JPH11105203A - Ultraviolet ray shielding container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To shield ultraviolet ray even for a transparent container by which a content can be seen through, and also, prevent a deterioration due to oxygen gas from arising by a method wherein a base material film and a transparent laminate sheet including at least an ultraviolet ray shielding layer are affixed to the container, and an in-mold forming is performed at the time of container forming. SOLUTION: A transparent laminate sheet 10 including at least an ultraviolet ray shielding layer 2 is affixed to a container at the time of forming of the container, or to the side part 8 and the bottom part 9 excepting the opening 6, with an adhesive, or with a forming resin 21, and a transparent ultraviolet ray shielding container 20 is formed. Also, on the laminated sheet 10 including an ultraviolet ray shielding part 11, the laminate sheet 10 having a transparent barrier part 12 for which a gas barrier layer 3 is additionally laminated, is affixed, and an in-mold forming is performed, and the ultraviolet ray shielding container 20 jointly having a gas barrier property is formed. Then, the ultraviolet ray shielding layer 2 is formed of a film wherein an ultraviolet ray shielding agent is kneaded into a thermoplastic resin, or the laminate sheet 10 wherein a coating including the ultraviolet ray shielding agent is coated on a transparent film, and a forming is performed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent molded container, in which a barrier laminate sheet is adhered to the container to impart ultraviolet and oxygen shielding properties for promoting a chemical change of the content, thereby altering the content by oxygen or light. Belongs to a transparent molded container that has prevented the above.

[0002]

2. Description of the Related Art Conventionally, a molded container made of a polyolefin resin, which is a general-purpose resin, has a water vapor barrier property, but the barrier property against ultraviolet rays, oxygen gas, etc., which promotes a chemical change of contents, is not always satisfactory. . In order to give the above molded container ultraviolet shielding properties, the container is colored or simply a light-shielding (opaque) ultraviolet shielding label such as aluminum foil, metallized film, or printing is attached with an adhesive or the like. In addition, a label formed by laminating a resin of a molded article and a film to be bonded by heat at the time of molding has been subjected to in-mold molding to bond with heat at the time of molding to have ultraviolet blocking properties. Further, in order to provide the molded container with an oxygen gas barrier property, a laminated sheet containing a transparent ethylene / vinyl acetate copolymer saponified material or the like may be used for the laminated label, or a material having another oxygen gas barrier property, for example, polyester. ,
Multi-layer molded containers made of nylon, vinylidene chloride or the like have been used.

[0003] However, a molded container on which a label in which a light-shielding film such as an aluminum foil, a metal-deposited film, or a print is laminated and a film that adheres to a resin of a molded product is adhered, has various barrier properties of the aluminum foil. Although the content has a preserving property in terms of both ultraviolet rays and oxygen to protect the contents due to the action, the product is inferior in the merchantability in which the contents cannot be seen. In addition, in the case where a transparent resin film having another oxygen gas barrier property is laminated, although the contents are visible, the contents are deteriorated by light, particularly ultraviolet rays (discoloration, fading, fragrance, oxidation of oil, etc.) There was a problem that shelf life at a store decreased.

[0004]

A molded container made of a general-purpose resin such as polypropylene or polystyrene, which is transparent to allow the contents to be exposed to ultraviolet light, which is a cause of deterioration of the contents (visible light is transmitted, the same applies hereinafter). It is an object of the present invention to provide a transparent ultraviolet shielding container that can be shielded by using a film and that prevents deterioration such as oxidation caused by oxygen gas by attaching a laminated sheet.

[0005]

