KR20210110592A - gas barrier laminate - Google Patents

Abstract

A gas barrier laminate having high elongation at break and excellent gas barrier properties, a gas barrier laminate comprising a process film, a base layer, and a gas barrier layer in this order, wherein the base layer comprises a polymer component ( A layer comprising a cured product of a curable resin composition containing A) and a curable component (B), wherein the gas barrier laminate satisfies the following requirements [1] and [2].
[1] The absolute value of the thermal contraction rate of the gas barrier laminate is 0.5% or less.
[2] The elongation at break of the gas barrier laminate is 1.9% or more.

Description

gas barrier laminate

The present invention relates to a gas-barrier laminate that is preferably used as a member for electronic devices such as liquid crystal displays and electroluminescence (EL) displays.

In displays, such as a liquid crystal display and an electroluminescence (EL) display, in order to implement|achieve thickness reduction, weight reduction, flexibility, etc., using a transparent plastic film instead of a glass plate is examined.

However, in general, a plastic film is easier to transmit water vapor or oxygen than a glass plate, and when a transparent plastic film is used as a substrate for a display, the water vapor or oxygen that has passed through the substrate acts on the elements inside the display device, etc. There is a problem that the performance of the device is lowered or the lifespan is shortened.

In order to solve this problem, it has been proposed to use a film having a property of suppressing permeation of water vapor or oxygen as a substrate of a display. Hereinafter, the property of suppressing the permeation of water vapor or oxygen is referred to as "gas barrier property", the film having gas barrier property is referred to as "gas barrier film", and the laminate having gas barrier property is referred to as "gas barrier layered body".

In recent years, higher performance displays and the like have been demanded, and in addition to the gas barrier film used as a member for electronic devices, etc., in addition to excellent gas barrier properties, heat resistance, solvent resistance, and interlayer adhesion are excellent, the birefringence is low, and optical isotropy is It has come to be calculated|required that it was excellent in various characteristics, such as this excellent thing.

For example, in Patent Document 1, a gas barrier film having a gas barrier layer on one side of a cured resin layer, the cured resin layer having a glass transition temperature of 140°C or higher, a thermoplastic resin, and a curable resin containing a curable monomer A gas barrier film, which is a layer made of a cured product of a composition, has been proposed.

International Publication No. 2013/065812

However, there is still room for improvement in the conventional gas-barrier laminate, and with the evolution of electronic devices, it is calculated|required to be equipped with higher bending resistance and to further improve gas-barrier property.

In view of the above problem, an object of the present invention is to provide a gas barrier laminate, which is preferably used as a member for electronic devices, which has high bending resistance and excellent gas barrier properties.

The inventors of the present invention, as a result of repeated studies in order to solve the above problems, a gas barrier laminate comprising a process film, a base layer, and a gas barrier layer in this order, wherein the base layer is a polymer component (A ) and a layer made of a cured product of a curable resin composition containing the curable component (B), and further setting the absolute value of the thermal shrinkage rate of the gas barrier laminate and the elongation at break of the underlying layer to predetermined values. To find out what can be solved, the present invention was completed.

That is, the present invention provides the following [1] to [6].

[1] A gas barrier laminate comprising a process film, a base layer, and a gas barrier layer in this order, comprising:

The said base layer is a layer which consists of a hardened|cured material of curable resin composition containing a polymer component (A) and a curable component (B),

A gas barrier laminate, wherein the gas barrier laminate satisfies the following requirements (1) and (2).

(1) The absolute value of the thermal contraction rate of the gas barrier laminate is 0.5% or less.

(2) The elongation at break of the gas barrier laminate is 1.9% or more.

[2] The gas barrier laminate according to the above [1], wherein the thickness of the base layer is 0.1 to 10 µm.

[3] The gas barrier laminate according to [1] or [2], wherein the gas barrier layer is a coating film.

[4] The gas barrier laminate according to any one of [1] to [3], wherein the curable component (B) contains a cyclization polymerizable monomer.

[5] The curable component (B) component further contains a polyfunctional (meth)acrylate compound, and the mass ratio of the cyclization polymerizable monomer to the polyfunctional (meth)acrylate compound is 95:5-30 : 70, the gas barrier laminate according to the above [4].

[6] The gas barrier laminate according to any one of [1] to [5], wherein the polymer component (A) has a glass transition temperature of 250°C or higher.

ADVANTAGE OF THE INVENTION According to this invention, the gas-barrier laminated body provided with high bending resistance and excellent gas-barrier property can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows the structure of the gas-barrier laminated body which concerns on embodiment of this invention.
2 is a process diagram showing an example of a method for producing a gas barrier laminate.

In this specification, it can be said that the prescription|regulation to be preferable can be selected arbitrarily, and it can be said that the combination of the prescription|regulations said to be preferable is more preferable.

In this specification, the description "XX to YY" means "XX or more and YY or less".

In this specification, with respect to a preferable numerical range (for example, a range, such as content), the lower limit and upper limit described in stages can be combined independently, respectively. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", combining "preferred lower limit (10)" and "more preferable upper limit (60)" to say "10 to 60" You may.

In this specification, for example, "(meth)acrylic acid" represents both "acrylic acid" and "methacrylic acid", and other similar terms are also the same.

EMBODIMENT OF THE INVENTION Hereinafter, the gas-barrier laminated body which concerns on embodiment of this invention is demonstrated.

1. Gas barrier laminate

A gas barrier laminate according to an embodiment of the present invention includes a process film, a base layer, and a gas barrier layer in this order. The base layer is a layer made of a cured product of a curable resin composition containing the polymer component (A) and the curable component (B), and the gas barrier laminate meets the following requirements [1] and [2] Satisfies.

[1] The absolute value of the thermal contraction rate of the gas barrier laminate is 0.5% or less.

[2] The elongation at break of the gas barrier laminate is 1.9% or more.

In the gas barrier laminate according to the embodiment of the present invention, when the underlying layer is a cured product of the curable resin composition, the underlying layer is excellent in solvent resistance. For this reason, for example, when forming a gas barrier layer as a coating film, it becomes difficult for a base layer to be eroded by a solvent at the time of coating. As a result, it can be made difficult to reduce the gas barrier property of a gas barrier laminated body. In addition, a coating film is a film obtained by apply|coating a coating material on a base material or a target object, and performing processing, such as hardening by drying, heating, etc. as needed. When a gas barrier layer is used as a coating film, it is a film obtained by apply|coating the coating material containing the component which forms the gas barrier layer mentioned later on a base layer, and hardening by drying, heating, etc. are performed. In addition, when the base layer is a coating film, the curable resin composition is applied to an object to be coated such as a process film, and only one or both of drying and curing treatment by heating or irradiation with active energy rays is performed. .

Moreover, by satisfying the above requirement [1], shrinkage of the gas barrier laminate during heating is suppressed. For this reason, for example, when the gas barrier layer is formed on the base layer by coating the material constituting the gas barrier layer and drying by heating, the gas barrier layer is deformed by shrinkage of the precursor of the base layer and the gas barrier layer. As a result, it is possible to avoid a decrease in gas barrier properties.

In addition, by satisfying the above requirement [2], the flexibility of the gas barrier laminate is increased, and the gas barrier laminate is excellent in bending resistance and is suitable for flexible device applications.

In the present specification, the thermal contraction rate of the gas barrier laminate is set in a thermomechanical analysis apparatus, the gas barrier laminate is heated to 130 ° C at 5 ° C / min, and then cooled to room temperature at 5 ° C / min, It is the value which measured the change rate of the displacement of the elongate direction before and behind the heating of a base layer, It is measured in the procedure shown in an Example in detail.

In addition, in this specification, the fracture|rupture elongation of a base layer is a value measured according to JISK7127:1999, and is measured in the procedure shown to an Example in detail.

1-1. lower layer

The base layer which the gas-barrier laminated body which concerns on embodiment of this invention has consists of a hardened|cured material of curable resin composition containing a polymer component (A) and a curable component (B). A single layer may be sufficient as a base layer, and may contain the several layer laminated|stacked.

[Polymer component (A)]

The glass transition temperature (Tg) of the polymer component (A) is preferably 250°C or higher, more preferably 290°C or higher, still more preferably 320°C or higher. When Tg is 250°C or higher, the thermal shrinkage of the underlayer is suppressed, and as a result, it becomes easy to adjust the thermal shrinkage rate of the gas barrier laminate to the above-mentioned range (in other words, it becomes easy to satisfy the above requirement [1]) ).

Here, Tg means the temperature of the maximum point of tanδ (loss elastic modulus/storage elastic modulus) obtained by viscoelasticity measurement (measured by tensile mode in the range of 0 to 250°C at a frequency of 11 Hz and a temperature increase rate of 3°C/min).

The weight average molecular weight (Mw) of the polymer component (A) is usually in the range of 100,000 to 3,000,000, preferably 200,000 to 2,000,000, more preferably 250,000 to 2,000,000, particularly preferably 500,000 to 1,000,000. Moreover, molecular weight distribution (Mw/Mn) becomes like this. Preferably it is 1.0-5.0, More preferably, it is the range of 2.0-4.5. A weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) are polystyrene conversion values measured by the gel permeation chromatography (GPC) method. By making Mw into 100,000 or more, it becomes easy to enlarge the breaking elongation of an underlayer.

As the polymer component (A), a thermoplastic resin is preferable, and an amorphous thermoplastic resin is more preferable. By using an amorphous thermoplastic resin, it becomes easy to obtain the base layer excellent in optical isotropy, and it becomes easy to obtain the gas barrier laminated body excellent in transparency. Moreover, since an amorphous thermoplastic resin is usually easy to melt|dissolve in an organic solvent, as mentioned later, a base layer can be efficiently formed using the solution casting method.

Here, the amorphous thermoplastic resin refers to a thermoplastic resin whose melting point is not observed in differential scanning calorimetry.

It is preferable that a polymer component (A) is especially soluble in low boiling point general-purpose organic solvents, such as benzene and methyl ethyl ketone (MEK). If it is soluble in a general-purpose organic solvent, it will become easy to form a base layer by coating.

As the polymer component (A), particularly preferred is an amorphous thermoplastic resin having a Tg of 250°C or higher, which is soluble in a low-boiling point general-purpose organic solvent such as benzene and MEK.

Moreover, as a polymer component (A), from a heat resistant viewpoint, the thermoplastic resin which has ring structures, such as an aromatic ring structure or an alicyclic structure, is preferable, and the thermoplastic resin which has an aromatic ring structure is more preferable.

As a specific example of a polymer component (A), a polyimide resin, polyarylate resin, etc. are mentioned. Since these resins are usually high in Tg and excellent in heat resistance, and are amorphous thermoplastic resins, coating film formation by a solution casting method is possible. Among these, polyimide resin is preferable at the point that it is easy to obtain a thing soluble in a general-purpose organic solvent, having high Tg and excellent heat resistance, and exhibiting favorable heat resistance.

The polyimide resin is not particularly limited as long as it does not impair the effects of the present invention, and for example, aromatic polyimide resin, aromatic (carboxylic acid component)-cyclic aliphatic (diamine component) polyimide resin, ring Type aliphatic (carboxylic acid component)-aromatic (diamine component) polyimide resins, cyclic aliphatic polyimide resins, fluorinated aromatic polyimide resins, and the like can be used. In particular, a polyimide resin having a fluoro group in the molecule is preferable. Generally, Tg of a polyimide resin is 250 degreeC or more.

Specifically, the polyimide resin obtained through polymerization with respect to a polyamic acid and chemical imidation reaction using an aromatic diamine compound and tetracarboxylic dianhydride is preferable.

