JPH04201334A - Laminated material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a laminate material, and particularly to a laminate material used in a tube container containing a fluid or semi-fluid substance.

[Conventional technology]

Tube containers for storing fluid or semi-fluid substances such as toothpaste, cosmetics, and food pastes are cylindrical containers made of laminated materials with physical properties such as appropriate stiffness, water resistance, and gas barrier properties. The body includes a body, a closure member having a shoulder and a neck and engaged with the upper open end of the body, and a cap detachably attached to the neck of the closure member. In order to provide water resistance and facilitate molding, laminated materials without a paper layer have been developed in recent years.

An example of such a laminated material is a thermoplastic resin layer/biaxially stretched resin film layer/printed layer/I! Covering resin layer/
A laminated material having a laminated structure of barrier layer/thermoplastic resin layer can be mentioned.

[Problem to be solved by the invention]

However, in the above-mentioned laminated materials, the base color of the laminated materials is determined by the color of the ink used as the printing layer and the color of the hiding resin layer, and for example, the base color of the laminated materials is monotonous such as white, milky white, cream color, etc. In addition, if the metallic luster of the aluminum foil as a barrier layer is used as the background color without using a concealing resin layer, the flatness of the metallic lustrous surface deteriorates due to minute irregularities and wrinkles that occur on the aluminum foil during the manufacturing stage, and vice versa. However, there is a problem that the image of extruded tubes deteriorates, and there has been a demand for a highly decorative laminate material that can further enhance the image of extruded tubes.

The present invention was devised in view of the above-mentioned circumstances, and provides a laminated layer having a metallic luster ground color and a light interference pattern, and whose metallic lustrous surface has a good surface condition with no unevenness. The purpose is to provide materials.

[Means to solve the problem]

In order to solve such problems, the present invention provides an intermediate support layer consisting of a biaxially stretched resin film layer having on at least one surface two or more metal thin film layers with a primer layer provided between the layers; an outermost layer located outside the support layer and made of a thermoplastic resin layer, an innermost layer located inside the intermediate support layer and made of a thermoplastic resin layer, and located between the innermost layer and the intermediate support layer. The structure includes a barrier layer. Note that the primer layer formed between the layers may be colored.

[Effect]

The intermediate support layer made of a biaxially stretched resin film layer has an outermost layer and an innermost layer made of a thermoplastic resin layer laminated on the outside and inside thereof, respectively, and a barrier layer is provided between the intermediate support layer and the innermost layer. At least one surface of the intermediate support layer is provided with two or more metal thin film layers with a primer layer provided between the layers. This results in
When looking at the laminated material from the outermost layer side, the metallic thin film layer of the intermediate support layer allows the background color of the metallic luster to be recognized.
Interference patterns due to interference of light reflected by more than one metal thin film layer are also recognized.

〔Example〕

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic cross-sectional view showing one embodiment of the laminate material of the present invention. In FIG. 1, the laminated material 1 of the present invention includes an intermediate support layer 2, and a thermoplastic resin layer 8, which is the outermost layer, and which is laminated on the outside of the intermediate support layer 2 (in the upper part of the drawing) with an anchor coat layer 9 interposed therebetween. , a waist adjustment film layer 12 laminated on the inside of the intermediate support layer 2 (lower part in the drawing) via an anchor coat layer 10 and a low-density polyethylene resin layer 11, and an anchor coat layer 13 and A barrier layer 15 laminated with a copolymer (acid copolymer) layer 14 of olefin and unsaturated carboxylic acid interposed therebetween;
A thermoplastic resin layer 17 as an innermost layer is laminated on this barrier layer 15 with an acid copolymer layer 16 interposed therebetween.

The intermediate support layer 2 includes a biaxially stretched resin film layer 3 having a back-printed printed layer 4 on the inside, and a biaxially stretched resin film laminated on the biaxially stretched resin film layer 3 via an adhesive layer 5. It is composed of layer 6. The biaxially stretched resin film layer 6 is provided with a metal vapor deposition layer 7 on at least one surface thereof (in the illustrated example, the surface that contacts the outer adhesive layer 5).

Examples of the biaxially stretched resin film used for the intermediate support layer 2 include transparent or translucent films made of polyethylene terephthalate, polypropylene, nylon, ethylene-vinyl acetate copolymer, and the like. The thickness of such biaxially stretched resin film layer 3 is 10 to 50μ.
The thickness of the biaxially stretched resin film layer 6 is about 10 to 50 m.
The thickness of the entire intermediate support layer 2 is about 20 to 1 μm.
The thickness is preferably about 00 μm. Further, the adhesive layer 5 may be a known adhesive such as a urethane adhesive.

