JP2002046209A - Barrier laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier laminated film which has the optimized chemical and physical properties of a metallic oxide vapor deposition layer in order to make it possible to develop a high barrier performance, even when the film is combined with ORMOCER showing the outstanding reproducibility and stability of a coating liquid. SOLUTION: In the barrier laminated film comprising a metallic oxide layer formed on a film base by a physical vapor deposition process (PVD process) and/or a low temperature plasma vapor growth process (CVD process) and an inorganic/organic hybrid polymer layer(ORMOCER layer) laminated on the metallic oxide layer, the barrier laminated film which has the metallic oxide layer composed of a silicon oxide and/or a silicon carbide oxide and satisfies all of the following conditions: a) film thickness: 100-5,000 Å, b) area/weight ratio: 0.2-2.0 m2/g and c) average pore diameter: 0.7-2.0 nm is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barrier laminate film having excellent gas barrier properties and transparency, for example, used as food packaging or industrial film.

[0002]

2. Description of the Related Art For packaging foods, pharmaceuticals, chemicals, etc.,
Gas barrier plastic films are used to prevent the permeation of water vapor and oxygen. Films having a high degree of gas barrier properties are used for applications that require even better water vapor and oxygen permeation prevention properties to prevent alteration of the contents.

[0003] As such a film, an aluminum foil has been conventionally known, but in addition to the problem of disposal after use, it is basically opaque and its contents cannot be seen from outside. There is a problem that cannot be done.

[0004] In addition, a substrate made of polyvinylidene chloride resin or a copolymer resin of vinylidene chloride and another polymer, or these vinylidene chloride-based resins are coated on a polypropylene resin, a polyester resin, or a polyamide resin to improve gas barrier properties. What is given is widely used especially as a packaging material, but because chlorine-based gas is generated by incineration, it is currently a problem in terms of environmental protection, and furthermore, gas barrier properties are not always sufficient, It cannot be used for contents that require high barrier properties.

Further, polyvinyl alcohol (PVA)
And ethylene vinyl alcohol copolymer (EVOH) are also used, but they show relatively excellent gas barrier properties under absolutely dry conditions, but have insufficient water vapor barrier properties, and deteriorate oxygen barriers under humidity conditions. Therefore, it cannot be said that the material is a sufficient gas barrier material under practical conditions. As one method of improving the humidity dependency, a method of depositing an inorganic oxide such as silicon oxide by a vacuum deposition method (Japanese Patent Laid-Open No. 4-713)
No. 9) has been proposed, but there has been a problem that deterioration of oxygen barrier properties cannot be improved under high humidity conditions of 70% or more.

Further, a vacuum evaporation method, for example, a physical evaporation method (P
VD) biaxially stretched polyethylene terephthalate (PE
A film in which a thin film of an inorganic oxide such as silicon oxide, aluminum oxide, or magnesium oxide is deposited on a plastic film substrate such as T) has been proposed. Such a film has a remarkable improvement in gas barrier properties, and furthermore has the advantage of being able to see the contents from outside because it is transparent.
There is no humidity dependency of the barrier property unlike H or the like. However, since the deposited film is formed by stacking inorganic oxide particles and necessarily includes a defect structure in the film, the barrier property is limited even if the film forming method is changed. Further, it has been pointed out that these vapor-deposited films have poor bending resistance and a problem that the barrier property is deteriorated by mechanical stress, and their applications are limited.

On the other hand, low-temperature plasma chemical vapor deposition (CVD)
Method) is attracting attention as a method capable of forming an inorganic oxide deposited layer with less thermal damage to the substrate. Although it has excellent properties such as good bending resistance and little decrease in barrier properties even when subjected to mechanical stress, similar to the PVD method, there is a limit to the barrier properties due to the defect structure in the film. There's a problem.

As described above, the PVD method or the CVD
The barrier properties of vapor-deposited films by the method are certainly superior to organic barrier materials, but have the problem that they do not reach the level of aluminum foil. A barrier film has been required.

As such a transparent and highly barrier film, a hybrid polymer (hereinafter referred to as O) obtained by hydrolytic polycondensation of an organometallic compound is used.
RMOCER. ) Is combined with a vapor-deposited film to compensate for the defect structure existing in the film, thereby improving the barrier property of the film (EP 0 792846).
A1).

The ORMOCER has an inorganic network structure and an organic network structure, and has a sol-gel process (B) in which hydrolysis and polycondensation of metal alkoxide and the like are controlled.
rinker et al., Sol-Gel-Science; The physics and chem
istry of Sol-Gel-Processing, Academic, NY 1
989), it is possible to develop excellent barrier properties against oxygen and water vapor by adjusting the amounts of the inorganic and organic components introduced.

An ORMOCER having such a barrier property against oxygen and water vapor is disclosed in, for example, JP-A-2-1608.
No. 36 discloses a starting compound used as a scratch-resistant material, that is, having a general formula R ′ _m SiX _(4-m) and AlR ₃ , and an element of a main group in the periodic table other than aluminum. Those obtained from a combination with a hydrolyzable organic compound can be used, and a predetermined gas barrier property can be obtained by combining these with the above-described metal oxide deposition layer.

However, for applications that require a higher degree of gas barrier properties to be exhibited, for example, for materials used for packaging food and electronic components, etc., whose life and characteristics are degraded by contact with oxygen or water vapor, It is difficult for a film substrate having a metal oxide vapor-deposited layer formed by an ordinary technique to exhibit sufficient gas barrier performance. This is because metal oxide deposited layers and ORMOCE
This is because adjustment of the affinity with the R layer is necessary, and a metal oxide vapor deposition layer having a normal metal oxide composition and ORMOCE
When the affinity is adjusted in combination with the R layer, ORM
The combination of the starting compounds of OCER becomes complicated, which causes problems in reproducibility of production, raw material cost, life of the coating liquid, and the like. Further, even when the composition of ORMOCER is changed to adjust the affinity with the metal oxide vapor deposition layer, the target barrier performance cannot be achieved in many cases.

