WO2019182119A1

WO2019182119A1 - Gas barrier laminate

Info

Publication number: WO2019182119A1
Application number: PCT/JP2019/012136
Authority: WO
Inventors: 博貴木下; 智史永縄
Original assignee: リンテック株式会社
Priority date: 2018-03-23
Filing date: 2019-03-22
Publication date: 2019-09-26
Also published as: JPWO2019182119A1; JP7222976B2; TW201940337A

Abstract

The present invention provides a gas barrier laminate which exhibits excellent flexibility, while comprising a base layer and a gas barrier layer. This gas barrier laminate is configured such that: the base layer contains a cured product of a curable resin composition that contains a curable monomer; and the curable monomer contains a curable monomer having a long spacer, said curable monomer having, in each molecule, a structure wherein one reactive functional group is connected to another reactive functional group via one or both of a polyalkylene group and a polyoxyalkylene group, with the total number of carbon atoms that constitute the main chains of the polyalkylene group and the polyoxyalkylene group being 18 or more.

Description

Gas barrier laminate

The present invention relates to a gas barrier laminate.

In recent years, display devices such as liquid crystal displays and organic electroluminescence (EL) displays, in order to realize thinning, weight reduction and flexibility, as a sealing material constituting the device, instead of conventional glass, The use of a thin transparent plastic film has been studied.
However, in general, the plastic film has a larger transmission of water vapor, oxygen, etc. in the atmosphere than glass, and when the transparent plastic film is used as a support substrate for a display device, the water vapor, oxygen, etc. transmitted through the support substrate, There is a problem that the device performance or the life is shortened by acting on elements inside the display device.
In order to solve this problem, a film having a characteristic of suppressing the permeation of water vapor and oxygen (hereinafter, this characteristic is referred to as “gas barrier property”, and a laminate having the gas barrier property is referred to as “gas barrier laminate”) is displayed. It has been proposed to be used as a sealing material for devices.
For example, Patent Document 1 describes a flexible display substrate in which a transparent gas barrier layer made of a metal oxide is laminated on the surface of a transparent plastic film by vapor deposition, ion plating, sputtering, or the like.
Patent Document 2 describes a gas barrier film having a gas barrier layer formed by subjecting a polysilazane film to plasma treatment on at least one surface of a substrate.
Under such circumstances, there is a demand for higher-performance display devices, etc. In addition to gas barrier properties, gas barrier laminates used for electronic device members have heat resistance, solvent resistance, and interlayer adhesion. There are increasing demands for excellent properties such as excellent birefringence and low optical isotropy.
For example, Patent Document 3 discloses a gas barrier having a layer made of a cured product of a curable resin composition containing a thermoplastic resin having a glass transition temperature (Tg) of 140 ° C. or higher and a curable monomer. A film is described.

JP 2010-192664 A JP 2012-204452 A International Publication No. 2013/065812

However, the gas barrier film of Patent Document 3 is excellent in heat resistance, solvent resistance, interlayer adhesion and the like in addition to gas barrier properties, but does not have sufficient flexibility. In the gas barrier film of Patent Document 3, if the ratio of the thermoplastic resin is increased in the blending ratio of the thermoplastic resin and the curable monomer in the curable resin composition, a layer made of a cured product of the curable resin composition Although improvement in flexibility was observed, it was not sufficient.

In view of the above, an object of the present invention is to provide a gas barrier laminate having excellent flexibility.

As a result of intensive studies to solve the above problems, the inventors of the present invention have made reactive functionalities in the chemical structure of the curable monomer constituting the underlayer of the gas barrier laminate including the underlayer and the gas barrier layer. By making the total number of carbon atoms constituting each main chain of the polyalkylene group or polyoxyalkylene group used as a spacer between the groups within a specific range, a gas barrier laminate excellent in flexibility can be obtained. The headline and the present invention were completed.
That is, the present invention provides the following [1] to [10].
[1] A gas barrier laminate including an underlayer and a gas barrier layer, wherein the underlayer includes a cured product of a curable resin composition containing a curable monomer, One reactive functional group has a structure in which one reactive functional group is connected to another reactive functional group via one or both of a polyalkylene group and a polyoxyalkylene group in the molecule, A gas barrier laminate comprising a curable monomer having a long spacer in which the total number of carbon atoms constituting each main chain of an oxyalkylene group is 18 or more.
[2] The curable monomer further has a structure in which one reactive functional group and another reactive functional group are linked without any polyalkylene group or polyoxyalkylene group, or 1 One reactive functional group has a structure linked to another reactive functional group via one or both of a polyalkylene group and a polyoxyalkylene group, and the polyalkylene group and the polyoxyalkylene The gas barrier laminate according to the above [1], comprising a curable monomer having a short spacer in which the total number of carbon atoms constituting the main chain of the group is 16 or less.
[3] The gas barrier laminate according to the above [1] or [2], wherein the underlayer further contains a thermoplastic resin.
[4] The gas barrier laminate according to [3], wherein the thermoplastic resin has a glass transition temperature (Tg) of 130 ° C. or higher.
[5] The gas barrier laminate according to the above [3] or [4], wherein the thermoplastic resin is a polysulfone resin or an alicyclic hydrocarbon resin.
[6] The gas barrier laminate according to any one of [1] to [5], wherein the underlayer has a thickness of 0.1 to 50 μm.
[7] The gas barrier laminate according to any one of [1] to [6], wherein the underlying layer has a breaking elongation of 3.5% or more.
[8] The gas barrier laminate according to any one of [1] to [7], wherein the gas barrier layer is a cured coating film.
[9] The gas barrier laminate according to any one of the above [1] to [8], wherein the gas barrier layer is obtained by modifying a layer containing a cured polysilazane compound.
[10] The gas barrier laminate according to any one of [1] to [9], wherein the gas barrier laminate further includes a process sheet.

According to the present invention, a gas barrier laminate having excellent flexibility can be provided.

It is a section lineblock diagram showing an example of a gas barrier layered product of the present invention.

[Gas barrier laminate]
The gas barrier laminate of the present invention is a gas barrier laminate including an underlayer and a gas barrier layer, wherein the underlayer includes a cured product of a curable resin composition containing a curable monomer, and the cured The reactive monomer has a structure in which one reactive functional group is linked to another reactive functional group in the molecule via one or both of a polyalkylene group and a polyoxyalkylene group, A curable monomer having a long spacer in which the total number of carbon atoms constituting each main chain of the polyalkylene group and the polyoxyalkylene group is 18 or more (hereinafter referred to as a curable monomer having a long spacer). , Sometimes referred to as “long spacer curable monomer”).
The present invention relates to a gas barrier laminate comprising a base layer and a gas barrier layer, wherein the spacer and the reactive functional group in the molecule of the long spacer curable monomer having a reactive functional group constituting the base layer, By providing a polyalkylene group and / or a polyoxyalkylene group, the total number of carbon atoms contained in the polyalkylene group or the polyoxyalkylene group is 18 or more, thereby providing excellent flexibility. . Further, by combining with a curable monomer having a specific short spacer described later, it is easy to obtain a gas barrier laminate that simultaneously satisfies not only flexibility but also solvent resistance.
In the present specification, the “spacer” means a molecular chain that imparts flexibility, such as a polyalkylene group or a polyoxyalkylene group.

