TW202031479A - Gas barrier laminate - Google Patents

Abstract

This gas barrier laminate has a high fracture elongation and good gas barrier properties, and is provided with a process film, a base layer, and a gas barrier layer, in this order, wherein the base layer is a layer comprising a cured product of a curable resin composition which contains a polymer component (A) and a curable monomer (B). The gas barrier laminate satisfies the following requirements [1] and [2]. [1] The absolute value of a thermal shrinkage of the gas barrier laminate is 0.5% or less. [2] The fracture elongation of the gas barrier laminate is 1.9% or more.

Description

Gas barrier laminate

The present invention relates to a gas barrier laminate that can be suitably used as a component for electronic devices such as a liquid crystal display or an electroluminescence (EL) display.

In liquid crystal displays or electroluminescence (EL) displays, in order to achieve thinner, lighter, flexible, etc., the use of transparent plastic films instead of glass plates is reviewed. However, in general, compared to glass plates, plastic films are easier to transmit water vapor or oxygen. If a transparent plastic film is used as the substrate of the display, the water vapor or oxygen that penetrates the substrate will act on the display device. There is a problem that the performance of the device decreases or the life of the device becomes shorter. In order to solve this problem, it has been proposed to use a thin film that can suppress the transmission of water vapor or oxygen as a substrate of a display. Hereinafter, the characteristic of suppressing the permeation of water vapor or oxygen is called "gas barrier property", the film with gas barrier property is called "gas barrier film", and the laminate with gas barrier property is called "gas barrier layer" Fit".

In recent years, higher performance displays have been required. For gas barrier films used as components for electronic devices, excellent gas barrier properties are required, plus heat resistance, solvent resistance, excellent interlayer adhesion, and low birefringence. , Excellent optical isotropy and other various characteristics. For example, Patent Document 1 proposes a gas barrier film which is a gas barrier film having a gas barrier layer on one side of a cured resin layer. The cured resin layer is composed of a thermoplastic resin with a glass transition temperature of 140°C or higher and a cured resin layer. A layer composed of a curable resin composition of a curable monomer. Prior art literature Patent literature

Patent Document 1: International Publication No. 2013/065812

The problem to be solved by the invention

However, there is still room for improvement in conventional gas barrier laminated systems. With the evolution of electronic devices, higher bending resistance and higher gas barrier properties are required.

In view of the above-mentioned problems, the subject of the present invention is to provide a gas-barrier laminate that has high bending resistance and excellent gas barrier properties and is suitable as a member for electronic devices. Means to solve the problem

In order to solve the above-mentioned problems, the inventors have repeated intensive and dedicated reviews and found that: a gas barrier laminate having an engineered film, a base layer, and a gas barrier layer in this order, the base layer is made of a polymer component (A ) And a layer composed of a cured product of a curable resin composition of the curable component (B), and the absolute value of the heat shrinkage rate of the gas barrier laminate and the breaking elongation of the base layer are set to specified values, and The above-mentioned problems can be solved and the present invention has been completed. That is, the present invention provides the following [1] to [6]. [1] A gas-barrier laminate, which is a gas-barrier laminate with an engineered film, a base layer and a gas barrier layer in sequence, The aforementioned base layer is a layer composed of a cured product of a curable resin composition containing a polymer component (A) and a curable component (B), The aforementioned gas barrier laminate satisfies the following requirements (1) and (2): (1) The absolute value of the heat shrinkage rate of the gas barrier laminate is 0.5% or less, (2) The elongation at break of the gas barrier laminate is over 1.9%. [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 layered product according to [1] or [2] above, wherein the gas barrier layer is a coating film. [4] The gas barrier laminate according to any one of [1] to [3] above, wherein the curable component (B) contains a cyclized polymerizable monomer. [5] The gas barrier laminate according to the above [4], wherein the curable component (B) component further contains a polyfunctional (meth)acrylate compound, and the cyclized polymerizable monomer and the poly The mass ratio of the functional (meth)acrylate compound is 95:5-30:70. [6] The gas barrier laminate according to any one of [1] to [5] above, wherein the glass transition temperature of the polymer component (A) is 250°C or higher. Effect of invention

According to the present invention, it is possible to provide a gas barrier laminate having high bending resistance and excellent gas barrier properties.

Implementation of the invention

In this specification, preferred regulations can be arbitrarily selected, and the combination of preferred regulations with each other can be said to be more suitable. In this manual, the description of "XX～YY" means "more than XX and less than YY". In this specification, with regard to a preferable numerical range (for example, a range of content, etc.), the lower limit and the upper limit are described step by step and can be combined independently. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", a combination of "preferable lower limit (10)" and "preferable upper limit (60)" can also become " 10～60". In this specification, for example, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are the same. Hereinafter, the gas barrier laminate of the embodiment of the present invention will be explained.

1. Gas barrier laminate The gas barrier laminated system of the embodiment of the present invention includes an engineered film, a base layer and a gas barrier layer in this order. Furthermore, the base layer is a layer composed of a cured product of a curable resin composition containing a polymer component (A) and a curable component (B), and the gas barrier laminate satisfies the following requirements [1] and [2 ]: [1] The absolute value of the heat shrinkage 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, since the base layer is a cured product of the curable resin composition, the base layer has excellent solvent resistance. Therefore, for example, when a gas barrier layer is used as a coating film, the base layer is not easily corroded by the solvent during coating. As a result, the gas barrier properties of the gas barrier laminate may not easily decrease. In addition, the term “coating film” refers to a film obtained by applying a coating material on a substrate or an object and subjecting it to treatment such as curing by drying or heating as necessary. When the gas barrier layer is used as a coating film, a coating material containing components for forming the gas barrier layer described later is applied to the base layer and cured by drying or heating. In addition, when the base layer is used as a coating film, the curable resin composition is applied to a coated body such as an engineering film, and the curing process is performed by drying, heating, or irradiation with active energy rays. Either or both. In addition, by satisfying the above-mentioned requirement [1], shrinkage of the gas barrier laminate during heating can be suppressed. Therefore, for example, when the material constituting the gas barrier layer is coated and heated and dried to form the gas barrier layer on the base layer, it is possible to avoid the deformation of the gas barrier layer due to the shrinkage of the base layer and the precursors of the gas barrier layer , As a result, the gas barrier properties are reduced. Furthermore, by satisfying the above-mentioned requirement [2], the flexibility of the gas-barrier laminate is increased, and the gas-barrier laminate has excellent bending resistance, making it suitable for flexible device applications. In the specification of this case, the heat shrinkage rate of the gas barrier laminate is to fix the gas barrier laminate in a thermomechanical analysis device, and then heat it up to 130°C at 5°C/min, then cool it to room temperature at 5°C/min, and measure the base layer The value obtained by the rate of change of displacement in the longitudinal direction before and after heating is measured in detail by the procedure shown in the examples. In addition, in the present specification, the breaking elongation of the base layer is a value measured in accordance with JIS K7127: 1999, and in detail, it is measured by the procedure shown in the examples.

1-1. Basal layer The base layer of the gas barrier laminate of the embodiment of the present invention is composed of a cured product of a curable resin composition containing a polymer component (A) and a curable component (B). The base layer may be a single layer, or may include a plurality of layers laminated.

[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, and particularly preferably 320°C or higher. Since Tg is 250°C or higher, the thermal shrinkage of the base layer can be suppressed, and as a result, it becomes easier to adjust the thermal shrinkage rate of the gas barrier laminate to the above range (that is, it is easy to satisfy the above requirement [1]). Here, Tg refers to the tanδ (loss modulus of elasticity/storage) obtained by viscoelasticity measurement (in the range of frequency 11Hz, heating rate 3°C/min, 0～250°C, measured by stretching mode) The temperature at the maximum point of the modulus of elasticity.

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. In addition, the molecular weight distribution (Mw/Mn) is preferably in the range of 1.0 to 5.0, and more preferably in the range of 2.0 to 4.5. The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) are the values in terms of polystyrene measured by gel permeation chromatography (GPC). Since the Mw is 100,000 or more, the fracture elongation of the base layer can be easily increased.

The polymer component (A) is preferably a thermoplastic resin, and more preferably an amorphous thermoplastic resin. Since the amorphous thermoplastic resin is used, it is easy to obtain a base layer having excellent optical isotropy, and it is easy to obtain a gas barrier laminate having excellent transparency. In addition, since amorphous thermoplastic resins are generally easily soluble in organic solvents, as will be described later, the underlayer can be efficiently formed by the solution casting method. Here, the term "amorphous thermoplastic resin" refers to a thermoplastic resin whose melting point is not observed in differential scanning calorimetry.

The polymer component (A) is particularly preferably soluble in a general-purpose organic solvent with a low boiling point, such as benzene or methyl ethyl ketone (MEK). As long as it is soluble in general-purpose organic solvents, the base layer can be easily formed by coating.

The polymer component (A) is particularly preferably an amorphous thermoplastic resin having a Tg of 250° C. or higher, which is soluble in low-boiling general-purpose organic solvents such as benzene or MEK.

In addition, as the polymer component (A), from the viewpoint of heat resistance, a thermoplastic resin having a ring structure such as an aromatic ring structure or an alicyclic structure is preferable, and a thermoplastic resin having an aromatic ring structure is more preferable .

Specific examples of the polymer component (A) include polyimide resin and polyarylate resin. These resins generally have high Tg and excellent heat resistance, and because they are amorphous thermoplastic resins, coating films can be formed by solution casting. Among these, a polyimide resin is preferable from the viewpoint of obtaining a polyimide resin that is soluble in a general-purpose organic solvent although it has a high Tg, is excellent in heat resistance, and exhibits good heat resistance.

The polyimide resin is not particularly limited as long as it does not impair the scope of the effects of the present invention. For example, aromatic polyimide resin, aromatic (carboxylic acid component)-cycloaliphatic (diamine component) ) Polyimide resin, cycloaliphatic (carboxylic acid component)-aromatic (diamine component) polyimide resin, cycloaliphatic polyimide resin and fluorinated aromatic polyimide resin, etc. . In particular, a polyimide resin having a fluorine group in the molecule is preferable. Generally speaking, the Tg of polyimide resin is 250°C or higher.

Specifically, it is preferable to use an aromatic diamine compound and a tetracarboxylic dianhydride, and a polyimide resin obtained by polymerization of polyamide acid and a chemical imidization reaction.

As an aromatic diamine compound, as long as it is soluble in a common solvent (such as N,N-dimethylacetamide (DMAC)) by reacting with the tetracarboxylic dianhydride used in combination, it has the specified For the aromatic diamine compound of the transparent polyimide, any aromatic diamine compound can be used. Specifically, m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diamine Diphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3, 4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-amine Phenyl)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-hexafluoropropane, 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-aminophenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide Ether, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfide, bis[3-(4-aminobenzene) Oxygen) phenyl] ash, bis[4-(4-aminophenyl)] ash, bis[3-(3-aminophenoxy)phenyl] ash, bis[4-(3-aminophenyl) Phenyl)] ash, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-amine Phenyloxy)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)benzene Yl]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-aminophenoxy) Yl)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(trifluoromethyl)-4,4'-diamine Biphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, etc.

