JP2013075430A - Barrier laminate, gas barrier film and device using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier laminate exhibiting improved heat resistance.SOLUTION: The barrier laminate has at least one organic layer and one inorganic barrier layer. The organic layer is formed by curing a polymerizable composition comprising a polymerizable compound having two or more polymerizable groups, and the total amount of uncured content in the organic layer is 1.5 mass% or less of the total mass of the organic layer.

Description

  The present invention relates to a barrier laminate, a gas barrier film, and a device using these. In particular, the present invention relates to a barrier laminate and a gas barrier film suitable for solar cell elements, organic EL elements, optical members, and sealing bags.

  Conventionally, a barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, oxidation, nitridation, silicon oxynitride, etc. is formed on the surface of a plastic film is used to wrap 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, organic EL elements, and the like, plastic film substrates have begun to be used in place 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 realizes 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 barrier layer as a barrier layer. Technology is disclosed. According to the specification, when only one organic layer and one inorganic barrier layer are laminated, the water vapor permeability is 0.011 g / m ² / day, and the technical value of multilayer lamination is clear. Is shown in

US Pat. No. 6,413,645

However, in consideration of industrial applicability, as described in Patent Document 1, when the organic layer and the inorganic barrier layer are multi-layered, productivity is lowered. 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 barrier layer is 0.005g / m ² / day or less in one set, organic inorganic laminate-type barrier especially achievable water vapor transmission rate of less than 0.001g / m ² / day Development of an organic EL device using a gas-conductive laminate, a gas barrier film having the barrier laminate, and 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, it is necessary to suppress the amount of gas generated from the organic layer that causes defects generated at high temperatures.

Here, the organic layer generally uses a method of curing a polymerizable composition containing a polymerizable compound. However, as a result of studies by the present inventor, it has been found that when a conventionally known polymerizable compound is cured, the uncured component volatilizes at a high temperature. When this reason was examined, it turned out that it originates in the non-polymerizable component (a catalyst, a by-product) being contained in the conventionally well-known polymeric compound though trace amount. FIG. 1 shows the state, where 1 is an inorganic barrier layer, 2 ′ is an organic layer formed using a polymerizable composition, and 3 is an inorganic barrier further provided on the surface of the organic layer. Shows the layer. In the conventional organic layer 2 ′, non-polymerizable components (catalysts, by-products) contained in the polymerizable compound remain, and when heating or degassing occurs in this state, the gas is released, and the gas barrier I had reduced the sex. Furthermore, in the configuration in which the organic layer 2 ′ is sandwiched between the inorganic barrier layers as shown in FIG. 1, the gas derived from the non-polymerizable component (catalyst, byproduct) 4 destroys the adjacent inorganic barrier layer 3. There was also. These phenomena are significantly affected when a device incorporating a barrier laminate is exposed to a high temperature process.
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 inventor's earnest study under the above-mentioned problems, by setting the uncured component of the organic layer to 1.5% by mass or less, high barrier properties can be maintained without being broken even at high temperatures. The present inventors have found that the above problems can be solved. Specifically, the above object has been achieved by the following means <1>, preferably by the following means <2> to <15>.

<1> having at least one organic layer and at least one inorganic barrier layer, wherein the organic layer is obtained by curing a polymerizable composition containing a polymerizable compound having two or more polymerizable groups; A barrier laminate in which the total of uncured components in the organic layer is 1.5% by mass or less of the total mass of the organic layer.
<2> The barrier laminate according to <1>, wherein one molecule of the polymerizable compound contains one or more aromatic rings.
<3> The barrier laminate according to <1>, wherein the polymerizable compound includes 2 to 8 aromatic rings and 2 to 8 polymerizable groups in one molecule.
<4> The barrier laminate according to any one of <1> to <3>, wherein the polymerizable group of the polymerizable compound is a (meth) acryloyloxy group.
<5> The barrier according to any one of <1> to <4>, wherein 75% by mass or more of the total solid content of the polymerizable composition is a polymerizable compound having two or more polymerizable groups. Laminate.
<6> The polymerizable compound according to any one of <1> to <5>, wherein the polymerizable compound is a compound represented by the general formula (1) and / or a compound represented by the general formula (2). Barrier laminate.
(In general formula (1), R ¹ and R ² each represent a hydrogen atom, a methyl group, or a cyclohexyl group, and R ³ represents a hydrogen atom, a methyl group, or a group represented by the following general formula (a). R ⁴ represents a methyl group or a group represented by the formula (a), R ⁵ represents a hydrogen atom or a group selected from the following group A. R ⁶ represents a monovalent group containing a polymerizable group. (The compound represented by the general formula (1) has at least two polymerizable groups.)
(In the general formula (a), R ¹ , R ² and R ⁹ each represent a hydrogen atom, a methyl group or a cyclohexyl group, and R ⁶ represents a monovalent substituent containing a polymerizable group. Represents an integer of 0 to 2. At the position of *, it is bonded to the general formula (1).
(Group A)
(In the formula, R ¹ and R ² each represent a hydrogen atom, a methyl group, or a cyclohexyl group, and R ⁶ represents a monovalent substituent containing a polymerizable group.)
(In the general formula (2), R ⁶ represents a monovalent substituent containing a polymerizable group. R ⁷ , R ⁸ and R ⁹ each represents a hydrogen atom, a methyl group or a cyclohexyl group; Represents 0 or 1.)
<7> The barrier laminate according to any one of <1> to <6>, wherein the inorganic barrier layer is provided on a surface of the organic layer.
<8> The barrier laminate according to any one of <1> to <6>, having a structure in which the inorganic barrier layer, the organic layer, and the inorganic barrier layer are laminated adjacent to each other in this order.
<9> A gas barrier film in which the barrier laminate according to any one of <1> to <8> is provided on a base film.
<10> A device having the barrier laminate according to any one of <1> to <8> or the gas barrier film according to <9>.
<11> A solar cell element or an organic EL element having the barrier laminate according to any one of <1> to <8> or the gas barrier film according to <9>.
<12> A device optical member having the barrier laminate according to any one of <1> to <8> or the gas barrier film according to <9>.
<13> A device sealing bag having the barrier laminate according to any one of <1> to <8> or the gas barrier film according to <9>.
<14> After removing impurities of the composition (A) containing a polymerizable compound, curing the polymerizable composition containing the composition (A) containing the polymerizable compound to form an organic layer, The method for producing a barrier laminate according to any one of <1> to <8>.
<15> A method for producing a device, comprising providing a barrier laminate by the method for producing a barrier laminate according to <14>.

