WO2013027787A1

WO2013027787A1 - Barrier laminate, gas barrier film, and device using barrier laminate or gas barrier film

Info

Publication number: WO2013027787A1
Application number: PCT/JP2012/071253
Authority: WO
Inventors: 向井　厚史; 青島　俊栄; 塚原　次郎
Original assignee: 富士フイルム株式会社
Priority date: 2011-08-24
Filing date: 2012-08-23
Publication date: 2013-02-28
Also published as: JP5635955B2; JP2013043384A

Abstract

The present invention provides a barrier laminate which comprises an inorganic layer and an organic layer that is provided on the surface of the inorganic layer, said organic layer containing a polymer that is obtained by polymerizing a polymerizable composition which contains a multifunctional (meth)acrylate, a compound represented by general formula (I), and a compound represented by general formula (II-a) and/or a compound represented by general formula (II-b). The barrier laminate of the present invention has excellent adhesion properties and excellent heat resistance.

Description

Barrier laminate, gas barrier film and device using the same

The present invention relates to a barrier laminate, a gas barrier film, and a device using these.

Conventionally, a barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, oxidation, nitridation, and silicon oxynitride is formed on the surface of a plastic film is used for packaging articles that require blocking of various gases such as water vapor and oxygen. In addition, it is widely used in packaging applications to prevent the deterioration of foods, industrial products and pharmaceuticals.

In recent years, in the fields of liquid crystal display elements and organic EL elements, plastic film substrates have begun to be used instead of heavy and fragile glass substrates. Since the plastic film substrate can be applied to a roll-to-roll method, it is advantageous in terms of cost. However, there is a problem that the plastic film substrate is inferior in water vapor barrier property as compared with the glass substrate. For this reason, when a plastic film substrate is used for a liquid crystal display element, water vapor enters the liquid crystal cell and a display defect occurs.

In order to solve this problem, Patent Document 1 discloses a technique for realizing a water vapor transmission rate of less than 0.005 g / m ² / day by using an alternating laminate of an organic layer and an inorganic layer as a barrier layer. Is disclosed. According to the specification, when only one organic layer and one inorganic layer are laminated, the water vapor transmission rate is 0.011 g / m ² / day, and the technical value of multilayer lamination is clearly It is shown.

US Pat. No. 6,413,645

However, in consideration of industrial applicability, as described in Patent Document 1, since the multi-layer stacking of the organic layer and the inorganic layer reduces productivity, it is necessary to supply a large amount of gas barrier film. It becomes a big problem. In order to manufacture a gas barrier film in a large amount at a low cost, it is required to develop a high barrier property even with the smallest possible number of layers. From these backgrounds, the organic layer, the set of the inorganic layer is 0.005g / m ² / day following a set, barrier properties particularly for organic-inorganic laminate type capable of achieving a moisture vapor transmission rate of less than 0.001g / m ² / day Development of a laminate, a gas barrier film having the barrier laminate, and an organic EL device using the gas barrier film is desired. A gas barrier film used as a substrate for a device such as an organic EL element needs to have high resistance to a process temperature. For this reason, the organic layer is required to be firmly adhered to the base material or the inorganic layer, and further, the amount of gas generated from the organic layer needs to be kept small.

Here, as a means for improving the adhesion between the organic layer and the inorganic layer, a method of adding several percent of a silane coupling agent to the organic layer is known. However, as a result of investigations by the present inventors, it has been found that conventionally known silane coupling agents are thermally decomposed at a high temperature to cause degassing such as methanol. FIG. 1 shows the state, where 1 is an inorganic layer, 2 ′ is an organic layer formed using a silane coupling agent provided on the surface of the inorganic layer, and 3 is a surface of the organic layer. The inorganic layer further provided in FIG. Alcohol 4 derived from the coupling agent remains in the conventional organic layer 2 ′. When heating or degassing occurs in this state, the alcohol gas is released and gas barrier properties are lowered. Furthermore, in the configuration in which the organic layer 2 ′ is sandwiched between inorganic layers as shown in FIG. 1, the gas derived from the alcohol 4 may destroy the adjacent inorganic layer 3. That is, when a device incorporating such a barrier laminate is exposed to a high-temperature process, the influence of residual byproducts appears significantly.
The object of the present invention is to provide a gas barrier laminate having a high barrier property capable of improving the heat-resistant temperature.

As a result of the inventor's earnest examination under the above problems, by adopting the following barrier laminate, high barrier properties can be maintained without being broken even at high temperatures, and the above problems are solved. I found out to solve it. Specifically, it was achieved by the following <1>. More preferably, it was achieved by the following <2> to <17>.
<1> An inorganic layer and an organic layer provided on the surface of the inorganic layer, wherein the organic layer is a polyfunctional (meth) acrylate, a compound represented by the general formula (I), and a general formula ( A barrier laminate comprising a polymer obtained by polymerizing a polymerizable composition containing at least one compound represented by II-a) and a compound represented by formula (II-b).
Formula (I)

(In the general formula (I), R ¹ to R ⁶ are each an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent, provided that R ¹ to R ⁶ At least one of them is a substituent containing a radically polymerizable carbon-carbon double bond.)
Formula (II-a)

(In the general formula (II-a), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents —CR ₂ —, —O—, —CO—, —CR═CR—, an arylene group, or Represents a heteroarylene group or a divalent linking group in which two or more of these are connected, A represents —O— or —NR—, and each R represents a hydrogen atom or a substituent, and if possible, It may be bonded to form a ring.)
Formula (II-b)

