JP4886504B2 - Manufacturing method of painted glass container - Google Patents

Description

  The present invention relates to a method for producing a coated glass container including a hot stamping process, and particularly, in the case of transferring several kinds of decorative paints even when transferring a large area metal foil in the hot stamping process. However, the present invention relates to a method for manufacturing a coated glass container in which a coated glass container having a uniform coating is obtained.

In recent years, the surface of a glass container such as a cosmetic container is often decorated with a beautiful metallic decoration in which letters and designs are raised by a hot stamping method.
A typical implementation method of such a hot stamp method will be described as follows.

FIG. 10 is a diagram for explaining an example of a conventional hot stamp method (see Patent Document 1).
According to such a hot stamp method, first, printing ink mainly composed of a thermosetting resin such as an epoxy resin is printed on the surface of the glass container 202 shown in FIG. 10A by a printing method such as screen printing. To do.
Next, as shown in FIG. 10B, a raised display portion 204a corresponding to a desired character or design is raised and formed on the surface of the glass container 202.
Next, the raised display portion 204a is allowed to stand at room temperature or forcedly dried at a predetermined temperature to make the raised display portion 204a in a semi-cured state that is substantially non-sticky.
Next, from the upper surface of the bulge display portion 204a, by pressing with a heating elastic body while applying a hot stamping foil subjected to aluminum vapor deposition, as shown in FIG. 10C, only the bulge display portion 204a is applied. Aluminum is transferred to form a metallic display portion 206 made of aluminum.
Finally, the glass container 202 including the metallic display portion 206 is baked at a predetermined temperature, so that the raised display portion 204a is completely cured and functions as the adhesive 204b.
According to such a hot stamp method, it is possible to obtain effects such as a short decoration time, no positional deviation at the time of overprinting, and a large stereoscopic effect as compared with conventional overprinting.

Further, as shown in FIG. 11, in order to improve the wear resistance and the like, after applying the base printing 302 to the metal product 301, the hot stamping method is performed to transfer the metal foil 306, and after that, A method of forming a top coating layer 307 on the surface of the transferred metal foil 306 has been proposed (see Patent Document 2).
That is, after applying the base printing 302 on the surface of the metal product 301 by printing means, printing is performed in a state where the ultraviolet curable ink or the electron beam curable ink 303 is raised at a predetermined location, and a hot stamp method is performed from there. In this method, the metal foil 306 is transferred and finally, a top coating layer 307 is formed on the surface of the transferred metal foil 306.

Furthermore, in order to improve wear resistance and the like, a method of previously forming a protective layer or a clear protective coating film on the surface of a metal foil transferred by a hot stamp method has been proposed (see Patent Documents 3 and 4). .
That is, in order to form a clear protective coating film, a two-component reactive urethane-based paint mainly composed of a polyol having a hydroxyl value (OH value) of 30 to 95% is used and a resin for forming a protective layer is used. In addition, a method using an acrylic resin or a vinyl chloride / vinyl acetate copolymer having compatibility with a two-component reactive urethane coating has been proposed.
Japanese Patent Publication No. 55-23222 (Claims) JP-A-7-205536 (Claims) JP-A-8-71490 (Claims) Japanese Patent Laid-Open No. 10-236090 (Claims)

  However, the hot stamping methods described in Patent Documents 1 and 2 have a problem in that a predetermined decorative coating cannot be applied on the transferred metal foil. That is, a decorative layer is provided on the surface of the metal foil so that the metal foil is selectively and easily peeled off from the hot stamping foil, or the decorative coating is repelled. There was a problem that uniform coating could not be applied. In particular, when several kinds of decorative paints are applied, there is a problem that the coating unevenness becomes remarkably large and a desired coating cannot be applied.

  Moreover, in the hot stamping methods described in Patent Documents 3 to 4, the type of resin for forming the protective layer and the clear protective coating film is excessively limited, and the hydroxyl value (OH value) is high. In addition, there was a problem that the metal foil was easily corroded. Further, due to the protective layer and the clear protective coating film, there was a problem that the peelability when hot stamping was lowered and it was difficult to transfer a large area metal foil. Furthermore, when a decorative coating is applied on the protective layer or the clear protective coating film, the decorative coating is repelled by the release layer or release agent on the surface thereof, and is uniform as in Patent Documents 1 and 2. There was a problem that could not be painted.

Of course, an attempt was made to reduce the thickness of the release layer on the surface of the metal foil and the coating amount of the release agent by providing an adhesive layer on the back side of the metal foil to enhance adhesion with the printing ink. Yes.
However, only an incomplete transfer state of the metal foil can be obtained, and in particular, there has been a problem that it is difficult to transfer a large-area metal foil with high accuracy.

Therefore, the inventors of the present invention have intensively studied and found that the above-mentioned problems can be solved by controlling the surface tension as the surface wetting index when pressing the hot stamping foil within a predetermined range. The title and the present invention have been completed.
That is, according to the present invention, it is possible to carry out a painting process after the hot stamping process, and even when a large-area metal foil is transferred in the hot stamping process, several decorative paints are used. It is an object of the present invention to provide a method for producing a coated glass container in which a coated glass container with a uniform coating can be efficiently obtained even when coating is applied.

According to this invention, the manufacturing method of the coated glass container characterized by including the process of following (1)-(4) is provided, and the problem mentioned above can be solved.
(1) Step of preparing a glass container (2) Step of applying and semi-curing printing ink to a predetermined portion of the glass container (3) Pressing the hot stamping foil using a heating elastic body, Correspondingly, it is a step of transferring a metal foil having a surface wetting index of 30 dyn / cm or more , and the area ratio of the transferred metal foil is a value within a range of 50 to 80% per unit area of 100 cm ^2. Metal foil transfer step (4) A process of coating the surface of the glass container with an acrylic melamine-based paint containing a lactone polyol compound from the transferred metal foil. Even if the painting process can be performed after the stamping process, and a large area of metal foil is transferred in the hot stamping process, several decorative paints are used. Even in the case of coating, it is possible to obtain a coating glass containers subjected to uniform painting quickly and efficiently.
In addition, by performing the metal foil transfer process in consideration of the area ratio of the metal foil in this way, even in the case of transferring a plurality of metal foils having different areas, shapes, etc. in the hot stamping process, the adhesiveness Thus, a coated glass container excellent in decorativeness can be produced in a shorter time and more efficiently.
In addition, by coating such an acrylic melamine-based paint, it is possible to carry out a painting process after the hot stamping process, and when transferring a metal foil of a large area in the hot stamping process. Even if it is a case where several kinds of decorative paints are applied, a coated glass container with a uniform coating can be obtained in a short time and efficiently.
In addition, the wettability index | exponent of the surface of metal foil can be measured by the method as described in the Example mentioned later.

