JPH026775B2 - - Google Patents

Description

Detailed Description of the Invention [Industrial Application Field] The first invention relates to a bottle made of saturated polyester that has both gas barrier properties, particularly high barrier properties against oxygen gas, and surface hardness. The second invention also relates to a method for processing a bottle to obtain a bottle made of saturated polyester that exhibits a frosted glass-like appearance in addition to the above-mentioned properties.

[Prior Art] Bottles made of saturated polyester have low moisture and gas permeability, are non-toxic, and have excellent transparency, so they are used as containers for cosmetics, liquid food, medical containers, etc. It is widely used as.

[Problems to be Solved by the Invention] By the way, the conventional bottles made of saturated polyester do not have gas barrier properties to stably store foods, medicines, etc. that are easily deteriorated by the presence of air for a long period of time. Moreover, because the surface hardness is low, 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. have.

[Means for Solving the Problems] The first invention provides ethylene-acetic acid on at least the outer surface of the wall of the bottle body of a ready-made saturated polyester bottle having a biaxially stretched bottle body. Vinyl copolymer, vinyl chloride polymer, vinyl acetate polymer, vinyl chloride-vinyl acetate copolymer, isocyanate polymer, chlorinated polyethylene, chlorinated polypropylene, soluble nylon, urea polymer, melamine polymer, A coating agent containing a film-forming component selected from a phenolic polymer, an epoxy polymer, a modified polymer of each, or a copolymer of these and a fine powder having oxygen adsorption performance is applied. A first step of forming a primer layer, and applying an ultraviolet curable resin containing a photosensitizer such as benzoin, benzyl, benzoin methyl ether, etc. to the surface of the primer layer obtained in the first step. A second step of forming a coating resin layer, and an ultraviolet irradiation treatment on the coating resin layer obtained in the second step,
and a third step of obtaining a coated resin layer with a cured film.

The second invention also provides a bottle made of ready-made saturated polyester having a biaxially stretched bottle body, which is coated with ethylene-vinyl acetate copolymer, vinyl chloride, and acetic acid on at least the outer surface of the bottle body wall. vinyl polymer,
Vinyl chloride-vinyl acetate copolymer, isocyanate polymer, chlorinated polyethylene, chlorinated polypropylene, soluble nylon, urea polymer, melamine polymer, phenol polymer, epoxy polymer, modified polymers of each a first step of forming a primer layer by applying a coating agent containing a film-forming component selected from , or a copolymer of these and a fine powder having oxygen adsorption performance; An ultraviolet curable resin containing, on the surface of the obtained primer layer, 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. a second step of coating to form a coating resin layer; a third step of obtaining a coating resin layer with a spoofing film by performing ultraviolet irradiation treatment on the surface of the coating resin layer obtained in the second step; It consists of

[Example] An example of the method for treating a saturated polyester bottle of the present invention will be described below based on the drawings.

FIG. 1 is a front view of a saturated polyester bottle whose body is biaxially stretched, which is used in the method for treating saturated polyester bottles of the present invention, and FIG. 2 is a saturated polyester bottle shown in FIG. 1. The first polyester bottle
FIG. 3 is a partially enlarged cross-sectional view of the wall of the bottle body obtained by the method of the invention; FIG. FIG. 3 is a partially enlarged cross-sectional view of a wall of a bottle body obtained by processing according to the method of the invention.

In the method for treating bottles made of saturated polyester according to the present invention, a bottle body 3 including a bottom 2 and a bottle opening 4 are
A bottle 1 consisting of is used, and the bottle 1 is
It is manufactured by a known manufacturing method using saturated polyester as a material, and the bottle body 3 is biaxially stretched.

In each of the methods of the present invention, the bottle 1 is first passed through a bath with a cleaning agent such as a fluorine-based solvent that does not have an adverse effect on the bottle itself, and fingerprints and dirt adhering to the outer surface of the wall 5 of the bottle 1 are removed. is removed, and a pretreatment is performed to form a uniform primer layer on the surface.