(In the general formula (II-b), R ²¹ represents a hydrogen atom and a methyl group. R ²² represents a single bond, an alkylene group, an arylene group, or two or more selected from these are an amide bond or This represents a linking group having a structure linked by an ester bond, having 2 to 82 atoms, and not having an aliphatic cyclic structure.The alkylene group and aryl group have a substituent. N2 represents an integer of 1 to 5.)
<2> The barrier laminate according to <1>, wherein the substituent containing a radically polymerizable carbon-carbon double bond in the general formula (I) is a (meth) acryloyloxy group.
<3> At least a polyfunctional (meth) acrylate, a compound represented by the general formula (I), a compound represented by the general formula (II-a), and a compound represented by the general formula (II-b) The barrier laminate according to <1> or <2>, wherein one type has an aromatic group.
<4> The barrier laminate according to any one of <1> to <3>, wherein the (meth) acrylate contained in the polymerizable composition is an aromatic (meth) acrylate.
<5> The organic layer according to any one of <1> to <3>, wherein the organic layer is formed by applying a polymerizable composition containing an aromatic (meth) acrylate to the surface of the inorganic layer and curing it. The barrier laminate according to the description.
<6> The barrier laminate according to any one of <1> to <5>, further comprising a second inorganic layer on the surface of the organic layer.
<7> The barrier laminate according to any one of <6>, further including a second organic layer on a surface of the second inorganic layer.
<8> Any one of <1> to <7>, wherein the inorganic layer and / or the second inorganic layer includes an oxide, nitride, carbide, or mixture of Si or Al. The barrier laminate according to 1.
<9> At least the first inorganic layer, the first organic layer, the second inorganic layer, the second organic layer, and the third inorganic layer are stacked adjacent to each other in this order, The barrier laminate according to any one of <1> to <8>, wherein the organic layer and the second organic layer contain a polymer obtained by polymerizing the polymerizable composition.
<10> Any one of <1> to <9>, wherein the number of carboxy groups in the compound represented by the general formula (II-a) or the compound represented by the general formula (II-b) is one The barrier laminate according to Item.
<11> A gas barrier film in which the barrier laminate according to any one of <1> to <10> is provided on a support.
<12> A gas barrier film according to <11>, further comprising an organic layer between the support and the barrier laminate.
<13> A device using the gas barrier film according to <11> or <12> as a substrate.
<14> A device sealed with the barrier laminate according to any one of <1> to <10> or the gas barrier film according to <11> or <12>.
<15> The device according to <13> or <14>, wherein the device is an organic EL element or a solar cell element.
<16> A sealing bag using the barrier laminate according to any one of <1> to <10> or the gas barrier film according to <11> or <12>.
<17> An inorganic layer and an organic layer provided on the surface of the inorganic layer are provided on the support, and the organic layer is a polyfunctional (meth) acrylate, a compound represented by the general formula (I), And applying a polymerizable composition containing at least one of the compound represented by the general formula (II-a) and the compound represented by the general formula (II-b) and heating at a temperature of 25 ° C. or higher. The method for producing a gas barrier film according to <11> or <12>, comprising curing by light beam, electron beam curing, or heat ray.

By adopting the organic layer in the present invention, the generation of outgas is less and it becomes possible to improve the adhesion between the inorganic layer and the organic layer. Furthermore, it has become possible to provide a barrier laminate having improved heat resistance.

It is a cross-sectional schematic diagram which shows the state from which gas discharge | releases from the conventional barriering laminated body. It is a cross-sectional schematic diagram which shows an example of the barriering laminated body of this invention. It is a section schematic diagram showing an example of composition of a gas barrier film of the present invention.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element. In this specification, (meth) acrylate is used in the meaning including both acrylate and methacrylate.

<Barrier laminate>
The barrier laminate of the present invention has an inorganic layer and an organic layer provided on the surface of the inorganic layer, and the organic layer is a polyfunctional (meth) acrylate, a compound represented by the general formula (I) And a polymerizable composition comprising at least one of a compound represented by general formula (II-a) and a compound represented by general formula (II-b) (hereinafter referred to as “polymerizable composition in the present invention”). It is characterized by containing a polymer obtained by polymerizing. By setting it as the barriering laminated body which has such an organic layer, the adhesiveness of an organic layer and an inorganic layer can be improved and heat resistance performance can be improved.
Formula (I)

(In the general formula (II-b), R ²¹ represents a hydrogen atom and a methyl group. R ²² represents a single bond, an alkylene group, an arylene group, or two or more selected from these are an amide bond or This represents a linking group having a structure linked by an ester bond, having 2 to 82 atoms, and not having an aliphatic cyclic structure.The alkylene group and aryl group have a substituent. N2 represents an integer of 1 to 5.)

The barrier laminate of the present invention is preferably a barrier laminate having a second inorganic layer on the surface of the organic layer, and more preferably on the surface of the second inorganic layer. And a barrier laminate having a second organic layer.
FIG. 2 is a schematic cross-sectional view showing an example of the barrier laminate of the present invention, wherein 1 is a first inorganic layer, 2 is an organic layer, 3 is a second inorganic layer, and 10 is a barrier property. Each of the laminates is shown.
When forming an organic layer, it is generally performed that a composition containing a polymerizable composition and a silane coupling agent is applied on an inorganic layer and cured. Here, for example, when a silane coupling agent as described in JP-A-2001-125079 is used, alcohol (methanol, ethanol) as a by-product of hydrolysis remains in the organic layer. It has been found that this remaining alcohol releases a large amount of outgas at a later process, eg, at the stage of incorporation into the device. In particular, as in this embodiment shown in FIG. 2, in the case where the organic layer is sandwiched between two inorganic layers, the gas derived from the silane coupling agent has destroyed the inorganic layer. In contrast, in the present invention, even if the silane coupling agent is hydrolyzed, the silane coupling agent does not substantially produce gaseous components other than ammonia, and thus the above-described problem does not occur. That is, the barrier laminate of the present invention can maintain a high gas barrier property even at high temperature or in a vacuum process, and can secure adhesion between the organic layer and the inorganic layer.

In FIG. 2, the organic layer 2 is only one layer, but may further include a second organic layer. In the case of having two or more organic layers, one layer adjacent to the inorganic layer may be at least the organic layer. That is, in the present invention, a configuration in which at least two organic layers and at least two inorganic layers are alternately laminated is preferable. Further, the number of layers constituting the barrier laminate is not particularly limited, but typically 2 to 30 layers are preferable, and 3 to 20 layers are more preferable.

(Organic layer)
At least one layer of the organic layers in the present invention contains a polymer obtained by polymerizing the polymerizable composition in the present invention.
In the present invention, the polyfunctional (meth) acrylate, the compound represented by the general formula (I), the compound represented by the general formula (II-a) and the compound represented by the general formula (II-b) At least one kind preferably has an aromatic group and may be an aromatic heterocyclic group, but more preferably has an aromatic hydrocarbon group.
In the present invention, the polyfunctional (meth) acrylate forms a heat-resistant three-dimensional network structure, and the compound represented by the general formula (I) is represented by the compound represented by the general formula (II-a) or the general formula ( It is presumed that the effect of the present invention is achieved by the covalent bond with the surface of the inorganic layer by the catalytic effect of the compound carboxylic acid represented by II-b). In this case, at least one of the compound represented by the general formula (I), the compound represented by the general formula (II-a), and the compound represented by the general formula (II-b) is polymerized by ethylene. Since these groups have groups, incorporation of these into the three-dimensional network structure also contributes to the effects of the present invention.