These aromatic diamine compounds may be used alone, or two or more kinds of aromatic diamine compounds may be used. Furthermore, from the viewpoint of transparency or 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) Yl)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'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4' -Aromatic diamine compounds having a fluorine group such as diaminobiphenyl, preferably at least one of the aromatic diamine compounds used is an aromatic diamine compound having a fluorine group, particularly preferably 2, 2 '-Bis(trifluoromethyl)-4,4'-diaminobiphenyl. The use of an aromatic diamine compound having a fluorine group makes it easier to obtain transparency, heat resistance, and solubility in solvents.

As the tetracarboxylic dianhydride, similar to the above-mentioned aromatic diamine compound, as long as it is soluble in a common solvent (for example, N,N-dimethylacetamide (DMAC)), and has specified transparency. As for the tetracarboxylic dianhydride of imine, any one can be used. Specifically, 4,4'-(1,1,1,3,3,3-hexafluoropropane-2,2-di Base) diphthalic acid dianhydride, pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 1,4-hydroquinone diphenyl ketone-3, 3',4,4'-tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid Dianhydride and so on. These tetracarboxylic dianhydrides may be used alone, or two or more types of tetracarboxylic dianhydrides may be used. Moreover, from the viewpoints of transparency, heat resistance, and solubility in solvents, it is preferable to use 4,4'-(1,1,1,3,3,3-hexafluoropropane-2,2-di Group) At least one type of tetracarboxylic dianhydride having a fluorine group such as diphthalic dianhydride.

The polymerization to the polyamide is carried out by reacting the aromatic diamine compound and the tetracarboxylic dianhydride under the dissolution of the produced polyamide in a solvent soluble. As a solvent used in the polymerization of polyamide acid, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1, Solvents such as 3-dimethyl-2-imidazolinone and dimethyl sulfoxide.

The polymerization reaction to polyamic acid is preferably performed while stirring in a reaction vessel equipped with a stirring device. For example, a method of dissolving a specified amount of aromatic diamine compound in the above solvent, adding tetracarboxylic dianhydride while stirring and reacting to obtain polyamide acid, dissolving the tetracarboxylic dianhydride in the solvent A method of adding an aromatic diamine compound while stirring and reacting to obtain a polyamide acid, a method of alternately adding an aromatic diamine compound and a tetracarboxylic dianhydride to react to obtain a polyamide acid, etc. .

Regarding the temperature of the polymerization reaction to the polyamide acid, there is no particular limitation, but it is preferably carried out at a temperature of 0 to 70°C, more preferably 10 to 60°C, and particularly preferably 20 to 50°C. Since the polymerization reaction proceeds within the above range, a high molecular weight polyamide acid with less coloration and excellent transparency can be obtained.

In addition, the aromatic diamine compound and tetracarboxylic dianhydride used in the polymerization of polyamide acid are used in approximately equal molar amounts, but in order to control the degree of polymerization of the obtained polyamide acid, the tetracarboxylic acid The molar amount of the dianhydride/the molar amount of the aromatic diamine compound (molar ratio) was changed in the range of 0.95 to 1.05. Furthermore, the molar ratio of the tetracarboxylic dianhydride to the aromatic diamine compound is preferably in the range of 1.001 to 1.02, more preferably 1.001 to 1.01. In this way, since the tetracarboxylic dianhydride is slightly excessive for the aromatic diamine compound, the degree of polymerization of the obtained polyamide acid can be stabilized, and the unit derived from the tetracarboxylic dianhydride can be arranged at the end of the polymer. As a result, a polyimide with less coloration and excellent transparency can be obtained.

In order to maintain the viscosity of the solution appropriately, the concentration of the resulting polyamide acid solution facilitates the operation of the subsequent steps, and it is preferable to adjust the concentration to an appropriate concentration (for example, about 10-30% by mass).

Add an imidizing agent to the obtained polyamide acid solution to perform a chemical imidization reaction. As the imidizing agent, carboxylic anhydrides such as acetic anhydride, propionic anhydride, succinic anhydride, phthalic anhydride, benzoic anhydride, etc. can be used. From the viewpoint of cost or ease of removal after the reaction, it is preferably used Acetic anhydride. The equivalent weight of the imidating agent used is greater than the equivalent weight of the amide bond of the polyamide acid undergoing the chemical imidation reaction, preferably 1.1 to 5 times the equivalent weight of the amide bond, more preferably 1.5 to 4 Times. In this way, using a slightly excessive amount of the amide bond with respect to the amide bond allows the amide reaction to proceed efficiently even at a relatively low temperature.

In the chemical imidization reaction, as the imidization accelerator, pyridine, picoline, quinoline, isoquinoline, trimethylamine, triethylamine, etc. aliphatic, aromatic or heterocyclic tertiary can be used Amines. Due to the use of such amines, the imidation reaction can be efficiently carried out at a low temperature. As a result, the coloration during the imidization reaction can be suppressed, and a more transparent polyimide can be easily obtained.

Regarding the chemical imidization reaction temperature, there is no particular limitation, but it is preferably 10°C or more and less than 50°C, more preferably 15°C or more and less than 45°C. Since the chemical imidization reaction is performed at a temperature above 10°C and less than 50°C, the coloration during the imidization reaction can be suppressed, and it is easy to obtain polyimide with excellent transparency.

Then, as needed, a polyimide weak solvent is added to the polyimide solution obtained by the chemical imidization reaction to precipitate the polyimide, and the powder is formed into powder and dried.

The polyimide resin is preferably soluble in a low-boiling organic solvent such as benzene or MEK, and more preferably soluble in MEK. If it is soluble in MEK, a layer of curable resin composition can be easily formed by coating and drying.

The polyimide resin containing a fluorine group is suitable from the viewpoint of being easily soluble in general-purpose organic solvents such as MEK with a low boiling point, and being easy to form a base layer by a coating method. As the polyimide resin having a fluorine group, an aromatic polyimide resin having a fluorine group in the molecule is preferred, and one having a skeleton represented by the following chemical formula in the molecule is preferred.

The polyimide resin having the skeleton represented by the above chemical formula has a very high Tg exceeding 300°C due to the high rigidity of the skeleton. Therefore, the heat resistance of the base layer can be greatly improved. In addition, the above-mentioned skeleton is linear, has relatively high flexibility, and easily increases the elongation at break of the base layer. In addition, the polyimide resin having the above-mentioned skeleton has a fluorine group and can be dissolved in a general-purpose organic solvent with a low boiling point such as MEK. Therefore, the solution casting method can be used for coating to form a base layer as a coating film, and the solvent removal by drying is also easy. The polyimide resin with the skeleton shown in the above chemical formula can use 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl and 4,4'-(1,1 ,1,3,3,3-hexafluoropropane-2,2-diyl)diphthalic dianhydride, obtained by the polymerization and imidization reaction of the above-mentioned polyamide acid.

The polyarylate resin is a resin composed of a polymer compound obtained by the reaction of an aromatic diol with an aromatic dicarboxylic acid or its chloride. Polyarylate resin also has a relatively high Tg and good elongation properties. The Tg of the polyarylate resin is in the range of about 170 to 300°C. Although it varies depending on the structure, there are some having Tg of 250°C or higher. The polyarylate resin is not particularly limited, and well-known ones can be used.

Examples of aromatic diols include bis(4-hydroxyphenyl)methane [bisphenol F], bis(3-methyl-4-hydroxyphenyl)methane, 1,1-bis(4'-hydroxyl Phenyl)ethane, 1,1-bis(3'-methyl-4'-hydroxyphenyl)ethane, 2,2-bis(4'-hydroxyphenyl)propane (bisphenol A), 2, 2-bis(3'-methyl-4'-hydroxyphenyl)propane, 2,2-bis(4'-hydroxyphenyl)butane, 2,2-bis(4'-hydroxyphenyl)octane Bis(hydroxyphenyl)alkanes; 1,1-bis(4'-hydroxyphenyl)cyclopentane, 1,1-bis(4'-hydroxyphenyl)cyclohexane [bisphenol Z], 1,1-bis(4'-hydroxyphenyl)-3,3,5-trimethylcyclohexane and other bis(hydroxyphenyl)cycloalkanes; 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-tertiarybutyl-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'-tertiarybutyl-4'-hydroxyphenyl)-1-phenylethane , 1,1-bis(3'-phenyl-4'-hydroxyphenyl)-1-phenylethane, 1,1-bis(4'-hydroxyphenyl)-1-(4'-nitro Phenyl)ethane, 1,1-bis(3'-bromo-4'-hydroxyphenyl)-1-phenylethane, 1,1-bis(4'-hydroxyphenyl)-1-phenyl Bis(hydroxyphenyl)phenylalkanes such as propane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)dibenzylmethane; bis(4-hydroxyphenyl)ether, Bis (hydroxyphenyl) ethers such as bis(3-methyl-4-hydroxyphenyl) ether; bis(4-hydroxyphenyl)ketone, bis(3-methyl-4-hydroxyphenyl)ketone, etc. Bis(hydroxyphenyl) ketones; Bis(4-hydroxyphenyl) sulfide, bis(3-methyl-4-hydroxyphenyl) sulfide, etc. Bis(hydroxyphenyl) sulfide; Bis( Bis(hydroxyphenyl)sulphurites such as 4-hydroxyphenyl) sulphurite and bis(3-methyl-4-hydroxyphenyl)sulphurite; bis(4-hydroxyphenyl)sulphurite [bisphenol S] , Bis(3-methyl-4-hydroxyphenyl) sulfonium and other bis(hydroxyphenyl) sulfonates; 9,9-bis(4'-hydroxyphenyl) pyrene, 9,9-bis(3'- Methyl-4'-hydroxyphenyl) bis(hydroxyphenyl) pyrene and the like.

Examples of aromatic dicarboxylic acids or their chlorides include phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyl dicarboxylic acid, and diphenoxyethane dicarboxylic acid. Acid, diphenyl ether 4,4'-dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and their chlorine物, etc. In addition, the polyarylate resin used may be a modified polyarylate resin. Among these, the polyarylate resin is preferably a resin composed of a polymer compound obtained by the reaction of 2,2-bis(4'-hydroxyphenyl)propane and isophthalic acid .

The polymer component (A) may be used alone or in combination of two or more, but from the viewpoint of adjusting the elongation characteristics and solvent resistance, it is preferable to use a single kind of polyimide resin , Using plural polyimide resins of different types, and adding at least one of polyimide resin and polyarylate resin to the polyimide resin.

As the polyamide resin, those soluble in organic solvents are preferred, and rubber-modified polyamide resins are preferred. As the rubber-modified polyamide resin, for example, what is described in JP 2004-035638 A can be used.