The printed layer 4 is formed by a known printing method such as gravure printing or offset printing, and the surface of the biaxially stretched resin film layer 3 on which the printed layer 4 is formed may be subjected to a corona treatment in advance.

The metal thin film layer 7 provided on the biaxially stretched resin film layer 6 is composed of two metal thin film layers 7a and 7b laminated with a primer layer 7c in between, as shown in FIG. . The metal thin film layers 7a and 7b are thin film layers of amphoteric oxides, and the amphoteric oxides include oxides of amphoteric metals such as tin, titanium, and aluminum (S n O, T t O
2.

Al2O3, SiO2, or composite oxides thereof) can be used. The amphoteric oxides forming the metal thin film layers 7a and 7b may be the same (or may be different).
It is preferable that each layer b has a thickness of 350 Å or more, and can be formed by a known method such as a vacuum evaporation method, a plating method, a sputtering method, or a transfer method, and the formed metal thin film layers 7a and 7b Shows semi-transparency. In addition, the primer layer 7
C is formed from a primer coating agent such as polyester resin, urethane resin, acrylic resin, polyamide resin, etc., and this primer layer 7C may be colored.

The thermoplastic resin layer 8, which is the outermost layer, is thermally fused with the thermoplastic resin layer 17, which is the innermost layer, when the laminate material 1 is made into a cylinder to form the body of the extruded tube. It consists of thermoplastic resins such as density polyethylene, linear low-density polyethylene, polypropylene, medium-density polyethylene, ethylene-vinyl acetate copolymer, polyester, polyacrylonitrile, and polyvinyl alcohol. The thickness of such thermoplastic resin layer 8 is preferably 50 μm or more. This is to prevent the aluminum foil layer 15 from being exposed from the end face of the laminate 1 when it is formed into a cylindrical shape as described above. Further, the thermoplastic resin layer 8 may be a single layer, or may have a laminated structure in which a thermoplastic resin is extruded and laminated on one side of a thermoplastic resin film. Furthermore, an antistatic agent, a slip agent, etc. may be added to the thermoplastic resin layer 8 depending on the use of the laminate 1.

The anchor coat layers 9, 10, 13 are formed using an anchor coat agent made of organic titanate, polyethyleneimine, a compound having an isocyanate group, or the like.

The low density polyethylene resin layer 11 is the anchor coat layer 1
It is for laminating a stiffness adjusting film on the intermediate support layer 2 provided with a thickness of about 10 to 50 μm. A waist adjustment film layer 12 is provided on the intermediate support layer 2 via a low density polyethylene resin layer 11.
is for adjusting the stiffness of the laminated material 1,
The material, thickness, etc. can be changed as appropriate depending on the use of the laminated material 1. That is, a resin film having a thickness of about 20 to 100 μm, such as a linear low-density polyethylene resin film, a low-density polyethylene resin film, a medium-density polyethylene resin film, or an unstretched polypropylene film, can be used. Note that if the stiffness adjustment film layer 12 is not required due to the stiffness required for the laminated material 1, the anchor coat can be formed without providing the low density polyethylene resin layer 11, the stiffness adjustment film layer 12, and the anchor coat layer 13. Acid copolymer layers 14 and below may be laminated directly to layer 10.

The acid copolymer layer 14 is for laminating a barrier layer 15 on the stiffness adjusting film layer 12 provided with the anchor coat layer 13. This acid copolymer layer 14 is formed by melt extruding an ethylene-methacrylic acid copolymer, an ethylene-acrylic acid copolymer, etc., and has a thickness of 2
The thickness is preferably about 0 to 100 μm.

As the barrier layer 15 laminated via the acid copolymer layer 14, an aluminum foil layer or a resin film of polyvinyl alcohol, polyvinylidene chloride, or the like can be used. The thickness of this barrier layer 15 is 6
The thickness is preferably about 50 μm.

The acid copolymer layer 16 is for laminating the thermoplastic resin layer 17 as the innermost layer on the barrier layer 15, and can be made of the same material as the acid copolymer layer 14 described above.

The innermost layer (7) and the thermoplastic resin layer (7) are made of the same thermoplastic resin as the thermoplastic resin layer (8), and the thickness thereof is preferably 50 μm or more. may be a single layer, or may have a laminated structure in which a thermoplastic resin is extruded and laminated on one side of a thermoplastic resin film.

In the laminated material 1 as described above, due to the metal thin film layer 7 constituting the intermediate support layer 2, the ground color of the metallic luster is recognized from the thermoplastic resin layer 8 side as the outermost layer.