In carrying out the method for producing a coated glass container of the present invention, in step (3), a hot stamping in which a peeling adjustment layer for forming a wetness index of the surface of 30 dyn / cm or more is formed on the surface of the metal foil. It is preferable to use a foil.
Thus, as a peeling adjustment layer, for example, by forming a metal foil including an epoxy acrylate resin or a resin layer containing a mixture of an epoxy resin and an acrylate resin, a large-area metal foil is transferred in a hot stamping process. Even when applying several types of decorative paints, it is possible to reliably form a coating film with excellent adhesion, and to improve the efficiency of a coated glass container with excellent decoration and durability. Can be manufactured automatically.
In addition, before implementing the process of coating the surface of a glass container, it is preferable to provide the confirmation process for confirming that the wetting index of the surface of a peeling adjustment layer is a predetermined range.

When implementing the manufacturing method of the coated glass container of this invention, it is preferable in a process (3) to include the process of carrying out the washing process or the silicic acid flame process on the surface of the said metal foil.
By carrying out in this way, a coating process can be carried out after the hot stamping process, and a coating film having further excellent adhesion can be reliably formed by a simple method.

When implementing the manufacturing method of the coated glass container of this invention, it is preferable to provide the opening part for exposing a glass surface in a part of the said metal foil while transferring metal foil in a process (3).
By carrying out in this way, even when a so-called hollow pattern metal foil is transferred, patterning can be performed with high accuracy, and a coating film having excellent adhesion can be formed on the metal foil. .

When implementing the manufacturing method of the coated glass container of this invention, it is preferable to press a hot stamping foil using a heating elastic body in a process (3), rotating a glass container.
By carrying out in this way, in the hot stamping process, it is possible to easily and accurately transfer a metal foil excellent in decorating properties to a cylindrical glass container or the like.

When implementing the manufacturing method of the coated glass container of this invention, it is preferable to transfer several metal foil in a process (3).
By carrying out in this way, a plurality of metal foils are transferred in the hot stamping process, and a coated glass container having further excellent decorativeness can be efficiently obtained.

When implementing the manufacturing method of the coated glass container of this invention, it is preferable to use the epoxy-type adhesive agent containing an antifoamer as a printing ink in a process (2).
By carrying out in this way, the adhesion between the metal foil and the printing ink is improved, and the metal foil excellent in decorativeness can be transferred in a firm state.

When implementing the manufacturing method of the coated glass container of this invention, it is preferable to prepare the glass container provided with the base layer on the surface in a process (1).
By carrying out in this way, it is possible to efficiently produce a coated glass container having further excellent decorativeness.

[First embodiment]
The hot stamping method for a glass container in the present invention is a method for producing a coated glass container characterized by including the following steps (1) to (4).
(1) Step of preparing a glass container (sometimes referred to as step (1))
(2) A step of applying a printing ink to a predetermined portion of the glass container and semi-curing (sometimes referred to as step (2)).
(3) to press the hot stamping foil with a heating elastic body, corresponding to the printing inks, wetting index of the surface is a step of transferring the metal foil is 30 dyn / cm or more, the transfer metal foil A metal foil transfer step in which the area ratio is a value within the range of 50 to 80% per unit area of 100 cm ² (sometimes referred to as step (3)).
(4) A step of coating the surface of the glass container with an acrylic melamine-based paint containing a lactone polyol compound from the transferred metal foil (sometimes referred to as a step (4)).
That is, as shown in FIG. 3 and FIG. 4, even in the case of transferring a metal foil having a large area or the like in the hot stamping step which is the step (3), a coating film having excellent adhesion is formed thereon. As a result, it is possible to efficiently produce a coated glass container excellent in decorativeness and durability.
Hereinafter, the manufacturing method of the coated glass container according to the embodiment of the present invention will be specifically described separately for each process while referring to FIGS. 3 and 4 as appropriate.

1. Glass container preparation process The glass container prepared in the glass container preparation process (1) shown in FIG. 3 is, for example, a glass container used for cosmetic containers, medicine storage, etc., and is suitable for the use and grade of the final product. It is preferable to prepare a glass container having
Further, in the printing ink application step (2) of the next step shown in FIG. 3, in order to form a raised display portion made of printing ink having further excellent adhesion to the glass container, sandblasting, hydrofluoric acid treatment, etc. It is also preferable to prepare a smoked glass container having a roughened surface in advance.
Furthermore, as the glass container to be prepared, since it is further excellent in aesthetics and durability, it is also preferable to use a coated glass container in which a coating material is applied in advance in whole or in part.

Moreover, it is preferable to prepare the glass container adjusted to predetermined temperature in a glass container preparation process (1). That is, in the next printing ink application step, the average temperature of the glass container is in the range of 20 to 60 ° C. in order to form a raised display portion made of printing ink having further excellent adhesion to the glass container. It is preferable to control the temperature distribution to a value within ± 10 ° C. as well as the value.
This is because when the average temperature of the glass container is less than 20 ° C., when the printing ink is applied, the glass container is not semi-cured and may remain in a fluid state for a long time. On the other hand, if the average temperature of the glass container exceeds 60 ° C., it may be difficult to control the cured state of the printing ink. Further, when the temperature distribution exceeds ± 10 ° C., similarly, it becomes difficult to control the curing state of the printing ink, and a raised display portion made of the printing ink having excellent adhesion to the glass container is formed. This may be difficult.
Therefore, in order to make the curing state of the printing ink better, it is more preferable to set the average temperature of the glass container to a value in the range of 25 to 50 ° C, and a value in the range of 30 to 45 ° C. More preferably. And it is more preferable to make the temperature distribution of a glass container into the value of +/- 8 degreeC, and it is still more preferable to control a temperature distribution to the value within +/- 5 degreeC.
In addition, in order to control the average temperature and temperature distribution of such a glass container to a predetermined range, a flame irradiation part is provided during the manufacturing process, and a flame is injected to the side surface of the glass container, or during the process, It is preferable to carry out by providing a drying chamber and blowing dry air or the like. At that time, it is more preferable to control the glass container while monitoring the average temperature and temperature distribution in real time.

2. 3. Printing ink application process In the printing ink application process (2) shown in FIG. 3, a printing ink is applied and then partially cured to form a raised display portion made of a semi-cured printing ink. It is a process. More specifically, as shown in FIG. 4B, a raised display portion 44a made of semi-cured printing ink is directly or indirectly formed on the surface of the glass container 42 shown in FIG. It is a process of forming.
Such a printing ink application step is a step for facilitating formation of a raised display portion having a uniform width and height even when the adhesiveness with the glass container is excellent and the line width is small. Further, the printing ink application process is an important process for accurately transferring the metal foil onto the metal foil transfer process in the next process.

Here, examples of the printing ink include resin inks mainly composed of a thermosetting resin such as an epoxy resin, a melamine resin, an alkyd resin, an acrylic resin, a urethane resin, or a polyester resin.
While these resin inks can be applied relatively uniformly on the glass container, they can be made into a semi-cured state by a simple drying process and exhibit excellent adhesion to the glass container. it can.

