JP3248374B2 - Gas barrier laminate - Google Patents

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 which is excellent in water resistance, chemical resistance, weather resistance, heat resistance, and flexibility, and exhibits remarkable gas barrier properties.

[0002]

2. Description of the Related Art There is an increasing demand for gas barrier materials having extremely low permeability of gases such as oxygen, nitrogen, carbon dioxide, water vapor and the like in the field of packaging materials and the like. Gas barrier materials
A molded article is made of a gas-impermeable material such as an ethylene-vinyl alcohol copolymer (EVOH), a vinylidene chloride-based copolymer, and polymethaxylylene adipamide. These gas-impermeable materials are used as other materials. Laminate or coat, Laminate aluminum foil to film-like material, Polyester aluminum or inorganic compound,
It is manufactured by a method such as vapor deposition on a film having relatively high rigidity and heat resistance such as biaxially oriented polyester stretched polypropylene.

However, it is no longer possible to achieve the gas barrier properties actually required by using gas-impermeable materials alone, and to provide higher gas barrier materials by laminating or coating means. Is being considered. On the other hand, in the case of the aluminum foil laminated film, the packaged contents cannot be seen from the outside, and some metal or inorganic compound vapor-deposited films are transparent. There is also a problem in adhesion, and gas barrier properties cannot be stably exhibited for a long period of time.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a gas barrier laminate having excellent adhesion of a deposited film and exhibiting a remarkable gas barrier property in consideration of the above problems.

[0005]

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

[0006]

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

[0007]

Embedded image

Wherein 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.
R ² represents a hydrogen atom or a lower alkyl group, R ³ represents the same or different lower alkyl group, aryl group or unsaturated aliphatic residue, and R ⁴ represents a hydrogen atom, a lower alkyl group or an acyl group. (However, R ¹ , R ² , R ⁵ , R
⁶ is at least one hydrogen atom), w is 0,
Any one of 1, 2 and z represents an integer of 1, 2, or 3 (w + z = 3)] and a compound having an epoxy group in the molecule and having an aromatic ring or a hydrogenated ring thereof. The gist lies in that a gas barrier adhesive layer containing (B) and a gas barrier vapor deposition layer are laminated.

Since the compound (B) is a compound having an aromatic ring or a hydrogenated ring thereof, the interlayer adhesion of the gas barrier laminate of the present invention is improved, and the gas barrier property is also improved. In particular, excellent gas barrier properties can be exhibited regardless of the use environment humidity.

It is also a preferred embodiment that the gas-barrier vapor-deposited layer of the present invention is a glass-deposited layer, particularly a silica-deposited layer, or a metal-deposited layer, particularly an aluminum-deposited layer, because it exhibits good gas-barrier properties. The gas barrier adhesive layer may further include an organometallic compound (C) represented by the following general formula (II). R ⁷ _mM (OR ⁸ ) _n (II) (wherein M represents a metal element, and R ⁷ may be the same or different and include 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 and 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 is equal to the valence of the metal element M)

[0011] The gas barrier laminate of the present invention may be a laminate in which a thermoplastic film is further laminated on the vapor deposition layer. According to this configuration, the flexibility is further improved and Printability, heat sealability, and the like can be imparted to the laminate.

[0012]

According to the present invention, instead of providing a vapor-deposited layer directly on a resin molded product substrate, a gas-barrier adhesive layer is first provided on the substrate, and further a vapor-deposited layer is provided, that is, the laminated structure is the maximum. It has the characteristics of By adopting this configuration, the gas-barrier vapor-deposited layer is surely adhered and the adhesive layer itself exhibits excellent gas-barrier properties, so that the laminate obtained in the present invention exhibits remarkable gas-barrier properties.

[0013] The gas barrier adhesive layer in the present invention is a dense layer mainly composed of a polysiloxane 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 unique chemical structure. The silane compound (A) has the following general formula
(I),

[0014]

Embedded image

(Where A ¹ , R ¹ , R ² , R ³ , R ⁴ , w,
The meaning of z is the same as described above. There is no particular limitation 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-aminopropylethyl dibutoxysilane, 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 needs to have a functional group having reactivity with an amino group in the silane compound (A) in the molecule. Epoxy groups are preferred from the viewpoint of reactivity with the groups. This functional group has a function of performing a cross-linking reaction with an amino group in the silane compound (A), and in order to enhance the cross-linking effect, it is preferable that two or more functional groups are present in the compound (B). In addition, the compound (B) needs to have an aromatic ring or a hydrogenated ring thereof, thereby improving the adhesiveness to the vapor deposition layer and exhibiting excellent gas barrier properties regardless of the humidity of the atmosphere. .