Next, an ethylene-vinyl acetate copolymer, a vinyl chloride polymer, a vinyl acetate polymer,
Vinyl chloride-vinyl acetate copolymer, isocyanate polymer, chlorinated polyethylene, chlorinated polypropylene, soluble nylon, urea polymer, melamine polymer, phenol polymer, epoxy polymer, modified polymers of each , or a film-forming component made of a resin selected from copolymers of these materials, and a fine powder having oxygen adsorption performance, such as activated carbon, activated iron oxide, palladium, hydrosulfite, iron carbide, and reduced iron. A coating agent in which powder is uniformly dispersed is applied, and if necessary, pre-dried to form a primer layer 6 having a thickness of about 0.1 to 5 μm. This primer layer 6 is
It is an intermediate layer necessary for forming a coating resin layer 7 described later firmly and integrally on the outer surface of the wall portion 5 of the bottle 1 made of saturated polyester, and is an intermediate layer that allows a trace amount of gas to pass through the coating resin layer 7. , the gas barrier property is further improved by trapping the oxygen with fine powder having oxygen adsorption performance that is uniformly dispersed in the primer layer 6, and when this configuration of the primer layer 6 is omitted, It is impossible to firmly and integrally form the resin layer 7 made of a synthetic resin capable of forming a hard surface on the outer surface of the wall 5 of the bottle 1 made of saturated polyester. Due to the presence of the fine powder having oxygen adsorption ability that is uniformly blended and dispersed in the primer layer 6, it is possible to further improve the gas barrier properties of the obtained saturated polyester bottle without using the film-forming component described above. It is preferable to form the primer layer 6 using a coating agent in which fine powder having an oxygen adsorption capacity of about 3 to 10% by weight is added to and dispersed in the resin. If the amount of this fine powder with oxygen adsorption ability 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, it will be difficult to form the primer layer 6 uniformly. do not have.

Next, in the first invention, the surface of the primer layer 6 is coated with a UV-curable resin having a hard surface forming ability and a photosensitizer added thereto.
A coating resin layer 7 having a thickness of about 45 μm is formed, and then the surface of the resin layer 7 is irradiated with ultraviolet rays to introduce a high degree of crosslinking into the coating resin layer 7. This coating resin layer 7 is made of an ultraviolet curable resin having a hard film-forming ability, such as unsaturated polyester resin, acrylic resin, alkyd resin, epoxy resin, urethane resin, acetal resin, and each modified resin or resin. A resin composition containing a known photosensitizer such as benzoin, benzyl, benzoin alkyl ether, benzophenone, Michler's ketones, chlorothioxanthone, 2-isopropylthioxanthone, etc. is added to the copolymer resin. However, when forming the coating resin layer 7, a small amount of a photopolymerization accelerator such as an amine compound, a chain transfer agent such as mercaptan, etc. may be added to the resin composition as necessary. Of course, it is possible to do so. In addition, the final step of UV irradiation treatment is from 200nm to
Ultraviolet irradiation treatment is performed using a high-pressure mercury lamp, metal halide lamp, etc. with a wavelength of approximately 600 nm.

In the second invention, a primer layer 16 is formed on the outer surface of the wall portion 15 of the bottle made of saturated polyester by a method completely similar to that of forming the primer layer in the first invention, and then The surface of the primer layer 16 is coated with an ultraviolet curable resin having a hard film-forming ability, to which a photosensitizer and a transparent or translucent inorganic material fine powder containing silicon dioxide as a main component are added. Coating resin layer 17
is formed, and then the surface of the resin layer 17 is subjected to ultraviolet irradiation treatment to introduce a high degree of crosslinking into the coating resin layer 17.

In addition, in the present second invention, the synthetic resin used for forming the primer layer and the fine powder having oxygen adsorption ability, and the ultraviolet curable resin and photosensitive resin having hard film forming ability used for forming the coating resin layer. As the sensitizer and the like, each of those explained in the first aspect of the present invention can be applied as is.

Furthermore, in the second invention, a coating agent whose composition component is an ultraviolet curable resin containing about 3 to 10% by weight of a transparent or translucent inorganic material fine powder containing silicon dioxide as a main component is used. The coating resin layer 17 is formed, and the addition of this inorganic material fine powder makes the resulting saturated polyester bottle have a frosted glass-like appearance and further improves the gas barrier properties, especially the barrier properties against oxygen gas. belongs to. If the amount of this inorganic material fine powder added is less than 3% by weight with respect to the ultraviolet curable resin, the above-mentioned properties will not be sufficiently imparted, and if it is more than 10% by weight, the coating resin layer 17 will not be uniformly formed. becomes difficult to do. Transparent or translucent inorganic material fine powder containing silicon dioxide as a main component can be, for example, bead-shaped glass or flake-shaped glass, but from the viewpoint of the gas barrier effect of the obtained bottle, flake-shaped glass is used. It is preferable to do so.

[Operations and Effects of the Invention] The method for treating bottles made of saturated polyester according to each of the present inventions has the above-mentioned configuration, and includes: a bottle body wall of a saturated polyester bottle having a biaxially stretched bottle body A primer layer consisting of a synthetic resin layer in which fine powder with oxygen adsorption ability is uniformly dispersed on the outer surface of the part and a coating resin layer with a hard surface are coated for a short period of time without applying special high temperature heating. Because it is formed into a strong, one-piece piece through a hardening process over time, it does not cause distortion due to heat deformation on saturated polyester bottles, which are relatively easy to deform, and has excellent gas barrier properties, especially oxygen gas barrier properties and surface It has the effect of being able to introduce hardness.