Also, among these resin inks, adhesion to glass containers, adhesion to metal foil, compatibility with patterns with narrow line width, mechanical strength after curing, controllability of semi-cured state, workability, etc. Therefore, it is more preferable to use a resin ink mainly composed of an epoxy resin.
That is, a resin ink mainly composed of an epoxy resin can exhibit a particularly excellent adhesion to a glass container or a metal foil, while being excellent in mechanical strength and heat resistance, and is hot. When stamping, the metal foil can be accurately transferred.
In addition, when using an epoxy resin, it is preferable to add a predetermined amount of a polyamine compound, an imidazole compound, a mercapto compound, a carboxylic acid compound, or the like as a curing agent.
It is also preferable to use a ceramic ink containing lead in place of the resin ink described above or in combination with the resin ink as the printing ink. With such a ceramic ink, there is little thermal deterioration, and heat curing at high temperatures is possible, so that it is possible to exhibit extremely excellent adhesion to a glass container.

Moreover, it is preferable that a silane coupling agent is included in printing ink so that it may become the range of 0.1-20 weight part with respect to 100 weight part of main components in printing ink.
The reason for this is that the adhesiveness of the printing ink to the glass container can be dramatically improved by including the silane coupling agent in this way. Moreover, since the adhesiveness of the printing ink with respect to metal foil can be improved by including a silane coupling agent, metal foil can be accurately transferred.
Furthermore, by including a silane coupling agent, it is possible to exert a defoaming effect and effectively prevent foaming in the printing ink. The part can be formed.
The type of the silane coupling agent is not particularly limited. For example, the silane coupling agent may be an amine silane coupling agent, an epoxy silane coupling agent, and a ureido silane coupling agent. It is preferable to use at least one silane coupling agent selected from the group consisting of:

In addition to the silane coupling agent described above, various additives are preferably included in the printing ink. Examples of such additives include antioxidants, ultraviolet absorbers, fluidity modifiers, viscosity modifiers, diluents, solvents, inorganic fillers, metal particles, and thermally expandable particles.
In particular, by including an antioxidant and an ultraviolet absorber, it is possible to prevent oxidative deterioration of the printing ink, and as a result, it is possible to effectively prevent a decrease in adhesion to the glass container over time.
Further, by including a fluidity adjusting agent, a viscosity adjusting agent, a diluent, or a solvent, it is possible to improve the applicability of the printing ink and the adhesion of the printing ink to the glass container. Further, by including an inorganic filler, metal particles, or thermally expandable particles, it becomes easy to adjust the form of the raised display portion made of printing ink.

The viscosity of the printing ink is preferably set to a value in the range of 100 to 100,000 cps (mPa · s, 25 ° C.).
This is because, when the viscosity of the printing ink is less than 100 cps, it may be difficult to form a raised display portion made of printing ink having a predetermined width or a predetermined height.
On the other hand, when the viscosity of the printing ink exceeds 100,000 cps, it is easy to entrain bubbles, and it may be difficult to form a raised display portion having a uniform thickness.
Therefore, since a better raised display part can be formed, it is more preferable to set the viscosity of the printing ink to a value within the range of 300 to 10,000 cps (25 ° C.), and 500 to 5,000 cps (25 More preferably, the value is within the range of [° C.].

The thickness of the raised display portion made of printing ink is preferably set to a value in the range of 0.1 μm to 100 μm.
This is because, when the thickness of the raised display portion is less than 0.1 μm, the effect of appearing to be lowered is lowered, and it may be difficult to accurately transfer the metal foil. . On the other hand, when the thickness of the raised display portion exceeds 100 μm, it may be difficult to print with high accuracy.
Therefore, the thickness of the raised display portion made of printing ink is more preferably set to a value within the range of 0.5 μm to 50 μm, and further preferably set to a value within the range of 1 μm to 25 μm.
In addition, although the width | variety of the protruding display part which consists of printing ink changes with the magnitude | sizes and shapes of a character, a figure, etc., it is preferable to set it as the value within the range of 1 micrometer-20 mm, for example.
This is because when the width of the raised display portion is less than 1 μm, the reproducibility of a pattern with a narrow line width may be poor. On the other hand, when the width of the raised display portion exceeds 20 mm, it may be difficult to transfer the metal foil with high accuracy.
Therefore, the width of the raised display portion made of printing ink is more preferably set to a value within the range of 5 μm to 10 mm, and further preferably set to a value within the range of 10 μm to 500 μm.

The method for applying the printing ink is not particularly limited, and a known printing method such as a screen printing method, a gravure printing method, and an offset printing method can be used.
However, screen printing can be particularly preferably used from the viewpoint of forming a high-quality raised display portion.

Here, FIGS. 5 and 6 schematically show screen printing apparatuses 51 and 61 preferably used in the printing ink application process, respectively. That is, in order to perform screen printing of a large area with high accuracy on the surface of a glass container that generally has a curved surface, smooth movement of the screen and smooth movement of the glass container surface synchronized with the movement of the screen are performed. Is important. Therefore, the screen printing apparatus 51 shown in FIG. 5 created in consideration of this movement is a screen printing apparatus (type 1) suitable for performing screen printing on the surface of the glass container 52 having a circular cross section. Similarly, the screen printing apparatus 61 shown in FIG. 6 is a screen printing apparatus (type 2) suitable for performing screen printing on the surface of a glass container 62 having an elliptical cross section.
That is, the screen printing apparatus 51 shown in FIG. 5 is suitable for a glass container 52 having a substantially circular cross-sectional shape and a relatively small cross-sectional area. For this reason, for example, two rotations arranged in two rows by two. It is preferable that a roller 56 is provided and the glass container 52 can be placed thereon.
On the other hand, the screen printing apparatus 61 shown in FIG. 6 is suitable for the glass container 84 having an elliptical cross-sectional shape and a relatively large cross-sectional area, and therefore, the upper surface has an elliptical shape corresponding to the cross-sectional shape of the glass container 84. It is preferable that a tray 80 having a shape is provided and a glass container 84 can be accommodated thereon.

Moreover, it is preferable that the applied printing ink (the raised display portion made of the printing ink) is dried and semi-cured as desired.
That is, in the case of containing a large amount of solvent or the like, it may be difficult to ensure adhesion between the hot stamped metal foil and the raised display portion in the next metal foil transfer step. Because there is.
However, if it is excessively dried, the applied printing ink is hardened, and conversely, it may be difficult to ensure adhesion between the metal foil and the raised display portion.
Therefore, when drying the applied printing ink, in order to keep the printing ink constituting the raised display portion in a semi-cured state without being completely cured, for example, at a temperature of 50 to 100 ° C. for 1 second to 10 minutes. It is preferable to heat to a certain extent.
The semi-cured printing ink means a state that is not completely cured (including an uncured state), and may be a cured state that can be activated by heating when performing hot stamping.