Specific examples of the compound (B) that can be used in the present invention include bisphenol A diglycidyl ether, resorcin diglycidyl ether, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, bisphenol F diglycidyl ether, and the following formula: Compounds represented

[0019]

Embedded image

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

[0021]

Embedded image

And one or more of these.
More than one species can be used.

The silane compound (A) alone causes a hydrolysis-condensation reaction to form an adhesive layer even when the compound (A) alone is used, whereas the compound (B) acts as a crosslinking agent for the silane compound (A), This has the effect of imparting flexibility to the three-dimensional network structure of the layer. 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 based on the silane compound (A). If the amount is less than 0.1% by weight, the flexibility of the adhesive layer becomes insufficient. More preferably, it is used in an amount of 1% by weight or more, further preferably 10% by weight or more. On the other hand, when the amount of the compound (B) is too large, the gas barrier property, which is a performance exhibited by the polysiloxane portion derived from the silane compound (A), and other properties such as water resistance, chemical resistance, weather resistance, and heat resistance deteriorate. Therefore, it is desirable that the upper limit of the compound (B) be 300% by weight based on the silane compound (A). 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 can be used for a hydrolysis reaction or a reaction with a solvent used as required at the time of coating. It is necessary to prevent these side reactions in order to secure a reaction point with the silane compound (A). Therefore, the compound (B) is reacted in advance with the amino group in the silane compound (A), and then the silane compound (A) is subjected to a hydrolysis-condensation reaction, followed by coating on the resin molded product base material. It is recommended to form an adhesive 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 connected to the amino group terminal of the silane compound (A) is obtained. After a certain degree of hydrolysis-condensation reaction with the alkoxysilane portion at the other end of the silane compound (A) (this is a composition for an adhesive layer), and then forming a film under the conditions described below, it is possible to obtain a denser and more viable product. An adhesive layer having flexibility can be obtained.

The adhesive layer of the present invention may contain an organometallic compound (C) represented by the following general formula (II). R ⁷ _mM (OR ⁸ ) _n (II) (wherein, M, R ⁷ , R ⁸ , m, and n have the same meanings as described above)

Specific examples include 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 and titanium tetrabutoxide; zirconium tetraethoxide and zirconium tetraisopropoxy Zirconium alkoxides such as zirconium tetrabutoxide;
Aluminum alkoxides such as aluminum triethoxide, aluminum triisopropoxide and aluminum tributoxide; acyloxysilanes such as tetraacetoxysilane and methyltriacetoxysilane; and silanols such as trimethylsilanol.
Species or two or more can be used. Alternatively, these hydrolysis condensates may be used.

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

The organometallic compound (C) reacts with a silanol group of the silane compound (A) to form a siloxane bond. For this reason, the molecular weight of the composition for an adhesive layer is increased, and the effect of preventing tacking of a coating film is improved. Particularly, tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane can be preferably used because the above-mentioned effects are large.

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

The molar ratio W of the silane compound (A) and water (W)
/ A is preferably 0.01 to 5.0. If it is smaller than 0.01, cracks are easily generated at the time of forming the coating film,
Further, 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 large, the hydrolysis reaction proceeds, and the storage stability of the coating liquid deteriorates.
0 or less, preferably 2.0 or less, more preferably 0.8
The following is assumed.

In the present invention, after reacting the silane compound (A) with the compound (B), a hydrolysis-condensation reaction of the silane compound (A) is performed, and then, if necessary, the organometallic compound (C) is converted. In addition, a method of reacting is preferable because the stability of the composition for an adhesive layer is the best. Moreover, the thing which hydrolyzed and condensed the organometallic compound (C) previously may be used.

The hydrolysis-condensation polymerization reaction proceeds in the presence of water. For example, when a coating method is used as a means for forming an adhesive layer, it is better to perform the reaction in a solvent used for coating. It is convenient because it can be coated as it is. The solvent is not particularly limited as long as it is a solvent that can share water enough to allow hydrolysis and condensation to proceed.Specifically, methanol, ethanol, isopropyl alcohol, butanol, pentanol, ethylene glycol, diethylene glycol, triethylene Alcohols such as 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; hexane; Hydrocarbons such as heptane and octane; acetates such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; other ethylpheno Ether, propyl ether, tetrahydrofuran and the like, can be used as a mixture of one or more of these. Of these, alcohols are preferably used. It is desirable to carry out the above-mentioned hydrolysis-condensation reaction in these solvents.

