JP3403880B2 - Transparent gas barrier laminated film and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transparent gas-barrier laminated film and a method for producing the same, and more specifically to optical isotropy, flatness, solvent resistance, water vapor barrier property, gas barrier property and flexibility. In addition to the excellent characteristics,
The present invention relates to a transparent gas barrier laminate film having good adhesion between layers, a liquid crystal display device, a photoconductive photoreceptor,
It can be used as a surface light emitter, a transparent substrate for optics such as organic electroluminescence, and the like.

[0002]

2. Description of the Related Art A glass substrate is generally used as a transparent substrate which has been increasingly applied to liquid crystal display devices and the like. However, in recent years, liquid crystal display elements are required to be lighter and larger, and in addition to high requirements for long-term reliability, freedom of shape, curved surface display, etc., it is difficult to make a large area which is heavy and easily broken. Film substrates made of transparent plastic or the like have been studied in place of ordinary glass substrates. Further, the plastic substrate not only meets the above-mentioned requirements, but also has a roll-to-roll system, which is advantageous in terms of productivity and cost reduction as compared with the glass substrate.

A transparent substrate having such a transparent plastic as a substrate and further improving the adhesiveness between a plastic film and an oxygen gas barrier layer made of a polyvinyl alcohol-based resin and further having a water vapor gas barrier property is disclosed in Japanese Patent Publication No. 52002/1993. It is described in, for example, Japanese Patent Publication No. 5-52003.

However, these have insufficient solvent resistance because polyvinyl alcohol is laminated on the outermost layer. Since solvent resistance is particularly required at the time of washing with an organic solvent in the liquid crystal cell manufacturing process and at the time of forming an alignment film, it is necessary to further provide a solvent resistant film on the transparent substrate, which results in a high cost.

[0005]

In the case of a transparent substrate such as a liquid crystal display element, there are the following requirements or problems regarding the characteristics in addition to the above requirements for solvent resistance.

If the substrate has low transparency or has birefringence, problems such as coloring of display and deterioration of contrast occur.

When the flatness is low, the gap of the liquid crystal layer is not uniform, and the liquid crystal alignment is uneven.
Since the substrate itself also has optical unevenness, the display color also becomes uneven.

Further, when a substrate having a poor oxygen gas barrier property and a water vapor barrier property is used, air and water vapor permeate and bubbles are generated inside the liquid crystal cell, which becomes a display impossible point and deteriorates the display quality of the display. This drawback becomes easy to occur and becomes a serious problem, especially under harsh conditions such as vehicle mounting.

Furthermore, since the flatness, transparency, and gas barrier property of these materials are easily deteriorated by mechanical and thermal influences, practicality utilizing the features of lightness and thinness, freedom of shape, and curved surface display is achieved. This makes it difficult to adapt to applications such as pagers, mobile phones, electronic organizers, and pen input devices that are greatly affected by external influences. In particular, in order to maintain such characteristics with respect to mechanical influence, good adhesion between the laminated layers is also required for manifesting the characteristics.

The present invention is intended to solve such a problem, and in a transparent gas barrier laminate film having a metal oxide layer having excellent gas barrier properties, it has excellent solvent resistance and, as described above, It is an object of the present invention to provide a transparent gas barrier laminate film which is excellent in transparency, optical isotropy, flatness and water vapor barrier property and has good adhesion between layers.

[0011]

The above object is to provide a (partial) hydrolyzate of a metal oxide layer and a specific alkoxysilane, a (partial) condensate thereof, or a mixture thereof on at least one surface of a transparent polymer film. The present invention has been completed based on the finding that a cured coating layer containing polyvinyl alcohol cross-linked with is achieved by a laminated film sequentially formed.

