JPH08238898A - Activator composition used for hydraulic transfer - Google Patents

Abstract

PURPOSE: To obtain the freshness of a transfer pattern at the time of finishing and to prevent adherence of dust, ink deviation by preparing activator composition by mixing resin, solvent, plasticizer and ultra-fine particle silica of predetermined quantities. CONSTITUTION: 20 pts.wt. of resin, solvent, plasticizer and resin and ultra-fine particle silica of 3 pts.wt. or less are mixed, and composition for activating a print pattern layer of a transfer film in the case of hydraulic transfer is prepared. since the silica has a refractive index similar to that of the resin of the composition and the particle size is submicron order, when it is dispersed in the composition, it becomes transparent, and even if it turns filmy, it still exhibits transparency. Since an oil supply amount is much bodied, the strain flow of the print pattern layer restored for the viscosity and ink deviation are prevented, and extensibility for following up the deformation of the transfer film upon pressing of the transfer medium is given.

Description

Detailed Description of the Invention

[0001]

[Object of the invention]

BACKGROUND OF THE INVENTION The present invention relates to a printing pattern layer on a transfer film in a so-called hydraulic transfer technique for transferring a grain of wood or a marble pattern to a three-dimensional object such as a curved surface by using a pressing force of water pressure. The present invention relates to an activator composition that imparts tackiness and the like.

[0002]

BACKGROUND OF THE INVENTION Heretofore, in these activator compositions, as disclosed in JP-A-63-197685, a resin component,
Those composed of a solvent component, a plasticizer component, and an extender pigment are suitable. As the extender pigment, precipitated barium sulfate was used, and as the resin component, nitrocellulose was added to a short oily alkyd resin. As seen in the above-mentioned publication, the extender pigment is, against the printed pattern layer to which tackiness or the like is imparted again, while preventing apparent adhesion of dust by drying apparently and imparting thixotropy while preventing ink misalignment. It was added for the purpose of preventing cracking as well so as not to impair the clarity of the transferred pattern at the time of finishing. However, when the water pressure transfer technology has become widespread as in recent years and a high design has been required, it has become impossible to overlook the deterioration of the image clarity due to the addition of a few percent thereof. That is,
Conventional activator compositions were cloudy when they were in a liquid state before use, and became extremely transparent only after forming a dry film. However, even this very problem has become a problem. Further, in the conventional activator composition, this barium sulfate tends to settle, and there is a problem that the desired performance cannot be obtained unless it is stirred again during use.

When the print amount of the ink in the print pattern layer is wide ranging from small to large due to the diversification of designs, the activator composition also needs a strong ink dissolving power in preparation for the case where the print amount is large. Is coming. When the ink dissolving power is insufficient, the smooth extension of the transfer film and the printed pattern layer is obstructed by the poorly dissolved portion and the fine unevenness on the transferred material, and the fine bubble-like swelling or the apex of the transfer pattern layer occurs. A defect called a crater-like so-called ink spot that pops up occurs. This is because the short oily alkyd resin itself is a relatively soft resin, so even if ink dissolution failure occurs, there is still the possibility of being able to flexibly deal with the fine irregularities of the transferred material. Since the nitrocellulose added to the oily alkyd resin is a relatively hard resin, the poor dissolution of the ink causes insufficient tracking of the fine irregularities of the transferred material, and inevitably the ink spots cannot be avoided. On the other hand, it was impossible to remove nitrocellulose, which is a non-drying resin that prevents the adhesion of dust by apparently drying the short oily alkyd resin and also adjusts the hardness. Furthermore, in a product that was hydraulically transferred using a conventional activator composition, air bubbles might be generated from the product coating film over time, but the applicant has found that nitrocellulose added as a resin component. Has high hygroscopicity, absorbs moisture in the atmosphere, accumulates, and eventually lifts the coating film as bubbles, and its behavior,
I determined the cause.

[0004]

[Technical Items Attempted to Develop] That is, the present invention ensures the clearness of the transferred pattern at the time of finishing, and prevents dust from adhering by apparent drying where the extender pigment has largely played a role. Effectively prevents film cracking during extension while preventing ink misalignment, does not require re-stirring at the time of use, and can also prevent ink spot defects, which may occur over time. It is an object of the present invention to provide an activator composition that can avoid the phenomenon of floating due to bubbles.