Furthermore, since the metal thin film layers 7a and 7b of the metal thin film layer 7 exhibit semi-transmission, the light reflected on the surface of the metal thin film layer 7a and
Interference occurs due to the difference in optical path of the light transmitted through the metal thin film layer 7a and the primer layer 7c and reflected on the surface of the metal thin film layer 7b, and an interference pattern is recognized.

Since the metal thin film layer 7 is formed of a biaxially stretched resin film, the occurrence of unevenness and wrinkles on the metal thin film layer 7 during the manufacturing stage is significantly less than when metal foil is used, and the surface It has good properties and a beautiful metallic luster background color can be obtained. In the illustrated example, the metal thin film layer 7 is composed of two metal thin film layers and one primer layer located between the layers, but it may further include multiple metal thin film layers.

, Such a laminated material 1 can be manufactured by lamination using known extrusion lamination.

FIG. 3 is a schematic cross-sectional view showing another embodiment of the laminated material of the present invention. A laminate 1' shown in FIG. 3 has the same structure as the laminate 1 except that the intermediate support layer is different from the laminate 1 described above. The intermediate support layer 2' in this laminate 1' includes a biaxially stretched resin film layer 6' and a biaxially stretched resin film layer 6'.
It is composed of a printed layer 4' provided on the outside of the film and a metal thin film layer 7' provided on the inside. Metal thin film layer 7'
has the same structure as the metal thin film layer 7 described above.

In addition, in FIG. 3, the same components as those of the laminated material shown in FIG. 1 are given the same numbers, and explanations thereof will be omitted.

FIG. 4 is a schematic cross-sectional view showing another embodiment of the laminated material of the present invention. In FIG. 4, the laminated material 21 of the present invention includes an intermediate support layer 22, and an outermost thermoplastic resin film layer laminated on the outside (upper part of the drawing) of the intermediate support layer 22 via an adhesive layer 29. 28, a barrier layer 31 laminated on the inside of the intermediate support layer 22 (lower side in the drawing) via an adhesive layer 30, and an innermost layer laminated on this barrier layer 31 via an adhesive layer 32. It has a thermoplastic resin film layer 33.

The intermediate support layer 22 of the laminate material 21 includes a biaxially stretched resin film layer 23 having a back-printed printed layer 24 on the inside like the intermediate support layer 2 described above, and a biaxially stretched resin film layer 23 with an adhesive layer 25 interposed therebetween. It is composed of a biaxially stretched resin film layer 26 having a metal thin film layer 27 laminated on the film layer 23. The material and thickness of each layer constituting this intermediate support layer 22 are the same as those for the above-mentioned intermediate support layer 2, and the metal thin film layer 2
7 has the same structure as the metal thin film layer 7 described above.

Further, the thermoplastic resin film layer 28 and the thermoplastic resin film layer 33 are made of a thermoplastic resin that can be used for the above-mentioned thermoplastic resin layer 8.17. Then, the thermoplastic resin film layer 28 and the thermoplastic resin film layer 3
3 is preferably composed of a thermoplastic resin of the same quality.

Further, the thickness of the thermoplastic resin film layer 28.33 can be controlled within the same range as the above-mentioned thermoplastic resin layer 8.17.

Furthermore, the material and thickness of the barrier layer 31 can also follow the barrier layer 15 shown in FIG.

Such a laminated material 2] can be manufactured by dry laminating with adhesive layers 29 and 30° 32 interposed therebetween. The adhesive used may be a known adhesive such as the I/Tan adhesive.

Next, the present invention will be explained in more detail by showing experimental examples.

EXPERIMENTAL EXAMPLE A laminate having the laminate structure shown in FIG. 1 was prepared by extrusion lamination as follows.

First, a biaxially stretched polyethylene terephthalate (PET) film (E510 manufactured by Toyobo Co., Ltd.) with a thickness of 12 μm was used.
One side of Sample No. 0) was subjected to corona treatment, and a printed layer was formed on this corona-treated side by gravure printing. Next, add a second layer on one side.
A metal thin film layer of a biaxially stretched PET film (RB12 Yokogura manufactured by Toyo Metallizing Co., Ltd.) with a thickness of 12 μm on which a metal thin film layer with a laminated structure as shown in the figure was formed and the above biaxially stretched PET film (E 5100). ) and the printed layer forming surface with urethane adhesive (A315/manufactured by Shikinichi Yakuhin Co., Ltd.).
A12) was dry-laminated to create a laminated film to serve as an intermediate support layer. Note that the metal thin film layer of the above-mentioned biaxially stretched PET film (RB12 horizontal film) is formed with a thickness of 1000 mm using SnO2 as an amphoteric oxide.

