WO2013175910A1 - Gas barrier layered product, and production method for gas barrier layered product - Google Patents

Abstract

Provided are a gas barrier layered product exhibiting excellent gas barrier properties, scratch resistance, and solvent resistance, and an efficient production method for such a layered product. Provided are a gas barrier layered product having a gas barrier layer on at least one surface of a substrate, and a production method for such a layered product. The present invention is characterized in that: the gas barrier layer is derived from a gas barrier material including a silicon-containing polymer and an energy-ray curable component; and the gas barrier material is subjected to energy-ray curing and plasma ion injection. The energy-ray curable component is either an energy-ray curable monomer or an energy-ray curable oligomer. It is preferable that the silicon-containing polymer be a polysilazane compound. It is also preferable that the water vapour transmission rate of such a gas barrier layered product be not more than 0.1g/(m²/day).

Description

Gas barrier laminate and method for producing gas barrier laminate

The present invention relates to a gas barrier laminate and a method for producing the gas barrier laminate, and more particularly, to a gas barrier laminate suitably used as a member for devices such as photoelectric conversion elements and organic electroluminescence elements, and a method for producing the gas barrier laminate. .

Conventionally, a polymer molded body such as a plastic film is inexpensive and excellent in workability, and thus has a desired function and is used in various fields.
In particular, in recent years, in an image display apparatus using a liquid crystal device or an organic electroluminescence device (organic EL element), a glass plate is used as a substrate for forming an electrode in order to realize a reduction in thickness, weight, and flexibility. Therefore, the use of transparent plastic films has been studied.
In the case of using a plastic film as such a substrate for electrode formation, development of a film having high gas barrier property and solvent resistance equivalent to that of a glass substrate, and also scratch resistance is desired.

As such a gas barrier plastic film, there has been proposed a method for manufacturing a gas barrier film applied to an easily manufactured organic EL element or the like without using heat treatment or the like (for example, see Patent Document 1).
More specifically, after forming a polysilazane film made of polysilazane on at least one surface of a plastic film, the polysilazane film is subjected to plasma treatment to form a gas barrier film, and a method for producing a gas barrier film It is.

In addition, a gas barrier plastic molded article having a cured product layer excellent in gas barrier properties, abrasion resistance, and adhesion to a substrate has been proposed (for example, see Patent Document 2).
More specifically, it is a gas barrier plastic molded article having two or more cured product layers formed on at least one surface of a transparent plastic substrate, and is an inner layer in contact with the outermost layer among the two or more cured products layers. Is a cured product layer derived from the following coating composition (A), and the outermost layer is a gas barrier plastic molded article having a cured product layer derived from the following coating composition (B).
Coating composition (A): Active energy ray-curable coating composition containing polyfunctional compound having two or more polymerizable functional groups and polysilazane Coating composition (B): Curing based on polysilazane Coating composition

Moreover, although it is not a gas barrier material, the transparent coating molded product derived from the coating composition containing an active energy ray hardening compound and polysilazane is proposed (for example, refer patent document 3).
More specifically, it is a transparent coated molded article having a transparent synthetic resin substrate and a transparent cured product layer formed on at least a part of the surface of the transparent synthetic resin substrate, and the transparent cured product layer is active. A transparent coated molded article, which is a cured product of a coating composition containing a polyfunctional compound having two or more energy ray-curable polymerizable functional groups and polysilazane.

JP 2007-237588 A JP 2001-322207 A JP-A-11-268196

However, in the method for producing a gas barrier film described in Patent Document 1, although a polysilazane film is formed on the film and then subjected to plasma treatment and used as a gas barrier film, gas barrier properties, solvent resistance, and There was a problem that the scratch resistance was insufficient.

Further, the gas barrier plastic molded article described in Patent Document 2 must form two or more cured product layers from a predetermined active energy ray-curable coating composition, resulting in a complicated structure, Despite the formation of a film or the use of an active energy ray-curable coating composition, there have been problems that the production time is long and the productivity is lowered. In addition, the plasma treatment for the cured product layer was not taken into consideration, and there was a problem that the gas barrier property was insufficient.