As an aromatic diamine compound, it is soluble in a common solvent (for example, N,N- dimethylacetamide (DMAC)) by reaction with tetracarboxylic dianhydride used together, and it is poly(i) which has predetermined|prescribed transparency. Arbitrary aromatic diamine compounds can be used as long as it is an aromatic diamine compound which gives a mid. Specifically, m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4' -diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2-bis (4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoro Ropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 1,3-bis(3-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis (4-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-amino) Phenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide )phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenyl)]sulfone; Bis[3-(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenyl)]sulfone, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4- aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl ]methane, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, 2,2-bis[4-(3-aminophenoxy)phenyl] Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl ]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-amino) Phenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3 ,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4 -(4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-fluoromethylphenoxy)-α,α -Dimethylbenzyl]benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-bis(trifluoro methyl)-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, etc. are mentioned.

These aromatic diamine compounds may be used independently and may use 2 or more types of aromatic diamine compounds. From the viewpoint of transparency and heat resistance, preferred aromatic diamine compounds include 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3, 3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [ 4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1 , 1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1 ,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 3,3′-bis(trifluoromethyl)-4,4′-dia and aromatic diamine compounds having a fluoro group, such as minobiphenyl and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and at least one kind of aromatic diamine compound to be used is It is preferable that it is an aromatic diamine compound which has a fluoro group, Especially preferably, it is 2,2'-bis(trifluoromethyl)-4,4'- diaminobiphenyl. By using the aromatic diamine compound which has a fluoro group, it becomes easy to obtain transparency, heat resistance, and the solubility with respect to a solvent.

As tetracarboxylic dianhydride, it is soluble in a common solvent (for example, N,N- dimethylacetamide (DMAC)) similarly to the said aromatic diamine compound, The tetracarboxylic which gives the polyimide which has predetermined|prescribed transparency. If it is acid dianhydride, any thing can be used, Specifically, 4,4'-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl) diphthalic dianhydride , pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,4-hydroquinonedibenzoate-3,3',4,4'-tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, etc. are illustrated. These tetracarboxylic dianhydride may be used independently and may use 2 or more types of tetracarboxylic dianhydride. And from the viewpoint of transparency, heat resistance, and solubility to a solvent, 4,4'-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)diphthalic dianhydride, etc., at least It is preferable to use tetracarboxylic dianhydride which has one type of fluoro group.

Superposition|polymerization with respect to a polyamic acid can be performed by making the said aromatic diamine compound and tetracarboxylic dianhydride react under melt|dissolution with respect to the solvent in which the polyamic acid produced|generated is soluble. Examples of the solvent used for polymerization of polyamic acid include N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazoli. Solvents, such as dinon and dimethyl sulfoxide, can be used.

It is preferable to carry out the polymerization reaction with respect to a polyamic acid, stirring in the reaction container provided with the stirring device. For example, a method in which a predetermined amount of an aromatic diamine compound is dissolved in the solvent, tetracarboxylic dianhydride is added while stirring, and reacted to obtain polyamic acid, tetracarboxylic dianhydride is dissolved in a solvent, , a method in which an aromatic diamine compound is introduced and reacted while stirring to obtain a polyamic acid, and a method in which an aromatic diamine compound and tetracarboxylic dianhydride are alternately added and reacted to obtain a polyamic acid.

Although there is no restriction|limiting in particular about the temperature of the polymerization reaction with respect to polyamic acid, It is preferable to carry out at the temperature of 0-70 degreeC, More preferably, it is 10-60 degreeC, More preferably, it is 20-50 degreeC. By carrying out the polymerization reaction within the above range, it becomes possible to obtain a high molecular weight polyamic acid with little coloration and excellent transparency.

Moreover, although the aromatic diamine compound and tetracarboxylic dianhydride used for superposition|polymerization with respect to polyamic acid usually use an equivalent molar amount, in order to control the polymerization degree of the polyamic acid obtained, molar amount/aromatic of tetracarboxylic dianhydride It is also possible to change the molar amount (molar ratio) of a diamine compound in the range of 0.95-1.05. And it is preferable that it is the range of 1.001-1.02, and, as for the molar ratio of tetracarboxylic dianhydride and an aromatic diamine compound, it is more preferable that it is 1.001-1.01. Thus, by making tetracarboxylic dianhydride slightly excess with respect to an aromatic diamine compound, while being able to stabilize the polymerization degree of the polyamic acid obtained, the unit derived from tetracarboxylic dianhydride can be arrange|positioned at the terminal of a polymer As a result, there is little coloring and it becomes possible to provide the polyimide excellent in transparency.

The concentration of the polyamic acid solution to be produced is preferably adjusted to an appropriate concentration (eg, about 10 to 30 mass%) so as to maintain the viscosity of the solution appropriately and to facilitate handling in subsequent steps. .

An imidation agent is added to the obtained polyamic acid solution, and chemical imidation reaction is performed. As the imidizing agent, carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, succinic anhydride, phthalic anhydride, and benzoic anhydride can be used, and acetic anhydride is preferably used from the viewpoint of cost and ease of removal after the reaction. The equivalent of the imidating agent to be used is not less than the equivalent of the amide bond of the polyamic acid subjected to the chemical imidization reaction, preferably 1.1 to 5 times the equivalent of the amide bond, and more preferably 1.5 to 4 times the equivalent of the amide bond. Thus, by using a slightly excess imidation agent with respect to an amide bond, the imidation reaction can be performed efficiently even at comparatively low temperature.

In the chemical imidation reaction, aliphatic, aromatic or heterocyclic tertiary amines such as pyridine, picoline, quinoline, isoquinoline, trimethylamine and triethylamine can be used as the imidization accelerator. By using such amines, imidation reaction can be performed efficiently at low temperature, As a result, it becomes possible to suppress coloring at the time of imidation reaction, and it becomes easy to obtain a more transparent polyimide.

Although there is no restriction|limiting in particular about the chemical imidation reaction temperature, It is preferable to carry out at 10 degreeC or more and less than 50 degreeC, It is more preferable to carry out at 15 degreeC or more and less than 45 degreeC. By performing a chemical imidation reaction at the temperature of 10 degreeC or more and less than 50 degreeC, coloring at the time of imidation reaction is suppressed and it becomes easy to obtain the polyimide excellent in transparency.

After that, if necessary, the poor solvent of the polyimide is added to the polyimide solution obtained by the chemical imidization reaction, the polyimide is precipitated, and the powder is formed and dried to form powder.

As polyimide resin, it is preferable that it is soluble in organic solvents of low boiling points, such as benzene and MEK, and it is more preferable that it is soluble in MEK. If it is soluble in MEK, the layer of curable resin composition can be formed easily by application|coating and drying.

Polyimide resin containing a fluoro group is preferable from a viewpoint that it becomes easy to melt|dissolve in general-purpose organic solvents with low boiling points, such as MEK, and it becomes easy to form a base layer by the application|coating method.

As a polyimide resin which has a fluoro group, the aromatic polyimide resin which has a fluoro group in a molecule|numerator is preferable, and what has skeleton shown in the molecule|numerator by the following general formula is preferable.

[Formula 1]

Polyimide resin which has frame|skeleton represented by the said Formula has high rigidity of the said frame|skeleton, and has very high Tg exceeding 300 degreeC. For this reason, the heat resistance of a base layer can be improved significantly. Moreover, the said skeleton is linear and comparatively high softness|flexibility, and it becomes easy to increase the breaking elongation of an underlayer. Moreover, the polyimide resin which has the said frame|skeleton can melt|dissolve in low boiling point general-purpose organic solvents, such as MEK, by having a fluoro group. Therefore, it can coat using the solution casting method, can form a base layer as a coating film, and the solvent removal by drying is also easy. The polyimide resin having a skeleton represented by the above formula is 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-(1,1,1,3, It can obtain by the polymerization and imidation reaction of the polyamic acid mentioned above using 3, 3- hexafluoro propane-2,2-diyl) diphthalic dianhydride.

Polyarylate resin is resin which consists of a high molecular compound obtained by reaction of aromatic diol, aromatic dicarboxylic acid, or its chloride. Polyarylate resin also has comparatively high Tg, and also has comparatively favorable elongation characteristic. Tg of polyarylate resin exists in the range of about 170-300 degreeC, and although it changes with the structure, Tg may be 250 degreeC or more. It does not specifically limit as polyarylate resin, A well-known thing can be used.

Examples of the aromatic diol include bis(4-hydroxyphenyl)methane [bisphenol F], bis(3-methyl-4-hydroxyphenyl)methane, 1,1-bis(4'-hydroxyphenyl) Ethane, 1,1-bis(3'-methyl-4'-hydroxyphenyl)ethane, 2,2-bis(4'-hydroxyphenyl)propane [bisphenol A], 2,2-bis(3'- Bis(hydroxyphenyl)alkanes such as methyl-4'-hydroxyphenyl)propane, 2,2-bis(4'-hydroxyphenyl)butane, and 2,2-bis(4'-hydroxyphenyl)octane ; 1,1-bis(4'-hydroxyphenyl)cyclopentane, 1,1-bis(4'-hydroxyphenyl)cyclohexane [bisphenol Z], 1,1-bis(4'-hydroxyphenyl)- bis(hydroxyphenyl)cycloalkanes such as 3,3,5-trimethylcyclohexane; Bis(4-hydroxyphenyl)phenylmethane, bis(3-methyl-4-hydroxyphenyl)phenylmethane, bis(2,6-dimethyl-4-hydroxyphenyl)phenylmethane, bis(2,3,6 -trimethyl-4-hydroxyphenyl)phenylmethane, bis(3-t-butyl-4-hydroxyphenyl)phenylmethane, bis(3-phenyl-4-hydroxyphenyl)phenylmethane, bis(3-fluoro -4-hydroxyphenyl)phenylmethane, bis(3-bromo-4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)-4-fluorophenylmethane, bis(3-fluoro-4 -Hydroxyphenyl)-4-fluorophenylmethane, bis(4-hydroxyphenyl)-4-chlorophenylmethane, bis(4-hydroxyphenyl)-4-bromophenylmethane, bis(3,5- Dimethyl-4-hydroxyphenyl)-4-fluorophenylmethane, 1,1-bis(4'-hydroxyphenyl)-1-phenylethane [bisphenol P], 1,1-bis(3'-methyl- 4'-hydroxyphenyl)-1-phenylethane, 1,1-bis(3'-t-butyl-4'-hydroxyphenyl)-1-phenylethane, 1,1-bis(3'-phenyl- 4'-hydroxyphenyl)-1-phenylethane, 1,1-bis(4'-hydroxyphenyl)-1-(4'-nitrophenyl)ethane, 1,1-bis(3'-bromo- 4'-hydroxyphenyl)-1-phenylethane, 1,1-bis(4'-hydroxyphenyl)-1-phenylpropane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyl bis(hydroxyphenyl)phenylalkanes such as phenyl)dibenzylmethane; bis(hydroxyphenyl)ethers such as bis(4-hydroxyphenyl)ether and bis(3-methyl-4-hydroxyphenyl)ether; bis(hydroxyphenyl)ketones such as bis(4-hydroxyphenyl)ketone and bis(3-methyl-4-hydroxyphenyl)ketone; bis(hydroxyphenyl)sulfides such as bis(4-hydroxyphenyl)sulfide and bis(3-methyl-4-hydroxyphenyl)sulfide; bis(hydroxyphenyl)sulfoxides such as bis(4-hydroxyphenyl)sulfoxide and bis(3-methyl-4-hydroxyphenyl)sulfoxide; bis(hydroxyphenyl)sulfones such as bis(4-hydroxyphenyl)sulfone [bisphenol S] and bis(3-methyl-4-hydroxyphenyl)sulfone; bis(hydroxyphenyl)fluorenes such as 9,9-bis(4'-hydroxyphenyl)fluorene and 9,9-bis(3'-methyl-4'-hydroxyphenyl)fluorene; and the like.

Examples of the aromatic dicarboxylic acid or its chloride include phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, and diphenylether 4,4' -dicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and their chlorides, etc. are mentioned. Moreover, the polyarylate-type resin to be used may be modified|denatured polyarylate-type resin. Among these, as polyarylate-type resin, resin which consists of a high molecular compound obtained by reaction of 2, 2-bis (4'-hydroxyphenyl) propane and isophthalic acid is preferable.

