JP2001191445A - Barrier composite film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a barrier composite film excellent in oxygen gas barrier properties and steam barrier properties. SOLUTION: A barrier composite film is constituted by providing a coating layer formed by the reaction of an organic chain-containing both-terminal functional silane monomer and a silane compound on at least one surface of a base material film through an inorganic membrane layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite film having excellent gas barrier properties against water vapor, oxygen, aroma components and the like, and suitable as a film for storing and packaging products in various fields.

[0002]

2. Description of the Related Art A substrate film is coated with an extremely thin inorganic oxide to greatly improve barrier properties, protect an inorganic oxide layer, processability as a packaging material, and the like. In view of the above, various composite films further coated with a synthetic resin are known.

For example, Japanese Patent Application Laid-Open No. 60-27532 discloses that an inorganic oxide thin film is formed on a polyolefin film and a synthetic resin layer is formed by dry lamination or extrusion lamination. 63-
237940 discloses a film in which a heat seal layer such as an ethylene-propylene copolymer is formed on a film obtained by sputtering iridium oxide, tin oxide, or the like. JP-A-1-202435 and JP-A-1-202436 disclose a microwave oven packaging material in which a silicon oxide vapor deposited layer and a heat seal layer or a protective layer are formed on the surface of a substrate film. A packaging material for a retort food is disclosed, wherein the heat seal layer is formed by laminating a resin film such as polypropylene, and the protective layer is formed by laminating a film or coating with a thermosetting resin. Also, Japanese Patent Laid-Open No. 1-2
No. 9723 discloses an inorganic oxide thin film formed on a film and further laminated with a biaxially stretched nylon film; Japanese Patent Application Laid-Open No. 3-86539 discloses an inorganic oxide thin film on a film. And then laminating or coating vinylidene chloride resin or the like; JP-A-4-173137 discloses that
Form an inorganic oxide thin film on the film, further vinyl chloride-vinyl acetate copolymer, polyamide, polyester,
There is disclosed one coated with an acrylic resin or coated with a hot melt material.

However, the above-mentioned composite film has a low adhesion strength between the base film and the inorganic oxide layer, and is subjected to a packaging material or a high temperature and high humidity where a mechanical external force acts during processing into a desired shape such as a bag or when used. When applied to a packaging material used below, there is a problem that a decrease in adhesion strength is promoted. Furthermore, packaging films used for foods, pharmaceuticals, precision parts, etc., require high transparency for the visibility and aesthetics of the contents, but the transparency tends to decrease as the adhesion strength decreases. There is a problem.

[0005] A plastic film coated with polyvinylidene chloride is excellent in that it has excellent barrier properties and transparency, and has a small reduction in barrier properties when a mechanical external force acts, but it contains chlorine atoms. Therefore, during incineration, dioxins may be generated by using it as a starting material, which may contaminate the surrounding environment.

The present invention provides a barrier composite film which is particularly excellent in oxygen gas barrier properties and water vapor barrier properties and has a small decrease in barrier properties even when a mechanical external force acts, which is suitable for packaging and preserving various products. The purpose is to:

[0007]

Means for Solving the Problems In order to satisfy the above-mentioned properties required for a packaging film, the present inventors have made a laminated structure of a base film, an inorganic thin film layer and a coating layer, The present invention has been found to be excellent in barrier properties, adhesion between layers, transparency, etc., to have properties equivalent to those of a film coated with polyvinylidene chloride, and to have no problem of environmental pollution at the time of incineration disposal. Was completed.

That is, in the present invention, at least one surface of the base film has a coating layer formed by a reaction between an organic chain-containing bifunctional functional silane monomer and a silane compound via an inorganic thin film layer. A barrier composite film.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The base film is formed by molding a known resin, and the resin as a raw material is appropriately determined according to the type of product (content) to be packaged when used as a packaging material. You can choose. Examples of such a resin include polyethylene, polypropylene, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer ionomer, polyolefin such as poly-4-methylpentene-1, polyethylene terephthalate, polybutylene terephthalate, and polyethylene isophthalate. Polyester such as polyethylene-2,6-naphthalate, nylon-6, nylon-12, nylon-6,6, nylon-6,10, nylon-6,12, nylon-MXD
Such as polyamide, polystyrene, styrene-acrylonitrile copolymer, styrene resin such as styrene-acrylonitrile-butadiene copolymer, polyvinyl alcohol, polyamideimide, polyimide, polyetherimide, polycarbonate, polysulfone, polyethersulfone, polyetherether. Ketones, polyarylates, polyphenylene sulfide, polyphenylene oxide, polyacrylonitrile, polytetrafluoroethylene, polytrifluoroethylene, fluororesins such as fluorinated ethylene-propylene copolymers, cellulose-based polymers such as cellophane, and configurations of the various polymers Copolymers containing units may be mentioned, and these may be used alone or in combination of two or more.