When polyimide resin or polyarylate resin is added to polyimide resin, the amount of resin added is relative to polyimide from the viewpoint of maintaining high Tg while imparting moderate flexibility. 100 parts by mass of the resin, preferably 100 parts by mass or less, more preferably 70 parts by mass or less, particularly preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, and preferably 1 part by mass or more, more preferably 3 parts by mass or more.

[Sclerosing component (B)] The curable component (B) is a component that can participate in a polymerization reaction, or a polymerization reaction and a crosslinking reaction, for example, a monomer having a polymerizable unsaturated bond that can participate in a polymerization reaction, or a polymerization reaction and a crosslinking reaction. In addition, in this specification, the term "hardening" refers to a broad concept including "polymerization reaction of monomers" or "polymerization reaction of monomers and subsequent crosslinking reactions of polymers". By using the curable component (B), a gas barrier laminate having excellent solvent resistance can be obtained.

The molecular weight of the curable component (B) is usually 3,000 or less, preferably 200 to 2,000, and more preferably 200 to 1,000. The number system of polymerizable unsaturated bonds in the curable component (B) is not particularly limited. The curable component (B) may be a monofunctional monomer having one polymerizable unsaturated bond, or may be a multifunctional monomer such as a bifunctional or trifunctional monomer having pluralities.

Examples of the aforementioned monofunctional monomers include monofunctional (meth)acrylic acid derivatives. The monofunctional (meth)acrylic acid derivative is not particularly limited, and well-known compounds 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 having a polyether structure Derivatives, etc.

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

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 represent a hydrogen atom or an organic group having 1 to 12 carbon atoms, and R ² and R ³ may be bonded to each other. A ring structure is formed, and R ⁴ represents a divalent organic group. Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group and the like, and a methyl group is preferred. Examples of the organic groups having 1 to 12 carbon atoms represented by R ² and R ³ include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, and propyl; carbons such as cyclopentyl and cyclohexyl Cycloalkyl groups having 3 to 12 atoms; aromatic groups having 6 to 12 carbon atoms such as phenyl, biphenyl and naphthyl groups. These groups may have substituents at any positions. In addition, R ² and R ³ may form a ring together, and the ring may further have a nitrogen atom or an oxygen atom in the 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 having a nitrogen atom, a (meth)acryloylmorpholine represented by the following formula can be cited as a preferable one.

By using a monofunctional (meth)acrylic acid derivative having a nitrogen atom as the curable component (B), a base layer with more excellent heat resistance can be formed.

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

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 cyclohexyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclodecyl and the like.

Specific examples of monofunctional (meth)acrylic acid derivatives having an alicyclic structure include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 1-adamantine (meth)acrylate Alkyl ester, 2-adamantyl (meth)acrylate, etc.

By using a monofunctional (meth)acrylic acid derivative having an alicyclic structure as the curable component (B), a base layer having more excellent optical properties can be formed.

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

In the formula, R ¹ represents the same meaning as above, and R ⁶ represents an organic group having 1 to 12 carbon atoms. Examples of the organic group having 1 to 12 carbon atoms represented by R ⁶ include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, and propyl groups; and those having 3 to 12 carbon atoms such as cyclohexyl. Cycloalkyl; C6-C12 aromatic groups such as phenyl, biphenyl, naphthyl, etc. j represents an integer of 2-20.

Specific examples of monofunctional (meth)acrylic acid derivatives having a polyether structure include ethoxylated ortho-phenylphenol (meth)acrylate and methoxy polyethylene glycol (meth)acrylic acid Ester, phenoxy polyethylene glycol (meth)acrylate, etc.

By using a monofunctional (meth)acrylic acid derivative having a polyether structure as the curable monomer (B), a base layer with excellent toughness can be formed.

Examples of the aforementioned polyfunctional monomer include polyfunctional (meth)acrylic acid derivatives. The polyfunctional (meth)acrylic acid derivative is not particularly limited, and well-known compounds can be used. For example, 2-6 functional (meth)acrylic acid derivatives can be mentioned. As a bifunctional (meth)acrylic acid derivative, the compound represented by the following formula is mentioned.

In the formula, R ¹ represents the same meaning as described above, and R ⁷ represents a divalent organic group. Examples of the divalent organic group represented by R ⁷ include groups represented by the following formulas.

(In the formula, 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).

Specific examples of the bifunctional (meth)acrylic acid derivative represented by the aforementioned formula include tricyclodecane dimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene Oxylated 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-propenyloxyethoxy)phenyl]茀, etc. Among these, from the viewpoint of heat resistance and toughness, it is preferable that the divalent organic group represented by R ⁷ in the above formula, such as tricyclodecane dimethanol di(meth)acrylate, has three Cyclodecane skeleton, propoxylated ethoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, etc. are represented by R ⁷ in the above formula The divalent organic group has a bisphenol skeleton, the divalent organic group represented by R ⁷ in the above formula, such as 9,9-bis[4-(2-propenyloxyethoxy)phenyl] 茀, etc. Those with a 9,9-biphenylene skeleton.

In addition, examples of bifunctional (meth)acrylic acid derivatives other than these include neopentyl glycol adipate di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol bis(methyl) )Acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified phosphoric acid di(meth)acrylate, di(acryloxyethyl) heterocyanuric acid Acid ester, allylated cyclohexyl di(meth)acrylate, etc.

Examples of trifunctional (meth)acrylic acid derivatives include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate , Propylene oxide is modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, etc. 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. Examples of the hexafunctional (meth)acrylic acid derivative include dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, and the like.

The curable component (B) can be used alone or in combination of two or more. Among these, the curable component (B) is preferably a polyfunctional monomer from the viewpoint of obtaining a base layer having more excellent heat resistance and solvent resistance. As a polyfunctional monomer, a bifunctional (meth)acrylic acid derivative is preferred from the viewpoint that it is easy to mix with the polymer component (A) and hardly cause curing shrinkage of the polymer, and can suppress curling of the cured product. . When the curable component (B) contains a polyfunctional monomer, its content is preferably 40% by mass or more in the total amount of the curable component (B), more preferably 50-100% by mass, and particularly preferably 80 ～100% by mass.

The curable component (B) preferably contains a cyclic polymerizable monomer. The so-called cyclized polymerizable monomer is a monomer that has the property of radical polymerization while cyclizing. Cyclic polymerizable monosystems are polymerized to form a ring structure in the molecule while growing into a linear polymer, which can improve the solvent resistance and heat resistance of the base layer more than those using general monofunctional curable monomers. As one of the reasons, it is believed that in the polymer of the cyclized polymerizable monomer, since the ring structure is formed in the polymer chain, it becomes a more rigid molecule than a general linear polymer, thereby increasing the heat resistance of the base layer. Increased sex. In addition, in the cyclized polymerizable monomer, although the molecule is designed to selectively cause the intramolecular cyclization reaction, an intermolecular reaction occurs in a part of the monomer, and the reaction remains in the constituent unit derived from the monomer The functional group. This reactive functional group reacts with other monomers to branch the polymer chain and form a cross-linked structure in the polymer of the cyclic polymerizable monomer. Therefore, it is considered that the heat resistance of the base layer is further improved, and the solvent resistance is also improved. On the other hand, most of the polymers of cyclized polymerizable monomers adopt linear structures, and the ring structure obtained by cyclization polymerization is softer than aromatic rings, so it can also take into account the flexibility of the base layer. The base layer shows High elongation at break (that is, easy to meet the above requirements [2]).

Specific cyclized polymerizable monomers include non-conjugated dienes, and for example, an α-allyloxy methacrylic monomer represented by the following formula (1) can be used.

(In 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 or branched, and may include a cyclic structure. The hydrocarbon group contained in the organic group is not particularly limited. As an example, the hydrocarbon group is a chain saturated hydrocarbon group with a carbon number of 1 or more, a chain unsaturated hydrocarbon group with a carbon number of 3 or more, an alicyclic hydrocarbon group with a carbon number of 3 or more, and an aromatic hydrocarbon group with a carbon number of 6 or more. Among these, the hydrocarbon group is preferably a chain saturated hydrocarbon group with 1 to 30 carbons, a chain unsaturated hydrocarbon group with 3 to 30 carbons, an alicyclic hydrocarbon group with 4 to 30 carbons, and a carbon 6 to 30 Aromatic hydrocarbon group. The substituent system is not particularly limited. For example, the substituents are halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, cyano group, trimethylsilyl group, and the like.

The chain saturated hydrocarbon group is not particularly limited. For example, the chain saturated hydrocarbon group is methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, tertiary butyl, n-pentyl, second pentyl, and third pentyl. , Neopentyl, n-hexyl, second hexyl, n-heptyl, n-octyl, second octyl, third octyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, ten Two bases, thirteen bases, fourteen bases, 15 bases, sixteen bases, seventeen bases, eighteen bases, nineteen bases, 20 bases, 26 bases, 30 bases, etc.

The chain unsaturated hydrocarbon group is not particularly limited. For example, the chain unsaturated hydrocarbon group is crotonyl, 1,1-dimethyl-2-propenyl, 2-methyl-butenyl, 3-methyl-2-butenyl, 3-methyl -3-butenyl, 2-methyl-3-butenyl, oleyl, linoleyl, linseed, etc.

The alicyclic hydrocarbon group is not particularly limited. For example, alicyclic hydrocarbon groups are cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, tricyclodecyl, isocampanyl Group, adamantyl, dicyclopentyl, dicyclopentenyl, etc.

The aromatic hydrocarbon group is not particularly limited. For example, aromatic hydrocarbon groups are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tert-butylphenyl, benzyl, diphenylmethyl, diphenylethyl Group, triphenylmethyl, cinnamyl, naphthyl, anthracenyl, etc.

The hydrocarbon group having an ether bond is not particularly limited. To give an example, the hydrocarbyl group with ether linkage is methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl , Ethoxyethoxyethyl and other chain ether groups; cyclopentyloxyethyl, cyclohexoxyethyl, cyclopentyloxyethoxyethyl, cyclohexoxyethoxyethyl, Dicyclopentenyloxyethyl group has both alicyclic hydrocarbon group and chain ether group; phenoxyethyl, phenoxyethoxyethyl group has both aromatic hydrocarbon group and chain ether group The group; epoxypropyl, β-methylepoxypropyl, β-ethylepoxypropyl, 3,4-epoxycyclohexylmethyl, 2-oxetanemethyl, 3- Methyl-3-oxetanemethyl, 3-ethyl-3-oxetanemethyl, tetrahydrofuranyl, tetrahydrofurfuryl, tetrahydropiperanyl, diazolyl, dioxa Cyclic ether groups such as cyclohexyl, etc.

In this embodiment, R ⁸ in the formula (1) is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a methyl group.

Among them, the alkyl ester of 2-allyloxymethacrylic acid having 1 to 4 carbon atoms, cyclohexyl 2-(allyloxymeth)acrylate, and 2-allyloxymethyl are more preferred. The alkyl ester of acrylic acid having 1 to 4 carbon atoms is particularly preferably methyl 2-(allyloxymeth)acrylate.