Although the polymer component (A) can be used individually by 1 type or in combination of 2 or more types, A thing using a single type of polyimide resin, A thing using two or more polyimide resins with different types, and polyamide to a polyimide resin What added at least one of resin and polyarylate resin is preferable from a viewpoint of being able to adjust an extending|stretching characteristic, and a viewpoint of solvent resistance.

As a polyamide resin, a thing soluble in an organic solvent is preferable, and rubber-modified polyamide resin is preferable. As a rubber-modified polyamide resin, the thing of Unexamined-Japanese-Patent No. 2004-035638 can be used, for example.

When adding a polyamide resin or polyarylate resin to the polyimide resin, the amount of the added resin is preferably 100 parts by mass relative to 100 parts by mass of the polyimide resin from the viewpoint of providing moderate flexibility while maintaining Tg high. Part by mass or less, more preferably 70 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, and preferably 1 part by mass or more, more preferably 3 parts by mass or less. More than that.

[Curable component (B)]

The curable component (B) is a component capable of participating in a polymerization reaction, or a polymerization reaction and a crosslinking reaction, for example, a monomer having a polymerizable unsaturated bond and capable of participating in a polymerization reaction, or a polymerization reaction and a crosslinking reaction am. In addition, in this specification, "curing" means a broad concept including this "polymerization reaction of a monomer" or "a polymerization reaction of a monomer and a subsequent crosslinking reaction of a polymer". By using a sclerosing|hardenable component (B), the gas-barrier laminated body excellent in solvent resistance can be obtained.

The molecular weight of a sclerosing|hardenable component (B) is 3,000 or less normally, Preferably it is 200-2,000, More preferably, it is 200-1,000.

The number of polymerizable unsaturated bonds in the curable component (B) is not particularly limited. A sclerosing|hardenable component (B) may be a monofunctional monomer which has one polymerizable unsaturated bond, and polyfunctional monomers, such as a bifunctional type and trifunctional type which have two or more, may be sufficient as it.

Monofunctional (meth)acrylic acid derivatives are mentioned as said monofunctional monomer.

It does not specifically limit as a monofunctional (meth)acrylic acid derivative, A well-known compound can be used. For example, a monofunctional (meth)acrylic acid derivative having a nitrogen atom, a monofunctional (meth)acrylic acid derivative having an alicyclic structure, and a monofunctional (meth)acrylic acid derivative having a polyether structure may be mentioned.

As a monofunctional (meth)acrylic acid derivative which has a nitrogen atom, the compound represented by a following formula is mentioned.

[Formula 2]

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² and R ³ each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, R ² and R ³ are bonded to each other Ring structure may be formed, and R ⁴ represents a divalent organic group.

A methyl group, an ethyl group, a propyl group, etc. are mentioned as a C1-C6 alkyl group represented by R<^{1>, A methyl group is preferable.}

As a C1-C12 organic group represented by R<^2> and R<^3> , C1-C12 alkyl groups, such as a methyl group, an ethyl group, and a propyl group; C3-C12 cycloalkyl groups, such as a cyclopentyl group and a cyclohexyl group; C6-C12 aromatic groups, such as a phenyl group, a biphenyl group, and a naphthyl group; can be heard These groups may have a substituent at arbitrary positions. Moreover, R<^2> and R<^3> may become one and may form a ring, and the ring may have a nitrogen atom or an oxygen atom further in frame|skeleton.

Examples of the divalent organic group represented by R ⁴ _{include groups represented by -(CH 2} ) _m - and -NH-(CH ₂ ) _m -. Here, m is an integer of 1-10.

Among these, as a monofunctional (meth)acrylic acid derivative which has a nitrogen atom, the (meth)acryloylmorpholine represented by a following formula is mentioned as a preferable thing.

[Formula 3]

By using the monofunctional (meth)acrylic acid derivative which has a nitrogen atom as a sclerosing|hardenable component (B), the base layer more excellent in heat resistance can be formed.

As a monofunctional (meth)acrylic acid derivative which has an alicyclic structure, the compound represented by a following formula is mentioned.

[Formula 4]

In the formula, R ¹ has the same meaning as above, and R ⁵ is a group having an alicyclic structure.

Examples of the group having an alicyclic structure represented by R ⁵ include a cyclohexyl group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, and a tricyclodecanyl group.

Specific examples of the monofunctional (meth)acrylic acid derivative having an alicyclic structure include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, and 2-a Dantyl (meth)acrylate, etc. are mentioned.

By using the monofunctional (meth)acrylic acid derivative which has an alicyclic structure as a sclerosing|hardenable component (B), the base layer which was more excellent in optical characteristics can be formed.

As a monofunctional (meth)acrylic acid derivative which has a polyether structure, the compound represented by a following formula is mentioned.

[Formula 5]

In formula, R<^1> represents the same meaning as the above, and R<^6> represents a C1-C12 organic group. As a C1-C12 organic group represented by R<^6> , C1-C12 alkyl groups, such as a methyl group, an ethyl group, and a propyl group; C3-C12 cycloalkyl groups, such as a cyclohexyl group; C6-C12 aromatic groups, such as a phenyl group, a biphenyl group, and a naphthyl group; and the like. j represents the integer of 2-20.

Specific examples of the monofunctional (meth)acrylic acid derivative having a polyether structure include ethoxylated o-phenylphenol (meth)acrylate, methoxy polyethylene glycol (meth) acrylate, and phenoxy polyethylene glycol (meth) acrylate. and the like.

By using the monofunctional (meth)acrylic acid derivative which has a polyether structure as a sclerosing|hardenable component (B), the base layer excellent in toughness can be formed.

Examples of the polyfunctional monomer include polyfunctional (meth)acrylic acid derivatives.

It does not specifically limit as a polyfunctional (meth)acrylic acid derivative, A well-known compound can be used. For example, a 2-6 functional (meth)acrylic acid derivative is mentioned.

As a bifunctional (meth)acrylic acid derivative, the compound represented by a following formula is mentioned.

[Formula 6]

In formula, R<^1> represents the same meaning as the above, and R<^7> represents a divalent organic group. As a divalent organic group represented by R<^7> , group represented by a following formula is mentioned.

[Formula 7]

(Wherein, s represents an integer from 1 to 20, t represents an integer from 1 to 30, u and v each independently represent an integer from 1 to 30, and "-" at both ends represents a bond shows hand)

Specific examples of the bifunctional (meth)acrylic acid derivative represented by the above formula include tricyclodecanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth) ) acrylate, ethoxylated bisphenol A di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 9,9-bis[4-( 2-acryloyloxyethoxy)phenyl]fluorene etc. are mentioned. Among these, from the viewpoint of heat resistance and toughness, a divalent organic group represented by ^{R 7} in the above formula, such as tricyclodecane dimethanol di (meth) acrylate, has a tricyclodecane skeleton, propoxylated ethoxy In the above formula, such as oxidized bisphenol A di(meth)acrylate and ethoxylated bisphenol A di(meth)acrylate, the ^{divalent organic group represented by R 7} has a bisphenol skeleton, 9,9-bis[4- It is preferable that the divalent organic group represented by ^R<7> in said formula, such as (2-acryloyloxyethoxy)phenyl]fluorene, has 9,9-bisphenyl fluorene skeleton.

In addition, as bifunctional (meth)acrylic acid derivatives other than these, neopentylglycol adipate di(meth)acrylate, hydroxypivalate neopentylglycoldi(meth)acrylate, caprolactone-modified dicyclopentenyldi( and meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, di(acryloxyethyl)isocyanurate, and allylated cyclohexyldi(meth)acrylate.

Examples of the trifunctional (meth)acrylic acid derivative include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, and propylene oxide-modified trimethylolpropane. tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, etc. are mentioned.

As a tetrafunctional (meth)acrylic acid derivative, pentaerythritol tetra(meth)acrylate etc. are mentioned.

Examples of the pentafunctional (meth)acrylic acid derivative include propionic acid-modified dipentaerythritol penta(meth)acrylate.

As a 6-functional (meth)acrylic acid derivative, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

A sclerosing|hardenable component (B) can be used individually by 1 type or in combination of 2 or more type.

Among these, a polyfunctional monomer is preferable at the point from which the base layer excellent in heat resistance and solvent resistance is obtained as for a sclerosing|hardenable component (B). As a polyfunctional monomer, a bifunctional (meth)acrylic acid derivative is preferable from a viewpoint that it is easy to mix with a polymer component (A), and cure shrinkage of a polymer is hard to occur and the curl of a hardened|cured material can be suppressed. When a sclerosing|hardenable component (B) contains a polyfunctional monomer, 40 mass % or more is preferable in the whole amount of a sclerosing|hardenable component (B), as for the content, 50-100 mass % is more preferable, 80-100 Mass % is more preferable.

It is preferable that sclerosing|hardenable component (B) contains the cyclization polymerizable monomer. A cyclization polymerizable monomer is a monomer which has the property of radical polymerization while cyclizing.

Although the cyclization polymerizable monomer grows into a linear polymer while forming a ring structure in the molecule by polymerization, the solvent resistance and heat resistance of the underlying layer can be improved compared to using a general monofunctional curable monomer. One of the reasons for this is that, in the polymer of the cyclopolymerizable monomer, since a ring structure is formed in the polymer chain, it becomes a stiffer molecule than a general linear polymer, which is thought to improve the heat resistance of the underlayer. Moreover, in a cyclization polymerizable monomer, although molecular design is carried out so that the cyclization reaction in a molecule|numerator may occur selectively, an intermolecular reaction occurs in some monomers, and a reactive functional group remains in the structural unit derived from the monomer. When this reactive functional group reacts with another monomer, branching of a polymer chain arises, and a crosslinked structure is formed in the polymer of a cyclization polymerizable monomer. It is thought that the heat resistance of a base layer further improves by this, and solvent resistance also improves. On the other hand, most of the polymers of the cyclopolymerizable monomers have a linear structure, and since the cyclic structure obtained by cyclization polymerization is flexible compared to an aromatic ring, the flexibility of the underlying layer is also compatible. , the underlying layer exhibits high elongation at break (in other words, it becomes easy to satisfy the above requirement [2]).

Non-conjugated dienes are mentioned as a specific cyclization polymerizable monomer, For example, the (alpha)- allyloxymethyl acrylic acid type monomer represented by the following formula (1) can be used.

[Formula 8]

(In the formula (1), R ⁸ represents a hydrogen atom or a monovalent organic group. The organic group is composed of a hydrocarbon and may have an ether group. The hydrogen atom of the hydrocarbon may be substituted with a halogen atom.)

The organic group may be linear, branched, or may contain a cyclic structure. The hydrocarbon group contained in an organic group is not specifically limited. For example, the hydrocarbon group is a chain saturated hydrocarbon group having 1 or more carbon atoms, a chain unsaturated hydrocarbon group having 3 or more carbon atoms, an alicyclic hydrocarbon group having 3 or more carbon atoms, and an aromatic hydrocarbon group having 6 or more carbon atoms. Among these, the hydrocarbon group is preferably a linear saturated hydrocarbon group having 1 to 30 carbon atoms, a chain unsaturated hydrocarbon group having 3 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms. The substituent is not particularly limited. For example, a substituent is a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a cyano group, a trimethylsilyl group, etc.

The chain saturated hydrocarbon group is not particularly limited. For example, the chain saturated hydrocarbon group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, a sec-amyl group, tert- amyl group, neopentyl group, n-hexyl group, sec-hexyl group, n-heptyl group, n-octyl group, sec-octyl group, tert-octyl group, 2-ethylhexyl group, capryl group, nonyl group, decyl group, undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, eicosyl group, seryl group, melicyl group, and the like.