This intermediate support layer is made of biaxially stretched PET film (E5100
) side using a polyethyleneimine anchor coating agent (Epomin P-1000 manufactured by Nippon Shokubai Kagaku Co., Ltd.) to form an anchor coat layer, and on this anchor coat layer, a low density polyethylene resin (manufactured by Mitsui Petrochemical Co., Ltd.) is used to form an anchor coat layer. Ml I P
) was extrusion laminated to a thickness of 70 μm.

In addition, the biaxially stretched PET film (R
An anchor coat layer is formed on the B12 horizontal side using the above polyethyleneimine anchor coat agent (Epomin P-1000), and a 20μ
low-density polyethylene resin (MIIP) extruded to a thickness of
), a milky white polyethylene resin film (5RWN, manufactured by Dainippon Jushi Co., Ltd.) with a thickness of 70 μm was sandwich-laminated so that its non-corona-treated side was in contact with a low-density polyethylene resin (MllP).

This milky white polyethylene resin film (5RWN, manufactured by Dainippon Jushi Co., Ltd.) was laminated as a waist adjustment film.

Next, the above milky white polyethylene resin film (SRW
An anchor coat layer is formed on the corona-treated side of N) using the above-mentioned polyethyleneimine anchor coat agent (Epomin P-1000), and on this anchor coat layer
A 10 μm thick aluminum foil for barrier wear (Nippon Foil Co., Ltd.
Co., Ltd.) was sand-laminated.

Furthermore, the above ethylene-methacrylic acid copolymer (AN4205) was extruded and laminated to a thickness of 30 μm on the above aluminum foil, and then a low density polyethylene resin (MIIP) was extruded and laminated to a thickness of 60 μm. material was created.

Next, a cylindrical body was formed from this laminated material with the 70 μm low-density polyethylene resin (outermost layer) outside, and an extruded tube was made using this chest. In this extruded tube, the laminated metal thin film layer provided on the biaxially stretched PET film (RB12 horizontal) can be clearly recognized as a metallic luster background color, and the interference pattern of light reflected by this metal thin film layer can also be recognized. It was an extruded tube with excellent decorative properties. The printed layer was also well recognized.

〔Effect of the invention〕

As described in detail above, according to the present invention, when the laminated material is viewed from the outermost layer side, the metal thin film layer of the intermediate support layer is recognized as a ground color with metallic luster, and the surface of two or more metal thin film layers is Interference patterns due to the interference of light reflected by the film can also be recognized.Also, since the metal thin film layer is formed on a biaxially stretched resin film, there is almost no unevenness on the metal thin film layer during the manufacturing stage, and therefore the surface roughness can be improved. It is possible to obtain a laminated material with good quality and rich decorative properties.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view showing one embodiment of the laminate material of the present invention;
Fig. 2 is a schematic cross-sectional view showing the structure of the metal thin film layer, Fig. 3 is a schematic cross-sectional view showing another embodiment of the laminated material of the present invention, and Fig. 4 is a schematic cross-sectional view showing another embodiment of the laminated material of the present invention. FIG. 1.21... Laminated material, 2.22... Intermediate support layer, 3
゜23... Biaxially stretched resin film layer, 4,24...
Printing layer, 5.25...Adhesive layer, 6,26...Biaxially stretched resin film layer, 7.7a, 7b, 27...Metal thin film layer, 7C...Primer layer, 8... Thermoplastic resin layer which is the outermost layer, 9.10.13... Anchor coat layer, 11... Low density polyethylene resin layer, 12...
waist adjustment film layer, 14.16... acid copolymer layer,
15°31...Barrier layer, 17...Thermoplastic resin layer which is the innermost layer, 28.33...Thermoplastic resin film layer, 29.30.32...Adhesive layer. Applicant's agent Yasushi Ishikawa 1. Zuna 2.

Claims (1)

[Claims] 1. An intermediate support layer consisting of a biaxially stretched resin film layer having on at least one side two or more metal thin film layers with a primer layer provided between the layers, and an intermediate support layer on the outside of the intermediate support layer. an outermost layer located inside the intermediate support layer and made of a thermoplastic resin layer; an innermost layer located inside the intermediate support layer and made of a thermoplastic resin layer; and a barrier layer located between the innermost layer and the intermediate support layer. A laminated material characterized by: 2. The laminated material according to claim 1, wherein the metal thin film layer is an amphoteric oxide thin film layer. 3. The laminate material according to claim 1 or 2, wherein the primer layer is colored. 4. The laminate material according to any one of claims 1 to 3, wherein the intermediate support layer has a biaxially stretched resin film layer having a printed layer laminated on the outside. 5. The laminated material according to any one of claims 1 to 4, wherein the thermoplastic resin constituting the outermost layer and the thermoplastic resin constituting the innermost layer are thermoplastic resins of the same quality.