As another specific cyclic polymerizable monomer, for example, a monomer represented by the following formula (2) can be cited.

(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 is an alkyl group having 6 or less carbon atoms).

As the cyclic polymerizable monomer represented by the formula (2), dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2, 2'-[Oxybis(methylene)]bis-2-acrylate, two(n-propyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, two (Isopropyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxybis(methylene)] Bis-2-acrylate, di(n-hexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, dicyclohexyl-2,2'-[oxybis(ethylene) (Methyl)] bis-2-acrylate and the like.

The curable component (B) more preferably contains the above-mentioned polyfunctional (meth)acrylate compound and a cyclic polymerizable monomer. By using these in combination, the thermal shrinkage of the base layer can be suppressed while adjusting the elongation at break of the base layer to the above-mentioned range. As a result, it becomes easier to adjust the thermal shrinkage rate of the gas barrier laminate to the above-mentioned range. In the curable component (B), the mass ratio of the cyclized polymerizable monomer and the polyfunctional (meth)acrylate compound is preferably 95:5-30:70, more preferably 90:10-35:65, especially Preferably, it is 90:10 to 40:60. Since the mass ratio of the cyclized polymerizable monomer to the polyfunctional (meth)acrylate compound is in the above range, it is easier to adjust the elongation at break of the base layer to the above range while reducing the heat of the gas barrier laminate Adjust the shrinkage to the above range.

[Curable resin composition] The curable resin composition for forming the base layer of the embodiment of the present invention can be formed by mixing the polymer component (A), the curable component (B), and the polymerization initiator described later or other components as desired , It is prepared by dissolving or dispersing in an appropriate solvent.

The total content of the polymer component (A) and the curable monomer (B) in the curable resin composition is preferably 40-99.5 mass%, more preferably, relative to the mass of the entire curable resin composition other than the solvent It is 60 to 99% by mass, and more preferably 80 to 98% by mass.

The content of the polymer component (A) and the curable component (B) in the curable resin composition, based on the mass ratio of the polymer component (A) to the curable component (B), is preferably the polymer component (A) ): Curable component (B)=30:70 to 90:10, more preferably 35:65 to 80:20. In the curable resin composition, since the mass ratio of the polymer component (A): the curable monomer (B) is in this range, the flexibility of the resulting base layer is likely to be increased, and it is easy to maintain the base layer The tendency of solvent resistance.

Moreover, as long as the content of the curable component (B) in the curable resin composition is within the above-mentioned range, for example, when the underlayer is obtained by a solution casting method or the like, the solvent can be efficiently removed, so that the drying process can be eliminated. Deformation problems such as curling or undulation caused by long time.

The curable resin composition may contain a polymerization initiator as desired. The polymerization initiator can be used without particular limitation as long as it can start the curing reaction. For example, a thermal polymerization initiator or a photopolymerization initiator can be mentioned.

Examples of the thermal polymerization initiator include organic peroxides and azo compounds. Examples of organic peroxides include dialkyl peroxides such as di-tert-butyl peroxide, tert-butyl cumyl peroxide, and dicumyl peroxide; ethyl peroxide Diethyl peroxides such as laurel peroxide, benzoyl peroxide, etc.; methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide , Ketone peroxides such as methylcyclohexanone peroxide; peroxyketals such as 1,1-bis(tertiary butylperoxy)cyclohexane; tertiary butyl hydroperoxide, dry Hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexyl Hydroperoxides such as alkane-2,5-dihydroperoxide; tertiary butyl peroxyacetate, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxy Peroxy esters such as benzoate and tert-butylperoxyisopropyl carbonate. As the azo compound, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropane Nitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1 '-Azobis(cyclohexane-1-carbonitrile), 2-(aminocarbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethyl Valeronitrile etc.

As the photopolymerization initiator, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2- Methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2 -Hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propanyl)benzyl]phenyl]-2-methyl-propane-1-one, 2-methyl-1- (4-Methylthienyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylbenzenes Ketone-based photopolymerization initiator; 2,4,6-trimethylbenzyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide Compound, ethyl (2,4,6-trimethylbenzyl)-phenylphosphonite, bis(2,6-dimethoxybenzyl)-2,4,4-tri Phosphorous photopolymerization initiator such as methyl-pentylphosphine oxide; bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H) -Pyrrol-1-yl)-phenyl]titanium and other titanocene-based photopolymerization initiators; 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzene) Methyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetoxime) Oxime ester-based photopolymerization initiator; benzophenone, p-chlorodiphenyl ketone, benzyl benzoic acid, methyl phthalate benzoate, 4-methyl benzophenone, 4 -Phenyl diphenyl ketone, hydroxy diphenyl ketone, acrylated diphenyl ketone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3'-dimethyl-4- Methoxy benzophenone, 2,4,6-trimethyl benzophenone, 4-(13-propenyl-1,4,7,10,13-pentaoxatridecyl)-two Diphenyl ketone photopolymerization initiator such as phenyl ketone; thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4- Diisopropylthioxanthone, 2,4-Dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4- Thioxanthone-based photopolymerization initiators such as isopropyl thioxanthone.

Among the above-mentioned photopolymerization initiators, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl) Phenylphosphine oxide, ethyl (2,4,6-trimethylbenzyl) phenylphosphonite, bis(2,6-dimethoxybenzyl)-2,4, Phosphorous photopolymerization initiator such as 4-trimethyl-pentylphosphine oxide. When the polymer component (A) is a thermoplastic resin having an aromatic ring, the polymer component (A) absorbs ultraviolet rays, and as a result, a curing reaction may be difficult to occur. However, by using the above-mentioned phosphorous photopolymerization initiator, the curing reaction can be efficiently performed by using light of a wavelength not absorbed by the above-mentioned polymer component (A). The polymerization initiator system may be used alone or in combination of two or more kinds.

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

In addition, the aforementioned curable resin composition system may contain triisopropanolamine and 4,4'-diethylamino groups in addition to the polymer component (A), the curable component (B), and the polymerization initiator. Initiation aid for photopolymerization such as benzophenone.

The solvent used in the preparation of the curable resin composition is not particularly limited. Examples include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, monochlorobenzene, etc.; methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether Alcohol-based solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone, etc.; ester-based solvents such as ethyl acetate and butyl acetate; ethyl cerol Solvent solvents such as Su, etc.; ether solvents such as 1,3-dioxolane, etc.

The content of the solvent in the curable resin composition is not particularly limited, but it is usually 0.1 to 1,000 g, preferably 1 to 100 g, based on 1 g of the polymer component (A). By appropriately adjusting the amount of the solvent, the viscosity of the curable resin composition can be adjusted appropriately.

In addition, the curable resin composition may further contain well-known additives such as plasticizers, antioxidants, and ultraviolet absorbers within the range that does not impair the purpose and effects of the present invention.

The method of curing the aforementioned curable resin composition can be appropriately determined according to the type of polymerization initiator and curable monomer used. The details are described in the item of the method of manufacturing the gas barrier laminate of the present invention described later.

[The nature and shape of the base layer, etc.] The gas barrier laminate of the embodiment of the present invention preferably satisfies the following requirement [2']. [2'] The breaking elongation of the base layer is 2.5% or more.

By becoming a base layer that satisfies the requirement [2'] and is suitable for the above requirement [1], deformation of the base layer caused by heating can be suppressed, and as a result, the gas barrier properties of the gas barrier laminate can be improved, and the gas barrier properties can be improved The flexibility of the laminate. The upper limit of the elongation at break of the base layer is not particularly limited, but it is usually 20% or less, preferably 15% or less. Here, if a cyclized polymerizable monomer is used, it is possible to increase the elongation at break while maintaining a relatively high elastic modulus at high temperature, and it becomes easier to satisfy the requirement [2']. On the other hand, if all the curable components (B) are cyclized polymerizable monomers, the gas barrier properties of the gas barrier laminate tend to decrease. The inventors conducted various reviews, and as a result, it was found that by suppressing the absolute value of the thermal shrinkage rate within a certain range, the decrease in gas barrier properties can be suppressed. This is because the base layer is affected by heat. For example, when the gas barrier layer is formed by coating, the base layer deforms in the plane direction. It is considered that the heat shrinkage rate is within a specified range. , Choosing materials, etc., can suppress the above phenomenon.

In order to satisfy the requirement [2'], for example, as the polymer component (A), a polyimide resin is used, or by adding a polyimide resin to introduce a soft skeleton, or the molecular weight of the polymer component (A) Increasing, as the curable component (B), it is effective to reduce the proportion of aromatic rings by using a cyclized polymerizable monomer to improve the elongation characteristics of the base layer. In addition, for example, a combination of a polyfunctional (meth)acrylate compound and a cyclized polymerizable monomer is used to increase the mesh structure, or as the polymerizable component (A), a rigid and glass transition temperature such as polyimide resin is selected The higher one can become the base layer suitable for the above requirements [1].

The thickness of the base layer is not particularly limited, as long as it is determined according to the purpose of the gas barrier laminate. The thickness of the base layer is usually 0.1 to 300 μm, preferably 0.1 to 100 μm, more preferably 0.1 to 50 μm, particularly preferably 0.1 to 10 μm, and even more preferably 0.2 to 10 μm.

If the base layer has a thickness of about 0.1 to 10 μm, for example, the thickness of the gas barrier laminate can be prevented from increasing, and a thin gas barrier laminate can be obtained. In the case of a thin gas-barrier laminate, the gas-barrier laminate does not become a requirement for increasing the thickness of the entire applicable device in applications such as organic EL displays that require thinning. Moreover, if it is a thin gas barrier laminate, the flexibility and bending resistance of the gas barrier laminate after assembly can be improved.

The aforementioned underlayer system is excellent in solvent resistance. Since it is excellent in solvent resistance, for example, even when an organic solvent is used when forming other layers on the surface of the base layer, the surface of the base layer hardly dissolves. Therefore, even when a resin solution containing an organic solvent is used on the surface of the base layer to form the gas barrier layer, the components of the base layer are not easily mixed into the gas barrier layer, so the gas barrier properties are not easily reduced.

From this viewpoint, the gel fraction of the aforementioned base layer is preferably 90% or more, and more preferably 94% or more. The base layer with a gel fraction of 90% or more has excellent solvent resistance, so even when an organic solvent is used when forming other layers by coating on the surface of the base layer, the base layer surface is almost insoluble and can be easily obtained A gas barrier laminate with excellent solvent resistance.

Here, the so-called gel fraction is a 150mm×150mm nylon mesh (#120) whose mass has been measured in advance, wrapped in a base layer cut into 100mm×100mm, immersed in toluene (100mL) for 3 days and then taken out. After drying at 120°C for 1 hour, and then leaving it at 23°C with a relative humidity of 50% for 3 hours to adjust the humidity, the mass is measured, and it is obtained by the following formula.