[0013]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an ORMOCER which is excellent in reproducibility and stability of a coating solution already proposed.
The main object of the present invention is to provide a barrier laminate film in which the chemical and physical properties of the metal oxide vapor-deposited layer are optimized so that a high level of barrier performance can be achieved even when combined with the above. .

[0014]

In order to achieve the above object, the present invention provides a method for forming a film on a film substrate by physical vapor deposition (PVD) and / or low-temperature plasma vapor deposition. In a barrier laminate film in which a metal oxide layer is formed by a growth method (CVD method) and an inorganic / organic hybrid polymer layer (ORMOCER layer) is stacked on the metal oxide layer, the metal oxide layer is Consisting of silicon oxide and / or silicon carbide oxide,
And a) a film thickness of 100 to 5000Å, b) a specific surface area of 0.2 to 2.0 m ² / g, and c) an average pore diameter of 0.7 to 2.0 nm. Provide a laminated film.

When the thickness of the metal oxide layer is 100 to 50,
The reason why the thickness is set within the range of 00 ° is that when the film thickness is smaller than 100 °, there is a possibility that the effect when combined with ORMOCER is hardly obtained, and when the film thickness exceeds 5000 °, the film base material has Can not follow the flexibility,
This is because there is a high possibility that a large amount of cracks that cause a decrease in barrier performance are generated in the metal oxide layer. Further, when the metal oxide layer is formed to be thick, the time required for production becomes long, which is not preferable from the viewpoint of productivity.

Further, the specific surface area of the metal oxide layer is set to 0.2 to
The range of 2.0 m ² / g is that the metal oxide layer is
This is because it is preferable that the specific surface area of the metal oxide layer be within the above-described range in order to exhibit high barrier performance when combined with RMOCER.

Further, the average pore diameter of the metal oxide layer is set to 0.1.
The specific surface area can be achieved by setting the content within the range of 7 to 2.0 nm.
If the average pore size is smaller than the above range, ORMOC
There is a possibility that the ER cannot penetrate into the structural defects in the film, and as a result, a problem that a high gas barrier property cannot be obtained may occur. This is likely to cause problems and requires the use of a large amount of ORMOCER,
As a result, cracks occur due to intense curing shrinkage, and the barrier performance may be degraded, which is not preferable.

As described above, in the barrier laminate film according to the first aspect, the metal oxide layer may have a requirement from the above three aspects (hereinafter, may be a morphological requirement of the metal oxide layer). ), The ORMOCER impregnates moderately into the metal oxide layer. As a result, a synergistic effect provides an effect that a gas barrier property that is much higher than that obtained by simply stacking a metal oxide layer and an ORMOCER layer can be obtained.

According to the present invention, in order to achieve the above object, a metal oxide layer is formed on a film substrate by a physical vapor deposition method (PVD method) and / or a low-temperature plasma vapor deposition method (CVD method). A barrier laminate film in which an inorganic / organic hybrid polymer layer (ORMOCER layer) is laminated on the metal oxide layer, wherein the metal oxide layer is made of silicon oxide and / or silicon carbide oxide; In addition, the substance constituting the metal oxide layer satisfies d) Si / O ratio: 1 / 1.2 to 1 / 1.8 (hereinafter, may be referred to as a compositional requirement of the metal oxide layer). The present invention provides a barrier laminated film characterized by the following.

In this case, since the material constituting the metal oxide layer is a silicon oxide and / or silicon carbide oxide within the above-mentioned composition ratio, ORMOCE
It is possible to form a metal oxide layer having the highest affinity for R, and the structure is because the wettability of the coating solution for ORMOCER is deteriorated and the chemical reaction between the metal oxide layer and the ORMOCER layer is suppressed. This does not cause such a problem that a thermal defect (molecules of oxygen and water vapor easily penetrates) is easily generated. Therefore, in the barrier laminate film of the present invention, a synergistic effect between the metal oxide layer and the ORMOCER layer can be effectively exhibited, and a high level of barrier properties can be provided.

According to the second aspect of the present invention, as described in the third aspect, the material constituting the metal oxide layer satisfies e) a film specific gravity of 1.8 to 2.2. Is preferred. Normal silicon oxide and / or
Alternatively, the specific gravity of the silicon carbide oxide changes due to the influence of the organic component contained in the starting material and the internal voids. In the present invention, a silicon oxide and / or silicon carbide oxide having a composition ratio in the above-mentioned range and having a film specific gravity in the above-mentioned range is ORMO.
It is more preferable in consideration of the affinity with the CER layer, and a metal oxide layer outside the above range is not preferable because a defect structure is likely to remain when combined with ORMOCER, and high barrier performance may not be expected to be exhibited. .

Further, in the present invention, in order to achieve the above object, a physical vapor deposition method (PVD method) and / or a low-temperature plasma vapor deposition method (PVD method) are used on a film substrate. A metal oxide layer is formed by CVD, and an inorganic / organic hybrid polymer layer (ORMOCER layer) is laminated on the metal oxide layer. And / or silicon carbide oxide;
In addition, the material constituting the metal oxide layer f) satisfies a surface free energy of 70 to 95 (hereinafter sometimes referred to as a characteristic requirement of the metal oxide layer). provide.

In such a barrier laminate film, since the surface free energy of the material constituting the metal oxide layer is within the above-mentioned range, the metal oxide layer has the above-mentioned ORMOCE.
It has excellent wettability and affinity with R. Therefore, structural reasons such as a decrease in wettability with respect to the coating solution for ORMOCER, which is generated when the metal oxide has a surface free energy outside this range, and a chemical reaction between the metal oxide layer / ORMOCER layer is suppressed. Defects hardly occur, and a barrier laminate film having high gas barrier properties can be obtained by a synergistic effect of the metal oxide layer and the ORMOCER layer.

In the invention described in claim 4, it is preferable that the material constituting the metal oxide layer satisfies g) a polarity value of 15 to 40, as described in claim 5. The metal oxide layer also has a large number of chemically active sites inside or on its surface.
This is because in order to obtain an affinity with MOCER, the polarity value associated with the chemically active site is preferably within the above range. When the polarity value of the metal oxide layer is out of this range, a chemical reaction between the metal oxide layer and the ORMOCER layer is suppressed, and a structural defect through which oxygen and water vapor molecules easily pass is easily generated, which is preferable. Absent.