<Underlayer>
The underlayer constituting the gas barrier laminate of the present invention contains a cured product of a curable resin composition containing a curable monomer.
<Curable resin composition>
The curable resin composition contains a curable monomer. Further, it preferably contains a thermoplastic resin described later, and can be prepared by mixing a polymerization initiator and other components and dissolving or dispersing them in a suitable solvent.

(Curable monomer)
The curable monomer used in the present invention has a structure in which one reactive functional group is linked to another reactive functional group via one or both of a polyalkylene group and a polyoxyalkylene group. And a long spacer curable monomer in which the total number of carbon atoms constituting each main chain of the polyalkylene group and the polyoxyalkylene group is 18 or more. For a long spacer, when one reactive functional group is linked to another reactive functional group via two or more polyalkylene groups or polyoxyalkylene groups, the polyalkylene group or polyoxyalkylene group respectively. The number of carbon atoms constituting the main chain is the total number of carbon atoms constituting the main chain of two or more polyalkylene groups or polyoxyalkylene groups. Further, when the curable monomer has three or more reactive functional groups in one molecule, the main chain of each of the polyalkylene group and the polyoxyalkylene group interposed between any two reactive functional groups The total number of carbon atoms constituting is necessarily 18 or more.
When the total number of carbon atoms constituting each main chain of the polyalkylene group and the polyoxyalkylene group as the long spacer is 16 or less, flexibility may be lowered. Further, from the viewpoint of improving the solvent resistance of the underlayer, the total number of carbon atoms constituting each main chain of the polyalkylene group and the polyoxyalkylene group is preferably 70 or less, and 42 or less. Is more preferable.

In the present invention, the reactive functional group includes a hydroxyl group of alcohol, a carbonyl group of ketone, a carboxyl group of carboxylic acid, a carboxylic acid halide group, a carboxylic anhydride group, an isocyanate group, an epoxy group, and a polymerizable unsaturated group. Etc. Of these, a polymerizable unsaturated group is preferred, and a carbon-carbon unsaturated double bond having radical polymerizability is more preferred. Specific examples include a vinyl group, a (meth) acryloyl group, a maleimide group, and the like, which are easily mixed with a thermoplastic resin, are less likely to cause curing shrinkage of the polymer, and are (meth) acryloyl groups from the viewpoint of easy polymerization. Is preferred.
One reactive functional group and the other reactive functional group may be the same or different, but are preferably the same.
In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, “(meth) acryloyl group” refers to one or both of methacryloyl group and acryloyl group, and “(meth) acrylic” “Acid” refers to one or both of methacrylic acid and acrylic acid.

The alkylene group constituting the polyalkylene group contained in the molecule of the long spacer curable monomer is not particularly limited, but an alkylene group having 2 to 30 carbon atoms is used. From the viewpoint of imparting flexibility to the base film, it is preferably linear, and specifically, an ethylene group, an n-propylene group, an n-butylene group, an n-pentene group, and the like are preferable, and the flexibility of the gas barrier laminate is preferable. From the viewpoint of further improving the properties, an ethylene group is preferable. A plurality of them can be used in combination.
Similarly, the oxyalkylene group constituting the polyoxyalkylene group contained in the molecule of the long spacer curable monomer is not particularly limited, and preferably an oxygen atom bonded to the alkylene group is preferable. Also, a plurality of them may be combined and used.
Further, the long spacer curable monomer may have a structure in which a polyalkylene group and a polyoxyalkylene group are linked as a spacer, and a three-dimensional structure in which a repeating structure of an alkylene group or a repeating structure of an oxyalkylene group is discontinuous. It may be arranged.

The long spacer curable monomer is preferably represented by the following formula (1).
Z- [Ym- (OY) nR] k (1)
Z is a k-valent organic group, and R represents a reactive functional group.
Y represents an alkylene group, and OY represents an oxyalkylene group.
k is an integer of 2 to 6, m and n are each independently 0 or an integer of 1 or more, and m and n are not 0 at the same time.
In one group represented by [Ym- (OY) nR], Y and OY may be discontinuous and the permutation is arbitrary. m is the sum of all alkylene groups in the group represented by [Ym- (O—Y) nR], and n is all oxy groups in the group represented by [Ym- (O—Y) nR]. This is the sum of alkylene groups. As each Y constituting Ym or each OY constituting (OY) n, two or more kinds of alkylene groups or oxyalkylene groups may be used. In k groups represented by [Ym- (OY) nR], the permutation of Y and OY, the values of m and n, the alkylene group and oxy used for Y and OY The types of alkylene groups are independent of each other.
When m or n is 1, Y or OY is a simple alkylene group or oxyalkylene group. In this case, Ym and (O—Y) n are represented as polyalkylene. Group, called polyoxyalkylene group.

For example, when k = 2, m is independently m1 and m2, and n is independently n1 and n2. Further, the following formula (2) is satisfied among m1, m2, n1, and n2.
2 · m1 + 2 · m2 + 2 · n1 + 2 · n2 ≧ 18 (2)

Generalizing the case where k is 2 to 6, when i and j are arbitrary integers, 1 ≦ i ≦ k, 1 ≦ j ≦ k, and i ≠ j, any two [Ym− (O− Y) When [Ymi- (OY) ni-R] and [Ymj- (OY) nj-R], which are groups represented by nR], are selected, mi and mj are independent of each other. And ni and nj are independent of each other, and the following expression (3) is always satisfied among mi, mj, ni, and nj.
2 · mi + 2 · ni + 2 · mj + 2 · nj ≧ 18 (3)

In the above formulas (1) and (3), the long spacer curable monomer may be k = 2 or k = 3, or k = 2.
When only the long spacer curable monomer is used, from the viewpoint of solvent resistance, the total number of carbon atoms constituting each main chain of the polyalkylene group and the polyoxyalkylene group is 18 or more and 26 or less. Preferably, it is 18 or more and 24 or less, more preferably 18 or more and 22 or less.
In the case where the curable monomer includes both a long spacer curable monomer and a short spacer curable monomer, from the viewpoint of both the flexibility of the gas barrier laminate and the solvent resistance of the underlayer. The total number of carbon atoms of the alkylene group and the oxyalkylene group is preferably 28 or more and 70 or less, and more preferably 28 or more and 42 or less.

Further, the curable monomer has a structure in which one reactive functional group and another reactive functional group are linked without any polyalkylene group or polyoxyalkylene group, or one reactivity The functional group has a structure linked to another reactive functional group through one or both of a polyalkylene group and a polyoxyalkylene group. The main group of the polyalkylene group and the polyoxyalkylene group It is preferable to include a curable monomer having a short spacer in which the total number of carbon atoms constituting the chain is 16 or less (hereinafter, the curable monomer having the short spacer is referred to as a “short spacer curable monomer”). Sometimes referred to as a “mer”. With respect to the short spacer, when one reactive functional group is connected to another reactive functional group via two or more polyalkylene groups or polyoxyalkylene groups, The number of carbon atoms constituting the main chain is the total number of carbon atoms constituting the main chain of two or more polyalkylene groups or polyoxyalkylene groups. Further, when the curable monomer has three or more reactive functional groups in one molecule, the main chain of each of the polyalkylene group and the polyoxyalkylene group interposed between any two reactive functional groups The total number of carbon atoms constituting is 16 or less with respect to at least one reactive functional group combination.