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

It is the cross-sectional schematic 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 at least one organic layer and at least one inorganic barrier layer, and the organic layer contains a polymerizable compound having two or more polymerizable groups. The total of uncured components in the organic layer is 1.5% by mass or less of the total mass of the organic layer. By setting it as the barriering laminated body which has such an organic layer, the adhesiveness of an organic layer and an inorganic barrier layer can be improved, and heat resistance can be improved.

The barrier laminate of the present invention is preferably a barrier laminate having a second inorganic barrier layer on the surface of the organic layer, and more preferably on the surface of the second inorganic barrier layer. Furthermore, it is 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 barrier layer, 2 is an organic layer, 3 is a second inorganic barrier layer, and 10 is Each of the barrier laminates is shown.
When forming an organic layer, it is generally performed that a polymerizable composition is applied on an inorganic barrier layer and cured. Here, for example, when a polymerizable composition as described in JP 2010-228446 A is used, uncured components (catalysts, byproducts, etc.) contained in the polymerizable compound remain in the organic layer. Resulting in. It has been found that this remaining uncured component releases a large amount of outgas at a subsequent process, for example, at the stage of incorporation into the device. In particular, as in the present embodiment shown in FIG. 2, when the organic layer is sandwiched between two inorganic barrier layers, the gas derived from the uncured component has destroyed the inorganic barrier layer. On the other hand, in the present invention, the above-described problems do not occur because the purification is performed in advance so that the non-polymerizable compound does not exist in the polymerizable compound. That is, the barrier laminate of the present invention can maintain a high gas barrier property even at a high temperature or in a vacuum process, and can secure adhesion between the organic layer and the inorganic barrier 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 barrier 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 barrier 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. The polymerizable composition in the present invention contains a polymerizable compound having two or more polymerizable groups in one molecule, but has a polymerization having one or more aromatic rings and two or more polymerizable groups in one molecule. It is more preferable to include a polymerizable compound, and it is more preferable to include a polymerizable compound having 2 to 8 aromatic rings and 2 to 8 polymerizable groups in one molecule, and 2 to 6 in one molecule. It is particularly preferable to include a polymerizable compound having an aromatic ring and 2 to 6 polymerizable groups. The polymerizable group is preferably a (meth) acryloyloxy group. The aromatic ring is preferably an aromatic ring, and more preferably a benzene ring. In the present invention, it is particularly preferable to include at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2).
In the present invention, when the compound having two or more polymerizable groups in the molecule forms a heat-resistant three-dimensional network structure, the uncured component is 1.5% by weight or less. Achieve. The means for adjusting the total of uncured components to 1.5% by mass or less of the total mass of the organic layer is achieved by removing impurities from the polymerizable composition. More specifically, this is achieved by purifying the composition (A) containing a polymerizable compound having two or more polymerizable groups in one molecule. Examples of the purification means include column chromatography, washing with water, recrystallization, distillation and the like. A commercially available or synthetic polymerizable compound is not a pure polymerizable compound, but is actually provided as a composition (A) containing a trace amount of impurities. Until now, a barrier laminate has been formed without paying attention to such a small amount of impurities. However, it has been found that barrier properties and adhesion can be remarkably improved by removing impurities from the composition (A) containing such a polymerizable compound.
Hereinafter, the compound represented by the general formula (1) and the compound represented by the general formula (2) will be described.