That is, the present invention relates to a transparent gas barrier laminate film having a metal oxide layer on at least one side of a transparent polymer film, in contact with the metal oxide layer, and on the outside thereof, the following general formula (1) A transparent gas barrier laminate film, characterized in that a cured coating containing polyvinyl alcohol crosslinked by a (partial) hydrolyzate of alkoxysilane, a (partial) condensate thereof, or a mixture thereof is laminated. is there.

R ¹ _n -Si (OR ² ) _4-n ... (1) (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms; a vinyl group; or a methacryloxy group, an amino group, an epoxy group And an organic group having at least one group selected from the group consisting of mercapto groups, R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2.)

The present invention also comprises the following (a) to (d) after forming a metal oxide layer (A layer) on at least one side of a transparent polymer film by a vapor phase growth method, and (a) ) /
(B) = 5/1 to 1/2 (weight ratio), pH 3-1
The method for producing a transparent gas barrier laminate film is characterized in that the coating agent layer adjusted to 1 is applied onto the layer A, and then the coating agent layer is heated to form a cured film. (A) polyvinyl alcohol, (b) the general formula (1)
(Partial) hydrolyzate of alkoxysilane, its (partial) condensate or mixtures thereof, (c) curing catalyst, and (d) solvent containing 50% by weight or more of a polyvinyl alcohol-soluble solvent in all solvents

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

When used for a transparent electrode of a liquid crystal display, the laminated film of the present invention has transparency such that the light transmittance at 550 nm is 80% or more and the retardation value is 30.
It is preferably nm or less. If the light transmittance at 550 nm is less than 80%, the image quality is not practically sufficient, and if the retardation value exceeds 30 nm, there are problems in terms of coloring and viewing angle characteristics.

In the present invention, examples of the transparent polymer film include transparent plastic films such as polyester, polycarbonate, polyarylate, polysulfone, and polyethersulfone. Among them, the transparency and the optical anisotropy are preferable. Polycarbonate and polyarylate films are more suitable from the viewpoint of the optical property of less property.

Examples of the metal oxide layer forming the layer A of the present invention include transparent insulating metal oxide layers of silicon, aluminum, magnesium, zinc and the like, and these transparent metal oxide layers are known. It is produced by a vapor phase growth method such as a sputtering method, a vacuum vapor deposition method, an ion plating method, a plasma CVD method, or the like, in which a material is vapor-deposited on a substrate film to form a film. Among them, as the metal oxide of the water vapor barrier layer, silicon oxide is particularly preferable in terms of adhesion to the transparent polymer film and the B layer, transparency, surface flatness, flexibility, film stress, cost and the like. preferable.

The composition of silicon oxide is determined by X-ray photoelectron spectroscopy,
It is analyzed and determined by X-ray microspectroscopy, Auger electron spectroscopy, Rutherford backscattering method, etc., but in terms of transmittance in the visible light region, flexibility, etc., the x value in the average composition represented by SiOx is The range of 1.5 ≦ x ≦ 2 is preferable. When the x value is less than 1.5, the flexibility and transparency deteriorate.

The layer A has a thickness of 5 nm to 200 nm.
Is preferred. If the thickness of the layer A is less than 5 nm, it is difficult to form a film uniformly, and a part where the film is not formed is generated, and water vapor permeates from this part, and the water vapor barrier property deteriorates, or the layer is further laminated thereon. When it does, it peels from such a part, and the adhesiveness deteriorates. On the other hand, 20
If it exceeds 0 nm, not only is the transparency poor, but the flexibility is poor and cracks occur, impairing the water vapor barrier property.

The cured coating containing polyvinyl alcohol crosslinked by the (partial) hydrolyzate of alkoxysilane, its (partial) condensate or a mixture thereof, which gives the layer B of the present invention, comprises (a) polyvinyl alcohol, (b) ) A (partial) hydrolyzate of alkoxysilane, its (partial) condensate or a mixture thereof, (c) a curing catalyst, and (d) a polyvinyl alcohol-soluble solvent in the total amount of solvent,
It can be obtained by applying a coating agent composed of a solvent containing 50% by weight or more and heating and curing it.

