JPH08165366A - Gas-barrier laminate - Google Patents

Abstract

PURPOSE: To obtain a gas-barrier laminate excellent in steam resistance and oxygen permeability by laminating a gas-barrier layer containing a specified silane compound and a compound having a functional group reactive therewith and a thermoplastic film on a base material comprising a resin molding. CONSTITUTION: This laminate is produced by laminating a gas barrier layer containing at least a silane compound represented by formula I [wherein A<1> is alkylene; R<1> is H, lower alkyl or a group of formula II (wherein A<2> is a direct bond or alkylene; and R<5> and R<6> are each H or lower alkyl), and R<2> is H or lower alkyl, provided that at least one of R<1> , R<2> , R<5> and R<6> is H; R<3> is lower alkyl, aryl, etc.; R<4> is H, lower alkyl, or acyl; and w is an integer of 0 to 2, and z is an integer of 1 to 3, provided that w+z=3] and a compound having a functional group reactive with the amino group of the silane compound and one or more thermoplastic films on a base material comprising a resin molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier laminate having excellent water vapor permeation resistance and oxygen permeation resistance as well as heat sealability, printability and safety.

[0002]

2. Description of the Related Art Demand for gas barrier materials having extremely low permeability to gases such as oxygen, nitrogen, carbon dioxide and water vapor is increasing in the field of packaging materials and the like. In order to impart gas barrier properties to a molded material such as a plastic film or sheet, a molded body is made of a gas impermeable material such as an ethylene-vinyl alcohol copolymer, a vinylidene chloride copolymer, or polymethaxylylene adipamide. Methods of making, laminating or coating these gas impermeable materials on other materials, laminating aluminum foil on film materials, vapor deposition of metal oxides, etc. are known.

However, among the gas-impermeable materials, ethylene-vinyl alcohol copolymer and polymetaxylylene adipamide have a large hygroscopic property, and there is a problem that the gas barrier property is significantly lowered due to the moisture absorption. Since the vinylidene chloride-based copolymer contains a chlorine atom, it may cause pollution. Also, with the aluminum foil laminated film, the packaged contents cannot be seen from the outside,
Since the metal vapor-deposited film of (3) deteriorates flexibility and the like, there is a problem that cracks are likely to occur in the vapor-deposited layer at the time of packaging and the gas barrier property deteriorates.

In order to solve these problems, it has been researched to perform surface treatment of a plastic film using polysiloxane having a dense molecular structure and excellent in weather resistance, hardness and chemical resistance. . For example, the present inventors have already applied for a polysiloxane-based composition for surface treatment (Japanese Patent Application No. 163509/1993).

However, films treated with these compositions have a problem that the water vapor permeability may be lowered in an extremely high humidity environment, and there is room for improvement in printability, heat sealability and safety. was there.

[0006]

In view of the above problems, the present invention provides a gas barrier laminate which is excellent in water vapor resistance, heat sealability, printability, and safety, and exhibits remarkable gas barrier properties. The purpose is to do.

[0007]

The gas barrier laminate of the present invention, which has solved the above-mentioned problems, has at least a silane compound (A) represented by the following general formula (I) on a resin molded body substrate,

[0008]

Embedded image [Wherein A ¹ is an alkylene group, R ¹ is a hydrogen atom, a lower alkyl group, or

[0009]

[Chemical 4]

(In the formula, A ² represents a direct bond or an alkylene group, and R ⁵ and R ⁶ represent a hydrogen atom or a lower alkyl group)
A group represented by, R ² is a hydrogen atom or a lower alkyl group, R ³ are the same or different lower alkyl group, an aryl group or an unsaturated aliphatic residue, R ⁴ is a hydrogen atom, a lower alkyl group or an acyl group (However, R ¹ , R ² , R ⁵ , and R
^At least one of ⁶ is a hydrogen atom), w is 0,
1 or 2, z represents an integer of 1, 2, or 3 (provided that w + z = 3)] and a functional group having reactivity with an amino group in the silane compound (A). The gist is that the gas barrier layer containing the compound (B) in the molecule and a single or a plurality of layers of thermoplastic film are laminated.