The chain unsaturated hydrocarbon group is not particularly limited. For example, the chain unsaturated hydrocarbon group includes a crotyl group, a 1,1-dimethyl-2-propenyl group, a 2-methyl-butenyl group, a 3-methyl-2-butenyl group, a 3-methyl-3-butenyl group, 2 -Methyl-3-butenyl group, oleyl group, linol group, linolene group, and the like.

The alicyclic hydrocarbon group is not particularly limited. For example, the alicyclic hydrocarbon group includes a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a 4-methylcyclohexyl group, a 4-tert-butylcyclohexyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group, a dicyclopentanyl group, a dicyclopentenyl group, and the like.

The aromatic hydrocarbon group is not particularly limited. For example, the aromatic hydrocarbon group includes a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a 4-tert-butylphenyl group, a benzyl group, a diphenylmethyl group, a diphenylethyl group, a triphenylmethyl group, a cinnamyl group, a naphthyl group, an anthranyl group, etc. am.

The hydrocarbon group having an ether bond is not particularly limited. For example, the hydrocarbon group having an ether bond is a chain ether such as a methoxyethyl group, a methoxyethoxyethyl group, a methoxyethoxyethoxyethyl group, a 3-methoxybutyl group, an ethoxyethyl group, and an ethoxyethoxyethyl group. energy ; a group having both an alicyclic hydrocarbon group and a chain ether group, such as a cyclopentoxyethyl group, a cyclohexyloxyethyl group, a cyclopentoxyethoxyethyl group, a cyclohexyloxyethoxyethyl group, and a dicyclopentenyloxyethyl group; a group having both an aromatic hydrocarbon group and a chain ether group, such as a phenoxyethyl group and a phenoxyethoxyethyl group; Glycidyl group, β-methylglycidyl group, β-ethylglycidyl group, 3,4-epoxycyclohexylmethyl group, 2-oxetanemethyl group, 3-methyl-3-oxetanemethyl group, 3-ethyl-3-ox cyclic ether groups such as cetanemethyl group, tetrahydrofuranyl group, tetrahydrofurfuryl group, tetrahydropyranyl group, dioxazolanyl group, and dioxanyl group.

In this embodiment, it is preferable that it is a C1-C6 hydrocarbon group, and, as for ^R<8> in Formula (1), it is more preferable that it is a methyl group.

Especially, a C1-C4 alkylester of 2-allyloxymethylacrylic acid and 2-(allyloxymethyl) cyclohexyl acrylic acid are preferable, and a C1-C4 alkylester of 2-allyloxymethylacrylic acid is more preferable. , 2-(allyloxymethyl)methyl acrylate is more preferable.

As another specific cyclization polymerizable monomer, the monomer represented by the following formula (2) is mentioned, for example.

[Formula 9]

(In formula (2), X is an oxygen atom or a methylene group, a is 0 or 1, b is 1 or 2, c is an integer of 1 or 2. R ⁹ represents an alkyl group having 6 or less carbon atoms)

Examples of the cyclization polymerizable monomer represented by the formula (2) include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene) ]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(i-propyl)-2,2'-[oxy Bis(methylene)]bis-2-propenoate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-hexyl)-2,2 '-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. are mentioned.

As for sclerosing|hardenable component (B), it is more preferable that the above-mentioned polyfunctional (meth)acrylate compound and a cyclization polymerizable monomer are contained. By using these together, the thermal contraction of the base layer is suppressed while adjusting the breaking elongation of the base layer to the above-mentioned range, and as a result, it becomes easy to adjust the thermal contraction rate of a gas barrier laminated body to the above-mentioned range.

In the curable component (B), the mass ratio of the cyclization polymerizable monomer to the polyfunctional (meth)acrylate compound is preferably 95:5 to 30:70, more preferably 90:10 to 35:65, further Preferably it is 90:10-40:60. When the mass ratio of the cyclization polymerizable monomer and the polyfunctional (meth)acrylate compound is in the above range, the thermal contraction rate of the gas barrier laminate is adjusted to the above-mentioned range while adjusting the elongation at break of the underlayer to the above-mentioned range. It is easier to adjust with

[Curable resin composition]

The curable resin composition used for forming the underlayer according to the embodiment of the present invention is mixed with a polymer component (A), a curable component (B), and a polymerization initiator or other components described later as desired, and suitable It can be prepared by dissolving or dispersing in a solvent.

The total content of the polymer component (A) and the curable component (B) in the curable resin composition is preferably 40 to 99.5 mass%, more preferably 60 to 99 mass%, based on the mass of the entire curable resin composition excluding the solvent. %, more preferably 80 to 98 mass%.

Content of polymer component (A) and curable component (B) in curable resin composition is mass ratio of polymer component (A) and curable component (B), Preferably, polymer component (A): sclerosing|hardenable component (B) = 30:70 to 90:10, more preferably 35:65 to 80:20.

In the curable resin composition, when the mass ratio of the polymer component (A): the curable component (B) is in such a range, the flexibility of the obtained base layer is more likely to be improved, and the solvent resistance of the base layer tends to be easily maintained. .

In addition, if the content of the curable component (B) in the curable resin composition is within the above range, for example, when the underlying layer is obtained by a solution casting method or the like, the solvent can be efficiently removed. The problem of deformation, such as curl and bending, is eliminated.

Curable resin composition can be made to contain a polymerization initiator as needed. A polymerization initiator can be used without a restriction|limiting in particular as long as it starts hardening reaction, For example, a thermal-polymerization initiator and a photoinitiator are mentioned.

Examples of the thermal polymerization initiator include organic peroxides and azo compounds.

Examples of the organic peroxide 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, and methylcyclohexanone peroxide; peroxyketals such as 1,1-bis(t-butylperoxy)cyclohexane; t-Butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-mentane hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2 Hydroperoxides, such as 5-dihydroperoxide; peroxyesters such as t-butylperoxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, and t-butylperoxyisopropyl carbonate; and the like.

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, etc. are mentioned.

As the photopolymerization initiator, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenyl-propane- 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-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- Alkylphenone-type photoinitiators, such as [4-(4-morpholinyl)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, such as phosphorus-type photoinitiators; titanocene-based photopolymerization initiators such as bis(η ⁵ -2,4-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-(2-methylbenzoyl)-9H-carbazole oxime ester photoinitiators such as -3-yl]-1-(O-acetyloxime); Benzophenone, p-chlorobenzophenone, benzoylbenzoic acid, o-benzoylbenzoate methyl, 4-methylbenzophenone, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl-diphenyl Sulfide, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl )-benzophenone-based photoinitiators such as benzophenone; Thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro thioxanthone-based photopolymerization initiators such as -4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone; and the like.

Among the above photoinitiators, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)- Phosphorus-type photoinitiators, such as phenylphosphinate and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl- pentyl phosphine oxide, are preferable.

When a polymer component (A) is a thermoplastic resin which has an aromatic ring, as a result of a polymer component (A) absorbing an ultraviolet-ray, a hardening reaction may hardly occur. However, by using said phosphorus type photoinitiator, hardening reaction can be advanced efficiently using the light of the wavelength which is not absorbed by the said polymer component (A).

A polymerization initiator can be used individually by 1 type or in combination of 2 or more type.

0.05-15 mass % is preferable with respect to the whole curable resin composition, as for content of a polymerization initiator, 0.05-10 mass % is more preferable, 0.05-5 mass % is still more preferable.

In addition to the polymer component (A), the curable component (B), and the polymerization initiator, the curable resin composition may contain a photopolymerization initiation auxiliary such as triisopropanolamine or 4,4'-diethylaminobenzophenone. do.

It does not restrict|limit especially as a solvent used for preparation of the said curable resin composition, For example, Aliphatic hydrocarbon-type solvents, such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; cellosolve solvents such as ethyl cellosolve; ether solvents such as 1,3-dioxolane; and the like.

Although content of the solvent in the said curable resin composition is not specifically limited, It is 0.1-1,000g normally with respect to 1g of polymer component (A), Preferably it is 1-100g. By appropriately adjusting the amount of the solvent, the viscosity of the curable resin composition can be appropriately adjusted.

Moreover, the said curable resin composition may further contain well-known additives, such as a plasticizer, antioxidant, and a ultraviolet absorber, within the range which does not impair the objective and effect of this invention.

The method of hardening the said curable resin composition can be suitably determined according to the kind of polymerization initiator and curable monomer to be used. The details are explained in the section of the method for manufacturing the gas barrier laminate of the present invention, which will be described later.

[The properties of the underlying layer, etc.]

The gas barrier laminate according to the embodiment of the present invention preferably satisfies the following requirements [2'].

[2'] The elongation at break of the underlayer is 2.5% or more.

By satisfying the requirement [2'] and making the underlayer suitable for the above-mentioned requirement [1], deformation of the underlayer by heating is suppressed, and consequently, the gas barrier properties of the gas barrier laminate are improved. and the flexibility of the gas barrier laminate can be increased. Although the upper limit of the breaking elongation of a base layer is not specifically limited, Usually, it is 20 % or less, Preferably it is 15 % or less.

Here, when a cyclization polymerizable monomer is used, the elongation at break can be improved, maintaining the elastic modulus at the time of high temperature comparatively high, and it becomes easy to satisfy|fill the requirement [2']. On the other hand, when all sclerosing|hardenable component (B) is made into a cyclization polymerizable monomer, there exists a tendency for the gas barrier property of a gas barrier laminated body to fall. As a result of various examinations by the present inventors, it became clear that the fall of gas barrier property was suppressed by suppressing the absolute value of thermal contraction rate within a fixed range. Since the underlying layer is affected by heat, for example, when the gas barrier layer is formed by coating, heating causes the underlayer to deform in the planar direction, so that the thermal shrinkage rate is within a predetermined range. It is thought that by selecting the material or the like, the above phenomenon will be suppressed.

In order to satisfy the requirement [2'], for example, as the polymer component (A), a polyimide resin is used, or a flexible skeleton is introduced by further adding a polyamide resin or the like, or the molecular weight of the polymer component (A) is It is effective to reduce the abundance ratio of an aromatic ring and to improve the extending|stretching property of a base layer by increasing the , or using a cyclopolymerizable monomer as the curable component (B).

Moreover, for example, by using a polyfunctional (meth)acrylate compound and a cyclization polymerizable monomer together, a network structure may be extended, or as a polymeric component (A), the rigid and glass transition typified by polyimide resin. It can be set as the base layer suitable for the said requirement [1] by selecting a thing with a high temperature.

The thickness of the base layer is not particularly limited, and may be determined according to the purpose of the gas barrier laminate. The thickness of the underlayer is usually 0.1 to 300 µm, preferably 0.1 to 100 µm, more preferably 0.1 to 50 µm, still more preferably 0.1 to 10 µm, still more preferably 0.2 to 10 µm.

When the underlayer is, for example, about 0.1 to 10 µm thick, it is possible to prevent the thickness of the gas barrier laminate from increasing, and a thin gas barrier laminate can be obtained. If it is a thin gas barrier laminated body, in uses, such as an organic electroluminescent display which thickness reduction is requested|required, since a gas barrier laminated body does not become a factor of increase in the thickness of the whole application device, it is preferable. Moreover, if it is a thin gas barrier laminated body, the flexibility and bending resistance after mounting of a gas barrier laminated body can be improved.

The said base layer is excellent in solvent resistance. Since it is excellent in solvent resistance, for example, when forming another layer on the surface of a base layer, even if it is a case where an organic solvent is used, the surface of a base layer hardly melt|dissolves. Therefore, for example, even when the gas barrier layer is formed on the surface of the base layer using a resin solution containing an organic solvent, the gas barrier property is lowered because the components of the base layer are difficult to mix with the gas barrier layer. hard to be

From this viewpoint, the gel fraction of the base layer is preferably 90% or more, and more preferably 94% or more. Since the base layer having a gel fraction of 90% or more has excellent solvent resistance, the surface of the base layer hardly dissolves and solvent resistance is An excellent gas barrier laminate can be easily obtained.