3. Metal Foil Transfer Step The metal foil transfer step (3) shown in FIG. 3 is a step of transferring the metal foil from the hot stamping foil using a heating elastic body. More specifically, it is a step of transferring the metal foil 46 in correspondence with the raised display portion 44a made of the semi-cured printing ink shown in FIG.
Here, FIGS. 7A to 7B show an example of a metal foil transfer device 80 used in the hot stamping method of the present invention.
First, FIG. 7A is a cross-sectional view of the metal foil transfer device 80 as viewed from the axial direction of the rotary roller 94 made of silicone rubber. FIG. It is a front view when it sees along the moving direction of the hot stamping foil 90. FIG.
As shown in FIG. 7A, the metal foil transfer device 80 includes a rotating roller 94 made of silicone rubber as a heating elastic body. The rotating roller 94 is provided with irregularities on the rotating roller 94, and has a function of pressing the glass container 82 through the hot stamping foil 90 by the convex portion 96, thereby breaking and transferring the metal foil.
Moreover, it is preferable that the rotating roller 94, the hot stamping foil 90, and the glass container 82 have a structure that can move together at a predetermined distance. If comprised in this way, while the pressing force of the rotating roller 94 with respect to the glass container 82 will be equalize | homogenized, even if it is a comparatively large area, it will become possible to transfer metal foil accurately.

In the metal foil transfer step, it is preferable to use a rotating roller made of silicone rubber having a hardness of 40 to 90 as the heating elastic body.
That is, by using a rotating roller having a predetermined range of hardness as the heating elastic body, only the transfer portion of the hot stamping foil corresponding to the desired pattern can be appropriately heated and pressed. In other words, even if a heating elastic body made of silicone rubber having a hardness of less than 40 is used, it is too soft and it may be difficult to break and transfer the metal foil with high accuracy. On the other hand, when a heating elastic body made of silicone rubber having a hardness of over 90 is used, it is too hard to uniformly press only a predetermined portion, and similarly, a metal foil can be accurately transferred. This is because it may be difficult. In addition, when a heating elastic body made of silicone rubber having a hardness of more than 90 is used, the glass container may be damaged when pressed.
Therefore, it is more preferable to use a heating elastic body made of silicone rubber having a hardness of 45 to 85, and a heating elastic body made of silicone rubber having a hardness of 50 to 80, because it is possible to transfer the metal foil with higher accuracy. More preferably, it is used.

In addition, since silicone rubber is used as the heating elastic body, it has excellent durability and has a predetermined releasability, and even if the silicone rubber is moved after the heat pressing, it is once transferred. The metal foil is less peeled off.
Therefore, the hot stamp peeling operation proceeds smoothly, and even a metal foil having a thin line width, for example, a metal foil having a thin line width of 1 mm or less, can be transferred with higher accuracy. It becomes possible.
The hardness of such silicone rubber can be appropriately changed depending on the amount of the crosslinking agent added to the silicone rubber, the type of crosslinking agent, or the crosslinking method. Also, the hardness of the silicone rubber can be changed by irradiating the surface of the silicone rubber with ultraviolet rays. The hardness of the silicone rubber can be measured with a hardness meter.

In addition, the metal foil transfer apparatus shown in FIG. 8 has a rotating roller made of silicone rubber as an example of the heating elastic body, but the form of the heating elastic body can be appropriately changed. It is not limited.
For example, as shown in FIG. 8B, although the heating elastic body has the form of a rotating roller, the surface has an uneven portion, and among these, the protruding portion 96 is used to form a hot stamping foil. It is preferable to transfer the metal foil.
By using such a heating elastic body, the metal foil can be selectively transferred only to the portion where the metal foil is desired to be transferred.
It is also preferable to use a stamp made of a sheet-like silicone rubber instead of a rotating roll as the heating elastic body. With this configuration, when the silicone rubber is deteriorated, it can be quickly changed. On the other hand, a metal foil transfer device having a mechanism for performing a hot stamping operation can be preferably used.

A structural example of the hot stamping foil 90 to be used will be described with reference to FIGS.
First, in the example of the hot stamping foil 90 shown in FIG. 7 (A), the hot stamping foil 90 is composed of a base material 91 and a metal foil layer 92 including a metal vapor-deposited layer. If it is 90, since it is very cheap, it can be used conveniently.
FIG. 8 shows another example of the hot stamping foil 102. The hot stamping foil 102 is formed on the base 104, the back layer 103 on the back side of the base 104, and the ventral side of the base 104. The peeling layer 105, the deposition anchor layer 106, the metal deposition layer 107, and the adhesive layer 108 are provided. By using such a hot stamping foil 102, the metal foil can be transferred with higher accuracy.

  For example, when the hot stamping foil 90 having the configuration shown in FIG. 7A is used, the hot stamping foil 90 is in a heated state in contact with the raised display portion 84 on the surface of the glass container 82. When pressed by a certain rotating roller, the wax, the acrylic resin, etc. contained in the adhesive layer (not shown) of the metal foil side layer 92 melts only at that portion. Therefore, as the metal foil as the metal vapor deposition layer breaks and peels and the semi-cured raised display portion 84 is activated, it can be firmly attached to the raised display portion 84 and transferred.

On the other hand, as for the hot stamping foil 90 in the portion not pressed by the rotating roller, the wax or acrylic resin contained in the adhesive layer is not sufficiently melted, and the metal foil as the metal vapor deposition layer is peeled off from the hot stamping foil 90 as it is. Therefore, it does not adhere to a region other than the raised display portion 84 of the glass container 82.
That is, only the portion pressed by the rotating roller is activated by heating the raised display portion 84 made of printing ink that is in a semi-cured state after the metal foil as the metal vapor deposition layer has been broken and peeled off. The Accordingly, the metallic foil adheres to the raised display portion 84, so that, for example, even if the metallic foil has a pattern with a thin line width of 1 mm or less, the metallic foil is accurately transferred and has excellent appearance. A display portion 86 can be formed.

Moreover, in order to perform hot stamping satisfactorily, although depending on the applied pressure, for example, the surface temperature of the heating elastic body is preferably set to a value in the range of 160 to 230 ° C.
The reason for this is that when the surface temperature of the heating elastic body is less than 160 ° C., the printing ink in the semi-cured state is not sufficiently activated, and the printing in the semi-cured state after the metal foil is broken and peeled off. This is because it may be difficult to adhere to the raised display portion made of ink. Further, when the surface temperature of the heating elastic body is less than 160 ° C., the wax, acrylic resin, etc. in the hot stamping foil are not sufficiently melted, and as a result, a hot stamp made of a fine-shaped metal foil can be carried out. This is because it may be difficult.
On the other hand, when the surface temperature of the heating elastic body exceeds 230 ° C., the printing ink in a semi-cured state is excessively activated, and the metal foil is peeled and peeled, and then adheres to the raised display portion. This is because it may be difficult, or the metal foil may be misaligned. In addition, when the surface temperature of such a heat elastic body exceeds 230 ° C., the hot stamping foil itself is thermally deformed, and as a result, it may be difficult to implement a hot stamp made of a fine-shaped metal foil. It is.
Therefore, the surface temperature of the heating elastic body is more preferably set to a value within the range of 170 to 220 ° C, and further preferably set to a value within the range of 180 to 210 ° C.