(In general formula (1), R ¹ and R ² each represent a hydrogen atom, a methyl group, or a cyclohexyl group, and R ³ represents a hydrogen atom, a methyl group, or a group represented by the following general formula (a). R ⁴ represents a methyl group or a group represented by the formula (a), R ⁵ represents a hydrogen atom or a group selected from the following group A. R ⁶ represents a monovalent group containing a polymerizable group. (The compound represented by the general formula (1) has at least two polymerizable groups.)
(In the general formula (a), R ¹ , R ² and R ⁹ each represent a hydrogen atom, a methyl group or a cyclohexyl group, and R ⁶ represents a monovalent substituent containing a polymerizable group. Represents an integer of 0 to 2. At the position of *, it is bonded to the general formula (1).
(Group A)
(In the formula, R ¹ and R ² each represent a hydrogen atom, a methyl group, or a cyclohexyl group, and R ⁶ represents a monovalent substituent containing a polymerizable group.)
(In the general formula (2), R ⁶ represents a monovalent substituent containing a polymerizable group. R ⁷ , R ⁸ and R ⁹ each represents a hydrogen atom, a methyl group or a cyclohexyl group; Represents 0 or 1.)
When two or more R ^{1 to} R ⁹ are contained in one molecule, they may be the same or different.

Examples of the substituent containing a polymerizable group for R ⁶ include —CR ¹⁰ ₂ — (R ¹⁰ is a hydrogen atom or a substituent), —CO—, —O—, a phenylene group, —S—, —C≡C—, One or more of —NR ¹¹ — (R ¹¹ is a hydrogen atom or substituent), —CR ¹² ═CR ¹³ — (R ¹² and R ¹³ are each a hydrogen atom or substituent), and a polymerizable group And a combination of one or more of —CR ¹⁴ ₂ — (R ¹⁴ is a hydrogen atom or a substituent), —CO—, —O— and a phenylene group, and a polymerizable group. Groups are more preferred.
As the substituent for R ^{10 to} R ¹⁴ , a methyl group and a hydroxyl group are preferable.
The molecular weight of at least one R ⁶ is preferably 10 to 250, and more preferably 70 to 150.
The position where R ⁶ is bonded is preferably bonded to at least the para position.
n shows the integer of 0-2.

In the compound represented by the general formula (1) or (2), it is preferable that at least two of R ⁶ have the same structure.
The polymerizable group possessed by the general formula (1) or (2) is preferably a (meth) acryloyl group or an epoxy group, and more preferably a (meth) acryloyl group.
The number of polymerizable groups contained in the general formula (1) or (2) 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.
600-1400 are preferable and, as for the molecular weight of the compound represented by General formula (1) or (2), 800-1200 are more preferable.
Of the compounds represented by the general formula (1) or (2), the compound represented by the general formula (1) is more preferable.

In the present invention, only one type of compound represented by the general formula (1) or (2) may be included, or two or more types may be included. When two or more types are contained, for example, a composition containing R ⁶ having the same structure and different numbers of R ⁶ and isomers thereof is exemplified.

  Specific examples of the polymerizable compound represented by the general formula (1) or (2) of the present invention include the following compounds. Needless to say, the compounds of the present invention are not limited thereto.

  The said compound can be obtained as a commercial item. 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 following compounds can also be used as the polymerizable compound having two or more polymerizable groups in one molecule used in the present invention other than those described above.

In the polymerizable composition of the present invention, the compounding amount of the polymerizable compound having two or more polymerizable groups in the molecule is preferably 30 to 99% by mass with respect to the solid content excluding the solvent, More preferably, it is 95 mass%.
The polymerizable composition in the present invention is a polymerizable compound (preferably represented by the general formula (1)) in which 60% by mass or more of the total solid content has 2 or more polymerizable groups in the molecule with respect to the solid content excluding the solvent. Or a compound represented by (2)), preferably 75% by mass or more of a polymerizable compound having two or more polymerizable groups in the molecule (preferably the general formula (1) or (2) It is preferable that it is comprised with the compound represented by these.

Other polymerizable compounds The polymerizable composition used for the organic layer in the present invention may contain other polymerizable compounds. The type of the polymerizable compound is not particularly defined, but is preferably a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group, more preferably ethylenically unsaturated. A compound having a bond at the terminal or side chain and / or a compound having an epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds, acrylamide compounds, styrene compounds, maleic anhydride, etc., (meth) acrylate compounds and / or Styrenic compounds are preferred, and (meth) acrylate compounds are more preferred. It is preferable that the compounding quantity of these compounds is 10 mass% or less with respect to solid content except the solvent of the polymeric composition in this invention.

As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
As the styrene compound, styrene, α-methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.

Specific examples of the (meth) acrylate compound preferably used in the present invention are shown below, but the present invention is not limited to these.