Here, (a) polyvinyl alcohol means one obtained by partial hydrolysis or complete hydrolysis of polyvinyl ester such as polyvinyl acetate. Among them, the average degree of polymerization is 250 to 3000 and the degree of saponification is Although 70 mol% or more of polyvinyl alcohol is preferably used in the present invention, polyvinyl alcohol having a saponification degree of 95 mol% or more is more preferable from the viewpoint of gas barrier properties. If the average degree of polymerization is less than 250, the durability, particularly water resistance, is poor, and if it exceeds 3000, there is a problem in working such that it is difficult to obtain a smooth coating film because the viscosity becomes large when used as a paint. Further, when the saponification degree is less than 70 mol%, sufficient properties cannot be expected in terms of gas barrier property.

Further, commercially available polyvinyl alcohol usually contains a small amount of sodium acetate. This sodium acetate acts as a condensation catalyst of the (partial) hydrolyzate of alkoxysilane, and thus promotes gelation of the coating agent. Therefore, the content of sodium acetate in polyvinyl alcohol is 1% by weight or less, more preferably 0.5% by weight or less, based on polyvinyl alcohol.

In the present invention, as the alkoxysilane which gives the (partial) hydrolyzate of the alkoxysilane, its (partial) condensate or a mixture thereof, the general formula (1) R ¹ _n —Si (OR ² ) _4-n ... Tetra, tri or dialkoxysilane represented by the formula (1) is preferable. Here, in the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms; a vinyl group; or an organic group having one or more groups selected from the group consisting of a methacryloxy group, an amino group, an epoxy group and a mercapto group, and R ² Is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2.

Here, the above-mentioned organic group is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which can contain a cyclic structure, and the hydrocarbon group has a part of its carbon atoms as an oxygen atom or a nitrogen atom. It may be substituted with a hetero atom such as an atom.

Examples of such alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane. , 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl ) -3-Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane,
Examples thereof include vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane. Above all, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane are preferable from the viewpoint of gas barrier property and durability of the obtained coating film. These compounds can be used alone or in combination of two or more.

The (partial) hydrolyzate of alkoxysilane and its (partial) condensate are those obtained by partially or entirely hydrolyzing the alkoxysilane, or by condensing part or all of the hydrolyzate. And a condensation product of the condensate and an unhydrolyzed raw material alkoxysilane, which are obtained by so-called sol-gel reaction.

When the alkoxysilane is used, it can be added as a component as it is, or after hydrolysis is carried out in advance, the (partial) hydrolyzate of the alkoxysilane and its (partial) condensate are added. Is also possible.

When the alkoxysilane is hydrolyzed, a usual method, for example, an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid or an alkali such as caustic soda or a method of hydrolyzing only with water can be used. However, when an acid is used, there is a problem that the polyvinyl alcohol contained in the obtained coating film undergoes a dehydration reaction and becomes colored, and in particular, a higher saponification degree having an excellent gas barrier property tends to cause intense coloring. Further, since there is a problem that the coating equipment is corroded by an acid, the method of hydrolysis using only water is preferable. It is also possible to carry out the hydrolysis after mixing the alkoxysilane and the solvent for the purpose of uniformly performing the hydrolysis. Depending on the purpose, it is possible to remove the alcohol and the like after the hydrolysis under heating and / or reduced pressure in an appropriate amount, and then to use, and then to add an appropriate solvent.

