JPH0331786B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for applying metallic decoration to a bottle made of saturated polyester having a biaxially stretched bottle body. The present invention provides a method for imparting excellent gas barrier properties and surface hardness to the surface of bottles.

Saturated polyester bottles with biaxially stretched bottle bodies have low moisture and gas permeability, are non-toxic, and have excellent transparency, making them suitable for cosmetic containers and liquid food containers. Although it is widely used as medical containers, etc., it cannot be said that its gas barrier properties are sufficient for long-term stable storage of food products, medicines, etc. that are susceptible to deterioration due to the presence of air.
In addition, because of its low surface hardness, it has the disadvantage that the surface of the container is easily scratched even if the walls of the container come into contact with each other during transport or filling operations. In addition, the hot stamping method, which is commonly used as a method of applying metallic decoration to plastic molded products, involves applying a hot stamping foil to the surface of the plastic molded product by applying a heat-sensitive adhesive layer on the foil to the surface of the plastic molded product. The metallic decoration method involves applying heat and pressure from above with the base film as the top surface, releasing the metal vapor deposited layer in the pressed area from the base film, and transferring it to the plastic molded product. Since it requires pressurization, it is relatively difficult to apply metallic decoration using this hot stamping method to saturated polyester bottles that have biaxially stretched bottle bodies that are relatively easily deformed by heat. There are also other drawbacks.

By having the structure as described in the claims, the present invention not only imparts clear patterns and letters with metallic luster to the surface of a saturated polyester bottle, but also provides excellent gas barrier properties and surface hardness. In particular, by adopting the configurations described in the second, third, and fourth claims, the degree of improvement in gas barrier properties is further increased. By adopting the configurations described in the third and fourth items, it is possible to obtain a bottle made of saturated polyester which has a frosted glass-like appearance in the background pattern on the base area other than the metallic decoration area.

The method for applying metallic decoration to a saturated polyester bottle according to the present invention will be explained below with reference to the drawings.

FIG. 1 is a front view of a saturated polyester bottle whose body is biaxially stretched, which is used in the method of applying metallic decoration to a saturated polyester bottle according to the present invention, and FIG. FIG. 3 is a partially enlarged cross-sectional view of the wall of the bottle body in which the primer layer and the hard film resin layer according to the first claim of the invention are formed on a saturated polyester bottle, which is shown in FIG. FIG. 4 is a partially enlarged cross-sectional view showing an example of the hot stamping foil used in the present invention. , 5A and 5B are partially enlarged cross-sectional views of the wall portion of the bottle body provided with metallic decoration obtained by the invention according to claim 1 obtained by different methods, respectively, and FIGS. The figure is a partially enlarged cross-sectional view of the wall of the body of a bottle made of the same kind of saturated polyester as shown in Figure 1, on which a primer layer and a hard coating resin layer are formed according to the second invention , FIG. 7 shows a part of the wall of the body of a bottle made of the same kind of saturated polyester as shown in FIG. 1, on which a primer layer and a hard film resin layer are formed in the third invention The enlarged sectional view, FIG. 8, shows a bottle body wall formed with a primer layer and a hard film resin layer according to the fourth aspect of the invention, on a bottle made of the same type of saturated polyester as shown in FIG. 1. It is a partially enlarged sectional view of the section.

In the present invention, as shown in FIG.
A bottle 1 made of saturated polyester is used, which includes a biaxially stretched bottle body 3 including a bottom 2 and a bottle opening 4.

In the first aspect of the invention, first, a bottle 1 made of saturated polyester is passed through a bath of a cleaning agent such as a fluorine-based solvent that does not have an adverse effect on the bottle 1 itself. Pretreatment is performed to remove fingerprints and dust adhering to the outer surface of the substrate, and to form a uniform primer layer on the surface.