It is preferable that the compound (B) is a compound having an aromatic ring or a hydrogenated ring thereof in order to enhance the gas barrier properties of the gas barrier laminate of the present invention. Moreover, since a film made of polyvinylidene chloride and / or an ethylene-vinyl alcohol copolymer has excellent gas barrier properties, use of these films as a thermoplastic film provides a laminate having even better gas barrier properties.

The gas barrier layer further has the following general formula:
The organometallic compound (C) represented by (II) may be contained. R ⁷ _m M (OR ⁸ ) _n (II) (wherein M represents a metal element, R ⁷ may be the same or different, and is a hydrogen atom, a lower alkyl group, a functional group directly bonded to a carbon chain, Represents an aryl group or an unsaturated aliphatic residue, R ⁸ may be the same or different, represents a hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, and n is an integer of 1 or more. In addition, m + n corresponds to the valence of the metal element M) Note that an adhesive layer may be provided between the thermoplastic film and the gas barrier layer or between the thermoplastic films to bond the thermoplastic film.

[0013]

The structure of the present invention is a gas barrier laminate in which a resin molded substrate is provided with a gas barrier layer, and an adhesive layer is optionally provided on the gas barrier layer to laminate a thermoplastic film, By adopting this constitution, a gas barrier laminate having excellent gas barrier properties and improved steam resistance, heat sealability, printability, and safety could be provided. Hereinafter, the present invention will be described in detail.

The gas barrier layer in the present invention is a dense chemical composed mainly of polysiloxanes obtained by reacting a silane compound (A) and a compound (B) having reactivity with an amino group in the compound (A). It is a gas barrier layer having a structure. The silane compound (A) is represented by the following general formula (I),

[0015]

Embedded image

(Wherein A ¹ , R ¹ , R ² , R ³ , R ⁴ , w,
(The meaning of z is the same as above.) It is not particularly limited as long as it is a silane compound having an amino group and a hydrolytic condensable group in the molecule.

Specific examples of the above (A) include N-β (aminoethyl) γ-aminopropyltrimethoxysilane,
N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriisopropoxysilane, N-β (aminoethyl) γ
-Aminopropyltributoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylmethyldibutoxysilane, N
-Β (aminoethyl) γ-aminopropylethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylethyldiethoxysilane, N-β (aminoethyl) γ
-Aminopropylethyldiisopropoxysilane, N-
β (aminoethyl) γ-aminopropylethyldibutoxysilane, γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiisopropoxysilane , Γ-aminopropylmethyldibutoxysilane, γ-
Aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiisopropoxysilane, γ-aminopropylethyldibutoxysilane, γ-aminopropyltriacetoxysilane, N-β- (N-vinyl Benzylaminoethyl) -γ-aminopropyltrimethoxysilane, N-β
-(N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltriethoxysilane and the like can be mentioned, and one or more of these can be used.

The compound (B) used in the present invention is required to have a functional group in the molecule which is reactive with the amino group in the silane compound (A), and the functional group is epoxy. Group, carboxyl group, isocyanate group, oxazolinyl group and the like. These functional groups have a function of cross-linking with an amino group in the silane compound (A), and it is preferable that two or more functional groups are present in the compound (B) in order to enhance the cross-linking effect. . These functional groups may be the same or different in the compound (B). From the viewpoint of reactivity with an amino group, an epoxy group or an isocyanate group is preferable. When the compound (B) has an aromatic ring or its hydrogenated ring,
This is a particularly preferred embodiment when applied in a high humidity environment because the gas barrier property can be made less dependent on humidity.