As the component (c) curing catalyst, aluminum acetylacetonate, aluminum ethylacetoacetate bisacetylacetonate, aluminum bisacetoacetate acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-i- Aluminum chelate compounds such as propoxide monomethylacetoacetate; alkali metal salts of carboxylic acids such as sodium acetate, potassium acetate, potassium formate; amine carboxylates such as dimethylamine acetate, ethanol acetoate, dimethylaniline formate; benzyl trimethyl hydroxide Quaternary ammonium salts such as ammonium, tetramethylammonium acetate, benzyltrimethylammonium acetate; tin octoate Metal carboxylates; triethylamine, triethanolamine, amine such as pyridine; and 1,8-diazabicyclo [5,4,0] -7
Undecen can be mentioned. Of these curing catalysts, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo [5,5] are particularly preferable from the viewpoints of solubility in the composition, stability, effects as a curing catalyst, and the like.
4,0] -7-undecene and the like. These compounds can be used alone or in combination of two or more. Further, if the catalyst is dissolved in a solvent or a dispersion liquid used for producing the composition and added, the measurement and the handling are easy.

Examples of the component (d) solvent include polyvinyl alcohol-soluble solvents such as dimethylimidazoline and water, as well as various alcohols, ketones, esters, ethers, cyclic ethers, dimethylformamide, dimethylsulfoxide and the like. To be The water used in the present invention is preferably ion-exchanged water or distilled water. Further, it is possible to use not only one kind of these polyvinyl alcohol-soluble solvents and solvents that can be used together but also a mixture of two or more kinds. In this case, it is necessary that the polyvinyl alcohol-soluble solvent is contained in 50% by weight or more in all the solvents.

The components (a) to (d) are preferably used in the following proportions. That is, the amount of the component (b) is 20 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the component (a). Here, the component (b) is R ¹ _n --SiO 2.
It is based on the weight of _{(4-n) / 2} . When the amount of the component (b) is less than 20 parts by weight, the solvent resistance tends to be poor, and when it exceeds 200 parts by weight, the gas barrier property tends to be low and the storage stability of the composition tends to be deteriorated. The more preferable range of the component (b) is 25 parts by weight or more and 150 parts by weight or less.

Further, the component (c) can be varied within a wide range depending on desired curing conditions. However, it is generally from about 0.01 to about 15% by weight, preferably from 0.05% to 10% by weight, based on the solids of the composition. If the addition amount is less than 0.01% by weight, a sufficient curing rate cannot be obtained,
If it exceeds 15% by weight, a precipitate is likely to be generated or a defect is likely to occur when a coating agent is applied.

Further, the component (d) is the components (a) and (b).
40 with respect to 100 parts by weight of the total solid content of (c) and
A range of 0 parts by weight or more and 99900 parts by weight or less is preferably used. When it is less than 400 parts by weight, the storage stability of the composition is deteriorated. On the other hand, when it exceeds 99900 parts by weight, the storage stability of the composition itself is improved, but the solid content in the composition is reduced, and the cured film obtained is The film thickness is limited.

As described above, the coating agent for providing the cured coating of the layer B of the present invention is the above-mentioned components (a), (b),
It contains (c) and (d), and its pH is adjusted to 3 or more and 11 or less. As a result, the film thickness is 2 μm
When the B layer has a light transmittance of 400 nm of not less than 85%, a cured coating having excellent transparency can be obtained. If the pH is less than 3, polyvinyl alcohol produces polyene by a dehydration reaction as described above, and the cured coating is likely to be colored. pH
When it exceeds 11, the reaction between the (partial) hydrolyzate of polyvinyl alcohol and the alkoxysilane and its partial condensate is insufficient, and it is difficult to obtain a transparent cured coating film. The compound used for adjusting the pH is not particularly limited as long as it is basic, but is preferably benzyltrimethylammonium hydroxide or 1,8-diazabicyclo [5,4,0].
-7-Undecene. These also act as the above-mentioned curing catalyst.

The above-mentioned component (a) is used as the coating agent.
In addition to (d), various surfactants can be added for the purpose of improving surface smoothness, and for example, silicone compounds, fluorine-based surfactants, organic surfactants and the like can be used. Further, various epoxy resins, melamine resins, amide resins, colloidal silica and the like which are compatible with the composition of the present invention may be added as a modifier. The additive components other than the components (a) to (d) may be heat resistance, weather resistance, water resistance, durability, adhesiveness, chemical resistance, or the like depending on the application to which the obtained laminated film is applied. It is possible to improve various practical properties of the layer B of the present invention.