Here, the gel fraction refers to a base layer cut to 100 mm × 100 mm, wrapped with a 150 mm × 150 mm nylon mesh (#120) having a mass previously measured, immersed in toluene (100 ml) for 3 days, and taken out. After drying at 120 degreeC for 1 hour and then leaving it to stand on the conditions of 23 degreeC 50% of relative humidity for 3 hours and performing humidity control, the mass is measured and it is obtained by the following formula|equation.

Gel fraction (%) = [(mass of residual resin after immersion)/(mass of resin before immersion)] x 100

The base layer is excellent in interlayer adhesiveness with a gas barrier layer. That is, the gas barrier layer may be formed on the base layer without forming the anchor coat layer.

The underlayer is preferably colorless and transparent. Since the underlayer is colorless and transparent, the gas barrier laminate according to the embodiment of the present invention can be suitably used for optical applications.

The underlayer has a low birefringence and excellent optical isotropy. The in-plane retardation of the underlayer is usually 20 nm or less, and preferably 15 nm or less. The retardation in the thickness direction is usually -500 nm or less, and preferably -450 nm or less. The value (birefringence) obtained by dividing the in-plane retardation by the thickness of the underlying layer is usually 100 × 10 ^-5 or less, and preferably 20 × 10 ^-5 or less.

When the in-plane retardation, the retardation in the thickness direction, and the birefringence of the underlying layer are within the above ranges, a gas barrier laminate having a low birefringence and excellent optical isotropy is obtained, and a gas barrier laminate according to an embodiment of the present invention It can be used suitably for an optical use.

The absolute value of the thermal contraction rate of the underlayer is 0.5% or less, preferably 0.3% or less, and more preferably 0.2% or less.

The elongation at break of the underlayer is preferably 2.5% or more, more preferably 2.6% or more, still more preferably 2.7% or more, and particularly preferably 3.0% or more. When the elongation at break of the underlying layer is 2.5% or more, it is easy to adjust the elongation at break of the gas barrier laminate to about 2% or more, and as a result, it is easy to obtain a gas barrier laminate having excellent bending resistance and excellent flexibility.

The tensile modulus of elasticity of the underlayer at 130°C is preferably 1.0 × 10 ³ MPa or more, 1.3 × 10 ³ MPa or more, more preferably 1.5 × 10 ³ MPa or more, still more preferably 2.0 × 10 ³ MPa or more. am. When the tensile modulus of elasticity of the underlayer at 130°C is 1.3×10 ³ MPa or more, the heat resistance of the underlayer can be made high, and the gas-barrier water vapor transmission rate of the gas barrier laminate is low, specifically, 1×10 It becomes easy to set it as ^-2 (g*m ^-2 *day ^{-1) or less.}

As mentioned above, the base layer is excellent in heat resistance, solvent resistance, interlayer adhesiveness, and transparency, and also has a low birefringence and is excellent in optical isotropy. Therefore, as will be described later, by forming a gas barrier layer by, for example, a solution casting method on a base layer having such characteristics, the gas barrier layer exhibits excellent gas barrier properties, and furthermore, It originates in at least one of the heat resistance and solvent resistance of a layer, and it is also prevented that gas-barrier property is inhibited by at least one of a heat|fever and a solvent. Moreover, it becomes the thing excellent in the heat resistance, interlayer adhesiveness, and transparency of the gas-barrier laminated body obtained. In addition, a gas barrier laminate having a low birefringence and excellent optical isotropy can be obtained.

1-2. gas barrier layer

The material of the gas barrier layer of the gas barrier laminate according to the embodiment of the present invention is not particularly limited as long as it has gas barrier properties. For example, the gas barrier layer which consists of an inorganic membrane, the gas barrier layer containing gas barrier resin, the gas barrier layer obtained by modifying|reforming the layer containing a high molecular compound, etc. are mentioned.

Among these, since a thin layer excellent in gas barrier properties and solvent resistance can be efficiently formed, the gas barrier layer is a gas barrier layer made of an inorganic film, and a layer containing a high molecular compound is subjected to a modification treatment, The resulting gas barrier layer is preferred.

It does not restrict|limit especially as an inorganic film, For example, an inorganic vapor deposition film is mentioned.

As an inorganic vapor deposition film, the vapor deposition film of an inorganic compound and a metal is mentioned.

As a raw material of the vapor deposition film of an inorganic compound, Inorganic oxides, such as a silicon oxide, aluminum oxide, magnesium oxide, a zinc oxide, indium oxide, a tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride; inorganic carbides; inorganic sulfides; inorganic oxynitrides such as silicon oxynitride; inorganic oxide carbide; inorganic nitride carbide; Inorganic oxynitride carbide etc. are mentioned.

As a raw material of a metal vapor deposition film, aluminum, magnesium, zinc, tin, etc. are mentioned.

These can be used individually by 1 type or in combination of 2 or more type.

Among these, from the viewpoint of gas barrier properties, inorganic oxide, inorganic nitride or metal as a raw material is preferable, and from the viewpoint of transparency, inorganic oxide or inorganic nitride is preferable. Moreover, a single layer may be sufficient as an inorganic vapor deposition film, and a multilayer may be sufficient as it.

The thickness of the inorganic vapor deposition film is preferably in the range of 10 to 2,000 nm, more preferably 20 to 1,000 nm, more preferably 30 to 500 nm, still more preferably 40 to 200 nm from the viewpoint of gas barrier properties and handling properties. am.

As a method of forming an inorganic vapor deposition film, a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, or a CVD method such as a thermal CVD (chemical vapor deposition) method, plasma CVD method, or optical CVD method can be mentioned. have.

Gas barrier layer containing gas barrier resin WHEREIN: As gas barrier resin used, polyvinyl alcohol or its partial saponification product, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polychloride and resins that do not easily permeate oxygen, such as vinylidene and polychlorotrifluoroethylene.

The thickness of the gas barrier layer containing the gas barrier resin is, from the viewpoint of gas barrier properties, preferably 10 to 2,000 nm, more preferably 20 to 1,000 nm, more preferably 30 to 500 nm, still more preferably It is in the range of 40-200 nm.

As a method of forming the gas barrier layer containing gas barrier resin, the method of apply|coating the solution containing gas barrier resin on a base layer, and drying the obtained coating film suitably is mentioned.

In a gas barrier layer obtained by subjecting a layer containing a high molecular compound (hereinafter, sometimes referred to as "polymer layer") to a reforming treatment, examples of the high molecular compound used include a silicon-containing high molecular compound, polyimide, polyamide, Polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylenesulfide, polyarylate, acrylic resin, cycloolefin-based polymer, Aromatic polymer etc. are mentioned. These high molecular compounds can be used individually by 1 type or in combination of 2 or more type.

Among these, as for the high molecular compound, a silicon-containing high molecular compound is preferable. As the silicon-containing high molecular compound, polysilazane-based compounds (Japanese Patent Publication No. 63-16325, Japanese Unexamined Patent Publication No. 62-195024, Japanese Unexamined Patent Publication No. 63-81122, and Japanese Unexamined Patent Publication No. 1-138108). , Japanese Patent Application Laid-Open No. 2-84437, Japanese Unexamined Patent Publication No. Hei 2-175726, Japanese Unexamined Patent Publication No. Hei 4-63833, Japanese Unexamined Patent Publication No. 5-238827, Japanese Unexamined Patent Publication No. 5-345826 , Japanese Unexamined Patent Publication No. 2005-36089, Japanese Unexamined Patent Publication No. Hei 6-122852, Japanese Unexamined Patent Publication No. Hei 6-299118, Japanese Unexamined Patent Publication No. 6-306329, Japanese Unexamined Patent Publication No. Hei 9-31333, Japanese Patent Application Laid-Open No. 10-245436, Japanese Patent Application Laid-Open No. 2003-514822, International Publication No. WO2011/107018, etc.), polycarbosilane-based compounds (Journal of Materials Science, 2569-2576, Vol. 13, 1978, Organometallics, 1336-1344, Vol. 10, 1991, Journal of Organometallic Chemistry, 1-10, Vol. 521, 1996, Japanese Unexamined Patent Publication No. 51-126300, Japanese Unexamined Patent Publication No. 2001-328991, Japanese Unexamined Patent Publication No. 2006-117917, Japanese Patent Application Laid-Open No. 2009-286891, Japanese Patent Application Laid-Open No. 2010-106100, etc.), polysilane-based compounds (RD Miller, J. Michl; Chemical Review, vol. 89, page 1359 (1989)) , N. Matsumoto; Japanese Journal of Physics, Vol. 37, page 5425 (1998), see Japanese Patent Application Laid-Open No. 2008-63586, Japanese Patent Application Laid-Open No. 2009-235358, etc.), and polyorganosiloxane-based compounds (Japan) See Japanese Patent Application Laid-Open No. 2010-229445, Japanese Patent Application Laid-Open No. 2010-232569, Japanese Patent Application Laid-Open No. 2010-238736, etc.) can

Among these, a polysilazane-type compound is preferable from a viewpoint of being able to form the gas barrier layer which has the outstanding gas barrier property. Examples of the polysilazane-based compound include inorganic polysilazane and organic polysilazane. Examples of the inorganic polysilazane include perhydropolysilazane, and examples of the organic polysilazane include a compound in which part or all of hydrogen in the perhydropolysilazane is substituted with an organic group such as an alkyl group. Among these, an inorganic polysilazane is more preferable from a viewpoint of being able to form the gas barrier layer which has easy availability and the outstanding gas barrier property.

In addition, as the polysilazane-based compound, a commercially available product such as a glass coating material may be used as it is.

A polysilazane-type compound can be used individually by 1 type or in combination of 2 or more type.

The said polymer layer may contain other components other than the high molecular compound mentioned above in the range which does not impair the objective of this invention. As other components, a hardening|curing agent, another polymer|macromolecule, antioxidant, a light stabilizer, a flame retardant, etc. are mentioned.

The content of the polymer compound in the polymer layer is preferably 50 mass% or more, and more preferably 70 mass% or more, from the viewpoint of forming a gas barrier layer having excellent gas barrier properties.

As a method of forming a polymer layer, for example, a solution for layer formation containing at least one kind of a polymer compound, other components as desired, and a solvent, etc. The method of apply|coating on the primer layer formed on the layer, drying the obtained coating film suitably, and forming it is mentioned.

When apply|coating the solution for layer formation, well-known apparatuses, such as a spin coater, a knife coater, and a gravure coater, can be used.

In order to dry the obtained coating film or to improve the gas-barrier property of a gas-barrier laminated body, it is preferable to heat a coating film. As a heating and drying method, a conventionally well-known drying method, such as hot air drying, hot roll drying, and infrared irradiation, can be employ|adopted. Heating temperature is 80-150 degreeC normally, and heating time is several tens of seconds - several tens of minutes normally.

When forming the gas barrier layer of a gas barrier laminate, for example, when using the above-mentioned polysilazane-type compound, the conversion reaction of polysilazane arises by heating after coating, and a gas barrier It becomes a coating film with excellent properties.

On the other hand, when a base layer with low heat resistance is used by heating at the time of forming such a coating film, there exists a possibility that a deformation|transformation may arise in a base layer. The deformation of the base layer may adversely affect the gas barrier properties of the gas barrier layer of the gas barrier laminate. However, since the base layer according to the embodiment of the present invention is excellent in heat resistance, it is difficult to deform even by heating at the time of coating and after coating. Accordingly, a decrease in the gas barrier properties of the gas barrier laminate resulting from the deformation of the underlying layer can also be avoided.

The thickness of a polymer layer is 20-1,000 nm normally, Preferably it is 30-800 nm, More preferably, it is 40-400 nm.

Even if the thickness of the polymer layer is nanometers, it is possible to obtain a gas barrier laminate having sufficient gas barrier performance by performing a modification treatment as described later.