Gel fraction (%)=[(The mass of residual resin after dipping)/ (The mass of resin before dipping)]×100

The interlayer adhesion between the base layer system and the gas barrier layer is excellent. That is, on the aforementioned base layer, it is not necessary to provide an anchor coating to form a gas barrier layer.

The base layer is preferably colorless and transparent. Since the base layer is colorless and transparent, the gas barrier laminate of the embodiment of the present invention can be preferably used for optical applications.

The base layer system has low birefringence and excellent optical isotropy. The in-plane phase difference of the aforementioned underlayer is usually 20 nm or less, preferably 15 nm or less. The retardation in the thickness direction is usually -500 nm or less, preferably -450 nm or less. In addition, the value obtained by dividing the in-plane retardation by the thickness of the base layer (birefringence) is usually 100×10 ^-5 or less, preferably 20×10 ^-5 or less. As long as the retardation in the plane of the base layer, the retardation in the thickness direction, and the birefringence are within the above ranges, a gas barrier laminate with low birefringence and excellent optical isotropy can be obtained. The gas barrier laminate of the embodiment is preferably used for optical applications.

The absolute value of the thermal shrinkage of the base layer is preferably 0.5% or less, more preferably 0.3% or less, and particularly preferably 0.2% or less.

The elongation at break of the base layer is preferably 2.5% or more, more preferably 2.6% or more, particularly preferably 2.7% or more, and particularly preferably 3.0% or more. If the elongation at break of the base 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. As a result, it is easy to obtain a gas barrier laminate with excellent bending resistance and flexibility.

The tensile modulus of elasticity of the base layer at 130°C is preferably 1.0×10 ³ MPa or more, more preferably 1.3×10 ³ MPa or more, particularly preferably 1.5×10 ³ MPa% or more, and even more preferably 2.0×10 ³ Above MPa. If the tensile modulus of elasticity of the base layer at 130°C is 1.3×10 ³ MPa or more, the heat resistance of the base layer can be improved, and the gas-barrier laminate water vapor transmission rate of gas barrier properties can be reduced. Specifically, it is easy to Be less than 1×10 ^-2 (g·m ^-2 ·day ^-1 ).

As described above, the base layer has excellent heat resistance, solvent resistance, interlayer adhesion, and transparency, and furthermore has a low birefringence and excellent optical isotropy. Therefore, as will be described later, a gas barrier layer is formed on a base layer with such characteristics by, for example, solution casting. The gas barrier layer exhibits excellent gas barrier properties and is due to the heat resistance and solvent resistance of the base layer. At least one of them also prevents damage to gas barrier properties due to at least one of heat and solvent. In addition, the obtained gas barrier laminate has excellent heat resistance, interlayer adhesion, and transparency. Furthermore, a gas barrier laminate with low birefringence and excellent optical isotropy can be obtained.

1-2. Gas barrier The material of the gas barrier layer of the gas barrier laminate of the embodiment of the present invention is not particularly limited as long as it has gas barrier properties. For example, a gas barrier layer made of an inorganic film, a gas barrier layer containing a gas barrier resin, a gas barrier layer obtained by subjecting a layer containing a polymer compound to a modification treatment, and the like can be cited. Among these, the gas barrier layer is preferably a gas barrier layer made of an inorganic film and a layer containing a polymer compound from the viewpoint of efficiently forming a thin layer with excellent gas barrier properties and solvent resistance. The gas barrier layer obtained by applying modification treatment.

The inorganic film is not particularly limited. For example, an inorganic vapor-deposited film can be mentioned. Examples of the inorganic vapor-deposited film include vapor-deposited films of inorganic compounds or metals. As raw materials for vapor deposition films of inorganic compounds, inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, etc.; inorganic nitrogen such as silicon nitride, aluminum nitride, and titanium nitride Inorganic carbides; inorganic sulfides; inorganic oxynitrides such as silicon oxynitride; inorganic oxycarbides; inorganic nitrogen carbides; inorganic oxynitride carbides. As the raw material of the metal vapor-deposition film, aluminum, magnesium, zinc, tin, and the like can be mentioned. These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of gas barrier properties, an inorganic vapor-deposited film using inorganic oxides, inorganic nitrides or metals as raw materials is preferred, and from the viewpoint of transparency, it is more preferred to Inorganic vapor deposition film made of inorganic oxide or inorganic nitride. In addition, the inorganic vapor-deposited film may be a single layer or multiple layers.

From the viewpoint of gas barrier properties and operability, 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, particularly preferably 30 to 500 nm, and even more preferably 40 to 200 nm.

As a method of forming an inorganic vapor deposition film, PVD (physical vapor deposition) methods such as vacuum vapor deposition, sputtering, and ion plating, or thermal CVD (chemical vapor deposition) methods, plasma CVD methods, and optical CVD methods are mentioned. CVD method and so on.

In the gas barrier layer containing a gas barrier resin, as the gas barrier resin used, polyvinyl alcohol, or its partial saponification products, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene Dichloroethylene, polychlorotrifluoroethylene and other resins that do not easily permeate oxygen.

From the viewpoint of gas barrier properties, the thickness of the gas barrier layer containing gas barrier resin is preferably 10 to 2,000 nm, more preferably 20 to 1,000 nm, particularly preferably 30 to 500 nm, and even more preferably 40 to 200 nm The scope.

As a method of forming a gas barrier layer containing a gas barrier resin, a method of coating a solution containing a gas barrier resin on a base layer and suitably drying the resulting coating film can be mentioned.

In the gas barrier layer obtained by subjecting a layer containing a polymer compound (hereinafter also referred to as "polymer layer") to a modification treatment, the polymer compound used may include silicon-containing polymer compounds, polymer Polyimide, polyamide, polyamide imine, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polytide, polyether sulfide, polyphenylene sulfide, Polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, etc. These polymer compounds can be used alone or in combination of two or more.

Among these, the polymer compound is preferably a silicon-containing polymer compound. Examples of silicon-containing polymer compounds include polysilazane compounds (see Japanese Patent Publication No. 63-16325, Japanese Patent Publication No. 62-195024, Japanese Patent Application Publication No. 63-81122, Japanese Patent Kaihei 1-138108, Japanese Patent Publication No. 2-84437, Japanese Patent Publication No. 2-175726, Japanese Patent Publication No. 4-63833, Japanese Patent Publication No. 5-238827, Japanese Patent Publication No. 5-345826 Bulletin, Japanese Patent Application Publication No. 2005-36089, Japanese Patent Application Publication No. 6-122852, Japanese Patent Application Publication No. 6-299118, Japanese Patent Application Publication No. 6-306329, Japanese Patent Application Publication No. 9-31333, Japanese Patent Application Publication No. 10-245436 Bulletin, JP 2003-514822 Bulletin, International Publication WO2011/107018, etc.), polycarbosilane compounds (refer to 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 Patent Application Publication No. 51-126300, Japanese Patent Application Publication No. 2001-328991, Japanese Patent Application Publication No. 2006-117917 , Japanese Patent Application Publication No. 2009-286891, Japanese Patent Application Publication No. 2010-106100, etc.), polysiloxane compounds (see RD Miller, J. Michl; Chemical Review, Vol. 89, page 1359 (1989), N. Matsumoto ; Japanese Journal of Physics, Volume 37, Page 5425 (1998), Japanese Patent Application Publication No. 2008-63586, Japanese Patent Application Publication No. 2009-235358, etc.), and polyorganosiloxane compounds (see Japanese Patent Application Publication No. 2010 -229445, Japanese Patent Application Publication No. 2010-232569, Japanese Patent Application Publication No. 2010-238736, etc.).

Among these, a polysilazane compound is preferable from the viewpoint of forming a gas barrier layer having excellent gas barrier properties. Examples of the polysilazane compound include inorganic polysilazane or organic polysilazane. Examples of inorganic polysilazanes include perhydropolysilazanes and the like. Examples of organic polysilazanes include compounds in which part or all of the hydrogen of perhydropolysilazane is replaced by organic groups such as alkyl groups. Wait. Among these, the inorganic polysilazane is more preferable from the viewpoint of easy availability and formation of a gas barrier layer with excellent gas barrier properties. In addition, the polysilazane compound can also be used as it is as a commercially available product such as a glass coating material. The polysilazane compound can be used alone or in combination of two or more.

In addition to the above-mentioned polymer compound, the aforementioned polymer layer may contain other components within a range that does not hinder the purpose of the present invention. Examples of other components include curing agents, other polymers, anti-aging agents, light stabilizers, flame retardants, and the like.

From the viewpoint of forming a gas barrier layer with excellent gas barrier properties, the content of the polymer compound in the polymer layer is preferably 50% by mass or more, more preferably 70% by mass or more.

As a method of forming a polymer layer, for example, a layer-forming solution containing at least one polymer compound, other components and solvents as desired is applied to the base layer by a well-known method or as desired The method of forming the primer layer on the base layer and drying the resulting coating film appropriately.

When applying the solution for forming a layer, well-known devices 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 increase the gas barrier properties of the gas barrier laminate, it is preferable to heat the coating film. As heating and drying methods, conventional drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used. The heating temperature is usually 80 to 150°C, and the heating time is usually tens of seconds to tens of minutes.

When forming the gas barrier layer of the gas barrier laminate, for example, when using the polysilazane compound as described above, the conversion reaction of the polysilazane occurs by heating after coating, and it becomes an excellent gas barrier. Coating film. On the other hand, by heating when forming such a coating film, when a base layer with low heat resistance is used, there is a possibility that the base layer is deformed. 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 of the embodiment of the present invention is excellent in heat resistance, it is difficult to deform even by heating during and after coating. Therefore, the reduction of the gas barrier properties of the gas barrier laminate due to the deformation of the base layer can also be avoided.

The thickness of the polymer layer is usually 20 to 1,000 nm, preferably 30 to 800 nm, and more preferably 40 to 400 nm. Even if the thickness of the polymer layer is on the nanometer level, a gas barrier laminate having sufficient gas barrier performance can be obtained by applying a modification treatment as described later. In addition, the above-mentioned polymer layer is preferably obtained by subjecting a coating film of a composition containing a silicon compound to a modification treatment. If the polymer layer is formed by subjecting a coating film of a composition containing a silicon compound to a modification treatment, it is more flexible than an inorganic film provided by vapor deposition or sputtering, for example.

Examples of the reforming treatment include ion implantation, vacuum ultraviolet light irradiation, and the like. Among these, ion implantation is preferred from the viewpoint of obtaining high gas barrier performance. In ion implantation, the amount of ions implanted into the polymer layer may be appropriately determined according to the purpose of use of the formed gas barrier laminate (required gas barrier properties, transparency, etc.).