The reactive functional group is the same as described above, preferably a polymerizable unsaturated group, and more preferably a carbon-carbon unsaturated double bond having radical polymerizability. Specific examples include a vinyl group, a (meth) acryloyl group, and a maleimide group, and a (meth) acryloyl group is preferable from the viewpoint of easy polymerization.
One reactive functional group and the other functional reactive group of the short spacer curable monomer may be the same or different, but are preferably the same.

The alkylene group and oxyalkylene group constituting the polyalkylene group and polyoxyalkylene group are the same as those described above.
The short spacer curable monomer may have a structure in which a polyalkylene group and a polyoxyalkylene group are connected as a spacer, and a configuration in which a repeating structure of an alkylene group or a repeating structure of an oxyalkylene group is discontinuous. It may be.

When the total number of carbon atoms constituting each main chain of the polyalkylene group and the polyoxyalkylene group as the short spacer is preferably 16 or less, the solvent resistance of the underlayer is easily improved. When the short spacer curable monomer is used alone, the flexibility of the gas barrier laminate may be easily lowered, but by using it together with the long spacer curable monomer, the solvent resistance of the underlayer, The flexibility of the gas barrier laminate can be achieved.

It is preferable that the said short spacer curable monomer is represented by following formula (11) similarly to the said long spacer curable monomer.
Z-[(Y) m- (OY) nR] k (11)
Z is a k-valent organic group, and R represents a reactive functional group.
Y represents an alkylene group, OY represents an oxyalkylene group, k is an integer of 2 to 6, m and n are each independently an integer of 0 or 1, m and n May take 0 at the same time.

When k = 2, m is independently m11 and m12, and n is independently n11 and n12. It is preferable that the following formula (12) is satisfied among m11, m12, n11, and n12.
2 · m11 + 2 · m12 + 2 · n11 + 2 · n12 ≦ 16 (12)

Generalizing the case where k is 2 to 6, when i and j are arbitrary integers, 1 ≦ i ≦ k, 1 ≦ j ≦ k, and i ≠ j, any two [Ym− (O− Y) When [Ymi- (OY) ni-R] and [Ym1j- (OY) n1j-R], which are groups represented by nR], are selected, m1i and m1j are independent of each other. N1i and n1j are independent of each other, and at least one combination of i and j satisfying the following formula (13) exists between m1i, m1j, n1i, and n1j.
2 · m1i + 2 · n1i + 2 · m1j + 2 · n1j ≦ 16 (13)

In the above formula (11) and formula (13), the short spacer curable monomer may be k = 2 or k = 3, or k = 2.

Of the organic groups represented by Z in Formula (1) and Formula (11), examples of the divalent group include groups represented by the following formula. “-” At both ends represents a bond.

Further, including the above, examples of the organic group include an aromatic group having 6 to 20 carbon atoms, or a divalent to hexavalent organic group having an alicyclic hydrocarbon group having 3 to 20 carbon atoms. The aromatic ring and alicyclic ring in the hydrocarbon group may be substituted or unsubstituted.
As aromatic hydrocarbon groups having 6 to 20 carbon atoms, 2 to 6 hydrogen atoms are removed from benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, chrysene ring, fluoranthene ring, pyrene ring, etc. And divalent to hexavalent groups formed by the above method.
Examples of alicyclic hydrocarbon groups include cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cyclononyl groups, cyclodecyl groups, cycloundecyl groups, cyclododecyl groups, etc. Dicyclopentanyl group, 1-adamantyl group, 2-adamantyl group, norbornyl group, isobornyl group and other divalent to hexavalent groups formed by removing a hydrogen atom from a condensed ring group.
Examples of the substituent of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, Examples thereof include sulfonamido groups, N-sulfonylamido groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, and halogen atoms such as chlorine and bromine.
The organic group is preferably a divalent to hexavalent organic group having an aromatic hydrocarbon group having 6 to 20 carbon atoms. Such a curable monomer having an organic group is more suitable because it is excellent in compatibility with a thermoplastic resin, and when the thermoplastic resin is a polysulfone resin, it is excellent in compatibility with the polysulfone resin. Examples of the divalent to hexavalent organic group having an aromatic hydrocarbon group having 6 to 20 carbon atoms include the above-mentioned aromatic hydrocarbon group having 6 to 20 carbon atoms, a bisphenol group, A fluorene group, a biphenyl group, etc. are mentioned.

The curable monomer used in the present invention preferably has a (meth) acryloyl group as a reactive functional group. From the viewpoint of controlling flexibility and solvent resistance, the above formula is included in the scope of the present invention. Having a bisphenol skeleton such as ethoxylated bisphenol A di (meth) acrylate having a long spacer and a short spacer, and 9,9-bis [4- (2-acryloyloxyethoxy) phenyl having a long spacer and a short spacer as well Those having a 9,9-bisphenylfluorene skeleton such as fluorene and those having a tricyclodecane skeleton such as tricyclodecane dimethanol di (meth) acrylate having a long spacer and a short spacer are preferred.
Bifunctional (meth) acrylic acid derivatives include neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphorus Examples include acid di (meth) acrylate, di (acryloxyethyl) isocyanurate, and allylated cyclohexyl di (meth) acrylate.

Trifunctional (meth) acrylic acid derivatives include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) ) Acrylate, tris (acryloxyethyl) isocyanurate and the like.
Examples of the tetrafunctional (meth) acrylic acid derivative include pentaerythritol tetra (meth) acrylate.
Examples of pentafunctional (meth) acrylic acid derivatives include propionic acid-modified dipentaerythritol penta (meth) acrylate.
Examples of the hexafunctional (meth) acrylic acid derivative include dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Among these, the curable monomer is usually preferably a polyfunctional monomer from the viewpoint of heat resistance and solvent resistance, and the polyfunctional monomer is easily mixed with a thermoplastic resin, and The bifunctional (meth) acrylic acid derivative is more preferable from the viewpoint that curing shrinkage of the polymer is less likely to curl the cured product.

The long spacer curable monomer can be used singly or in combination of two or more.
Similarly, the short spacer curable monomers can be used singly or in combination of two or more.

(Thermoplastic resin)
The curable resin composition used for the underlayer of the present invention preferably contains a thermoplastic resin.
The thermoplastic resin is not particularly limited, but is preferably an amorphous thermoplastic resin. By using an amorphous thermoplastic resin, it becomes easy to obtain a resin film and a gas barrier laminate excellent in transparency.
Here, the amorphous thermoplastic resin refers to a thermoplastic resin whose melting point is not observed in differential scanning calorimetry.