[0005]

Configuration of the Invention

That is, the activator composition used for hydraulic transfer according to the first invention of the present application is a composition for activating a printed pattern layer of a transfer film in hydraulic transfer, It is characterized by comprising a resin component, a solvent component, a plasticizer component, and ultrafine silica particles.

The activator composition used in the hydraulic transfer according to the second invention of the present application is a composition for activating the printed pattern layer of the transfer film in the hydraulic transfer, which comprises a resin component, It is characterized by comprising a solvent component, a plasticizer component, and ultrafine particle silica, and the ultrafine particle silica is contained in an amount of 3 parts by weight or less based on 20 parts by weight of the resin component.

The activator composition used in the hydraulic transfer according to the third invention of the present application is a composition for activating the printed pattern layer of a transfer film in the hydraulic transfer, which comprises a resin component, It is characterized in that it is composed of a solvent component, a plasticizer component, and ultrafine particle silica, and that cellulose acetobutyrate is used as a resin component together with a short oily alkyd resin.

The activator composition used in the hydraulic transfer according to the fourth invention of the present application is a composition for activating the printed pattern layer of a transfer film in the hydraulic transfer, which comprises a resin component, It is composed of a solvent component, a plasticizer component, and ultrafine particle silica, and uses cellulose acetobutyrate together with a short oily alkyd resin as a resin component. To do.

The activator composition used for hydraulic transfer according to the fifth invention of the present application is a composition for activating a printed pattern layer of a transfer film in hydraulic transfer, which comprises a resin component, 1 part by weight of cellulose acetobutyrate together with 20 parts by weight of a short oily alkyd resin is used as a resin component, which is composed of a solvent component, a plasticizer component, and ultrafine silica.
30 parts by weight of butyl cellosolve and 80 parts by weight of butyl carbitol acetate are used as a solvent component, 30 parts by weight of dibutyl phthalate are used as a plasticizer component, and 2 parts by weight of ultrafine silica is used.

[0010]

The ultrafine silica particles have a refractive index close to that of the resin component in the activator composition and a particle size on the order of submicrons. Even if the agent composition forms a dry film, it is transparent. In addition, since the so-called oil supply amount is large and the viscosity increases, it is possible to follow the deformation of the transfer film that accompanies the transfer target while preventing distortion flow of the print pattern layer that has restored adhesiveness etc. again, so-called ink misalignment, and give. In addition, since the particle size is on the order of submicron, and its specific gravity is similar to that in the activator composition, it does not settle and exhibits a uniform dispersion state. In particular, cellulose acetobutyrate is used together with a short oily alkyd resin as a resin component, and ultrafine particle silica is used as an alkyd resin 20.
When the amount is 3 parts by weight or less relative to the parts by weight, these are well balanced. Cellulose acetobutyrate is a resin that is softer than nitrocellulose, so it imparts a certain degree of hardness to the short oily alkyd resin and accelerates the apparent drying. Maintains appropriate softness that can follow unevenness. At the same time, since it is a resin having a low hygroscopicity, it absorbs and accumulates no moisture in the atmosphere, and improves the floating caused by bubbles in the product coating film.

[0011]

EXAMPLES First, the basic flow and basic matters of the hydraulic transfer technique in which the activator composition of the present invention is used will be described. In the hydraulic transfer technique, an appropriate pattern such as wood grain or a marble pattern is previously printed on a base film by a printing means such as gravure printing, for example, a water-soluble film containing polyvinyl alcohol as a main component, and after drying, a roll or Prepare as a cut sheet-shaped transfer film. here,
The inks used for printing on the base film are easy to form a dry film by temporarily adhering to the base film,
It contains as a vehicle a resin that adheres to the surface of the transferred material and that easily swells in the activator composition. Then, at the time of transfer, the activator composition is applied only to the printed pattern layer side by using an application means such as a roll coater while continuously or individually pulling out the transfer film.
Here, the activator composition contains a solvent capable of swelling the inks, erodes the surface of the transfer target, or rapidly dissolves the undercoat layer when the transfer target is undercoated. It is desirable that it is not allowed to do so, and the basic conditions such as the addition of a resin having an affinity for this solvent are provided.