In order to solve the above-mentioned problems, the present invention relates to a method of forming a base film and a transparent laminated sheet including at least an ultraviolet shielding layer on a side excluding a container or an opening when forming the container. It is a transparent ultraviolet shielding container that is attached and in-mold-molded to a part, or a side part and a bottom part. Further, the present invention provides a UV barrier container having a gas barrier property, in which a transparent barrier laminate sheet in which a gas barrier layer is further laminated is adhered to the laminated sheet including the ultraviolet ray blocking layer and in-mold molded. Then, the layer containing the ultraviolet ray blocking layer was bonded and in-mold molded by laminating a film in which a ultraviolet ray blocking agent was kneaded into a thermoplastic resin or a transparent sheet coated and formed with a coating material containing the ultraviolet ray blocking agent. It is an ultraviolet shielding container. Further, the gas barrier film is a UV barrier container having a gas barrier property, which is a transparent film made of a metal oxide vapor-deposited film.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The ultraviolet shielding container 20 of the present invention
As in a molded container 20 shown in FIG. 1, a transparent laminated sheet 10 including at least the ultraviolet shielding layer 2 is attached to the container or the side portion 8 and the bottom portion 9 excluding the opening 6 with an adhesive at the time of molding the container. A transparent ultraviolet shielding container 20 which is thermally bonded with a molding resin 21 to the side portion 8 and the bottom portion 9 excluding the opening 6 at the time of molding the container. Further, the laminated sheet 10 having the transparent barrier portion 12 in which the gas barrier layer 3 is further laminated is attached to the laminated sheet 10 including the transparent ultraviolet shielding portion 11.
It is an ultraviolet shielding container 20 which also has a gas barrier property by in-mold molding. And the said ultraviolet shielding layer 2
The ultraviolet shielding container 20 is a laminated sheet 10 made of a film obtained by kneading an ultraviolet shielding agent into a thermoplastic resin or a transparent film coated with a coating material containing an ultraviolet shielding agent. Further, the gas barrier layer 3 is a UV barrier container 20 having a gas barrier property made of a transparent film made of a metal oxide vapor-deposited film.

As shown in FIG. 1, the ultraviolet shielding container 20 of the present invention has a transparent ultraviolet shielding laminate sheet 10 of the present invention adhered to a cylindrical side portion 8 and a bottom portion 9 and has an opening at the top. The opening 6 is formed of a flange 6 and a flange 7 and is fitted or sealed with the lid 7 after filling with the contents, though not shown. And on the side 8 and the bottom 9
This is a package using a molded container 20 to which a laminated sheet 10 is attached and which has an ultraviolet shielding property or an ultraviolet shielding property and a gas barrier property.

For molding the container, a usual thermoplastic resin molding method such as injection molding or pressure molding, vacuum molding, blow molding or injection blow molding can be applied. Then, at the time of molding, the laminated sheet is temporarily attached to the mold so as to be in contact with the molding resin side, and if necessary, the laminated sheet is fixed by vacuum / suction through a suction hole provided in the mold. In-mold molding in which the molding resin in a molten state is bonded by heat is a preferable method.

The resin used for the container is not limited to thermoplastic resins such as polystyrene, polypropylene, polyethylene, polyester, polyamide and polyvinyl chloride selected from ordinary thermoplastic resins, but also unsaturated polyesters, melamine resins and urea resins. And the like can be used.

As shown in FIG. 1 (B), the transparent ultraviolet-shielding laminated sheet 10 used in the present invention is provided with a pattern layer 5 on a base film to be a printing film 4, if necessary. Next, a film including the ultraviolet ray shielding layer 2 is laminated by dry lamination or the like via an adhesive layer,
Alternatively, the ultraviolet shielding layer 2 is formed by applying a coating liquid containing an ultraviolet shielding layer. And when performing in-mold molding with the molding resin, it is further thermally bonded to the molding resin,
Dry lamination, extrusion coating, etc. of a film of a material with little deformation such as expansion and contraction by the heat,
The heat-bonding resin layer 1 is formed by lacquer coating or the like to form a transparent ultraviolet shielding laminate sheet 10 having a transparent ultraviolet shielding portion 11.

The transparent barrier ultraviolet shielding laminate sheet 10B having gas barrier properties used in the present invention is shown in FIG.
As shown in (1), the ultraviolet shielding layer 2 is formed on the base film to be the print film 4 as in the above-mentioned laminated sheet. Further, a gas barrier film is laminated on the surface of the ultraviolet blocking layer 2 by dry lamination or the like, or a material having gas barrier properties is applied to form the gas barrier layer 3. When the in-mold molding is performed as described above, the transparent barrier ultraviolet shielding laminate sheet 10 further provided with the heat bonding resin layer 1 and the transparent gas barrier ultraviolet shielding section 12 is provided.
Construct B. Although not shown, a resist method,
It is also possible to use a metallic film provided with a partial vapor deposition portion of metal aluminum formed by using a soluble primer method for the layer structure.