Moreover, as the thermoplastic resin, a thermoplastic resin having a ring structure such as an aromatic ring structure or an alicyclic structure is preferable because a resin film having excellent heat resistance is easily obtained, and a thermoplastic resin having an aromatic ring structure is preferable. A resin is more preferable.

Specific examples of the thermoplastic resin include polysulfone resin, polyarylate resin, polycarbonate resin, and alicyclic hydrocarbon resin. Among these, a polysulfone resin and an alicyclic hydrocarbon resin are preferable because a resin film excellent in heat resistance and optical isotropy is easily obtained.

The polysulfone resin is a polymer having a sulfone group in the main chain. The polysulfone resin is not particularly limited, and known ones can be used. Examples of the polysulfone resin include polyethersulfone resin, polysulfone resin, polyphenylsulfone resin, and the like. Further, the polysulfone resin used in the present invention may be a modified polysulfone resin. Among these, polyethersulfone resin or polysulfone resin is preferable.

The polyarylate resin is a resin made of a polymer compound obtained by a reaction between an aromatic diol and an aromatic dicarboxylic acid or a chloride thereof. The polyarylate resin is not particularly limited, and known ones can be used.

The polycarbonate-based resin is a polymer having a carbonate group in the main chain. The polycarbonate resin is not particularly limited, and known resins can be used. Examples of the polycarbonate resin include aromatic polycarbonate resins and aliphatic polycarbonate resins. Of these, aromatic polycarbonate resins are preferred because of excellent heat resistance, mechanical strength, transparency, and the like.
Aromatic polycarbonate resins are prepared by reacting aromatic diols with carbonate precursors by interfacial polycondensation or melt transesterification, polymerizing carbonate prepolymers by solid phase transesterification, or opening cyclic carbonate compounds. It can be obtained by a method of polymerizing by a ring polymerization method.

The alicyclic hydrocarbon-based resin is a polymer having a cyclic hydrocarbon group in the main chain. The alicyclic hydrocarbon-based resin is not particularly limited, and known ones can be used. Examples of the alicyclic hydrocarbon resins include monocyclic olefin polymers, norbornene polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. . Commercially available products include Apel (Mitsui Chemicals ethylene-cycloolefin copolymer), TOPAS (Polyplastics company, ethylene-cycloolefin copolymer), Arton (JSR company norbornene polymer), Zeonoa (norbornene polymer manufactured by Nippon Zeon Co., Ltd.) and the like can be mentioned.
A thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

When the gas barrier layer is a cured coating film, from the viewpoint of heat resistance in the temperature conditions when drying the coating film, the thermoplastic resin preferably has a glass transition temperature (Tg) exceeding 130 ° C, and 135 ° C. More preferably.
Here, the glass transition temperature (Tg) is tan δ (loss elastic modulus / storage elastic modulus) obtained by viscoelasticity measurement (frequency 11 Hz, temperature measurement rate 0 ° C to 250 ° C and tensile mode in the range of 0 ° C to 250 ° C). ) Is the maximum point temperature.
The weight average molecular weight (Mw) of the thermoplastic resin (A) is usually 100,000 to 3,000,000, preferably 200,000 to 2,000,000, more preferably 500,000 to 2,000,000. 000 range. The molecular weight distribution (Mw / Mn) is preferably in the range of 1.0 to 5.0, more preferably 2.0 to 4.5. The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) are values in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

In the curable resin composition, the content of the curable monomer and the thermoplastic resin is, in mass ratio, preferably curable monomer: thermoplastic resin = 70: 30 to 10:90, Preferably, it is 65:35 to 20:80.
When the mass ratio between the curable monomer and the thermoplastic resin is in the above range, solvent resistance or flexibility is easily obtained.
The long spacer curable monomer and the short spacer curable monomer included in the scope of the present invention are used at the same time, and the total number of carbon atoms of the alkylene group and the oxyalkylene group of the long spacer curable monomer is When it is 28 or more, from the viewpoint of achieving both the flexibility of the gas barrier laminate and the solvent resistance of the underlayer, the mass ratio with each curable monomer is preferably a long spacer curable monomer: Short spacer curable monomer = 80: 20 to 20:80, more preferably 70:30 to 30:70, and still more preferably 60:40 to 40:60.
Moreover, when the total number of carbon atoms of the alkylene group and oxyalkylene group of the long spacer curable monomer is 27 or less, the viewpoint of both the flexibility of the gas barrier laminate and the solvent resistance of the underlayer Therefore, the mass ratio of each curable monomer is preferably long spacer curable monomer: short spacer curable monomer = 100: 0 to 60:40, more preferably 100: 0 to 70:30 is preferred.
The curable monomer and the thermoplastic resin in the curable resin composition satisfy the above mass ratio, and the mass ratio of the long spacer curable monomer and the short spacer curable monomer is in the above range. Then, the base layer is easy to obtain flexibility while maintaining the solvent resistance.
Further, if the content of the curable monomer in the curable resin composition is in the above range, for example, when the cured resin layer is obtained by a solution casting method or the like, the solvent can be efficiently removed, so The problem of curling due to long process time is eliminated.

In the curable resin composition used in the present invention, a polymerization initiator can be contained. The polymerization initiator can be used without particular limitation as long as it initiates the curing reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.

Examples of the thermal polymerization initiator include organic peroxides and azo compounds.
Examples of organic peroxides include dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, and dicumyl peroxide; diacyl peroxides such as acetyl peroxide, lauroyl peroxide, and benzoyl peroxide. ; Ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide; peroxyketals such as 1,1-bis (t-butylperoxy) cyclohexane; T-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, diisopropyl Hydroperoxides such as benzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide; t-butylperoxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxide Peroxyesters such as oxybenzoate and t-butylperoxyisopropyl carbonate;
Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2 , 4-dimethylvaleronitrile), azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) ) Isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and the like.

Photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2 -Methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpho Alkylphenone-based photopolymerization initiators such as nyl) phenyl] -1-butanone; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethyl (2 , 4,6-trimethylbenzoyl) -phenylphosphinate, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, etc .; -Titanocene photopolymerization initiator such as cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl] titanium; 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- Oxime ester photopolymerization initiators such as (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime); benzophenone, p-chlorobenzophenone, benzoylbenzoic acid, o-benzoylbenzoic acid Methyl, 4-methylbenzophenone, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethyl Benzophenone photopolymerization initiators such as benzophenone and 4- (13-acryloyl-1,4,7,10,13-pentaoxatridecyl) -benzophenone; thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4 -Dimethyl Thioxanthone photopolymerization initiators such as thioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone; Can be mentioned.

Among the above photopolymerization initiators, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl)- Phosphorus photopolymerization initiators such as phenylphosphinate and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide are preferred.
A polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

The content of the polymerization initiator is preferably 0.05 to 15% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.05 to 5% by mass with respect to the entire curable resin composition.