When preparing the coating agent which gives the cured coating of the layer B of the present invention, for example, the components (a), (b), (c) and (d) may be mixed at once. In addition, as the component (b), a method in which a treatment such as hydrolysis is performed in advance is used to further mix other components. Both are useful methods for preparing the coating agent, but preferably (a) and (d)
It is preferable that the solution is made uniform by mixing the alkoxysilane with the solution and the component (c) is added to adjust the pH. Moreover, you may heat at each preparation step of a coating agent as needed.

The coating agent for giving the cured coating of the layer B of the present invention is applied on the transparent polymer film on which the layer A is laminated. The method includes dip coating, spray coating, flow coating, roll coating, bar coating, A commonly used method such as spin coating is used. The thickness of the B layer is preferably in the range of 0.01 to 100 μm.
If it is less than 0.01 μm, the gas barrier property is insufficient,
If it exceeds 100 μm, it takes time to cure the film, which is not economically preferable.

The transparent polymer film applied usually evaporates and removes the solvent from room temperature to a temperature not higher than the heat distortion temperature of the film. Then, it is heated and cured at a temperature of 50 to 150 ° C. for 1 minute or more. In this process, the component (a) polyvinyl alcohol in the coating agent is crosslinked by the (partial) hydrolyzate of the component (b) alkoxysilane, etc., and a reaction such as B is formed as a transparent cured film. It is formed.

The cured coating has particularly good adhesion when the metal oxide layer of the layer A is a silicon oxide film, especially a SiOx (1.5≤x≤2) film.

If necessary, the surface of the transparent polymer film and / or the surface of the metal oxide of the A layer is subjected to surface modification such as corona treatment or anchor coat treatment to improve the adhesion between the coatings. It is possible.

As described above, according to the present invention, in addition to the features of excellent transparency, optical isotropy, flatness, solvent resistance, water vapor barrier property, gas barrier property, and flexibility, adhesion between layers is improved. It is possible to provide a transparent gas-barrier laminated film having good properties.

[0043]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the invention is not limited to the following examples.

In the examples, parts and% are based on weight unless otherwise specified.

Various measurements in the examples were carried out as follows. Appearance of layer B: Coloring, coating unevenness, etc. were examined by visual observation. B layer transparency: A B layer alone having a film thickness of 2 μm was measured with a spectrophotometer (U-3500, manufactured by Hitachi Ltd.) at a wavelength of 400.
The transmittance of parallel rays of nm was measured. Transparency: The transmittance of parallel rays having a wavelength of 550 nm was measured using the above spectrophotometer. Also made by Nippon Denshoku, COH-3
The haze value (ΔH%) was measured using 00A. Optical isotropic: Multi-wavelength birefringence measuring device M, manufactured by JASCO Corporation
The retardation value for light having a wavelength of 590 nm was measured using -150. Planarity: TOPO-3D manufactured by WYCO was used to measure the surface roughness Ra. Here, Ra is a center line average roughness obtained when a rectangular surface having a side length of 256 μm on the film surface is measured at an interval of 1 μm at a magnification of 400 times based on the measurement principle of phase shift interferometry. That is. Solvent resistance: Dipped in a 1.0% NaOH aqueous solution at 25 ° C. for 5 minutes, thoroughly washed with running water, dried, and visually observed for appearance. Solvent resistance: Immersed in a 5.0% HCl aqueous solution at 25 ° C. for 10 minutes, thoroughly washed with running water, dried, and visually observed. Solvent resistance: A few drops of N-methylpyrrolidone at 80 ° C. were dropped on the B layer, left for 5 minutes, thoroughly washed with running water, and the appearance was visually observed. Water vapor barrier property: Percontran W1A manufactured by MOCON
Was used to measure the water vapor permeability in an atmosphere of 40 ° C. and 90% RH. Gas barrier property: OX-TRAN 2 manufactured by MOKON
Oxygen permeability was measured using a / 20 type in an atmosphere of 30 ° C and 50% RH. Gas barrier property: OX-TRAN 2 manufactured by MOKON
Oxygen permeability was measured using a / 20 type in an atmosphere of 30 ° C and 90% RH. Adhesion: A knife is used to make vertical and horizontal cuts at intervals of 1 mm to form 100 cross-cuts. Cellophane tape (product name: Cellophane, manufactured by Nichiban Co., Ltd.) was applied on top of the tape, and then peeled off at a stretch in a direction of 90 degrees from the surface, and the adhesiveness was evaluated by the number of eyes left on the surface. Therefore, 100/100 means complete adhesion and 0/100 means complete peeling (according to JIS K5400). Flexibility: A laminated film was wound around a lot of 10 mmφ and observed for appearance change such as crack generation. Durability: The state of the cured film after natural cooling was observed by keeping it in a constant temperature and humidity oven at 60 ° C. and 90% RH for 100 hours, and the change in adhesion was observed. PH of coating agent: Measured by a method according to JIS Z8802 using a pH meter manufactured by Horiba Ltd.

