JPS59106955A - Manufacture of laminate - 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 The present invention relates to a method for producing a laminate, and more particularly to a method for producing a laminate mainly made of plastic or paper material and having an impregnated inorganic layer that is transparent and has barrier properties against permeation of substances. Regarding the method.

Conventional packaging materials, especially packaging materials used for containers that can withstand long-term storage of food at room temperature (pouches, 1-tet cans, etc.), whose main layer is plastic or paper, have gas barrier properties. To ensure safety, most of the materials were made of laminates containing metal foil such as aluminum foil.

Therefore, transparent plastic or paper material (ρrie is cellophane) is used.

In the case of containers such as laminates whose main layer is parchment paper, there are problems in that they lose their transparency, making it impossible to see the contents, and they also lose the soft feel characteristic of plastic and paper materials.

Such problems undermine the superiority of plastic-based containers over metal containers. Also, in the case of containers made of laminates with paper materials such as kraft paper as the main layer, depending on the type of contents, it may be necessary to erase the image of a metal container, but if metal foil is included, such requirements may be met. was difficult to meet. .

Conventionally, a metal aluminum layer with a thickness of about 100 to 200× is formed on a base layer of a plastic film by vacuum evaporation to achieve a visible light transmittance of about 20 to 4
It is known that a 0% half-mirror film can be obtained. However, what is the oxygen gas permeability of the film of this ridge, for example, when the base layer is 12 μm thick? In case of polyethylene terephthalate film, 45-60 qm”day-at
m (at 27°C.

MoCon method), and in the case of a stretched polypropylene film with a thickness of 25 μm, 60 to 100φ2・day・atm
(at 27°C + MoCon method), and is unsuitable for use in packaging containers intended for long-term storage of foods that are severely affected by oxidation.

The present invention has been made in view of the problems of the prior art described above.
A method for producing a laminate whose main layer is plastic or paper material having an inorganic layer with excellent permeation resistance of liquid substances, etc.
The purpose is to provide.

In other words, when the combined light transmittance of the base layer and the organic thin film described below is 100%, the light rays in the laminated body made of the same base layer and the organic thin film manufactured by the present invention (5) have a mirror-like surface. Defined as having no luster.

In order to achieve the above object, the present invention provides a base layer mainly made of plastics or paper with a thickness of about 300 to 300 mm.
A 0X vapor-deposited metal aluminum layer is formed, and the surface of the metal aluminum layer is coated with a thin film formed from a resin composition in which the residual acidic free substances per 100 g do not exceed 0.06 microIJ. The present invention provides a method for producing a laminate, characterized in that the metal aluminum layer' is converted into a transparent inorganic layer by contacting the laminate with water and/or steam at a temperature of 75° C. or higher.

The present invention will be described below with reference to the drawings.

FIG. 1 shows an example of a laminate 1 manufactured by the method of the present invention, in which 2 is a base layer, 3 is a transparent inorganic layer, and 4 is an organic thin film (hereinafter referred to as thin film). The laminate 1 includes a base layer 2 as shown in FIG. 2, and a thickness of about 300 to 3000
It is obtained by treating the laminate 1' consisting of the vapor-deposited gold aluminum layer 3' of X and the thin film 4 with heated water or steam. The vapor-deposited metal aluminum layer 3' (hereinafter referred to as metal aluminum layer) with a thickness of approximately (6) 300 to 3000X is formed by depositing metal aluminum on the base layer 2 by vacuum evaporation, ion blasting, or sintering.
Footings and the like are formed by firmly attaching them using a so-called vapor phase plating method.

The base layer 2 needs to have mechanical strength (especially in the case of a film) and heat resistance to withstand this formation. In addition, it has hot water resistance, thermal dimensional stability, and resistance to heated water or steam treatment.
It is necessary to have properties such as water swelling resistance.