The solvent used for the preparation of the curable resin composition is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; dichloromethane Halogenated hydrocarbon solvents such as ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, 2 -Ketone solvents such as pentanone, isophorone and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; cellosolv solvents such as ethyl cellosolve; ether solvents such as 1,3-dioxolane;

The content of the solvent with respect to the thermoplastic resin contained in the curable resin composition is not particularly limited, but is usually 0.1 to 1000 g, preferably 1 to 100 g with respect to 1 g of the thermoplastic resin. By adjusting the amount of the solvent, the viscosity of the curable resin composition can be adjusted appropriately.

Moreover, the said curable resin composition may further contain well-known additives, such as a plasticizer, antioxidant, and an ultraviolet absorber, in the range which does not impair the objective and effect of this invention.
The method for curing the curable resin composition can be appropriately determined according to the type of polymerization initiator and curable monomer used.

The total content of the curable monomer, the thermoplastic resin, and the polymerization initiator in the curable resin composition is preferably 50% or more, more preferably 70%, based on the total amount of the curable resin composition. More preferably, it is 90% or more. However, it excludes when it has a plasticizer.

The thickness of the base layer of the gas barrier laminate of the present invention is not particularly limited, and may be appropriately determined depending on the application. The thickness of the underlayer is usually 0.05 to 100 μm, preferably 0.1 to 50 μm, more preferably 0.5 to 30 μm, and further preferably 3 to 15 μm.

The elongation at break of the underlayer is preferably 3.5% or more, more preferably 4.5% or more, and further preferably 6.0% or more. If the elongation at break of the underlayer is within this range, excellent flexibility is easily obtained. Increasing the thermoplastic resin content ratio of the curable monomer and the thermoplastic resin in the curable resin composition for forming the underlayer increases the elongation at break of the underlayer. There are things to do. However, when the curable monomer does not contain a long spacer curable monomer, even if the content ratio of the thermoplastic resin is increased, the elongation at break of the underlayer should be in such a high range. Is not easy. In the present invention, since the curable monomer contains a long spacer curable monomer, the breaking elongation of the underlayer can be adjusted to such a high range.

The base layer is preferably provided with solvent resistance. When the underlayer has solvent resistance, for example, even when an organic solvent is used to form another layer on the surface of the underlayer, components existing on the underlayer surface migrate to the other layer. Can be suppressed. Therefore, for example, even when the gas barrier layer is formed on the surface of the underlayer using a resin solution containing an organic solvent such as xylene, the gas barrier property is reduced because the components of the underlayer are not easily mixed into the gas barrier layer. It is hard to decline.

<Gas barrier layer>
The material of the gas barrier layer is not particularly limited as long as it has gas barrier properties. For example, examples of the gas barrier layer include a vapor-phase film-forming inorganic layer, a gas barrier resin layer such as polyvinyl alcohol, and a layer obtained by modifying a layer containing a polymer compound.
Further, the gas barrier layer of the present invention may be obtained by vapor deposition, sputtering, etc. like a vapor-phase film-forming inorganic layer, or may be one obtained by curing a coating film. From the viewpoint of further improving the flexibility, it is preferable that the gas barrier layer is a cured coating film.
In the present invention, the gas barrier layer is preferably a vapor-phase film-forming inorganic layer and a polymer compound because the gas barrier layer is thin and can efficiently form a layer having excellent gas barrier properties. In addition, the gas barrier layer is suitable for obtaining a cured coating film, and it is easy to obtain a gas barrier laminate having a high gas barrier property, and a layer containing a polymer compound is subjected to a modification treatment such as ion implantation. It is more preferable that Moreover, as another aspect, when the solvent resistance of the underlayer is not sufficient, the gas barrier layer is preferably a vapor-deposited inorganic layer.

The thickness of the gas barrier layer is appropriately adjusted and used from the viewpoints of gas barrier properties and handleability, but is usually in the range of 10 to 2000 nm, preferably 20 to 1000 nm, more preferably 30 to 500 nm, and still more preferably 40 to 200 nm. .

The gas barrier layer may be a laminate of single gas barrier layers, in which case the thickness of the single gas barrier layer is preferably 10 to 600 nm, more preferably 30 to 500 nm.

The inorganic substance constituting the vapor-phase film-forming inorganic layer is not particularly limited, and examples thereof include metals such as aluminum, magnesium, zinc, and tin; silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, and the like. Inorganic oxides; inorganic nitrides such as silicon nitride, aluminum nitride, titanium nitride; inorganic carbides; inorganic sulfides; inorganic oxynitrides such as silicon oxynitride; inorganic oxide carbides; inorganic nitride carbides; inorganic oxynitride carbides Can be mentioned. These can be used singly or in combination of two or more.

As a method for forming a vapor phase inorganic layer, a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method or an ion plating method, a thermal CVD (chemical vapor deposition) method, a plasma CVD method, or a photo CVD method is used. The CVD method such as the method may be mentioned.

As a method of forming a gas barrier layer that is a cured coating film, for example, a method of applying a solution containing a polymer compound or the like as a material of the gas barrier layer by a known coating method, and appropriately drying the obtained coating film Is mentioned.

As a high molecular compound used for forming a layer obtained by subjecting a layer containing a high molecular compound to a modification treatment, a silicon-containing high molecular compound is preferable, and as a silicon-containing high molecular compound, a polysilazane compound, a polycarbosilane compound, Examples include polysilane compounds and polyorganosiloxane compounds. Among these, a polysilazane compound is preferable from the viewpoint of forming a gas barrier layer having excellent gas barrier properties.

Examples of the polysilazane compound include inorganic polysilazanes such as perhydropolysilazane, and organic polysilazanes in which part or all of hydrogen in perhydropolysilazane is substituted with an organic group such as an alkyl group. These polysilazane compounds may be used alone or in combination of two or more.
In addition, as the polysilazane compound, a commercially available product as a glass coating material or the like can be used as it is.

The layer containing the polymer compound may contain other components in addition to the polymer compound described above as long as the object of the present invention is not impaired. Examples of other components include curing agents, other polymers, anti-aging agents, light stabilizers, and flame retardants.

Examples of the modification treatment include ion treatment, plasma treatment, ultraviolet irradiation treatment, and the like.

In the ion implantation process, ions implanted into the layer containing the polymer compound include ions of rare gases such as argon, helium, neon, krypton, and xenon; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur Ions of alkane gases such as methane and ethane; ions of alkene gases such as ethylene and propylene; ions of alkadiene gases such as pentadiene and butadiene; alkyne gases such as acetylene and methylacetylene Ions of aromatic hydrocarbon gases such as benzene and toluene; ions of cycloalkane gases such as cyclopropane and cyclohexane; ions of cycloalkene gases such as cyclopentene and cyclohexene; gold, silver, etc. conductive metal ion; silane (SiH ₄₎ the Ions of the organic silicon compound; and the like.
These ions may be used alone or in combination of two or more.
Among these, at least selected from the group consisting of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton, because it can be more easily injected and a gas barrier layer having particularly excellent gas barrier properties can be obtained. One kind of ion is preferred.

What is necessary is just to determine suitably the injection quantity of the ion inject | poured into the layer containing a silicon-containing high molecular compound according to the intended purpose etc. of the gas barrier film to form.