Moreover, it is preferable to make the pressurization time by the heating elastic body in the case of hot stamping into the value within the range of 0.1-30 seconds.
The reason for this is that when the pressurization time is less than 0.1 seconds, the printing ink in the semi-cured state is not sufficiently activated, and the metal foil is peeled and peeled off, and then in the semi-cured state. This is because it may be difficult to adhere to the raised display portion made of ink. In addition, when the pressing time is less than 0.1 seconds, the wax or acrylic resin in the hot stamping foil is not sufficiently melted, and as a result, it is difficult to implement a hot stamp made of a metal foil having a fine shape. This is because there is a case of becoming.
On the other hand, if the pressurization time exceeds 30 seconds, the printing ink in a semi-cured state is excessively activated, and after the metal foil is broken and peeled, it is difficult to adhere to the raised display portion. This is because the position of the metal foil may be shifted. In addition, when the pressing time exceeds 30 seconds, the hot stamping foil itself may be thermally deformed or the production efficiency may be excessively reduced.
Therefore, the pressurizing time by the heating elastic body during hot stamping is more preferably set to a value within the range of 0.5 to 20 seconds, and further preferably set to a value within the range of 1 to 10 seconds.

Furthermore, the pressure applied by the heating elastic body during hot stamping is preferably set to a value within the range of 0.098 to 9.8 MPa (1 to 100 Kgf / cm ² ).
This is because when the pressure is less than 0.098 MPa, it may be difficult to break and peel the metal foil in the hot stamping foil.
On the other hand, if the pressure exceeds 9.8 MPa, the metal foil may be misaligned or the glass container may be damaged.
Accordingly, the pressure applied by the heating elastic body during hot stamping is more preferably set to a value within the range of 0.49 to 7.35 MPa, and further preferably set to a value within the range of 0.98 to 4.9 MPa. preferable.

Moreover, it is preferable to transfer a plurality of metal foils using a plurality of hot stamp foils, for example, 2 to 10 types of hot stamp foils.
By carrying out in this way, when hot stamping on the same place of the glass container, it is possible to give a beautiful metallic decoration in which characters and designs are further raised.
In addition, when hot stamping is performed at different locations on the glass container, it is possible to give a metallic decoration with a more aesthetic appearance.
Further, it is also preferable to transfer a plurality of metal foils using a plurality of hot stamp foils only for some characters and symbols.

In the metal foil transfer step, a metal foil having a surface wetting index of 30 dyn / cm or more is transferred.
The reason for this is that, by carrying out in this way, it is possible to carry out the painting process after the hot stamping process, and even when transferring a large area metal foil in the hot stamping process, This is because even when several kinds of decorative paints are applied, a coated glass container with a uniform coating can be obtained in a short time and efficiently.
However, if the surface wetting index value becomes excessively large, when transferring a metal foil with a large area or transferring a metal foil having a fine pattern in the hot stamping process, these metal foils are accurately transferred. May be difficult to do.
Therefore, the wetting index of the surface of the metal foil is preferably set to a value in the range of 30 to 70 dyn / cm, and more preferably set to a value in the range of 40 to 60 dyn / cm.

In addition, it is preferable to provide the confirmation process for confirming that the wet index of the surface of metal foil is a predetermined range. And the wetting index of the surface of the metal foil is the type of the metal foil, the type of the surface treatment agent for the metal foil, the treatment amount of the surface treatment agent, the surface treatment method for the metal foil, the presence / absence of a release adjusting layer described later, the metal foil The surface can be appropriately changed by surface cleaning or the like.
Furthermore, as a simple method for adjusting the wetting index of the surface of the metal foil, as a modifier compound containing a silane atom, a modifier compound having a boiling point of 10 to 120 ° C., for example, tetramethylsilane or hexamethyldisiloxane is used. It is preferable to perform a silicic acid flame treatment in which a flame derived from the contained fuel gas is sprayed entirely or partially on the surface of the solid substance. More specifically, it is preferable to perform itro processing (Ishimat Japan Co., Ltd., registered trademark).
This is because, according to such itro treatment, the wetting index of the surface of the metal foil can be adjusted to an arbitrary value in a short time, and between the surface of the metal foil and the coating film thereon. This is because the adhesion can be dramatically improved.

Here, with reference to FIG. 1, the relationship between the surface wettability index | exponent in metal foil and the adhesiveness using an adhesive tape is demonstrated.
That is, the horizontal axis of FIG. 1 shows the surface wetting index (dyn / cm) of the metal foil, and the vertical axis of FIG. 1 shows the adhesive tape (mending tape, manufactured by Sumitomo 3M Limited). , The width is equivalent to 10 mm), and the adhesion force (g / 10 mm) as 90 ° peeling force (peeling speed 100 mm / min) is measured.
And the line A in FIG. 1 shows the case where the area ratio of the metal foil is 10%, and similarly the line B shows the case where the area ratio of the metal foil is 50%.
As can be easily understood from the line A shown in FIG. 1, when the wetting index of the surface of the metal foil exceeds 25 (dyn / cm), the adhesion between the metal foil and the cured coating film formed thereon rises. , Has improved rapidly. Further, although the line B in FIG. 1 has the same tendency, the rise slightly shows a gentle tendency compared to the line A.
Therefore, although slightly different depending on the area ratio of the metal foil, by setting the surface wetting index of the metal foil to a value of 25 (dyn / cm) or more, the adhesion between the metal foil and the adhesive tape affixed thereon is It is understood that it effectively enhances. That is, the same effect is expected to be exerted on the coating film on the glass surface including the metal foil.

Next, the relationship between the surface wetting index of the metal foil and the adhesion of the cured coating film formed on the metal foil will be described with reference to FIG.
The formed cured coating film is a cured coating film having a thickness of 25 μm formed under the baking conditions of 160 ° C. for 20 minutes in accordance with Reference Example 1 .
That is, the horizontal axis of FIG. 2 shows the wetting index (dyn / cm) of the surface of the metal foil, and the vertical axis of FIG. 2 is measured by a cross-cut test based on JIS K 5600. In the cured coating film, the number of peelings per 100 grids (pieces / 100 grids) is shown. And the characteristic curve of FIG. 2 has shown the case where the product ratio of metal foil is 10%.
As can be easily understood from FIG. 2, when the surface wetting index of the metal foil exceeds 25 (dyn / cm), the number of peels in the cross-cut test (pieces / 100 cross-cut) rapidly decreases, and thereafter It shows a tendency to stabilize.
Therefore, although it is expected to be slightly different depending on the area ratio of the metal foil, by setting the surface wetting index of the metal foil to a value of 30 (dyn / cm) or more, the metal foil and the cured coating formed thereon are formed. It is understood that the adhesion of the film is effectively increased.