The degree of vulva of the above-mentioned required properties varies depending on the method of forming the metal aluminum layer 3' and the conditions of heated water or steam treatment, but plastics that meet these conditions and can be used for the base layer 2 include: Linear polyester resins such as oriented polyethylene terephthalate, low density polyethylene, high density polyethylene, holiflopylene, ethylene-propylene copolymers, etc. Polyolefin resin, acrylic resin.

Polystyrene resin, AS resin, ABS resin, polyamide resin, polyimide horse resin,? Liimino resin, 1'
? Vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate co-11 polymer, vinylidene copolymer, urea resin, phenolic resin, epoxy resin,
Melamine resin, urethane resin, xylene-formaldehyde resin, acetal resin, coumaron indene resin, diallyl phthalate resin.

Examples include fluororesins, blends or laminates thereof, and the like. The base layer 2 may be in the form of a film or sheet, or may be a molded body (for example, a bottle, a cup, or a can).

Cellophane is also used as a base layer mainly made of paper.

Examples include parchment paper, kraft paper, etc. whose both sides are covered with plastics (for example, polyethylene film).

The thickness of the metal aluminum layer 3' is approximately 300~3000X
It is preferable that This is because if it is thinner than about 300X, it is difficult to form a continuous film, and discontinuous portions (holes) remain even after conversion to the inorganic layer 3, resulting in a decrease in gas barrier properties. On the other hand, even if it is thicker than about 3000^, the gas barrier property will not be improved much, and not only will it lead to higher material and work costs, but it will also take a long time to convert the entire thickness into an inorganic layer and make it transparent. This is because the formed inorganic layer has poor workability.

The thin film 4 consists of a metal aluminum layer 31 and a transparent inorganic layer 3.
The inorganic layer 3 has a composition necessary for converting the inorganic layer 3 into an inorganic material, and has a function of preventing the formed inorganic layer 3 from coming off due to friction or the like. Therefore, it is desirable to use a strong organic coating.
Furthermore, during heating water or steam treatment, water vapor is permeated,
It is thin so as to smoothly convert the metal aluminum layer 3' into a transparent inorganic layer 3, and has a water vapor permeability (at 100°C) of 5 x 10-8 to 1 x 10-10 measured by the following method. 5crn2(STP)1
- It is necessary to satisfy sec-crnHg.

Furthermore, it is desirable that the material has heat resistance to the extent that it does not change in quality due to the above treatment.

Measurement of water vapor permeation at 100°C is carried out as follows. An organic thin film is coated on the tin-plated steel sheet in the same manner as in case (9) above the vapor-deposited metal aluminum layer in the practical row. However, the film thickness is 40μ
Adjust so that it is around m. Next, the organic thin film is peeled off from the tin-plated steel plate using the mercury amalgam method, the thickness is measured, and the film is vacuum-dried day and night to obtain a sample film.

Both the high-concentration side chamber and the low-concentration side chamber have gas inlets and outlets.
A water vapor permeability measurement cell made by Shinchu with a permeation area of approximately 3127α2 (diameter 6.0 crn) was prepared, and the sample membrane was set therein. This is kept in a constant temperature bath at 100°C, and high purity helium (commercially available) is introduced into the high and low concentration side chambers. The low concentration side chamber helium is guided to the thermal conductivity detector. Distilled water at 100°C in which dissolved oxygen and nitrogen were replaced with helium was introduced into the high concentration side chamber, and the amount of water vapor permeating through the organic thin film was measured with a thermal conductivity detector. Calculate water vapor transmission.

(1:O) The base material of the thin film 4 includes polyolefin resins such as low-density polyethylene, high-density polyethylene, polynolopyrene, and ethylene-zolopyrene copolymers, linear polyester resins, polyamide resins, polyvinyl chloride resins, and vinyl chloride resins.
Vinyl acetate copolymer, polyvinyl acetate resin, ethylene-
Vinyl acetate copolymer, ABS resin, ethylene-vinyl alcohol copolymer, phenol resin, furan resin, xylene-formaldehyde resin, urea resin, melamine resin, coumaron indene resin, alkyd resin, thermosetting acrylic resin, epoxy resin , urethane resins, thermosetting polyester resins, saturated polyester resins, diallyl phthalate resins, acrolein resins, bismaleimide resins, cycloentane diene resins, triallyl 7 anurate resins, etc., and two or more of these Examples include organic polymers such as resin compositions that may not be combined.