Subsequently, when the transfer film is floated on the water surface of the aquarium with the surface coated with the activator composition facing upward, the base film in the transfer film absorbs water to swell and soften, and at the same time, the printed pattern layer. Is also swelled and activated by the activator composition, and becomes a sticky state immediately after printing.
Therefore, in anticipation of the time, while the transfer target such as ABS resin is brought into contact with the transfer film from the sky, the transfer film and the transfer film are both pushed into the water so that a part or all of the transfer film is immersed. As a result, the transfer film is brought into close contact with the surface of the transfer object while coping with the large curved surface and the fine irregularities. After that, pull up this transfer target from water,
Separately, wash away the remaining base film by taking a hot water shower at the booth, blow hot air etc. to volatilize the solvent contained in the ink and activator composition, and if necessary, clear top coat to complete And In addition, if the transfer target is pushed in while being inclined with respect to the water surface, the air between the transfer target and the transfer film is eliminated,
The so-called pinhole defect can be avoided, and the transfer process can be continuously performed by flowing the water in the water tank and causing the transferred body to descend and incline with respect to the water surface in the steady flow.

The basic flow and basic matters of the hydraulic transfer technique have been described above. To provide an understanding of the activator composition of the present invention, the details after application of the activator composition will be described again. That is, when the transfer film coated with the activator composition is floated on the water surface, the base film in the transfer film is swollen with water, and at the same time, the printed pattern layer is swollen with the activator composition, and the transfer film is integrated. However, since it takes a relatively long time for the base film to swell by absorbing water, the printed pattern layer swells for a relatively short time. If the swelling is not carried out in synchronism, the transfer film may be wrinkled, and the printed patterns may adhere to each other or the printed pattern layer may be cracked.

For this reason, the base film is not merely water-soluble but has a composition optimally adjusted for this synchronous swelling, and the activator composition also consists only of a solvent component for swelling inks. Rather, it imparts extensibility that does not crack when the transfer film, that is, the print pattern layer is deformed, yet prevents unnecessary ink misalignment of the print pattern layer, and resin and plasticizer components so that it can be dried within an appropriate time. Further, an extender pigment was added. That is, the solvent component dissolves the ink to restore the tackiness until the end of transfer, the resin component ensures initial adhesion and prevents ink diffusion, and the plasticizer imparts plasticity to the resin component and extends the pigment. Has constituted one activator composition in which each component shares or complements its function such that the ink surface is apparently dried and the ink misregistration is controlled while imparting extensibility.

By the way, the conventional typical activator composition was as follows. As a resin component, a short oily alkyd resin 9% by weight, nitrocellulose 1% by weight, as a solvent component, butyl cellosolve 14% by weight, butyl carbitol acetate 35% by weight, as a plasticizer component, dibutyl phthalate 18% by weight, as an extender pigment, precipitated barium sulfate. 23% by weight

After the printed pattern layer is in close contact with the transferred material, the remaining base film is washed off, dried and then top-coated with a clear coat. However, the transferred pattern transferred to the transferred material is actually The activator composition will be visible through the spread and dry film layer and the clear layer of the topcoat. Therefore, when the dried film of the activator composition is somewhat inferior in transparency, the resulting transferred pattern is inferior in sharpness. Conventionally, as described above, precipitating barium sulfate is used as an extender pigment. Precipitating barium sulfate is a fine powder of 0.5 to 1.5 μm, although it is fine, and its refractive index is 1.64. And the refractive index of the vehicle part in the activator composition are somewhat different, the transparency of the dry film of the activator composition is somewhat impaired, and the specific gravity is about 4.48, which is the vehicle in the activator composition. Since it is relatively different from the specific gravity of the part, it was necessary to re-stir at the time of use. However, if you remove this extender pigment, this time,
By the time the top coat is applied, dust may be attached, the transfer pattern may be disturbed, or the transfer pattern may become dirty.