According to the first aspect of the present invention, as described in the sixth aspect, the substance constituting the metal oxide layer includes: d) Si / O ratio: 1/1. 1.8 is preferably satisfied. By satisfying the morphological requirements of the metal oxide layer of the barrier laminate film described in claim 1 and satisfying the compositional requirements of the metal oxide layer, the gas barrier properties of the obtained barrier laminate film can be improved. It is because it becomes better.

Further, in the invention described in claim 1 or claim 6, as described in claim 7, the substance constituting the metal oxide layer comprises: f) surface free energy: 70 to 95; It is preferable to satisfy the following. This is because the morphological requirements in the metal oxide layer of the barrier laminate film and the characteristic requirements are simultaneously satisfied, and furthermore, the morphological and composition requirements in the metal oxide layer of the barrier laminate film. This is because, when these characteristic requirements are simultaneously satisfied, the gas barrier properties of the obtained barrier laminate film are improved.

Further, in the barrier laminate film according to any one of the first to seventh aspects, as described in the eighth aspect, the ORMOCER
Preferably, the thickness of the layer is in the range from 0.05 to 0.95 μm. By setting the thickness of the ORMOCER layer in the range of 0.05 to 0.95 μm as described above, the ORMOCER layer may be hardened or shrunk during manufacturing or may be bent during use.
This is because cracks do not occur in the CER layer, and as a result, there is no problem that gas barrier properties are deteriorated.

Further, in the barrier laminate film according to any one of claims 1 to 8, as described in claim 9, the film substrate has a thickness of 5 μm to 2 mm. It is preferably polyethylene terephthalate having a thickness in the range (hereinafter, may be referred to as PET). If the thickness is within the above range, there is no problem in productivity and flexibility, and PET is excellent in stability against humidity and temperature changes,
This is because reproduction is easy and stable quality can be secured.

[0029]

DETAILED DESCRIPTION OF THE INVENTION Definition of ORMOCER Before describing the barrier laminate film of the present invention, first, an ORMOCER forming an ORMOCER layer used in the present invention is defined.

The ORMOCER used in the present invention is:
Japanese Unexamined Patent Publication No. Hei 2 (1994) proposes a coating material having high scratch strength by hydrolyzing and polycondensing a silicon-containing metal alkoxide and / or a derivative thereof with an aluminum compound and, if necessary, a compound containing another metal element. -1
60836 refers to an inorganic / organic hybrid polymer described in JP-A-60836.

Specifically, the ORMOCER of the present invention
The term “inorganic / organic hybrid polymer” refers to a hydrolyzed and polycondensed polymer using the following components a and b, and if necessary, the following component c as a starting compound.

1. Regarding the component a The component a is an at least one silane containing an organic functional group and represented by the following chemical formula (1), and / or an oligomer derived therefrom.

R ′ _m SiX _(4-m) (1) where m is 1, 2 or 3.

Residues X may be the same or different and include hydrogen, halogen, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N
R ″ ₂ (R ″ = H and / or alkyl).

The residues R ', which may be identical or different, are an alkyl, alkenyl, alkynyl, allyl, allylalkyl, alkylallyl, allylalkenyl, alkenylallyl, allylalkynyl or alkynylallyl group. Also, the residue R ′ may be interrupted by an O or S atom or —NR ″. Furthermore, halogen, amino, amide, aldehyde, keto, alkylcarbonyl, carboxyl, mercapto, cyano, hydroxyl, alkoxy, It may have one or more substituents selected from the group consisting of alkoxycarbonyl, sulfonic acid, phosphoric acid, acryloxy, methacryloxy, epoxide, or vinyl group.

The above-mentioned alkyl group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, has a straight chain, a side chain, or is cyclic, and is preferably a lower alkyl group having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms. Is preferred. Specifically, methyl, ethyl, n
-Propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, dodecyl, octadecyl or cyclohexyl are preferred.

The alkenyl group and the alkynyl group may be, for example, a straight chain having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms,
A side-chain or cyclic group having at least one double or triple bond, especially a lower alkenyl or alkynyl group such as vinyl, allyl, 2-butenyl,
Ethynyl and propargyl are preferred.

The above alkoxy, acyloxy, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylallyl, allylalkyl,
Alkenyl allyl, allyl alkenyl, alkynyl allyl, allyl alkynyl and substituted amino or amide groups are those derived from the above alkyl, alkenyl and alkynyl groups.

Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, isobutoxy, β-methoxyethoxy, acetyloxy, propionyloxy, monomethylamino, monoethylamino , Dimethylamino, diethylamino, N-ethylanilino, methylcarbonyl,
Ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, benzyl, 2-phenylethyl, tolyl and styryl. Preferred allyl groups are phenyl, hydroxyphenyl, biphenyl and naphthyl, of which phenyl is preferred.

These residues may be unsubstituted or substituted by one or more substituents, for example, halogen, lower alkyl or alkoxy and nitro. Among them, a halogen atom (for example, F,
Cl, Br), especially fluorine atoms, which give excellent hydrophobicity of the final product and especially good resistance to condensed water. For this reason, fluorinated silanes are particularly advantageous.

Among the halogens directly bonded to the central atom, fluorine, chlorine and bromine are preferred, and chlorine is particularly preferred.

2. Regarding the component b The component b is at least one aluminum compound represented by the following chemical formula (2) and / or an oligomer derived therefrom and / or an aluminum salt of an inorganic or organic acid which is optionally a complex.

AlR ₃ (2) Here, the residues R may be the same or different and are halogen, alkyl, alkoxy, acyloxy or hydroxy having 10 or less carbon atoms, preferably 4 or less carbon atoms. May be completely or partially replaced by a chelating ligand.

3. About the c component The c component is a main group Ia- of the periodic table other than aluminum.
Va or one or more low volatile oxides of the elements of subgroups IIb, IIIb, Vb-VIIIb, which are soluble in the reaction medium.

The component c is preferably derived from the following elements: That is, alkaline earth metals such as Mg and Ca, B, Si, Sn, Pb, P, As, Sb, B
i, Cr, Mo, W, Mn, Fe, Co, Ni, Zn,
And / or V, with B, Si, Sn, Zn, and P being particularly preferred. If necessary, lanthanides and actinides can be used.