Moreover, although the transparent coating molded article described in Patent Document 3 uses polysilazane or an active energy ray curable compound, the gas barrier property is not basically taken into consideration, and the cured product is subjected to plasma treatment. As a result, there was a problem that the gas barrier property was insufficient.

Thus, as a result of intensive studies on such problems, the present inventors have developed a gas barrier material comprising a silicon-containing polymer (sometimes referred to as a silicon-containing compound) and an energy ray-curable component. The present inventors have found the fact that a laminate having excellent productivity and excellent gas barrier properties, scratch resistance and solvent resistance can be obtained by performing energy beam curing treatment and plasma ion implantation treatment, and completed the present invention. Is.
That is, an object of the present invention is to provide a gas barrier laminate excellent in gas barrier properties and an efficient method for producing such a gas barrier laminate.

According to the present invention, a gas barrier laminate having a gas barrier layer on at least one surface of a substrate, wherein the gas barrier layer is derived from a gas barrier material comprising a silicon-containing polymer and an energy ray-curable component. In addition, the gas barrier material is provided with an energy ray hardening treatment and a plasma ion implantation treatment. The gas barrier laminate can solve the above-described problems and has an excellent gas barrier property. A gas barrier laminate having scratch resistance and solvent resistance can be obtained efficiently.

Further, in constituting the gas barrier laminate of the present invention, it is preferable that the energy ray curable component is an energy ray curable monomer and / or oligomer.
By including such a resin, a laminate having excellent gas barrier properties, scratch resistance and solvent resistance can be obtained.

In constituting the gas barrier laminate of the present invention, the silicon-containing polymer is preferably a polysilazane compound.
Thus, by using a polysilazane compound as the silicon-containing polymer, more excellent gas barrier properties can be obtained.

Further, in constituting the gas barrier laminate of the present invention, the water vapor transmission rate is preferably 0.1 g / (m ² · day) or less.
Thus, if the water vapor transmission rate of a laminated body is the said range, it can use suitably as members for electronic devices, such as a photoelectric conversion element and an organic electroluminescent element, for example.

Further, in configuring the gas barrier laminate of the present invention, the plasma ion implantation process generates plasma in an atmosphere containing a plasma generation gas and applies a negative high voltage pulse to the surface of the treatment layer. Plasma ion implantation for implanting ions in plasma is preferable.
Thus, by performing plasma ion implantation treatment, a gas barrier laminate having better gas barrier properties can be obtained.

In constituting the gas barrier laminate of the present invention, the energy ray curable component is preferably a polyfunctional (meth) acrylate monomer having 3 or more functional groups.
Thus, by using a polyfunctional (meth) acrylate monomer having 3 or more functional groups, it is possible to obtain a gas barrier laminate having high hardness after curing and further excellent scratch resistance.

In constituting the gas barrier laminate of the present invention, it is preferable that the amount of the energy ray curable component is set to a value within the range of 1 to 500 parts by weight with respect to 100 parts by weight of the silicon-containing polymer.
By setting the ratio of the energy ray-curable component to be blended, a good balance can be obtained between the scratch resistance and chemical resistance and the gas barrier property.

Another aspect of the present invention is a method for producing a gas barrier laminate having a gas barrier layer on at least one surface of a substrate, which comprises the following steps (1) to (2): It is a manufacturing method of a laminated body.
(1) A step of laminating a gas barrier material containing a silicon-containing polymer and an energy beam curable component on at least one surface of a substrate (2) An energy beam curing process and a plasma ion implantation process are performed on the gas barrier material. Thus, the step of forming the gas barrier layer, that is, by forming the gas barrier layer in this way, a gas barrier laminate excellent in gas barrier properties can be obtained efficiently.

Further, in carrying out the method for producing a gas barrier laminate of the present invention, in step (2), the gas barrier material is subjected to energy beam curing treatment and then subjected to plasma ion implantation treatment to form a gas barrier layer. It is preferable.
That is, by forming the gas barrier layer in this way, a gas barrier laminate having further excellent gas barrier properties can be efficiently obtained.