(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 using a photoinitiator, it is preferable that the content is 0.1 mol% or more of the total amount of the polymerizable compounds, and more preferably 0.5 to 2 mol%. 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 (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Esacure series (eg, 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 barrier 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. Examples of the extrusion coating method to be used include the coating method.
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 barrier 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 barrier layer)
The inorganic barrier layer is usually a thin film layer made of a metal compound. As a method for forming the inorganic barrier 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 barrier layer is not particularly limited as long as it satisfies the above performance, but is, for example, a metal oxide, a metal nitride, a metal oxynitride, or a metal carbide, and Si, Al, In, Sn, An oxide, nitride, carbide or oxynitride, oxynitride carbide, or the like containing one or more metals selected from Zn, 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 barrier 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 barrier 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 barrier layer formed according to the present invention is preferably less than 1 nm as an average roughness (Ra value) of 1 μm square, and more preferably 0.5 nm or less. For this reason, the inorganic barrier layer is preferably formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.

  Although it does not specifically limit regarding the thickness of an inorganic barrier layer, It attaches to 1 layer, Usually, it exists in the range of 5-500 nm, Preferably it is 20-200 nm. Two or more inorganic barrier layers may be laminated. In the present invention, in an embodiment in which two or more inorganic barrier layers are provided, the adhesion between the layers is 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. When two or more layers are laminated, it is desirable that each inorganic barrier layer is designed so as to be within the above-mentioned preferable range. Further, as described above, as disclosed in US Published Patent Application 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 layer and inorganic barrier layer)
Lamination of the organic layer and the inorganic barrier layer can be performed by sequentially and repeatedly forming the organic layer and the inorganic barrier layer according to a desired layer configuration. When the inorganic barrier layer is formed by a vacuum film formation method such as a sputtering method, a vacuum evaporation method, an ion plating method, or a plasma CVD method, the organic layer can also be formed by a vacuum film formation method such as the flash evaporation method. preferable. In particular, the present invention can exhibit high barrier properties when at least two organic layers and at least two inorganic barrier layers are alternately laminated. Further, a configuration in which two or more organic layers sandwiched between two inorganic barrier layers are included, for example, a configuration in which an inorganic barrier layer, an organic layer, an inorganic barrier layer, an organic layer, and an inorganic barrier layer are adjacent to each other in that order. Then, higher barrier properties can be exhibited. In particular, in the present invention, by providing an inorganic barrier layer on the surface of the organic layer derived from the polymerizable aromatic silane coupling agent, adhesion between the organic layer and the inorganic barrier 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.

(Use of barrier laminates)
The barrier laminate of the present invention is usually provided on a support, and can be used for various applications by selecting the 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 barrier layers are alternately provided on the base film 5. Specifically, the organic layer 6, the inorganic barrier layer 1, the organic layer 2, and the inorganic barrier layer 3 are provided in this order from the base film 5 side 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 barrier layer 13. The organic layer 6 may be an organic layer obtained by polymerizing the polymerizable composition in the present invention, or may be another organic layer.
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 barrier layer and the organic layer from the base film side, or may be laminated in the order of the organic layer and the inorganic barrier layer. The uppermost layer of the barrier laminate of the present invention may be an inorganic barrier 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 barrier layer, and can be appropriately selected according to the purpose of use. Specifically, as the plastic film, metal support (aluminum, copper, stainless steel, etc.) polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, 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 for a device such as an organic EL element described later, the plastic film is preferably made of a material having heat resistance. Specifically, it is preferable that the glass transition temperature (Tg) is 100 ° C. or higher and / or the linear thermal expansion coefficient is 40 ppm / ° C. or lower and is made of a transparent material having high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive. As such a thermoplastic resin, for example, 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: Japanese Patent Laid-Open No. 2001-150584 compound: 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 described in JP-A 2002-80616: 300 ° C. or more) (the parenthesized data are Tg). 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 barrier laminate of the gas barrier film faces the inside of the cell and is arranged 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. ) Or a linear barrier plate combined 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 substrate 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 Corporation: Elmec Co.), 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 for 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 Japanese Patent Application Laid-Open No. 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, in order from the bottom, 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 It has the structure which consists of a film | membrane. 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 liquid crystal cell is not particularly limited, but more preferably TN type (Twisted Nematic), STN type (Super Twisted Nematic) or 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 tellurium (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. I-III-VI group 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. It is preferable that it is an I-III-VI group compound semiconductor solar cell element, such as a system (so-called CIGSS system).

(Other)
As other application examples, the thin film transistor described in JP-A-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., 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. Regarding these details, 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.

(Reference Example 1)
(Production of raw material epoxy compound) 4,4 ′-(1,3-phenylenebis (2,2-propylidene)) bisphenol (225.0 g) was dissolved in epichlorohydrin (241.0 g), and then 60 Stir at 6 ° C. for 6 hours. At this time, a total of 4.4 g of a 48% aqueous sodium hydroxide solution was added dropwise at the start of the reaction and twice after 2 hours from the start of the reaction. Thereafter, a 48% aqueous sodium hydroxide solution (4.4 g) was added dropwise over 2 hours under reduced pressure, and at the same time, water added to the reaction system and water produced in the reaction system were removed.