The thin film 4 may be composed of two or more types of layers.

The thin film 4 is formed on the metal aluminum layer 3' by painting, laminating, etc.

The thin film 4 is made of epoxy-amine curable resin or epoxy-
When the base material is a basic substance having an amine group, such as a urethane-based curable resin, the inorganic layer 3 becomes completely transparent even after treatment with heated water. In order to suppress the effect of making the substance transparent, after forming the thin film 4 made of epoxy-amine resin, a substance that reacts with amines, such as a curable urethane resin containing incyanate groups, may be applied and dried. In this case, the light transmittance decreases.

If the base material of the thin film 4 contains acid groups, such as alkyd resin, acrylic resin, or polyester resin, or if it is a phosphoric acid-added epoxy-urea paint, etc., a basic compound may be blended to remove acid groups or The acid (phosphoric acid in the above example) is consumed, and the residual acidic free substances (herein referred to as free substances including acid groups) do not exceed 0.006 milliequivalents per 100 g of the resulting resin composition. This is important in obtaining a transparent inorganic layer 3.

In other words, thin films containing acidic substances, such as polyester thin films and organic polymer thin films such as paints containing carboxylic acids as additives, cannot be processed by heated water treatment etc. due to the effects of acid groups. A metallic color remains and it is not transparent.

In this case, alkali metal and/or alkaline earth metal hydroxides (e.g. NaOH, KOH, Ca(OH)
21Mg(OH)2), primary and/or refined secondary amine compounds (e.g. ethylenediamine polymers such as dimethylene triamine and dimethylenetetramine, carbon numbers such as 1,4-diaminobutane, 1,5-noaminobutane, etc.) 4
~18 aliphatic linear diamines, aliphatic cyclic diamines such as cyclohexylene diamine, methylenebis (cyclohexyldiamine), aromatic diamines such as noaminotoluene, diaminodiphenylmethane, etc.), polyhydric alcohol adduct urethane Prepolymer, alkaline or alkaline earth metal salt type phenolic resin monomer unit 0.0
1~. By blending a phenolic resin prepolymer containing 10 moles of phenolic resin prepolymer, an ammonia aresol type phenolic resin prepolymer, a urea resin prepolymer, and a salt such as an ammonium salt compound (a dipping-based compound as described above), a transparent inorganic layer 3 can be formed. can be obtained.

Furthermore, even if the base material of the thin film 4 does not contain acid groups or acids, such as polyethylene, the transparency of the vapor-deposited metal aluminum layer can be promoted by adding the above-mentioned basic compound. Ru. For example, if the basic compound is an alkali metal hydroxide, increase the amount by 0.2 parts by weight (100 parts by weight of the resin composition constituting the thin film 4).
(relative to weight part), the light transmittance will be approximately 75.
% transparent inorganic layer 3 is obtained. However, blending in an amount exceeding 1 part by weight is not preferable because the barrier properties deteriorate.

When blending an amine compound, the blending amount of the amine compound contained in the thin film 4 is preferably 0.1 to 10 parts by weight. If the amount is less than 0.01 parts by weight, the conversion promoting effect will not be sufficient, while if it exceeds 10 parts by weight, the promoting effect will not be particularly improved, but rather will tend to cause problems such as embrittlement of the thin film 4.