As described above, the transparent laminated sheet used in the present invention is more basic than the base film to be the printing film 4, the ultraviolet shielding layer 2, and, if necessary, the gas barrier layer 3 and the heat bonding resin layer 1. Is formed. However,
The configuration order of the lamination is not limited as described above, and a film made of the same resin as the molding container can be configured on both sides of the lamination sheet to prevent curling when used as a label. Thus, the laminated sheet provided with the surface resin layer 1A can have the same physical properties such as surface gloss as the molded container, or the molded resin can be adhered to both sides of the laminated sheet so that the laminated sheet does not peel off or fall off from the end. There can be no strong adhesion. Further, for the purpose of reversing the constitutional order of the ultraviolet ray shielding layer 2 and the gas barrier layer 3 or preventing elution of the ultraviolet ray shielding agent, the ultraviolet ray shielding layer can be sandwiched by two barrier films from both sides. For example, a barrier agent is applied to the ultraviolet blocking layer, or a film (for example, a vinylidene chloride coat / polyester film, a vinylidene chloride coat / stretched polypropylene film) in which a gas barrier film and a printing substrate are shared, and printing is performed. The number of layers to be constituted can be arbitrarily increased or decreased according to the purpose of use, for example, by using an omitted film.

The base film is preferably obtained not only in a form suitable for printing but also in a rolled form suitable for bonding with other films constituting a laminated sheet, and is preferably a stretched or unstretched film of a thermoplastic resin or a film thereof. A material obtained by laminating another material or processing by coating or the like is preferably used. For example, polyester, polypropylene,
Polyethylene, polystyrene, polycarbonate, saponified ethylene / vinyl acetate copolymer, acrylic resin,
Polyamide, polyvinyl chloride, cellulose acetate films, cellophane, and two or more of these films are used by laminating them by an ordinary lamination method.

The material that blocks ultraviolet rays can be selected from ordinary ultraviolet absorbers and the like. The ultraviolet absorber absorbs harmful ultraviolet rays having a wavelength of 390 nm, preferably 290 nm or less, which are chemically active and contained in sunlight, fluorescent lamps and the like. This ultraviolet absorber converts into heat energy in the molecule. For example, benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, formamidine, hindered amine-based compounds, etc. are used alone or in combination. These ultraviolet absorbers can be kneaded with a raw resin to form a film, or can be coated on a film by selecting a suitable binder to form a paint. The ultraviolet shielding layer can also be obtained by applying ultrafine metal oxide particles using a suitable binder.

The gas barrier layer is formed by coating a suitable base film with an aqueous dispersion of polyvinylidene chloride, which is a material having barrier properties, a solution of polyvinyl alcohol, ZnO ₂ , ITO, SiOx, aluminum oxide, etc. There is a film provided with metal oxide by evaporation or sputtering. Further, a vinyl chloride / vinyl acetate copolymer or an aromatic polyamide may be formed into a film to form a laminated structure.
And the film provided with these barrier layers is 10 to
Those having a thickness of 188 μm and provided with a picture layer by ordinary gravure printing, flexographic printing or the like are also preferable in that they can be used as a printing substrate.

The laminated sheet used for the molded container of the present invention is formed by ordinary dry lamination of a base film and another film, or sandwich lamination (for example, polyethylene lamination) using a thermoplastic resin as an adhesive layer. . Dry lamination adhesive
General polyester, polyester polyurethane, polyether, polyether polyurethane, vinyl chloride
A two-component reactive adhesive using a vinyl acetate copolymer and a polyisocyanate as a curing agent, or a one-component reactive adhesive of a polyether polyurethane polyisocyanate type or a polyester polyurethane polyisocyanate type is used.

When an ultraviolet blocking layer or a gas barrier layer is formed by coating, a usual coating method such as gravure coating, gravure reverse coating, rubber roll coating,
It is determined by the characteristics of the material and the amount of coating, such as with an air knife coat. The drying and curing are also performed by ordinary thermal drying, thermal curing, or ionizing radiation.

The thermal adhesive resin layer 1 of the laminated sheet used for in-mold molding is, as a general rule, formed by laminating a film formed of the same material as the container by melt extrusion coating (including co-extrusion coating). Can be. In addition, a copolymer of a molding resin or a low-melting-point heat-adhesive resin to which a tackifier is added may be used. This method is particularly effective when the laminated sheet is formed of a stretched film. The thickness of the heat-adhesive resin layer is 2 to 60 μm, and the heat-adhesive resin layer can be formed to have a relatively small thickness using resin varnish coating or co-extrusion coating.

When performing in-mold molding as a label, as shown in FIG. 1, the laminated sheet is a fan-shaped side sticking laminated sheet 13 shown in FIG. 2A and a circular center shown in FIG. 2B. The laminated sheet 14 to be adhered to the bottom having the gate hole 16 provided in the portion is produced. Then, the sheet 13 is temporarily attached to the female side 8 and the sheet 14 is temporarily attached to the bottom 9. If necessary, the respective sheets are vacuum-suctioned and fixed from the vacuum suction holes provided in the female, A male mold is inserted, and a molded resin 21 which is hot-melted is injected from a gate to produce a molded container 20 to which a laminated sheet is adhered.

