CN113226750B

CN113226750B - Gas barrier laminate

Info

Publication number: CN113226750B
Application number: CN201980086465.4A
Authority: CN
Inventors: 木下博贵; 永绳智史
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2018-12-27
Filing date: 2019-12-25
Publication date: 2023-05-19
Anticipated expiration: 2039-12-25
Also published as: JPWO2020138207A1; WO2020138207A1; CN113226750A; JP7398394B2; TW202031479A; KR20210110592A

Abstract

The present invention relates to a gas barrier laminate having a high elongation at break and excellent gas barrier properties, which comprises, in order, a process film, a base layer and a gas barrier layer, wherein the base layer is a layer formed from 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 of the gas barrier laminate is 0.5% or less; [2] the gas barrier laminate has an elongation at break of 1.9% or more.

Description

Gas barrier laminate

Technical Field

The present invention relates to a gas barrier laminate preferably used as a member for electronic devices such as a liquid crystal display and an Electroluminescence (EL) display.

Background

For displays such as liquid crystal displays and Electroluminescence (EL) displays, the use of transparent plastic films instead of glass plates has been studied in order to achieve reduction in thickness, weight, flexibility, and the like.

However, in general, when a transparent plastic film is used as a substrate of a display, water vapor, oxygen, etc. are more likely to permeate than a glass plate, and the water vapor, oxygen, etc. after permeation through the substrate act on elements inside the display device, etc., resulting in problems such as reduced device performance and shortened lifetime.

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

In recent years, there has been a demand for a display or the like having higher performance, and for a gas barrier film used as a member for electronic equipment or the like, there has been a demand for excellent properties such as heat resistance, solvent resistance, interlayer adhesiveness, low birefringence, and excellent optical isotropy, as well as excellent gas barrier properties.

For example, patent document 1 proposes a gas barrier film having a gas barrier layer on one side of a cured resin layer formed from a cured product of a curable resin composition containing a thermoplastic resin having a glass transition temperature of 140 ℃ or higher and a curable monomer.

Prior art literature

Patent literature

Patent document 1: international publication No. 2013/065812

Disclosure of Invention

Problems to be solved by the invention

However, there is room for improvement in conventional gas barrier laminates, and with the development of electronic devices, there is a demand for higher bending resistance and further improvement in gas barrier properties.

In view of the above problems, an object of the present invention is to provide a gas barrier laminate having high bending resistance and excellent gas barrier properties, which is suitable for use as a member for electronic equipment.

Means for solving the problems

As a result of intensive studies to solve the above problems, the inventors have found that the above problems can be solved by setting the base layer to a layer formed from a cured product of a curable resin composition containing a polymer component (a) and a curable component (B) and setting the absolute value of the heat shrinkage rate of the gas barrier laminate and the elongation at break of the base layer to given values, in a gas barrier laminate comprising a process film, a base layer and a gas barrier layer in this order, and have completed the present invention.

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

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

the base layer is a layer formed from a cured product of a curable resin composition containing a polymer component (A) and a curable component (B),

the gas barrier laminate satisfies the following requirements [1] and [2].

(1) The absolute value of the heat shrinkage of the gas barrier laminate is 0.5% or less.

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

[2] The gas barrier laminate according to item [1], wherein the thickness of the underlayer is 0.1 to 10. Mu.m.

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

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

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

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

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a gas barrier laminate having high bending resistance and excellent gas barrier properties can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of the structure of a gas barrier laminate according to an embodiment of the present invention.

Fig. 2 is a process diagram showing an example of a method for producing the gas barrier laminate.

Symbol description

1. Art film

2. Substrate layer

2a base layer before curing

3. Gas barrier layer

10. Gas barrier laminate

10a gas barrier laminate after removal of process film

Detailed Description

In the present specification, the preferable conditions may be arbitrarily selected, and combinations of the preferable conditions may be considered more preferable.

In the present specification, the expression "XX to YY" means "XX or more and YY or less".

In the present specification, the lower limit value and the upper limit value described in the section may be independently combined with each other in a preferable numerical range (for example, a range of content or the like). For example, according to the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" may be combined to obtain "10 to 60".

In the present specification, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", for example, and other similar expressions are also used.

The gas barrier laminate according to the embodiment of the present invention will be described below.

1. Gas barrier laminate

The gas barrier laminate according to the embodiment of the present invention includes, in order, a process film, a base layer, and a gas barrier layer. Wherein the base layer is a layer formed from 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 of the gas barrier laminate is 0.5% or less.

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

In the gas barrier laminate according to the embodiment of the present invention, the solvent resistance of the base layer can be excellent by making the base layer a cured product of the curable resin composition. Therefore, for example, in the case of forming the gas barrier layer in the form of a coating film, the underlayer is not easily eroded by the solvent when applied. As a result, the gas barrier properties of the gas barrier laminate can be made less likely to deteriorate. The coating film is a film obtained by applying a coating material to a substrate or an object and, if necessary, performing a treatment such as curing by drying or heating. In the case of using the gas barrier layer as a coating film, the coating material containing a component for forming the gas barrier layer, which will be described later, is applied to the base layer, and cured by drying, heating, or the like. In the case of forming the base layer into a coating film, the curable resin composition is applied to an object such as a process film, and either or both of the curing treatments such as drying, heating, and irradiation with active energy rays are performed.

Further, by satisfying the above requirement [1], shrinkage of the gas barrier laminate at the time of heating can be suppressed. Therefore, for example, when the gas barrier layer is formed on the base layer by applying a material constituting the gas barrier layer and performing heat drying, deformation of the gas barrier layer and further deterioration of the gas barrier property due to shrinkage of the base layer and the precursor of the gas barrier layer can be prevented.

Further, by satisfying the above requirement [2], the flexibility of the gas barrier laminate becomes high, and the gas barrier laminate becomes a material excellent in bending resistance and suitable for flexible device applications.

In the present specification, the heat shrinkage rate of the gas barrier laminate is a value obtained by setting the gas barrier laminate in a thermomechanical analysis device, heating to 130 ℃ at 5 ℃/min, cooling to normal temperature at 5 ℃/min, and measuring the rate of change in displacement of the base layer in the longitudinal direction before and after heating, and specifically, the measurement can be performed by the procedure shown in the examples.

In the present specification, the elongation at break of the base layer is a value measured in accordance with JIS K7127:1999, and specifically, the elongation at break can be measured by the procedure shown in examples.

1-1 substrate layer

The base layer of the gas barrier laminate according to the embodiment of the present invention is formed from 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 stacked together.

[ Polymer component (A) ]

The glass transition temperature (Tg) of the polymer component (A) is preferably 250℃or higher, more preferably 290℃or higher, and still more preferably 320℃or higher. When the Tg is 250 ℃ or higher, the heat shrinkage of the base layer can be suppressed, and as a result, the heat shrinkage rate of the gas barrier laminate can be easily adjusted to the above range (that is, the requirement [1] can be easily satisfied).

Here, tg means a temperature at which tan δ (loss modulus/storage modulus) obtained by viscoelastic measurement (measurement based on a stretching mode at a frequency of 11Hz and a heating rate of 3 ℃/min in a range of 0 to 250 ℃) is at a maximum point.

The weight average molecular weight (Mw) of the polymer component (a) is generally in the range of 100,000 ～ 3,000,000, preferably 200,000 ～ 2,000,000, more preferably 250,000 ～ 2,000,000, particularly preferably 500,000 ～ 1,000,000. The molecular weight distribution (Mw/Mn) is preferably in the range of 1.0 to 5.0, more preferably 2.0 to 4.5. The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) are values in terms of polystyrene as measured by a Gel Permeation Chromatography (GPC) method. When the Mw is 100,000 or more, the elongation at break of the base layer is easily increased.

The polymer component (a) is preferably a thermoplastic resin, and more preferably an amorphous thermoplastic resin. By using an amorphous thermoplastic resin, a base layer excellent in optical isotropy is easily obtained, and a gas barrier laminate excellent in transparency is easily obtained. Further, since the amorphous thermoplastic resin is generally easily dissolved in an organic solvent, the underlayer can be efficiently formed by a solution casting method as described later.

Here, the amorphous thermoplastic resin means a thermoplastic resin in which the melting point is not observed in the differential scanning calorimeter measurement.

Particularly, the polymer component (A) is preferably soluble in a low-boiling point general-purpose organic solvent such as benzene or Methyl Ethyl Ketone (MEK). When soluble in general organic solvents, the base layer is easily formed by coating.

The polymer component (a) is particularly preferably an amorphous thermoplastic resin having a Tg of 250 ℃ or higher and being soluble in a low-boiling organic solvent such as benzene and methyl ethyl ketone.

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

Specific examples of the polymer component (a) include polyimide resins, polyarylate resins, and the like. These resins generally have a high Tg and excellent heat resistance, and are amorphous thermoplastic resins, and thus can be formed into coating films by a solution casting method. Among these resins, polyimide resins are preferred from the viewpoints of high Tg, excellent heat resistance, and easy availability of components that are soluble in general-purpose organic solvents while exhibiting good heat resistance.

As the polyimide resin, there is no particular limitation as long as it is within a range that does not impair the effects of the present invention, and for example, there can be used: aromatic polyimide resins, aromatic (carboxylic acid component) -cyclic aliphatic (diamine component) polyimide resins, cyclic aliphatic (carboxylic acid component) -aromatic (diamine component) polyimide resins, cyclic aliphatic polyimide resins, fluorinated aromatic polyimide resins, and the like. Polyimide resins having fluorine groups in the molecule are particularly preferred. Generally, polyimide resins have a Tg of 250℃or higher.

Specifically, a polyimide resin obtained by polymerizing an aromatic diamine compound and a tetracarboxylic dianhydride into a polyamic acid and subjecting the polyamic acid to a chemical imidization reaction is preferable.