Next, as shown in FIG. 2, ethylene-vinyl acetate copolymer, vinyl chloride polymer,
Thermoplastic synthetic resin selected from vinyl acetate polymer, vinyl chloride-vinyl acetate copolymer, isocyanate polymer, chlorinated polyethylene, chlorinated polypropylene, soluble nylon, urea polymer, melamine polymer, A coating agent consisting of a polymer solution containing a thermosetting synthetic resin selected from phenolic polymers, epoxy polymers, modified polymers of these, and copolymers of these is applied, and the necessary A primer layer 6 having a thickness of about 0.1 to 5 μm is formed by pre-drying according to the conditions. This primer layer 6 is an intermediate layer necessary for forming a hard film resin layer 7, which will be described later, firmly and integrally on the outer surface of the body wall 5 of the bottle 1 made of saturated polyester. If the structure of the layer 6 is omitted, it is not necessary to firmly and integrally form the hard coating resin layer 7 made of a synthetic resin having a hard coating ability on the outer surface of the wall portion 5 of the bottle 1 made of saturated polyester. It is possible.

Subsequently, on the surface of the primer layer 6, a coating agent made of a polymer solution containing a synthetic resin having hard film-forming ability to which a photosensitizer has been added is applied to a thickness of about 10 to 45 μm. A resin layer is formed, and then the surface of the resin layer is subjected to ultraviolet irradiation treatment to introduce a high degree of crosslinking into the resin layer, thereby forming a hard film resin layer 7. This hard film resin layer 7 is made of synthetic resins capable of forming a hard film, such as unsaturated polyester resins, acrylic resins, alkyd resins, epoxy resins, urethane resins, acetal resins, and modified resins or combinations thereof. In the polymer resin, photosensitizer,
For example, this hard coating resin is formed by a resin component to which a known photosensitizer such as benzoin, benzyl, benzoin alkyl ether, benzophenone, Michler's ketones, chlorothioxanthone, 2-isopropylthioxanthone is added. In forming the layer 7, it is of course possible to further add a small amount of a photopolymerization accelerator such as an amine compound, a chain transfer agent such as a mercaptan, etc. to the resin component as necessary.
Further, the ultraviolet irradiation treatment performed when forming the hard coating resin layer 7 can be performed using a high-pressure mercury lamp, a metal halide lamp, or the like having a wavelength of about 200 nm to 600 nm.

Thereafter, as shown in FIG. 3, the hard film resin layer 7 formed on the outer surface of the body wall 5 of the bottle 1 made of saturated polyester is coated with vinyl resin, epoxy resin, urethane resin, etc. Using acrylic resin-based or ester resin-based silk screen printing ink, shapes such as patterns and letters are printed using the silk screen printing method, and printing ink M is applied to the 7 surfaces of the hard film resin layer. In the process from incomplete curing to complete curing of the silk screen printing ink M, a separate hot stamping foil 8 is laminated on the surface of the printing ink M, heated and pressurized, and hot stamped onto the printing ink M. Portion 9 containing the metal vapor deposited layer in the foil 8 for use
By mold-releasing and transferring, bottles made of saturated polyester are obtained, each having bottle body wall portions 5a and 5b having metallic decorations as shown in FIGS. 5A and 5B.

In the process, the hot stamping foil 8 that is laminated on the surface of the printing ink M during the process from incomplete curing to complete curing of the silk screen printing ink M provided on the hard film resin layer 7 is, for example, As shown in FIG. 4, a top coat layer 12 is provided on one side of a polyester film 10 via a release agent layer 11, and a vacuum metal vapor deposited layer 13 of aluminum or the like is provided on the top coat layer 12.
is formed, and further on the surface of this vacuum metal vapor deposited layer 13,
It is composed of a multilayer sheet with an adhesive layer 15 provided through an undercoat layer 14, and is widely used for metallic decoration by ordinary and hot stamping. Figure 5A mentioned above
, the polyester film 10 and release agent layer 11 are removed from the hot stamping foil 8 having the structure shown in FIG. , an adhesive layer 15, an undercoat layer 14, a vacuum metal vapor deposition layer 13, and a top coat layer 1.
2 are sequentially laminated, and the hot stamping process of laminating a separately manufactured hot stamping foil 8 on the surface of the printing ink M and applying heat and pressure is performed using a rubber press. . In addition, in FIG. 5B, the polyester film 8 and release agent layer 11 are removed from the hot stamping foil 8 so that the portion 9 containing the metal vapor deposited layer is embedded in the layer of silk screen printing ink M. This is a result of a hot stamping process in which a separate hot stamping foil 8 is laminated on the surface of the printing ink M and then heated and pressed using a stamping method.