In the barrier composite film of the present invention, a primer layer can be formed between the base film and the inorganic thin film layer in order to enhance the adhesion between the two layers.

The primer layer is not particularly limited as long as it has good adhesiveness to both the base film and the inorganic thin film layer. For example, the primer layer is mainly composed of propylene and is made of other olefin monomers such as ethylene and butene. It can be formed by the obtained copolymer.

The content of the olefin monomer is preferably 0.1 to 100 parts by weight of propylene based on the raw material.
To 16 parts by weight, more preferably 0.3 to 8 parts by weight, still more preferably 1 to 6 parts by weight.

[0013] The thickness of the primer layer is preferably 0.01 to 10 µm, more preferably 0.1 to 2 µm, in consideration of the thickness of the entire barrier composite film while ensuring sufficient adhesive strength.

In the barrier composite film of the present invention, a skin layer can be formed on one surface side of the base film in order to impart slipperiness. This skin layer is formed on the other side when the coating layer is formed only on one side of the base material,
When the coating layer is formed on both sides of the substrate, it can be formed on either one of the coating layer surfaces.

The skin layer can be formed of the same resin as that forming the base film. Further, an anti-blocking agent can be added to the skin layer in order to improve the slipperiness. As the anti-blocking agent, the average particle size is 0.1 to 10 μm, preferably 0.1 to
5 μm, more preferably 0.2 to 3 μm. Such anti-blocking agents include silica, alumina, synthetic zeolite, kaolin, talc, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, aluminum hydroxide, quartz powder, calcium carbonate,
Inorganic powder such as barium sulfate, polyester, polycarbonate, polymethyl methacrylate, acrylic resin such as polymethyl methacrylate-polyethyl acrylate copolymer, nylon-6, nylon-12, nylon-
Thermoplastic resins such as polyamides such as 6,6, nylon-6,10 and nylon-6,12, crosslinked acrylic resins, melamine resins, crosslinked benzoguanamine resins, urea resins, epoxy resins, phenol resins, unsaturated polyester resins, etc. An organic powder composed of a thermosetting resin may be used. The compounding amount of the antiblocking agent is preferably 1500 to 6000 p, based on the weight of the plastic forming the skin layer.
pm, more preferably 1800 to 4000 ppm.

The ratio (Ta / Td) of the thickness (Ta) of the skin layer to the average particle size (Td) of the antiblocking agent is preferably 1 in order to increase the slipperiness and prevent the antiblocking agent from falling off. / 5-2, more preferably 1/4
~ 1.

The thickness of the skin layer (excluding the anti-blocking agent) is preferably 0.05 in consideration of the thickness of the entire barrier moisture-proof film while ensuring sufficient slipperiness.
To 15 μm, more preferably 0.1 to 10 μm, even more preferably 0.3 to 3 μm.

In particular, in order to increase the moisture resistance of the barrier composite film, that is, to lower the water vapor transmission rate, it is preferable to add a petroleum resin and / or a terpene to the above-mentioned base film.

Examples of the petroleum resin include a resin containing a cyclopentadiene-based or higher olefin-based hydrocarbon as a main raw material or a resin obtained by hydrogenating the resin at a hydrogenation ratio of 80% or more. The petroleum resin preferably does not contain a polar group.

Examples of the terpene include pinene, kalen, myrcene, ocimene, limonene, terpinolene, terpinene, sabinene, tricyclene, pisabolene, zingiperene, santalen, camphorene, millen, and totalen, and hydrogenation of these at 80% or more. Can be mentioned. The terpene preferably does not contain a polar group.

The total amount of the petroleum resin and the terpene is preferably 2 to 30 parts by weight, more preferably 2 to 25 parts by weight, based on 100 parts by weight of the resin used for the base film.
More preferably, it is 4 to 20 parts by weight.