Examples of the injected ions include ions of rare gases such as argon, helium, neon, krypton, and xenon; ions of fluorocarbons, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; methane, ethane, Ions of alkane-based gases such as propane, butane, pentane, and hexane; ions of olefinic gases such as ethylene, propylene, butene, and pentene; and alkadiene-based gases such as pentadiene and butadiene Ions; ions of acetylene gases such as acetylene and methylacetylene; ions of aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene, and phenanthrene; cycloalkane gases such as cyclopropane and cyclohexane The ions; cyclopentene, cyclohexene and other cycloolefin gas ions; gold, silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, aluminum and other conductive metal ions ; Silane (SiH ₄ ) or organosilicon compound ions, etc.

Examples of organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-third butoxysilane, etc. Tetraalkoxysilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, (3,3,3-tri Fluoropropyl) unsubstituted or substituted alkyl alkoxysilanes such as trimethoxysilane; Aryl alkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane; Disiloxane such as hexamethyldisiloxane (HMDSO); Bis(dimethylamino)dimethylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylamino)dimethylsilane, diethylaminotrimethylsilane, two Amino silanes such as methylamino dimethyl silane, tetra (dimethylamino) silane, tris (dimethylamino) silane, etc.; Hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetramethyldisilazane, etc. Silazane; Cyanate silane such as tetraisocyanate silane; Halogenated silanes such as triethoxyfluorosilane; Alkenyl silanes such as diallyldimethylsilane and allyltrimethylsilane; Di-tertiary butyl silane, 1,3-disilane, bis(trimethylsilyl)methane, tetramethylsilane, tris(trimethylsilyl)methane, tris(trimethylsilyl)silane , Unsubstituted or substituted alkyl silanes such as benzyl trimethyl silane; Bis(trimethylsilyl)acetylene, trimethylsilylacetylene, 1-(trimethylsilyl)-1-propyne and other silylalynes; Silylenes such as 1,4-bistrimethylsilyl-1,3-butadiyne and cyclopentadienyltrimethylsilane; Arylalkylsilanes such as phenyldimethylsilane and phenyltrimethylsilane; Alkynyl alkyl silanes such as propargyl trimethyl silane; Alkenyl alkyl silanes such as vinyl trimethyl silane; Disilane such as hexamethyl disilane; Silicone such as octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, and hexamethylcyclotetrasiloxane; N,O-bis(trimethylsilyl)acetamide; Bis(trimethylsilyl)carbodiimide; Wait. These ion systems can be used alone or in combination of two or more.

Among them, in terms of easier injection and obtaining a gas barrier layer with particularly excellent gas barrier properties, it is preferably selected from the group consisting of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon and krypton At least one ion.

The method of implanting ions is not particularly limited, and a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma, and the like can be mentioned. Among them, from the viewpoint of easily obtaining a gas barrier film, the latter method of injecting plasma ions is preferred.

As the plasma ion implantation method, (α) a method of injecting ions in a plasma generated by an external electric field into the polymer layer is preferred, or (β) without using an external electric field, and will exist only by applying A method of implanting ions in the plasma generated by the electric field caused by the negative high voltage pulse of the aforementioned layer into the polymer layer.

In the above method (α), it is preferable to set the pressure during ion implantation (pressure during plasma ion implantation) to 0.01 to 1 Pa. When the pressure during plasma ion implantation is within the above-mentioned range, ions can be implanted simply and efficiently and uniformly, and the desired gas barrier layer can be efficiently formed.

The aforementioned method (β) does not need to increase the degree of pressure reduction, the processing operation is simple, and the processing time can be greatly shortened. In addition, the entire layer can be processed uniformly, and when a negative high voltage pulse is applied, ions in the plasma can be continuously injected into the polymer layer with high energy. Furthermore, no special other means such as radio frequency (high frequency, hereinafter referred to as "RF") or high-frequency power sources such as microwaves are required, and only negative high-voltage pulses can be applied to the layer, and the good quality Ions are uniformly injected into the polymer layer.

In any of the aforementioned methods (α) and (β), the pulse width when a negative high voltage pulse is also applied, that is, when ions are implanted is preferably 1-15 μsec. When the pulse width is in such a range, ions can be injected uniformly more easily and efficiently.

In addition, the applied voltage when generating plasma is preferably -1 to -50 kV, more preferably -1 to -30 kV, particularly preferably -5 to -20 kV. If the applied voltage is less than -1 kV for ion implantation, the amount of ion implantation (doping amount) becomes insufficient, and the desired performance cannot be obtained. On the other hand, if ion implantation is performed at a value greater than -50kV, the film will be charged during ion implantation, and defects such as coloration of the film will easily occur.

As the ion species for plasma ion implantation, the same as those exemplified as the ion implantation described above can be given.

When injecting ions in the plasma into the polymer layer, a plasma ion implantation device is used. Specific examples of the plasma ion implantation device include: (i) Feedthrough of applying a negative high-voltage pulse to a polymer layer (hereinafter also referred to as "ion-implanted layer"), superimposing high-frequency power, and using Plasma evenly surrounds the ion implanted layer to induce, inject, collide, and accumulate ions in the plasma (Japanese Patent Laid-Open No. 2001-26887), (ii) Install an antenna in the chamber and apply high frequency Electricity is used to generate plasma. After the plasma reaches the ion implanted layer, positive and negative pulses are alternately applied to the ion implanted layer. The positive pulse induces electrons in the plasma to collide and heat the ion implanted layer. A device that controls the pulse constant and performs temperature control while applying negative pulses to induce and inject ions in the plasma (Japanese Patent Laid-Open No. 2001-156013), (iii) Use external electric fields such as microwaves and other high-frequency power sources Plasma ion implantation device that generates plasma and applies high-voltage pulses to induce and inject ions in the plasma. (iv) No external electric field is used but only in the plasma generated by the electric field generated by the application of high-voltage pulses Plasma ion implantation equipment for ion implantation.

Among these, since the processing operation is simple and the processing time can be greatly shortened, and it is suitable for continuous use, it is preferable to use the plasma ion implantation device of (iii) or (iv). Regarding the method of using the plasma ion implantation apparatus of (iii) and (iv), the one described in International Publication WO2010/021326 can be cited.

In the plasma ion implantation device of (iii) and (iv) above, a high-voltage pulse power supply is used as a plasma generating means for generating plasma, so there is no need for special high-frequency power sources such as RF or microwave. Means, only applying negative high-voltage pulses can generate plasma, continuously inject ions in the plasma into the polymer layer, and mass-produce the polymer layer with the part modified by ion implantation on the surface. That is, a gas barrier laminate in which a gas barrier layer is formed.

The thickness of the part where the ions are implanted can be controlled by the type of ion, applied voltage, processing time and other implantation conditions, as long as it is determined according to the thickness of the polymer layer and the purpose of use of the gas barrier laminate, but usually It is 5～1,000nm.

The ion implantation system can be confirmed by using X-ray photoelectron spectroscopy (XPS) to perform elemental analysis measurement around 10 nm from the surface of the polymer layer.

If the gas barrier layer has gas barrier properties, it can be confirmed from the low water vapor transmission rate of the gas barrier layer. The water vapor transmission rate of the gas barrier layer in an environment of 40°C and a relative humidity of 90% is usually 1.0 g/m ² /day or less, preferably 0.8 g/m ² /day or less, more preferably 0.5 g/m ² / It is less than day, particularly preferably less than 0.1g/m ² /day. The water vapor transmission rate can be measured by a well-known method.

1-3. Engineering film The engineered film has the function of protecting the base layer, the gas barrier layer, or the other layers mentioned above when storing and transporting the gas-barrier laminate, and is peeled off in a specified step.

When the gas barrier laminate has an engineered film, the gas barrier laminate may have an engineered film on one side or an engineered film on both sides. In the latter case, it is preferable to use two types of engineering films, so that the engineering film peeled first becomes the engineering film that is easier to peel. When an engineered film is provided on the base layer side, compared to a gas barrier laminate without an engineered film, it can be a gas barrier laminate with high maneuverability while protecting the base layer.

The engineering film is preferably in the form of a sheet or film. The sheet-like or film-like shape is not limited to the long ones, but also includes short-striped flat ones.

Examples of engineered films include paper substrates such as cellophane, coated paper, and fine paper; laminated papers laminated with thermoplastic resins such as polyethylene or polypropylene on these paper substrates; such papers The base material is filled with cellulose, starch, polyvinyl alcohol, acrylic-styrene resin, etc.; or polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Polyester film such as ester or polyolefin film such as polyethylene or polypropylene; plastic film such as glass, etc.

In addition, from the viewpoint of ease of handling, the engineered film may have a release agent layer on a paper substrate or a plastic film. The release layer can be formed using a conventionally known release agent such as a silicone release agent, a fluorine release agent, an alkyd release agent, or an olefin release agent. The thickness of the release agent layer is not particularly limited, but is usually 0.02 to 2.0 μm, preferably 0.05 to 1.5 μm.

From the viewpoint of ease of handling, the thickness of the engineered film is preferably 1 to 500 μm, more preferably 5 to 300 μm.

The surface roughness Ra (arithmetic mean roughness) of the engineered film is preferably 10.0 nm or less, more preferably 8.0 nm or less. In addition, the surface roughness Rt (maximum surface height) is preferably 100 nm or less, more preferably 50 nm or less. If the surface roughness Ra and Rt exceed 10.0 nm and 100 nm, respectively, the surface roughness of the layer in contact with the engineered film becomes larger, and the gas barrier properties of the gas barrier laminate may decrease. In addition, the surface roughness Ra and Rt are the values obtained by the optical interferometry in a measurement area of 100 μm×100 μm.

1-4. Gas barrier laminate As described above, the gas barrier laminate system of the embodiment of the present invention includes an engineered film, a base layer, and a gas barrier layer in this order. When the gas barrier laminate is actually used, the engineered film is peeled from the gas barrier laminate, and it is attached to a display or electronic device for use.

As mentioned above, the gas barrier laminate of the embodiment of the present invention satisfies the following requirements [1]: [1] The absolute value of the heat shrinkage rate of the gas barrier laminate is 0.5% or less.

In order to meet the requirement [1], for example, as described above, it is only necessary to use a polyfunctional (meth)acrylate compound and a cyclic polymerizable monomer as the curable component (B) contained in the curable resin composition for forming the base layer. In order to increase the mesh structure, as the polymerizable component (A), a polyimide resin represented by a rigid but flexible structure is selected.

In addition, as described above, the gas barrier laminate of the embodiment of the present invention satisfies the following requirement [2]. [2] The elongation at break of the gas barrier laminate is 1.9% or more. The elongation at break of the gas barrier laminate is preferably 2.0% or more. Since the elongation at break of the gas barrier laminate is in such a range, the flexibility of the gas barrier laminate can be improved. The upper limit of the elongation at break of the base layer is not particularly limited, but it is usually 17% or less, preferably 13% or less.