  After completion of the reaction, excess epichlorohydrin was removed, toluene was added to the resulting resinous material, and the generated sodium chloride was removed by washing with water. Furthermore, 10% aqueous sodium hydroxide solution (6.4 g) and benzyltriethylammonium chloride (0.4 mL) were added, and the mixture was stirred at 80 ° C. for 90 minutes. After standing to separate, the aqueous layer was removed. A 5% aqueous solution of sodium dihydrogen phosphate was added to the toluene solution of the resin obtained, and the mixture was neutralized by stirring at 80 ° C. for 30 minutes. Thereafter, toluene is concentrated and removed, and a reaction product containing 4,4 ′-[1,3-phenylenebis (2,2-propylidene)] bis [phenyleneoxymethyleneoxirane] as a main component as a raw material epoxy compound. 113.8 g was obtained.

(Synthesis Example 1)
(Production of α, α′-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] -α, α, α ′, α′-tetramethyl-m-xylene) Stirrer blade, thermometer, tip Into a 300 mL three-necked flask equipped with a reflux condenser equipped with a calcium chloride tube and a capillary for blowing air, 4,4 ′-[1,3-phenylenebis (2, 2-propylidene)] bis [phenyleneoxymethyleneoxirane] as a main component, bisphenol compound (epoxy equivalent 248) (37.2 g), acrylic acid (12.96 g), tetra-n-butylammonium bromide (2.42 g), Hydroquinone monomethyl ether (0.025 g), 2,6-di-tert-butyl-4-methylphenol (0.025 g) and Tolue (150 g) were charged, and this was stirred while blowing air, heat, allowed to react for 8 hours under reflux, to give the EA-1-A.

  After completion of the reaction, the acid value of the obtained reaction mixture (solution) was 8.0 mgKOH / g. The reaction mixture EA-1-A was cooled to room temperature, diluted with ethyl acetate (250 mL), washed twice with 5% aqueous sodium hydrogen carbonate (100 mL) and twice with water (100 mL). The organic layer was separated. This was dried over anhydrous sodium sulfate and filtered. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain the target epoxy acrylate compound (EA-1-B) (47.5 g) (99% yield) as a viscous light yellow liquid. .

The viscosity of this epoxy acrylate compound at 40 ° C. was 39500 mPa · s, the refractive index at 25 ° C. was 1.562, and the 10% weight reduction temperature by TG / DSC (differential scanning calorimetry) in a nitrogen stream was 387 ° C. It was.

(Reference Example 2)
(Manufacture of raw material epoxy compounds)
294.5 g of 4,4 ′-(1-methylethylidene) bis (2-cyclohexylphenol) was dissolved in epichlorohydrin (694.0 g), and then water (1.3 g) was added thereto, For 5 hours. At this time, a 48% sodium hydroxide aqueous solution was added dropwise in total (12.4 g) in two portions at the start of the reaction and 2 hours after the start of the reactor. Thereafter, a 48% aqueous sodium hydroxide solution (130.0 g) was added dropwise over 2 hours under reduced pressure, and at the same time, water added to the reaction system and water produced in the reaction system were removed.

  After completion of the reaction, excess epichlorohydrin was removed, methyl isobutyl ketone was added to the resulting resin layer, and the generated sodium chloride was removed by washing with water. Furthermore, 10% aqueous sodium hydroxide solution (229.5 g) and benzyltriethylammonium chloride (0.5 mL) were added, and the mixture was stirred at 80 ° C. for 90 minutes. After standing to separate, the aqueous layer was removed.

  A 5% aqueous solution of sodium dihydrogen phosphate was added to the resulting methyl isobutyl ketone solution of the resin, and the mixture was neutralized by stirring at 80 ° C. for 30 minutes. After standing to separate, the aqueous layer was removed. Thereafter, methyl isobutyl ketone was concentrated and removed, and 308.0 g of a reaction product containing 4,4 ′-(1-methylethylidene) bis (2-cyclohexylphenyleneoxymethyleneoxirane) as a main component as a raw material epoxy compound was obtained. Obtained.

(Synthesis Example 2)
The 4,4 ′-(1-methyl) obtained in Reference Example 2 above was added to a 500 mL four-necked flask equipped with a stirring blade, a thermometer, a reflux condenser with a calcium chloride tube attached to the tip, and a capillary for blowing air. Ethylidene) bis (2-cyclohexylphenyleneoxymethyleneoxirane) (63.4 g), acrylic acid (20.73 g), tetrabutylammonium bromide (3.87 g), hydroquinone monomethyl ether (0.042 g), 2,6-di -Tert-butyl-4-methylphenol (0.042 g) and toluene (240 g) were charged, and the mixture was stirred while air was blown into it, and heated and refluxed for 8 hours to obtain EA-2-A.