(Compound represented by general formula (II-a) and compound represented by general formula (II-b))
Formula (II-a)

(In the general formula (II-a), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents —CR ₂ —, —O—, —CO—, —CR═CR—, an arylene group, or Represents a heteroarylene group or a divalent linking group in which two or more of these are connected, A represents —O— or —NR—, and each R represents a hydrogen atom or a substituent, and if possible, It may be bonded to form a ring.)
R ¹¹ is preferably hydrogen.
R ¹² is preferably a divalent linking group in which two or more of —CR ₂ —, —O—, —CO—, an arylene group, and a heteroarylene group are linked, and —CR ₂ —, —O— And a divalent linking group in which two or more of —CO— are linked, or a divalent linking group composed of a combination of these linking groups and an arylene group or heteroarylene group is more preferred, —CR ₂ —, —O A divalent linking group composed of a combination of two or more of — and —CO— and an arylene group is more preferable.
The arylene group and heteroarylene group are preferably 6-membered rings.
When R is a substituent, examples of the substituent R described later are exemplified, and an alkyl group (for example, a methyl group) or a group represented by —R ¹² —COOH is preferable. In this case, R ¹² has the same meaning as R ¹² described above, and the preferred range is also the same.
R ¹² preferably has 5 to 10 atoms constituting the main skeleton of the linking group (the number of atoms constituting the chain portion linking A and COOH). From a structural viewpoint, R ¹² is preferably a chain structure having an ester bond in the structure.

Formula (II-b)

(In the general formula (II-b), R ²¹ represents a hydrogen atom and a methyl group. R ²² represents a single bond, an alkylene group, an arylene group, or two or more selected from these are an amide bond or This represents a linking group having a structure linked by an ester bond, having 2 to 82 atoms, and not having an aliphatic cyclic structure.The alkylene group and aryl group have a substituent. N2 represents an integer of 1 to 5.)
R ²¹ is preferably a hydrogen atom.
In the general formula (II-b), R ²² has a structure in which a single bond, an alkylene group, an arylene group, or two or more selected from these are connected by an amide bond or an ester bond, It represents a linking group having 2 to 82 atoms and having no aliphatic cyclic structure. The alkylene group and aryl group may have a substituent. The linking group is an n-valent linking group, and n is an integer of 2 or more, preferably a divalent to pentavalent linking group, and more preferably a divalent linking group.
R ²² preferably has 5 to 10 atoms constituting the main skeleton of the linking group (the number of atoms constituting the longest chain portion linking the benzene ring and COOH). Structurally, R ²² is preferably a single bond or a chain structure having an ester bond in the structure. R ²² is a single bond, —CR ₂ —, —O—, —CO—, —CR═CR—, an arylene group, a heteroarylene group, or a divalent linking group in which two or more of these are linked. It is preferably a single bond or —CR ₂ —, —O—, —CO—, —CR═CR—, or more preferably a divalent linking group in which two or more of these are linked. Or, a divalent linking group comprising a combination of —CH ₂ — and / or —O— and an ester bond is more preferable. Here, R is a hydrogen atom or a substituent, and examples of the substituent include the following substituent R. R is preferably a hydrogen atom.

Examples of the linking group for R ²² include alkylene groups (eg, 1,3-propylene group, 2,2-dimethyl-1,3-propylene group, 2-butyl-2-ethyl-1,3-propylene group, 1 , 6-hexylene group, 1,9-nonylene group, 1,12-dodecylene group, 1,16-hexadecylene group, etc.), arylene group (for example, phenylene group, naphthylene group), ether group, imino group, carbonyl group, And a divalent residue in which a plurality of these divalent groups are bonded in series.
These groups may have a substituent, and examples of the substituent that can be substituted include the substituent R described later.

Substituent R
Examples of the substituent R include an alkyl group (for example, methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. ), Alkenyl groups (eg, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), aryl groups (eg, phenyl, p-methylphenyl, naphthyl, anthryl, phenanthryl, pyrenyl) Etc.), halogen atoms (eg, fluorine, chlorine, bromine, iodine), acyl groups (eg, acetyl group, benzoyl group, formyl group, pivaloyl group, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.) ), Aryloxycarbonyl group (for example, phenyloxycarbonyl group, etc.) Etc. The. These substituents may be further substituted. If possible, these substituents may be combined with each other or with a substituted hydrocarbon group to form a ring, and the substituent may be further substituted.
n2 represents an integer of 1 to 5, and is preferably 1.

In the present invention, among the compound represented by the general formula (II-a) and the compound represented by the general formula (II-b), the compound represented by the general formula (II-a) is more preferable. A compound represented by the general formula (II-a) and having an aromatic group (further, an aromatic hydrocarbon group) is more preferable.

Hereinafter, preferred specific examples of the compound represented by the general formula (II-a) or the compound represented by the general formula (II-b) are shown, but the present invention is not limited thereto.

The above compound can be synthesized by the method described in Japanese Patent No. 4466821.

The total amount of the compound represented by the general formula (II-a) and the compound represented by the general formula (II-b) used in the present invention is 1 to 50% by mass in the polymerizable composition. It is preferably included in the range, more preferably 5 to 30% by mass, and still more preferably 5 to 15% by mass. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

(Compound represented by formula (I))
Formula (I)

(In the general formula (I), R ¹ to R ⁶ are each an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent, provided that R ¹ to R ⁶ At least one of them is a substituent containing a radically polymerizable carbon-carbon double bond.)

R ¹ to R ⁶ are each a substituted or unsubstituted alkyl group or aryl group. R ¹ to R ⁶ are preferably an unsubstituted alkyl group or an unsubstituted aryl group, except in the case of a substituent containing a radically polymerizable carbon-carbon double bond. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable. As the aryl group, a phenyl group is preferable. R ¹ to R ⁶ are particularly preferably a methyl group.

At least one of R ¹ ~ R ⁶ is a radical polymerizable carbon - having a substituent containing a carbon double bond, two are radically polymerizable carbon of R ¹ ~ R ⁶ - carbon double bonds A substituent is preferred. Further, among R ¹ to R ³ , the number of those having a substituent containing a radically polymerizable carbon-carbon double bond is 1, and among R ⁴ to R ⁶ , the radically polymerizable carbon-carbon dioxygen is one. The number of those having a substituent containing a heavy bond is particularly preferably 1.
The substituents in which the silane coupling agent represented by the general formula (I) includes two or more radically polymerizable carbon-carbon double bonds may be the same or different. However, the same is preferable.