4. About the ratio of each component The said a component in the starting material at the time of synthesize | combining ORMOCER, the said b component, and the said c added as needed.
The ratio of the components is as follows: the component a is 25 to 95 mol% with respect to the total number of moles of the (monomer) starting compound, and the component b is the total number of moles of the (monomer) starting compound. 5 to
75% by mole, and the above-mentioned component c as (monomer)
It is a proportion of 0 to 70 mol% based on the total number of moles of the starting compound.

B. About the barrier laminate film of the present invention Hereinafter, the barrier laminate film of the present invention using such ORMOCER will be described in detail. Since the present invention can be divided into a first embodiment, a second embodiment, and a third embodiment, each will be described below in order.

1. First Embodiment In a first embodiment of the barrier laminate film of the present invention, a metal oxide layer is formed on a film substrate by physical vapor deposition (PVD) and / or low-temperature plasma vapor deposition (CVD). In the barrier laminate film formed and formed by laminating an inorganic / organic hybrid polymer layer (ORMOCER layer) on the metal oxide layer, the metal oxide layer is made of silicon oxide and / or silicon carbide oxide. And a) film thickness: 100-5000５, b) specific surface area: 0.2-2.0 m ² / g, and c) average pore diameter: 0.7-2.0 nm. Things.

As described above, the first embodiment of the barrier laminate film of the present invention comprises the above-described ORMOC on a film substrate.
Since the metal oxide layer formed together with the ER layer satisfies the morphological requirements of the metal oxide layer, the ORMOCER in the ORMOCER layer formed on the metal oxide layer penetrates the voids of the metal oxide. , ORMOCER can form a metal oxide layer appropriately impregnated. As described above, the laminated film having the metal oxide layer in a state in which the voids in the metal oxide layer are appropriately impregnated with the ORMOCER can dramatically improve the gas barrier property by a synergistic effect.

In the present embodiment, the principle of exhibiting more excellent gas barrier properties by combining the metal oxide layer and the ORMOCER layer is not clear, but the basic barrier performance is not clear. It is considered that the ORMOCER layer compensates for the structural defects of the excellent metal oxide layer deposited layer, resulting in a laminated film having excellent barrier performance and bending resistance.

The morphological requirements of the metal oxide layer, which is a feature of this embodiment, will be described below.

First, in the present embodiment, the film thickness is preferably in the range of 100 to 5000 °, particularly preferably in the range of 200 to 1000 °. This is because when the film thickness is smaller than the above range, even if the metal oxide layer is formed on the film substrate, the gas barrier property of the metal oxide layer itself is not large, so that the gas barrier necessary for a laminated film is required. From the viewpoint that it may not be possible to obtain a high gas barrier property from the viewpoint that the synergistic effect when combined with the ORMOCER layer may not be expected in some cases. It is. On the other hand, when the thickness of the metal oxide layer is larger than the above range, it may not be possible to follow the flexibility of the film substrate during use or the like, and cracks may occur in the metal oxide layer after use. And the likelihood of cracks occurring in the metal oxide layer during curing shrinkage is high, resulting in lower gas barrier properties,
This is because a necessary high gas barrier property cannot be achieved in some cases. Further, disadvantages when the film thickness is made larger than the above range include a point that the time required for the production becomes longer, which is not preferable from the viewpoint of productivity.

In the present embodiment, furthermore, metal oxidation
The specific surface area of the material layer is 0.2 to 2.0 m ^Two/ G range
It is preferable that it is 1.3 to 1.8 m.^Two/ G range
Preferably, it is within the range. The specific surface area of the metal oxide layer is
If less than the above range, ORMOCER is metal oxide
The layer is not adequately impregnated and consequently
Advanced gas barrier properties by synergistic effect with MOCER
Is not preferred because it cannot be obtained. That is to say,
The resulting metal oxide layer is a stack of metal oxide particles
And a defect structure is always included in the layer. This implementation
In an embodiment, a metal oxide layer including the defect structure portion
Apply ORMOCE coating solution on top
By forming the R layer, defects in the metal oxide layer
ORMOCER penetrates into the structural part,
The metal oxide layer impregnated with ORMOCER may be
it can. In this way, ORMOCER is moderately metal oxide
By being impregnated in the layer, the metal oxide layer and OR
The gas barrier properties of the MOCER layer are based on
Considered to be dramatically improved compared to laminates
You. The range of the specific surface area of the metal oxide layer is smaller than the above range
In this case, there is a defective part for ORMOCER to invade.
It means that there is not much in the metal oxide layer,
And the amount of ORMOCER penetrating into the metal oxide layer is small.
Disappears. Therefore, the difference between the metal oxide layer and ORMOCER
It is highly likely that synergistic effects cannot be obtained effectively
This is undesirable.

On the other hand, when the specific surface area of the metal oxide layer is larger than the above range, it means that many defective portions exist in the metal oxide layer as described above. Therefore,
When the specific surface area of the metal oxide layer is larger than the above range,
It is not preferable because there is a high possibility that a problem will occur in the strength aspect, and therefore, many cracks are generated in the metal oxide layer when bent or the like during use, and as a result, the gas barrier property is likely to be reduced. It is.

Further, in the present embodiment, the average pore diameter in the metal oxide layer is preferably in the range of 0.7 to 2.0 nm, and particularly preferably in the range of 0.7 to 1.6 nm. It is preferred that When the average pore diameter in the metal oxide layer is smaller than the above range, ORMOC is contained in the pores.
Since the ER is hard to penetrate, the ORM in the metal oxide layer
The OCER content is small, and as a result, it is highly likely that the synergistic effect of ORMOCER and the metal oxide layer cannot be effectively obtained as in the case of the above specific surface area, which is not preferable.

On the other hand, when the average pore diameter of the metal oxide layer is larger than the above range, the metal oxide layer has a large defect structure therein as in the case of the above specific surface area, and in terms of strength, The problem described above is highly likely to occur, and in particular, the gas barrier property is likely to be reduced due to the occurrence of cracks in the metal oxide layer due to bending or the like during use, which is not preferable.