Any aromatic diamine compound may be used as long as it is an aromatic diamine compound that can obtain polyimide having a predetermined transparency, which is soluble in a general-purpose solvent (for example, N-Dimethylacetamide (DMAC)) by reaction with a commonly used tetracarboxylic dianhydride. Specific examples thereof include: m-phenylenediamine, p-phenylenediamine, 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3' -diaminodiphenyl sulfide, 3,4' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, 3' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, and 4,4' -diaminodiphenyl sulfone, 3' -diaminobenzophenone, 3' -diaminodiphenyl methane, 3,4' -diaminodiphenyl methane, 4' -diaminodiphenyl methane, 2-bis (4-aminophenyl) propane, 2-bis (3-aminophenyl) propane, and 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2-bis (4-aminophenyl) -1, 3-hexafluoropropane 2, 2-bis (3-aminophenyl) -1, 3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1, 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' -bis (4-aminophenoxy) biphenyl, 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, bis [3- (4-aminophenoxy) phenyl ] sulfide, bis [3- (3-aminophenoxy) phenyl ] sulfide, bis [3- (4-aminophenoxy) phenyl ] sulfone, bis [4- (4-aminophenyl) ] sulfone, bis [3- (3-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenyl) ] sulfone, bis [4- (3-aminophenoxy) phenyl ] ether, bis [4- (4-aminophenoxy) phenyl ] ether, bis [3- (3-aminophenoxy) phenyl ] ether, bis [4- (3-aminophenoxy) phenyl ] methane, bis [4- (4-aminophenoxy) phenyl ] methane, bis [3- (3-aminophenoxy) phenyl ] methane, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [ 3-aminophenoxy ] propane, 2, 2-bis [3- (3-aminophenoxy) phenyl ] -1, 3-hexafluoropropane 2, 2-bis [3- (3-aminophenoxy) phenyl ] -1, 3-hexafluoropropane 2, 2-bis [3- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, 1, 3-bis [4- (4-amino-6-trifluoromethylphenoxy) -alpha, α -dimethylbenzyl ] benzene, 1, 3-bis [4- (4-amino-6-fluoromethylphenoxy) - α, α -dimethylbenzyl ] benzene, 2 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, and the like.

These aromatic diamine compounds may be used alone or in combination of two or more kinds. Among them, preferred aromatic diamine compounds from the viewpoints of transparency and heat resistance include: 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane 2, 2-bis [3- (3-aminophenoxy) phenyl ] -1, 3-hexafluoropropane 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, 2-bis [3- (3-aminophenoxy) phenyl ] -1, 3-hexafluoropropane 2, 2-bis [3- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, 1, 3-bis [4- (4-amino-6-trifluoromethylphenoxy) -alpha, an aromatic diamine compound having a fluorine group such as α -dimethylbenzyl ] benzene, 3 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, and 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl is preferably used, and at least one of the aromatic diamine compounds used is an aromatic diamine compound having a fluorine group, and particularly preferably 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl. By using an aromatic diamine compound having a fluorine group, transparency, heat resistance, and solubility in a solvent can be easily obtained.

As the tetracarboxylic dianhydride, similarly to the aromatic diamine compound, any tetracarboxylic dianhydride which is soluble in a general-purpose solvent (for example, N-Dimethylacetamide (DMAC)) and has a polyimide having a predetermined transparency can be used, and specific examples thereof include: 4,4' - (1, 3-hexafluoropropane-2, 2-diyl) diphthalic dianhydride, pyromellitic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 1, 4-hydroquinone dibenzoate-3, 3',4,4' -tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydrides may be used alone or two or more kinds thereof may be used. Among them, from the viewpoints of transparency, heat resistance and solubility in a solvent, it is preferable to use at least one tetracarboxylic dianhydride having a fluorine group such as 4,4' - (1, 3-hexafluoropropane-2, 2-diyl) diphthalic dianhydride.

The polymerization to the polyamic acid can be performed by reacting the aromatic diamine compound and the tetracarboxylic dianhydride under conditions in which the aromatic diamine compound and the tetracarboxylic dianhydride are dissolved in a solvent in which the generated polyamic acid can be dissolved. As the solvent used in the polymerization to the polyamic acid, there can be used: solvents such as N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide.

The polymerization reaction to the polyamic acid is preferably carried out while stirring in a reaction vessel equipped with a stirring device. For example, there may be mentioned: a method in which a predetermined amount of an aromatic diamine compound is dissolved in the solvent, and a tetracarboxylic dianhydride is added while stirring to react, thereby obtaining a polyamic acid; a method in which tetracarboxylic dianhydride is dissolved in a solvent, and an aromatic diamine compound is added while stirring to react, thereby obtaining a polyamic acid; and a method in which an aromatic diamine compound and a tetracarboxylic dianhydride are alternately charged and reacted to obtain a polyamic acid.

The polymerization reaction to the polyamic acid is not particularly limited, and is preferably carried out at a temperature of 0 to 70 ℃, more preferably 10 to 60 ℃, still more preferably 20 to 50 ℃. By carrying out the polymerization reaction in the above-mentioned range, a polyamide acid having a high molecular weight, which is less colored and excellent in transparency, can be obtained.

In addition, although the aromatic diamine compound and the tetracarboxylic dianhydride used for polymerization of the polyamic acid are used in substantially equimolar amounts, the molar amount of the tetracarboxylic dianhydride/the molar amount (mole fraction) of the aromatic diamine compound may be changed within a range of 0.95 to 1.05 in order to control the polymerization degree of the obtained polyamic acid. Further, the molar fraction of the tetracarboxylic dianhydride and the aromatic diamine compound is preferably in the range of 1.001 to 1.02, more preferably 1.001 to 1.01. By slightly excessively adding the tetracarboxylic dianhydride to the aromatic diamine compound in this manner, the polymerization degree of the obtained polyamic acid can be stabilized, and the unit derived from the tetracarboxylic dianhydride can be disposed at the terminal of the polymer, and as a result, a polyimide having less coloration and excellent transparency can be obtained.

The concentration of the polyamic acid solution to be formed is preferably adjusted to an appropriate concentration (for example, about 10 to 30 mass%) so that the solution can be maintained at a reasonable viscosity and the subsequent steps can be easily performed.

An imidizing agent is added to the obtained polyamic 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, and from the viewpoints of cost and ease of removal after reaction, acetic anhydride is preferably used. The equivalent weight of the imidizing agent used is not less than the equivalent weight of the amide bond of the polyamic acid to be subjected to the chemical imidization reaction, preferably 1.1 to 5 times, more preferably 1.5 to 4 times the equivalent weight of the amide bond. By using a slight excess of the imidizing agent relative to the amide bond in this manner, the imidization reaction can be efficiently performed at a lower temperature.

In the chemical imidization reaction, aliphatic, aromatic or heterocyclic tertiary amines such as pyridine, picoline, quinoline, isoquinoline, trimethylamine, and triethylamine can be used as imidization accelerators. By using such an amine, imidization reaction can be efficiently performed at a low temperature, and as a result, coloring at the time of imidization reaction can be suppressed, and thus a more transparent polyimide can be easily obtained.

The chemical imidization reaction temperature is not particularly limited, and is preferably 10℃or higher and lower than 50℃or lower, more preferably 15℃or higher and lower than 45 ℃. By performing the chemical imidization at a temperature of 10 ℃ or higher and lower than 50 ℃, coloration during the imidization reaction can be suppressed, and a polyimide excellent in transparency can be easily obtained.

Thereafter, if necessary, a poor solvent for polyimide is added to the polyimide solution obtained by the chemical imidization reaction to precipitate polyimide, and the resultant polyimide solution is powdered to form a powder, and dried.

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

Polyimide resins containing fluorine groups are preferred from the viewpoint of easy dissolution in a low-boiling organic solvent such as MEK and easy formation of a base layer by a coating method.

The polyimide resin having a fluorine group is preferably an aromatic polyimide resin having a fluorine group in a molecule, and preferably a polyimide resin having a skeleton represented by the following chemical formula in a molecule.

[ chemical formula 1]

Polyimide resins having a skeleton represented by the above chemical formula have extremely high Tg exceeding 300 ℃ because of the high rigidity of the above skeleton. This can greatly improve the heat resistance of the base layer. The skeleton is linear, has high flexibility, and is easy to increase the elongation at break of the base layer. Further, the polyimide resin having the above skeleton can be dissolved in a low-boiling point general-purpose organic solvent such as methyl ethyl ketone by having a fluorine group. Therefore, the coating can be performed by a solution casting method, whereby a base layer is formed in the form of a coating film, and the solvent can be easily removed by drying. Polyimide resins having a skeleton represented by the above chemical formula can be obtained by polymerization and imidization of the polyamic acid using 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl and 4,4' - (1, 3-hexafluoropropane-2, 2-diyl) diphthalic dianhydride.

The polyarylate resin is a resin containing a polymer compound obtained by reacting an aromatic diol with an aromatic dicarboxylic acid or a chloride thereof. The polyarylate resin also has a higher Tg and also has better elongation characteristics. The polyarylate resin has a Tg of 170 to 300 ℃ or so, and is structurally different, and includes a polyarylate resin having a Tg of 250 ℃ or higher. The polyarylate resin is not particularly limited, and known ones can be used.

Examples of the aromatic diol include: bis (4-hydroxyphenyl) methane [ bisphenol F ], bis (3-methyl-4-hydroxyphenyl) methane, 1-bis (4 '-hydroxyphenyl) ethane, 1-bis (3' -methyl-4 '-hydroxyphenyl) ethane bis (hydroxyphenyl) alkanes such as 2, 2-bis (4' -hydroxyphenyl) propane [ bisphenol a ], 2-bis (3 '-methyl-4' -hydroxyphenyl) propane, 2-bis (4 '-hydroxyphenyl) butane, and 2, 2-bis (4' -hydroxyphenyl) octane; bis (hydroxyphenyl) cycloalkanes such as 1, 1-bis (4 ' -hydroxyphenyl) cyclopentane, 1-bis (4 ' -hydroxyphenyl) cyclohexane [ bisphenol Z ], and 1, 1-bis (4 ' -hydroxyphenyl) -3, 5-trimethylcyclohexane; bis (4-hydroxyphenyl) phenylmethane, bis (3-methyl-4-hydroxyphenyl) phenylmethane, bis (2, 6-dimethyl-4-hydroxyphenyl) phenylmethane, bis (2, 3, 6-trimethyl-4-hydroxyphenyl) phenylmethane, bis (3-tert-butyl-4-hydroxyphenyl) phenylmethane, bis (3-phenyl-4-hydroxyphenyl) phenylmethane, bis (3-fluoro-4-hydroxyphenyl) phenylmethane, bis (3-bromo-4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) -4-fluorophenylmethane, bis (3-fluoro-4-hydroxyphenyl) -4-fluorophenylmethane, bis (4-hydroxyphenyl) -4-chlorophenyl methane, bis (4-hydroxyphenyl) -4-bromophenyl methane, bis (3, 5-dimethyl-4-hydroxyphenyl) -4-fluorophenyl methane, 1-bis (4 '-hydroxyphenyl) -1-phenylethane [ bisphenol P ], 1-bis (3' -methyl-4 '-hydroxyphenyl) -1, 1' -tert-butylphenyl ethane, 1 '-bis (3' -tert-butylphenyl) -1-4-hydroxyphenyl ethane, bis (hydroxyphenyl) phenyl alkanes such as 1, 1-bis (3 ' -phenyl-4 ' -hydroxyphenyl) -1-phenylethane, 1-bis (4 ' -hydroxyphenyl) -1- (4 ' -nitrophenyl) ethane, 1-bis (3 ' -bromo-4 ' -hydroxyphenyl) -1-phenylethane, 1-bis (4 ' -hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane and bis (4-hydroxyphenyl) dibenzylmethane; bis (hydroxyphenyl) ethers such as bis (4-hydroxyphenyl) ether and bis (3-methyl-4-hydroxyphenyl) ether; bis (hydroxyphenyl) ketones such as bis (4-hydroxyphenyl) ketone and bis (3-methyl-4-hydroxyphenyl) ketone; bis (hydroxyphenyl) sulfides such as bis (4-hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide; bis (hydroxyphenyl) sulfoxides such as bis (4-hydroxyphenyl) sulfoxide and bis (3-methyl-4-hydroxyphenyl) sulfoxide; bis (hydroxyphenyl) sulfones such as bis (4-hydroxyphenyl) sulfone [ bisphenol S ], bis (3-methyl-4-hydroxyphenyl) sulfone and the like; bis (hydroxyphenyl) fluorenes such as 9, 9-bis (4 ' -hydroxyphenyl) fluorene and 9, 9-bis (3 ' -methyl-4 ' -hydroxyphenyl) fluorene; etc.