Specific examples of the compound (B) usable in the present invention include ethylene glycol diglycidyl ether,
Diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6- Aliphatic diglycidyl ethers such as hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether; glycerol triglycidyl ether,
Diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate,
Polyglycidyl ethers such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether; Aliphatic and aromatic diglycidyl esters such as adipic acid diglycidyl ester and o-phthalic acid diglycidyl ester; Bisphenol A diglycidyl ether, Resorcin diglycidyl ether, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, bisphenol F diglycidyl ether, and compounds represented by the following formula

[0020]

[Chemical 6]

Glycidyls having an aromatic ring such as or a hydrogenated ring thereof (including nuclear-substituted derivatives); or oligomers having a glycidyl group as a functional group (for example, in the case of bisphenol A diglycidyl ether oligomer, Can be represented);

[0022]

[Chemical 7]

Isocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylylene diisocyanate and dicyclohexylmethane diisocyanate;
Examples thereof include dicarboxylic acids such as tartaric acid and adipic acid; carboxyl group-containing polymers such as polyacrylic acid; oxazolinyl group-containing polymers and the like, and one or more of these can be used.

The silane compound (A) causes a hydrolysis-condensation reaction even with the compound (A) alone to form a film, but the compound (B) plays a role as a cross-linking agent with respect to the silane compound (A) and thus acts as a gas barrier layer. It has the effect of imparting flexibility to the three-dimensional network structure. That is, since it has a function to balance the molecular weight between the crosslinking points, it is recommended to use 0.1% by weight or more with respect to the silane compound (A). 0.
If it is less than 1% by weight, the flexibility of the gas barrier layer becomes insufficient. It is more preferably used in an amount of 1% by weight or more, and further preferably 10% by weight or more. On the other hand, when the amount of the compound (B) is too much, the gas barrier property which is the performance exhibited by the polysiloxane portion derived from the silane compound (A),
In addition, since the water resistance, chemical resistance, weather resistance, heat resistance and the like deteriorate, the upper limit of the compound (B) is the silane compound (A).
To 300% by weight is desirable. It is preferably 200% by weight or less, more preferably 80% by weight or less.

When a compound having an isocyanate group and / or an epoxy group in the molecule is used as the compound (B), these functional groups may undergo a hydrolysis reaction or a reaction with a solvent optionally used at the time of coating. Since they easily occur, it is necessary to prevent these side reactions in order to secure reaction points with the silane compound (A). Therefore, by reacting the compound (B) with the amino group in the silane compound (A) in advance, the silane compound (A) is hydrolyzed and condensed, and then coated on the resin molded body substrate. It is recommended to form a gas barrier layer. That is, by reacting the functional group of the compound (B) with the amino group of the silane compound (A), a compound in which the compound (B) is linked to the terminal end of the amino group of the silane compound (A) is obtained. A more dense and flexible gas barrier layer can be obtained by subjecting the alkoxysilane moiety at the other end of the silane compound (A) to a hydrolysis-condensation reaction to some extent and then forming a film under the conditions described below. .

The gas barrier layer of the present invention has the following general formula (II)
It may contain an organometallic compound (C) represented by R ⁷ _m M (OR ⁸ ) _n (II) (where M, R ⁷ , R ⁸ , m and n have the same meanings as described above)

As a specific example, tetramethoxysilane,
Tetraethoxysilane, tetraisopropoxysilane,
Tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycid Xypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,
Alkoxysilanes such as γ-chloropropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane; titanium alkoxides such as titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide; zirconium tetraethoxide, zirconium tetraisopropoxy. And zirconium alkoxides such as zirconium tetrabutoxide;
Aluminum alkoxides such as aluminum triethoxide, aluminum triisopropoxide and aluminum tributoxide; acyloxyxylans such as tetraacetoxysilane and methyltriacetoxysilane; silanols such as trimethylsilanol.
One kind or two or more kinds can be used. Alternatively, these hydrolyzed condensates may be used.

The organometallic compound (C) and / or its hydrolyzed condensate is used in an amount of 0 to 5 relative to the silane compound (A).
It is suitable to use about 00 mol%, preferably 5 to 300 mol%. If it is used in an amount of more than 500 mol%, the amino group in the silane compound (A) may be used as a catalyst to form particles, and gelation may occur rapidly, which is not preferable.