The second claimed invention, as in the case of the first claimed invention described above, first has the following:
A bottle made of saturated polyester having a biaxially stretched bottle body is passed through a detergent bath to undergo pretreatment for forming a primer layer.

Next, as shown in FIG. 6, ethylene-vinyl acetate copolymer, vinyl chloride polymer, vinyl acetate polymer, vinyl chloride-vinyl acetate, etc. Thermoplastic synthetic resin selected from copolymers, isocyanate polymers, chlorinated polyethylene, chlorinated polypropylene, soluble nylon, urea polymers, melamine polymers, phenolic polymers, epoxy polymers, each modified polymer,
A fine powder having oxygen adsorption performance in a thermosetting synthetic resin selected from copolymers of these things;
For example, apply a coating agent in which fine powder of activated carbon, activated iron oxide, palladium, hydrosulfite, iron carbide, reduced iron, etc. Form layer 16.

This primer layer 16 is an intermediate layer for firmly and integrally forming a hard film resin layer 17 made of a synthetic resin capable of forming a hard film on the outer surface of the bottle body wall 15 of the bottle made of saturated polyester. ,
In addition, the trace amount of gas that permeates through the hard film resin layer 17 formed through the primer layer 16 is captured by the fine powder with oxygen adsorption ability that is uniformly dispersed in the primer layer 16, thereby making it possible to remove the metal. This further improves the gas barrier properties of decorated saturated polyester bottles. In order to further improve the gas buyer properties of the obtained saturated polyester bottle by the presence of a fine powder having oxygen adsorption ability that is uniformly blended and dispersed in this primer layer 16, it is possible to improve the gas buyer properties of the resulting saturated polyester bottle. Thermosetting synthetic resin medium 3-10
Adding fine powder with oxygen adsorption capacity of about % by weight,
Preferably, the primer layer 16 is formed using a dispersed coating agent. This is because if the amount of the fine powder with oxygen adsorption ability added is less than 3% by weight, the effect of further improving gas barrier properties will not be sufficient, and if it is more than 10% by weight, the primer layer 16 will not be uniformly formed. This is because it becomes difficult.

The subsequent steps in the second aspect of the invention include the formation of a hard film resin layer, silk screen printing, and lamination of hot stamping foil, heating, and pressurization in the first aspect of the invention. The process of releasing and transferring the metal vapor deposited layer in hot stamping foil is carried out in sequence to obtain a saturated polyester bottle with metallic decoration.