Epoxy-phenolic curing resin (However, (1↓) When the phenol resin contained is an ammonia aresol type phenol resin that does not contain acid) When using a different thin film, it becomes transparent by heating water treatment etc. In order to obtain the inorganic layer 3, it is necessary to use a resin with a polymerization ratio of epoxy resin/phenol resin in the range of 98/2 to 60/40. stomach)
When using a thin film made of a curable resin, it is necessary to use a resin having an epoxy resin/urea resin ratio of 9515 to 80/2 o. In either case, if the above upper limit is exceeded, the coating film becomes brittle, while if it is below the above lower limit, it is difficult to make it transparent.

The thickness of the thin film 4 is 0.5 to 1000 μm depending on the type of these resins, etc., and the type and content of the above-mentioned additives.
It is desirable that the diameter is more preferably within the range of 2 to 500 μm. This is because if it is thinner than 0.5 μm, its function as a protective film will not be sufficient, whereas if it is thicker than 1000 μm, it will lead to an unnecessary increase in cost.

In order to convert the metal aluminum layer 3' into a transparent non-porous inorganic layer 3, the laminate 1' having the above structure can be treated with heated water such as immersion in heated water, sprayed with steam, or kept in a steam atmosphere. undergo steam treatment. The processing temperature is approximately 7
The temperature is preferably 5° C. or higher and the temperature at which the base layer 2 begins to flow or the thermal decomposition temperature or lower. At temperatures as low as about 75° C., substantially no conversion occurs, while the substrate 2
This is because, if the temperature exceeds the above-mentioned temperature, the metal aluminum layer 3' cannot cope with the deformation of the base layer 2, and cracks occur in the metal aluminum layer 3' and the inorganic layer 3, resulting in a problem that the function deteriorates.

The processing time varies depending on the thickness, type, etc. of the metal aluminum layer 3' and the thin film 4, but is usually several tens of seconds to several hours.
Alternatively, the treatment time can be shortened by using appropriate amounts of additives such as alkali metal hydroxides and alkaline earth metal hydroxides.

The laminate 1 manufactured as described above can be used as a container or container material, etc., as it is, or by forming another plastic layer, coating film, printed film, etc. on the surface of the base layer 2 and/or thin film 4. It will be done.

For example, when manufacturing an ie house having a film-like laminate 1 and an open bottom part, two blanks of the laminate 1 using a heat-sealable film such as polyethylene or polynolopyrene film as the base layer 2, or Two blanks of a laminate formed by laminating these heat-sealable films on the base layer 20 side of the laminate 1 may be stacked on top of each other, and three sides may be heat-sealed with the heat-sealable films.

In addition, the laminate 1 before heating water or steam treatment can also be used as it is.
Alternatively, a container is manufactured using another plastic layer, coating film, printed film, etc. formed on the surface of the base layer 2 and/or thin film 4, and after filling with the contents and sealing, the container is sterilized with hot water or retort heat sterilization. The laminate 1' may be converted into the laminate 1 in this treatment step. For example, in the same manner as in the case of the laminate 1, an i4 house is manufactured using the laminate 1', and after filling this house with the contents,
The opening is heat-sealed, and then a retort treatment is performed at 120° C. for 30 minutes, and in this treatment step (1) the metallic-colored laminate 1' may be converted into a transparent laminate IK. This case has the advantage that it is possible to confirm whether or not retort sterilization has been performed.

In addition, if the thin film 4 contains a resin that does not like to come into contact with the contents for food hygiene reasons, and if the thin film 4 is to be placed on the inner surface of the container, a separate coating film may be formed on the thin film 4, or a plastic coating film may be formed on the thin film 4. From the viewpoint of hygiene, it is desirable to use a container material that has been affixed with.

As mentioned above, by forming a vapor-deposited metal aluminum layer with a thickness of 100 to 200×, a transparent film in the shape of a half mirror can be obtained, but in this case, the oxygen gas barrier property is poor. Therefore, a method has been proposed in which a transparent metal compound layer is formed directly on the metal aluminum layer by vacuum deposition, but in this deposition method, M (metal), MO (metal compound), etc. are subjected to a gas phase reaction. Yoshi MAOB (A-1~, B=o~)
To form a uniform film, sophisticated technology and expensive equipment are required, resulting in high processing costs.