Since the thickness of the gas barrier layer is generally significantly thinner than that of the base layer, the elongation at break of the gas barrier laminate is greatly affected by the base layer and tends to be close to the value of the break elongation of the base layer. Therefore, as long as the base layer satisfies the above requirements [2'], even if the gas barrier laminate has a breaking elongation slightly smaller than that of the base layer due to the influence of the gas barrier layer, etc., it is easy to meet the requirements [2 ] The gas barrier laminate.

The thickness of the gas barrier laminate can be appropriately determined according to the intended use of the electronic device, etc. From the viewpoint of operability, the substantial thickness of the gas barrier laminate of the embodiment of the present invention is preferably 0.3-50 μm, more preferably 0.5-25 μm, and particularly preferably 0.7-12 μm. Also, the so-called "substantial thickness" refers to the thickness in use. That is, although the above-mentioned gas barrier laminate may have an engineered sheet or the like, the thickness of the portion (engineered sheet, etc.) that is removed during use is not included in the "substantial thickness".

The base layer of the embodiment of the present invention can be made to have excellent flexibility. Furthermore, if the thickness of the gas barrier laminate is reduced, the bending resistance of the gas barrier laminate after assembly can be further improved.

Since the gas barrier laminate of the embodiment of the present invention has the above-mentioned 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 is optically isotropic. Excellent performance. The in-plane phase difference of the gas barrier laminate is usually 20 nm or less, preferably 15 nm or less. The retardation in the thickness direction is usually -500 nm or less, preferably -450 nm or less. In addition, 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 of the gas barrier laminate, the retardation in the thickness direction, and the birefringence are within the above ranges, the gas barrier laminate of the embodiment of the present invention is excellent in optical isotropy and can be preferably used For optical purposes.

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

The gas barrier laminate of the 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 layered product of the embodiment of the present invention may have a base layer and a gas barrier layer each, or may have two or more base layers and/or gas barrier layers.

Fig. 1 shows a specific configuration example of the gas barrier laminate according to the embodiment of the present invention. The gas barrier laminate (10) shown in Figure 1 has a gas barrier layer (3) on one side of the base layer (2), on the surface of the base layer (2) opposite to the gas barrier layer (3) With engineering film (1). When the engineered film (1) is removed by peeling, the part represented by the symbol 10a containing the base layer (2) and the gas barrier layer (3) becomes the gas barrier laminate after the engineered film is removed.

The gas barrier laminated system of the embodiment of the present invention is not limited to the one shown in FIG. 1, it may have gas barrier layers on both sides of the base layer, or the base layer and the gas barrier layer may be combined as a set. Complex array. In addition, within a range that does not impair the purpose of the present invention, one layer or two or more other layers may be further included. Examples of other layers include a conductive layer, an impact absorbing layer, an adhesive layer, a bonding layer, and an engineered sheet. In addition, the placement position of other layers is not particularly limited.

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

There is no particular limitation on the method of forming the conductive layer. For example, a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, etc. can be mentioned.

The thickness of the conductor layer may be appropriately selected according to its use and the like. It is usually 10 nm to 50 μm, preferably 20 nm to 20 μm.

The shock absorption layer is used to protect the gas barrier layer when an impact is applied to the gas barrier layer. The material for forming the impact absorbing layer is not particularly limited, and examples thereof include acrylic resins, urethane resins, silicone resins, olefin resins, and rubber materials.

The method of forming the impact absorbing layer is not particularly limited. For example, a solution containing the material for forming the impact absorbing layer and other components such as solvents as desired can be applied to the layer to be laminated. On the layer, the obtained coating film is dried and heated as necessary to form a method. In addition, the impact absorbing layer may be formed separately on the release base material, and the resulting film may be transferred to the layer to be laminated and laminated. The thickness of the impact absorbing layer is usually 1-100 μm, preferably 5-50 μm.

The adhesive layer is a layer used when attaching the gas barrier laminate to the adherend. The material for forming the adhesive layer is not particularly limited, and well-known adhesives, adhesives, heat-sealing materials, etc., such as acrylic, silicone, and rubber may also be used.

The bonding layer is a layer used when the base layer and the gas barrier layer are regarded as one group, and the plural groups are bonded together to produce a gas barrier laminate. The bonding layer is a layer for bonding the base layer contained in one of the adjacent groups and the gas barrier layer contained in the other to maintain the laminated structure. The bonding layer may be a single layer or a plurality of layers. Examples of the bonding layer include a layer formed by a single-layer structure formed using an adhesive, or a layer formed by forming an adhesive on both sides of the support layer.

The material used to form the bonding layer is not particularly limited as long as it can bond the base layer and the gas barrier layer to each other and maintain the laminated structure. Well-known adhesives can be used, but the base layer and the gas barrier layer can be bonded at room temperature. From the viewpoint of the groups of gas barrier layers, an adhesive is preferable. Examples of the adhesive used in the bonding layer include acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, and the like. Among these, acrylic adhesives and urethane adhesives are preferred from the viewpoints of adhesiveness, transparency, and operability. Furthermore, it is preferably an adhesive capable of forming a cross-linked structure as described later. In addition, the adhesive may be in any form such as a solvent-based adhesive, an emulsion-type adhesive, and a hot-melt adhesive.

2. Manufacturing method of gas barrier laminate The gas barrier laminate system of the embodiment of the present invention is manufactured using engineering films. By using engineered films, gas barrier laminates can be manufactured efficiently and easily. In particular, a method having the following steps 1 to 3 is preferred.

Step 1: Use a curable resin composition containing a polymer component (A) with a Tg of 250°C or higher and a curable component (B) on the engineering film to form a curable resin layer; Step 2: Harden the curable resin layer obtained in Step 1 to form a base layer made of the hardened resin layer; Step 3: A step of forming a gas barrier layer on the base layer obtained in Step 2.

FIG. 2 shows an example of the manufacturing process of the gas barrier laminate according to the embodiment of the present invention. Figure 2(a) corresponds to the above step 1, Figure 2(b) corresponds to the above step 2, and Figure 2(c) corresponds to the above step 3.

(step 1) First, use a curable resin composition containing a polymer component (A) with a Tg of 250°C or higher and a curable component (B) on the engineering film to form a curable resin layer (symbol 2a in Figure 2(a)) .

As the engineering film and curable resin composition used, the same ones as described above can be mentioned. The method of coating the curable resin composition on the engineering film is not particularly limited. Spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, and die coating can be used. , Gravure coating and other well-known coating methods.

The method of drying the obtained coating film is not particularly limited, and conventional drying methods such as hot air drying, hot roll drying, infrared irradiation, and the like can be used. As described above, the curable resin composition used to form the underlayer in the embodiment of the present invention contains a polymer component (A) having a very high Tg, but because it contains the curable component (B), it will be used When the coating film obtained by the solution casting method is dried, the solvent can be efficiently removed.

The drying temperature of the coating film is usually 30 to 150°C, preferably 50 to 100°C. The thickness of the dried coating film (curable resin layer) is not particularly limited, but from the viewpoint of almost no difference from the thickness after curing, it may be the same as the thickness of the above-mentioned underlayer.

(Step 2) Next, the curable resin layer obtained in step 1 is cured to form a cured resin layer. This hardened resin layer becomes the base layer (symbol 2 in Figure 2(b)). The method for hardening the curable resin layer is not particularly limited, and well-known methods can be used. For example, when the curable resin layer is formed using a curable resin composition containing a thermal polymerization initiator, the curable resin layer can be cured by heating the curable resin layer. The heating temperature is usually 30 to 150°C, preferably 50 to 100°C.

Furthermore, when the curable resin layer is formed using a curable resin composition containing a photopolymerization initiator, the curable resin layer can be cured by irradiating the curable resin layer with active energy rays. The active energy ray system can be irradiated with a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, etc.

The wavelength of the active energy ray is preferably 200 to 400 nm, more preferably 350 to 400 nm. The irradiation amount is usually in the range of illuminance 50 to 1,000 mW/cm ² and light amount 50 to 5,000 mJ/cm ² , preferably 1,000 to 5,000 mJ/cm ² . The irradiation time is usually 0.1 to 1,000 seconds, preferably 1 to 500 seconds, and more preferably 10 to 100 seconds. Considering the heat load of the light irradiation step, in order to satisfy the aforementioned light quantity, multiple irradiations may be performed.

At this time, in order to prevent the deterioration of the polymer component (A) or the coloration of the base layer caused by the irradiation of active energy rays, the active energy rays can be irradiated to the light through a filter that can absorb light of a wavelength unnecessary for the curing reaction Curable resin composition. With this method, since the light system of the wavelength that is not necessary for the curing reaction and degrades the polymer component (A) is absorbed by the filter, the degradation of the polymer component (A) can be suppressed, and a colorless and transparent substrate can be easily obtained Floor. As the filter, a resin film such as a polyethylene terephthalate film can be used. When a resin film is used, it is preferable to provide a step of laminating a resin film such as a polyethylene terephthalate film on the curable resin layer between step 1 and step 2. Also, the resin film is usually peeled off after step 2.

In addition, by irradiating electron rays to the curable resin layer, the curable resin layer can also be cured. When electron beams are irradiated, the curable resin layer can generally be cured without using a photopolymerization initiator. When irradiating electron beams, an electron beam accelerator can be used. The radiation dose is usually in the range of 10 to 1,000 krad. The irradiation time is usually 0.1 to 1,000 seconds, preferably 1 to 500 seconds, and more preferably 10 to 100 seconds.

The curing of the curable resin layer can be carried out in an inert gas environment such as nitrogen as needed. By curing in an inert gas environment, it is easy to avoid oxygen or moisture that interferes with curing.

(Step 3) Then, on the base layer obtained in step 2, a gas barrier layer (symbol 3 in FIG. 2(c)) is formed. As a method of forming the gas barrier layer, the method described previously can be suitably used. For example, when the gas barrier layer is a layer obtained by subjecting a layer containing a silicon-containing polymer compound to a modification process, it can be formed by a step of forming a layer containing a silicon-containing polymer compound on the base layer, and The layer containing silicon-containing polymer compound is subjected to a step of modification treatment to form a gas barrier layer.

The gas barrier layer contained in the gas barrier laminate can be formed by various methods such as extrusion molding or coating, but depending on the method of forming the gas barrier layer, there are gas barrier laminates The case where the gas barrier performance is reduced. In particular, when forming a gas barrier layer with heating, for example, coating and drying are used to form a gas barrier layer, the base layer is physically or chemically affected, and the gas barrier properties and other properties may be reduced. However, the base layer of the embodiment of the present invention is a layer composed of a cured product of a curable resin composition containing the polymer component (A) and the curable component (B), as described above, because the polymer component (A) The Tg of) is 250°C or higher, and the underlayer is not easily affected by the heating when forming the gas barrier layer. Therefore, the formed gas barrier layer is not easily affected by the deformation of the base layer during the manufacturing process. For example, the gas barrier layer is unlikely to generate microcracks and other problems that reduce the gas barrier properties.