The substituent containing a radically polymerizable carbon-carbon double bond is preferably represented by —XY. Here, X is a single bond, an alkylene group having 1 to 6 carbon atoms, or an arylene group, preferably a single bond, a methylene group, an ethylene group, a propylene group, or a phenylene group. Y is a radically polymerizable carbon-carbon double bond group, and is preferably an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, a propenyl group, a vinyloxy group, or a vinylsulfonyl group. ) An acryloyloxy group is more preferred.

R ¹ to R ⁶ may have a substituent other than a substituent containing a radical polymerizable carbon-carbon double bond. Examples of substituents include alkyl groups (eg, methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group). Etc.), aryl groups (eg phenyl group, naphthyl group etc.), halogen atoms (eg fluorine, chlorine, bromine, iodine), acyl groups (eg acetyl group, benzoyl group, formyl group, pivaloyl group etc.), acyloxy Groups (for example, acetoxy group, acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl groups (for example, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl groups (for example, phenyloxycarbonyl group, etc.), sulfonyl groups ( For example, methanesulfonyl group, benzenesulfonate Group, etc.).

Although the specific example of a compound represented by general formula (I) below is shown, this invention is not limited to these.

The silane coupling agent used in the present invention is preferably contained in the polymerizable composition in the range of 1 to 30% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 25% by mass. %. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.
Moreover, it is preferable that the polymeric composition used by this invention does not contain silane coupling agents other than the silane coupling agent represented with general formula (I) substantially. “Substantially free” means, for example, 0.1% by mass or less of the total components of the polymerizable composition.

Polyfunctional (meth) acrylate The polymerizable composition in the present invention contains a polyfunctional (meth) acrylate. The number of functional groups is preferably 3-6. Moreover, (meth) acrylate containing an aromatic group is more preferable, and (meth) acrylate having an aromatic hydrocarbon group is more preferable. Of course, it does not exclude including monofunctional (meth) acrylate in addition to polyfunctional (meth) acrylate.

Although the specific example of a (meth) acrylate type compound is shown below, this invention is not limited to these.

Furthermore, in this invention, the methacrylate type compound represented by General formula (3) can be employ | adopted preferably.
General formula (3)

(In the general formula (3), R ¹ represents a substituent and may be the same or different. N represents an integer of 0 to 5, and may be the same or different. Provided that at least one of R ¹ contains a polymerizable group.)

As the substituent of R ¹ , —CR ² ₂ — (R ² is a hydrogen atom or a substituent), —CO—, —O—, a phenylene group, —S—, —C≡C—, —NR ³ — ( R ³ is a hydrogen atom or a substituent), and —CR ⁴ ═CR ⁵ — (R ⁴ and R ⁵ are each a hydrogen atom or a substituent) and a polymerizable group. A group consisting of a combination of one or more of —CR ² ₂ — (wherein R ² is a hydrogen atom or a substituent), —CO—, —O— and a phenylene group and a polymerizable group is preferable.
R ² is a hydrogen atom or a substituent, and is preferably a hydrogen atom or a hydroxy group.
It is preferable that at least one of R ¹ includes a hydroxy group. By including a hydroxy group, the curing rate of the mechanical layer is improved.
The molecular weight of at least one R ¹ is preferably 10 to 250, more preferably 70 to 150.
The position where R ¹ is bonded is preferably bonded to at least the para position.
n represents an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 1.

In the compound represented by the general formula (3), it is preferable that at least two of R ¹ have the same structure. Furthermore, it is more preferable that n is 1, and at least two of the four R ^{1 s} have the same structure, and n is 1, and the four R ^{1 s} have the same structure. Is more preferable. The polymerizable group of the general formula (3) is preferably a (meth) acryloyl group or an epoxy group, and more preferably a (meth) acryloyl group. The number of polymerizable groups that the general formula (3) has is preferably 2 or more, and more preferably 3 or more. The upper limit is not particularly defined, but is preferably 8 or less, and more preferably 6 or less.
The molecular weight of the compound represented by the general formula (3) is preferably 600 to 1400, and more preferably 800 to 1200.

In this invention, only 1 type of compounds represented by General formula (3) may be included, and 2 or more types may be included. When two or more types are contained, for example, a composition containing R ¹ having the same structure and different number of R ¹ and isomers thereof is exemplified.

Although the specific example of a compound represented by General formula (3) below is shown, this invention is not limited by this. Moreover, in the following compound, although four n of general formula (3) has illustrated the case where all are 1, 1 or 2 or 3 is 0 among four n of general formula (3). One (for example, bifunctional or trifunctional compound) or one in which two or more of three in the general formula (3) are two or more (R ¹ is one ring, Those having two or more bonds, such as pentafunctional and hexafunctional compounds, are also exemplified as preferred compounds of the present invention.

The compound represented by the general formula (3) can be obtained as a commercial product. Moreover, the said compound is also compoundable by a well-known method. For example, epoxy acrylate can be obtained by reaction of an epoxy compound and acrylic acid. These compounds usually generate bifunctional, trifunctional, pentafunctional and isomers thereof during the reaction. When it is desired to separate these isomers, they can be separated by column chromatography, but in the present invention, they can also be used as a mixture.

The blending amount of the polyfunctional (meth) acrylate in the polymerizable composition of the present invention is preferably 50 to 99% by mass, more preferably 85 to 95% by mass, based on the solid content excluding the solvent. .

In the polymerizable composition of the present invention, 90% by mass or more of the total solid content is a polyfunctional (meth) acrylate, a compound represented by the general formula (I), a compound represented by the general formula (II-a), and It is preferably composed of a compound represented by the general formula (II-b).

(Polymerization initiator)
The organic layer in the present invention is usually obtained by coating and curing a polymerizable composition. In the present invention, an organic layer mainly composed of a polymer is formed by irradiating the polymerizable composition with heat or various energy rays for polymerization and crosslinking. Examples of energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, X-rays, and gamma rays. At this time, a thermal polymerization initiator is used for polymerization with heat, a photopolymerization initiator is used for polymerization with ultraviolet light, and a photopolymerization initiator and a sensitizer are used for polymerization with visible light. In the above, it is preferable to superpose | polymerize and bridge | crosslink the polymeric compound containing a photoinitiator with an ultraviolet-ray.
When a photopolymerization initiator is used, its content is preferably 0.1 mol% or more, more preferably 0.5 to 2 mol% of the total amount of the polymerizable compounds. By setting it as such a composition, the polymerization reaction via an active component production | generation reaction can be controlled appropriately. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure, commercially available from Ciba Specialty Chemicals. 819), Darocure series (for example, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Esacure series (for example, Ezacure TZM, Ezacure, commercially available from Lamberti) TZT etc.).