(1) However, according to the present invention, the metal aluminum layer formed on the base layer (aluminum has a low melting point, so ordinary vacuum evaporation equipment etc. can be used) is passed through the thin film that is the protective film. It is converted into a translucent and non-porous inorganic layer (presumed to be mainly a water-conserving aluminum oxide layer) by heated steam, so it is possible to create a transparent intermediate layer at low cost using ordinary equipment. This has the effect that a laminate having an inorganic layer can be manufactured.

Examples will be described below.

Example 1 Epicoat 100 manufactured by Shell Chemical Co., Ltd. was applied to the vapor deposition surface of a 25 μm thick biaxially stretched polyethylene terephthalate film on which a 500× thick metal aluminum layer was vapor deposited.
7 epoxy resin - toluene, methyl ethyl ketone (1
/1) An epoxy-amine resin paint obtained by blending 024 g of diethylene triamine (commercial product, special grade) with 50.9 g of a mixed solvent solution (solid content: 30 wt%) was applied using a bar coater. After baking this film in a dry heat oven at 200°C for 5 minutes (coating thickness 6-7 μm after baking), 1
A transparent film was obtained by immersion in hot water at 00°C for 40 minutes.

0.3 mm thick tin plated steel (tin content: 50150)
An epoxy-amine resin paint with the same composition as above was applied using a bar coater and baked in a dry heat oven at 200°C for 5 minutes. - Cleared and vacuum dried at 50°C day and night (film thickness 46 μm).

The water vapor permeability of this thin film was measured at 100°C using the method described above.
/an2se c ant Hg and ivy.

The oxygen gas permeability of this transparent film was measured using an oxygen gas permeability tester Oxytran manufactured by MoCon, and was found to be 1.
5~2CC/m-day-atm (at 27℃)
Met.

For reference, metal aluminum 2 used in the above experiment
Axis) TE Shinho! When J ethylene terephthalate film is subjected to the same treatment without the application of epoxy-amine resin paint, it becomes transparent, albeit mottled.

When the oxygen gas permeability of this transparent film was measured in the same way, it was 50 to 60 CC7m-day-atm (at
27°C).

Example 2 100 parts by weight of an epoxy resin (Ebicor) 1004 manufactured by Shell Chemical Co., Ltd. was added to the vapor deposition surface of a metal aluminum vapor-deposited polyethylene terephthalate film similar to that in Example 1.
The resulting paint was mixed with 10 parts by weight of -P'diaminodiphenylmethane and applied by Percoter. After baking this film in a dry heat oven at 190℃ for 15 minutes (
A transparent film was obtained by superheated steam treatment at 120° C. for 15 minutes.

The oxygen gas permeability of this film is 15-2 CC/m2. day, atm (at 27°C).

In addition, solid content 30 wt%, toluene-methyl ethyl ketone (1/1) mixed solvent solution, 0.3 ml thick tin-plated steel plate (tin content "50150)" and epoxy resin-P-P of the same composition as above. 'Diaminonophenylmethane paint was applied with a bar coater, dried for 15 minutes at 190℃ (2 harms), and baked in a heat open.Later, a thin film of Jepoxy-P-P'diaminonophenylmethane resin was applied to the tin-plated steel using the mercury amalgam method. It was peeled off from a commercially available product and vacuum dried at 50°C day and night (film thickness 50 μm).
As a result of measuring the water vapor permeability at 0°C, it was found to be 8X1ocm (
STP)Cm/CIIL2・sec-mHg.