The organometallic compound (C) reacts with the silanol group of the silane compound (A) to form a siloxane bond. Therefore, the molecular weight of the gas barrier layer composition is increased, and the effect of preventing tacking of the coating film is improved. In particular, tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane can be preferably used because of their large effects.

The hydrolysis-condensation reaction of the silane compound (A) itself proceeds in the presence of water. For example, when γ-aminopropyltrimethoxysilane is used, it is represented by the following formula. H ₂ NC ₃ H ₆ -Si (OCH ₃ ) ₃ + 3H ₂ O → H ₂ NC ₃ H ₆ -Si (OH) ₃ + 3CH ₃ OH H ₂ NC ₃ H ₆ -Si (OH) ₃ → H ₂ NC ₃ H _6- SiO _3/2 +3/2 H ₂ O

Molar ratio W of silane compound (A) and water (W)
/ A is preferably 0.01 to 5.0. If it is less than 0.01, cracks are likely to occur during film formation, and it takes time to dry the film, resulting in poor productivity. W / A is more preferably 0.1 or more. If the amount of water is too much, the hydrolysis reaction proceeds and the storage stability of the gas barrier layer composition deteriorates. Therefore, W / A is 5.0 or less, preferably 2.0 or less, more preferably 0. It should be 8 or less.

In the present invention, after reacting the silane compound (A) with the compound (B), the silane compound (A) is hydrolyzed and condensed, and then the organometallic compound (C) is added, if necessary. In addition, the method of reacting is preferable because the stability of the composition for the gas barrier layer becomes the best. Alternatively, the organometallic compound (C) previously hydrolyzed and condensed may be used.

The hydrolysis polycondensation reaction proceeds in the presence of water, but when a coating method is adopted as a means for forming a gas barrier layer, it is better to carry out it in a solvent used at the time of coating. It is convenient because it can be applied as it is.
The solvent is not particularly limited as long as it is a solvent capable of sharing water such that hydrolysis condensation can proceed, but specifically, methanol, ethanol, isopropyl alcohol, butanol, pentanol, ethylene glycol,
Alcohols such as diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether and triethylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, benzene and xylene Hydrocarbons such as hexane, heptane, octane; Acetates such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate;
Others ethylphenol ether, propyl ether,
Tetrahydrofuran and the like can be mentioned, and one or more of these can be mixed and used. Of these, alcohols are preferably used. It is also desirable to carry out the above-mentioned hydrolysis condensation reaction in these solvents.

As described above, the composition for the gas barrier layer is obtained with water and the solvent used if necessary. The solid content of the composition is preferably 5 to 50% by weight.
If it is less than 5% by weight, thick coating is difficult, and it is too dilute, and as a result, the water content (W / A) easily exceeds 3.0, and the storage stability of the composition deteriorates. If it exceeds 50% by weight, the storage stability will be deteriorated. In the gas barrier layer composition used in the present invention, various inorganic and organic additives such as a curing catalyst, a wettability improver, a plasticizer, a defoaming agent, and a thickener are added within a range that does not impair the effects of the present invention. Agents can be added as needed.

In the present invention, the gas barrier layer composition is first formed into a layer on at least one side of a base material made of a resin molded body by means such as coating and dried to form a gas barrier layer. The resin molded body substrate is not particularly limited, such as a film-shaped material or a molded body such as a container. As the resin material, for example, ethylene-vinyl alcohol copolymer;
Polyvinylidene chloride resin; Polyolefin resin such as polyethylene and polypropylene; Polyethylene terephthalate, polyethylene isophthalate, polyethylene
Polyester resins such as 2,6-naphthalate, polybutylene terephthalate and their copolymers; polyoxymethylene; polyamide resins; polystyrene, poly (meth) acrylic acid ester, polyacrylonitrile, polyvinyl acetate, polycarbonate, cellophane, Polyimide, polyetherimide, polyphenylene sulfone,
Thermoplastic resins such as polysulfone, polyether ketone, ionomer resin, polyvinyl alcohol, and fluororesin; melamine resin, polyurethane resin, epoxy resin,
Phenolic resins, unsaturated polyester resins, alkyd resins, urea resins, thermosetting resins such as silicon resins, and the like, these may include known additives, surface activation treatment such as corona treatment, What carried out the well-known anchor process, such as urethane resin, may be used.