1 (a) and 1 (b) are views for explaining a gas barrier laminate of the present invention.

[First embodiment]
The first embodiment is a gas barrier laminate having a gas barrier layer 10 on at least one surface of a substrate 12, wherein the gas barrier layer 10 includes a silicon-containing polymer and an energy ray-curable component. The gas barrier laminate 50 is characterized in that the gas barrier material is subjected to an energy ray hardening process and a plasma ion implantation process.
Hereinafter, the gas barrier laminate of the first embodiment will be specifically described with reference to the drawings as appropriate.

1. Base Material The type of the base material 12 is not particularly limited, and examples thereof include a plastic resin film and a glass substrate (including a ceramic substrate).
Here, as resin used for the plastic resin film, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyphenylene sulfide Examples include arylate, acrylic resin, cycloolefin polymer, and aromatic polymer.
Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate.
Examples of cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof.

The thickness of the substrate may be determined according to the purpose of use, etc., but is preferably 1 to 1000 μm, more preferably 5 to 100 μm from the viewpoint of flexibility and easy handling. preferable.
Further, the total light transmittance of the substrate is not particularly limited, but when the laminate is used as a member for an electronic device such as a photoelectric conversion element or an organic electroluminescence element, it is preferably 80% or more. More preferably, it is 85% or more.

2. Gas Barrier Layer The gas barrier layer 10 can be obtained by subjecting a gas barrier material containing a silicon-containing polymer and a curable component to a curing treatment and a plasma ion implantation treatment.
Note that the gas barrier layer is a layer having a characteristic of suppressing permeation of oxygen, water vapor, or the like (hereinafter referred to as “gas barrier property”). The gas barrier layer 10 may be a single layer or a plurality of layers.

(1) Silicon-containing polymer The silicon-containing polymer (sometimes referred to as a silicon-containing compound) is an organic compound as long as it is a polymer containing silicon in the molecule (including a compound containing silicon). Or an inorganic compound.
Examples include polyorganosiloxane compounds, polycarbosilane compounds, polysilane compounds, polysilazane compounds, and the like.
Among these, a polysilazane compound is preferable from the viewpoint that an excellent gas barrier property can be expressed. If the silicon-containing polymer is a polysilazane compound, the polysilazane compound can be made to have a higher gas barrier property by converting the surface layer into silica by converting to silica by energy ray curing treatment and plasma ion implantation treatment described later. .

Here, the polysilazane compound is a polymer compound having a repeating unit containing —Si—N— bond (silazane bond) in the molecule, specifically, a repeating unit represented by the following general formula (1): It is preferable that it is a compound which has this.
Further, the number average molecular weight of the polysilazane compound to be used is not particularly limited, but is preferably a value within the range of 100 to 50,000.

(In the general formula (1), Rx, Ry and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted group. A non-hydrolyzable group such as an alkenyl group, an unsubstituted or substituted aryl group or an alkylsilyl group, and the subscript n represents an arbitrary natural number.)

Examples of the alkyl group of the above-described unsubstituted or substituted alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples thereof include alkyl groups having 1 to 10 carbon atoms such as butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group.
Examples of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
Examples of the alkenyl group of the above-described unsubstituted or substituted alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group. Examples include alkenyl groups having 2 to 10 carbon atoms.
In addition, examples of the substituent for the alkyl group, cycloalkyl group, and alkenyl group described above include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; ) Acryloyloxy group; unsubstituted or substituted aryl group such as phenyl group, 4-methylphenyl group, 4-chlorophenyl group; and the like.
Examples of the unsubstituted or substituted aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
In addition, examples of the substituent for the aryl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; methoxy group and ethoxy group Nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group; phenyl group, 4-methylphenyl group, 4-chlorophenyl group, etc. An unsubstituted or substituted aryl group; and the like.
Examples of the alkylsilyl group described above include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, and ethylsilyl group. .
Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and particularly preferably a hydrogen atom.