Example 3 ＼ Vapor deposition surface of metal aluminum vapor-deposited polyethylene terephthalate film similar to Example 1 (Shell Chemical Co., Ltd.)
An aromatic incyanate compound (manufactured by Takeda Pharmaceutical Co., Ltd.) was added to 100 parts by weight of epoxy resin (Ebiko) 1001 (manufactured by Takeda Pharmaceutical Co., Ltd.).
Takenate A-3, solid content 30 wt%) with solid content of 8
An epoxy-urethane paint containing 7 parts by weight was applied using a bar coater. This film is 190
After dry heat open baking for 15 minutes at 120° C. (coating film thickness 7 μm after baking), a transparent film was obtained by superheated steam treatment at 120° C. for 15 minutes. The oxygen gas permeability of this film is 2.0 to 2.5 CC7m -d
ay-atmC2 product) (at 27°C).

In addition, solid content: 30 wt%, luene-methyl ethyl ketone (1/1) mixed solvent solution, epoxy-urethane paint with the same composition as above on 03-thick tin plated steel (tin (i"50150)) Apply with a bar coater 1
It was baked in a dry heat oven at 90°C for 15 minutes.

Thereafter, a thin film of jepoxy-urethane resin was removed from a tin-plated steel plate by the mercury amalgam method and vacuum-dried at 50° C. day and night (the thickness of the thin film was 40 μm).

The water vapor permeability of this thin film was measured at 100°C using the method described above.
It was small.

Example 4 25 parts by weight of ammonia resol type bisphenol A type phenol resin was added to 100 Nt parts of Ebiko 1009 resin (manufactured by Shell Chemical Co., Ltd.) on the vapor deposition surface of the same metal aluminum vapor-deposited polyethylene terephthalate film as in Example 1. The Epoquine-phenol resin paint obtained by blending was applied using a bar coater. After baking this film in a dry heat oven at 190℃ for 15 minutes (
A transparent film was obtained by superheated steam treatment at 120° C. for 30 minutes (coating film thickness after baking: 5 μm).

The oxygen gas permeability of this transparent film is 0.4 cc
It was 7m2・day-atm (at 27°C).

In addition, an epoxy-phenol resin paint with the same composition as above was applied to a tin-plated steel plate (tin content: 50150) with a thickness of 0.3 mm using a mixed solvent solution of toluene-methyl ethyl ketone (1/1) with a solid content of 28 wt%. was coated with a bar coater and baked in a dry heat oven at 190°C for 15 minutes.Then, a thin film of jepoxy-phenol resin was coated on a tin-plated steel plate using the mercury amalgam method and dried under vacuum at 50°C day and night. (The thickness of the thin film is 60 μm).The water vapor permeability of this thin film at 100°C was measured using the method described above.3.
5 x 10 cm (STP) cm/cIIL2・
It was 5ec-IHg.

Example 5 100 parts by weight of epoxy resin Epicoat 1007 manufactured by Shell Chemical Co., Ltd. and 1 Beckamine P-138 (urea resin) manufactured by Dainippon Ink Co., Ltd. were added to the vapor deposition surface of the same metal aluminum vapor-deposited polyethylene terephthalate film as in Example 1.
An epoxy 7 urea resin paint prepared by mixing 5 parts by weight was applied using a bar coater. 20 pieces of this film
After baking in a dry heat oven for 15 minutes at 0°C (coating film thickness after baking: 7 μm), a transparent film was obtained by superheating steam treatment at 120°C for 45 minutes.

The oxygen gas permeability of this transparent film is 0.5cc/
m'day-atm (at 27°C).

Solid content 30wt%,) luene-methyl ethyl ketone (1
/1) Mixed solvent solution, acid value 0.5 KoHmy/g,
Sales of tin-plated steel with a thickness of 0.3 mm (tin content: 50150)
An epoxy urea resin paint having the same formulation as above was applied on top using a bar coater, and baked in a dry heat oven at 200°C for 15 minutes. later by mercury amalgam method) epoxy 7
Peel off the urea resin paint from tin plated steel and apply glue 5.
It was vacuum dried at 0°C (the thickness of the thin film was 65 μm). The water vapor permeability of this thin film at 100°C was measured using the method described above, and the result was 3.8 x 10. 'Cnt5(STP)
Cm/CTL°sec゛mHg.