Moreover, it is also preferable to use the hot stamping foil in which the peeling adjustment layer for setting the wettability index | exponent of the said surface to 30 dyn / cm or more is formed in the surface of metal foil.
The reason for this is that, by forming a metal foil provided with a peeling adjustment layer, even in the case of transferring a large-area metal foil in the hot stamping process, several kinds of decorative paints are applied. This is because a coating film excellent in adhesion can be reliably formed, and a coated glass container excellent in decoration and durability can be efficiently produced.
In addition, as a peeling adjustment layer, the primer layer which consists of a silica particle, a silicone type resin, a urethane type resin, or an epoxy resin, and other resin layers correspond. And in order to exhibit the function of a peeling adjustment layer effectively, it is preferable to make the thickness into the value within the range of 0.01-20 micrometers.

Moreover, it is preferable to make the area ratio of the transferred metal foil a value within the range of 50 to 80% per 100 cm ² .
The reason for this is that by considering the area ratio of the metal foil in this way, even in the case of transferring a plurality of patterns of metal foil having different areas, shapes, etc. in the hot stamping process, the coating film having excellent adhesion It is because it can form reliably. That is, when the area ratio of the metal foil is less than 50%, the surface conductivity changes, and conversely, electrostatic coating may be difficult. On the other hand, when the area ratio of the metal foil exceeds 80%, it becomes difficult to accurately transfer the metal foil having a predetermined pattern, or the surface conductivity is changed, so that electrostatic coating can be performed. This is because it may be difficult.
Therefore, it is possible to stably carry out electrostatic coating and to produce a coated glass container excellent in decorativeness in a shorter time and efficiently, so that the area ratio of the metal foil is 50 to 70% per 100 cm ^2. It is more preferable to set the value within the range.

Moreover, it is preferable to wash | clean the surface of the transferred metal foil, and to make the wetting index of the said surface into the value of 30 dyn / cm or more.
The reason for this is that, by carrying out in this way, it becomes possible to remove the release agent and the like attached to the surface of the metal foil, and to stably carry out the painting process. This is because a coating film having further excellent adhesion can be formed.
In addition, when cleaning the surface of the metal foil, it is preferable to use glycol, alcohol, or the like as a cleaning agent. When it is desired to further increase the cleaning power, the amine compound is used, for example, with respect to the total amount of the cleaning agent. Therefore, it is preferable to add in the range of 0.1 to 30% by weight.
However, cleaning the surface of the metal foil may damage the surface or reduce the glossiness.
Therefore, when adjusting the wetting index of the surface of the transferred metal foil only by washing, it is more preferable to set the value within the range of 30 dyn / cm to 50 dyn / cm, and the value within the range of 35 dyn / cm to 45 dyn / cm. More preferably.

Moreover, it is preferable to provide an opening for transferring the metal foil and exposing the glass surface to a part of the metal foil.
This is because, by carrying out in this way, even when transferring a so-called hollow metal foil, patterning can be performed with high accuracy, and a coating film with excellent adhesion can be formed on the metal foil. This is because it can be done.
In addition, the shape of the opening is not particularly limited, but for example, one or more of a circle, an ellipse, a polygon, a line, a star, a letter, a number, a flower, and the like The combination of is mentioned. Therefore, a complicated metal foil pattern such as an arabesque pattern can be formed, and a coated glass container excellent in decorativeness can be obtained.

4). Painting process In the painting process, an acrylic melamine-based paint containing a lactone polyol compound is coated as a kind of paint.
Here, as the type of formaldehyde resin constituting the acrylic melamine paint, melamine resin, phenol resin, urea resin, guanamine resin and derivatives thereof are representative. More specifically, an alkyl etherified melamine resin (the alkyl portion is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group) has water resistance and weather resistance. It is more suitable because it is excellent.
In addition, a polyol-modified formaldehyde resin constituted by reacting a formaldehyde resin with a polyol compound, for example, a hydroxyl group-containing acrylic resin, a hydroxyl group-containing epoxy resin, a hydroxyl group-containing polyester resin, a hydroxyl group-containing urethane resin, or the like is used. It is also preferable.
The reason for this is that by using such a polyol-modified formaldehyde resin, the adhesion to glass can be improved, and the smoothness and thin film properties of the cured coating film can be further improved.

The acrylic melamine-based paint preferably contains a curing agent (including a curing catalyst; the same applies hereinafter) of a formaldehyde resin.
Examples of such curing agents include dimethyl oxalate, diethyl oxalate, maleic anhydride, phthalic anhydride, monochloroacetic acid sodium salt, monochloroacetic acid potassium salt, α, α-dichlorohydrin, ethylamine hydrochloride, Examples thereof include triethanolamine hydrochloride, ammonium chloride, ammonium sulfate, ammonium chloride salt, ammonium sulfate salt, urea derivative, and diammonium sulfonic acid diammonium salt alone or in combination of two or more.
Moreover, it is preferable to make the addition amount of the hardening | curing agent of formaldehyde resin into the value within the range of 0.1-30 weight part with respect to 100 weight part of formaldehyde resin.
The reason for this is that when the addition amount of the curing agent becomes a value of less than 0.1 parts by weight, the addition effect may not be manifested. On the other hand, when the addition amount of the curing agent exceeds 30 parts by weight, This is because it may be difficult to control the reactivity of the formaldehyde resin.

Moreover, a lactone polyol compound is added as a polyol compound in an acrylic melamine paint .

Further, as the lactone polyol compound, a lactone monomer (.gamma.-lactone, beta-lactone, .delta.-lactone) and is adding a compound obtained by ring-opening with an alcohol, or an aromatic liquid and an alkaline agent preferably .
That is, it is more preferable to use a lactone polyol compound because the effect of improving the strength of the cured coating film can be expressed by adding a relatively small amount.

Moreover, it is preferable to make the hydroxyl value in the polyol compound used for an acrylic melamine-type coating material into the value within the range of 5-300 mgKOH / g.
This is because when the hydroxyl value is less than 5 mgKOH / g, the amount of the curable reactive group is too small, and the reactivity with the formaldehyde resin and the silane coupling agent and the curability of the polyol compound itself are lowered. This is because there are cases. On the other hand, when the hydroxyl value exceeds 300 mgKOH / g, hydrophilic groups remain in the resulting coating film, and the water resistance, acid resistance, and alkali resistance of the coating film may decrease.
Therefore, the hydroxyl value in the polyol compound is more preferably set to a value within the range of 10 to 250 mgKOH / g, and further preferably set to a value within the range of 30 to 200 mgKOH / g.

Moreover, it is preferable to make the number average molecular weight in the polyol compound used for an acrylic melamine-type coating material into the value within the range of 500-20,000.
The reason for this is that when the number average molecular weight is less than 500, the mechanical strength of the resulting coating film may be reduced. On the other hand, when the number average molecular weight exceeds 20,000, the viscosity of the coating composition is high. This is because the coating property may be deteriorated due to excessively increasing.
Therefore, the number average molecular weight in the polyol compound is more preferably set to a value within the range of 1,000 to 18,000, and further preferably set to a value within the range of 1,800 to 15,000.