Examples of the aromatic dicarboxylic acid or its chloride include: phthalic acid, isophthalic acid, terephthalic acid, 4' -biphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether 4,4' -dicarboxylic acid, 4' -diphenyl sulfone dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, chlorides thereof, and the like. The polyarylate resin used may be a modified polyarylate resin. Among them, the polyarylate resin is preferably a resin containing a polymer compound obtained by reacting 2, 2-bis (4' -hydroxyphenyl) propane with isophthalic acid.

The polymer component (a) may be used alone or in combination of two or more, and is preferably a component using a single polyimide resin, a component using a plurality of polyimide resins of different types, or a component in which at least one of a polyamide resin and a polyarylate resin is added to the polyimide resin, from the viewpoint of being able to adjust elongation characteristics and solvent resistance.

The polyamide resin is preferably an organic solvent-soluble polyamide resin, and more preferably a rubber-modified polyamide resin. As the rubber-modified polyamide resin, for example, those described in Japanese patent application laid-open No. 2004-035638 can be used.

When the polyamide resin or the polyarylate resin is added to the polyimide resin, the amount of the resin to be added is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, and further preferably 1 part by mass or more, more preferably 3 parts by mass or more, based on 100 parts by mass of the polyimide resin.

[ curable component (B) ]

The curable component (B) is a component that can participate in polymerization or can participate in polymerization and crosslinking, and is, for example, a monomer that has a polymerizable unsaturated bond, can participate in polymerization or can participate in polymerization and crosslinking. In the present specification, the term "curing" means a broad concept including "polymerization of a monomer" or "polymerization of a monomer" and subsequent crosslinking of a polymer ". By using the curable component (B), a gas barrier laminate excellent in solvent resistance can be obtained.

The molecular weight of the curable component (B) is usually 3,000 or less, preferably 200 to 2,000, more preferably 200 to 1,000.

The number of polymerizable unsaturated bonds in the curable component (B) is not particularly limited. The curable component (B) may be a monofunctional monomer having 1 polymerizable unsaturated bond, or may be a multifunctional monomer such as a difunctional monomer or a trifunctional monomer having a plurality of polymerizable unsaturated bonds.

The monofunctional monomer may be a monofunctional (meth) acrylic acid derivative.

The monofunctional (meth) acrylic acid derivative is not particularly limited, and a known compound can be used. Examples include: monofunctional (meth) acrylic acid derivatives having nitrogen atoms, monofunctional (meth) acrylic acid derivatives having alicyclic structures, monofunctional (meth) acrylic acid derivatives having polyether structures, and the like.

Examples of the monofunctional (meth) acrylic acid derivative having a nitrogen atom include compounds represented by the following formula.

[ chemical formula 2]

Wherein R is ¹ Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² R is R ³ Each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, R ² And R is ³ May also be bonded to form a ring structure, R ⁴ An organic group having a valence of 2.

As R ¹ Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, and the like, and methyl is preferred.

As R ² R is R ³ Examples of the organic group having 1 to 12 carbon atoms include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl and propyl; cycloalkyl groups having 3 to 12 carbon atoms such as cyclopentyl and cyclohexyl; an aromatic group having 6 to 12 carbon atoms such as a phenyl group, a biphenyl group, and a naphthyl group. These groups may have a substituent at any position. In addition, R ² And R is ³ May also together form a ring, which may further have a nitrogen atom, oxygen atom in the backboneAn atom.

As R ⁴ Examples of the organic group having a valence of 2 include- (CH) ₂ ) _m -、-NH-(CH ₂ ) _m -the group shown. Wherein m is an integer of 1 to 10.

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

[ chemical formula 3]

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

Examples of the monofunctional (meth) acrylic acid derivative having an alicyclic structure include compounds represented by the following formula.

[ chemical formula 4]

Wherein R is ¹ Meaning the same as above, R ⁵ Is a group having an alicyclic structure.

As R ⁵ Examples of the group having an alicyclic structure include: cyclohexyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclodecyl, and the like.

Specific examples of the monofunctional (meth) acrylic acid derivative having an alicyclic structure include: isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, and the like.

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

Examples of the monofunctional (meth) acrylic acid derivative having a polyether structure include compounds represented by the following formula.

[ chemical formula 5]

Wherein R is ¹ Meaning the same as above, R ⁶ An organic group having 1 to 12 carbon atoms. As R ⁶ Examples of the organic group having 1 to 12 carbon atoms include: alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl and propyl; cycloalkyl groups having 3 to 12 carbon atoms such as cyclohexyl groups; an aromatic group having 6 to 12 carbon atoms such as a phenyl group, a biphenyl group, and a naphthyl group; etc. j represents an integer of 2 to 20.

Specific examples of the monofunctional (meth) acrylic acid derivative having a polyether structure include: ethoxylated ortho-phenylphenol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and the like.

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

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

The polyfunctional (meth) acrylic acid derivative is not particularly limited, and a known compound may be used. Examples include: 2-6 functional (meth) acrylic acid derivatives.

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

[ chemical formula 6]

Wherein R is ¹ Meaning the same as above, R ⁷ An organic group having a valence of 2. As R ⁷ Examples of the 2-valent organic group include groups represented by the following formulas.

[ chemical formula 7]

-O-(CH ₂ ) _s -O-

-O(CH ₂ CH ₂ O) _t -

(wherein s represents an integer of 1 to 20, t represents an integer of 1 to 30, u and v each independently represent an integer of 1 to 30, and "-" at both ends represents a bonding position.)

Specific examples of the difunctional (meth) acrylic acid derivative represented by the above formula include: tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 1, 10-decane diol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 9-bis [4- (2-acryloyloxyethoxy) phenyl]Fluorene, and the like. Among these compounds, from the viewpoints of heat resistance and toughness, preferred are: r in the above formula such as tricyclodecanedimethanol di (meth) acrylate ⁷ R in the above formula is represented by a compound having a 2-valent organic group with a tricyclodecane skeleton, propoxylated ethoxylated bisphenol A di (meth) acrylate, or the like ⁷ Compounds of which the 2-valent organic groups have a bisphenol skeleton, 9-bis [4- (2-acryloyloxyethoxy) phenyl ]]Fluorene and the like in the above formula ⁷ A compound having a 2-valent organic group having a 9, 9-diphenylfluorene skeleton.

Further, as the bifunctional (meth) acrylic acid derivative other than the above, there may be mentioned: neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, di (acryloxyethyl) isocyanurate, allylated cyclohexyl di (meth) acrylate, and the like.

As trifunctional (meth) acrylic acid derivatives, there may be mentioned: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, and the like.

As the tetrafunctional (meth) acrylic acid derivative, there may be mentioned: pentaerythritol tetra (meth) acrylate, and the like.

As the pentafunctional (meth) acrylic acid derivative, there may be mentioned: propionic acid modified dipentaerythritol penta (meth) acrylate, and the like.

As hexafunctional (meth) acrylic acid derivatives, there may be mentioned: dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.

The curable component (B) may be used singly or in combination of two or more.

Among these, the curable component (B) is preferably a polyfunctional monomer because a base layer having more excellent heat resistance and solvent resistance can be obtained. The polyfunctional monomer is preferably a difunctional (meth) acrylic derivative from the viewpoints of easy mixing with the polymer component (a), less occurrence of curing shrinkage of the polymer, and suppression of curling of the cured product. When the curable component (B) contains a polyfunctional monomer, the content thereof is preferably 40% by mass or more, more preferably 50 to 100% by mass, and still more preferably 80 to 100% by mass, based on the total amount of the curable component (B).

The curable component (B) preferably contains a cyclized polymerizable monomer. The cyclized polymerizable monomer is a monomer having a property of undergoing radical polymerization while cyclizing.

The cyclized polymerizable monomer can form a linear polymer having a ring structure in the molecule by polymerization, and can improve solvent resistance and heat resistance of the base layer as compared with the conventional monofunctional curable monomer. One of the reasons for this is that the heat resistance of the underlayer can be improved by forming a ring structure in the polymer chain of the cyclized polymerizable monomer, and thus forming a rigid molecule as compared with a conventional linear polymer. In addition, it is considered that in the cyclized polymerizable monomer, molecular design is performed so that intramolecular cyclization reaction selectively occurs, and intermolecular reaction occurs in part of the monomer, and therefore reactive functional groups remain in the structural unit derived from the monomer. The reactive functional group reacts with another monomer to form a branch of a polymer chain, and a crosslinked structure is formed in the polymer of the cyclized polymerizable monomer. Thus, 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 the cyclized polymerizable monomers are formed into linear structures, and the ring structure obtained by the cyclized polymerization is also soft as compared with the aromatic ring, and therefore, the flexibility of the base layer can be also considered, and the base layer exhibits a high elongation at break (i.e., the above-mentioned requirement [2] is easily satisfied).

Specific examples of the cyclized polymerizable monomer include non-conjugated dienes, and for example, an α -allyloxymethyl acrylic monomer represented by the following formula (1) can be used.