Specifically, as the polysilazane compound, an inorganic polysilazane compound in which Rx, Ry, and Rz are all hydrogen atoms in the general formula (1), an organic polysilazane in which at least one of Rx, Ry, and Rz is not a hydrogen atom, Or a modified polysilazane etc. are mentioned.
Examples of such inorganic polysilazane compounds include compounds having structures represented by the following general formulas (2) to (3) and formula (4).

That is, it has a linear structure having a repeating unit represented by the following general formula (2), and has a number average molecular weight of 3 to 10 SiH ₃ groups in one molecule within a range of 690 to 2000. One perhydropolysilazane (see Japanese Patent Publication No. 63-16325) can be mentioned.

(In the general formula (2), the subscript b represents an arbitrary natural number.)

Moreover, perhydropolysilazane having a linear structure having a repeating unit represented by the following general formula (3) and a branched structure may be mentioned.

(In general formula (3), Y ¹ is a hydrogen atom or a group represented by the following general formula (3 ′), and subscripts c and d each represent an arbitrary natural number.)

(In General Formula (3 ′), Y ² is a hydrogen atom or a group represented by General Formula (3 ′), subscript e represents an arbitrary natural number, and * represents a bonding position.)

Furthermore, for example, perhydropolysilazane having a perhydropolysilazane structure represented by the following formula (4) and having a linear structure, a branched structure and a cyclic structure in the molecule can be mentioned.

An organic polysilazane compound in which at least one of Rx, Ry, and Rz in the general formula (1) is not a hydrogen atom but an organic group is also suitable.
Examples of the organic polysilazane compound include compounds having structures represented by the following general formulas (5) to (7), the following formula (8), and the general formula (9).

That is, compounds having a cyclic structure having a degree of polymerization of 3 to 5 mainly using a structure represented by the following general formula (5) as a repeating unit can be mentioned.

-(Rx'SiHNH)-(5)

(In general formula (5), Rx ′ has an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted group. This represents an aryl group or an alkylsilyl group, and the same applies to the following general formulas.)

Further, compounds having a cyclic structure mainly having a degree of polymerization of 3 to 5 using the structure represented by the following general formula (6) as a repeating unit can be mentioned.

-(Rx'SiHNRz ')-(6)

(In general formula (6), Rz ′ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, or an alkylsilyl group.)

Further, compounds having a cyclic structure having a degree of polymerization of 3 to 5 mainly using the structure represented by the following general formula (7) as a repeating unit can be mentioned.

-(Rx'Ry'SiNH)-(7)

(In General Formula (7), Ry ′ has an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted group. An aryl group or an alkylsilyl group.)

Moreover, a polyorgano (hydro) silazane compound having a structure represented by the following formula (8) in the molecule can be mentioned.

Furthermore, a polysilazane compound having a repeating structure represented by the following general formula (9) can be mentioned.

(In the general formula (9), Y ³ is a hydrogen atom or a group represented by the following general formula (9 ′), and the subscripts f and g represent arbitrary natural numbers.)

(In general formula (9 ′), Y ⁴ represents a hydrogen atom or a group represented by general formula (9 ′), subscript h represents an arbitrary natural number, and * represents a bonding position.)

In addition, the organic polysilazane compound mentioned above can be manufactured by a well-known method.
For example, it can be obtained by reacting ammonia or a primary amine with the reaction product of an unsubstituted or substituted halogenosilane compound represented by the following general formula (10) and a secondary amine.
In addition, the secondary amine, ammonia, and primary amine to be used can be suitably selected according to the structure of the target polysilazane compound.

R ¹ _4-m SiX _m (10)

(In the general formula (10), X represents a halogen atom, R ¹ is a substituent of any one of Rx, Ry, Rz, Rx ′, Ry ′ and Rz ′ described above, and m is 1 to 3) Is an integer.)

