

Comparative example 6

The procedure of Example 15 was repeated, this time with 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

An aqueous solution of the following components was

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- ie - Hi

components produced to form a film-forming composition, the 6% dipropylene glycol and 0.4% nonionic surfactant plasticizers and modifying agent based on the resin was added. The composition became a thin film with 0.035 mm thick and printed with a marble pattern on its surface. After applying a prescribed amount of a solvent having an affinity for a printing ink on the printed surface the film was used immediately 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

Polyethylene oxide with a molecular weight of

4,000,000 (B ₂ ). 5 "

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 (B-) 20 parts

Methyl cellulose (B ₂ ) 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

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MSl

Xanthan gum (B ₂ ) 10 parts

Transfer printing was carried out by floating the film on the surface in 0.01% aqueous Dissolve borax at 25 C, press the standard beaker against the film and immerse it in the solution. The one with it The results obtained are shown in Table V below.

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Table V

Time to Expansion Rate Adaptation Reproducible

at the start at the time of the blocking ^ - ability of the pattern

the over- Starts the over- point (height of

load load (%) the floor in mm) (Sec.)

Removability of the
Films by washing
with water

Ex. 15th 50 40 135 Well CD See. 20th 25th 30-50 bad ex. 6th >> »
α » Ex. 16 40- 45 130 Well cn ÖO Ex. 17th 40 25th 135 Well Ex. 18th 45 • 30 120 Well

Well

ti

it

Example 19

A 0.5% solution of borax in a water / methanol (Weight ratio 1: 1) -solvent mixture was applied in the form of a layer on the back of the obtained in Example 9, a thin film printed with a pattern was applied 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 floated on the surface of 25 ° C water with the printed surface facing up, and after 50 seconds (the rate of expansion of the film 30 %) , the conformance test was carried out by pressing the bottom of the standard beaker against the thin film and immersing it Mug in the water. The grain pattern was transferred to the entire base and side of the cup and there was no overlap of the film.

After completing the conformance test, the film adhering to the cup was dissolved and easily removed by Spraying of atomized. Ordinary temperature water on the beaker, so that only the grain pattern remained on it. The results obtained are shown in Table VI.

Example 20

The procedure of Example 19 was repeated, this time using a 1.0% solution of boric acid in a water / -

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- t / L -

¹ p

Methanol (weight ratio 1: 1) -solvent mixture in the form of a layer on the thin film obtained in Example 12 and printed with a pattern in an amount of 6%, based on the Polyvin} ⁷ ! alcohol. The results obtained are shown in Table VI.

Examples 21-23

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

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ORIGINAL INSPECTED

Table VI

Time to expansion rate at start at time of over start of transmission transmission (%)

CO
O
(O
00
* «· ■
^ * Ex. 19th (Sec.)
50 30th ^e Ex. 20th 45 30th J ^ Ex. 21st 30th 35 Ex. 22nd 40 25th Ex. 23 45 35

Adaptive
Blocking
point (height
from the ground
in mm) Reproduce
availability of the
Pattern Removability of the
Films by washing
with water 120
120 Well
It Well
ti 125
130 Il
It ti
It 135 dd It

• co co

Claims (11)

Claims 1. Method of transferring a to a thin film a polyvinyl alcohol resin pattern printed on a surface of an object by pressing the Object or object on the floating on the surface of water with the printed surface facing up thin film and immersion of the object or. Object in the water, characterized in that one incorporated boric acid or a salt thereof into the thin film or water. 2. The method according to claim 1, characterized in that the boric acid or a salt thereof is incorporated into the thin film of a polyvinyl alcohol resin in an amount of 0.02 to 10% by weight , based on the polyvinyl alcohol resin. 3. The method according to claim 1 or 2, characterized in that the boric acid or a salt thereof is incorporated into the thin film of a polyvinyl alcohol resin by mixing the boric acid or a salt thereof with a film-forming composition and a thin film from the mixture obtained manufactures. 909U7 / OBI * 4. The method according to claim 1 or 2, characterized in that the boric acid or its salt in the thin film of a Polyvinyl alcohol resin is incorporated by adding a solution of boric acid or a salt thereof to at least one side of the thin Films. 5. The method according to any one of claims 1 to 4, characterized in that the boric acid or its salt in a concentration of 0.002 to 0.5 wt -% of the water incorporated.. 6. The method according to any one of claims 1 to 5, characterized in that that the polyvinyl alcohol resin has an average degree of polymerization of 300 to 3000 and an average Degree of hydrolysis from 65 to 97 mol / l. 7. The method according to any one of claims 1 to 6, characterized in that that the thickness of the thin film is 0.01 to 0.1 mm. 8. A method according to any one of claims 1 to 7, characterized in that the thin film contains a polyvinyl alcohol resin or consists of 98 to 50 parts by jS from a polyvinyl alcohol resin (Α) and 2 to 50 wt -.% Of at least one Component (Β.) And / or a component (B «), where component (B,) is at least one selected from the group consisting of starch, alginic acid salt and xanthine gum, and component (B ~) is at least one such which is selected from the group consisting of polyacrylamide, polyethylene oxide and methyl cellulose. 9. The method according to claim 8, characterized in that the §09847 / 0684 ORIGINAL Thin film of a polyvinyl alcohol resin both at least 1% by weight of component (B.) and at least 0.5% by weight the component (B «) contains. 10. The method according to any one of claims 1 to 9, characterized in that the boric acid salt is borax. 11. The method according to claim 2, characterized in that the amount of boric acid or a salt thereof within the Range from 0.1 to 2 wt .- #. 109847/0684 ORIGINAL INSPEOTPD