(Formation method of organic layer)
As a method for layering the polymerizable composition, it is usually formed by applying the polymerizable composition on a support such as a base film or an inorganic layer. Application methods include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or the hopper described in US Pat. No. 2,681,294. Extrusion coating methods used are exemplified, and among these, the coating method can be preferably employed.
The light to irradiate is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The radiation energy is preferably 0.1 J / cm ² or more, 0.5 J / cm ² or more is more preferable. When a (meth) acrylate compound is employed as the polymerizable compound, the polymerization is inhibited by oxygen in the air, and therefore it is preferable to reduce the oxygen concentration or oxygen partial pressure during polymerization. When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of 0.5 J / cm ² or more under a reduced pressure condition of 100 Pa or less.

The organic layer in the present invention is preferably smooth and has high film hardness. The smoothness of the organic layer is preferably less than 1 nm as average roughness (Ra value) of 1 μm square, and more preferably less than 0.5 nm. The polymerization rate of the monomer is preferably 85% or more, more preferably 88% or more, further preferably 90% or more, and particularly preferably 92% or more. The polymerization rate here means the ratio of the reacted polymerizable group among all the polymerizable groups (for example, acryloyl group and methacryloyl group) in the monomer mixture. The polymerization rate can be quantified by an infrared absorption method.

The film thickness of the organic layer is not particularly limited, but if it is too thin, it is difficult to obtain film thickness uniformity, and if it is too thick, cracks are generated due to external force and the barrier property is lowered. From this viewpoint, the thickness of the organic layer is preferably 50 nm to 2000 nm, and more preferably 200 nm to 1500 nm.
The surface of the organic layer is required to be free of foreign matters such as particles and protrusions. For this reason, it is preferable that the organic layer is formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.
It is preferable that the organic layer has a high hardness. It has been found that when the hardness of the organic layer is high, the inorganic layer is formed smoothly and as a result, the barrier ability is improved. The hardness of the organic layer can be expressed as a microhardness based on the nanoindentation method. The microhardness of the organic layer is preferably 100 N / mm or more, and more preferably 150 N / mm or more.

(Inorganic layer)
The inorganic layer is usually a thin film layer made of a metal compound. As a method for forming the inorganic layer, any method can be used as long as it can form a target thin film. For example, there are a physical vapor deposition method (PVD) such as a vapor deposition method, a sputtering method, and an ion plating method, various chemical vapor deposition methods (CVD), and a liquid phase growth method such as plating and a sol-gel method. In the present invention, high barrier properties can be maintained even when the sputtering method is used. The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance. For example, it is a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide, such as Si, Al, In, Sn, Zn. An oxide, nitride, carbide or oxynitride, oxynitride carbide, or the like containing one or more metals selected from Ti, Cu, Ce, Ta, or the like can be preferably used. Among these, a metal oxide, nitride, or oxynitride selected from Si, Al, In, Sn, Zn, and Ti is preferable, and a metal oxide, nitride, or oxynitride of Si or Al is particularly preferable. These may contain other elements as secondary components. In the present invention, even when a metal oxide is used as a material for the inorganic layer and a film is formed by a plasma process, it is extremely significant in that a barrier laminate having a high barrier property can be obtained. In the present invention, a mixed oxide of silicon nitride, silicon oxide, silicon nitride, silicon oxide, or silicon carbide is particularly preferable. By adopting these inorganic substances, the adhesion between the organic layer and the inorganic layer is further improved. More preferably, silicon nitride is desirable in that a dense film can be obtained and a barrier laminate having high barrier properties can be obtained.
The smoothness of the inorganic layer formed according to the present invention is preferably less than 1 nm, more preferably 0.5 nm or less, as an average roughness (Ra value) of 1 μm square. For this reason, it is preferable that the inorganic layer be formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.

The thickness of the inorganic layer is not particularly limited, but it is usually in the range of 5 to 500 nm, preferably 20 to 200 nm per layer. Two or more inorganic layers may be laminated. In the present invention, in an embodiment in which two or more inorganic layers are provided, the adhesion between the layers can be improved, and the failure rate when used in an electronic device can be reduced. When two or more layers are provided, each layer may have the same composition or a different composition. Moreover, when laminating | stacking two or more layers, it is desirable to design so that each inorganic layer may exist in said preferable range. Further, as described above, as disclosed in US Patent Publication No. 2004-46497, the interface with the organic layer is not clear, and the composition may include a layer whose composition changes continuously in the film thickness direction. .

(Lamination of organic and inorganic layers)
The organic layer and the inorganic layer can be stacked by sequentially repeating the organic layer and the inorganic layer according to a desired layer configuration. When the inorganic layer is formed by a vacuum film formation method such as sputtering, vacuum vapor deposition, ion plating, or plasma CVD, the organic layer is also preferably formed by a vacuum film formation method such as the flash vapor deposition method. . In particular, the present invention can exhibit high barrier properties when at least two organic layers and at least two inorganic layers are alternately laminated. Furthermore, in a configuration in which two or more organic layers sandwiched between two inorganic layers are included, for example, in a configuration in which an inorganic layer, an organic layer, an inorganic layer, an organic layer, and an inorganic layer are adjacent to each other in that order, the higher Barrier property can be exhibited. In particular, in the present invention, by providing an inorganic layer on the surface of the organic layer derived from the polymerizable aromatic silane coupling agent, the adhesion between the organic layer and the inorganic layer is improved, which is more preferable.

(Functional layer)
The device of the present invention may have a functional layer on the barrier laminate or at other positions. The functional layer is described in detail in paragraph numbers 0036 to 0038 of JP-A-2006-289627. Examples of functional layers other than these include matting agent layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, and antifouling layers. , Printing layer, easy adhesion layer and the like.

Applications of Barrier Laminate The barrier laminate of the present invention is usually provided on a support, and can be used for various applications by selecting this support. In addition to the base film, the support includes various devices, optical members, and the like. Specifically, the barrier laminate of the present invention can be used as a barrier layer of a gas barrier film. The barrier laminate and gas barrier film of the present invention can be used for sealing devices that require barrier properties. The barrier laminate and gas barrier film of the present invention can also be applied to optical members. Hereinafter, these will be described in detail.