[ chemical formula 8]

(in the formula (1), R ⁸ Represents a hydrogen atom or a 1-valent organic group. The organic group may contain hydrocarbon or ether groups. The hydrogen atom of the hydrocarbon may be substituted with a halogen atom. )

The organic group may be branched, or may contain a cyclic structure. The hydrocarbon group contained in the organic group is not particularly limited. Examples of the hydrocarbon group include: a chain saturated hydrocarbon group having 1 or more carbon atoms, a chain unsaturated hydrocarbon group having 3 or more carbon atoms, an alicyclic hydrocarbon group having 3 or more carbon atoms, an aromatic hydrocarbon group having 6 or more carbon atoms, and the like. Of these hydrocarbon groups, preferred are: a chain saturated hydrocarbon group having 1 to 30 carbon atoms, a chain unsaturated hydrocarbon group having 3 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms. The substituent is not particularly limited. Examples of the substituent include: 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. Examples of the chain saturated hydrocarbon group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, sec-octyl, tert-octyl, 2-ethylhexyl, octyl (capryl), nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, hexadecyl, heptadecyl, stearyl, nonadecyl, eicosyl, hexacosyl, triacontyl, and the like.

The chain unsaturated hydrocarbon group is not particularly limited. Examples of the chain unsaturated hydrocarbon group include: crotyl, 1-dimethyl-2-propenyl, 2-methyl-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 2-methyl-3-butenyl, oleyl, linoleyl, octadecatrienyl, and the like.

The alicyclic hydrocarbon group is not particularly limited. Examples of the alicyclic hydrocarbon group include: cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, tricyclodecyl, isobornyl, adamantyl, dicyclopentyl, dicyclopentenyl, and the like.

The aromatic hydrocarbon group is not particularly limited. Examples of the aromatic hydrocarbon group include: phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tert-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, anthracenyl and the like.

The hydrocarbon group having an ether bond is not particularly limited. Examples of the hydrocarbon group having an ether bond include: chain ether groups such as methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, and ethoxyethoxyethyl; cyclopentyloxy ethyl group, cyclohexyloxy ethyl group, cyclopentyloxy ethoxyethyl group, cyclohexyloxyethoxyethyl group, dicyclopentenyloxyethyl group and the like having both alicyclic hydrocarbon groups and alicyclic hydrocarbon groupsA group of a chain ether group; groups having both an aromatic hydrocarbon group and a chain ether group, such as a phenoxyethyl group and a phenoxyethoxyethyl group; glycidyl, beta-methylglycidyl, beta-ethylglycidyl, 3, 4-epoxycyclohexylmethyl, 2-oxetanylmethyl, 3-methyl-3-oxetanylmethyl, 3-ethyl-3-oxetanylmethyl, tetrahydrofuranyl, tetrahydrofurfuryl, tetrahydropyranyl, ditetrahydrofuranyl

Cyclic ether groups such as an oxazolidinyl group and a dioxanyl group.

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

Among them, alkyl esters of 2-allyloxymethyl acrylic acid having 1 to 4 carbon atoms and cyclohexyl 2- (allyloxymethyl) acrylate are preferable, alkyl esters of 2-allyloxymethyl acrylic acid having 1 to 4 carbon atoms are more preferable, and methyl 2- (allyloxymethyl) acrylate is still more preferable.

Examples of other specific cyclized polymerizable monomers include monomers represented by the following formula (2).

[ chemical formula 9]

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

Examples of the cyclized polymerizable monomer represented by formula (2) include: dimethyl 2,2' - [ oxybis (methylene) ] bis-2-propionate, diethyl 2,2' - [ oxybis (methylene) ] bis-2-propionate, di (n-propyl) 2,2' - [ oxybis (methylene) ] bis-2-propionate, di (isopropyl) 2,2' - [ oxybis (methylene) ] bis-2-propionate, di (n-butyl) 2,2' - [ oxybis (methylene) ] bis-2-propionate, di (n-hexyl) 2,2' - [ oxybis (methylene) ] bis-2-propionate, -dicyclohexyl 2,2' - [ oxybis (methylene) ] bis-2-propionate, and the like.

The curable component (B) more preferably contains the above-described polyfunctional (meth) acrylate compound and a cyclized polymerizable monomer. When these are used in combination, the elongation at break of the base layer is easily adjusted to the above range, and at the same time, the heat shrinkage of the base layer is suppressed, and as a result, the heat shrinkage of the gas barrier laminate is easily adjusted to the above range.

In the curable component (B), the mass ratio of the cyclized polymerizable monomer to the polyfunctional (meth) acrylate compound is preferably 95:5 to 30:70, more preferably 90:10 to 35:65, and still more preferably 90:10 to 40:60. By adjusting the mass ratio of the cyclized polymerizable monomer to the polyfunctional (meth) acrylate compound in the above range, it is easier to adjust the elongation at break of the base layer to the above range and adjust the heat shrinkage of the gas barrier laminate to the above range.

[ curable resin composition ]

The curable resin composition for forming the base layer according to the embodiment of the present invention can be prepared by mixing the polymer component (a), the curable component (B), and a polymerization initiator, which will be described later, and other components, which are used as needed, and dissolving or dispersing them in an appropriate solvent.

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

The content of the polymer component (a) and the curable component (B) in the curable resin composition is preferably the mass ratio of the polymer component (a) to the curable component (B), and more preferably the mass ratio of the polymer component (a): the curable component (B) =30:70 to 90:10, and more preferably 35:65 to 80:20.

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

In addition, when the content of the curable component (B) in the curable resin composition is in the above range, for example, in the case where the base layer is obtained by a solution casting method or the like, the solvent can be removed efficiently, and therefore, the problem of deformation such as curling or waviness due to the long-term drying step can be eliminated.

The curable resin composition may contain a polymerization initiator as needed. The polymerization initiator may be used without particular limitation as long as it is a component that initiates a curing reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.

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

Examples of the organic peroxide include: dialkyl peroxides such as di-t-butyl peroxide, t-butylcumene peroxide, and dicumyl peroxide; diacyl peroxides such as acetyl peroxide, lauroyl peroxide, benzoyl peroxide, etc.; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3, 5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; peroxy ketals such as 1, 1-bis (t-butylperoxy) cyclohexane; hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, 1, 3-tetramethylbutyl hydroperoxide, terpene hydroperoxide, diisopropylbenzene hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydroxide; peroxyesters such as t-butyl peroxyacetate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxybenzoate, and t-butyl peroxyisopropyl carbonate; etc.

Examples of the azo compound include: 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis (2-cyclopropylpropionitrile), 2' -azobis (2, 4-dimethylvaleronitrile), azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 1' -azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2, 4-dimethylvaleronitrile and the like.

As the photopolymerization initiator, there may be mentioned: 2, 2-dimethoxy-1, 2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy)Radical) phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl]Phenyl group]-2-methyl-propan-1-one, 2-methyl-1- (4-methylsulfanyl-phenyl) -2-morpholinopropan-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 alkyl benzophenone photopolymerization initiators; phosphorus photopolymerization initiators such as 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phenylphosphonate, and bis (2, 6-dimethoxybenzoyl) -2, 4-trimethyl-pentylphosphine oxide; bis (eta) ⁵ -2, 4-cyclopentadienyl-1-yl) -bis [2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl]Titanium and other titanocene photopolymerization initiators; 1, 2-octanedione-1- [4- (phenylthio) -2- (O-benzoyl oxime)]1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]Oxime ester photopolymerization initiators such as ethanone-1- (O-acetooxime); benzophenone photopolymerization initiators such as benzophenone, p-chlorobenzophenone, benzoyl benzoic acid, methyl o-benzoyl benzoate, 4-methylbenzophenone, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 '-methyl-diphenyl sulfide, 3' -dimethyl-4-methoxybenzophenone, 2,4, 6-trimethylbenzophenone, 4- (13-acryl-1, 4,7,10, 13-pentaoxatridecyl) -benzophenone; thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone; etc.

Among the above photopolymerization initiators, phosphorus photopolymerization initiators such as 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phenylphosphonate, and bis (2, 6-dimethoxybenzoyl) -2, 4-trimethyl-pentylphosphine oxide are preferable.

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 phosphorus photopolymerization initiator, the curing reaction can be efficiently performed by using light having a wavelength which is not absorbed by the polymer component (a).

The polymerization initiator may be used singly or in combination of two or more.

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

The curable resin composition may contain a photopolymerization initiator aid such as triisopropanolamine or 4,4' -diethylaminobenzophenone in addition to the polymer component (a), the curable component (B), and the polymerization initiator.

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

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

The curable resin composition may further contain known additives such as plasticizers, antioxidants, and ultraviolet absorbers within a range that does not impair the objects and effects of the present invention.

The method of curing the curable resin composition may be appropriately determined depending on the type of the polymerization initiator and the curable monomer used. Details of the method for producing the gas barrier laminate of the present invention will be described below.

[ Properties of basal lamina ]

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

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

By forming the base layer suitable for the above-described requirement [1] while satisfying the requirement [2' ], deformation of the base layer due to heating can be suppressed, and as a result, the gas barrier properties of the gas barrier laminate can be improved, and 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, and is usually 20% or less, preferably 15% or less.

Here, if a cyclized polymerizable monomer is used, the elongation at break can be increased while maintaining the elastic modulus at high temperature at a high level, so that it is easy to satisfy the requirement [2' ]. On the other hand, if the curable component (B) is a cyclized polymerizable monomer in its entirety, the gas barrier properties of the gas barrier laminate tend to be lowered. The present inventors have found through repeated studies that the decrease in gas barrier properties can be suppressed by controlling the absolute value of the heat shrinkage within a certain range. This is considered to be because the underlayer is easily affected by heat, and therefore, the underlayer is deformed in the plane direction by heating when forming the gas barrier layer by coating, for example, and the above phenomenon can be suppressed by selecting a material or the like so that the heat shrinkage rate falls within a predetermined range.

In order to satisfy the requirement [2' ], the following method is effective: for example, the elongation characteristics of the underlayer can be improved by using a polyimide resin as the polymer component (a), by introducing a soft skeleton by further adding a polyamide resin or the like, by increasing the molecular weight of the polymer component (a), or by using a cyclized polymerizable monomer as the curable component (B) to reduce the ratio of aromatic rings present.

Further, for example, a base layer suitable for the above-mentioned element [1] can be obtained by adding a network structure by using a polyfunctional (meth) acrylate compound in combination with a cyclized polymerizable monomer, or selecting a component having a high glass transition temperature and rigidity typified by a polyimide resin as the polymerizable component (a).