The short oily alkyd resin is basically a non-drying and relatively soft resin and is therefore basically excellent as a resin component of the activator composition. After that, some stickiness remains, so it is necessary to try to dry it apparently, and it is also necessary to supplement the hardness to some extent in terms of preventing ink misalignment. Therefore, conventionally, nitrocellulose, which is also a relatively hard resin, has been added. However, if the ink-dissolving power of the activator composition is insufficient as compared with the printing amount of the ink, the above ink droplet defect may occur. Also, there is a drawback that it absorbs moisture in the atmosphere due to its hygroscopicity and, after accumulation, makes the product coating film rise as bubbles. However, it has been common knowledge that nitrocellulose is indispensable because only the short oily alkyd resin can be used.

[0018]

EXAMPLES Therefore, the activator composition used in the hydraulic transfer of the present invention comprises a resin component, a solvent component, a plasticizer component, and ultrafine particle silica.
It is 3 parts by weight or less with respect to 0 parts by weight, and further, cellulose acetobutyrate is used together with a short oily alkyd resin as a resin component, and ultrafine silica is 3 parts by weight or less with respect to 20 parts by weight of alkyd resin. It is a feature. The specific composition ratio and the like need to be appropriately changed depending on the properties of the inks in the printed pattern, the design effect of the transferred pattern, etc., but the optimum composition ratio in the examples is as a resin component, a short oily alkyd resin 20 Parts by weight Cellulose acetobutyrate 1 part by weight Solvent content butyl cellosolve 30 parts by weight Butyl carbitol acetate 80 parts by weight Plasticizer component dibutyl phthalate 30 parts by weight Ultrafine silica 2 parts by weight ultrafine silica.

In the examples, as the ultrafine particle silica, the trade name Aerosil (AE) of Japan Aerosil Co., Ltd.
ROSIL (registered trademark), which is obtained by a dry flame hydrolysis method and has a silicon dioxide content of 9%.
High purity of 9.8%, anhydrous, standard product diameter 0.01μ
It is a synthetic silica having a particle size of m to 0.02 μm. Therefore, using a transfer film printed with a wood grain pattern, the ABS resin plate whose surface has been roughened with various sandpapers, the conventional composition and the composition of the above-mentioned example are changed in their coating amounts. Then, when the hydraulic transfer was tried by a conventional method, the following results were obtained.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

[0023]

[Table 4]

That is, Tables 1 to 3 summarize the results for each coating amount, and Table 1 shows the results when a gravure roll having a depth of 85 μm and # 85 was used for coating the activator composition. 2 shows the results when using a gravure roll having a depth of 60 μm and # 100, and Table 3 shows the results when using a gravure roll having a depth of 30 μm and # 100.
The conditions are set so that the coating amount of the activator composition gradually decreases as In addition, the numbers in the uppermost column in Tables 1 to 3 are the numbers of sandpaper used when the surface of the ABS resin plate was roughened, and the smaller the number, the rougher it was.
It indicates that the surface of the ABS resin plate is rough. Table 4 also shows the results of other tests conducted on a normal ABS resin plate that does not roughen the surface. In addition,
The numbers 1 to 5 in the table are the scores by visual evaluation, and the larger the number, the better the result.

As can be seen from the results shown in Table 1, even if the surface of the material to be transferred is somewhat rough, it is a conventional composition as long as the amount of the activator composition applied and the dissolving power of the ink are adequate. Even though the composition of the example is sufficient, a satisfactory product can be obtained, while the surface becomes rough, and as can be seen from the results in Table 2, the coating amount of the activator composition is reduced. When the dissolving power of is insufficient, the defects due to the conventional composition become remarkable. On the other hand, in the case of the composition of Example, if the surface is not so rough, the acceptable product is still obtained. As shown in the results of Table 3, when the coating amount of the activator composition is reduced and the dissolving power of the ink is too insufficient, it is difficult to pass the conventional composition product and the example composition product, but it is still difficult. The composition is better. In addition, these are mainly tested for the degree of occurrence of ink spot defects, but since the coating amount of the activator composition gradually increases from Table 3 to Table 1, the conditions are set under Table 1 below. Comparing what was done and what was done under the conditions of Table 2 and Table 3 one after another, the conventional composition gradually became whitish and the color vividness decreased. On the other hand, no remarkable change occurred in any of the composition compositions of the examples. The comparison results are shown in Table 4 as hue and image clarity.