<Gas barrier film>
The gas barrier film has a base film and a barrier laminate formed on the base film. FIG. 3 shows an example of the configuration of the gas barrier film of the present invention, and shows a configuration in which organic layers and inorganic layers are alternately provided on the base film 5. Specifically, in order from the base film 5 side, the organic layer 6, the inorganic layer 1, the organic layer 2, and the inorganic layer 3 are provided so that their surfaces are adjacent to each other. The organic layer 6 is also called an undercoat layer and improves the adhesion between the base film 5 and the inorganic layer 13. The organic layer 6 may be an organic layer containing a polymer obtained by polymerizing the polymerizable composition in the present invention, or may be another organic layer. In this invention, the adhesiveness of the base film 5 and an organic layer is improved by employ | adopting the organic layer containing the polymer which polymerizes the polymeric composition in this invention for the organic layer adjacent to the base film 5. Can be made. In particular, it is effective when the base film is PET or PEN.
In the gas barrier film, the barrier laminate of the present invention may be provided only on one side of the base film, or may be provided on both sides. The barrier laminate of the present invention may be laminated in the order of the inorganic layer and the organic layer from the base film side, or may be laminated in the order of the organic layer and the inorganic layer. The uppermost layer of the barrier laminate of the present invention may be an inorganic layer or an organic layer.
A gas barrier film may have structural components (for example, functional layers, such as an easily bonding layer) other than a barriering laminated body and a base film. The functional layer may be placed on the barrier laminate, between the barrier laminate and the base film, or on the side where the barrier laminate on the base film is not placed (back side).

(Plastic film)
The gas barrier film in the present invention usually uses a plastic film as the base film. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a laminate such as an organic layer and an inorganic layer, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include metal support (aluminum, copper, stainless steel, etc.) polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, and fluorinated polyimide resin. , Polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin Examples thereof include thermoplastic resins such as filn copolymers, fluorene ring-modified polycarbonate resins, alicyclic ring-modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

When the gas barrier film of the present invention is used as a substrate of a device such as an organic EL element described later, the plastic film is preferably made of a material having heat resistance. Specifically, the glass transition temperature (Tg) is preferably 100 ° C. or higher and / or the linear thermal expansion coefficient is 40 ppm / ° C. or lower and is preferably made of a transparent material having high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive. Examples of such thermoplastic resins include polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate ( PAr: 210 ° C., polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: compound of JP 2001-150584 A: 162 ° C.), polyimide (for example, Mitsubishi Gas Chemical) Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of JP 2000-227603 A) : 205 ° C), acryloyl compound (Compound disclosed in Japanese Patent Application Laid-Open No. 2002-80616: 300 ° C. or higher) (Tg is shown in parentheses). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

When the gas barrier film of the present invention is used in combination with a polarizing plate, it is preferable that the gas barrier film is disposed so that the barrier laminate of the gas barrier film faces the inside of the cell and is located on the innermost side (adjacent to the element). At this time, since the gas barrier film is disposed inside the cell from the polarizing plate, the retardation value of the gas barrier film is important. The usage form of the gas barrier film in such an embodiment includes a gas barrier film using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (1/4 wavelength plate + (1/2 wavelength plate) + linearly polarizing plate. It is preferable to use a linear polarizing plate in combination with a gas barrier film using a base film having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate.

As a base film having a retardation of 10 nm or less, cellulose triacetate (Fuji Film Co., Ltd .: Fuji Tac), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace, Kaneka: Elmec Co., Ltd.), cycloolefin polymer (JSR Co., Ltd.) ): Arton, Nippon Zeon Co., Ltd .: Zeonoa), cycloolefin copolymer (Mitsui Chemicals Co., Ltd .: Appel (pellet), Polyplastic Co., Ltd .: Topas (pellet)) Polyarylate (Unitika Co., Ltd.): U100 (pellet) )), Transparent polyimide (Mitsubishi Gas Chemical Co., Ltd .: Neoprim) and the like.
Moreover, as a quarter wavelength plate, the film adjusted to the desired retardation value by extending | stretching said film suitably can be used.

Since the gas barrier film of the present invention is used as a device such as an organic EL element, the plastic film is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, more preferably 90% or more. It is. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. be able to.
Even when the gas barrier film of the present invention is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.
The thickness of the plastic film used in the gas barrier film of the present invention is appropriately selected depending on the application and is not particularly limited, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. The functional layer is described in detail in paragraph numbers 0036 to 0038 of JP-A-2006-289627. Examples of functional layers other than these include matting agent layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, and antifouling layers. , Printing layer, easy adhesion layer and the like.

<Device>
The barrier laminate and gas barrier film of the present invention can be preferably used for devices whose performance is deteriorated by chemical components in the air (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.). Examples of the device include electronic devices such as an organic EL element, a liquid crystal display element, a thin film transistor, a touch panel, electronic paper, and a solar cell, and are preferably used for the organic EL element.

The barrier laminate of the present invention can also be used for device film sealing. That is, it is a method of providing the barrier laminate of the present invention on the surface of the device itself as a support. The device may be covered with a protective layer before providing the barrier laminate.

The gas barrier film of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after forming a protective layer on the device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

When the conventional barrier laminate and gas barrier film are incorporated in a device and heated at a temperature of 80 ° C. or higher in that state, the alcohol gas derived from the silane coupling agent is released and the device is damaged. It was. However, since the barrier laminate and the gas barrier film of the present invention do not release a large amount of alcohol gas even when heated at a temperature of 80 ° C. or higher (for example, 80 to 200 ° C.), it is effective to damage the device. Can be suppressed.

(Organic EL device)
Examples of organic EL elements using a gas barrier film are described in detail in JP-A-2007-30387. Since the manufacturing process of the organic EL device includes a drying process after the ITO etching process and a process under high humidity conditions, it is extremely advantageous to use the gas barrier film of the present invention.

(Liquid crystal display element)
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization in order from the bottom It has a structure consisting of a film. Of these, the substrate of the present invention can be used as the upper transparent electrode and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably TN type (Twisted Nematic), STN type (Super Twisted Nematic), HAN type (Hybrid Aligned Nematic), VA type (Vertically Alignment), ECB type (Electrically Controlled Birefringence) OCB type (Optically Compensated Bend), CPA type (Continuous Pinwheel Alignment), and IPS type (In Plane Switching) are preferable.

(Solar cell)
The barrier laminate and gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the barrier laminate and the gas barrier film of the present invention are preferably sealed so that the adhesive layer is closer to the solar cell element. The solar cell is required to withstand a certain amount of heat and humidity, but the barrier laminate and the gas barrier film of the present invention are suitable. The solar cell element in which the barrier laminate and the gas barrier film of the present invention are preferably used is not particularly limited, and for example, a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem Amorphous silicon solar cell elements composed of structural types, III-V compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductors such as cadmium telluride (CdTe) Solar cell element, copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur system (so-called CIGS system), etc. Group I-III-VI compound semiconductor solar cell element, dye-sensitized solar cell element, organic solar cell Child, and the like. Among these, in the present invention, the solar cell element is made of a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur. A group I-III-VI compound semiconductor solar cell element such as a system (so-called CIGSS system) is preferable.