The third aspect of the invention, as shown in FIG. 7, has a bottle body that has been biaxially stretched in exactly the same manner as in the first aspect of the invention. A primer layer 26 is applied to the outer surface of the bottle body wall 25 of the bottle made of saturated polyester.
, and then compose a synthetic resin having a hard film-forming ability to which a photosensitizer and transparent or translucent inorganic material fine powder containing silicon dioxide as a main component are added to the surface of the primer layer 26. A coating agent consisting of a polymer solution as a component is applied to form a resin layer with a thickness of approximately 10 to 45μ, and the surface of the resin layer is subsequently subjected to ultraviolet irradiation treatment to create a hard coating resin with a high degree of crosslinking. Form layer 27. This hard film resin layer 27 is constructed using a coating agent whose component is a synthetic resin containing transparent or translucent inorganic material fine powder whose main component is silicon dioxide. The inorganic material fine powder contained in the saturated polyester bottle is used to give the resulting saturated polyester bottle a frosted glass-like appearance on the base area other than the metallic decoration area. It is also used to further improve barrier properties, especially barrier properties against oxygen gas. The coating agent used to form this hard film resin layer 27 generally needs to contain about 3 to 10% by weight of the inorganic material fine powder; This is because if the amount of fine powder added is less than 3% by weight, the above-mentioned properties are not sufficiently imparted, and if it is more than 10% by weight, it becomes difficult to uniformly form the hard coating resin layer 27. In addition, examples of the transparent or translucent inorganic material fine powder containing silicon dioxide as a main component include bead-shaped glass and flake-shaped glass, but from the viewpoint of the gas barrier effect of the obtained bottle, flake-shaped Preferably, glass is used.

The subsequent steps in the third aspect of the invention are carried out in exactly the same way as the steps after the formation of the hard coating resin layer 7 in the first aspect of the invention. Screen printing is performed, the hot stamping foil is laminated, heated, and pressurized, and the steps of releasing and transferring the metal vapor deposited layer on the hot stamping foil are carried out in sequence, and a frosted glass-like pattern is applied to the base area other than the metallic decoration area. A bottle made of saturated polyester is provided with a metallic decoration that gives the appearance a pattern-like appearance.

The fourth aspect of the invention is the primer layer 1 according to the second aspect of the invention.
6, as shown in FIG.
A primer layer 36 having a thickness of approximately 0.1 to 5 μm is formed on the outer surface of the primer layer 36 in which fine powder having oxygen adsorption ability is uniformly dispersed. Next, on the surface of this primer layer 36, the same steps as those after the formation of the primer layer 26 in the third aspect of the invention described above are performed in sequence, that is, the formation of a hard film resin layer 37, and silk screen printing. , Lamination of foil for hot stamping, heating, pressurization, release of metal vapor deposited layer on foil for hot stamping,
Each step of the transfer process is carried out to create a saturated polyester bottle with a metallic decoration that gives the base area other than the metallic decoration part a frosted glass-like appearance and also has high gas barrier properties. It's something you get.

The method of applying metallic decoration to a bottle made of saturated polyester according to the present invention has the above-mentioned structure. , the primer layer and the hard film resin layer having a hard surface are formed firmly and integrally in a short curing process without applying special high temperature heating, and then a vinyl resin-based resin layer is applied to the surface of the hard film resin layer. , epoxy resin system,
Patterns such as letters and designs are formed using a urethane resin-based, acrylic resin-based, or ester resin-based silk screen printing ink using the silk screen printing method, and the printing ink is cured from incomplete to completely cured. In the process, a separate hot stamping foil is layered on the printing surface, heated and pressurized,
Metallic decoration is applied to a saturated polyester bottle by releasing and transferring the metal vapor deposited layer of the hot stamping foil only onto the printing ink area, and the hard coating is formed on the resin surface by silk screen printing. Because it produces a pattern that emits a metallic luster that matches the printed patterns such as letters and designs, it is possible to create a pattern with accurate metallic decoration that does not shift in position, while the body of the bottle is relatively easily deformed by heat. It has the effect of being able to form a bottle made of biaxially stretched saturated polyester without the risk of causing distortion due to thermal deformation.

In addition, in the method of the present invention, the hard coating resin layer provided on the wall of the body of the saturated polyester bottle to which the metallic decoration is applied imparts the same surface hardness and gas barrier properties to the saturated polyester bottle. It also has the action and effect of forcing.

Furthermore, claims 2, 3, and 4
In the second invention, a fine powder having oxygen adsorption ability is contained in the primer layer, or a transparent or translucent inorganic material fine powder containing silicon dioxide as a main component is contained in the hard coating resin layer. This action also provides the action and effect of providing a higher level of gas barrier properties.