As described above, a composition for an adhesive layer can be obtained by using water and a solvent used as required. The solid content of the composition is preferably 5 to 50% by weight. If the content is less than 5% by weight, thick coloring is difficult, and the composition is too dilute, so that the water content (W / A) tends to exceed 3.0, and the storage stability of the composition deteriorates. Even if it exceeds 50% by weight, the storage stability deteriorates. In the adhesive layer composition used in the present invention, various inorganic and organic additives such as a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent, and a thickener are added as long as the effects of the present invention are not impaired. Agents can be added as needed.

In the present invention, the adhesive layer composition is first formed into a layer by means such as coating on at least one surface of a substrate made of a resin molded product, and dried to form an adhesive layer. The resin molded body substrate is not particularly limited, such as a film-like material or a molded body such as a container. Examples of the resin material include ethylene-vinyl alcohol copolymer; polyvinylidene chloride-based resin; polyolefin-based resin such as polyethylene and polypropylene; polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and the like. Polyoxymethylene; Polyamide resin; Polystyrene, poly (meth) acrylate, polyacrylonitrile, polyvinyl acetate, polycarbonate, cellophane, polyimide, polyetherimide, polyphenylene sulfone, polysulfone , Polyether ketone, ionomer resin, polyvinyl alcohol, thermoplastic resin such as fluorine resin; melamine resin, polyurethane resin, epoxy resin, phenol Fats, unsaturated polyester resins, alkyd resins, urea resins, thermosetting resins such as silicon resins, and the like, which may contain known additives, surface activation treatment such as corona treatment, and urethane. Known anchor treatments such as resin may be performed.

In the present invention, in order to obtain a laminate having the highest gas barrier properties, a base material having a resin excellent in gas barrier properties, such as an ethylene-vinyl alcohol copolymer or a polyvinylidene chloride resin, is used. It is preferred to use.

The method for coating the adhesive layer is not particularly limited.
Roll coating, dip coating, bar coating, nozzle coating, or a combination thereof is employed. The method for drying the adhesive layer is not particularly limited, but drying in an environment of 50 ° C. or more and a relative humidity of 5% RH or more for 1 second or more improves gas barrier properties and ensures high performance without variation between lots. Is preferred because an adhesive layer of

The thickness of the adhesive layer of the present invention after drying is 0.0
It is preferably about 1 to 20 μm. When the thickness is less than 0.01 μm, the coating is not uniform and pinholes are easily generated, and physical properties such as adhesion to a vapor deposition layer described later and gas barrier properties as a laminate are hardly exhibited. 0.1 μm or more is preferable,
It is more preferably at least 0.5 μm. On the other hand, when the thickness is more than 20 μm, cracks are easily generated in the coating film, 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 gas barrier vapor deposition layer, and the vapor deposition layer is provided on the adhesive layer.

As the gas barrier vapor deposition layer, a vapor deposition layer of a glass material or a metal vapor deposition layer can be selected.
Silica (silicon oxide) is preferable as the material for the glass vapor deposition layer, and aluminum is preferable for the metal vapor deposition layer.
Since the adhesive layer of the present invention is a polysiloxane-based layer, when a Si-based material is used as a material for the vapor deposition layer, the adhesion between the adhesive layer and the vapor deposition layer is greatly enhanced, and the vapor deposition layer is made uniform. Can be. In addition, since the vapor deposition layer has excellent flexibility, cracks and the like do not occur, and a high-performance gas barrier laminate can be provided. Note that such actions and effects were also observed when the deposited layer was made of aluminum.

As a vapor deposition method, a physical vapor deposition method (P vapor deposition method, sputtering method, ion plating method, etc.) may be used.
A known method such as VD) or chemical vapor deposition (CVD) can be employed. The thickness of the deposited film is not particularly limited, but is about 50 to 5000 °.