Moreover, it is preferable that the said polymer layer is what modified|reformed the coating film of the composition containing a silicon compound. A polymer layer can be made into a thing richer in flexibility than the inorganic film formed by vapor deposition or sputtering, for example, if it modified|reformed the coating film of the composition containing a silicon compound.

Examples of the modification treatment include ion implantation and vacuum ultraviolet light irradiation. Among these, ion implantation is preferable at the point from which high gas barrier performance is acquired. In the ion implantation, the amount of ions implanted into the polymer layer may be appropriately determined according to the purpose of use of the gas barrier laminate to be formed (necessary gas barrier properties, transparency, etc.).

Examples of the ions to be implanted include ions of rare gases such as argon, helium, neon, krypton, and xenon; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur;

ions of alkane-based gases such as methane, ethane, propane, butane, pentane, and hexane; ions of alkene-based gases such as ethylene, propylene, butene, and pentene; ions of alkadiene-based gases such as pentadiene and butadiene; ions of alkyne-based gases such as acetylene and methylacetylene; ions of aromatic hydrocarbon-based gases such as benzene, toluene, xylene, indene, naphthalene, and phenanthrene; ions of cycloalkane-based gases such as cyclopropane and cyclohexane; ions of cycloalkene-based gases such as cyclopentene and cyclohexene;

ions of conductive metals such as gold, silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum;

ions of silane (SiH ₄ ) or organosilicon compounds; and the like.

Examples of the organosilicon compound include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetran-butoxysilane, and tetrat-butoxysilane;

Unsubstituted or substituted groups such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and (3,3,3-trifluoropropyl)trimethoxysilane alkylalkoxysilane having;

arylalkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane;

disiloxanes such as hexamethyldisiloxane (HMDSO);

Bis(dimethylamino)dimethylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylamino)dimethylsilane, diethylaminotrimethylsilane, dimethylaminodimethylsilane, tetrakisdimethylaminosilane, tris(dimethylamino)silane, etc. aminosilane;

Silazanes, such as hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, and tetramethyldisilazane;

cyanate silanes such as tetraisocyanate silane;

halogenosilanes such as triethoxyfluorosilane;

alkenyl silanes such as diallyl dimethyl silane and allyl trimethyl silane;

Unsubstituted or substituted groups such as di-t-butylsilane, 1,3-disilabutane, bis(trimethylsilyl)methane, tetramethylsilane, tris(trimethylsilyl)methane, tris(trimethylsilyl)silane, benzyltrimethylsilane alkylsilane having;

silyl alkynes such as bis(trimethylsilyl)acetylene, trimethylsilylacetylene, and 1-(trimethylsilyl)-1-propyne;

silylalkenes such as 1,4-bistrimethylsilyl-1,3-butadiine and cyclopentadienyltrimethylsilane;

arylalkylsilanes such as phenyldimethylsilane and phenyltrimethylsilane;

alkynylalkylsilanes such as propargyltrimethylsilane;

alkenylalkylsilanes such as vinyltrimethylsilane;

disilane such as hexamethyldisilane;

siloxanes such as octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, and hexamethylcyclotetrasiloxane;

N,O-bis(trimethylsilyl)acetamide;

bis(trimethylsilyl)carbodiimide;

and the like.

You may use these ions individually by 1 type or in combination of 2 or more type.

Among them, at least one selected from the group consisting of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton, since a gas barrier layer that can be injected more easily and has particularly excellent gas barrier properties is obtained. ions are preferred.

Although it does not specifically limit as a method of implanting ions, A method of irradiating ions (ion beam) accelerated by an electric field, a method of implanting ions in plasma, etc. are mentioned. Among them, the latter method of implanting plasma ions is preferable from the viewpoint of simply obtaining a gas barrier film.

As the plasma ion implantation method, (α) a method in which ions present in plasma generated using an external electric field are implanted into the polymer layer, or (β) a negative applied to the layer without using an external electric field. A method of implanting ions present in plasma generated only by an electric field by a high voltage pulse of

In the method (α), the pressure at the time of ion implantation (pressure at the time of plasma ion implantation) is preferably 0.01 to 1 Pa. When the pressure at the time of plasma ion implantation is in such a range, ions can be uniformly implanted simply and efficiently, and a target gas barrier layer can be efficiently formed.

In the method (β), it is not necessary to increase the pressure reduction degree, the treatment operation is simple, and the treatment time can be significantly shortened. In addition, the entire layer can be treated uniformly, and ions in the plasma can be continuously implanted into the polymer layer with high energy when a negative high voltage pulse is applied. In addition, it does not require special other means such as radio frequency (high frequency, hereinafter abbreviated as "RF") or a high frequency power source such as microwave, just applying a negative high voltage pulse to the layer, of ions can be uniformly implanted.

In any of the methods (α) and (β), it is preferable that the pulse width when applying the negative high voltage pulse, that is, when ion implantation is performed, is 1 to 15 µsec. When the pulse width is in such a range, ions can be implanted more simply and efficiently and uniformly.

Moreover, the applied voltage at the time of generating a plasma becomes like this. Preferably it is -1 to -50 kV, More preferably, it is -1 to -30 kV, Especially preferably, it is -5 to -20 kV. When the applied voltage is less than -1 kV, when ion implantation is performed, the ion implantation amount (dose amount) becomes insufficient, and desired performance becomes difficult to obtain. On the other hand, when ion implantation is performed at a value larger than -50 kV, the film is charged during ion implantation, and problems such as coloring of the film tend to occur, which is not preferable.

Examples of the ion species to be implanted with plasma ions include those exemplified above as ions to be implanted.

When implanting ions in plasma into the polymer layer, a plasma ion implantation device is used.

Specifically, as a plasma ion implantation device, (i) a layer in which high-frequency power is superimposed on a feed-through for applying a negative high-voltage pulse to the polymer layer (hereinafter, sometimes referred to as "ion-implanting layer"), followed by ion implantation. A device that evenly surrounds with plasma and attracts, implants, collides, and deposits ions in plasma (Japanese Patent Laid-Open No. 2001-26887), (ii) an antenna is formed in the chamber, and high-frequency power is applied to generate plasma After the plasma reaches the periphery of the ion-implanted layer, positive and negative pulses are alternately applied to the ion-implanted layer to induce and collide electrons in the plasma with a positive pulse to heat the ion-implanted layer and control the pulse constant. A device for attracting and implanting ions in plasma by applying a negative pulse while controlling temperature (Japanese Patent Application Laid-Open No. 2001-156013), (iii) generating plasma using an external electric field such as a high-frequency power source such as microwave a plasma ion implantation device that attracts and implants ions in plasma by applying a voltage pulse; apparatus and the like.

Among these, it is preferable to use the plasma ion implantation apparatus of (iii) or (iv) from the point which a process operation is simple, a process time can also be shortened significantly, and is suitable for continuous use.

As for the method of using the plasma ion implantation apparatus of said (iii) and (iv), what was described in international publication WO2010/021326 is mentioned.

In the plasma ion implantation apparatus of (iii) and (iv) above, since the plasma generating means for generating plasma is also used by a high voltage pulse power supply, special other means such as a high frequency power source such as RF or microwave are not required. By simply applying a negative high voltage pulse, plasma is generated, ions in the plasma are continuously implanted into the polymer layer, and a polymer layer having a portion modified by ion implantation on the surface, that is, a gas barrier layer is formed. A barrier laminate can be mass-produced.

The thickness of the portion into which the ions are implanted can be controlled according to implantation conditions such as the type of ion, applied voltage, and treatment time, and may be determined according to the thickness of the polymer layer, the purpose of use of the gas barrier laminate, and the like. 5 to 1,000 nm.

The implantation of ions can be confirmed by performing elemental analysis measurement in the vicinity of 10 nm from the surface of the polymer layer using X-ray photoelectron spectroscopy (XPS).

It can be confirmed that the gas barrier layer has gas barrier properties from the fact that the water vapor transmission rate of the gas barrier layer is small.

The gas barrier layer has a water vapor transmission rate of usually 1.0 g/m 2 /day or less, preferably 0.8 g/m 2 /day or less, and more preferably 0.5 g/m 2 in an atmosphere of 40° C. and 90% relative humidity. /day or less, more preferably 0.1 g/m 2 /day or less. The water vapor transmission rate can be measured by a well-known method.

1-3. process film

A process film has a role of protecting a base layer, a gas barrier layer, and the other layer mentioned above when storing, conveying, etc. a gas barrier laminated body, and it peels in a predetermined process.

When a gas-barrier laminated body has a process film, the gas-barrier laminated body may have a process film on one side, and may have a process film on both surfaces. In the latter case, it is preferable to use two types of process films and to make the process film peeled earlier into the thing which peels more easily. When it has a process film on the underlayer side, compared with the gas-barrier laminated body which does not have a process film, it can be set as the gas-barrier laminated body with high handling property, protecting a base layer.

It is preferable that a process film is a sheet form or a film form. A sheet-like or film-like thing is not limited to a long thing, The thing of a short flat plate shape is also included.

As a process film, Paper base materials, such as glassine paper, coated paper, and high quality paper; laminated paper in which a thermoplastic resin such as polyethylene or polypropylene is laminated on these paper substrates; What gave the peeling process to the said paper base material with cellulose, starch, polyvinyl alcohol, an acryl- styrene resin, etc.; Or plastic films, such as polyester films, such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films, such as polyethylene and polypropylene; Glass etc. are mentioned.

Moreover, what formed the release agent layer on a paper base material or a plastic film may be sufficient as a process film from the point of handling easiness. A release layer can be formed using conventionally well-known release agents, such as a silicone type release agent, a fluorine type release agent, an alkyd type release agent, and an olefin type release agent.

Although the thickness in particular of a release agent layer is not restrict|limited, Usually, it is 0.02-2.0 micrometers, More preferably, it is 0.05-1.5 micrometers.

From the point of handling easiness, 1-500 micrometers is preferable and, as for the thickness of a process film, 5-300 micrometers is more preferable.

10.0 nm or less is preferable and, as for surface roughness Ra (arithmetic mean roughness) of a eutectic film, 8.0 nm or less is more preferable. Moreover, 100 nm or less is preferable and, as for surface roughness Rt (maximum cross-sectional height), 50 nm or less is more preferable.

When the surface roughness Ra and Rt exceed 10.0 nm and 100 nm, respectively, the surface roughness of the layer in contact with the eutectic film becomes large, and there is a possibility that the gas barrier property of the gas barrier laminate may be lowered.

In addition, surface roughness Ra and Rt are the values obtained by the optical interference method in the measurement area of 100 micrometers x 100 micrometers.

1-4. gas barrier laminate

As mentioned above, the gas barrier laminated body which concerns on embodiment of this invention is equipped with a process film, a base layer, and a gas barrier layer in this order. When actually using a gas-barrier laminated body, a process film is peeled from a gas-barrier laminated body, and it sticks to a display or an electronic device, and uses it.

As described above, the gas barrier laminate according to the embodiment of the present invention satisfies the following requirement [1].

[1] The absolute value of the thermal contraction rate of the gas barrier laminate is 0.5% or less.

In order to satisfy the requirement [1], for example, as described above, as the curable component (B) contained in the curable resin composition for forming the underlayer, a polyfunctional (meth)acrylate compound and cyclization polymerization What is necessary is just to make a network structure increase by using a sex monomer together, or to select what is equipped with the rigid and flexible structure typified by polyimide resin as a polymeric component (A).

Moreover, as mentioned above, the gas barrier laminated body which concerns on embodiment of this invention satisfy|fills the following requirements [2].

[2] The elongation at break of the gas barrier laminate is 1.9% or more.

It is preferable that the breaking elongation of a gas barrier laminated body is 2.0 % or more. When the breaking elongation of the gas barrier laminate exists in such a range, the flexibility of a gas barrier laminate can be made high. Although the upper limit of the breaking elongation of a base layer is not specifically limited, Usually, it is 17 % or less, Preferably it is 13 % or less.