The laminated sheet to be formed from the laminated sheet can be provided with features by adding shapes other than those described above. For example, it is possible to prevent the movement of the sheet during molding by partially cutting the corners of the fan-shaped side-attached laminated sheet 13 and securely attaching it to the inner surface of the female mold. Further, it may be a simple circular sheet having no gate hole 16 at the center of the side-attached laminated sheet 14. This sheet is made of a heat-resistant film (eg, aromatic polyester film) that does not melt due to the heat of the molding resin, or a heat-resistant reaction-curable adhesive (polyester-polyisocyanate-type adhesive). It is necessary to use a laminated sheet. It is also possible to temporarily attach the laminated sheet having no holes to the bottom of the female mold and adhere it to the male mold with the molding resin to be injected. Such a technology has already been disclosed in which the object of the present invention is to exhibit the effects of blocking ultraviolet rays and gas barrier properties.

In order to attach the laminate to the molded container of the present invention, in addition to the above-mentioned in-mold molding, it is also possible to use an adhesive to adhere. The adhesive is basically composed of an elastomer such as synthetic resin, natural rubber, or synthetic rubber, and a tackifier of rosin or a derivative thereof, and is a material having excellent heat resistance and light resistance using an acrylate copolymer. Can be preferably used in the present invention.

Hereinafter, the ultraviolet shielding container of the present invention will be described in more detail with reference to examples.

【Example】

(Examples 1 to 3) Laminate sheets having a transparent ultraviolet shielding portion with the layer constitution shown in Table 1 were produced, and in-mold molding was performed by injection molding. In addition, each film is
The laminated sheet of each experimental example was formed by dry lamination with a polyester isocyanate-based adhesive.

As shown in FIG. 1 (A), the molded containers of Examples 1 to 3 are obtained by adding the laminated sheet 10 of Example 1 to the cylindrical side of an in-mold label container 20 having a threading portion 17 below. It is provided on the part 8 and the bottom part 9. The container has an opening 6 and a flange 7 and an inner diameter of 62.5 m.
m, a height of 77 mm, and an inner volume of 210 cc.

The side sticking sheet 13 provided on the side 8
Is composed of a base film provided with a gas barrier layer or a base film not provided with a gas barrier layer and a laminated sheet including an ultraviolet blocking layer, and is formed in a fan shape as shown in FIG. The inner surface of the side sticking sheet 13 is a component of the layer of the heat-adhesive resin layer 1 (the layer described as the HS resin layer B in Table 1), which is a layer made of the injected polypropylene resin (the molding resin 21). )). The surface resin layer 1A is formed of a film or a coating made of the same resin as the molding resin 21. Since the surface resin layer 1A is formed on the surface of the molding container 20, the surface resin layer 1A has an antistatic property to prevent adhesion of dust. is there. Further, as for the bottom part 9, a bottom sticking laminated sheet 14 in which a gate hole 16 is provided in the center and processed into a circular shape as shown in FIG.

Next, as shown in FIG. 1, the laminated sheet 13 for attaching the side portion and the laminated sheet 14 for attaching the bottom portion are placed at the positions of the female mold corresponding to the side portion 8 and the bottom portion 9 of the molded container. Although not shown, the sheet is sucked and fixed from the female mold vacuum suction hole, and after pressing the male mold from above, polypropylene, which is the molding resin 21, is injected through the gate, and the usual in-mold molding by injection molding is performed. UV-shielding container in which the thermal adhesive resin 1 of the laminated sheets 13 and 14 on the side and bottom of Examples 1 to 3 is adhered to the polypropylene resin (molded resin 21) injected from the molded container. 20 were produced. The molded container 20 has a thickness of 0.5 to 0.
8 mm, polypropylene is used as the container body.
In addition, the same molded product, to which the laminated sheet was not attached, was used as a sample of Comparative Example 1.

Further, using the polystyrene as a molding material, the laminated sheet 10 of Example 4 shown in Table 1 was adhered to the side of The ultraviolet shielding container 20 of Example 4 which was processed into a laminated sheet to be adhered and adhered to the container was produced. The molded container produced a polystyrene container having a thickness of 0.5 to 0.8 mm in which the laminated sheet was attached to the side and the bottom. In addition, the same molded product, and the laminated sheet 1
A sample of Comparative Example 2 was prepared without sticking 0.