If necessary, various additives such as an antioxidant, an ultraviolet absorber, a heat stabilizer, an antistatic agent, a plasticizer, a filler, a higher fatty acid amide,
Lubricants such as higher fatty acids or metal salts thereof, higher fatty acid esters, natural waxes such as carnauba wax, and synthetic waxes such as polyethylene wax can be blended.

The base film may be a single-layer film or a laminated film, and the thickness is not particularly limited. However, in consideration of workability when a barrier composite film is used as a packaging material, it is preferable. It is 10 to 100 μm, more preferably 10 to 50 μm.

The base film is formed by an inflation method, T
It can be obtained by applying a melt molding method such as a die method, a casting method using a solution, or the like. Further, both stretched and unstretched may be used, but in particular, the area ratio (length × width) is 2 × 2 to 6
Polyolefin films, polyester films, and polyamide films that are biaxially stretched × 12 times, preferably 3 × 3 to 5 × 10 times are preferred.

At least one surface of the substrate film may be subjected to a surface treatment in order to enhance the adhesion to the inorganic thin film layer and the coating layer. The surface treatment includes corona discharge treatment, vacuum plasma treatment, cathode sputtering treatment, flame plasma treatment,
Chromic acid treatment, surface roughening treatment and the like can be mentioned.

The inorganic thin film layer can be formed on one or both surfaces of the substrate film, and the inorganic component is preferably one capable of forming a transparent thin film. Such inorganic components include Group 2A elements of the periodic table (Be, Mg, C
a, Sr, Ba, Ra), transition elements (Sc-2 of No. 21)
No. 9 Cu, No. 39 Y-47 Ag, La, No. 72 Hf-79 Au), Group 2B element (Zn, Cd, H
g) 3B group elements (B, Al, Ga, In, Tl), 4
Examples include those containing one or more elements selected from Group B elements (Si, Ge, Sn, Pb) and Group 6B elements (Te, Po), and oxides of these elements are preferable.

The inorganic thin film layer further comprises a Group 3B element (B,
Al, Ga, In, Tl), 4B group elements (Si, Ge,
It is preferable to use one or more oxides selected from Sn, Pb) and Group 6B elements (Te, Po).
In particular, one or two or more selected from tin oxide, aluminum oxide, indium oxide, a composite oxide thereof, and silicon oxide are preferable because of excellent transparency.

When the barrier composite film of the present invention is applied to a packaging material for electromagnetic wave heating, the inorganic thin film layer is formed of an inorganic component having low conductivity, for example, Mg, Al, Zn, or the like.
Non-conductive inorganic substances such as oxides, carbides and nitrides of Si, Ge, and Sn can be used, and silicon oxide and aluminum oxide are preferable.

The thickness of the inorganic thin film layer is preferably 100
５5000Å, more preferably 200〜3000Å, and even more preferably 300〜1500Å. Thickness 10
When it is 0 ° or more, it becomes easy to form a thin film having a uniform thickness, and sufficient barrier properties and mechanical strength can be imparted. When the thickness is 5000 ° or less, transparency and appearance can be enhanced while maintaining excellent barrier properties.

The inorganic thin film layer is transparent and has a light transmittance (total light transmission amount × 100 / incident light amount; JIS K671).
7) is preferably 70% or more, more preferably 75% or more.

The barrier composite film of the present invention is the largest in that it has a coating layer formed by the reaction of an organic chain-containing bifunctional silane monomer and a silane compound on the inorganic thin film layer. There is a characteristic, and the barrier properties and mechanical strength can be greatly increased by the synergistic action of the coating layer and the inorganic thin film layer.

For example, an aluminum oxide thin film formed on a base film by vapor deposition or the like is inferior in thickness uniformity as compared with an aluminum foil, and the possibility of pinhole generation cannot be completely excluded. . When a coating layer made of polyvinylidene chloride or polyvinyl alcohol is formed on the inorganic thin film layer, the inorganic thin film layer and the coating layer may be able to improve the barrier property due to uneven thickness and the presence of pinholes. Because of the large difference in surface energy between them, a strong adhesion cannot be obtained, and the effect of improving the barrier properties is not sufficient. However, since the coating layer of the present invention forms a chemical bond with a hydroxyl group present on the surface of the inorganic thin film layer, even if a mechanical external force acts on the inorganic thin film layer at the time of processing into a packaging material or the like, damage such as cracks may occur. Since it can be prevented from occurring, high barrier properties can be maintained.