The metal oxide layer used in this embodiment satisfying the above-mentioned morphological requirements is manufactured by the above-mentioned PVD method and / or CVD method, and by changing the manufacturing conditions, the above-mentioned morphological requirements are satisfied. A filling metal oxide layer is formed. The metal oxide used in the present embodiment is not particularly limited as long as it can be formed by such a method.
Silicon oxide and / or silicon carbide oxide is preferably used from the viewpoint of affinity with RMOCER, production stability, safety and cost.

In this embodiment, an ORMOCER layer is formed on these metal oxide layers. Such an ORMOC
As the material for forming the ER layer, those described in the section of the definition of ORMOCER are used. The thickness of the ORMOCER layer used in this embodiment is 0.05 to 0.95 μm.
m, more preferably within a range of 0.1 m.
It is formed so as to be adjusted within a range of 1 to 0.5 μm. When the thickness of the ORMOCER layer is smaller than the above range, even if the metal oxide layer satisfies the above-mentioned morphological requirements, the amount of ORMOCER is insufficient, so that a synergistic gas barrier property between the metal oxide layer and ORMOCER cannot be expected. On the other hand, when the thickness is larger than the above range, the curing shrinkage becomes severe, cracks occur in the coating film, and as a result, it is not preferable because the expression of high barrier performance may not be expected. . Further, a large amount of ORMOCER is used, which is disadvantageous in terms of cost.

Examples of the film substrate used in the present embodiment include all commonly available plastic films such as polyamide, polyethylene, polypropylene and polyester. Polyethylene terephthalate, which is excellent, easy to reproduce, and can ensure stable quality, is more preferably used.

The thickness of the film substrate used in the present embodiment is 5 μm to 2 m from the viewpoint of productivity and flexibility.
m, particularly preferably in the range of 10 μm to 200 μm.

An example of the method for producing the barrier laminate film of the present embodiment will be described below.

First, a silicon oxide and / or silicon carbide oxide layer is formed on a film substrate by the above-mentioned PVD method and / or CVD method. At this time, the metal oxide layer is manufactured so as to satisfy the morphological requirements of the metal oxide layer by adjusting the manufacturing conditions and the like of the PVD method and / or the CVD method.

Next, on the metal oxide layer, the ORM
Component a, component b and, if necessary, component c described in the definition of OCER are converted into a predetermined solvent, for example, alcohols,
Dissolve in ketones, esters, ethers, hydrocarbons, water, amines, etc., and add an amount of water smaller than the stoichiometric amount necessary to completely hydrolyze the hydrolyzable groups. The prepared coating solution is applied by stirring. As a method of applying the coating liquid at this time, various coating methods conventionally used, for example, a method such as spray coating, spin coating, and bar coating can be used. Then, the ORMOCER layer can be formed by irradiating, for example, heat or the like to cure the coating liquid, whereby a barrier laminate film can be manufactured.

The film thickness, specific surface area,
The method for measuring the average pore diameter is as follows.

(1) Film thickness The film thickness was determined by actual measurement from a cross-sectional SEM photograph of the film substrate.

(2) Specific surface area Specific surface area measurement apparatus BELSORP 28SA manufactured by Nippon Bell Co., Ltd.
After using a vapor-deposited film, and each film alone cut into strips and filled in a sample holder, the amount of nitrogen adsorbed is measured under the following conditions, and the specific surface area of the vapor-deposited film and the film simplex is calculated from the BET method, The specific surface area of the deposited film was obtained by subtracting the specific surface area of the film itself from the specific surface area of the deposited film.

<Measurement conditions> Pre-measurement treatment conditions: After filling the measurement sample, 120
Drying under reduced pressure at ℃ for 1 hour ・ Air constant temperature chamber: 40 ℃ ・ Adsorption temperature: 77.0．K ・ Initial introduction amount: 10.0 Torr ・ Introduction pressure difference: 0.0 Torr ・ Saturated vapor pressure: 760.00 Torr ・ Adsorption break Area: 0.162 nm ^2. Maximum adsorption pressure: 0.99000 P / Ps Minimum desorption pressure: 0.10000 p / Ps Equilibrium time: 300 SEC (3) Average pore diameter Nitrogen adsorption amount under the same measurement conditions as the specific surface area described above. After measuring the average pore diameter of the vapor-deposited film was obtained by the Dollimore & Heal method.

2. Second Embodiment In a second embodiment of the barrier laminate film of the present invention, a metal oxide layer is formed on a film substrate by physical vapor deposition (PVD) and / or low-temperature plasma vapor deposition (CVD). In the barrier laminate film formed and formed by laminating an inorganic / organic hybrid polymer layer (ORMOCER layer) on the metal oxide layer, the metal oxide layer is made of silicon oxide and / or silicon carbide oxide. And the material constituting the metal oxide layer satisfies d) Si / O ratio: 1 / 1.2 to 1 / 1.8.

As described above, the second embodiment of the barrier laminate film of the present invention provides the above-mentioned ORMOC on a film substrate.
Since the metal oxide layer formed together with the ER layer satisfies the above compositional requirements of the metal oxide layer, when forming the ORMOCER layer on the metal oxide layer, the affinity between the ORMOCER and the metal oxide layer is increased. It is possible to improve the performance. Accordingly, the ORMOCER easily penetrates into the pores in the metal oxide layer, and the metal oxide layer and the OR
A synergistic effect on the gas barrier property with the MOCER can be expected, and furthermore, structural defects such as the suppression of the chemical reaction between the metal oxide layer / ORMOCER layer (oxygen and water vapor molecules are easily transmitted). Does not occur. Therefore, in the barrier laminate film of the present embodiment, the metal oxide layer and the ORM
The synergistic effect with the OCER layer can be effectively exerted, and a high level of barrier properties can be provided.

In the present embodiment, as described above, the material constituting the metal oxide layer has an Si / O ratio of 1/1.
Preferably, the ratio satisfies 1 / 1.8, but most preferably, the Si / O ratio is in the range of 1 / 1.5 to 1 / 1.8. This is because by setting the content within the above range, the affinity between the metal oxide layer and ORMOCER can be improved as described above.