The method for implanting ions into the layer containing a silicon-containing polymer compound is not particularly limited, and examples include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma, and the like. Among them, in the present invention, the latter method of implanting plasma ions is preferable because a gas barrier layer can be easily obtained.

The plasma ion implantation method is not particularly limited, and is a method of implanting ions existing in plasma generated using an external electric field, or a plasma generated only by an electric field generated by a negative high voltage pulse without using an external electric field. Known methods such as a method of implanting ions present therein can be mentioned.

Examples of the ultraviolet rays used for the ultraviolet irradiation treatment include vacuum ultraviolet light.
As the ultraviolet irradiation treatment for modifying by irradiation with vacuum ultraviolet light, for example, a method described in JP-A-2017-095758 can be employed.

The gas barrier laminate of the present invention may further have other layers.
Examples of the other layers include a dissolution preventing layer, a process sheet, and an adhesive layer.

If the solvent resistance of the underlayer is not sufficient, a dissolution preventing layer may be provided between the underlayer and the gas barrier layer. The dissolution preventing layer is not particularly limited as long as it has a high solvent resistance, but it is formed from a layer formed from an inorganic material or a curable composition containing the short spacer curable monomer as a main component of the resin component. And the like. From the viewpoint of easily obtaining the flexibility of the gas barrier laminate, the thickness of the dissolution preventing layer is preferably not more than 0.3 times, more preferably not more than 0.2 times the thickness of the underlayer. .

The process sheet, for example, has a role of a support when forming the underlayer, and also has a role of protecting the underlayer when handling, transporting, storing, etc. in the process. It is peeled off when used.
It does not specifically limit as a process sheet, Paper; Plastic films, such as a polyethylene terephthalate; Glass etc. are mentioned.
Moreover, as a process sheet | seat, what provided the release agent layer on the paper or the plastic film from the point of the ease of handling may be sufficient. The release layer can be formed using a conventionally known release agent such as a silicone release agent, a fluorine release agent, an alkyd release agent, or an olefin release agent.
The thickness of the release agent layer is not particularly limited, but is usually 0.02 to 2.0 μm, preferably 0.05 to 1.5 μm.

The thickness of the process sheet is preferably 1 to 500 μm and more preferably 5 to 300 μm from the viewpoint of ease of handling.

The method for applying the curable resin composition used in the present invention on the process sheet is not particularly limited. For example, bar coating method, spin coating method, dipping method, roll coating method, gravure coating method, knife coating method, air knife coating method, roll knife coating method, die coating method, screen printing method, spray coating method, gravure offset method, etc. Known methods can be used. The method for drying the obtained coating film is not particularly limited. For example, a known drying method such as a hot air drying method, a hot roll drying method, or an infrared irradiation method can be used.
The drying temperature of the coating film is appropriately adjusted depending on the solvent used and the like, but is usually 30 to 150 ° C., preferably 50 to 100 ° C. The heating time is usually several seconds to several tens of minutes.
In addition, the method of forming a base layer on a process sheet is not restricted to this, For example, you may obtain a base layer on a process sheet by transferring the base layer formed separately on a process sheet.

The adhesive layer can be used, for example, when it is attached to another resin film or an adherend. From the viewpoint of maximizing the sealing performance of the gas barrier laminate, it is preferable that the gas barrier layer be as close as possible to the object to be sealed. Therefore, the adhesive layer is opposite to the side of the gas barrier layer on which the base layer is laminated. It is preferable to be laminated on the side. Further, it is preferable that the layer interposed between the gas barrier layer and the adhesive layer is kept to a minimum, such as an adhesion improving layer used for improving interlayer adhesion. In this case, in order to protect the adhesive layer until the gas barrier laminate is used, a release film may be provided on the side of the adhesive layer opposite to the side on which the gas barrier layer is laminated.
Examples of the layer structure of the gas barrier laminate that is one embodiment of the present invention include the following embodiments.
Process sheet / underlayer / gas barrier layer / adhesive layer / release film Process sheet / underlayer / dissolution-preventing layer / gas barrier layer / adhesive layer / release film The mode of the layer configuration described above seals the gas barrier laminate. The state before using as a stop material is represented.
When the gas barrier laminate is used as a sealing material, the release film is usually peeled and removed, and the exposed adhesive layer surface and the surface of the object to be sealed are bonded to obtain a sealed body. is there. In addition, after bonding the surface of the adhesive layer of the sealing material and the surface of the object to be sealed, the process sheet is usually peeled and removed, and the underlying layer is exposed to form the layer structure shown below. it can.
・ Underlayer / Gas barrier layer / Adhesive layer ・ Underlayer / Dissolution prevention layer / Gas barrier layer / Adhesive layer As mentioned above, the process sheet has a sufficient function as a support for the gas barrier laminate as described above. If not, it functions as a support or protective material for the gas barrier laminate until it is peeled off.

The adhesive layer may be used in the gas barrier laminate of the present invention in which a plurality of gas barrier laminates are laminated with the adhesive layer interposed.
The configuration of the gas barrier laminate in this case is not particularly limited. For example, when two gas barrier laminates comprising a base layer and a gas barrier layer are laminated, examples of the configuration of the gas barrier laminate include the following.
(Underlayer / Gas barrier layer / Adhesive layer / Underlayer / Gas barrier layer)
(Underlayer / Gas barrier layer / Adhesive layer / Gas barrier / Underlayer)
(Gas barrier layer / Under layer / Adhesive layer / Under layer / Gas barrier layer)

The material for forming the adhesive layer is not particularly limited, and a thermosetting adhesive, a moisture sensitive adhesive, a heat sealable adhesive, a pressure sensitive adhesive (pressure sensitive adhesive), and the like can be used. Among these, an adhesive that does not require special treatment for adhesion is preferable. Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives.
The formation method of an adhesive layer is not specifically limited, A well-known method can be utilized.
The thickness of the pressure-sensitive adhesive layer is usually 0.5 to 200 μm, preferably 1 to 100 μm.
As said peeling film, the same thing as the above-mentioned process sheet can be used.

It can be confirmed from the value of the water vapor transmission rate of the gas barrier laminate that the gas barrier laminate of the present invention has gas barrier properties.
The water vapor permeability of the gas barrier laminate in an atmosphere of 40 ° C. and 90% relative humidity is usually 1 g · m ⁻² · day ⁻¹ or less, preferably 0.8 g · m ⁻² · day ⁻¹ or less. More preferably 0.5 g · m ⁻² · day ⁻¹ or less, and still more preferably 0.1 g · m ⁻² · day ⁻¹ or less. The water vapor transmission rate can be measured by a known method like the evaluation method of the examples.

[Sealed body]
The sealing body of the present invention is formed by sealing an object to be sealed using the gas barrier laminate of the present invention as a sealing material.
Examples of the object to be sealed include at least one selected from the group consisting of organic EL elements, organic EL display elements, inorganic EL elements, inorganic EL display elements, electronic paper elements, liquid crystal display elements, and solar cell elements. .