[0027]

[Table 1] However, "HS resin layer" ・ PP3405: CPP3405 Unstretched polypropylene film Thickness: 40 μm, manufactured by Toray Industries, Inc. ・ OPP: OPP P316 Stretched polypropylene film with heat sealing properties, manufactured by Toyobo Co., Ltd. ・ PP3401: CPP3401, unstretched polypropylene film Prevention product Thickness 40 μm “Base film, UV blocking layer, gas barrier layer” manufactured by Toray Industries, Ltd. ・ PET: stretched polyester thickness 12 μm ・ PET evaporation A: aluminum oxide evaporated stretched polyester thickness 12 μm: stretched polyester thickness 12 μm ・ PET evaporated Si: Si Ox vapor-deposited PET film, Si Ox300Å thickness 12 μm ・ KET-UV: Senecy KET-UV30, UV-blocking agent PET PET Daicel Chemical Industries, Ltd. Product name GLS30: Unstretched polystyrene Film thickness of 30μm Oishisangyo (trade name) manufactured by

With respect to the molded containers of Examples 1 to 4 and Comparative Examples 1 and 2, the following items were measured and evaluated. -Ultraviolet light transmittance The light transmittance at 310 and 390 nm was measured with a spectrophotometer UV2200 manufactured by Shimadzu Corporation.・ Discoloration and discoloration Place the dried orange on the molding container in each Example, and
The contents were irradiated with a fluorescent lamp of 0 W for 288 hours, and the contents were visually evaluated for discoloration and fading. ○: No change △: Small change ×: Large change ・ Moisture permeability MOPER PERMATRAN, temperature 40
The measurement was performed after purging for 3 days at 90 ° C. and a relative humidity of 90%. -Oxygen Permeability Purification was performed by using OXTRAN manufactured by MOCON Corporation at a temperature of 23 ° C, an outer relative humidity of 45%, and an inner relative humidity of 90% for 3 days. (Below)

[0029]

[Table 2] However, oxygen permeability: cm ³ / pkg · day · atm Water vapor permeability: g / pkg · day · atm

[0030]

As described above in detail, the molded container of the present invention is formed by sticking the ultraviolet-shielding transparent laminated sheet to the side and bottom of the container. Therefore, the contents filled in the container are excellent in the merchantability that can be identified from the outside without impairing the transparency of the container. In addition, since the ultraviolet rays are blocked, the contents are prevented from being deteriorated by light, and oxidation promoted by light is prevented, thereby providing an effect of extending the expiration date.

[Brief description of the drawings]

FIG. 1A is a sectional view of an ultraviolet shielding container showing a basic concept of the present invention. (B) It is a schematic sectional drawing of the ultraviolet-shielding laminated sheet of this invention. (C) It is the cross-sectional schematic of the laminated sheet which added the gas barrier property to the ultraviolet-shielding laminated sheet further.

FIG. 2A is a plan view of a punched laminated sheet to be attached to a side portion. (B) It is a punching top view of the laminated sheet | seat attached to a bottom part.

[Explanation of Signs] 1 Thermal adhesive resin layer 1A Surface resin layer 2 UV blocking layer 3 Gas barrier layer 4 Print film, base film 5 Picture layer 6 Opening 7 Flange 8 Side 9 Bottom 10 UV blocking laminate sheet 10B Barrier UV-blocking laminated sheet 11 Transparent UV-blocking section 12 Gas-barrier UV blocking section 13 Laminated sheet for side attachment 14 Laminated sheet for bottom attachment 16 Gate hole 17 Threading section 20 Molding container 21 Molding resin

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B65D 81/30 B65D 81/30 B G09F 3/04 G09F 3/04 Z

Claims (5)

[Claims] 1. A transparent ultraviolet ray shielding container, wherein a base film and a transparent laminated sheet containing at least an ultraviolet ray shielding layer are adhered to a container at the time of molding the container and are molded in-mold. 2. A transparent laminated sheet including the ultraviolet ray blocking layer is attached to a side portion and a bottom portion excluding an opening at the time of forming a container.
A transparent ultraviolet shielding container characterized by being molded in-mold. 3. The laminated sheet including the ultraviolet ray blocking layer,
3. The ultraviolet shielding container according to claim 1, wherein a transparent laminated sheet having a transparent gas barrier layer laminated thereon is bonded and in-molded. 4. The ultraviolet shielding layer is formed by coating a film obtained by kneading an ultraviolet shielding agent into a thermoplastic resin or a transparent film with a paint containing the ultraviolet shielding agent. 4. The ultraviolet shielding container according to any one of items 1 to 3. 5. The ultraviolet shielding container according to claim 1, wherein the gas barrier layer is a metal oxide deposited film.