[Examples 1 to 8 and Comparative Examples 1 to 9] A polycarbonate resin having a bisphenol component of bisphenol A alone and an average molecular weight of 37,000 was dissolved in methylene chloride in an amount of 20 wt%. Then, this solution was cast on a polyester film having a thickness of 175 μm by a die coating method. Then, it was dried in a drying oven until the residual solvent concentration reached 13% by weight, and peeled from the polyester film. Then, the obtained polycarbonate film was dried in a drying oven at a temperature of 120 ° C. while balancing the vertical and horizontal tensions until the residual solvent concentration became 0.08% by weight.

The transparent film thus obtained had a thickness of 103 μm and a light transmittance of 91 at a wavelength of 550 nm.
%Met.

Next, a metal oxide layer was formed on one side of this polycarbonate film. S as this metal oxide
a small piece of iO was deposited by heating in a vacuum of 5 × 10 ^-5 torr,
A silicon oxide film having a thickness of 50 nm was formed. This silicon oxide had an average composition of SiO _x , and x was about 1.7.

Next, with the composition shown in Table 1, eight kinds of coating agents a to g and o (Examples 1 to 8) for providing the layer B of the transparent optical gas barrier laminate film of the present invention were selected. Prepared. In preparing the coating agent, the alkoxysilane was mixed with the solution containing the component (a) polyvinyl alcohol and the component (d) solvent to make the solution uniform, and then the component (c) curing catalyst was added. The pH was adjusted.

For comparison, four kinds of coating agents h to k (Comparative Examples 1 to 4) having the composition shown in Table 2 were prepared in the same manner as the above a to g.

In the above examples and comparative examples,
In the preparation of the coating agent, as component (a) polyvinyl alcohol, Gosenol NM-11Q (saponification degree 99% or more) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. or Co., Ltd.
Kuraray's Poval 228 (saponification degree: about 88%) was used, and the component (c) benzyltrimethylammonium hydroxide was a 40% aqueous solution. Also, the coating agent p
H11.2 was adjusted with NaOH and pH 2.0 was adjusted with 2N-hydrochloric acid. Further, the alkoxysilane part is a charged part, and the weight of the component (b) is converted into SiO ₂ .