The coating method of the gas barrier layer is not particularly limited, and a roll coating method, a dip coating method, a bar coating method, a nozzle coating method, or a combination thereof is adopted. The method for drying the gas barrier layer is not particularly limited, but drying it for 1 second or longer in an environment of 50 ° C. or higher and relative humidity of 5% RH or higher improves the gas barrier property and provides high performance without variation among lots. This is preferable because the gas barrier layer of is obtained.

The thickness of the gas barrier layer of the present invention is preferably about 0.01 to 20 μm after drying. When the thickness is less than 0.01 μm, the coating film is not uniform and pinholes are easily generated, and at the same time, physical properties such as adhesion to a thermoplastic film described later and gas barrier properties as a laminate are difficult to be exhibited. 0.1 μm
The above is preferable, and 0.5 μm or more is more preferable. On the other hand, if it is thicker than 20 μm, cracks are likely to occur in the coating, which is not preferable. The thickness is preferably 10 μm or less, and more preferably 5 μm or less.

Another essential constituent layer in the laminate of the present invention is a thermoplastic film layer, which is provided on the gas barrier layer. As the thermoplastic film, one which is heat-sealable, safe, printable, and excellent in steam resistance must be used so as to meet the object of the present invention. When all of these properties cannot be covered by itself, it is recommended to laminate a plurality of thermoplastic films.

As a specific example of the thermoplastic film, a general-purpose polyolefin film such as polypropylene, polyethylene, ethylene-vinyl acetate copolymer, etc. can be heat-sealed and has excellent steam resistance, and polystyrene, polyvinylidene chloride, and Polyester such as polyethylene terephthalate has a poor heat-sealing property, but is mentioned as having excellent steam resistance. Cellophane, nylon, and ethylene-vinyl alcohol copolymer are preferably used by laminating them with another thermoplastic film, and show excellent gas barrier properties. A film obtained by coating a thermoplastic film with polyvinylidene chloride or polyacrylonitrile is also preferably used. The object to be coated may be paper or a metal material other than the resin base material exemplified above. Among the thermoplastic films, a film made of polyvinylidene chloride or an ethylene-vinyl alcohol copolymer is a very excellent gas barrier thermoplastic film, and therefore it is recommended to use them for the laminate of the present invention.

For lamination of the thermoplastic film and the gas barrier layer, dry lamination using a known adhesive, extrusion lamination method, hot melt lamination method, coating method and the like can be adopted. When the thermoplastic film is made to have a plurality of layers, the same means may be employed to carry out a plurality of laminations, or the films previously laminated by the coextrusion method or the laminating method may be laminated. The thermoplastic film that can be used in the present invention may of course contain known additives such as antistatic agents, lubricants, ultraviolet absorbers and colorants.

The adhesive that can be used at the time of lamination is not particularly limited and may be appropriately selected depending on the type of the thermoplastic film. Polyurethane-based, polyester-based, epoxy-based, alkyl titanate-based, polyethyleneimine-based, polybutadiene Examples thereof include ethylene series, ethylene-vinyl acetate copolymer series, low molecular weight polyethylene and wax. In order to improve the adhesiveness, a method using an anchor coating agent or surface treatment such as corona discharge treatment or glow discharge treatment may be performed.

The thickness of the thermoplastic film can be appropriately changed according to the application, and the thickness of one layer is in the range of 1 to 200 μm. , Preferably 10 to 100 μm, more preferably 20 to 50 μm.

Since the gas barrier laminate of the present invention has a constitution in which a thermoplastic film is laminated on a polysiloxane-based gas barrier layer, it has water vapor permeability and other gases even in an extremely high humidity environment. Permeability does not decrease, and various properties required in the field of packaging materials such as printability, heat sealability, and safety can be improved, and the field of application has greatly expanded.