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

When the base layer is formed to have a thickness of, for example, about 0.1 to 10 μm, 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, in applications such as an organic EL display in which a thin thickness is required, the gas barrier laminate is preferable because it does not cause an increase in the thickness of the entire application device. In addition, if the gas barrier laminate is thin, the flexibility and bending resistance after the gas barrier laminate is mounted can be improved.

The solvent resistance of the base layer is excellent. Since the solvent resistance is excellent, for example, even when an organic solvent is used in forming other layers on the surface of the underlayer, the surface of the underlayer is not substantially dissolved. Therefore, even when the gas barrier layer is formed using a resin solution containing an organic solvent on the surface of the underlayer, for example, the component of the underlayer is less likely to be mixed into the gas barrier layer, and therefore the gas barrier property is less likely to be degraded.

From this viewpoint, the gel fraction of the base layer is preferably 90% or more, more preferably 94% or more. Since the base layer having a gel fraction of 90% or more has excellent solvent resistance, even when an organic solvent is used for forming other layers on the surface of the base layer by coating, the surface of the base layer is not substantially dissolved, and a gas barrier laminate having excellent solvent resistance can be easily obtained.

Here, the gel fraction was obtained as follows: the substrate layer cut into 100mm×100mm was wrapped with a 150mm×150mm nylon net (# 120) of which mass was measured in advance, immersed in toluene (100 mL) for 3 days, taken out, dried at 120 ℃ for 1 hour, left at 23 ℃ for 50% relative humidity for 3 hours, and then subjected to conditioning, and the mass was measured to obtain a gel fraction by the following formula.

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

The interlayer adhesion between the base layer and the gas barrier layer is excellent. That is, the gas barrier layer may be formed without providing a tie coat layer on the base layer.

The base layer is preferably colorless and transparent. The gas barrier laminate according to the embodiment of the present invention can be preferably used for optical applications by making the base layer colorless and transparent.

The base layer has a low birefringence and excellent optical isotropy. The retardation in the plane of the underlayer is usually 20nm or less, preferably 15nm 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 underlayer (birefringence) is usually 100×10 ^-5 Hereinafter, it is preferably 20X 10 ^-5 The following is given.

When the in-plane retardation, the thickness-direction retardation, and the birefringence of the underlayer are within the above ranges, a gas barrier laminate having a low birefringence and excellent optical isotropy can be obtained, and the gas barrier laminate according to the embodiment of the present invention can be preferably used for optical applications.

The absolute value of the heat shrinkage of the base layer is 0.5% or less, preferably 0.3% or less, and more 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, still more preferably 2.7% or more, and particularly preferably 3.0% or more. When the elongation at break of the base layer is 2.5% or more, the elongation at break of the gas barrier laminate is easily adjusted to a level of 2% or more, and as a result, a gas barrier laminate excellent in bending resistance and flexibility is easily obtained.

The tensile modulus of the base layer at 130℃is preferably 1.0X10 ³ MPa or more, 1.3X10 ³ MPa or more, more preferably 1.5X10 ³ MPa or more, more preferably 2.0X10 ³ And more than MPa.The tensile modulus of the base layer at 130℃was 1.3X10 ³ When the pressure is equal to or higher than MPa, the heat resistance of the base layer can be improved, and the gas barrier layer of the gas barrier laminate has a low water vapor transmission rate, and specifically, can easily achieve a water vapor transmission rate of 1×10 ^-2 (g·m ^-2 ·day ^-1 ) The following is given.

The base layer is excellent in heat resistance, solvent resistance, interlayer adhesion, and transparency, and is low in birefringence and excellent in optical isotropy as described above. Therefore, as described later, by forming a gas barrier layer on a base layer having such characteristics by, for example, a solution casting method, the gas barrier layer can be made to exhibit excellent gas barrier properties, and also, it is possible to prevent the gas barrier properties from being impaired by at least one of heat and a solvent due to at least one of heat resistance and solvent resistance of the base layer. Further, the obtained gas barrier laminate can be made excellent in heat resistance, interlayer adhesion and transparency. Further, a gas barrier laminate having a low birefringence and excellent optical isotropy can be obtained.

1-2 gas barrier layer

The material and the like of the gas barrier layer of the gas barrier laminate according to the embodiment of the present invention are not particularly limited as long as the gas barrier layer has gas barrier properties. For example, there may be mentioned: a gas barrier layer formed of an inorganic film, a gas barrier layer containing a gas barrier resin, a gas barrier layer obtained by modifying a layer containing a polymer compound, and the like.

Among these, the gas barrier layer is preferably a gas barrier layer formed of an inorganic film or a gas barrier layer obtained by modifying a layer containing a polymer compound, in view of being able to efficiently form a thin layer having excellent gas barrier properties and solvent resistance.

The inorganic film is not particularly limited, and examples thereof include inorganic vapor deposition films.

Examples of the inorganic vapor-deposited film include: an inorganic compound and a metal.

Examples of the material of the vapor deposition film of the inorganic compound include: inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride; an inorganic carbide; an inorganic sulfide; inorganic nitrogen oxides such as silicon oxynitride; an inorganic carbon oxide; an inorganic carbonitride; inorganic carbon nitrogen oxides, and the like.

Examples of the raw material of the metal vapor deposited film include: aluminum, magnesium, zinc, tin, and the like.

These materials may be used singly or in combination of two or more.

Among these, from the viewpoint of gas barrier properties, an inorganic vapor-deposited film using an inorganic oxide, an inorganic nitride, or a metal as a raw material is preferable, and from the viewpoint of transparency, an inorganic vapor-deposited film using an inorganic oxide or an inorganic nitride as a raw material is preferable. The inorganic deposition film may be a single layer or a plurality of layers.

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

As a method for forming the inorganic vapor deposited film, there can be mentioned: PVD (physical vapor deposition) methods such as vacuum vapor deposition, sputtering, ion plating, thermal CVD (chemical vapor deposition), plasma CVD, and photo CVD.

In the gas barrier layer including the gas barrier resin, the gas barrier resin used may be: polyvinyl alcohol, or a partially saponified product thereof, an ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, and polytrifluoroethylene, etc., which are not easily permeable to oxygen, etc.

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

As a method for forming the gas barrier layer containing the gas barrier resin, a method of applying a solution containing the gas barrier resin to the base layer and appropriately drying the obtained coating film can be mentioned.

The polymer compound used 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 may be: silicon-containing polymer compounds, polyimide, polyamide, polyamideimide, polyphenylene oxide, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, and the like. These polymer compounds may be used singly or in combination of two or more.

Among them, the polymer compound is preferably a silicon-containing polymer compound. The silicon-containing polymer compound may be: polysilazane compounds (see Japanese patent application laid-open No. 63-16325, japanese patent application laid-open No. 62-195024, japanese patent application laid-open No. 63-81122, japanese patent application laid-open No. 1-138108, japanese patent application laid-open No. 2-84437, japanese patent application laid-open No. 2-175726, japanese patent application laid-open No. 4-63833, japanese patent application laid-open No. 5-238827, japanese patent application laid-open No. 5-345826, japanese patent application laid-open No. 2005-36089, japanese patent application laid-open No. 6-122852, japanese patent application laid-open No. 6-299118, japanese patent application laid-open No. 6-306329, japanese patent application laid-open No. 9-31333, japanese patent application laid-open No. 10-245436, japanese patent application laid-open No. 2003-514822, international publication WO2011/107018 and the like), polycarbosilane compounds (see 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 laid-open No. 51-126300, japanese patent application laid-open No. 2001-328991, japanese patent application laid-open No. 2006-117917, japanese patent application laid-open No. 2009-286891, japanese patent application laid-open No. 2010-106100, etc.), polysilanes (see R.D.Miller, J.Michl; chemical Review, volume 89, page 1359 (1989), n.matsumoto; japanese Journal of Physics, volume 37, page 5425 (1998), japanese patent application laid-open No. 2008-63586, japanese patent application laid-open No. 2009-235358, etc.), and polyorganosiloxane compounds (see Japanese patent application laid-open No. 2010-229445, japanese patent application laid-open No. 2010-232569, etc.), japanese patent application laid-open No. 2010-238736, etc.), and the like.

Among them, polysilazane compounds are preferable from the viewpoint of forming a gas barrier layer having excellent gas barrier properties. As polysilazane compounds, there may be mentioned: inorganic polysilazane, organic polysilazane. Examples of the inorganic polysilazane include perhydro polysilazane, and examples of the organic polysilazane include compounds in which part or all of hydrogen in the perhydro polysilazane is substituted with an organic group such as an alkyl group. Among them, inorganic polysilazane is more preferable from the viewpoints of easy acquisition and formation of a gas barrier layer having excellent gas barrier properties.

The polysilazane compound may be used as it is as a commercially available product such as a glass coating material.

The polysilazane compound may be used singly or in combination of two or more.

The polymer layer may contain other components in addition to the polymer compound described above, as long as the object of the present invention is not impaired. As other components, there may be mentioned: curing agents, other polymers, antioxidants, light stabilizers, flame retardants, and the like.

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

Examples of the method for forming the polymer layer include: a method in which a layer-forming solution containing at least one polymer compound, other components used if necessary, a solvent, and the like is applied to a base layer or an undercoat layer formed on the base layer if necessary by a known method, and the obtained coating film is appropriately dried to form a polymer layer.

In the case of applying the layer forming solution, a known apparatus such as a spin coater, a blade coater, or a gravure coater can be used.

In order to dry the obtained coating film or to improve the gas barrier property of the gas barrier laminate, the coating film is preferably heated. As the heating and drying method, conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used. The heating temperature is usually 80 to 150 ℃, and the heating time is usually tens of seconds to tens of minutes.

In the case of forming a gas barrier layer of a gas barrier laminate, for example, in the case of using the polysilazane compound as described above, a polysilazane conversion reaction occurs by heating after coating, and a coating film excellent in gas barrier properties is obtained.

On the other hand, when a base layer having low heat resistance is used, there is a risk that the base layer is deformed by heating at the time of forming such a coating film. Deformation of the base layer may adversely affect the gas barrier properties of the gas barrier layer of the gas barrier laminate. However, since the base layer according to the embodiment of the present invention is excellent in heat resistance, deformation is not caused even by heating during and after application. Therefore, the reduction of the gas barrier properties of the gas barrier laminate caused by the deformation of the base layer can also be avoided.

The thickness of the polymer layer is usually 20 to 1,000nm, preferably 30 to 800nm, more preferably 40 to 400nm.