Since the thickness of the gas barrier layer is usually significantly thinner than that of the underlayer, the elongation at break of the gas barrier laminate is greatly affected by the underlayer, and tends to be close to the elongation at break of the underlayer. Therefore, if the underlying layer satisfies the above-mentioned requirement [2'], even if the breaking elongation of the gas barrier laminate is slightly smaller than the breaking elongation of the underlayer due to the influence of the gas barrier layer or the like, the requirement [2] ], it is easy to obtain a gas barrier laminate satisfying

The thickness of the gas-barrier laminate can be appropriately determined according to the intended use of the electronic device or the like. The substantial thickness of the gas barrier laminate according to the embodiment of the present invention is preferably 0.3 to 50 µm, more preferably 0.5 to 25 µm, and still more preferably 0.7 to 12 µm from the viewpoint of handling properties.

In addition, "substantial thickness" means the thickness in a use state. That is, the gas-barrier laminate may have a process sheet or the like, but the thickness of the portion (eg, process sheet) to be removed during use is not included in the “substantial thickness”.

The base layer according to the embodiment of the present invention can be made excellent in flexibility, and when the thickness of the gas barrier laminate is made small, the bending resistance after mounting of the gas barrier laminate can be further improved.

Since the gas barrier laminate according to the embodiment of the present invention has the above-described base layer and gas barrier layer, it is excellent in heat resistance, solvent resistance, interlayer adhesion and gas barrier properties, and has low birefringence and optical isotropy. great. The in-plane retardation of the gas barrier laminate is usually 20 nm or less, and preferably 15 nm or less. The retardation in the thickness direction is usually -500 nm or less, and preferably -450 nm or less. The value (birefringence) obtained by dividing the in-plane retardation by the thickness of the gas barrier laminate is usually 100 × 10 ^-5 or less, preferably 20 × 10 ^-5 or less.

If the in-plane retardation, the retardation in the thickness direction, and the birefringence of the gas barrier laminate are within the above ranges, the gas barrier laminate according to the embodiment of the present invention has excellent optical isotropy and can be preferably used for optical applications. have.

The gas barrier laminate according to the embodiment of the present invention has a water vapor transmission rate at 40°C and an atmosphere of 90% relative humidity, usually 1.0 × 10 ^-2 g/m 2 /day or less, preferably 8.0 × 10 ^-3 g /m 2 /day or less, more preferably 6.0 x 10 ^-3 g/m 2 /day or less.

A gas barrier laminate according to an embodiment of the present invention has a base layer and a gas barrier layer on at least one side of the base layer. The gas barrier laminate according to the embodiment of the present invention may have a base layer and a gas barrier layer one layer each, or may have two or more base layers and/or gas barrier layers.

The specific structural example of the gas barrier laminated body which concerns on embodiment of this invention is shown in FIG.

The gas barrier laminate 10 shown in FIG. 1 has a gas barrier layer 3 on the single side|surface of the base layer 2, The surface on the opposite side to the gas barrier layer 3 of the base layer 2 to have the eutectic film (1). When the eutectic film 1 is peeled off, the portion indicated by the reference numeral 10a including the base layer 2 and the gas barrier layer 3 turns into a gas barrier laminate after the eutectic film is removed.

The gas barrier laminate according to the embodiment of the present invention is not limited to that shown in FIG. 1, and may have a gas barrier layer on both surfaces of the base layer, and a plurality of sets of the base layer and the gas barrier layer as one set. may be laminated. Moreover, in the range which does not impair the objective of this invention, you may contain another layer in one layer or two or more layers.

As another layer, a conductor layer, an impact-absorbing layer, an adhesive bond layer, a bonding layer, a process sheet|seat etc. are mentioned, for example. In addition, the arrangement position of another layer is not specifically limited.

Examples of the material constituting the conductor layer include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specifically, tin oxide (ATO) doped with antimony; tin oxide (FTO) doped with fluorine; Semiconducting metal oxides, such as tin oxide, the zinc oxide (GZO) doped with germanium, zinc oxide, indium oxide, indium tin oxide (ITO), and zinc indium oxide (IZO); metals such as gold, silver, chromium, and nickel; a mixture of these metals and conductive metal oxides; inorganic conductive substances such as copper iodide and copper sulfide; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and the like.

There is no restriction|limiting in particular in the formation method of a conductor layer. For example, a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, etc. are mentioned.

What is necessary is just to select the thickness of a conductor layer suitably according to the use etc. It is usually 10 nm to 50 μm, preferably 20 nm to 20 μm.

The impact absorbing layer is for protecting the gas barrier layer when an impact is applied to the gas barrier layer. Although it does not specifically limit as a material which forms an impact-absorbing layer, For example, an acrylic resin, a urethane resin, a silicone resin, an olefin resin, a rubber-type material, etc. are mentioned.

There is no particular limitation on the method for forming the shock absorbing layer, for example, a shock absorbing layer forming solution containing the material for forming the shock absorbing layer and other components such as a solvent if desired is applied on the layer to be laminated, , the method of drying the obtained coating film, heating etc. as needed, and forming it is mentioned.

Moreover, you may transfer and laminate|stack the film obtained by separately forming a shock-absorbing layer into a film on the peeling base material on the layer to be laminated|stacked.

The thickness of the impact-absorbing layer is usually 1 to 100 µm, preferably 5 to 50 µm.

An adhesive bond layer is a layer used when affixing a gas-barrier laminated body to a to-be-adhered body. It does not specifically limit as a material which forms an adhesive bond layer, Well-known adhesives, such as an acrylic type, silicone type, rubber type, adhesive, a heat sealing material, etc. can also be used.

A bonding layer is a layer used when making a base layer and a gas barrier layer into one set, bonding several sets together, and manufacturing a gas barrier laminated body, etc. The bonding layer is a layer for maintaining the laminated structure by bonding the underlying layer included in one of the adjacent sets and the gas barrier layer included in the other. A single layer may be sufficient as a bonding layer, and multiple layers may be sufficient as it. As a bonding layer, what consists of a layer of the single-layer structure formed using the adhesive agent, and what consists of the layer formed using the adhesive agent on both surfaces of a support layer is mentioned.

The material used when forming the bonding layer is not particularly limited as long as it can bond sets of the underlying layer and the gas barrier layer to each other and maintain the laminated structure, and a known adhesive can be used. It is preferable that it is an adhesive at the point which can bond sets of a layer and a gas barrier layer together.

As an adhesive used for a bonding layer, an acrylic adhesive, a urethane adhesive, a silicone adhesive, a rubber adhesive, etc. are mentioned. Among these, an acrylic adhesive and a urethane-type adhesive are preferable from the point of adhesive force, transparency, and handleability. Moreover, the adhesive which can form the crosslinked structure as mentioned later is preferable.

Moreover, the thing of any form of a solvent type adhesive, an emulsion type adhesive, a hot-melt type adhesive, etc. may be sufficient as an adhesive.

2. Manufacturing method of gas barrier laminate

The gas barrier laminate according to the embodiment of the present invention is manufactured using a process film. By using a process film, a gas-barrier laminated body can be manufactured efficiently and easily. In particular, the method which has the following steps 1-3 is preferable.

Step 1: Step of forming a curable resin layer on a process film using a curable resin composition containing a polymer component (A) having a Tg of 250°C or higher and a curable component (B)

Step 2: Step of curing the curable resin layer obtained in Step 1 to form a base layer comprising a cured resin layer

Step 3: Step of forming a gas barrier layer on the base layer obtained in Step 2

An example of the manufacturing process of the gas-barrier laminated body which concerns on embodiment of this invention in FIG. 2 is shown. Fig. 2(a) corresponds to step 1, Fig. 2(b) corresponds to step 2, and Fig. 2(c) corresponds to step 3, respectively.

(Process 1)

First, a curable resin layer (symbol 2a in Fig. 2(a)) is formed on a process film using a curable resin composition containing a polymer component (A) having a Tg of 250°C or higher and a curable component (B).

As a process film and curable resin composition to be used, the thing similar to what was mentioned above is mentioned.

The method of coating the curable resin composition on the eutectic film is not particularly limited, and a spin coat method, a spray coat method, a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, a gravure coat method, etc. of known coating methods can be used.

The method in particular of drying the obtained coating film is not restrict|limited, Conventionally well-known drying methods, such as hot air drying, hot roll drying, infrared irradiation, can be used. As mentioned above, although curable resin composition used in order to form the base layer which concerns on embodiment of this invention contains the polymer component (A) which has very high Tg, By containing the curable component (B), a solution cast When drying the coating film obtained using the method, a solvent can be efficiently removed.

The drying temperature of a coating film is 30-150 degreeC normally, Preferably it is 50-100 degreeC.

Although the thickness in particular of a dry coating film (curable resin layer) is not restrict|limited, What is necessary is just to make it similar to the thickness of the base layer mentioned above since there is little difference from the thickness after hardening.

(Process 2)

Next, the curable resin layer obtained in step 1 is hardened|cured, and the cured resin layer is formed. This cured resin layer becomes a base layer (symbol 2 in FIG.2(b)).

It does not specifically limit as a method of hardening|curing curable resin layer, A well-known method is employable. For example, when curable resin layer is a thing formed using curable resin composition containing a thermal-polymerization initiator, curable resin layer can be hardened by heating curable resin layer. Heating temperature is 30-150 degreeC normally, Preferably it is 50-100 degreeC.

Moreover, when curable resin layer is a thing formed using curable resin composition containing a photoinitiator, curable resin layer can be hardened by irradiating an active energy ray to curable resin layer. The active energy ray can be irradiated using a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like.

200-400 nm is preferable and, as for the wavelength of an active energy ray, 350-400 nm is more preferable. Irradiation dose is 50-1,000 mW/cm<2> of illumination intensity normally, 50-5,000 mJ/cm<2> of light quantity, Preferably it is the range of 1,000-5,000 mJ/cm<2>. Irradiation time is 0.1 to 1,000 second normally, Preferably it is 1-500 second, More preferably, it is 10 to 100 second. In order to satisfy the above-mentioned light quantity in consideration of the thermal load of the light irradiation process, you may irradiate multiple times.

In this case, in order to prevent deterioration of the polymer component (A) by irradiation with active energy rays and coloration of the underlying layer, the curable resin composition is irradiated with active energy rays through a filter that absorbs light of a wavelength unnecessary for the curing reaction. also be According to this method, since light having a wavelength that is unnecessary for curing reaction and deteriorates the polymer component (A) is absorbed by the filter, deterioration of the polymer component (A) is suppressed, and a colorless and transparent base layer is obtained. it gets easier

As a filter, resin films, such as a polyethylene terephthalate film, can be used. When using a resin film, it is preferable to provide the process of laminating|stacking resin films, such as a polyethylene terephthalate film, on curable resin layer between process 1 and process 2. In addition, a resin film peels after process 2 normally.

Moreover, curable resin layer can also be hardened by irradiating an electron beam to curable resin layer. When irradiating an electron beam, curable resin layer can be hardened, even if it does not use a photoinitiator normally. When irradiating an electron beam, an electron beam accelerator etc. can be used. The dose is usually in the range of 10 to 1,000 krad. Irradiation time is 0.1 to 1,000 second normally, Preferably it is 1-500 second, More preferably, it is 10 to 100 second.

You may perform hardening of curable resin layer in inert gas atmosphere, such as nitrogen gas, as needed. By hardening in an inert gas atmosphere, it becomes easy to avoid that oxygen, water|moisture content, etc. interfere with hardening.

(Process 3)

Thereafter, a gas barrier layer (symbol 3 in Fig. 2(c)) is formed on the base layer obtained in step 2.

As a method of forming a gas barrier layer, the method demonstrated previously can be employ|adopted suitably.