(Other)
As other application examples, the thin film transistor described in JP-T-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., and described in JP-A-2000-98326 Electronic paper, solar cells described in JP-A-9-18042, and the like.
Moreover, resin films, such as a polyethylene film and a polypropylene film, and the barriering laminated body or gas barrier film of this invention can be laminated | stacked, and it can use as a bag for sealing. For details of these, descriptions in JP-A-2005-247409, JP-A-2005-335134, and the like can be referred to.

<Optical member>
Examples of the optical member using the gas barrier film of the present invention include a circularly polarizing plate.
(Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film of the present invention as a substrate. In this case, the lamination is performed so that the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

(Example 1)
Preparation of organic layer coating solution The following (meth) acrylate, the following silane coupling agent, a compound corresponding to the following general formula (II-a) or (II-b), and a polymerization initiator (Lamberti, Esacure KTO46) A 40% methyl ethyl ketone (MEK) solution of the composition consisting of
The following (meth) acrylate, the following silane coupling agent, and the compounding amount of the compound corresponding to the following general formula (II-a) or (II-b) are blended at a ratio (weight ratio) shown in Table 1, 2 weight% of polymerization initiators were mix | blended with respect to these 100 weight part in total.

Preparation of Gas Barrier Film On the polyethylene naphthalate film (Teijin DuPont, Teonex Q65FA, thickness 100 μm), the organic layer coating solution prepared as described above was prepared with methyl ethyl ketone so that the dry film thickness was 1000 nm. In an atmosphere of 100 ppm nitrogen, it was cured by irradiation with an ultraviolet irradiation amount of 0.5 J / cm ² to prepare an organic layer. On the surface of the organic layer, SiN was formed by plasma CVD so that the film thickness was 40 nm. Furthermore, the same organic layer, inorganic layer, and organic layer were laminated | stacked, and the barrier film was produced.
About the obtained gas barrier film, the water-vapor-permeation rate and adhesiveness were measured with the following method.

(Meth) acrylate

Silane coupling agent

In the above formula, R represents CH ₂ CHCOOCH ₂ .
The silane coupling agent was synthesized in consideration of the method described in JP-A-2009-67778.

Number of atoms constituting the main skeleton of the compound (II-1) linking group corresponding to the general formula (II-a) or (II-b): 8

(II-2) Number of atoms constituting the main skeleton of the linking group: 6

(II-3)

(II-4)

(II-5)

[Barrier performance]
The water vapor transmission rate (g / m ² / day) was measured using the method described in G. NISATO, PCPBOUTEN, PJSLIKKERVEER et al. SID Conference Record of the International Display Research Conference, pages 1435-1438. The temperature at this time was 40 ° C. and the relative humidity was 90%. The results are shown in the table below.

[Adhesion test]
In order to evaluate the adhesion of the gas barrier film, a cross-cut test based on JIS K5400 was performed. The surface of the gas barrier film having the above layer structure was cut by 90 ° with respect to the film surface with a cutter knife at intervals of 1 mm, and 100 grids with intervals of 1 mm were produced. A 2 cm wide Mylar tape [manufactured by Nitto Denko, polyester tape (No. 31B)] was applied thereto, and the tape attached using a tape peeling tester was peeled off. Of the 100 grids on the laminated film, the number of cells remaining without peeling (n) was counted. The results are expressed in%.

Sample No. above. In 1 to 4, the inorganic layer was changed to a 50 nm thick AlO film formed by sputtering, and the others were performed in the same manner.

As is clear from the above results, it was found that the same effect was obtained even if the material of the inorganic layer was changed.

Sample No. above. In 1-4, the acrylate of the organic layer was changed to the same amount of the following compound, and the others were performed in the same manner.
(Meth) acrylate

As is clear from the above results, it was found that the same effect was obtained even if the material of the organic layer was changed.

Sample No. above 3, the compound corresponding to the general formula (II-a) or (II-b) was changed to the same amount of phosphoric acid monomer (KAYAMER PM-21, manufactured by Nippon Kayaku Co., Ltd.). It was created. The adhesiveness was evaluated by placing in an atmosphere of 85 ° C. and 85% for 1000 hours.

The sample using the phosphoric acid monomer deteriorated the adhesion after wet heat, and in the present invention, the adhesion after wet heat was improved.

(Example 2)
Preparation of organic layer coating solution In the same manner as in Example 1, except that the organic layer coating solution was prepared according to the following table. The silane coupling agent KBM used in the comparative example is (manufactured by Shin-Etsu Chemical, KBM5103).

Preparation of Gas Barrier Film On a polyethylene naphthalate film (manufactured by Teijin DuPont, Teonex Q65FA, thickness 100 μm), SiN was formed by plasma CVD so as to have a film thickness of 40 nm, thereby forming an inorganic layer. On the inorganic layer, the organic layer coating solution adjusted as described above was formed with methyl ethyl ketone so that the dry film thickness was 1000 nm, and irradiated with an ultraviolet ray irradiation amount of 0.5 J / cm ² in an atmosphere of 100 ppm nitrogen. And cured to produce an organic layer. On the surface of the organic layer, SiN was formed by a plasma CVD method so as to have a film thickness of 40 nm to form an inorganic layer. The obtained gas barrier film has a configuration in which an organic layer is sandwiched between an inorganic layer and an inorganic layer.

[Heat resistance test]
For the purpose of evaluating the heat resistance of the gas barrier film, the gas barrier film was placed in a thermostat at 200 ° C. and held for 1 hour. 10 cm square was observed, and the presence or absence of a swollen portion due to gas generation in the organic layer sandwiched between the inorganic layer and the inorganic layer was evaluated. The thing without a swelling part was represented by (circle), and the thing with a swelling part was represented by x. A case where a silane coupling agent KBM-5103 (Shin-Etsu Chemical Co., Ltd.) containing a large amount of volatile gas was used was taken as a comparative example.

[Adhesion test]
The adhesion was evaluated in the same manner as in Example 1.

As is clear from the above results, the compound of the present invention was found to be excellent in barrier properties and adhesion.