Further, as can be seen from the results in Table 4, there is no remarkable difference in the throwing power of the film between the conventional composition product and the example composition product, and the example composition product is superior in the ink extensibility. In terms of pattern blurring, the composition of the example composition was inferior to that of the conventional composition. Note that the hue and sharpness are
It is also seen whether the hue of the transfer pattern is not whitish, or it is not a blurry color as if it was covered with a veil, and the throwing power of the film is that the base film is the activator composition. It reacts chemically and becomes hard,
It is to see if the extensibility is hindered by becoming brittle, and the extensibility of the ink is to see if the ink, which has regained its adhesiveness, can be extended without tearing. Is to see if the ink on the print pattern layer, which is a gravure mark, is dripped from the edge or the like and becomes ambiguous.

The above experimental results confirm the effectiveness of the compositions of the examples, because they are ultrafine silica particles instead of the conventional extender barium sulphate, which is a precipitated extender. Change to nitrocellulose as a minute,
This is because it is cellulose acetobutyrate. Here, silica is naturally produced as quartz, silica stone, and diatomaceous earth, and silica is exemplified as the use of the extender pigment in the above-mentioned JP-A-63-197685, but in general, Even though silica is used, silica powder is merely used as a delustering agent by being added to paints and inks. However, the silica used in the activator composition of the present invention does not have to be anything as long as it is a generic silica, and it is absolutely necessary that it is ultrafine particles of submicron order. That is, since it is ultrafine silica, the so-called oil supply amount is large, and while preventing ink misalignment by thickening the inks whose viscosity has been restored again, an activator composition that aims to achieve apparent drying is obtained. Since it fulfills the basic function and has ultrafine particles and a uniform particle size, it can exhibit a smooth surface when formed into a dry film. Further, similarly, it does not mean that any pigments may be used as long as they are ultrafine particles, and even if they are pigments that can be satisfied in terms of transparency, they may hinder the extensibility. Do not let it settle down because of its high specific gravity. In other words, since it is ultrafine silica, it is possible for the first time to achieve the basic function as an activator composition of imparting extensibility while trying to dry apparently while preventing ink misalignment. Since they are fine particles and their refractive index and specific gravity are more similar to those of the vehicle part in the activator composition, they can be transparent not only in the activator composition but also in the form of a film. It is possible to apply it as a transfer pattern. At the same time, there is no need to re-stir at the time of use.

On the other hand, cellulose acetobutyrate is a mixed ester prepared by adding nitric acid and acetic acid to cellulose and is a resin that is harder than short oily alkyd resins but softer than nitrocellulose, and also less hygroscopic than nitrocellulose. Is. Therefore, because it is a non-drying resin of the short oily alkyd resin, the stickiness after evaporation of the solvent avoids dust adhesion as if it was apparently dried, and it is rather soft oily short alkyd resin. The resin is made a little harder so that ink misalignment can be prevented. In addition, even if the ink dissolving power is insufficient, such as the coating amount of the activator composition is insufficient compared to the printing amount of the ink, since the added cellulose acetobutyrate is not as hard as conventional nitrocellulose, the original The softness of the short oily alkyd resin comes to life, which maximizes ink spreadability and eliminates ink spot defects.

Regarding the phenomenon in which the coating film of the product floats up as bubbles with the passage of time, a conventional composition product and an example composition product were prepared, and the same conditions were used under an atmosphere of a temperature of 50 ° C. and a relative humidity of 98%. After allowing to stand for 500 hours to promote moisture absorption, a 1 mm interval was cut with a cutter, cellophane tape was applied and peeled off, and a cross-cut test was conducted. A part of the conventional composition was peeled off. On the other hand, the composition of the example did not peel off. From this result, it can be estimated that the situation in which the product coating film floats up as bubbles after absorbing moisture in the atmosphere over time and accumulating.