As a method of forming a layer containing a silicon-containing polymer compound or applying a modification treatment, the previously described method can be adopted. In addition, as a method of applying the modification treatment, it is preferable to transfer a long thin film containing a silicon-containing polymer compound layer on the base layer obtained in step 2 while conveying it in a certain direction. The layer containing the silicon-containing polymer compound is subjected to modification treatment to produce a gas barrier laminate. With this manufacturing method, for example, a long gas barrier laminate can be continuously manufactured.

In addition, the engineering film is usually peeled off in a specified step according to the purpose of the gas barrier laminate, as shown in Figure 2(c), and becomes the gas barrier laminate (10a) after the engineering film (3) is removed. ). For example, other layers can be formed after step 3, and then the engineering film can be peeled off, or the engineering film can be peeled off after step 3. In addition, the engineering film may be peeled off between step 2 and step 3.

In this way, the manufacturing method with the aforementioned steps 1 to 3 uses an engineered film to form a curable resin layer, but the gas barrier laminate system obtained by this method may or may not have an engineered film. According to the method for producing the gas barrier laminate described above, the gas barrier laminate of the embodiment of the present invention can be produced efficiently, continuously and easily. Example

Next, the present invention will be explained in more detail with examples, but the present invention is not limited by these examples at all.

The measurement and evaluation of the physical properties of the base layer and the gas barrier laminate of each of the Examples and Comparative Examples were performed by the following procedures.

＜Solvent resistance of the base layer＞ The base layer was cut into test pieces of 25 mm×25 mm, and the test pieces were immersed in a xylene solvent for 2 minutes. The changes in the test pieces before and after the immersion were visually observed, and the solvent resistance was evaluated according to the following criteria. A: No change. B: A slight change in appearance is seen, but there is no practical problem. C: The appearance changes such as whitening, swelling, curling, undulation, etc., which are practically impeded.

＜Heat shrinkage rate of gas barrier laminate＞ The gas barrier laminate was cut into 5mm×30mm test pieces, and the first polyethylene terephthalate (PET) film corresponding to the base layer side of the engineering film was peeled off and removed. The thermomechanical analysis device TMA4000SE ( NETZSCH Japan Co., Ltd.), after setting the distance between the chucks to 20mm, the temperature is raised to 130°C at 5°C/min, and then cooled to room temperature at 5°C/min. In addition, the rate of change of displacement in the longitudinal direction before and after heating (a value expressed as a percentage of the ratio of the amount of displacement to the distance between chucks of 20 mm) was regarded as the heat shrinkage rate. Furthermore, the contraction of the gas barrier laminate is regarded as a negative value, and the elongation is regarded as a positive value.

<Water Vapor Transmission Rate of Gas Barrier Laminate (WVTR)> The gas barrier laminate was cut into a circular test piece with an area of 50 cm ² and a water vapor transmission rate measuring device (manufactured by MOCON Corporation, device name: AQUATRAN was used) ), the water vapor transmission rate (g/m ² /day) was measured at a gas flow rate of 20 sccm at 40°C and 90% RH. In addition, the lower limit of detection of the measuring device is 0.0005 g/m ² /day. Since the gas barrier laminate has poor self-standing properties when the PET film used to form the base layer is peeled off, the measurement was performed in a state where the PET film was laminated. Since the water vapor transmission rate of the gas barrier layer is much lower than that of the PET film, the effect of the lamination of the PET film on the WVTR is so small that it is almost negligible.

＜Fracture elongation of base layer and gas barrier laminate＞ The base layer was cut into 15mm×150mm test pieces, and the elongation at break was measured in accordance with JIS K7127:1999. Specifically, the above-mentioned test piece was set at a distance between chucks of 100 mm by a tensile tester (Autograph manufactured by Shimadzu Corporation), and then a tensile test was performed at a speed of 200 mm/min to measure the elongation at break [%]. In addition, when the test piece does not have a yield point, the tensile breaking strain is regarded as the breaking elongation, and when it has a yield point, the tensile breaking induced strain is regarded as the breaking elongation. In addition, the same test was also performed on a gas barrier laminate (non-engineered film) provided with a gas barrier layer.

[Example 1] The curable resin composition 1 to be a base layer was prepared by the following procedure. <Curing resin composition 1> As a polymer component, pellets of polyimide resin (PI) (manufactured by Kawamura Sangyo Co., Ltd., product name KPI-MX300F, Tg=354°C, weight average molecular weight 280,000) 100 The mass part was dissolved in methyl ethyl ketone (MEK) to prepare a 15 mass% solution of PI. Next, to this solution, 122 parts by mass of tricyclodecane dimethanol diacrylate (A-DCP manufactured by Shinnakamura Chemical Industry Co., Ltd.) as a curable monomer and bis(2,4, 5 parts by mass of 6-trimethylbenzyl)-phenylphosphine oxide (Irgacure 819 manufactured by BASF Corporation) and mixed to prepare curable resin composition 1. In addition, the curable monomer and polymerization initiator used in this example and other experimental examples are raw materials that do not contain solvent and have 100% solid content. Next, as an engineering film, the first PET film (PET100A-4100 manufactured by Toyobo Co., Ltd., thickness 100μm) with an easy-adhesive layer on one side was used, and a curable resin was applied to the opposite side of the PET film to the easy-adhesive layer. The composition was dried by heating the coating film at 90°C for 3 minutes. In addition, on this dried coating film, a second PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4100, thickness 50μm) with an easy-adhesive layer on one side was placed on the opposite side of the easy-adhesive surface Laminating, using a belt conveyor type ultraviolet irradiation device (manufactured by EYE GRAPHICS, product name: ECS-401GX), using a high-pressure mercury lamp (manufactured by EYE GRAPHICS, product name: H04-L41), at a height of 100 mm, ultraviolet lamp Under the condition that the output is 3kw, the light wavelength is 365nm, the illuminance is 400mW/cm ² , and the light quantity is 800mJ/cm ² (measured with the ultraviolet light meter UV-351 manufactured by ORC Manufacturing Co., Ltd.), the second PET film is irradiated with ultraviolet light to cause the curing reaction A base layer with a thickness of 5 μm is formed. Then, the second PET film was peeled off to expose the base layer, and a coating agent (MERCK) mainly composed of a polysilazane compound (perhydropolysilazane (PHPS)) was coated on the base layer by spin coating. Amiakucar NL-110-20 manufactured by PERFORMANCE MATERIALS, solvent: xylene)), heated and dried at 130°C for 2 minutes to form a 200nm thick polymer compound layer (polysilazane layer) containing perhydropolysilazane . Next, a plasma ion implantation device (manufactured by JEOL Ltd., RF power supply: "RF"56000; manufactured by Kurita Manufacturing Co., Ltd., high-voltage pulse power supply: PV-3-HSHV-0835) was used at a gas flow rate of 100 sccm and a duty ratio of 0.5% , Apply DC voltage -6kV frequency 1,000Hz, apply RF power 1,000W, chamber pressure 0.2Pa, DC pulse width 5μsec, processing time 200 seconds, inject ions from argon gas into the polymer compound layer (polysilicon nitrogen The surface of the alkane layer) forms a gas barrier layer. In this way, by laminating a gas barrier layer on the base layer, a gas barrier laminate is produced.

[Example 2] In addition to being a curable monomer, 61 parts by mass of dicyclopentadiene diacrylate (A-DCP manufactured by Shinnakamura Chemical Industry Co., Ltd.), allyl ether acrylate of a cyclized polymerizable monomer (Japan Co., Ltd. Except for 61 parts by mass (FX-AO-MA manufactured by Catalyst), a gas barrier laminate was produced in the same manner as in Example 1.

[Comparative Example 1] Except that as the curable monomer, only 122 parts by mass of allyl ether acrylate (FX-AO-MA manufactured by Nippon Shokubai Co., Ltd.) was used as a cyclized polymerizable monomer, the gas was produced in the same manner as in Example 1. Barrier laminated body.

[Comparative Example 2] The same as Comparative Example 1 except that 100 parts by mass of polyimide resin (PSF) pellets (manufactured by BASF, ULTRASON S6010, Tg=187°C, weight average molecular weight 60,000) were used as the polymer component instead of polyimide resin To make a gas barrier laminate.

[Comparative Example 3] In addition to the dissolving solvent of the particles, toluene is used instead of MEK, and as the polymer component, 100 parts by mass of polycarbonate resin (PC) particles (Tg≦190℃, weight average molecular weight less than 100,000) are used instead of polyimide resin Except this, in the same manner as in Example 1, a gas barrier laminate was produced.

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

As can be seen from Table 1, regarding Examples 1 and 2, the base layer system has excellent solvent resistance and fracture elongation, and the gas barrier laminate system after the engineering film is removed has excellent fracture elongation and heat shrinkage, and has excellent gas barrier properties. The water vapor transmission rate of the laminate is also excellent. On the other hand, regarding Comparative Examples 1 to 3, although the solvent resistance of the base layer is good, the absolute value of the heat shrinkage rate of the gas barrier laminate after the removal of the engineered film is greater than that of Example 1. The gas barrier layer The water vapor transmission rate of the combined body is also lower than that of Example 1 by more than one digit. In addition, the elongation at break of the base layer and the gas barrier laminate is worse than the example. Industrial possibilities

With the gas barrier laminate of the present invention, since it can have high elongation at break and can further improve gas barrier properties, it can be applied to electronic devices that require both gas barrier properties and flexibility or bending resistance, such as Flexible organic EL elements, etc., and flexible thermoelectric conversion elements, etc., are components that are easily degraded by the atmosphere and constitute elements of various electronic devices.

1: Engineering film 2: basal layer 2a: Base layer before hardening 3: Gas barrier layer 10: Gas barrier laminate 10a: Gas barrier laminate after removal of engineering film

Fig. 1 is a schematic cross-sectional view showing the structure of the gas barrier laminate according to the embodiment of the present invention. [Fig. 2] A process diagram showing an example of the method of manufacturing a gas barrier laminate.

Claims (6)

A gas-barrier laminate, which is a gas-barrier laminate with an engineered film, a base layer and a gas barrier layer in sequence, The aforementioned base layer is a layer composed of a cured product of a curable resin composition containing a polymer component (A) and a curable component (B), The aforementioned gas barrier laminate satisfies the following requirements [1] and [2]: [1] The absolute value of the heat shrinkage 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 gas barrier laminate of claim 1, wherein the thickness of the aforementioned base layer is 0.1 to 10 μm. The gas barrier laminate according to claim 1 or 2, wherein the gas barrier layer is a coating film. The gas barrier laminate according to any one of claims 1 to 3, wherein the curable component (B) contains a cyclized polymerizable monomer. The gas barrier laminate according to claim 4, wherein the curable component (B) component further contains a polyfunctional (meth)acrylate compound, and the cyclized polymerizable monomer and the polyfunctional (meth) The mass ratio of acrylate compounds is 95:5~30:70. The gas barrier laminate according to any one of claims 1 to 5, wherein the glass transition temperature of the aforementioned polymer component (A) is 250°C or higher.

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