For the purpose of further improving the flexibility of the gas barrier laminate of the present invention and imparting printability, heat sealability and the like, it is also possible to laminate a thermoplastic film on the above-mentioned vapor deposited layer. . Specific examples of the thermoplastic film include polypropylene, polyethylene, ethylene-vinyl acetate copolymer, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, cellophane, nylon, polyacrylic resin, and ethylene-vinyl alcohol copolymer. Coalescence, polyvinyl alcohol and the like. As a laminating method, a known method such as a dry laminating method, an extrusion method, or a hot melt laminating method can be adopted, and a known adhesive can be used at that time.

[0041]

EXAMPLES 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. <Oxygen Permeability> Measured under the conditions of a temperature of 20 ° C. and a humidity of 90% RH using an oxygen permeability measuring device manufactured by MOCON. The unit of the measured value in the table is cc / m ² · 24 hrs
-It is atm. <Oxygen permeability after boiling> After boiling for 10 minutes in boiling water,
The measurement was carried out under the conditions of a temperature of 20 ° C. and a humidity of 90% RH using an oxygen permeability measuring device manufactured by MOCON.

<Water vapor permeability> JIS Z 0208
It was measured according to Method B. The unit of the measured value in the table is g / m
A ² · 24hrs. <Flexibility> The film was bent at 180 °, and those with cracks were evaluated as x, and those without cracks were evaluated as ○.

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. Next, resorcinol diglycidyl ether 22
g and 10 g of toluene were added dropwise in 20 minutes.
After holding for 3 hours, methanol 18g and water 1.25g
Was added and the mixture was aged for 1 hour while cooling to 30 ° C., and then 42 g of tetramethoxysilane and 50 parts of toluene were added.
g was added to obtain Composition 1 for a gas barrier layer. This composition was applied to a 12 μm polyethylene terephthalate (PET) film so that the thickness after drying became 3 μm.
It was dried at 0 ° C. and 20% RH for 5 seconds to obtain a substrate coating film 1. The film 1 was set in a high-frequency induction heating film deposition machine, and silicon monoxide was deposited at a rate of 80 m / min under a vacuum of 10 ^-4 Torr. The thickness of the deposited layer of the obtained deposited film 1 was 500 °. The properties of the deposited film 1 were tested, and the results are shown in Table 1.

Examples 2 to 5 Example 1 was repeated except that various conditions were changed as shown in Table 1.
A vapor deposition film was prepared in the same manner as described above, and a characteristic test was performed. The results are shown in Table 1.

Example 6 AP was placed in a flask equipped with a stirrer, a thermometer and a cooler.
40 g of TMS and 50 g of methanol were charged and heated to 70 ° C. Next, bisphenol A diglycidyl ether 1
A mixture of 0 g and 10 g of toluene was added dropwise in 20 minutes.
C. for 3 hours, then methanol (18 g) and water (1.25)
g of the mixed solution was added, and the mixture was aged for 1 hour while cooling to 30 ° C. to obtain a composition for a gas barrier layer. Using this composition, application was performed in the same manner as in Example 1, and then evaporation was performed to obtain an evaporation film 6. Table 1 shows the results of the property test of the deposited film 6.

Example 7 An adhesive obtained by mixing a 10: 1 (weight ratio) urethane coating agent A310 and A3 made by Takeda Pharmaceutical Co., Ltd. with the vapor-deposited film obtained in Example 1 was dried to a thickness of 0%. It was applied so as to have a thickness of 0.5 μm, dried, and then bonded to a 50 μm-thick polypropylene film. The flexibility of this laminate is ○,
The oxygen permeability was 0.2 cc / m ² · 24 h before the boiling test.
rs · atm, after boiling is 0.5cc / m ² · 24hrs
-It was atm. The water vapor permeability is 0.3 g /
m was ² · 24hrs.

Example 8 The substrate coating film 1 prepared in Example 1 was set in a high-frequency induction heating type vapor deposition machine for a film, and 10 ^-4.
Under a Torr vacuum, 99.9% pure aluminum was deposited at a rate of 200 m / min. The thickness of the deposited layer of the obtained deposited film was 400 °. A polypropylene film was bonded to this vapor-deposited film in the same manner as in Example 7. The flexibility of this laminate was ○, and the oxygen permeability was 0.6 cc / m ² · 24 hrs · at before the boiling test.
m, after boiling, was 1.1 cc / m ² · 24 hrs · atm. The water vapor transmission rate is 0.6 g / m ² · 24.
hrs.