The coating layer may be formed at least on the inorganic thin film layer. The coating layer may be formed of a silane monomer having an organic chain and having both terminal functional groups (hereinafter, referred to as a “silane monomer”) and a silane compound. Formed from a polycondensation reaction using water vapor as an initiator, and comprises a polysiloxane having a three-dimensional network structure having an organic chain portion (soft segment) and a siloxane chain portion (hard segment). The silane monomer has an organic chain in the molecular chain,
There is no particular limitation as long as it has a functional group bonded to a silicon atom at both ends. Examples of such a silane monomer include those represented by the following general formula (1).

[0034]

Embedded image

Wherein R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group or an acyl group; R ₃ and R ₄ may be the same or different; Or an alkyl group, A represents a divalent organic chain having an aromatic ring, and a and b represent a number of 1 to 3. Examples of the alkyl group represented by R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group, and a butyl group. Of these, a methyl group is preferable.

The alkyl groups represented by R ₃ and R ₄ include
Examples include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the acyl group include an acetyl group and a propionyl group.

The divalent organic chain having an aromatic ring represented by A is not particularly limited as long as it has an aromatic ring represented by the following formula in the molecule. It may have a substituent such as an ether bond, a hydroxyl group, an alkyl group or an acyl group.

[0038]

Embedded image

The silane compound is not particularly limited as long as it reacts with the functional terminal of the silane monomer to form a polymer.

Examples of such a silane compound include the following general formula (2): (R ₆ ) _4-n Si (OR ₅ ) _n (2) wherein R ₅ is a hydrogen atom, an alkyl group or An acyl group; R ₆ represents a hydrogen atom, an alkyl group, or an aromatic group;
Represents a number of 2 to 4. ].

Examples of the alkyl group represented by R ₅ include a methyl group, an ethyl group, a propyl group and a butyl group.
Examples of the acyl group include an acetyl group and a propionyl group.

The alkyl group represented by R ₆ includes an alkyl group having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, and the aromatic group includes a phenyl group.

N is preferably 3 or 4, and particularly preferably 4.

As the silane compound represented by the general formula (2), tetraalkoxysilane having 1 to 3 carbon atoms in the alkoxy group is preferable, and tetramethoxysilane is most preferable.

As the silane compound, a so-called silane coupling agent can be used. As such a silane coupling agent, Si (O 2
R ₅ ) It is not particularly limited as long as it has a group [R ₅ has the same meaning as described above] and a functional group. Specific examples of the functional group include:
Examples include a vinyl group, an epoxy group, an acryloyl group, a methacryloyl group, an amino group, a mercapto group, and an isocyanate group.

The ratio of the silane monomer to the silane compound is based on 100 parts by weight of the silane monomer based on the raw material.
The amount of the silane compound is preferably 50 to 500 parts by weight, more preferably 100 to 300 parts by weight.

The coating layer in the present invention contains other silane monomers, hydrolyzed condensates of silane compounds, organic or inorganic polymer compounds such as silicone resins and water glass, and various additives such as silica and plasticizers. May be.

The thickness of the coating layer is preferably 0.1 to 10 μm in consideration of the thickness of the composite film having sufficient barrier properties while providing sufficient oxygen gas and water vapor barrier properties.
More preferably, it is 0.1 to 5 μm.

The relationship between the thickness of the coating layer and the thickness of the inorganic thin film layer is as follows.
The ratio (T / t) of the thickness (T μm) of the coating layer to the thickness (t μm) of the inorganic thin film layer is preferably 0.2 to 1
000, more preferably 0.3 to 500, and still more preferably 0.7 to 130.

The total thickness of the barrier composite film of the present invention can be appropriately set in consideration of durability and the like required according to the packaging object when applied as a packaging material. It is about 500 μm, more preferably about 10 to 100 μm.

When the thickness of the base film is 10 to 40 μm and the total thickness of the inorganic thin film layer and the coating layer is 0.5 to 5 μm, the barrier composite film of the present invention has a temperature of 20 ° C. Oxygen gas permeability at 40, 60 and 80% RH is preferably 0.05 to 10 ml / m ² · 24 h
r, more preferably 0.05 to 7 ml / m ² · 24 hr,
More preferably, it is 0.05 to 5 ml / m ² · 24 hr.