[0044]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In addition, the evaluation method of the characteristic test was performed as follows. <Flexibility> Gelbo flex tester (manufactured by Rigaku Kogyo Co., Ltd.)
Stroke motion with a twist of 400 ° is performed at a speed of 40 times / min under the conditions of 20 ° C. and 65% RH, and then the oxygen transmission rate manufactured by MOCON at 20 ° C. and 90% RH is used. The oxygen permeability was measured using a measuring device, and the oxygen permeability that was more than twice the oxygen permeability before the test with the Gelbo Flex Tester was rated as ×, and the value not exceeding 2 times was rated as ◯.

<Transparency> The laminated films are visually compared, and those having no difference in transparency as compared with those before lamination are marked with ◯,
Those that caused turbidity such as white turbidity were marked with x. <Oxygen permeability> The oxygen permeability was measured at 20 ° C. and 90% RH using an oxygen permeability measuring device manufactured by MOCON (which is an original value before the flexibility test). The unit of the measured value in the table is cc / m ² · 24 hrs · atm.

<Heat Sealability> The laminated film was folded so that the outermost layer of the thermoplastic film was on the inside, and 190 ° C.
Heat sealing was performed at a sealing pressure of 2 kg / cm ² , and those that could be welded were rated as ◯ and those that were not fused were rated as x. <Water vapor permeability> According to JIS Z 0208 method. The unit of the measured value in the table is g / m ² · 24 hrs.

Example 1 A flask equipped with a stirrer, a thermometer and a condenser was charged with γ-
40 g of aminopropyltrimethoxysilane (hereinafter abbreviated as APTMS) and 50 g of toluene were charged and heated to 70 ° C. Then resorcinol diglycidyl ether 22
g and toluene 10g mixed solution was added dropwise in 20 minutes, and the temperature was 70 ° C.
After keeping at room temperature for 3 hours, methanol 18g and water 1.25g
The mixture was added and the mixture was aged for 1 hour while being cooled to 30 ° C., then 42 g of tetramethoxysilane and 5 parts of toluene were added.
0 g was added to obtain Composition 1 for gas barrier layer. This composition was applied to a 12 μm PET film so that the thickness after drying would be 3 μm, and dried at 100 ° C. and 20% RH for 5 seconds.

To this film, an adhesive prepared by mixing urethane coating agents A310 and A3 manufactured by Takeda Pharmaceutical Co., Ltd. in a ratio of 10: 1 (weight ratio) was applied so that the thickness after drying would be 0.5 μm, and dried. Then, a polypropylene film having a thickness of 50 μm was attached to obtain a laminated film 1. The characteristic test evaluation results are shown in Table 1.

Examples 2 to 11 Example 1 except that various conditions were changed as shown in Table 1.
A laminated film was obtained in the same manner as in. The characteristic test evaluation results are shown in Table 1.

Example 12 AT was placed in a flask equipped with a stirrer, thermometer and condenser.
40 g of PMS and 50 g of methanol were charged and heated to 70 ° C. Then, a mixed solution of 10 g of bisphenol A diglycidyl ether and 10 g of toluene was added dropwise over 20 minutes to give 7
After keeping at 0 ° C for 3 hours, 18 g of methanol and 1.2 of water were added.
5 g of the mixed solution was added, and the mixture was aged for 1 hour while being cooled to 30 ° C. to obtain a gas barrier layer composition. This composition was applied to a 12 μm PET film and dried in the same manner as in Example 1, and laminated on a 100 μm polypropylene film.
Table 1 shows the characteristic test evaluation results of the obtained laminated film.

Comparative Example 1 AT was placed in a flask equipped with a stirrer, a thermometer and a condenser.
40 g of PMS, 70 g of methanol and 1.5 g of water were charged and reacted at 30 ° C. for 2 hours to obtain a composition for a gas barrier layer for comparison. This composition was treated in the same manner as in Example 1 with 12 μm.
It was coated on an mPET film, dried, and laminated with 50 μm polypropylene. Table 1 shows the characteristic test evaluation results of the obtained comparative laminated film 1.