Moreover, the addition amount (content) of the polyol compound used for an acrylic melamine-type coating material is made into the value within the range of 0.1-100 weight part with respect to 100 weight part of formaldehyde-type resins, It is characterized by the above-mentioned.
The reason for this is that when the amount of the polyol compound added is less than 0.5 parts by weight, the adhesion of the cured coating film may be significantly reduced. On the other hand, when the amount of the polyol compound added exceeds 100 parts by weight, the reactivity of the curable fluorescent composition may be significantly reduced, or the adhesion and moisture resistance of the resulting cured coating film may be reduced. Because.
Therefore, it is more preferable to set the addition amount (content) of the polyol compound to a value within the range of 1 to 80 parts by weight with respect to 100 parts by weight of the formaldehyde resin, and a value within the range of 5 to 50 parts by weight. More preferably.
Referring to FIG. 9, the amount of the polyol compound added and the adhesion of the cured coating film to the glass (the number of peels per 100 grids in the cured coating film measured by a cross-cut test based on JIS K 5600) The relationship with (pieces / 100th grid) is easily understood. The initial evaluation result is indicated by a solid line, and the evaluation result after the moisture resistance test (60 ° C. × 95% RH, 24 hours) is indicated by a dotted line. Moreover, the cured coating film evaluated is a cured coating film having a thickness of 25 μm formed under baking conditions of 160 ° C. × 20 minutes in accordance with Reference Example 1 .

Moreover, the coating glass container which was further excellent in the decorating property can be obtained by combining several in a coating process using several coating materials.
For example, when a cylindrical glass container is applied in the height direction, the application location is divided into three parts (A, B, C), and a coating film containing a blue colorant is applied to the application location A. Forming and forming a transparent coating film using a paint that does not contain a colorant at the application site B, and further forming a coating film using a paint that contains a red colorant at the application site C, An unprecedented coated glass container with extremely excellent decorativeness can be obtained.
Further, for example, when a cylindrical glass container is applied in the height direction, the place is divided into three parts (A, B, C), and the application place A contains a comparatively large amount of blue colorant. A first blue coating film is formed using a coating, and a second blue coating film is formed at a coating location B using a paint that contains a medium amount of a blue colorant. By forming the third blue coating film using a paint containing a small amount of an agent, it is possible to obtain a coated glass container that exhibits a gradation effect and has an unprecedented decorative property.

5. Curing process The curing process of the printing ink is to completely cure the printing ink in a semi-cured state after transferring the metal foil, by sufficiently heating or irradiating light, and for the glass container and printing. This is a step of improving the adhesion between the ink and the adhesion between the metal foil and the printing ink.
In other words, this printing ink curing process completes a hot stamping method for glass containers, and a glass container with a beautiful metallic decoration with finer characters and patterns swelled compared to conventional ones. Can be provided.
However, depending on the application of the glass container, there may be a mixture of letters and graphics made of printing ink without transferring the metal foil. In that case, complete curing of only the printing ink is intended. Will be.

In the printing ink curing step, when printing ink made of a thermosetting resin is used, the heating temperature is preferably set to a value within the range of 140 ° C to 200 ° C.
This is because, when the heating temperature is less than 140 ° C., the printing ink is not sufficiently cured, and the adhesion between the glass container and the printing ink and the adhesion between the metal foil and the printing ink. This is because there is a case where the value does not improve.
On the other hand, when the heating temperature exceeds 200 ° C., the printing ink in a semi-cured state is suddenly cured, internal cracks are generated, the metal foil is thermally deformed, or the gloss of the metal foil is lowered. It is because there is a case where it is.
Therefore, the heating temperature is more preferably set to a value within the range of 150 to 180 ° C, and further preferably set to a value within the range of 160 to 170 ° C.
The heating time depends on the heating temperature, but is preferably a value within the range of 30 seconds to 30 minutes, for example.

[ Reference Example 1 ]
1. Hot stamping method (1) Glass container preparation step While moving a cylindrical glass container placed on a belt conveyor, the glass container was sufficiently washed with a water shower and then dried by heating.
Next, while moving the glass container placed on the belt conveyor in the same manner, the flame of the gas burner was sprayed from both sides of the glass container to increase the temperature of the glass container and to dry the glass surface.
Then, while moving the glass container placed on the belt conveyor in an environmental atmosphere in which dry air circulates, the ambient humidity of the glass container is set to 50% RH, the average temperature is set to 27 ° C., and the glass container The temperature distribution was made uniform (within ± 5 ° C.).

(2) Printing ink application process Screen printing black ink containing the following components (A) to (C) was mixed and prepared using a stirrer. In addition, a diluent (D) was added to the black ink to adjust the pot life (maximum 3.5 hours) so that the coating operation could be performed smoothly.
(A) No. 1900 Black (DMC Square Japan Co., Ltd.)
30g
In addition, No. 1900 black is composed of an organic pigment, an antifoaming agent (silane coupling agent), an epoxy resin, an ester resin, a printability improver, an ether solvent, and xylene.
(B) Medium (T & D CERATEC Co., LTD.) 30g
The medium is composed of an antifoaming agent (silane coupling agent), an epoxy resin, and a solvent.
(C) Curing agent No. 10 (manufactured by T & D CERATEC Co., LTD.) 15g
In addition, hardening | curing agent No. 10 is composed of a polyamine resin, xylene, and n-butanol.
(D) No. 100 Diluent (DMC Square Japan Co., Ltd.)

Next, as a screen printing apparatus, a curved surface / planar screen printer SK-250-V type (manufactured by Shinei Kogyo Co., Ltd.) is used, and a pattern having a line width of 0.5 mm with respect to a glass container, Printing ink was applied so as to form a mixed pattern including a pattern having a line width.
Next, the glass container was heated at 50 ° C. for 1 minute to semi-cure the printing ink, thereby forming a raised display portion composed of a mixed pattern having a predetermined line width.
In the transfer step, the area of the raised display portion was adjusted so that the area ratio of the metal foil was about 10% per 100 cm ² .

(3) Transfer process Next, using a hot stamping device (manufactured by Navitas Co., Ltd.), a heated elastic body whose surface temperature is adjusted to 200 ° C. with respect to the raised display part in a semi-cured state is 30 kgf / cm ^{2 The} hot stamping foil was pressed under conditions of 2 seconds. Next, a metallic foil was attached to the raised display portion, and the metallic foil was transferred to form a metallic display portion.
As the heating elastic body, a rotating roller shown in FIG. 7B made of silicone rubber having a hardness of 65 measured with a hardness meter was used.
The basic structure of the hot stamping foil is basically the same as that described in FIG. That is, the hot stamping foil 102 of Reference Example 1 includes a base material 104 (16 μm polyethylene terephthalate), a back layer 103 (0.5 μm silicone-modified polyester layer) on the back side of the base material, and a ventral side of the base material. Peeling layer 105 (0.5 μm carnauba wax layer), vapor deposition anchor layer 106 (mixed layer of 1 μm polymethyl methacrylate and epoxy resin), metal vapor deposition layer 107 (500 μm formed by vacuum vapor deposition) An aluminum film) and an adhesive layer 108 (a mixed layer of 2.5 μm vinyl chloride resin and vinyl acetate resin).
Furthermore, the area ratio of the metal foil was adjusted to be about 10% per 100 cm ² .