Comparative Example 1 AP was placed in a flask equipped with a stirrer, a thermometer and a cooler.
40 g of TMS, 70 g of methanol and 1.5 g of water were charged and reacted at 30 ° C. for 2 hours to obtain a composition 1 for comparison. Using this composition, coating was performed in the same manner as in Example 1, and then vapor deposition was performed to obtain a vapor-deposited film 1 for comparison. Table 1 shows the results of the property test of the comparative deposited film 1.

Comparative Example 2 Using a 20 μm OPP (biaxially oriented polypropylene) film, silicon monoxide was deposited in the same manner as in Example 1. The thickness of the deposited layer was 500 °. Table 1 shows the results of the characteristic test of the comparative vapor-deposited film 2.

Comparative Example 3 Aluminum was deposited in the same manner as in Example 7 using a 20 μm OPP (biaxially oriented polypropylene) film. The thickness of the deposited layer was 400 °. On the evaporation layer,
A polypropylene film was attached in the same manner as in Example 10. Table 1 shows the results of the characteristic test of the comparative vapor-deposited film 3.

[0051]

[Table 1]

The abbreviations of the compounds used in Table 1 are as follows. APTMS: γ-aminopropyltrimethoxysilane APTES: γ-aminopropyltriethoxysilane MS: Tetramethoxysilane ES: Tetraethoxysilane RDGE: Resorcinol diglycidyl ether BisADGE: Bisphenol A diglycidyl ether PET: Stretched polyethylene terephthalate film OPP: Stretched Polypropylene film ONy: stretched nylon 6 film EVOH: stretched ethylene-vinyl alcohol copolymer film

[0053]

The gas-barrier laminate of the present invention has a structure in which an adhesive layer having excellent gas barrier properties is provided under a vapor-deposited layer, so that the adhesion of the vapor-deposited layer is greatly enhanced and the vapor-deposited layer is made uniform. I was able to plan. In addition, by combining the vapor deposition layer of the present invention with the adhesive property, the performance of both flexibility and gas barrier properties is improved, so that there is no inconvenience such as crack generation, and good gas barrier properties are obtained even after boiling treatment. The gas barrier laminate shown below could be provided. Further, by laminating a thermoplastic film on a vapor deposition layer, a gas barrier laminate having more excellent flexibility can be provided, and printability, heat sealability, and the like can be imparted by selecting a film type. Became. The gas barrier laminate of the present invention is useful for packaging materials, storage containers and the like.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-345383 (JP, A) JP-A-5-331417 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C08J 7/04

Claims (7)

(57) [Claims] 1. A silane compound (A) represented by the following general formula (I) on a resin molded product base material: Wherein A ¹ is an alkylene group, R ¹ is a hydrogen atom, a lower alkyl group, or Wherein A ² represents a direct bond or an alkylene group, R ⁵ and R ^{6 each} represent a hydrogen atom or a lower alkyl group, R ² represents a hydrogen atom or a lower alkyl group, and R ³ represents the same or different lower alkyl group. An alkyl group, an aryl group or an unsaturated aliphatic residue, R ⁴ represents 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 represents any of 0, 1, and 2 and z represents an integer of 1, 2, or 3 (provided that w + z = 3)], and having an epoxy group in the molecule and an aromatic ring or its aromatic ring. A gas-barrier laminate comprising a gas-barrier adhesive layer containing a compound having a hydrogenated ring (B) and a gas-barrier vapor-deposited layer. 2. The gas barrier laminate according to claim 1, wherein the gas barrier vapor deposition layer is a glass vapor deposition layer. 3. The gas barrier laminate according to claim 2, wherein the glass-deposited layer is a silica-deposited layer. 4. The gas barrier laminate according to claim 1, wherein the gas barrier vapor deposition layer is a metal vapor deposition layer. 5. The gas barrier laminate according to claim 4, wherein the metal deposition layer is an aluminum deposition layer. 6. The gas barrier according to claim 1, wherein the gas barrier adhesive layer further contains an organometallic compound (C) represented by the following general formula (II). Laminate. R ⁷ _mM (OR ⁸ ) _n (II) (wherein M represents a metal element, and R ⁷ may be the same or different and include 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 and 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 is equal to the valence of the metal element M) 7. A gas-barrier laminate comprising a gas-barrier laminate according to claim 1 and a thermoplastic film further laminated thereon.