In the present invention, it is also preferable to use modified polysilazane as the polysilazane compound.
Examples of such a modified polysilazane include a polymetallosilazane containing a metal atom (the metal atom may be crosslinked), and repeating units of [(SiH ₂ ) _i (NH) _j ] and [(SiH ₂ ). _k O] (subscripts i, j and k are each independently 1, 2 or 3). Polyborosilazane, polysilazane and metal alkoxide produced by reacting a boron compound with polysiloxazan or polysilazane. Polymetallosilazane produced by reacting with polysilazane, inorganic silazane high polymer, modified polysilazane, copolymerized silazane in which organic components are introduced into polysilazane, and low temperature with addition or addition of a catalytic compound for promoting ceramicization to polysilazane Ceramicized polysilazane, silicon alkoxide-added polysilazane, glycidol-added polysilazane Silazanes, acetylacetonato complexes addition polysilazane include metal carboxylate added polysilazane.
In addition, a polysilazane composition obtained by adding amines and / or acids to the above-described polysilazane compound or a modified product thereof, obtained by adding alcohol such as methanol or hexamethyldisilazane to a terminal N atom to perhydropolysilazane. Compounds and the like.

(2) Energy ray curable component The energy ray curable component is not particularly limited as long as it is a compound having a property of being cured by irradiation with energy rays. For example, energy ray curable monomers and oligomers are used. Alternatively, either one or the like has a polymer having energy ray curability. Among these, from the viewpoint of high hardness after curing and excellent scratch resistance, it is preferable to use either energy ray curable monomer or oligomer.
Here, the energy ray-curable component is characterized by being cured by irradiating energy rays (for example, ultraviolet rays) and having excellent scratch resistance and solvent resistance.

In addition, the energy ray curable monomer and / or oligomer has a polymerizable unsaturated bond in the molecule, and more specifically has one or more (meth) acryloyl groups. .
The (meth) acryloyl group means both an acryloyl group and a methacryloyl group.

Examples of the energy ray curable monomer include monofunctional monomers and / or oligomers, and polyfunctional monomers and / or oligomers.
Among these, a multifunctional monomer and / or oligomer is more preferable from the viewpoint of excellent scratch resistance.

Here, the monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (Meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, adamantane (Meth) acrylate, tricyclodecane acrylate, phenylhydroxypropyl acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified acrylate, tetrahydride Furfuryl (meth) acrylate, morpholine acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) (Meth) acrylate derivatives such as acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate; (meth) acrylic acid, (meth) acrylonitrile; styrene derivatives such as styrene and α-methylstyrene; (Meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, (meth) acrylamide derivatives such as dimethylaminopropyl (meth) acrylamide; It is done.
These can be used individually by 1 type or in combination of 2 or more types.

Examples of the polyfunctional monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol adipate di ( (Meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl Bifunctional (meth) acrylates such as di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, and allylated cyclohexyl di (meth) acrylate; trimethylolpropane tri (meth) acrylate Relate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloyloxyethyl) Trifunctional (meth) acrylates such as isocyanurate; tetrafunctional (meth) acrylates such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate and propionic acid-modified dipentaerythritol Pentafunctional (meth) acrylates such as penta (meth) acrylate; dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol Ruhekisa (meth) hexafunctional acrylates such as (meth) acrylate.
These can be used individually by 1 type or in combination of 2 or more types.
Among these, polyfunctional (meth) acrylates having 3 or more functional groups are preferable, and hexafunctional (meth) acrylates are more preferable from the viewpoint of easily obtaining a gas barrier layer having high hardness after curing and excellent scratch resistance.