Even if the thickness of the polymer layer is nano-scale, a gas barrier laminate having sufficient gas barrier properties can be obtained by performing a modification treatment as described later.

The polymer layer is preferably a layer obtained by modifying a coating film of a composition containing a silicon compound. When the polymer layer is a layer obtained by modifying a coating film of a composition containing a silicon compound, it can be formed into a layer having higher flexibility than an inorganic film formed by vapor deposition or sputtering, for example.

The modification treatment includes ion implantation, vacuum ultraviolet irradiation, and the like. Among them, ion implantation is preferable in terms of obtaining high gas barrier properties. In the ion implantation, the amount of ions to be implanted into the polymer layer may be appropriately determined depending on the purpose of use (necessary gas barrier property, transparency, etc.) of the formed gas barrier laminate, and the like.

As the implanted ions, there may be mentioned: ions of rare gases such as argon, helium, neon, krypton, and xenon; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, and the like; ions of an alkane gas such as methane, ethane, propane, butane, pentane, hexane, etc.; ions of olefin gases such as ethylene, propylene, butene, and pentene; ions of an alkane-diene gas such as pentadiene or butadiene; ions of alkyne gases such as acetylene and methylacetylene; ions of aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene, and phenanthrene; ions of cycloalkane-based gases such as cyclopropane and cyclohexane; ions of cycloolefin gases such as cyclopentene and cyclohexene;

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

silane (SiH) ₄ ) Or ions of organosilicon compounds; etc.

As the organosilicon compound, there may be mentioned: tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, and the like;

unsubstituted or substituted alkylalkoxy silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and (3, 3-trifluoropropyl) trimethoxysilane;

aryl alkoxy silanes such as diphenyl dimethoxy silane and phenyl triethoxy silane;

disiloxane such as Hexamethyldisiloxane (HMDSO);

aminosilanes such as bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, diethylaminotrimethylsilane, dimethylaminodimethylsilane, tetramethylamino silane, and tris (dimethylamino) silane;

silazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethyltetrasilazane, tetramethyldisilazane, and the like;

Cyanato silanes such as tetraisocyanato silane;

halosilanes such as triethoxyfluorosilane;

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

unsubstituted or substituted alkylsilanes such as di-t-butylsilane, 1, 3-disilyltetrasilane, bis (trimethylsilyl) methane, tetramethylsilane, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, and benzyltrimethylsilane;

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

silyl olefins such as 1, 4-bis (trimethylsilyl) -1, 3-diacetylene and cyclopentadienyl trimethylsilane;

aryl alkyl silanes such as phenyl dimethyl silane and phenyl trimethyl silane;

alkynyl alkylsilanes such as propynyl trimethylsilane;

alkenyl alkylsilanes such as vinyl trimethylsilane;

disilanes such as hexamethyldisilane;

siloxanes such as octamethyl cyclotetrasiloxane, tetramethyl cyclotetrasiloxane, and hexamethylcyclotetrasiloxane;

n, O-bis (trimethylsilyl) acetamide;

bis (trimethylsilyl) carbodiimide; etc.

These ions may be used singly or in combination of two or more.

Among them, at least one ion selected from the group consisting of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton is preferable in that the implantation can be performed more easily, and particularly, a gas barrier layer having excellent gas barrier properties can be obtained.

The method of implanting ions is not particularly limited, and examples thereof include: a method of irradiating ions (ion beam) accelerated by an electric field, a method of implanting ions into plasma, and the like. Among them, the latter method of implanting plasma ions is preferable in view of the easiness of obtaining a film having gas barrier properties.

As the plasma ion implantation method, preferable is: (alpha) a method of implanting ions present in a plasma generated using an external electric field into a polymer layer; or (beta) a method of implanting ions present in the plasma generated by the electric field generated by the negative high-voltage pulse applied to the above layer, into the polymer layer without using an external electric field.

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

The method (beta) does not need to improve the vacuum degree, has simple and convenient treatment operation and can greatly shorten the treatment time. In addition, the entire layer can be uniformly treated, and ions in the plasma can be continuously injected into the polymer layer with high energy when a negative high voltage pulse is applied. In addition, a radio frequency (hereinafter, abbreviated as "RF") power source or other special means such as a Radio Frequency (RF) power source or a microwave source is not required, and ions of high quality can be uniformly injected into the polymer layer only by applying a negative high voltage pulse to the layer.

In either of the above methods (α) and (β), the pulse width at the time of applying a negative high voltage pulse, that is, at the time of ion implantation is preferably 1 to 15 μsec. When the pulse width is in such a range, ions can be implanted more simply and uniformly with good efficiency.

The voltage applied at the time of plasma generation is preferably-1 to-50 kV, more preferably-1 to-30 kV, and particularly preferably-5 to-20 kV. When ion implantation is performed at a value of an applied voltage of less than-1 kV, the ion implantation amount (dose) becomes insufficient, and it is difficult to obtain desired performance. On the other hand, when ion implantation is performed at a value of more than-50 kV, the film is charged during ion implantation, and defects such as coloring of the film are likely to occur, which is not preferable.

As ion species to be subjected to plasma ion implantation, those exemplified as the implanted ions described above are exemplified.

When ions in the plasma are injected into the polymer layer, a plasma ion injection device is used.

Specific examples of the plasma ion implantation apparatus include: (i) A device that applies a high-frequency power to a polymer layer (hereinafter also referred to as "layer to be ion-implanted") and applies a negative high-voltage pulse to feed through the layer to be ion-implanted so that the periphery of the layer to be ion-implanted is uniformly surrounded by plasma, thereby inducing, implanting, colliding, and depositing ions in the plasma (japanese patent application laid-open No. 2001-26887); (ii) An apparatus for generating plasma by providing an antenna in a chamber and applying high-frequency power, alternately applying positive and negative pulses to a layer to be ion-implanted after the plasma reaches the periphery of the layer to be ion-implanted, thereby heating the layer to be ion-implanted by causing electrons in the plasma to collide with each other by the positive pulse, controlling a pulse constant, and controlling a temperature, and simultaneously applying a negative pulse to induce and implant ions in the plasma (japanese patent application laid-open No. 2001-156013); (iii) A plasma ion implantation device for generating plasma by using an external electric field such as a high-frequency power source such as a microwave, and inducing and implanting ions in the plasma by applying a high-voltage pulse; (iv) A plasma ion implantation apparatus or the like that uses only ion implantation in a plasma generated by an electric field generated by applying a high voltage pulse without using an external electric field.

Among these apparatuses, the plasma ion implantation apparatus of (iii) or (iv) is preferably used because the treatment operation is simple, the treatment time can be greatly shortened, and the apparatus is suitable for continuous use.

The method using the plasma ion implantation apparatus of (iii) and (iv) may be the method described in International publication No. WO 2010/021326.

In the plasma ion implantation apparatuses (iii) and (iv), the plasma generating means for generating plasma is also used as the high-voltage pulse power source, and therefore, other special means such as RF, microwave, and the like are not required, and ions in the plasma can be continuously implanted into the polymer layer by simply generating plasma by applying a negative high-voltage pulse, and mass production of the gas barrier laminate in which the polymer layer having a portion modified by ion implantation on the surface, that is, the gas barrier layer, is formed can be achieved.

The thickness of the portion to be implanted with ions may be controlled by the type of ions, the applied voltage, the treatment time, and other implantation conditions, and may be determined according to the thickness of the polymer layer, the purpose of use of the gas barrier laminate, and the like, and is usually 5 to 1,000nm.

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

The gas barrier layer was confirmed to have gas barrier properties based on the low water vapor permeability.

The gas barrier layer has a water vapor permeability of usually 1.0g/m in a gas atmosphere having a relative humidity of 90% at 40 DEG C ² Less than/day, preferably 0.8g/m ² Less than/day, more preferably 0.5g/m ² Preferably less than/day, more preferably 0.1g/m ² And/day or less. The water vapor permeability can be measured by a known method.

1-3 Process film

The process film is a film which has a function of protecting the base layer, the gas barrier layer, and the other layers described above when the gas barrier laminate is stored or transported, and is peeled off in a given step.

When the gas barrier laminate has a process film, the gas barrier laminate may have a process film on one side or may have a process film on both sides. In the latter case, it is preferable to use two process films and make the process film to be peeled off first a material that is more easily peeled off. When the process film is provided on the base layer side, a gas barrier laminate having higher handleability while protecting the base layer than a gas barrier laminate having no process film can be obtained.

The process film is preferably a sheet-like or film-like film. The sheet-like or film-like shape is not limited to the long strip shape, and includes a rectangular flat plate shape.

As the process film, there may be mentioned: paper substrates such as cellophane, coated paper, and fine paper; laminated paper obtained by laminating thermoplastic resins such as polyethylene and polypropylene on these paper substrates; a material obtained by subjecting the paper base material to a caulking treatment with cellulose, starch, polyvinyl alcohol, acrylic-styrene resin or the like; or a plastic film such as a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or a polyolefin film such as polyethylene or polypropylene; glass, and the like.

In addition, the process film may be a material having a release agent layer provided on a paper base material or a plastic film, in terms of ease of handling. The release agent layer may 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. Mu.m, more preferably 0.05 to 1.5. Mu.m.

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

The surface roughness Ra (arithmetic average roughness) of the process film is preferably 10.0nm or less, more preferably 8.0nm or less. The surface roughness Rt (maximum cross-sectional height) is preferably 100nm or less, more preferably 50nm or less.

When the surface roughness Ra and Rt exceeds 10.0nm and 100nm, respectively, the surface roughness of the layer in contact with the process film may be increased, and the gas barrier properties of the gas barrier laminate may be lowered.

The surface roughness Ra and Rt are values obtained by an optical interferometry method with a measurement area of 100 μm×100 μm.

1-4 gas barrier laminate

As described above, the gas barrier laminate according to the embodiment of the present invention includes the process film, the base layer, and the gas barrier layer in this order. In practical use of the gas barrier laminate, the process film is peeled from the gas barrier laminate and attached to a display or an electronic device.

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

In order to satisfy the requirement [1], for example, the network structure may be increased by using a polyfunctional (meth) acrylate compound and a cyclized polymerizable monomer in combination as described above as the curable component (B) contained in the curable resin composition for forming the base layer, or a component having a rigid but soft structure typified by a polyimide resin may be selected as the polymerizable component (a).

As described above, the gas barrier laminate according to the embodiment of the present invention satisfies the following requirement [2].

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

The elongation at break of the gas barrier laminate is preferably 2.0% or more. By setting the elongation at break of the gas barrier laminate 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 is usually 17% or less, preferably 13% or less.