Evaluation by Organic EL Light-Emitting Element An organic EL element was prepared using the gas barrier film obtained above. First, an ITO film (resistance: 30Ω) was formed on the gas barrier film by sputtering. The following compound layers were sequentially deposited on this substrate (anode) by vacuum deposition.
(First hole transport layer)
Copper phthalocyanine: film thickness 10nm
(Second hole transport layer)
N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm
(Electron injection layer)
Lithium fluoride: film thickness 1nm
On top of this, metal aluminum was deposited to a thickness of 100 nm to form a cathode, and a 3 μm thick silicon nitride film was formed thereon by a parallel plate CVD method to produce an organic EL device.
Next, using the thermosetting adhesive (Epotech 310, Daizonichimori Co., Ltd.), the barrier laminate is the organic EL element side on the prepared organic EL element and the gas barrier film prepared above. Then, the adhesive was cured by heating at 65 ° C. for 3 hours. A total of 10 organic EL elements sealed in this way were produced.
As a result, when the gas barrier film of the comparative example was used, the gas barrier film used as the ITO film substrate was damaged and a good element could not be obtained. On the other hand, when the gas barrier film of the present invention was used, the gas barrier film used as the ITO film substrate was not damaged, and a good organic EL device was obtained.

Creation of solar cell A solar cell module was created using the gas barrier film created above. Specifically, a standard cure type ethylene-vinyl acetate copolymer was used as a filler for the solar cell module. A solar cell module was prepared by sandwiching and filling amorphous silicon solar cells with an ethylene-vinyl acetate copolymer having a thickness of 450 μm on a 10 cm square tempered glass and further installing a gas barrier film thereon. As installation conditions, vacuuming was performed at 150 ° C. for 3 minutes, and then pressure bonding was performed for 9 minutes. The solar cell module produced by this method operated well and exhibited good electrical output characteristics even in an environment of 85 ° C. and 85% relative humidity.

Creation of a sealing bag A sealing bag was created using the gas barrier film created above. The base film side of the gas barrier film and a back (polyethylene bag) made of a resin film were fused by a heat seal method to create a sealing bag. Cefazolin sodium (manufactured by Otsuka Pharmaceutical Factory) was encapsulated in the obtained sealing bag as a drug, stored for 6 months at 40 ° C. and 75% relative humidity, and evaluated for changes in color. It was hardly seen.

Since the gas barrier film of the present invention has a high barrier performance, it can be widely used in various devices that require barrier properties. In the gas barrier film of the present invention, since the smoothness of the organic layer can be improved, the inorganic layer can also be provided smoothly. As a result, the smoothness of the outermost surface can be improved, and the performance of the device formed on the gas barrier film can be improved.

DESCRIPTION OF SYMBOLS 1 Inorganic layer 2 Organic layer 3 Inorganic layer 4 Alcohol 5 Base film 6 Organic layer 10 Barrier laminated body

Claims

An organic layer provided on the surface of the inorganic layer, the organic layer comprising a polyfunctional (meth) acrylate, a compound represented by the general formula (I), and a general formula (II-a And a polymer obtained by polymerizing a polymerizable composition containing at least one compound represented by general formula (II-b).
Formula (I)

(In the general formula (I), R 1 to R 6 are each an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent, provided that R 1 to R 6 At least one of them is a substituent containing a radically polymerizable carbon-carbon double bond.)
Formula (II-a)

(In the general formula (II-a), R 11 represents a hydrogen atom or a methyl group. R 12 represents —CR 2 —, —O—, —CO—, —CR═CR—, an arylene group, or Represents a heteroarylene group or a divalent linking group in which two or more of these are connected, A represents —O— or —NR—, and each R represents a hydrogen atom or a substituent, and if possible, It may be bonded to form a ring.)
Formula (II-b)

(In the general formula (II-b), R 21 represents a hydrogen atom and a methyl group. R 22 represents a single bond, an alkylene group, an arylene group, or two or more selected from these are an amide bond or This represents a linking group having a structure linked by an ester bond, having 2 to 82 atoms, and not having an aliphatic cyclic structure.The alkylene group and aryl group have a substituent. N2 represents an integer of 1 to 5.)
The barrier laminate according to claim 1, wherein the substituent containing a radically polymerizable carbon-carbon double bond in the general formula (I) is a (meth) acryloyloxy group.
At least one of a polyfunctional (meth) acrylate, a compound represented by the general formula (I), a compound represented by the general formula (II-a), and a compound represented by the general formula (II-b); The barrier laminate according to claim 1, which has an aromatic group.
The barrier laminate according to any one of claims 1 to 3, wherein the (meth) acrylate contained in the polymerizable composition is an aromatic (meth) acrylate.
The barrier laminate according to any one of claims 1 to 3, wherein the organic layer is obtained by applying a polymerizable composition containing an aromatic (meth) acrylate to the surface of the inorganic layer and curing the composition. body.
The barrier laminate according to any one of claims 1 to 5, further comprising a second inorganic layer on the surface of the organic layer.
The barrier laminate according to claim 6, further comprising a second organic layer on the surface of the second inorganic layer.
The barrier laminate according to any one of claims 1 to 7, wherein the inorganic layer and / or the second inorganic layer includes an oxide, nitride, carbide, or mixture thereof of Si or Al. body.
At least a first inorganic layer, a first organic layer, a second inorganic layer, a second organic layer, and a third inorganic layer are stacked adjacent to each other in this order, and the first organic layer and The barrier laminate according to any one of claims 1 to 8, wherein the second organic layer contains a polymer obtained by polymerizing the polymerizable composition.
The barrier according to any one of claims 1 to 9, wherein the number of carboxy groups in the compound represented by the general formula (II-a) or the compound represented by the general formula (II-b) is one. Laminate.
A gas barrier film provided with the barrier laminate according to any one of claims 1 to 10 on a support.
The gas barrier film according to claim 11, further comprising an organic layer between the support and the barrier laminate.
A device using the gas barrier film according to claim 11 as a substrate.
A device sealed with the barrier laminate according to any one of claims 1 to 10 or the gas barrier film according to claim 11 or 12.
The device according to claim 13 or 14, wherein the device is an organic EL element or a solar cell element.
A sealing bag using the barrier laminate according to any one of claims 1 to 10 or the gas barrier film according to claim 11 or 12.
An inorganic layer and an organic layer provided on the surface of the inorganic layer are provided on the support, and the organic layer is a polyfunctional (meth) acrylate, a compound represented by the general formula (I), and After applying a polymerizable composition comprising at least one compound represented by the formula (II-a) and the compound represented by the general formula (II-b), heating at a temperature of 25 ° C. or higher, The manufacturing method of the gas barrier film of Claim 11 or 12 including hardening by electron beam hardening or a heat ray.