Then, a polycarbonate film (20
0x300x0.1mm) on the metal oxide layer (A layer)
On a 50 nm thick SiO _1.7 layer provided as
The compositions a to k and o 24 hours after the pH adjustment are coated on each with a wire bar, and the temperature is adjusted to 130 ° C.
It was dried by heating for 1 minute. Various tests were carried out using the test pieces thus obtained. A test piece obtained in the same manner as in Example 1 except that alkoxysilane was not used as Comparative Example 5 and a test piece obtained in the same manner as in Example 1 except that polyvinyl alcohol was not used as Comparative Example 6 were used. Various tests were carried out using Furthermore, as Comparative Example 7, a polycarbonate film (200 × 300 ×) provided with SiO _1.7 having a thickness of 50 nm as a metal oxide layer.
0.1 mm) only, a polycarbonate film (200 × 300 × 0.1 mm) provided with SiO _1.3 having a thickness of 50 nm as a metal oxide layer as Comparative Example 8, and further no metal oxide layer is laminated as Comparative Example 9. Various tests were performed using the test pieces obtained in the same manner as in Example 1 except for the above.

The obtained results are shown in Tables 1 and 2.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

EFFECTS OF THE INVENTION According to the present invention, a transparent gas barrier property having excellent gas barrier properties and solvent resistance, excellent transparency, optical isotropy, flatness and water vapor barrier properties, and good adhesion between layers. A laminated film can be provided.

Continuation of the front page (56) Reference JP-A-3-252625 (JP, A) JP-A-8-267637 (JP, A) JP-A-8-267641 (JP, A) JP-A-7-164591 (JP , A) JP-A-9-117986 (JP, A) JP-A-8-267639 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 G02F 1/1333 500

Claims (8)

(57) [Claims] 1. A transparent gas barrier laminate film having a metal oxide layer on at least one side of a transparent polymer film, the alkoxy having the following general formula (1) being in contact with the metal oxide layer and outside thereof. A laminated film having a transparent gas barrier, comprising a cured coating containing a polyvinyl alcohol crosslinked with a (partial) hydrolyzate of silane, a (partial) condensate thereof, or a mixture thereof. _{^{R 1 n -Si (OR 2)}} 4-n ···· (1) ( wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms; vinyl group; or methacryloxy group, an amino group, an epoxy group and a mercapto group An organic group having at least one group selected from the group consisting of, R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2.) 2. A transparent gas barrier laminate film comprising 55
The transparent gas barrier laminate film according to claim 1, which has a light transmittance of 0% or more at 0 nm and a retardation value of 30 nm or less. 3. The metal oxide layer is SiOx (provided that 1.x.
5 ≦ x ≦ 2) and the average composition has a thickness of 5 nm to 200
The transparent gas barrier laminate film according to claim 1 or 2, which is a silicon oxide having a thickness of nm. 4. The transparent gas barrier laminate film according to claim 1, wherein the alkoxysilane is tetramethoxysilane, tetraethoxysilane or a mixture thereof. 5. The layer B has a thickness of 400 μm when the thickness is 2 μm.
The transparent gas barrier laminate film according to any one of claims 1 to 4, which has a light transmittance of 85% or more. 6. The saponification degree of polyvinyl alcohol is 95%.
It is above, The transparent gas barrier laminated film of any one of Claims 1-5. 7. The transparent gas barrier laminate film according to claim 1, wherein the transparent polymer film is a polycarbonate resin or a polyarylate resin. 8. After forming a metal oxide layer (A layer) on at least one surface of a transparent polymer film by a vapor phase growth method,
It consists of the following (a) to (d), (a) / (b) = 5/1
A coating agent layer having a pH of 3 to 11 (weight ratio) and adjusted to pH 3 to 11 is applied onto the layer A, and then the coating agent layer is heated to form a cured film. A method for producing a transparent gas barrier laminate film. (A) polyvinyl alcohol, (b) a (partial) hydrolyzate of the alkoxysilane according to claim 1, a partial condensate thereof or a mixture thereof, (c) a curing catalyst, and (d) a polyvinyl alcohol-soluble solvent as a whole solvent. Solvent containing 50% by weight or more