Since the thickness of the gas barrier layer is generally significantly smaller 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 a value close to the elongation at break of the base layer. Therefore, if the base layer satisfies the requirement [2' ], even if the gas barrier laminate has a somewhat smaller elongation at break than the base layer due to the influence of the gas barrier layer or the like, a gas barrier laminate satisfying the requirement [2] is easily obtained.

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

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

The base layer according to the embodiment of the present invention may be a layer having excellent flexibility, and when the thickness of the gas barrier laminate is further reduced, the bending resistance of the gas barrier laminate after being mounted may be further improved.

The gas barrier laminate according to the embodiment of the present invention has the above-described underlayer and gas barrier layer, and therefore is excellent in heat resistance, solvent resistance, interlayer adhesiveness, and gas barrier properties, low in birefringence, and excellent in optical isotropy. The in-plane phase difference of the gas barrier laminate is usually 20nm or less, preferably 15nm 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 phase difference by the thickness of the gas barrier laminate (birefringence) is usually 100×10 ^-5 Hereinafter, it is preferably 20X 10 ^-5 The following is given.

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

The gas barrier laminate according to the embodiment of the present invention has a water vapor transmission rate of usually 1.0X10 s in a gas atmosphere having a relative humidity of 90% at 40 ℃ ^-2 g/m ² Preferably 8.0X10 times or less per day ^-3 g/m ² Less than/day, more preferably 6.0X10 ^-3 g/m ² And/day or less.

The gas barrier laminate according to the embodiment of the present invention includes a base layer and a gas barrier layer on at least one surface of the base layer. The gas barrier laminate according to the embodiment of the present invention may have 1 layer each of the base layer and the gas barrier layer, or may have 2 or more base layers and/or gas barrier layers.

A specific structure of the gas barrier laminate according to the embodiment of the present invention is shown in fig. 1, for example.

The gas barrier laminate (10) shown in fig. 1 is a laminate having a gas barrier layer (3) on one surface of a base layer (2) and a process film (1) on the surface of the base layer (2) opposite to the gas barrier layer (3). When the process film (1) is peeled off and removed, the part indicated by the symbol 10a, which includes the base layer (2) and the gas barrier layer (3), becomes a gas barrier laminate after the removal of the process film.

The gas barrier laminate according to the embodiment of the present invention is not limited to the laminate shown in fig. 1, and may have gas barrier layers on both surfaces of the base layer, or may be a laminate in which a plurality of groups of the base layer and the gas barrier layer are laminated. Further, the laminate may further have 1 layer or 2 or more layers within a range not to impair the object of the present invention.

As the other layer, for example, there may be mentioned: a conductor layer, an impact absorbing layer, an adhesive layer, a bonding layer, a process sheet, and the like. The arrangement position of the other layers is not particularly limited.

As a material constituting the conductor layer, there can be mentioned: metals, alloys, metal oxides, conductive compounds, mixtures thereof, and the like. Specific examples thereof include: doped with Antimony Tin Oxide (ATO); fluorine doped tin oxide (FTO); semiconductive metal oxides such as tin oxide, germanium-doped zinc oxide (GZO), zinc oxide, indium Tin Oxide (ITO), and zinc indium oxide (IZO); metals such as gold, silver, chromium, nickel, etc.; mixtures of these metals with conductive metal oxides; inorganic conductive materials such as copper iodide and copper sulfide; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; etc.

The method of forming the conductor layer is not particularly limited. Examples include: vapor deposition, sputtering, ion plating, thermal CVD, plasma CVD, and the like.

The thickness of the conductor layer may be appropriately selected according to the application and the like. Usually 10nm to 50. Mu.m, preferably 20nm to 20. Mu.m.

The impact absorbing layer is a layer for protecting 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, rubber materials, and the like.

The method of forming the impact absorbing layer is not particularly limited, and examples thereof include: and a method in which an impact absorbing layer is formed by applying an impact absorbing layer forming solution containing the above material for forming an impact absorbing layer and other components such as a solvent, if necessary, to the layers to be laminated, drying the obtained coating film, and heating, if necessary.

Alternatively, the impact absorbing layer may be formed on a separate release substrate, and the resulting film may be transferred to a layer to be laminated.

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

The adhesive layer is a layer used when the gas barrier laminate is adhered to an adherend. The material for forming the adhesive layer is not particularly limited, and a known adhesive, an adhesive, a heat sealing material, or the like of acrylic, silicone, rubber, or the like may be used.

The bonding layer is a layer used in the case of manufacturing a gas barrier laminate by combining a plurality of layers with a base layer and a gas barrier layer. The bonding layer is a layer for bonding the base layer contained in one of the adjacent groups to the gas barrier layer contained in the other group to maintain the laminated structure. The bonding layer may be a single layer or a plurality of layers. As the bonding layer, there may be mentioned: the support layer is formed by forming a layer formed by using an adhesive on both sides of the support layer.

The material used for forming the bonding layer is not particularly limited as long as it is a material capable of bonding the groups of the base layer and the gas barrier layer to each other to maintain the laminated structure, and a known adhesive may be used, but an adhesive is preferable in view of being capable of bonding the groups of the base layer and the gas barrier layer to each other at normal temperature.

As the adhesive for the bonding layer, there may be mentioned: acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, and the like. Among them, acrylic adhesives and urethane adhesives are preferable from the viewpoints of adhesion, transparency and handleability. In addition, an adhesive capable of forming a crosslinked structure as described later is preferable.

The adhesive may be any of solvent-based adhesives, emulsion-based adhesives, hot melt-based adhesives, and the like.

2. Method for producing gas barrier laminate

The gas barrier laminate according to the embodiment of the present invention is produced using a process film. By using the process film, a gas barrier laminate can be produced efficiently and easily. Particularly preferred is a method comprising the following steps 1 to 3.

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

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

And step 3: a step of forming a gas barrier layer on the underlayer obtained in step 2

Fig. 2 shows an example of a process for producing the gas barrier laminate according to the embodiment of the present invention. Fig. 2 (a) corresponds to the step 1, fig. 2 (b) corresponds to the step 2, and fig. 2 (c) corresponds to the step 3.

(Process 1)

First, a curable resin composition containing a polymer component (a) having a Tg of 250 ℃ or higher and a curable component (B) is used for a process film to form a curable resin layer (symbol 2a in fig. 2 a).

The process film and the curable resin composition used may be the same as those described above.

The method of applying the curable resin composition to the process film is not particularly limited, and may be used: known coating methods such as spin coating, spray coating, bar coating, doctor blade coating, roll coating, knife coating, die coating, and gravure coating.

The method for drying the obtained coating film is not particularly limited, and conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used. As described above, the curable resin composition for forming the base layer according to the embodiment of the present invention contains the polymer component (a) having a very high Tg, and by containing the curable component (B), the solvent can be efficiently removed when the coating film obtained by the solution casting method is dried.

The drying temperature of the coating film is usually 30 to 150℃and preferably 50 to 100 ℃.

The thickness of the dried coating film (curable resin layer) is not particularly limited, and is not substantially different from the thickness after the occurrence of curing, and therefore, the thickness of the dried coating film (curable resin layer) may be the same as that of the above-mentioned base layer.

(Process 2)

Next, the curable resin layer obtained in step 1 is cured to form a cured resin layer. The cured resin layer becomes a base layer (symbol 2 in fig. 2 (b)).

The method for curing the curable resin layer is not particularly limited, and a known method can be used. For example, in the case where the curable resin layer is a layer 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℃and preferably 50 to 100 ℃.

In addition, in the case where the curable resin layer is a layer formed using a curable resin composition containing a photopolymerization initiator, the curable resin layer can be cured by irradiation of active energy rays to the curable resin layer. The active energy rays may be irradiated using a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like.

The wavelength of the active energy ray is preferably 200 to 400nm, more preferably 350 to 400nm. The irradiation amount is usually 50 to 1,000mW/cm ² The light quantity is 50-5,000 mJ/cm ² Preferably 1,000 to 5,000mJ/cm ² Is not limited in terms of the range of (a). The irradiation time is usually 0.1 to 1,000 seconds, preferably 1 to 500 seconds, and more preferably 10 to 100 seconds. In view of the heat load of the illumination step, the irradiation may be performed a plurality of times so as to satisfy the light quantity.

In this case, in order to prevent deterioration of the polymer component (a) and coloration of the underlayer due to irradiation of active energy rays, the curable resin composition may be irradiated with active energy rays through a filter that absorbs light of a wavelength unnecessary for the curing reaction. According to this method, light having a wavelength which is not required for the curing reaction and which causes degradation of the polymer component (a) can be absorbed by the filter, and thus degradation of the polymer component (a) can be suppressed, and a colorless transparent base layer can be easily obtained.

As the filter, a resin film such as a polyethylene terephthalate film can be used. When a resin film is used, a step of laminating a resin film such as a polyethylene terephthalate film on the curable resin layer is preferably provided between the step 1 and the step 2. The resin film is usually peeled off after step 2.

The curable resin layer may be cured by irradiating the curable resin layer with an electron beam. When the electron beam is irradiated, the curable resin layer can be cured, usually without using a photopolymerization initiator. In the case of irradiating an electron beam, an electron beam accelerator or the like may be used. The irradiation amount 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 curable resin layer may be cured in an inert gas atmosphere such as nitrogen gas, if necessary. By curing in an inert gas atmosphere, the curing is easily prevented from being hindered by oxygen, moisture, or the like.

(step 3)

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

As a method for forming the gas barrier layer, the method described above can be suitably employed.

For example, in the case where the gas barrier layer is a layer obtained by subjecting a layer containing a silicon-containing polymer compound to a modification treatment, the gas barrier layer may be formed by a step of forming a layer containing a silicon-containing polymer compound on the underlayer and a step of subjecting the layer containing a silicon-containing polymer compound to a modification treatment.

The gas barrier layer contained in the gas barrier laminate may be formed by various methods such as extrusion molding and coating, but depending on the method of forming the gas barrier layer, the gas barrier performance of the gas barrier laminate may be lowered. In particular, when the gas barrier layer is formed by a formation method involving heating, for example, coating and drying, there is a risk that the substrate layer is physically or chemically affected and the properties such as gas barrier properties are lowered.