In another embodiment, the ratio of the active agent composition is changed to that of Aerosil without changing the composition ratio other than Aerosil.
When changed to 3 parts by weight, 3 parts by weight, and 4 parts by weight, the addition of 1 part by weight was slightly inferior to the apparent dryness, but was sufficiently practical, and the addition of 3 parts by weight. It was close to the best. However,
With up to 4 parts by weight, ultrafine silica thickens and restrains the ink too much, lacks extensibility, delays synchronization with the swelling of the base film, and causes cracks in the transfer pattern, and is no longer used. Was unbearable. From these, it is desirable that the amount of the ultrafine silica added is 3 parts by weight or less with respect to the resin component, particularly, in the examples, 20 parts by weight of the alkyd resin. In addition, various kinds of resin components, solvent components, plasticizer components and their composition ratios were tried variously, and as long as the solvent component and the plasticizer component were selected within a common sense range, the resin was used together with the ultrafine particle silica. A short oily alkyd resin and cellulose acetobutyrate are used as the components, and the ultrafine particle silica has 3 parts by weight or less with respect to 20 parts by weight of the alkyd resin. I confirmed that I could play. Among them, again, the above-mentioned composition compositions of Examples exhibited the most excellent effects.

In the above description, the ABS resin is used as an example of the transferred material, but the material is not limited to the ABS resin, the AS resin, the vinyl chloride resin, the polystyrene resin, the noryl resin, the phenol resin, the urea resin. Needless to say, it can be similarly applied to melamine resin, FRP, epoxy resin, thermoplastic, thermosetting resin, metal body, wood, stone and the like. Also, the timing of applying the activator composition was described as after the transfer film was floated on the water surface, but the transfer film was floated on the water surface first, and the transfer film absorbed water and waited for swelling to be spray-coated. There is no denying the use of the activator composition in the order in which it is applied by means or the like. Further, in the above description, the water-soluble film is used as the base film, but the base film may swell in the liquid at the time of transfer, and may even be sufficiently attached to the curved surface of the transferred material. For example, if it is swellable without being dissolved, it can be used.
Furthermore, in the above-mentioned examples, the description was made assuming that Aerosil by the dry flame hydrolysis method was used as the ultrafine particle silica, but the present invention is not limited to this, and other ultrafine particle silica can be similarly used.

[0032]

As described above, according to the present invention, it is possible to prevent dust from adhering for apparent drying, which has been largely dominated by conventional extender pigments, and to prevent coating film cracking during extension while preventing ink misalignment. In addition, there is no need for re-stirring at the time of use, and excellent sharpness can be imparted to the transferred pattern at the time of finishing. Further, it is possible to prevent ink spot defects and to avoid the phenomenon of floating of the product coating film caused by air bubbles that may occur over time, and thus it is possible to meet the ever-increasing demand for higher design.

Claims (5)

[Claims] 1. A composition for activating a print pattern layer of a transfer film in hydraulic transfer, comprising a resin component, a solvent component, a plasticizer component, and ultrafine silica. Activator composition used. 2. A composition for activating a printed pattern layer of a transfer film in hydraulic transfer, comprising a resin component, a solvent component, a plasticizer component, and ultrafine particle silica, wherein the ultrafine particle silica is a resin component 20. An activator composition used for hydraulic transfer, characterized by having 3 parts by weight or less based on parts by weight. 3. A composition for activating a print pattern layer of a transfer film in hydraulic transfer, comprising a resin component, a solvent component, a plasticizer component, and ultrafine silica, and a short oily alkyd resin as the resin component. An activator composition for use in hydraulic transfer, characterized in that it is composed of cellulose acetobutyrate. 4. A composition for activating a printed pattern layer of a transfer film in hydraulic transfer, comprising a resin component, a solvent component, a plasticizer component and ultrafine silica, and a short oily alkyd resin as the resin component. With cellulose acetobutyrate, ultrafine silica is alkyd resin 20
An activator composition used for hydraulic transfer, characterized by having 3 parts by weight or less based on parts by weight. 5. A composition for activating a printed pattern layer of a transfer film in hydraulic transfer, comprising a resin component, a solvent component, a plasticizer component and ultrafine silica, and a short oily alkyd resin as the resin component. Using 1 part by weight of cellulose acetobutyrate together with 20 parts by weight, 30 parts by weight of butyl cellosolve and 80 parts by weight of butyl carbitol acetate as a solvent component, and 3 parts of dibutyl phthalate as a plasticizer component.
An activator composition used in hydraulic transfer, characterized in that 0 part by weight and 2 parts by weight of ultrafine silica are used.