(Method for producing sealing body)
The method for producing the encapsulant of the present invention is not particularly limited. For example, when the gas barrier laminate of the present invention used as an encapsulant has the following mode, the process sheet is first peeled and removed. The surface of the exposed adhesive layer and the surface of the object to be sealed are bonded together and bonded under desired conditions to obtain a sealed body.
Process sheet / underlayer / dissolution prevention layer / gas barrier layer / adhesive layer / release film Normally, the process sheet is peeled and removed after bonding the surface of the adhesive layer and the surface of the object to be sealed. .
According to such a method for producing a sealing body, even when the underlayer does not have a sufficient function as a support for the gas barrier film, that is, when the underlayer is very thin, etc. Even so, since the process sheet functions as a support for the gas barrier film until the process sheet is peeled and removed, the gas barrier laminate is prevented from being broken or deformed, and the handleability is excellent.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Evaluation of the solvent resistance, optical isotropy, and water vapor transmission rate (WVTR) and elongation at break of the gas barrier laminate were performed by the following methods.

(1) Solvent resistance The base layer is cut into 25 mm × 25 mm test pieces, the test pieces are immersed in a xylene solvent for 2 minutes, and the changes in the test pieces before and after immersion are visually observed. Sex was evaluated.
○: No change.
Δ: Some curling is observed, but there is no practical problem.
X: Changes in external shape such as whitening, swelling, curling, etc. occur.
(2) Optical isotropy The underlayer is cut into 10 mm × 10 mm test pieces, and the in-plane retardation of the underlayer (retardation) is measured using a phase difference measuring device (manufactured by Oji Scientific Instruments, KOBRA-WR). The optical isotropy was measured according to the following criteria.
○: Retardation value is less than 10 nm ×: Retardation value is 10 nm or more (3) Water vapor transmission rate (WVTR)
The gas barrier laminate is cut into a circular test piece having an area of 50 cm ² and using a water vapor transmission rate measuring device (manufactured by MOCON, device name: AQUATRAN) at a gas flow rate of 20 sccm at 40 ° C. and 90% RH. The water vapor transmission rate (g · m ⁻² · day ⁻¹ ) was measured. The lower limit of detection of the measuring device is 0.0005 g · m ⁻² · day ⁻¹ . Since the gas barrier laminate was inferior in self-supporting property when the PET film used to form the underlayer was peeled off, the measurement was performed in a state where the PET film was laminated. Since the water vapor transmission rate of the gas barrier layer is much smaller than that of the PET film, the influence on the WVTR due to the lamination of the PET film is small.
(4) Elongation at break The underlayer was cut into 15 mm × 150 mm test pieces, and the elongation at break was measured according to JIS K7127: 1999. Specifically, the test piece was set to a distance between chucks of 100 mm with a tensile tester (manufactured by Shimadzu Corporation, Autograph), and then a tensile test was performed at a speed of 200 mm / min to determine the elongation at break (% ) Was measured. When the test piece did not have a yield point, the tensile breaking strain was taken as the elongation at break, and when the test piece had a yield point, the tensile break nominal strain was taken as the breaking elongation.

(Example 1)
(1) Formation of foundation layer Curable resin composition 1 used as a foundation layer was prepared as follows.
<Curable resin composition 1>
As a thermoplastic resin, 100 parts by mass of polysulfone resin (PSF) pellets (manufactured by BASF, ULTRASON S6010, Tg = 187 ° C.) are mixed solvent of 1,3-dioxolane and toluene (mass ratio of 1,3-dioxolane: toluene) Is 7: 3) to prepare a 25% by mass solution of PSF. Subsequently, ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-BPE-10, the total number of carbon atoms in the oxyethylene chain between two acryloyl groups: 20) is added to this solution as a curable monomer. 122 parts by mass and 5 parts by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, Irgacure 819) as a polymerization initiator were added and mixed to prepare curable resin composition 1 did. The curable monomer and polymerization initiator used in this example and other experimental examples do not contain a solvent and are all raw materials having a solid content of 100%.
Next, a curable resin composition is applied by hand coating to the surface opposite to the easy-adhesion layer surface of a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., PET100A-4100, thickness 100 μm) as a process sheet. The resulting coating film was heated at 90 ° C. for 3 minutes to dry the coating film.
Further, on this dried coating film, a PET film (Toyobo Co., Ltd., PET100A-4100, thickness 100 μm) is laminated so that the surface opposite to the easy-adhesion surface faces, and a belt conveyor type ultraviolet irradiation device ( Using an i-graphics product name: ECS-401GX, using a high-pressure mercury lamp (product name: H04-L41), an ultraviolet lamp height of 100 mm, an ultraviolet lamp output of 3 kW, a light wavelength A curing reaction was performed under the conditions of an illuminance of 365 nm of 400 mW / cm ² and a light amount of 800 mJ / cm ² (measured with an ultraviolet light meter UV-351, manufactured by Oak Manufacturing Co., Ltd.) to form a base layer having a thickness of 25 μm.

(2) Lamination of gas barrier layer Next, the PET film laminated on the coating film is peeled off, and a polysilazane compound (a coating agent containing Perhydropolysilazane (PHPS) as a main component (manufactured by Merck Performance Materials Co., Ltd.) is formed on the underlayer. Amiacca NL-110-20, solvent: xylene) was applied by spin coating, and vacuum dried for 6 hours to form a polymer compound layer (polysilazane layer) having a thickness of 200 nm containing perhydropolysilazane.
Next, using a plasma ion implantation apparatus (manufactured by JEOL Ltd., RF power supply: “RF” 56000; Kurita Seisakusho, high voltage pulse power supply: PV-3-HSHV-0835), the gas flow rate is 100 sccm and the duty ratio is 0. .5%, DC voltage −6 kV, frequency 1000 Hz, applied RF power 1000 W, chamber internal pressure 0.2 Pa, DC pulse width 5 μsec, treatment time 200 seconds, polymer gas layer (polysilazane layer) ) To form a gas barrier layer. Thus, the gas barrier layer was produced by laminating the gas barrier layer on the base layer.
The obtained underlayer single layer was evaluated for solvent resistance, optical isotropy, elongation at break, and water vapor transmission rate (WVTR) of the gas barrier laminate. The results are shown in Table 1.

(Example 2)
(1) Formation of foundation layer Example 1 except that the foundation layer (thickness after drying: 25 μm) was formed using the following curable resin composition 2 instead of the curable resin composition 1 in Example 1. Similarly, a gas barrier laminate was produced by laminating a gas barrier layer on the base layer.
The obtained underlayer single layer was evaluated for solvent resistance, optical isotropy, elongation at break, and water vapor transmission rate (WVTR) of the gas barrier laminate. The results are shown in Table 1.
<Curable resin composition 2>
As a thermoplastic resin, 100 parts by mass of polysulfone resin (PSF) pellets (manufactured by BASF, ULTRASON S6010, Tg = 187 ° C.) was mixed with 1,3-dioxolane and toluene (1,3-dioxolane: toluene = 7: A 25% by mass solution of PSF was prepared by dissolving in 3). Next, ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., ABE-300, total number of carbon atoms of oxyethylene chain between two acryloyl groups: 6) as a curable monomer was added to this solution 61 mass Part, 61 parts by mass of ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-BPE-20, the total number of carbon atoms in the oxyethylene chain between two acryloyl groups: 34), and bis A curable resin composition 2 was prepared by adding and mixing 5 parts by weight of (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by BASF).