The compositional requirements in this embodiment include:
Further, the material constituting the metal oxide layer preferably has a film specific gravity in the range of 1.8 to 2.2. The specific gravity of the film defines the composition of the silicon oxide and / or silicon carbide oxide from a different angle. This is undesirable in that it may cause a problem in the affinity of the layer for ORMOCER.

Other points in this embodiment, for example, ORM
The points relating to the OCER layer and the like are the same as those in the first embodiment, and the description thereof is omitted here. However,
The morphological requirements in the first embodiment are satisfied by adjusting the manufacturing conditions of the PVD method and / or the CVD method, but the compositional requirements (Si / O ratio and film specific gravity) in the present embodiment are satisfied. Regarding the above, a metal oxide layer satisfying the requirements can be obtained by adjusting the raw materials when performing the PVD method and / or the CVD method in addition to the above.

The method of measuring the Si / O ratio and the specific gravity of the film in this embodiment is as follows. (1) Si / O ratio X-ray photoelectron spectrometer ES manufactured by VG Scientific, UK
The ratio of Si and O in the film was measured under the following measurement conditions using CALAB MKII.

<Apparatus settings> X-ray source: Mg Kα (non-monochromatic) X-ray output: 300 W (15 kV, 20 mA) Lens used: normal type Measurement area: about 5 mm × 2 mm Charge neutralization: Not performed ・ Photoelectron escape angle: 90 ° (sample normal) ・ Distance between X-ray source and sample surface: Measured in the state where it was closest manually ・ Sample mounting position: X, 15.5; Y, 15.5 Z, 18.0 ・ Measurement chamber vacuum degree: about 3.0 × 10 ^-7 Pa ・ Sample surface cleaning: not performed

<Measurement Conditions> A narrow scan spectrum method was used. a) Si 2p orbital ・ Measurement energy range: 95 to 115 eV (range of binding energy) ・ Number of measurement points: 401 ・ Step size: 0.05 eV ・ Number of scans: 5 times ・ Pass energy: 20 eV

B) O 1s orbital ・ Measurement energy range: 525 to 545 eV (range of binding energy) ・ Number of measurement points: 401 ・ Step size: 0.05 eV ・ Number of scans: 5 ・ Pass energy: 20 eV

<Method of Determining Si / O Ratio> The Si / O ratio was determined from the intensity ratio of Si and O included in the measurement range.

(2) Membrane specific gravity In addition to (1), carbon included in the measurement range was measured on C 1s orbit under the following conditions.

C) C 1s orbit ・ Measurement energy range: 282 to 302 eV (range of binding energy) ・ Number of measurement points: 401 ・ Step size: 0.05 eV ・ Number of scans: 10 times ・ Pass energy: 20 eV

The Si, O, and C of 10 obtained by the above measurement
Calculate the element ratio in the range of nm × 10 nm × 10 nm,
The film density of the coating was determined from the theoretical weight of the elements, assuming that each element ratio was constant in the coating.

3. Third Embodiment In a third embodiment of the barrier laminate film of the present invention, a metal oxide layer is formed on a film substrate by physical vapor deposition (PVD) and / or low-temperature plasma vapor deposition (CVD). In the barrier laminate film formed and formed by laminating an inorganic / organic hybrid polymer layer (ORMOCER layer) on the metal oxide layer, the metal oxide layer is made of silicon oxide and / or silicon carbide oxide. And the substance constituting the metal oxide layer satisfies f) surface free energy: 70 to 95.

As described above, since the present embodiment satisfies the above-described characteristic requirements of the metal oxide layer, the metal oxide layer has excellent wettability and affinity with the ORMOCER. . Therefore, as in the case of the above compositional requirements, the ORMOCER easily penetrates into the pores in the metal oxide layer, and a synergistic effect on the gas barrier property between the metal oxide layer and the ORMOCER can be expected. Further, since the affinity and the wettability are good, there is a low possibility that a problem such as suppression of a chemical reaction between the metal oxide layer and the ORMOCER layer occurs. As a result, molecules of oxygen and water vapor are easily transmitted. This has the effect that structural defects are less likely to occur. Therefore, a barrier laminate film having extremely high gas barrier properties can be obtained.

In the present embodiment, the surface free energy of the substance constituting the metal oxide layer is preferably in the range of 75 to 95. This is because, in the case of having such a surface free energy, affinity with ORMOCER is good, so that a barrier laminate film having extremely high gas barrier properties can be obtained for the above-described reason.

The characteristic requirements in this embodiment include:
Further, the polarity value of the substance constituting the metal oxide layer is 15
It is preferably within the range of from 40 to 40. The metal oxide layer also has a large number of chemically active sites inside or on its surface, but in order to obtain an affinity with ORMOCER, the polarity value related to these active sites must be within the above range. This is because it is preferable. If the polarity value of the metal oxide layer is out of this range, the metal oxide layer / ORMOCE
It is not preferable because a chemical reaction between the R layers is suppressed, and a structural defect in which oxygen and water vapor molecules easily pass is easily generated.

Other points in this embodiment, for example, ORM
The points relating to the OCER layer and the like are the same as those in the first embodiment, and the description thereof is omitted here. However,
The morphological requirements in the first embodiment were satisfied by adjusting the production conditions and the like of the PVD method and / or the CVD method. However, regarding the characteristic requirements (surface energy and polarity) in the present embodiment, In addition to these, a metal oxide layer that satisfies the requirements can be obtained by adjusting the raw materials when performing the PVD method and / or the CVD method.

The method of measuring the surface free energy and the polarity value in this embodiment is as follows.

(1) Surface free energy Using an automatic contact angle meter CA-Z manufactured by Kyowa Interface Science Co., Ltd., water, formamide and ethylene glycol were used.
From the contact angle at 5 ° C., a paper by Foekes et al. (Ind. Eng. Chem.,
56 (12), 40 (1964)) and the surface free energy was quantified using surface free energy analysis software (EG-1) produced by Kyowa Interface Science Co., Ltd.