  After completion of the reaction, the acid value of the obtained reaction mixture (solution) was 7.7 mgKOH / g. The reaction mixture was cooled to room temperature, diluted with 400 mL of ethyl acetate, washed once with 120 mL of 2% aqueous sodium hydroxide and twice with 120 mL of water, and the organic layer was separated. This was dried over anhydrous sodium sulfate and then filtered. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain the target epoxy acrylate compound (EA-2-B) (80 g) as a pale yellow viscous liquid. The yield was 99% or more.

(Reference Example 3)
(Manufacture of raw material epoxy compounds)
2,2 ′, 3,5 ′, 6,6′-hexamethylbiphenol (in a nitrogen stream) was added to a 1 L (liter) four-necked flask equipped with a thermometer, dropping funnel, condenser and stirrer. 67.5 g), epichlorohydrin (462.5 g), and dimethyl sulfoxide (170 g) were added and dissolved therein. This solution was heated to 55 ° C., and flaky sodium hydroxide (20 g) was added in portions over 100 minutes, followed by reaction at 55 ° C. for 2 hours and further at 70 ° C. for 30 minutes. After completion of the reaction, excess epichlorohydrin, dimethyl sulfoxide and the like were distilled off using a rotary evaporator under heating and reduced pressure at 130 ° C., and methyl isobutyl ketone (96 g) was added to dissolve the residue.

  The solution of methyl isobutyl ketone obtained above was heated to 70 ° C., 5 g of 30% aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour. After the reaction, the reaction solution was repeatedly washed with pure water until the pH of the washing solution became neutral. The aqueous layer was phase-separated and removed, and methyl isobutyl ketone was distilled off from the organic layer under heating and reduced pressure using a rotary evaporator to obtain an epoxy compound (86 g).

(Synthesis Example 3)
The epoxy compound (86 g) obtained above and acrylic acid (32.5 g) were dissolved at 60 ° C. (epoxy compound: acrylic acid = 0.5: 1 molar ratio), and then triethylbenzyl chloride (1. 7 g) and hydroquinone (0.05 g) as a polymerization inhibitor were added, heated to 90 to 95 ° C., and reacted with stirring. During the reaction, the acid value and the epoxy equivalent were measured, and the reaction was carried out for 14 hours with the time when the acid value reached 2.0 mgKOH / g or less as the end point of the reaction, yielding an epoxy acrylate compound (EA-3-A) in a yield of 98%. Got in. The obtained target product was a viscous liquid at a temperature of 60 ° C.

  The reaction mixture was cooled to room temperature, diluted with 250 mL of ethyl acetate, washed once with 100 mL of 2% aqueous sodium hydroxide and twice with 100 mL of water, and the organic layer was separated. This was dried over anhydrous sodium sulfate and then filtered. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain the target epoxy acrylate compound (EA-3-B) (50 g) as a pale yellow viscous liquid. The yield was 99% or more.

(Synthesis Example 4)
4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (4.25 g), triethylamine (3.34 g), tetrahydrofuran (7 g) Charged and cooled to 0 ° C. Thereafter, acrylic acid chloride (2.99 g) was added dropwise, stirred at a reaction temperature of 0 ° C. for 1 hour, and then stirred at 25 ° C. for 3 hours. The reaction mixture is diluted with ethyl acetate (50 mL), washed twice with water (50 mL), once with saturated aqueous sodium bicarbonate (80 mL), once with water (50 mL), and saturated brine. The organic layer was separated by washing once. This was dried over anhydrous magnesium sulfate and then filtered. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain the objective polymerizable compound (EA-4-B) (72.1 g) as an ethyl acetate solution.

(Synthesis Example 5)
A mixture of bisphenol A diglycidyl ether (96.5 g) (epoxy equivalent 170.2) and di-tert-butyl-p-cresol (DBPC) (0.13 g) was heated to 95 ° C., stirred and gas-introduced frit Was used to saturate the air. Over this period, isooctanoic acid Cr ^III (Hexcem) (0.258 g) dissolved in acrylic acid (7.4 ml) was added dropwise over 22 minutes. The remaining acrylic acid (21.3 ml, total 87.3 g, 95 eq%) was metered in over 40 minutes. After stirring at 100 ° C. for a further 5 hours, the mixture was cooled to room temperature to obtain a uniform, transparent, slightly greenish liquid (EA-5-A) containing the desired epoxy acrylate compound.

The reaction mixture was cooled to room temperature, diluted with ethyl acetate (500 mL), washed once with 150 mL of 2% aqueous sodium hydroxide and twice with 150 mL of water, and the organic layer was separated. This was dried over anhydrous sodium sulfate and then filtered. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain the target epoxy acrylate compound (EA-5-B) (140 g) as a pale yellow viscous liquid. The yield was 99% or more.