However, as described above, the base layer according to the embodiment of the present invention is a layer formed from a cured product of a curable resin composition containing the polymer component (a) and the curable component (B), and the Tg of the polymer component (a) is 250 ℃ or higher, and therefore, the base layer is less likely to be affected by heating at the time of forming the gas barrier layer. Therefore, the gas barrier layer formed is less susceptible to the deformation of the base layer in the manufacturing process, and the gas barrier layer is less susceptible to the occurrence of, for example, a problem of deterioration in gas barrier properties due to the occurrence of microcracks or the like.

As a method for forming the layer containing the silicon-containing polymer compound and a method for performing the modification treatment, the methods described above can be used.

Further, as a method for performing the modification treatment, it is preferable to manufacture a gas barrier laminate by performing the modification treatment on the layer containing the silicon-containing polymer while conveying the elongated film formed with the layer containing the silicon-containing polymer in a predetermined direction on the base layer obtained in the step 2.

According to this production method, for example, an elongated gas barrier laminate can be produced continuously.

The process film is generally peeled off in a predetermined step according to the use of the gas barrier laminate, and the like, to form a gas barrier laminate (10 a) from which the process film (3) is removed as shown in fig. 2 (c). For example, the process film may be peeled off after forming another layer or the like after the step 3, or the process film may be peeled off after the step 3. The process film may be peeled off between the step 2 and the step 3.

As described above, the production method having the steps 1 to 3 is a method of forming a curable resin layer using a process film, and the gas barrier laminate obtained by this method may or may not have a process film.

According to the above-described method for producing a gas barrier laminate, the gas barrier laminate according to the embodiment of the present invention can be produced continuously and easily with good efficiency.

Examples

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

The physical properties of the base layer and the gas barrier laminate in each of examples and comparative examples were measured and evaluated in the following order.

< solvent resistance of base layer >

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

A: no change occurs.

B: there appears to be a slight change in shape, but there is no practical problem.

C: appearance changes such as whitening, swelling, curling, waving, etc. occur, and practical use is hindered.

< Heat shrinkage of gas Barrier laminate >

The gas barrier laminate was cut into test pieces of 5mm×30mm, and the 1 st polyethylene terephthalate (PET) film corresponding to the base layer side of the process film was peeled off and removed, and the gap between the jigs was set to 20mm using a thermo-mechanical analyzer TMA4000SE (NETZSCH Japan corporation), and then heated to 130 ℃ at 5 ℃/min, and then cooled to room temperature at 5 ℃/min. The rate of change in displacement in the longitudinal direction before and after heating (a value indicating a ratio of the displacement amount to the jig pitch of 20mm in percent) was taken as the heat shrinkage rate. The gas barrier laminate was set to a negative value when shrinkage occurred and to a positive value when elongation occurred.

< Water Vapor Transmission Rate (WVTR) >, of gas Barrier laminate

Cutting the gas barrier laminate into 50cm ² Area ofThe water vapor permeability (g/m) was measured at a gas flow rate of 20sccm using a water vapor permeability measuring apparatus (manufactured by MOCON Co., ltd., apparatus name: AQUATAN) under a condition of 90% RH at 40 ℃ ² /day). The lower limit of detection of the measuring apparatus was 0.0005g/m ² And/day. Since the gas barrier laminate has poor self-supporting properties if the PET film for forming the base layer is peeled off, the PET film is measured in a state where the PET film is laminated. Since the vapor transmission rate of the gas barrier layer is much smaller than that of the PET film, the effect on WVTR by lamination of the PET film is low to a negligible extent.

< elongation at break of substrate layer and gas barrier laminate >

The base layer was cut into test pieces of 15 mm. Times.150 mm, and the elongation at break was measured in accordance with JIS K7127:1999. Specifically, the test piece was set in a tensile tester (Autograph, manufactured by Shimadzu corporation), the gap between clamps was set to 100mm, and then a tensile test was performed at a speed of 200mm/min to measure the elongation at break [% ]. When the test piece does not have a yield point, the tensile breaking strain is defined as the elongation at break, and when the test piece has a yield point, the tensile breaking nominal strain is defined as the elongation at break. The same test was also performed on a gas barrier laminate (no process film) provided with a gas barrier layer.

Example 1

A curable resin composition 1 serving as a base layer was prepared in the following order.

< curable resin composition 1>

100 parts by mass of pellets of polyimide resin (PI) (product name KPI-mx300F, tg =354 ℃ and weight average molecular weight 28 ten thousand, manufactured by hekun industries co., ltd.) were dissolved in Methyl Ethyl Ketone (MEK) as a polymer component to prepare a 15 mass% solution of PI. Next, 122 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by new yo chemical industry co., ltd., a-DCP) as a curable monomer and 5 parts by mass of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF corporation, irgacure 819) as a polymerization initiator were added to the solution and mixed to prepare a curable resin composition 1. The curable monomer and the polymerization initiator used in this example and other examples contained no solvent, and were all raw materials having a solid content of 100%.

Then, a 1 st PET film (PET 100A-4100, thickness 100 μm, manufactured by Toyo-Co., ltd.) having an easy-to-adhere layer on one side was used as a process film, and a curable resin composition was applied to the PET film on the side opposite to the easy-to-adhere layer, and the coating film was heated at 90℃for 3 minutes and dried.

Then, a 2 nd PET film (Cosmo Shine A4100, manufactured by Toyo-yo Co., ltd., thickness: 50 μm) having an easy-to-adhere layer on one side thereof was laminated on the dried coating film, and the film was opposed to the opposite side to the easy-to-adhere side, and a conveyor type ultraviolet irradiation apparatus (manufactured by Eye Graphics Co., product name: ECS-401 GX) was used to apply a high-pressure mercury lamp (manufactured by Eye Graphics Co., product name: H04-L41) to the film so as to output an illuminance of 400mW/cm at a wavelength of 365nm with an ultraviolet lamp height of 100mm, an ultraviolet lamp output of 3kw, and a light intensity of 3kw ² Light quantity 800mJ/cm ² (manufactured by ORC MANUFACTURING Co., ltd., measured by an ultraviolet photometer UV-351) was subjected to a curing reaction by irradiation with ultraviolet rays through a 2 nd PET film, thereby forming a base layer having a thickness of 5. Mu.m.

Then, the 2 nd PET film was peeled off to expose a base layer, and a polysilazane compound (a coating agent (AQUARICMA NL-110-20, manufactured by Merck high performance materials Co., ltd., solvent: xylene)) containing perhydro polysilazane (PHPS) as a main component was applied to the base layer by spin coating, followed by heat drying at 130℃for 2 minutes, thereby forming a polymer compound layer (polysilazane layer) containing perhydro polysilazane and having a thickness of 200 nm.

Then, a plasma ion implantation apparatus (RF power supply manufactured by Nippon electronic Co., ltd.: RF 56000; high-voltage pulse power supply manufactured by Kagaku Kogyo Co., ltd.: PV-3-HSHV-0835) was used to implant ions derived from argon gas into the surface of the polymer compound layer (polysilazane layer) under conditions of a gas flow rate of 100sccm, a duty ratio of 0.5%, a DC voltage of-6 kV, a frequency of 1,000Hz, an RF power of 1,000W, a chamber internal pressure of 0.2Pa, a DC pulse width of 5 μsec, and a treatment time of 200 seconds, thereby forming a gas barrier layer. In this way, a gas barrier laminate is produced by laminating a gas barrier layer on a base layer.

Example 2

A gas barrier laminate was produced in the same manner as in example 1, except that 61 parts by mass of dicyclopentadiene diacrylate (A-DCP, manufactured by Xinzhou chemical Co., ltd.) and 61 parts by mass of allyl ether acrylate (FX-AO-MA, manufactured by Japan catalyst, manufactured by Nippon chemical Co., ltd.) as a cyclized polymerizable monomer were used as the curable monomer.

Comparative example 1

A gas barrier laminate was produced in the same manner as in example 1, except that 122 parts by mass of allyl ether acrylate (manufactured by japan catalyst, FX-AO-MA, ltd.) was used as the curable monomer as the cyclized polymerizable monomer.

Comparative example 2

A gas barrier laminate was produced in the same manner as in comparative example 1, except that 100 parts by mass of pellets of polysulfone resin (PSF) (BASF corporation, ultra son S6010, tg=187 ℃, and weight average molecular weight 6 ten thousand) were used as the polymer component instead of the polyimide resin.

Comparative example 3

A gas barrier laminate was produced in the same manner as in example 1, except that toluene was used as a solvent for dissolving the pellets instead of MEK, 100 parts by mass of pellets (Tg 190 ℃ below and a weight average molecular weight of less than 10 ten thousand) of a polycarbonate resin (PC) was used as a polymer component instead of a polyimide resin.

The measurement results of each example and comparative example are shown in table 1.

TABLE 1

Meaning of abbreviations in table 1

PI: polyimide resin

PSF: polysulfone resin

PC: polycarbonate resin

DCP: tricyclodecane dimethanol diacrylate

AE: allyl ether type acrylic ester

As is clear from table 1, in examples 1 and 2, the base layer was excellent in solvent resistance and elongation at break, and the gas barrier laminate after removal of the process film was also excellent in elongation at break and heat shrinkage, and the gas barrier laminate was also excellent in water vapor permeability.

On the other hand, in comparative examples 1 to 3, although the solvent resistance of the base layer was good, the absolute value of the heat shrinkage of the gas barrier laminate after removal of the process film was larger than that of example 1, and the water vapor permeability of the gas barrier laminate was also reduced by 1 order of magnitude or more than that of example 1. Further, the elongation at break of both the base layer and the gas barrier laminate was also inferior to that of examples.

Industrial applicability

The gas barrier laminate of the present invention has a high elongation at break and can further improve gas barrier properties, and therefore can be applied to electronic devices requiring both gas barrier properties and flexibility and bending resistance, for example, flexible organic EL devices and members for elements constituting various electronic devices that are susceptible to atmospheric degradation, such as flexible thermoelectric conversion devices.

Claims

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

the gas barrier laminate satisfies the following requirements [1] to [3]:

[1] the absolute value of the heat shrinkage of the gas barrier laminate is 0.5% or less,

[2] the gas barrier laminate has an elongation at break of 1.9% or more,

[3]the gas barrier laminate has a water vapor permeability of 8.0X10 at 40 ℃ in a gas atmosphere having a relative humidity of 90% ^-3 g/m ² And/day or less.

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

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

4. The gas barrier laminate according to claim 1 or 2, wherein the curable component (B) contains a cyclized polymerizable monomer.

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

6. The gas barrier laminate according to claim 1 or 2, wherein the glass transition temperature of the polymer component (a) is 250 ℃ or higher.

7. The gas barrier laminate according to claim 1 or 2, wherein the polymer component (a) is a polyimide resin.