For example, when the gas barrier layer is a layer obtained by performing a modification treatment on a layer containing a silicon-containing polymer compound, a step of forming a layer containing a silicon-containing polymer compound on an underlying layer, and the silicon-containing polymer compound A gas barrier layer can be formed by the process of performing a reforming process in the layer containing.

The gas barrier layer included in the gas barrier laminate can be formed by various methods such as extrusion molding and coating methods, but depending on the method of forming the gas barrier layer, the gas barrier performance of the gas barrier laminate is reduced. There are cases. In particular, when a gas barrier layer is formed by a formation method involving heating, for example, coating/drying, the underlying layer is physically or chemically affected, and there is a fear that properties such as gas barrier properties may be deteriorated. .

However, as mentioned above, the base layer which concerns on embodiment of this invention is a layer which consists of hardened|cured material of curable resin composition containing a polymer component (A) and a curable component (B), The polymer component (A) Since Tg is 250 degreeC or more, an underlayer is hard to be affected by the heating at the time of forming a gas barrier layer. For this reason, the gas barrier layer to be formed is less likely to be affected by the deformation of the underlying layer during the manufacturing process, resulting in, for example, microcracks in the gas barrier layer, thereby reducing the gas barrier properties. it gets difficult

As a method of forming a layer containing a silicon-containing high molecular compound or a method of performing a modification treatment, those described above can be employed.

Further, as a method of performing the modification treatment, a long film in which a layer containing a silicon-containing polymer compound is formed on the base layer obtained in step 2 is conveyed in a fixed direction to the layer containing the silicon-containing polymer compound. , it is preferable to perform a reforming treatment to produce a gas barrier laminate.

According to this manufacturing method, a long gas-barrier laminated body can be manufactured continuously, for example.

In addition, the process film is normally peeled in a predetermined process depending on the use of a gas barrier laminated body etc., and, as shown in FIG.2(c), the gas barrier laminated body after the process film 3 removal. (10a) becomes For example, another layer etc. are formed after process 3, and a process film may be peeled after that, and a process film may be peeled after process 3. Moreover, you may peel a process film between process 2 and process 3.

Thus, although the manufacturing method which has the said process 1-3 forms a curable resin layer using a process film, the gas barrier laminated body obtained by this method may have a process film, and does not need to have it. .

According to the manufacturing method of the gas barrier laminated body mentioned above, the gas barrier laminated body which concerns on embodiment of this invention can be manufactured efficiently, continuously and easily.

Example

Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Measurement and evaluation of the physical property values of the base layer and the gas barrier laminate of each Example and Comparative Example were performed in the following procedure.

<Solvent resistance of the underlayer>

The base layer was cut into a 25 mm × 25 mm test piece, the test piece was immersed in a xylene solvent for 2 minutes, the change in the test piece before and after immersion was visually observed, and solvent resistance was evaluated according to the following criteria.

A: No change.

B: A slight change in appearance is seen, but there is no problem practically.

C: Appearance changes such as whitening, swelling, curling, and curvature are caused, which impairs practical use.

<Thermal shrinkage of gas barrier laminate>

The gas barrier laminate was cut into a 5 mm x 30 mm test piece, and the first polyethylene terephthalate (PET) film on the underlayer side corresponding to the eutectic film was peeled off and removed, and a thermomechanical analyzer TMA4000SE (Nech Japan Co., Ltd.) After setting the distance between the chucks to 20 mm using In addition, the rate of change of the displacement in the elongate direction before and after heating (the value in which the ratio of the amount of displacement with respect to the distance between chucks of 20 mm was expressed as a percentage) was taken as the thermal shrinkage ratio. In addition, the case where the gas-barrier laminate was contracted was made into a negative value, and the case where it extended was made into a positive value.

<Water Vapor Transmission Rate (WVTR) of Gas Barrier Laminate>

The gas barrier laminate was cut into a circular test piece having an area of 50 cm 2 , and using a water vapor transmission rate measuring apparatus (manufactured by MOCON, equipment name: AQUATRAN), the water vapor transmission rate ( g/m 2 /day) was measured. In addition, the detection lower limit of a measuring apparatus is 0.0005 g/m<2>/day. Since the gas-barrier laminate is inferior in self-reliance when the PET film used for forming the base layer is peeled off, it measured in the state in which the said PET film was laminated|stacked. Since the water vapor transmission rate of the gas barrier layer is much smaller than that of the PET film, the effect on the WVTR by lamination of the PET film is negligible.

<Elongation at break of underlayer and gas barrier laminate>

The underlayer was cut into a 15 mm x 150 mm test piece, and the breaking elongation was measured according to JIS K7127: 1999. Specifically, the test piece is subjected to a tensile test at a rate of 200 mm/min after setting the chuck distance to 100 mm in a tensile tester (manufactured by Shimadzu Corporation, Autograph) to determine the elongation at break [%]. measured. In addition, when a test piece does not have a yield point, tensile rupture strain was made into rupture elongation, when it had a yield point, tensile rupture nominal strain. Moreover, the same test was implemented also about the gas barrier laminated body (without a process film) in which the gas barrier layer was formed.

[Example 1]

Curable resin composition 1 used as a base layer was prepared in the following procedure.

<Curable resin composition 1>

As a polymer component, 100 parts by mass of pellets of polyimide resin (PI) (manufactured by Kawamura Industrial Co., Ltd., product name KPI-MX300F, Tg = 354°C, weight average molecular weight 280,000) are dissolved in methyl ethyl ketone (MEK), and PI 15 A mass % solution was prepared. Then, to this solution, 122 parts by mass of tricyclodecanedimethanol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DCP) as a curable monomer, and bis(2,4,6-trimethylbenzoyl)- as a polymerization initiator 5 parts by mass of phenylphosphine oxide (manufactured by BASF, Irgacure819) was added and mixed to prepare curable resin composition 1. In addition, the sclerosing|hardenable monomer and polymerization initiator used in this Example and other experimental examples do not contain a solvent, and all are raw materials of 100% of solid content.

Next, as a process film, the 1st PET film (made by Toyobo Co., Ltd., PET100A-4100, thickness 100 micrometers) which has an easily bonding layer on one side is used, and on the surface opposite to the easily bonding layer surface of this PET film, curability The resin composition was apply|coated, and the coating film was dried by heating at 90 degreeC for 3 minute(s).

Further, on this dried coating film, a second PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4100, thickness 50 µm) having an easily bonding layer on one side is laminated so that the opposite side to the easily bonding surface faces the belt, Using a conveyor-type UV irradiation device (manufactured by Eye Graphics, product name: ECS-401GX), a high-pressure mercury lamp (manufactured by Eye Graphics, product name: H04-L41), UV lamp height 100 mm, UV lamp output 3 kw, Under the conditions of an illuminance of 365 nm of light wavelength of 400 mW/cm 2 and a light quantity of 800 mJ/cm 2 (manufactured by Oak Corporation, measured with a UV photometer UV-351), UV irradiation through the second PET film to cure the curing reaction It carried out and formed the base layer with a thickness of 5 micrometers.

Next, the second PET film is peeled to expose the underlying layer, and a coating agent containing a polysilazane compound (perhydropolysilazane (PHPS) as a main component (manufactured by Merck Performance Materials, Ami Arkka NL-) on the underlayer 110-20, solvent: xylene)) by spin coating and drying by heating at 130° C. for 2 minutes to form a 200 nm thick polymer compound layer (polysilazane layer) containing perhydropolysilazane. did.

Next, using a plasma ion implanter (manufactured by Nippon Electronics Co., Ltd., RF power supply: "RF" 56000; Kurita Seisakusho Co., Ltd., high voltage pulse power supply: PV-3-HSHV-0835), gas flow rate 100 sccm, Duty ratio Under the conditions of 0.5%, applied DC voltage -6 kV, frequency 1,000 Hz, applied RF power 1,000 W, chamber internal pressure 0.2 Pa, DC pulse width 5 μsec, and processing time 200 seconds, ions derived from argon gas were added to the polymer compound layer (polysilazane layer). ) to form a gas barrier layer. Thus, by laminating|stacking a gas barrier layer on the base layer, the gas barrier laminated body was produced.

[Example 2]

As the curable monomer, dicyclopentadiene diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DCP) 61 parts by mass, allyl ether type acrylate (Nippon Catalyst Co., Ltd., FX-AO-MA) 61 mass parts as a cyclization polymerizable monomer A gas-barrier laminate was produced in the same manner as in Example 1 except that the negative was used.

[Comparative Example 1]

A gas barrier laminate was produced in the same manner as in Example 1 except that only 122 parts by mass of an allyl ether type acrylate (produced by Nippon Catalyst, FX-AO-MA), which is a cyclization polymerizable monomer, was used as the curable monomer.

[Comparative Example 2]

In the same manner as in Comparative Example 1, except that 100 parts by mass of pellets of polysulfone resin (PSF) (manufactured by BASF, ULTRASON S6010, Tg = 187°C, weight average molecular weight 60,000) were used as the polymer component instead of the polyimide resin as the polymer component, A gas barrier laminate was produced.

[Comparative Example 3]

As a dissolution solvent of the pellets, toluene instead of MEK, as a polymer component, instead of polyimide resin, polycarbonate resin (PC) pellets (Tg ≤ 190 ° C., weight average molecular weight less than 100,000) 100 parts by mass) except that 100 parts by mass were used It carried out similarly to 1, and produced the gas-barrier laminated body.

Table 1 shows the measurement results of each Example and Comparative Example.

As is clear from Table 1, in Examples 1 and 2, the underlayer is excellent in solvent resistance and elongation at break, and the gas barrier laminate after removal of the eutectic film is excellent in elongation at break and thermal shrinkage, and gas barrier property The water vapor transmission rate of the laminate is also excellent.

On the other hand, in Comparative Examples 1 to 3, although the solvent resistance of the underlying layer was good, the absolute value of the thermal shrinkage rate of the gas barrier laminate after removal of the eutectic film was larger than in Example 1, and the water vapor transmission rate of the gas barrier laminate was also Compared with Example 1, it is falling by 1 digit or more. Moreover, any breaking elongation of a base layer and a gas-barrier laminated body is a result inferior to an Example.

Industrial Applicability

According to the gas barrier laminate of the present invention, while having a high elongation at break, the gas barrier property can be further improved, so that an electronic device requiring gas barrier property, flexibility, and bending resistance at the same time, for example, , flexible organic EL elements, and the like, and flexible thermoelectric conversion elements, etc., can be applied to members for elements constituting various electronic devices that are susceptible to atmospheric deterioration.

1: Process film
2: lower layer
2a: underlying layer before curing
3: gas barrier layer
10: gas barrier laminate
10a: gas barrier laminate after process film removal

Claims (6)

A gas barrier laminate comprising a process film, a base layer, and a gas barrier layer in this order, comprising:
The said base layer is a layer which consists of a hardened|cured material of curable resin composition containing a polymer component (A) and a curable component (B),
A gas barrier laminate, wherein the gas barrier laminate satisfies the following requirements [1] and [2].
[1] The absolute value of the thermal contraction rate of the gas barrier laminate is 0.5% or less.
[2] The elongation at break of the gas barrier laminate is 1.9% or more. The method of claim 1,
The thickness of the said base layer is 0.1-10 micrometers, The gas barrier laminated body. 3. The method according to claim 1 or 2,
The gas barrier layer is a coating film, a gas barrier laminate. 4. The method according to any one of claims 1 to 3,
The said curable component (B) contains a cyclization polymerizable monomer, The gas barrier laminated body. 5. The method of claim 4,
The said curable component (B) contains a polyfunctional (meth)acrylate compound further, and the mass ratio of the said cyclization polymerizable monomer and the said polyfunctional (meth)acrylate compound is 95:5-30:70, Gas barrier laminate. 6. The method according to any one of claims 1 to 5,
The glass transition temperature of the said polymer component (A) is 250 degreeC or more, The gas barrier laminated body.

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