Further, according to the third and fourth claims, there is provided a bottle made of saturated polyester having a metallic decoration that has a frosted glass-like appearance on the base part other than the metallic decoration part. It has the function and effect of being able to obtain the following.

[Brief explanation of drawings]

FIG. 1 is a front view of a saturated polyester bottle whose body is biaxially stretched, which is used in the method of applying metallic decoration to a saturated polyester bottle according to the present invention, and FIG. FIG. 3 is a partially enlarged cross-sectional view of the wall of the bottle body in which the primer layer and the hard film resin layer according to the first claim of the invention are formed on a saturated polyester bottle, which is shown in FIG. FIG. 4 is a partially enlarged cross-sectional view showing an example of the hot stamping foil used in the present invention. , FIGS. 5A and 5B are partially enlarged cross-sectional views of the wall portion of the bottle body provided with metallic decoration obtained by respective different embodiments according to the first aspect of the invention, FIG. 6 shows a part of the wall of the body of a bottle made of the same kind of saturated polyester as shown in FIG. An enlarged sectional view, FIG. 7, shows a bottle made of saturated polyester of the same type as shown in FIG.
FIG. 8 is a partially enlarged cross-sectional view of the wall of the bottle body on which the primer layer and the hard coating resin layer are formed in the invention, and FIG. It is a partially enlarged sectional view of the wall portion of the bottle body on which the primer layer and the hard film resin layer are formed in the fourth aspect of the invention. 1: Bottle made of saturated polyester having biaxially stretched bottle body 3, 5, 15, 25, 35: Bottle body wall of bottle made of saturated polyester, 6, 16,
26, 36: Primer layer, 7, 17, 27, 3
7: Hard film resin layer, M: Silk screen printing ink, 8: Hot stamping foil, 9:
Portions including the metal vapor deposited layer transferred to the surface of the hard coating resin layer, 5a, 5b: Wall portion of the bottle body with metallic decoration.

Claims (1)