(Reference Example 1)
(Production of raw material epoxy compound) 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (196.3 g) was dissolved in epichlorohydrin (241.0 g) and then stirred at 60 ° C. for 6 hours. did. At this time, a total of 4.4 g of a 48% aqueous sodium hydroxide solution was added dropwise at the start of the reaction and twice after 2 hours from the start of the reaction. Thereafter, a 48% aqueous sodium hydroxide solution (4.4 g) was added dropwise over 2 hours under reduced pressure, and at the same time, water added to the reaction system and water produced in the reaction system were removed.

After completion of the reaction, excess epichlorohydrin was removed, toluene was added to the resulting resinous material, and the generated sodium chloride was removed by washing with water. Furthermore, 10% aqueous sodium hydroxide solution (6.4 g) and benzyltriethylammonium chloride (0.4 mL) were added, and the mixture was stirred at 80 ° C. for 90 minutes. After standing to separate, the aqueous layer was removed. A 5% aqueous solution of sodium dihydrogen phosphate was added to the toluene solution of the resin obtained, and the mixture was neutralized by stirring at 80 ° C. for 30 minutes. Thereafter, toluene was concentrated and removed to obtain 99.3 g of a reaction product mainly composed of 1,1,2,2-tetrakis [4-oxymethyleneoxirane] phenyl] ethane as a raw material epoxy compound.

(Synthesis Example 6)
(Production of 1,1,2,2-tetrakis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ethane) Stirrer blade, thermometer, reflux condenser with tip attached calcium chloride tube and air blowing Into a 300 mL three-necked flask equipped with a capillary for the above, a compound (epoxy equivalent) of 1,1,2,2-tetrakis [4-oxymethyleneoxirane] phenyl] ethane obtained in Reference Example 1 as a main component 155.7) (28.0 g), acrylic acid (12.96 g), tetra-n-butylammonium bromide (2.42 g), hydroquinone monomethyl ether (0.025 g), 2,6-di-tert-butyl-4 -Methylphenol (0.025g) and toluene (150g) were charged, stirred while blowing air into this, heated Under reflux and reacted for 8 hours to obtain the EA-6-A.

After completion of the reaction, the acid value of the obtained reaction mixture (solution) was 6.0 mgKOH / g. The reaction mixture EA-6-A was cooled to room temperature, diluted with ethyl acetate (250 mL), washed twice with 5% aqueous sodium hydrogen carbonate (100 mL) and twice with water (100 mL). The organic layer was separated. This was dried over anhydrous sodium sulfate and filtered. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain the target epoxy acrylate compound (EA-6-B) (40.9 g) (99% yield) as a viscous light yellow liquid. .

(Synthesis Example 7)
2,6-bis- (4-hydroxybenzyl) -4-methylphenol (3.21 g), triethylamine (3.34 g) and tetrahydrofuran (7 g parts) were charged and cooled to 0 ° C. Thereafter, acrylic acid chloride (2.99 g) was added dropwise, stirred at a reaction temperature of 0 ° C. for 1 hour, and then stirred at 25 ° C. for 3 hours. The reaction mixture is diluted with ethyl acetate (50 mL), washed twice with water (50 mL), once with saturated aqueous sodium bicarbonate (80 mL), once with water (50 mL), and saturated brine. The organic layer was separated by washing once. This was dried over anhydrous magnesium sulfate and then filtered. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain the objective polymerizable compound (EA-7-B) (54.4 g) as an ethyl acetate solution.

Example 1
Preparation of organic layer coating solution Polymerizable compound (EA-1-B) (7 parts by weight), silane coupling agent (KBM-5130, manufactured by Shin-Etsu Chemical Co., Ltd.) (1 part by weight), polymerization initiator (organic layer coating solution) An organic layer coating solution consisting of methyl ethyl ketone (MEK) (32 parts by weight) was prepared.

Preparation of Gas Barrier Film On the polyethylene naphthalate film (Teijin DuPont, Teonex Q65FA, thickness 100 μm), the organic layer coating solution adjusted as described above was adjusted 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 barrier layer, and organic layer were laminated | stacked and the barrier film was produced.

Silane coupling agent (KBM-5130)

  About the obtained gas barrier film, the quantity of the uncured component in an organic layer, water-vapor-permeability, adhesiveness, and heat resistance were evaluated with the following method.

[Quantification of uncured components in organic layer]
On the glass substrate having a size of 10 cm × 10 cm, the organic layer coating solution prepared as described above was formed into a film by adjusting the methyl ethyl ketone so that the dry film thickness was 1000 nm. The organic layer was produced by irradiating and curing at cm ² . The obtained glass substrate with an organic layer was immersed in a petri dish containing 50 ml of methyl ethyl ketone. After standing for 1 hour, methyl ethyl ketone was taken out, and methyl ethyl ketone was distilled off at 50 ° C. The weight of the remaining impurities was measured. The results are shown in the table below. The unit is expressed in mass%.

[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.