(Example 3)
In Example 2, except that the base layer (thickness after drying: 25 μm) was formed using the curable resin composition 3 instead of the curable resin composition 2, the same as in Example 1, on the base layer A gas barrier laminate was produced by laminating a gas barrier layer.
The obtained underlayer single layer was evaluated for solvent resistance, optical isotropy, elongation at break, and water vapor transmission rate (WVTR) of the gas barrier laminate. The results are shown in Table 1.
<Curable resin composition 3>
In the curable resin composition 2, the curable monomer is ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., ABE-300, the total number of carbon atoms of the oxyethylene chain between two acryloyl groups: 6). 52.3 parts by mass and 69.7 parts by mass of ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-BPE-20, total number of carbon atoms of oxyethylene chain between two acryloyl groups: 34) A curable resin composition 3 was prepared in the same manner as the curable resin composition 2 except that the curable resin composition 2 was changed.

Example 4
In Example 1, instead of the gas barrier layer (polysilazane layer into which ions were implanted), a gas barrier layer made of silicon nitride having a thickness of 60 nm was laminated by a sputtering method. Example 1 except that ethoxylated bisphenol A diacrylate (A-BPE-20) was used instead of ethoxylated bisphenol A diacrylate (A-BPE-10) (referred to as curable resin composition 1 ′). Similarly, a gas barrier laminate was produced.
The obtained underlayer single layer was evaluated for solvent resistance, optical isotropy, elongation at break, and water vapor transmission rate (WVTR) of the gas barrier laminate. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, a gas barrier was formed on the underlayer in the same manner as in Example 1, except that the following curable resin composition 4 was used instead of the curable resin composition 1 to form an underlayer (thickness after drying: 25 μm). A gas barrier laminate was produced by laminating the layers.
The obtained underlayer single layer was evaluated for solvent resistance, optical isotropy, elongation at break, and water vapor transmission rate (WVTR) of the gas barrier laminate. The results are shown in Table 1.
<Curable resin composition 4>
As a thermoplastic resin, 100 parts by mass of polysulfone resin (PSF) pellets (manufactured by BASF, ULTRASON S6010, Tg = 187 ° C.) was mixed with 1,3-dioxolane and toluene (1,3-dioxolane: toluene = 7: A 25% by mass solution of PSF was prepared by dissolving in 3). Next, ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., ABE-300, the total number of carbon atoms in the oxyethylene chain between two acryloyl groups: 6) 122 mass And 1 part by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, Irgacure 819) as a polymerization initiator were added and mixed to prepare a curable resin composition 4. .

(Comparative Example 2)
In Example 1, a gas barrier was formed on the underlayer in the same manner as in Example 1 except that the following curable resin composition 5 was used instead of the curable resin composition 1 to form an underlayer (thickness after drying: 25 μm). A gas barrier laminate was produced by laminating the layers.
The solvent resistance and optical isotropy of the obtained underlayer single layer, and the water vapor transmission rate (WVTR) and elongation at break of the gas barrier laminate were evaluated. The results are shown in Table 1.
<Curable resin composition 5>
As a thermoplastic resin, 100 parts by mass of polysulfone resin (PSF) pellets (manufactured by BASF, ULTRASON S6010, Tg = 187 ° C.) were mixed with 1,3-dioxolane and toluene (1,3-dioxolane: toluene = 7: A 25% by mass solution of PSF was prepared by dissolving in 3). Next, tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DCP, total number of carbon atoms of oxyethylene chain between two acryloyl groups: 2) is added to this solution as a curable monomer. A curable resin composition 5 is prepared by adding and mixing 1 part by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, Irgacure 819) as a polymerization initiator. did.

The chemical structural formulas of curable monomers used in Examples and Comparative Examples are shown below. Here, s and t represent positive integers.

In Examples 1 to 4, by using a long spacer curable monomer as an underlayer of the gas barrier laminate, a gas barrier laminate having a high elongation at break and excellent flexibility can be obtained. I understood.
Further, in Example 1, it was found that a gas barrier laminate having excellent flexibility and solvent resistance was obtained due to the small number of carbon atoms in the spacer of the long spacer curable monomer.
Further, in Examples 2 and 3, as the base layer of the gas barrier laminate, excellent flexibility is obtained by combining the mass ratio of the long spacer curable monomer and the short spacer curable monomer within a specific range. It was also found that a gas barrier laminate having solvent resistance can be obtained.
On the other hand, Comparative Examples 1 and 2 using only the short spacer curable monomer are inferior in flexibility as compared with Examples.

According to the gas barrier laminate of the present invention, since it has excellent flexibility as well as gas barrier properties, an electronic device that requires both gas barrier properties and flexibility, for example, a flexible organic EL element In addition, it is expected to be applied to members for elements that constitute various electronic devices that easily deteriorate in the atmosphere, such as flexible thermoelectric conversion elements.

1: Gas barrier laminate 2: Underlayer 3: Gas barrier layer

Claims

A gas barrier laminate including an underlayer and a gas barrier layer, wherein the underlayer includes a cured product of a curable resin composition containing a curable monomer, and the curable monomer is contained in a molecule. One reactive functional group has a structure linked to another reactive functional group via one or both of a polyalkylene group and a polyoxyalkylene group, and the polyalkylene group and the polyoxyalkylene group A gas barrier laminate comprising a curable monomer having a long spacer in which the total number of carbon atoms constituting each main chain is 18 or more.
The curable monomer further has a structure in which one reactive functional group and another reactive functional group are linked without any polyalkylene group or polyoxyalkylene group, or one reactivity The functional group has a structure linked to another reactive functional group through one or both of a polyalkylene group and a polyoxyalkylene group. The main group of the polyalkylene group and the polyoxyalkylene group The gas barrier laminate according to claim 1, comprising a curable monomer having a short spacer in which the total number of carbon atoms constituting the chain is 16 or less.
The gas barrier laminate according to claim 1 or 2, wherein the underlayer further contains a thermoplastic resin.
The gas barrier laminate according to claim 3, wherein a glass transition temperature (Tg) of the thermoplastic resin is 130 ° C or higher.
The gas barrier laminate according to claim 3 or 4, wherein the thermoplastic resin is a polysulfone resin or an alicyclic hydrocarbon resin.
The gas barrier laminate according to any one of claims 1 to 5, wherein the thickness of the underlayer is 0.1 to 50 µm.
The gas barrier laminate according to any one of claims 1 to 6, wherein the elongation at break of the underlayer is 3.5% or more.
The gas barrier laminate according to any one of claims 1 to 7, wherein the gas barrier layer is a cured coating film.
The gas barrier laminate according to any one of claims 1 to 8, wherein the gas barrier layer is obtained by modifying a layer containing a cured polysilazane compound.
The gas barrier laminate according to any one of claims 1 to 9, wherein the gas barrier laminate further comprises a process sheet.