(2) Polarity value From the surface free energy obtained by the above measurement, the polarity component of the surface free energy was extracted using the analysis software (EG-1), and the polarity value was quantified.

4. Combination of each embodiment In the present invention, as long as it has a metal oxide layer that satisfies the morphological, compositional, and characteristic requirements described in each of the above embodiments, a high gas barrier property can be obtained. In any case, a barrier laminate film having good quality can be obtained. However, among these requirements, a barrier laminate film having a metal oxide layer that satisfies two or more requirements has a higher barrier property, so that a higher quality barrier laminate film is required. Can be said to be more preferable.

That is, the film thickness, the specific surface area and the average particle size, which are the morphological requirements of the metal oxide layer, are within the above-mentioned ranges, and the Si / O ratio, which is the composition requirement of the metal oxide layer, is as described above. A barrier laminate film having a metal oxide layer within the above range is preferable, and a film having a specific gravity within the above range is more preferable. This is because the morphological and characteristic requirements of the metal oxide layer, that is, the surface free energy is within the above-mentioned range, preferably, if the polarity value is within the above-mentioned range, further the compositional requirements The same applies to the case of characteristic requirements. In the present invention, a barrier laminate film having all of the morphological, compositional, and characteristic requirements of the metal oxide layer, that is, a barrier laminate film having a metal oxide layer all within the above range is the most preferred embodiment. Among them, a metal oxide layer that satisfies the requirement of film specific gravity in addition to the Si / O ratio in compositional requirements and / or a metal oxide layer that satisfies the requirement of polarity value in addition to surface free energy in characteristic requirements It can be said that the barrier laminate film having the above is a more preferable embodiment.

The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the scope of the claims of the present invention. It is included in the technical scope of the invention.

In the above embodiment, the effect of the barrier laminate film of the present invention is defined as a gas barrier property. This gas barrier property has not only a permeability preventing property of gas such as oxygen but also a vapor permeability preventing property. It is a concept that includes.

[0093]

EXAMPLES Hereinafter, the barrier laminate film of the present invention will be specifically described with reference to examples. Note that the present invention is not limited to the following embodiments.

[Production Example 1] Biaxially stretched PET having a thickness of 12 μm
Film (manufactured by Teijin Limited, trade name: NSC, single-sided corona treatment)
Was used to form a metal oxide layer of silicon oxide having a thickness of 550 ° on one side by the PVD method under the following conditions.

(PVD method conditions) Target for thermal evaporation: silicon monoxide (purity 99.9%) Degree of vacuum in vacuum chamber: 1 × 10 ^-4 mbar Heating power: 0.037 w Film transport speed: 50 m / min・ Evaporation surface: sealant layer formation of polyurethane adhesive

[Production Example 2] Biaxially stretched PET having a thickness of 12 µm
Film (manufactured by Teijin Limited, trade name: NSC, single-sided corona treatment)
With a thickness of 300 mm by the CVD method under the following conditions.
Was formed on one side.

(CVD method conditions) Reaction gas mixture ratio: tetramethoxysilane / oxygen gas /
Helium = 10/50/40 (unit: sccm) ・ Degree of vacuum in vacuum chamber: 5.5 × 10 ^-6 mbar ・ Degree of vacuum in evaporation chamber: 6.5 × 10 ^-2 mbar ・ Cooling ・ Supply power of electrode drum: 18 kW ・Conveyance speed of film: 50m / min ・ Evaporation surface: Corona treated surface

[Production Example 3] Biaxially stretched PET having a thickness of 12 µm
Film (manufactured by Teijin Limited, trade name: NSC, single-sided corona treatment)
Was used to form a metal oxide layer of silicon oxide having a thickness of 120 ° on one surface by a CVD method under the following conditions.

(Conditions for CVD method) Reaction gas mixture ratio: hexamethyldisiloxane / oxygen gas / helium = 1/10/10 (unit: slm) Vacuum degree in vacuum chamber: 5.5 × 10 ⁻⁶ mbar Vapor deposition Degree of vacuum in chamber: 6.5 × 10 ^-2 mbar ・ Cooling ・ Supply power of electrode drum: 18kW ・ Film transfer speed: 80m / min ・ Evaporation surface: Corona treated surface

[Production Example 4] Biaxially stretched PET having a thickness of 12 µm
Film (manufactured by Teijin Limited, trade name: NSC, single-sided corona treatment)
Was used to form a metal oxide layer of silicon oxide having a thickness of 30 ° on one surface by a CVD method under the following conditions.

(Conditions of CVD method) Reaction gas mixture ratio: tetramethoxysilane / oxygen gas /
Helium = 10/50/40 (unit: sccm) ・ Degree of vacuum in vacuum chamber: 5.5 × 10 ^-6 mbar ・ Degree of vacuum in evaporation chamber: 6.5 × 10 ^-2 mbar ・ Cooling ・ Supply power of electrode drum: 18 kW ・Film transport speed: 100 m / min. Vapor deposition surface: Corona treated surface

[Production Example 5] Biaxially stretched PET having a thickness of 12 µm
Film (manufactured by Teijin Limited, trade name: NSC, single-sided corona treatment)
And a thickness of 6000 by the CVD method under the following conditions.
A metal oxide layer composed of silicon oxide was formed on one side.

(CVD method conditions) Reaction gas mixture ratio: tetramethoxysilane / oxygen gas /
Helium = 10/50/40 (unit: sccm) ・ Degree of vacuum in vacuum chamber: 5.5 × 10 ^-6 mbar ・ Degree of vacuum in evaporation chamber: 6.5 × 10 ^-2 mbar ・ Cooling ・ Supply power of electrode drum: 18 kW ・Film transport speed: 7 m / min. ・ Evaporation surface: Corona treated surface

[Physical Properties] Table 1 shows the physical properties of the PET films of Production Examples 1 to 5 on which the metal oxide layer composed of silicon oxide was formed.