Examples of the energy ray curable oligomer include polyester (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, and the weight average molecular weight is 1,000 to 50,000. Is more preferable, and 2000 to 40000 is more preferable. These can be used individually by 1 type or in combination of 2 or more types.
Further, as the polyester (meth) acrylate oligomer, for example, by esterifying hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, or It can be obtained by esterifying a hydroxyl group at the terminal of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid.
The epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it.
The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.
Furthermore, the polyol (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

Examples of the polymer having energy ray curable include an acrylate copolymer having an energy ray curable group in the side chain.
This acrylic ester copolymer is obtained by reacting an acrylic copolymer having a functional group-containing monomer unit with an unsaturated group-containing compound having a substituent bonded to the functional group, and the weight average molecular weight is It is preferably 100,000 or more, more preferably 200,000 to 2,500,000, and further preferably 500,000 to 1,500,000 from the viewpoint of heat resistance.

The amount of the energy ray curable component is preferably set to a value within the range of 1 to 500 parts by weight of the energy ray curable component with respect to 100 parts by weight of the silicon-containing polymer.
The reason for this is that if the blending amount of the energy ray-curable component is less than 1 part by weight, sufficient scratch resistance and chemical resistance may not be obtained, and conversely if it exceeds 500 parts by weight. This is because the gas barrier property tends to decrease.
Therefore, the amount of the energy ray curable component is preferably 10 to 100 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the silicon-containing polymer.

Here, when ultraviolet rays are used as energy rays, the polymerization curing time and the amount of light irradiation can be reduced by adding a photopolymerization initiator.
The photopolymerization initiator is not particularly limited. For example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, benzoylbenzoates, α- Examples include acyloxime esters, sulfides, thioxanthones, acylphosphine oxide photopolymerization initiators, diacylphosphine oxide compounds, and the like alone or in combination of two or more.
The blending amount of the photopolymerization initiator is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the energy ray curable component, and is a value within the range of 0.5 to 5 parts by weight. Is more preferable.

(3) Preparation of gas barrier layer forming material The gas barrier layer forming material contains the above-mentioned silicon-containing polymer, energy ray curable component, photopolymerization initiator used as required, and various additives in an appropriate solvent. Can be blended.
Examples of such additives include polymers that do not have energy beam curability, UV absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, antifoaming agents, thickeners, antisettling agents, and pigments. , Coloring dyes, infrared absorbers, fluorescent brighteners, dispersants, antistatic agents, antifogging agents, curable catalysts, silane coupling agents, organic solvents, and the like.
Examples of such solvents include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, and butanol. Alcohols, acetone, methyl ethyl ketone, ketones such as 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolv solvents such as ethyl cellosolve.
The concentration and viscosity of the gas barrier layer forming material thus prepared are not particularly limited as long as they can be coated, and can be appropriately selected according to the situation.

(4) Energy beam curing process / plasma ion implantation process The energy beam curing process and the plasma ion implantation process performed on the layer containing the silicon-containing polymer and the curable component are specifically described in the second embodiment. To do.

(5) Thickness The thickness of the gas barrier layer is preferably set to a value within the range of 0.05 to 50 μm.
This is because an excellent gas barrier property can be obtained by using a gas barrier layer having such a thickness.
Therefore, the thickness of the gas barrier layer is more preferably set to a value within the range of 0.05 to 20 μm, and further preferably set to a value within the range of 0.1 to 5 μm.

3. Laminated body The laminated body of this invention should just have the gas barrier layer 10 formed in the at least one surface of the base material 12, as shown in FIG. 1, and the gas barrier layer 10 is shown in FIG. It may be formed on one side of the substrate 12 or may be formed on both sides as shown in FIG.

(1) Water vapor transmission rate Moreover, it is preferable to make the water vapor transmission rate of the laminated body of this invention into the value below 0.1 g / (m < ² > * day).
The reason for this is that an excellent gas barrier property can be obtained quantitatively by setting such a value of water vapor permeability.
However, when the value of the water vapor transmission rate of the gas barrier layer is excessively low, usable materials are excessively limited, and the manufacturing yield is remarkably reduced.
Therefore, it is more preferable to set the value of the water vapor transmission rate of the gas barrier layer to a value within the range of 0.001 to 0.1 g / (m ² · day).
The water vapor transmission rate of the gas barrier sheet can be measured by a known method, for example, preferably measured according to JIS K 7129 or JIS Z 0208.