Further, the barrier composite film of the present invention comprises:
When it is of the above-mentioned predetermined thickness, it is kept at 20.degree.
The oxygen gas permeability at 0, 60 and 80% RH is preferably 0.05 to 10 ml / m ² · 24 hr, more preferably 0.05 to 7 ml / m ² · 24 hr, and still more preferably 0.05 to 5 ml / m ² · 24 hr. m ² · 24 hr. further,
The decrease rate of the oxygen gas permeability after holding the boiling water with respect to the oxygen gas permeability before holding the boiling water is preferably 200.
%, More preferably 100% or less, further preferably 50% or less.

When the thickness of the base film is 10 to 40 μm and the total thickness of the inorganic thin film layer and the coating layer is 0.5 to 5 μm, the barrier composite film of the present invention has a temperature of 40 ° C. on the coating layer surface side. The water vapor permeability at 80% RH is preferably 0.05 to 30 g / m ² · 24 hr, more preferably 0.05 to 15 g / m ² · 24 hr, and still more preferably 0.05 to 10 g / m ² · 24 hr. is there.

Further, the barrier composite film of the present invention comprises:
When it is of the above-mentioned predetermined thickness, 40 ° C., 80 ° C. on the side of the coating layer when held in boiling water at a temperature of 100 ° C. for 30 minutes.
% RH is preferably from 0.05 to
30 g / m ² · 24 hr, more preferably 0.05 to 15
g / m ² · 24 hr, more preferably 0.05 to 10 g
/ M ² · 24 hr.

The barrier composite film of the present invention comprises
The peel strength of the base film, the inorganic thin film layer and the coating layer at 60 ° C. and 60% RH is preferably 100 gf / 15 m.
m, more preferably 150 gf / 15 mm or more, even more preferably 200 gf / 15 mm or more.

Further, the barrier composite film of the present invention comprises:
23 ° C., 60 ° C. after storage at 40 ° C., 90% RH for 1 week
% RH, peel strength of the base film and the inorganic thin film layer and the coating layer is preferably 100 gf / 15 mm or more,
It is more preferably at least 150 gf / 15 mm, even more preferably at least 200 gf / 15 mm. Further, the rate of decrease in the adhesion strength after storage under the above conditions with respect to the adhesion strength before storage is preferably 70% or less, more preferably 50% or less, and further preferably 40% or less.

The oxygen gas and water vapor transmission rates are values measured at 1 atmosphere (1013.25 hPa).

Next, a method for producing the barrier composite film of the present invention will be described.

First, an inorganic thin film layer is formed on one or both surfaces of a base film. The method for forming the inorganic thin film layer is not particularly limited, and examples thereof include a vacuum deposition method, a sputtering method, an ion plating method, and a chemical vapor deposition method (C
VD) can be applied.

Next, a coating layer formed by a reaction between a silane monomer and a silane compound is formed on the inorganic thin film layer. This coating layer is formed, for example, by applying a mixture of a silane monomer, a silane compound, and a solvent, and air-drying in the air or leaving it under heated and humidified conditions.

As the solvent, acetone, toluene, 2-
Butanone, tetrahydrofuran, dioxane, diethyl ether, cyclohexanone, xylene, ethyl acetate,
Butyl acetate, dimethylformamide, methanol, ethanol, 2-propanol and the like can be used.

As a coating method, a roll coating method,
Dip coating, bar coating, nozzle coating and the like can be applied.

When the barrier composite film of the present invention is used as a packaging material, for example, in consideration of the case where it is formed into a bag, one side or both sides may be provided with a heat-sealing property in order to impart a heat-sealing property. Films may be laminated.

The barrier composite film of the present invention has a barrier property against gases such as water vapor, oxygen gas, carbon dioxide and various odor components, and of course also has a barrier property against liquids.