The wetting index (room temperature 25 ° C.) of the surface of the transferred metal foil was measured as the surface tension. That is, after washing the surface of the metal foil with isopropyl alcohol, several types of standard solutions are dropped onto the surface of the metal foil with a dropper, and the standard solution does not become water droplets but can be uniformly applied to the surface of the metal foil. Was the wetting index of the surface of the metal foil. As a result, the surface tension as a wetting index on the surface of the metal foil of Reference Example 1 was 26 dyn / cm.

In addition, as an evaluation of the transferred metal foil, the adhesion force (90 mm peeling force (peeling speed 100 mm / min)) measured using an adhesive tape (mending tape, manufactured by Sumitomo 3M Limited, equivalent to a width of 10 mm) ( g / 10 mm). As a result, the adhesion on the surface of the metal foil of Reference Example 1 was 150 g / 10 mm.

(4) Coating process In a mixing vessel equipped with a stirrer, the following compounding materials (A1 to D1) are charged, stirred at room temperature for 30 minutes (rotation speed: 1000 rpm), and heat having a viscosity of 40 mPa · s (25 ° C.). A curable composition was obtained. Subsequently, the obtained thermosetting composition was electrostatically coated using the spray gun.
A1: Acrylic melamine resin (manufactured by Fujikura Kasei Co., Ltd., PG2220A) 100 parts by weight B1: Lactone polyol compound (hydroxyl number 200 mg KOH / g, number average molecular weight 1,000) 10 parts by weight C1: ureidopropyltriethoxysilane 5 parts by weight D1: 50 parts by weight of xylene

(5) Printing ink curing step A glass container that has been subjected to hot stamping and painting is heated in an oven at 150 ° C. for 10 minutes to completely cure the semi-cured raised display portion, did.

2. Evaluation of Painted Glass Container As an evaluation of the coated glass container, a cross-cut test based on JIS K-5400 was performed, and the number of metal foil peeling (100 pieces / 100 cross-cut) per 100 check board was measured.

[ Reference Examples 2 to 5 ]
In Reference Examples 2 to 5 , the hot stamping method was carried out in the same manner as in Reference Example 1 except that the wetting index on the surface of the metal foil was set to 28, 32, 38, and 44 dyn / cm after the metal foil transfer step. After that, the adhesion was measured, and a cross-cut test was performed on the painted glass container.
That is, after the metal foil transfer step, itro treatment (Ishimat Japan Co., Ltd., registered trademark) was performed for different times to adjust the wetting index of the surface of the metal foil. The obtained results are shown in Table 1.

[Comparative Examples 1-3]
In Comparative Examples 1 to 3, in the metal foil transfer step, a release agent was applied to the surface of the metal foil, and the wetness index was set to 10, 20, and 23 dyn / cm, as in Reference Example 1 , Adhesion strength measurement and a cross cut test were performed. The obtained results are shown in Table 1.

[Examples 6 to 10]
In Examples 6 to 10, in the metal foil transfer step, the hot stamp method was performed in the same manner as in Reference Example 1 except that the area ratio of the metal foil was about 50% per 100 cm ² , and the adhesion strength measurement was performed. Carried out. The obtained results are shown in Table 2.

[Comparative Examples 4 to 6]
In Comparative Examples 4 to 6, in the metal foil transfer step, a release agent was applied to the surface of the metal foil, the wetting index was 10, 20, and 23 dyn / cm, and the area ratio of the metal foil was about 100 cm ^2. The hot stamping method was carried out in the same manner as in Reference Example 1 except that the amount was about 50%, and the adhesion was measured. The obtained results are shown in Table 2.

  As described above, the method for manufacturing a coated glass container according to the present invention controls the wetness index of the surface of the transferred metal foil within a predetermined range corresponding to the printing ink, so that the coating process in the next process Even if a large area of metal foil is transferred or several kinds of decorative paint are applied in the hot stamping process, a uniform coating can be applied. The coated glass container can be obtained efficiently.

FIG. 1 is a diagram provided for explaining the relationship between the wetting index of the surface of the metal foil and the adhesion force. FIG. 2 is a diagram provided for explaining the relationship between the wetting index of the surface of the metal foil and the number of peeled coating films in the cross cut test. Drawing 3 is a figure offered in order to explain the process flow of the manufacturing method of the paint glass container of the present invention. FIG. 4 is a diagram for explaining the hot stamping method of the present invention. FIGS. 5A to 5B are diagrams for explaining a screen printing apparatus (type 1) used in the present invention. 6 (A) to 6 (B) are diagrams for explaining a screen printing apparatus (type 2) used in the present invention. FIG. 7 is a diagram for explaining the metal foil transfer device used in the present invention. FIG. 8 is a diagram for explaining the structure of the hot stamping foil used in the present invention. FIG. 9 is a diagram provided for explaining the influence of the added amount of the polyol compound in the coating film. FIGS. 10A to 10D are diagrams for explaining a conventional hot stamping method. FIG. 11 is a schematic cross-sectional view of a decorative layer including a metal foil transferred by a conventional hot stamp method.

Explanation of symbols

51, 61: Screen printing devices 42, 52, 82, 84: Glass container 44a: Raised display part 56: Rotating roller

Claims (8)

The manufacturing method of the coating glass container characterized by including the process of following (1)-(4).
(1) Step of preparing a glass container (2) Step of applying and semi-curing printing ink to a predetermined portion of the glass container (3) Pressing a hot stamping foil using a heating elastic body, A step of transferring a metal foil having a surface wetting index of 30 dyn / cm or more corresponding to the ink , wherein the area ratio of the transferred metal foil is within a range of 50 to 80% per unit area of 100 cm ² (4) A process of coating the surface of the glass container with an acrylic melamine-based paint containing a lactone polyol compound from the transferred metal foil. In the step (3), a hot stamping foil in which a peeling adjustment layer for making the surface wettability index 30 dyn / cm or more is formed on the surface of the metal foil is used. The manufacturing method of the painted glass container of description.   The method for producing a coated glass container according to claim 1 or 2, wherein the step (3) includes a step of cleaning or silicic acid flame treating the surface of the metal foil. The said process (3) WHEREIN: While transferring the said metal foil, the opening part for exposing a glass surface is provided in a part of the said metal foil, The Claim 1 characterized by the above-mentioned. The manufacturing method of the painted glass container of description. In the step (3), the hot stamping foil is pressed using the heating elastic body while rotating the glass container, The painted glass container according to any one of claims 1 to 4 , Production method. In the said process (3), several metal foil is transcribe | transferred, The manufacturing method of the coated glass container as described in any one of Claims 1-5 characterized by the above-mentioned. In the said process (2), the epoxy-type adhesive agent containing an antifoamer is used as the said printing ink, The manufacturing method of the coated glass container as described in any one of Claims 1-6 characterized by the above-mentioned. In the said process (1), the glass container provided with the base layer on the surface is prepared, The manufacturing method of the coated glass container as described in any one of Claims 1-7 characterized by the above-mentioned.

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