(28) Example 6 The epoxy urea resin paint used in Example 5 was hydroxylated in an amount of 0.025 parts per 100 parts by weight of the solid content on the vapor deposition surface of the same metal aluminum vapor deposited polyethylene terephthalate film as in Example 1. IJum (commercial product, special grade)
The paint containing the above was applied using a bar coater. After baking this film in a dry heat oven at 200°C for 15 minutes (coating thickness 7 μm after baking), a transparent film was obtained by superheating steam treatment at 120°C for 10 minutes, and the film was described in Example 5. Compared to the epoxy urea resin film that does not contain sodium hydroxide, the processing time can be reduced to about 1/3. The oxygen gas permeability of this transparent film is 0.7 CC7m-day-atm (at 27°C
)Met.

In addition, a solid content of 30 wt%, a mixed solvent solution of toluene and methyl ethyl ketone in equal parts, and an epoxy LA paint (with NaOH added) of the same composition as above was applied on a tin-plated steel sheet with a thickness of 0.3 mm (tin amount + 50750 mm). It was coated with a bar coater and baked in a dry heat oven (2i) at 200°C for 15 minutes. Afterwards, a thin film of epoxy urea (NaOH added) resin was applied to the tin-plated steel by the mercury amalgam method, and vacuum-dried at 50°C day and night (the thickness of the thin film was 65μ).
0 The water vapor permeability of this thin film was measured at 100°C using the method described above, and the result was 36 x 10 cm (STP).
cIIV/cIrL, -sec-cmHg 0

[Brief explanation of the drawing]

FIG. 1 is a longitudinal sectional view of an example of a laminate manufactured by the method of the present invention, and FIG. 2 is a longitudinal sectional view of an example of a laminate used to manufacture the laminate of FIG. 1. . DESCRIPTION OF SYMBOLS 1... Laminate, 1'... Laminate, 2... Base layer, 3
...Inorganic layer, 3'...Metal aluminum layer, 4.
...Thin film. (Fig. 1, Fig. 2)

Claims (9)

[Claims] (1) A vapor-deposited metal aluminum layer with a thickness of about 300 to 3000X is formed on a base layer mainly made of Derasnax or paper material, and a 100X metal aluminum layer is formed on the surface of the metal aluminum layer.
By contacting a laminate coated with a thin film formed from a sugar beet composition in which the residual acidic free substances per gram does not exceed 0.06 milliequivalents, with water and/or steam at a temperature of 75°C or higher. B. A method for producing a laminate, which comprises converting the metal aluminum layer into a transparent inorganic layer. (2) A vapor-deposited metal aluminum layer with a thickness of about 300 to 3000× is formed on the base layer mainly made of plastic, paper, or paper, and a layer of 10× is deposited on the surface of the metal aluminum layer.
A laminate coated with a thin film formed from a resin composition containing a basic substance and in which the residual acidic free substances do not exceed 0.06 meq. 1. A method for producing a laminate, characterized in that the metal aluminum layer is transferred and converted into a transparent inorganic layer by contacting with a laminate. (3) The method for producing a laminate according to claim 2, wherein the basic substance is a primary amine compound. (4) The method for producing a laminate according to claim 2, wherein the basic substance is a secondary amine compound. (5) The method for producing a laminate according to claim 2, wherein the basic substance is an alcohol adduct urethane prepolymer. (6) The method for producing a laminate according to claim 2, wherein the basic substance is a phenolic resin prepolymer containing 1 to 10 moles of alkali metal salt type phenolic resin monomer unit. (7) The method for producing a laminate according to claim 2, wherein the basic substance is a phenolic resin prepolymer containing 0.01 to 10 moles of alkaline earth metal salt type phenolic resin monomer unit. (8) The method for producing a laminate according to claim 2, wherein the basic substance is an ammonia resol type phenolic resin prepolymer. (9) The method for producing a laminate according to claim 2, wherein the basic substance is a urea resin prepolymer. Method.