The barrier composite film of the present invention has a desired barrier property due to the synergistic effect of the interaction between the organic and siloxane chains in the coating layer and the properties of the base film, the inorganic thin film layer and the coating layer. The desired properties such as flexibility, mechanical strength and transparency are provided. Therefore,
The barrier composite film of the present invention is formed into a desired shape such as a bag, a tube, or a sheet, and includes confectionery, fresh food, dried food, processed meat, and other foods, sanitary goods, daily miscellaneous goods, It can be used as a film for retort treatment and microwave heating of luxury goods and foods, as a packaging film for pharmaceuticals, precision electronic parts, precision mechanical parts, etc., and as a production film for balloons and balloons.

[0066]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Synthesis Example 1 1 mol of γ-aminopropyltrimethoxysilane and 0.5 mol of resorcinol diglycidyl ether were reacted in a methanol solvent at 50 to 70 ° C. for 5 hours to obtain a silane monomer represented by the following formula (3). Was.

[0067]

Embedded image

Synthesis Example 2 1 mol of γ-aminopropyltrimethoxysilane and 0.5 mol of bisphenol A diglycidyl ether were treated in the same manner as in Synthesis Example 1 to obtain a silane monomer represented by the following formula (4).

[0069]

Embedded image

The test method in the following examples is as follows. (1) Oxygen gas permeability (ml / m ² · 24 hr) The oxygen gas permeability at a temperature of 20 ° C., 40, 60 and 80% RH, and the oxygen gas permeability when held in boiling water at 100 ° C. for 30 minutes. It was measured. The measurement was performed with an oxygen permeability measuring device (OX-TRAN 2/20, manufactured by MOCON). In addition, the test of keeping in boiling water at 100 ° C. for 30 minutes was performed on a laminate in which an unstretched polypropylene film having a thickness of about 50 μm was previously laminated on the coating layer of the barrier composite film by a dry lamination method.

Gelbotest was performed according to ASTM-E-3.
Performed according to the method specified in 92-74. The outline of the test method is as follows. For the gelbo test, a gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd., comprising a fixed disk having a thickness of 13 mm and a diameter of 87 mm, and a rotatable disk having the same dimensions and having a distance of 174 mm from the fixed disk was used. did.

First, a barrier film was wound around a rotatable movable disk and fixed. Next, the rotating movable disk was rotated 440 ° while being advanced by 89 mm in the direction of the fixed disk to twist and bend the cylindrical barrier film. Subsequently, the rotatable disk was further advanced by 64 mm without rotating. Thereafter, the above-described series of operations is performed in the reverse order,
The rotatable disk was returned to its original position. One reciprocation of such a rotatable disk was performed once (the required time was 1 second), and a total of 50 times were performed. In each case, the oxygen gas permeability at 20 ° C. and 80% RH was measured. (2) Water vapor transmission rate (g / m ² · 24 hr) Water vapor transmission rate at 40 ° C. and 90% RH, and 100 ° C.
Was measured for 30 minutes in boiling water. The measurement was performed using a steam excess ratio measuring device (PERMATR).
AN W200, manufactured by MOCON). (3) Adhesion strength of coating layer (gf / 15 mm) An unstretched polypropylene film having a thickness of about 50 μm is laminated on the coating layer of the barrier composite film by a dry laminating method, and then the thickness is reduced to 15 mm using a template. Cut. After that, a tensile tester (RTM, manufactured by Orientec, Inc.)
-100), the both ends of the barrier composite film and the unstretched polypropylene film were sandwiched between fixing fixtures facing each other at a distance of 100 mm, and T-peeling was performed at a crosshead speed of 300 mm / min. Example 1 A biaxially oriented polyethylene terephthalate (OPE) having a thickness of 12 μm was used as a base film, and the surface thereof was subjected to corona discharge treatment to obtain about 0.667 × 10 ⁻⁵ kPa (= 5 × 10 ⁵ kPa).
^-5 Torr) vacuum, using an electron beam irradiation device,
The evaporation source made of O, SiO2, etc. is heated to a thickness of 200
The silicon oxide vapor-deposited film of と し て was formed as an inorganic thin film layer (composite film 1).