In particular, in the method for treating saturated polyester bottles of the present invention, when the primer layer is formed using a thermoplastic synthetic resin, the gas barrier is improved compared to a saturated polyester bottle that is not treated according to the present invention. It can improve sexual performance by about 20-40%,
In addition, if the primer layer is made of epoxy resin and the coating resin layer is made of acrylic or acrylic/urethane resin, the gas barrier property will be 30 to 60.
It can be significantly improved by about %.

In addition, in the methods of each of the present inventions, the outermost surface of the wall of the bottle body is made of a curable resin with a high degree of cross-linking, so it can be rubbed with stainless wool or has a hardness of 3H or more. It can be made into an excellent hard surface that does not leave any scars even when rubbed with a sharp pencil lead of about 4H.

Furthermore, by selecting a colored fine powder with oxygen adsorption ability to be dispersed in the synthetic resin for forming the primer layer, it is possible to obtain a bottle with ultraviolet blocking performance. In the invention method, by selecting and using transparent fine powder having oxygen adsorption ability, a bottle having the appearance of transparent glass can be obtained.
The bottle can be made of saturated polyester and has various properties depending on the requirements.

In addition, in the second invention, a transparent or translucent inorganic material containing silicon dioxide as a main component is applied to the outer surface of the bottle body wall of the bottle made of saturated polyester whose bottle body is biaxially stretched. The coating resin layer, in which fine powder is mixed and dispersed, is formed into a strong, integrated layer in a short curing process without special high-temperature heating, so the bottle body is relatively easily deformed by heat. A bottle made of saturated polyester whose parts are biaxially stretched has a frosted glass-like appearance, excellent gas barrier properties, especially oxygen gas barrier properties, and a hard surface without causing distortion due to deformation. It has the effect of being able to be introduced extremely efficiently.

Furthermore, in the method of treating bottles made of saturated polyester according to each method of the present invention, a primer layer is formed prior to forming a coating resin layer consisting of a curable resin layer by ultraviolet irradiation, and the presence of the primer layer is This improves the adhesion to the coating resin layer, which is made of a resin layer that can be cured by ultraviolet irradiation. Since the function is performed by the primer layer,
It also has the effect that a biaxially stretched saturated polyester bottle having a coating resin layer of good quality can be obtained.

[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 for treating saturated polyester bottles of the present invention, and FIG. 2 is a saturated polyester bottle shown in FIG. 1. The first polyester bottle
FIG. 3 is a partially enlarged cross-sectional view of the wall of the bottle body treated by the method of the invention, and FIG. 3 is a saturated polyester bottle of the same type as shown in FIG. FIG. 3 is a partially enlarged sectional view of a wall of a bottle body treated by the method. 1: Bottle made of saturated polyester, 3: Biaxially stretched bottle body, 5, 15: Wall of bottle body, 6,
16: Primer layer, 7, 17: Coating resin layer.

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, is coated with an ethylene-vinyl acetate copolymer, a vinyl chloride polymer, or a vinyl acetate. Polymers, vinyl chloride-vinyl acetate copolymers, isocyanate polymers, chlorinated polyethylene, chlorinated polypropylene, soluble nylon, urea polymers, melamine polymers, phenolic polymers, epoxy polymers, A coating agent containing a film-forming component selected from modified polymers or copolymers of these materials and fine powder having oxygen adsorption ability is applied to form a primer layer, and then the primer layer is A coating resin layer made of an ultraviolet curable resin containing a photosensitizer such as benzoin, benzyl, or benzoin methyl ether is formed on the surface, and then the surface of the coating resin layer is subjected to ultraviolet irradiation treatment. How to treat bottles made of saturated polyester. 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- Vinyl acetate copolymers, isocyanate polymers, chlorinated polyethylene, chlorinated polypropylene, soluble nylon, urea polymers, melamine polymers, phenolic polymers, epoxy polymers, modified polymers of these, or A primer layer is formed by applying a coating agent containing a film-forming component selected from among copolymers of polyester and fine powder having oxygen adsorption performance, and then benzoin, benzyl , a coating resin layer is formed using an ultraviolet curable resin containing a photosensitizer such as benzoin methyl ether, and transparent or translucent inorganic material fine powder containing silicon dioxide as a main component, and then A method for treating bottles made of saturated polyester, characterized by subjecting the surface of the coating resin layer to ultraviolet irradiation treatment.