[Claims] 1. A bottle made of saturated polyester having a biaxially stretched bottle body, at least on the outer surface of the bottle body wall, containing an ethylene-vinyl acetate copolymer, a vinyl chloride polymer, and a vinyl acetate copolymer. Thermoplastic synthetic resin selected from polymers, vinyl chloride-vinyl acetate copolymers, isocyanate polymers, chlorinated polyethylene, chlorinated polypropylene, and soluble nylon, or urea polymers, melamine polymers, and phenolic polymers. A primer layer is formed by applying a polymer solution containing a thermosetting synthetic resin selected from polymers, epoxy polymers, respective modified polymers, and copolymers of these. On the surface of the primer layer, benzoin, benzyl,
A polymer solution containing a photosensitizer such as benzoin methyl ether and a synthetic resin capable of forming a hard film is applied, and the coated surface is irradiated with ultraviolet rays to form a hard film resin layer. Then, on the hard coating resin layer surface, a vinyl resin type,
Silk screen printing is performed using an epoxy resin-based, urethane resin-based, acrylic resin-based, or ester resin-based printing ink, and the printing ink adhering to the surface of the hard coating resin layer changes from incomplete to complete hardening. , a separately made hot stamping foil is laminated on the printing surface and heated and pressurized to release and transfer the metal vapor deposited layer of the hot stamping foil onto the printing ink. How to apply metallic decoration. 2. A saturated polyester bottle having a biaxially stretched bottle body is coated with ethylene-vinyl acetate copolymer, vinyl chloride polymer, vinyl acetate polymer, vinyl chloride- Thermoplastic synthetic resin selected from vinyl acetate copolymers, isocyanate polymers, chlorinated polyethylene, chlorinated polypropylene, and soluble nylon, or urea polymers, melamine polymers, phenolic polymers, and epoxy polymers. A primer layer is formed by applying a polymer solution containing a thermosetting synthetic resin selected from coalescence, each modified polymer, and a copolymer of these, and a fine powder having oxygen adsorption performance. Then, on the surface of the primer layer, a polymer solution consisting of a synthetic resin having a hard film-forming ability and containing a photosensitizer such as benzoin, benzyl, benzoin methyl ether, etc. is applied. A hard film resin layer is formed by irradiating the coated surface with ultraviolet rays, and then a vinyl resin-based, epoxy resin-based, urethane resin-based, acrylic resin-based, or ester resin-based printing ink is applied to the surface of the hard film resin layer. Silk screen printing is performed on the surface of the hard coating resin layer, and during the process from incomplete curing to complete curing of the printing ink adhering to the surface of the hard coating resin layer, a separate hot stamping foil is laminated on the printing surface and heated and heated. A method for applying metallic decoration to a saturated polyester bottle, characterized by releasing and transferring a metal vapor deposited layer of a hot stamping foil onto pressure printing ink. 3. A saturated polyester bottle having a biaxially stretched bottle body is coated with ethylene-vinyl acetate copolymer, vinyl chloride polymer, vinyl acetate polymer, vinyl chloride- Thermoplastic synthetic resin selected from vinyl acetate copolymers, isocyanate polymers, chlorinated polyethylene, chlorinated polypropylene, and soluble nylon, or urea polymers, melamine polymers, phenolic polymers, and epoxy polymers. A primer layer is formed by applying a polymer solution containing a thermosetting synthetic resin selected from coalescence, each modified polymer, and a copolymer of these, and then
A photosensitizer such as benzoin, benzyl, benzoin methyl ether, etc. on the surface of the primer layer,
A polymer solution containing a transparent or translucent inorganic fine powder containing silicon dioxide as a main component and a synthetic resin capable of forming a hard film is applied, and the coated surface is subjected to ultraviolet irradiation treatment. to form a hard film resin layer, and then perform silk screen printing on the surface of the hard film resin layer with a vinyl resin-based, epoxy resin-based, urethane resin-based, acrylic resin-based, or ester resin-based printing ink, In the process from incomplete curing to complete curing of the printing ink adhering to the surface of the hard coating resin layer,
A separate hot stamping foil is laminated on the printing surface and heated and pressurized to release the metal vapor deposited layer of the hot stamping foil onto the printing ink.
A method of applying metallic decoration to a bottle made of saturated polyester, which is characterized by transfer. 4. A saturated polyester bottle having a biaxially stretched bottle body is coated with ethylene-vinyl acetate copolymer, vinyl chloride polymer, vinyl acetate polymer, vinyl chloride- Thermoplastic synthetic resin selected from vinyl acetate copolymers, isocyanate polymers, chlorinated polyethylene, chlorinated polypropylene, and soluble nylon, or urea polymers, melamine polymers, phenolic polymers, and epoxy polymers. A primer layer is formed by applying a polymer solution containing a thermosetting synthetic resin selected from coalescence, each modified polymer, and a copolymer of these, and a fine powder having oxygen adsorption performance. A hard film containing a photosensitizer such as benzoin, benzyl, benzoin methyl ether, etc. and transparent or translucent inorganic material fine powder containing silicon dioxide as a main component is formed on the surface of the primer layer. A polymer solution containing a synthetic resin having forming ability as a component is applied, the coated surface is irradiated with ultraviolet rays to form a hard film resin layer, and then the surface of the hard film resin layer is coated with vinyl resin, epoxy, etc. Silk screen printing is performed with resin-based, urethane resin-based, acrylic resin-based, or urethane resin-based printing ink, and in the process from incomplete curing to complete curing of the printing ink attached to the surface of the hard coating resin layer, A separate hot stamping foil is laminated on the printing surface and heated.
A method for applying metallic decoration to a bottle made of saturated polyester, characterized by applying pressure to release and transfer a metal vapor deposited layer of a hot stamping foil onto a printing ink.