Next, a mixture of the silane monomer represented by the formula (3) obtained in Synthesis Example 1 and tetramethoxysilane (weight ratio 100: 250) was dried on the silicon oxide vapor-deposited film. Was applied with a Meyer bar so that the thickness became 2.0 μm, and was naturally dried to form a coating layer, thereby obtaining a transparent barrier composite film having a thickness of about 14 μm. Each measurement shown in Table 1 was performed on this barrier composite film. Table 1 shows the results. Example 2 Biaxially stretched nylon having a thickness of 15 μm as a base film
Except that 6 films (OPA) were used, an inorganic thin film layer was formed in the same manner as in Example 1 (composite film 2), and a barrier composite film was obtained in the same manner as in Example 1.
Each measurement shown in Table 1 was performed on this barrier composite film. Table 1 shows the results. Example 3 The same OPE as in Example 1 was used as the base film, and the surface thereof was subjected to corona discharge treatment to obtain about 0.667 × 10 ⁻⁵ kPa.
Under a vacuum of (5 × 10 ⁻⁵ Torr), aluminum is heated and evaporated using an electron beam irradiator, and further reacted with oxygen in the vicinity of the base film to form an aluminum oxide deposited film having a thickness of 300 ° on an inorganic thin film. It was formed as a layer (composite film 3). Thereafter, a barrier composite film was obtained in the same manner as in Example 1. About this barrier composite film,
Each measurement shown in Table 1 was performed. Table 1 shows the results. Example 4 An inorganic thin film layer was formed in the same manner as in Example 3 except that a biaxially oriented polypropylene film (OPP) having a thickness of 20 μm was used as the base film (composite film 4), and further as in Example 3. Thus, a barrier composite film was obtained. Each measurement shown in Table 1 was performed on this barrier composite film. Table 1 shows the results. Examples 5 and 6 A barrier composite film was obtained in the same manner as in Example 1 except that the thickness of the coating layer was changed. Each measurement shown in Table 1 was performed for these barrier composite films. Table 1 shows the results
Shown in Example 7 A barrier composite film was obtained in the same manner as in Example 1 except that the silane monomer was changed to that represented by the formula (4) obtained in Synthesis Example 2. About this barrier composite film,
Each measurement shown in Table 1 was performed. Table 1 shows the results. Example 8 On the inorganic thin film layer of the composite film 1, the silane monomer represented by the formula (3) obtained in Synthesis Example 1, tetramethoxysilane and γ-aminopropyltrimethoxysilane (weight ratio: 100: 250: 50) Was applied with a Meyer bar so that the thickness after drying was 2.0 μm, and was naturally dried to form a coating layer to obtain a barrier composite film. Each measurement shown in Table 1 was performed on this barrier composite film. Table 1 shows the results. Examples 9 and 10 A barrier composite film was obtained in the same manner as in Example 8, except that the composite films 3 and 4 were used, respectively. Each measurement shown in Table 1 was performed for these barrier composite films. Table 1 shows the results. Examples 11 and 12 A barrier composite film was obtained in the same manner as in Example 8, except that the thickness of the coating layer was changed. Each measurement shown in Table 1 was performed for these barrier composite films. Table 1 shows the results
Shown in Example 13 A barrier composite film was obtained in the same manner as in Example 8, except that the silane monomer was changed to that represented by the formula (4) obtained in Synthesis Example 2. About this barrier composite film,
Each measurement shown in Table 1 was performed. Table 1 shows the results. Comparative Examples 1 to 4 The composite films 1 to 4 were set as Comparative Examples 1 to 4, and the respective measurements shown in Table 1 were performed. Table 1 shows the results. Comparative Example 5 A vinylidene chloride copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Saran Resin F216) was coated on the inorganic thin film layer of the composite film 1 with toluene / tetrahydrofuran = 1: 2.
(Weight ratio) The solution dissolved in the mixed solution was applied with a Mayer bar so that the thickness after drying was 2.0 μm. Then, it was forcibly dried in a hot air circulating oven set at 100 ° C. to form a coating layer, and a 14 μm-thick transparent composite film was obtained. Each measurement shown in Table 1 was performed on this composite film. Table 1 shows the results. Comparative Example 6 Polyvinyl alcohol having a saponification degree of 98% or more (trade name, manufactured by Kuraray Co., Ltd.) was placed on the inorganic thin film layer of the composite film 1.
(Kuraray Povar PVA105) was dispersed in ion-exchanged water cooled to 5 ° C. or lower, and then a solution heated and dissolved at 80 ° C. was applied using a Mayer bar so that the thickness after drying was 2.0 μm. Then, it was forcibly dried in a hot air circulating oven set at 100 ° C. to form a coating layer, and a 14 μm-thick transparent composite film was obtained. Each measurement shown in Table 1 was performed on this composite film. Table 1 shows the results.