[0105]

[Table 1]

[Production Example 6] The OR method was performed according to the method of Example 1 described in JP-A-2-160836.
A MOCER coating solution was prepared. That is, 94.5
g of γ-glycidyloxypropyltrimethoxysilane, 11 g of γ-aminopropyltrimethoxysilane,
57.5 g of propyltrimethoxysilane and 49 g
Was stirred in a three-necked flask for 5 minutes while cooling with ice. To this mixture, 3.4 g of distilled water was slowly added dropwise, and the mixture was stirred for 5 minutes. Then 6.3 g of distilled water was added to the mixture and stirring was continued for 15 minutes. Finally, 54 g of water was added to the mixture, and the mixture was stirred at room temperature for 2 hours to obtain a transparent and uniform coating liquid.

[Example 1] The coating solution prepared in Production Example 6 was applied on the metal oxide layer of the PET film on which the metal oxide layer made of silicon oxide produced in Production Example 1 was formed. Heated at ° C for 2 hours. The thickness of the ORMOCER layer after curing was 0.25 μm. This barrier laminate film was used as Example 1.

Example 2 The coating solution prepared in Production Example 6 was applied on the metal oxide layer of the PET film on which the metal oxide layer made of silicon oxide produced in Production Example 2 was formed. Heated at ° C for 2 hours. The thickness of the ORMOCER layer after curing was 0.25 μm. This barrier laminate film was used as Example 2.

[Comparative Example 1] The coating solution prepared in Production Example 6 was applied to the metal oxide layer of the PET film on which the silicon oxide metal oxide layer produced in Production Example 3 was formed. Heated at ° C for 2 hours. The thickness of the ORMOCER layer after curing was 0.25 μm. This barrier laminate film was used as Comparative Example 1.

[Comparative Example 2] The coating solution prepared in Production Example 6 was applied on the metal oxide layer of the PET film on which the silicon oxide metal oxide layer produced in Production Example 4 was formed. Heated at ° C for 2 hours. The thickness of the ORMOCER layer after curing was 0.25 μm. This barrier laminate film was used as Comparative Example 2.

[Comparative Example 3] The coating solution prepared in Production Example 6 was applied on the metal oxide layer of the PET film on which the silicon oxide metal oxide layer produced in Production Example 5 was formed. Heated at ° C for 2 hours. The thickness of the ORMOCER layer after curing was 0.25 μm. This barrier laminate film was used as Comparative Example 3.

[Evaluation] Films having only the metal oxide layer formed in Examples 1 and 2 and Comparative Examples 1 to 3 and Production Examples 1 to 3 were referred to as Comparative Examples 4 to 6, respectively. Oxygen and water vapor permeability were measured under the following conditions. Table 2 shows the results.

1. Oxygen permeability measurement condition 23 ℃, 90% RH using OX-TRAN2 / 20 type from MOCON
It measured on condition of. 2. Water Vapor Permeability Measurement Conditions The measurement was performed at 40 ° C. and 90% RH using PERMATRAN manufactured by MOCON.

[0114]

[Table 2]

[0115]

According to the present invention, since the metal oxide layer satisfies any of the morphological, compositional, or characteristic requirements, it is formed on the metal oxide layer. ORMOCER can be appropriately contained in pores in the metal oxide layer. Therefore, when the obtained barrier laminate film is laminated with an ORMOCER layer alone or a metal oxide layer alone, the ORMOC layer
This has an effect that the gas barrier property is much higher than the gas barrier property when the ER layer and the metal oxide layer are simply laminated. Therefore, it can be used for applications requiring high gas barrier properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 14/10 C23C 14/10 16/42 16/42 // C08L 67:00 C08L 67:00 F term ( Reference) 4F006 AA12 AA35 AB74 BA05 CA07 DA01 EA02 4F100 AA16B AA17B AA17C AA20B AD08B AH06 AH08 AK01C AK42A AK52 AL06C AT00A BA03 BA07 BA10A BA10C DE01B GB15 GB23 JA20 JD02 BA02BA02BA02BA02A02BA JA20

Claims (9)

[Claims] A physical vapor deposition method (PVD) on a film substrate.
Method) and / or low temperature plasma vapor deposition (CVD)
Method), a metal oxide layer is formed, and an inorganic / organic hybrid polymer layer (ORMOCE) is formed on the metal oxide layer.
R layer), wherein the metal oxide layer is made of silicon oxide and / or silicon carbide oxide, and a) film thickness: 100-5000Å b) specific surface area: 0 0.2 to 2.0 m ² / g, and c) an average pore diameter of 0.7 to 2.0 nm. 2. A physical vapor deposition method (PVD) on a film substrate.
Method) and / or low temperature plasma vapor deposition (CVD)
Method), a metal oxide layer is formed, and an inorganic / organic hybrid polymer layer (ORMOCE) is formed on the metal oxide layer.
R layer), wherein the metal oxide layer is made of silicon oxide and / or silicon carbide oxide, and the material constituting the metal oxide layer is d) Si / A barrier laminate film characterized by satisfying an O ratio of 1 / 1.2 to 1 / 1.8. 3. The barrier laminate film according to claim 2, wherein the material constituting the metal oxide layer satisfies e) a film specific gravity of 1.8 to 2.2. 4. A physical vapor deposition method (PVD) on a film substrate.
Method) and / or low temperature plasma vapor deposition (CVD)
Method), a metal oxide layer is formed, and an inorganic / organic hybrid polymer layer (ORMOCE) is formed on the metal oxide layer.
R layer), wherein the metal oxide layer is composed of silicon oxide and / or silicon carbide oxide, and the material constituting the metal oxide layer is f) surface free Energy: A barrier laminate film characterized by satisfying 70-95. 5. The barrier laminate film according to claim 4, wherein the substance constituting the metal oxide layer satisfies g) a polarity value of 15 to 40. 6. The barrier laminate film according to claim 1, wherein the substance constituting the metal oxide layer satisfies d) Si / O ratio: 1 / 1.2 to 1 / 1.8. . 7. The barrier laminate film according to claim 1, wherein the substance constituting the metal oxide layer satisfies f) surface free energy: 70 to 95. 8. The thickness of the ORMOCER layer is 0.0
The barrier laminate film according to any one of claims 1 to 7, wherein the thickness is within a range of 5 to 0.95 µm. 9. The barrier laminate according to claim 1, wherein the film substrate is polyethylene terephthalate having a thickness in a range of 5 μm to 2 mm. the film.