Comparative Example 2 The composition 1 for gas barrier layer obtained in Example 1 was 12 μm thick.
It was applied to a PET film so that the thickness after drying would be 3 μm, and dried at 100 ° C. and 20% RH for 5 seconds. Table 1 shows the results of the characteristic test evaluation of the obtained comparative film 2.

[0053]

[Table 1]

The abbreviations of the compounds used in Table 1 are as follows. APTMS: γ-aminopropyltrimethoxysilane APTES: γ-aminopropyltriethoxysilane MS: Tetramethoxysilane ES: Tetraethoxysilane MMS: Methyltrimethoxysilane TTB: Titanium tetrabutoxide RDGE: Resorcinol diglycidyl ether BisADGE: Bisphenol A di Glycidyl ether EGDGE: Ethylene glycol diglycidyl ether XDI: Xylylene diisocyanate CPP: Unstretched polypropylene film PVDC: Stretched polyvinylidene chloride film EVOH: Stretched ethylene-vinyl alcohol copolymer film PVDCcortOPP: PVDC is coated on a stretched polypropylene film of 50 μm to 3 μm. Film OPP: Stretched polypropylene film PAN : Stretched polyacrylonitrile film

As is clear from Table 1, all the gas barrier laminates of the present invention showed good characteristics. In Comparative Example 1 using only the silane compound A, the oxygen permeability is inferior, and it cannot be used in applications requiring gas barrier properties.
Further, in the case of Comparative Example 2 in which the thermoplastic film was not laminated, there was no heat-sealing property and the water vapor permeability was low.

[0056]

Since the gas barrier laminate of the present invention has a structure in which a thermoplastic film is laminated on a polysiloxane-based gas barrier layer, it has water vapor permeability and other properties even in an extremely high humidity environment. Gas permeability does not decrease. Also, while maintaining high gas barrier properties, printability,
Since various properties required in the field of packaging materials such as heat sealability and safety could be improved, the field of application has greatly expanded.

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Claims (5)

[Claims] 1. A silane compound (A) represented by the following general formula (I) on a resin molded body substrate: [Wherein A ¹ is an alkylene group, R ¹ is a hydrogen atom, a lower alkyl group, or (In the formula, A ² is a direct bond or an alkylene group, and R ⁵ and R ^{6 are}
Is a hydrogen atom or a lower alkyl group), R ² is a hydrogen atom or a lower alkyl group, R ³ is the same or different lower alkyl group, an aryl group or an unsaturated aliphatic residue, and R ⁴ is a hydrogen atom. , A lower alkyl group or an acyl group (provided that at least one of R ¹ , R ² , R ⁵ and R ⁶ is a hydrogen atom), w is 0, 1 or 2 and z is 1 or 2. Which represents any integer of 3 (provided that w + z = 3)] and a compound (B) having in the molecule a functional group having reactivity with an amino group in the silane compound (A). And a single or a plurality of layers of thermoplastic films are laminated, a gas barrier laminate. 2. The gas barrier laminate according to claim 1, wherein the compound (B) according to claim 1 is a compound having an aromatic ring or a hydrogenated ring thereof. 3. The gas barrier laminate according to claim 1, wherein at least one layer of the thermoplastic film according to claim 1 is a polyvinylidene chloride and / or ethylene-vinyl alcohol copolymer film. 4. The gas barrier laminate according to claim 1, wherein the gas barrier layer further contains an organometallic compound (C) represented by the following general formula (II). body. R ⁷ _m M (OR ⁸ ) _n (II) (wherein M represents a metal element, R ⁷ may be the same or different, and is a hydrogen atom, a lower alkyl group, a functional group directly bonded to a carbon chain, Represents an aryl group or an unsaturated aliphatic residue, R ⁸ may be the same or different, represents a hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, and n is an integer of 1 or more. And m + n matches the valence of the metal element M) 5. Between the gas barrier layer and the thermoplastic film,
Alternatively, a gas barrier laminate having an adhesive layer laminated between thermoplastic films.