[0074]

[Table 1]

As is clear from Table 1, the barrier film of the present invention has excellent oxygen gas and water vapor barrier properties,
The adhesive strength is also excellent, and their properties are not significantly reduced even after heating or when deformed by applying an external force. In addition, since the light transmittance is high, not only the visibility is excellent, but also when it is applied as a coating film at the time of microwave heating of food etc. The contents can be cooked.

[0076]

The barrier composite film of the present invention has particularly excellent barrier properties against oxygen gas and water vapor, and further has the flexibility, mechanical strength and transparency required for packaging materials.
Excellent printability and the like. Therefore, it is particularly suitable as a packaging material for various products required to suppress oxidation and drying.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Chiho Yokoe 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Ryuta Miyake 64-1-A101, Akaoji-cho, Takatsuki-shi, Osaka ( 72) Inventor Toshihide Maruyama 1-3-4-204 Shimodera, Naniwa-ku, Osaka-shi, Osaka AK03A AK41A AK42 AK46A AK48 AK52B AK80A EJ38A GB15 JD02 JD03 JD04 JK06 JN08C YY00

Claims (15)

[Claims] Claims: At least one surface of a substrate film,
A barrier composite film having a coating layer formed by a reaction between an organic chain-containing bifunctional functional silane monomer and a silane compound via an inorganic thin film layer. 2. The barrier composite film according to claim 1, wherein the base film is a biaxially stretched polyolefin film, polyester film or polyamide film. 3. The barrier composite film according to claim 1, wherein the base film contains a petroleum resin and / or a terpene. 4. An inorganic thin film layer comprising a group 2A element, a transition element, a group 2B element, a group 3B element, a group 4B element and a group 6B element of the periodic table.
4. The barrier composite film according to claim 1, which is composed of an oxide of at least one metal element selected from group III elements. 5. The barrier composite film according to claim 1, wherein the inorganic thin film layer is composed of silicon oxide. 6. The barrier composite film according to claim 1, wherein the inorganic thin film layer is made of aluminum oxide. 7. The inorganic thin film layer has a thickness of 100 to 1000.
The barrier composite film according to any one of claims 1 to 6, which is Å. 8. The barrier composite film according to claim 1, wherein the light transmittance of the inorganic thin film layer is 70% or more. 9. An organic chain-containing biterminal functional silane monomer represented by the following general formula (1):
9. The barrier composite film according to any one of 8. Embedded image [Wherein, R ₁ and R ₂ may be the same or different and each represent a hydrogen atom, an alkyl group, or an acyl group;
R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or an alkyl group, A represents a divalent organic chain having an aromatic ring, and a and b represent 1 to 3 numbers. ] 10. A silane compound represented by the following general formula (2): (R ₆ ) _4-n Si (OR ₅ ) _n (2) wherein R ₅ represents a hydrogen atom, an alkyl group or an acyl group. , R ₆ represent a hydrogen atom, an alkyl group, or an aromatic group;
Represents a number of 2 to 4. Claim 1
10. The barrier composite film according to any one of items 9 to 9. 11. The barrier composite film according to claim 1, wherein the thickness of the coating layer is 0.05 to 15 μm. 12. The ratio (T / t) of the thickness (Tμm) of the coating layer to the thickness (tμm) of the inorganic thin film layer is 0.2.
The barrier composite film according to any one of claims 1 to 11, wherein 13. The base film has a thickness of 10 to 40 μm.
m, the total thickness of the inorganic thin film layer and the coating layer is 0.5 to 5 μm
m, 20 ° C., 40, 60 and 8 on the side of the coating layer
Oxygen gas permeability at 0% RH is 0.05 to 10 ml
/ M ² · 24 hr. 14. The base film has a thickness of 10 to 40 μm.
m, the total thickness of the inorganic thin film layer and the coating layer is 0.5 to 5 μm
When a m, barrier composite film as claimed in any one of claims 3 to 12 40 ° C. of the coating layer surface, the water vapor permeability at 80% RH is 0.05~30g / m ² · 24hr. 15. The peeling strength of the base film, the inorganic thin film layer and the coating layer after storage at 40 ° C. and 90% RH for one week is 100 gf / 15 mm or more. Barrier composite film.