[Inorganic layer film-forming properties]
The transparency of the produced gas barrier film was visually evaluated. When there was no cloudiness, it was marked as ◯, and when there was cloudiness, it was marked as ×. 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%.

[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 □ was observed, and the presence or absence of a swollen portion due to gas generation in the organic layer sandwiched between the inorganic barrier layer and the inorganic barrier layer was evaluated. The thing without a swelling part was represented by (circle), and the thing with a swelling part was represented by x.

(Examples 2 to 7)
The barrier performance and adhesion test were performed in the same manner as in Example 1 except that EA-1-B was changed to the compounds shown in Table 1 below. The results are shown in Table 1.

(Example 8)
After diluting 60 g of ethyl acetate with 15 g of NK oligo EA-6320 (manufactured by Shin-Nakamura Chemical Co., Ltd.), which is an epoxy acrylate, and washing twice with 60 mL of a saturated aqueous sodium bicarbonate solution, the organic layer was separated. This was dried over anhydrous magnesium sulfate and then filtered. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain 100 g of the target epoxy acrylate compound (EA-8-B) as a pale yellow viscous liquid. The yield was 99% or more.

(Comparative Examples 1-7)
Barrier performance and adhesion tests were performed in the same manner as in Example 1 except that EA-1-B was changed to the compounds shown in Table 1 below in Synthesis Example 1. The results are shown in Table 1.

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 15 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 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 barrier 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 barrier layer 2 Organic layer 3 Inorganic barrier layer 4 Alcohol 5 Base film 6 Organic layer 10 Barrier laminated body

Claims (15)

  The organic layer has at least one organic layer and at least one inorganic barrier layer, and the organic layer is obtained by curing a polymerizable composition containing a polymerizable compound having two or more polymerizable groups. A barrier laminate in which the total of uncured components is 1.5% by mass or less of the total mass of the organic layer. The barrier laminate according to claim 1, comprising one or more aromatic rings in one molecule of the polymerizable compound. The barrier laminate according to claim 1, wherein the polymerizable compound contains 2 to 8 aromatic rings and 2 to 8 polymerizable groups in one molecule.   The barrier laminate according to any one of claims 1 to 3, wherein the polymerizable group of the polymerizable compound is a (meth) acryloyloxy group.   The barrier laminate according to any one of claims 1 to 4, wherein 75% by mass or more of the total solid content of the polymerizable composition is a polymerizable compound having two or more polymerizable groups. The barrier laminate according to any one of claims 1 to 5, wherein the polymerizable compound is a compound represented by the general formula (1) and / or a compound represented by the general formula (2).
(In general formula (1), R ¹ and R ² each represent a hydrogen atom, a methyl group, or a cyclohexyl group, and R ³ represents a hydrogen atom, a methyl group, or a group represented by the following general formula (a). R ⁴ represents a methyl group or a group represented by the formula (a), R ⁵ represents a hydrogen atom or a group selected from the following group A. R ⁶ represents a monovalent group containing a polymerizable group. (The compound represented by the general formula (1) has at least two polymerizable groups.)
(In the general formula (a), R ¹ , R ² and R ⁹ each represent a hydrogen atom, a methyl group or a cyclohexyl group, and R ⁶ represents a monovalent substituent containing a polymerizable group. Represents an integer of 0 to 2. At the position of *, it is bonded to the general formula (1).
(Group A)
(In the formula, R ¹ and R ² each represent a hydrogen atom, a methyl group, or a cyclohexyl group, and R ⁶ represents a monovalent substituent containing a polymerizable group.)
(In the general formula (2), R ⁶ represents a monovalent substituent containing a polymerizable group. R ⁷ , R ⁸ and R ⁹ each represents a hydrogen atom, a methyl group or a cyclohexyl group; Represents 0 or 1.)   The barrier laminate according to claim 1, wherein the inorganic barrier layer is provided on a surface of the organic layer.   The barrier laminate according to any one of claims 1 to 6, having a structure in which the inorganic barrier layer, the organic layer, and the inorganic barrier layer are laminated adjacent to each other in this order.   The gas barrier film which provided the barriering laminated body of any one of Claims 1-8 on the base film.   The device which has the barriering laminated body of any one of Claims 1-8, or the gas barrier film of Claim 9.   The solar cell element or organic EL element which has the barriering laminated body of any one of Claims 1-8, or the gas barrier film of Claim 9.   The device optical member which has the barriering laminated body of any one of Claims 1-8, or the gas barrier film of Claim 9.   The bag for device sealing which has the barriering laminated body of any one of Claims 1-8, or the gas barrier film of Claim 9.   The method includes removing an impurity from the composition (A) containing a polymerizable compound and then curing the polymerizable composition containing the composition (A) containing the polymerizable compound to form an organic layer. The manufacturing method of the barriering laminated body of any one of -8.   The manufacturing method of the device including providing a barriering laminated body with the manufacturing method of the barriering laminated body of Claim 14.