(2) Surface hardness Moreover, it is preferable that the surface hardness measured with the surface hardness measuring apparatus of the laminated body gas barrier layer of this invention is 2.0 GPa or more. When the surface hardness is 2.0 GPa or more, a laminate having good scratch resistance of the gas barrier layer can be obtained.

(3) Other layers The laminate of the present invention includes, for example, an inorganic compound layer, an adhesive layer, a conductor layer, a primer layer, a refractive index adjustment layer, a light diffusion layer, an easy adhesion layer, an antiglare treatment layer, The other layers may be a single layer or a plurality of layers.
Here, the inorganic compound layer is a layer composed of one kind or a combination of two or more kinds of inorganic compounds, and such an inorganic compound layer is provided together with the gas barrier layer for the purpose of improving the durability and improving the gas barrier property. It is preferable.
Moreover, as an inorganic compound which comprises an inorganic compound layer, it can generally form into a vacuum and has a gas barrier property, for example, an inorganic oxide, an inorganic nitride, an inorganic carbide, an inorganic sulfide, and these composites. Inorganic oxynitrides, inorganic oxycarbides, inorganic nitriding carbides, inorganic oxynitriding carbides, etc.

The material for forming the adhesive layer is not particularly limited, and for example, acrylic resin, urethane resin, silicone resin, olefin resin, rubber material, and the like can be used.

Moreover, a conductor layer is a layer for providing electroconductivity to a laminated body.
Here, examples of the material constituting the conductor layer include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. More specifically, antimony-doped tin oxide (ATO); fluorine-doped tin oxide (FTO); tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Conductive metal oxides; metals such as gold, silver, chromium and nickel; mixtures of these metals and conductive metal oxides; inorganic conductive materials such as copper iodide and copper sulfide; organics such as polyaniline, polythiophene and polypyrrole Examples thereof include conductive materials.

Further, the primer layer plays a role of improving interlayer adhesion between the base material and the gas barrier layer.
That is, by providing such a primer layer, a gas barrier layer that is extremely excellent in interlayer adhesion and surface smoothness can be obtained.

The refractive index adjustment layer is a layer provided for controlling reflection.
The refractive index adjusting layer can be formed using a high refractive material or a low refractive material so that desired performance can be obtained.

Further, the light diffusion layer is a layer provided for diffusing light, and the viewing angle can be expanded when the sheet of the present invention is used as a member for an electronic device such as a liquid crystal display device. The light diffusion layer can be formed by a conventionally known method.

Further, the antiglare treatment layer is a layer provided for the purpose of preventing visual interference of transmitted light due to reflection of external light.
The antiglare treatment layer can be formed by a conventionally known method using a coating agent containing a filler such as silica particles.
As described above, since the laminate of the present invention is excellent in gas barrier properties, scratch resistance and solvent resistance, it can be suitably used as a sealing material or substrate for photoelectric conversion elements and organic EL elements. .

[Second Embodiment]
The second embodiment is a method for producing a gas barrier laminate having a gas barrier layer on at least one surface of a base material, comprising the following steps (1) to (2): It is a manufacturing method.
(1) A step of laminating a gas barrier material containing a silicon-containing polymer and an energy beam curable component on at least one surface of a substrate (2) An energy beam curing process and a plasma ion implantation process are performed on the gas barrier material. A step of forming a gas barrier layer

1. Process (1)
Step (1) is a step of laminating a gas barrier material containing a silicon-containing polymer and an energy ray-curable component on at least one surface of the substrate. Specifically, the silicon-containing polymer, energy This is a step of applying a gas barrier layer-forming coating solution containing a linear curable component, and drying and removing the solvent as necessary.
Here, the method for laminating the gas barrier material containing the silicon-containing polymer and the energy beam curing component is not particularly limited, and a known method can be used. Examples thereof include a method of forming on a substrate by a known coating method such as a screen printing method, a knife coating method, a roll coating method, a die coating method, an ink jet method, a spin coating method, and the like.

2. Step (2)
Step (2) is a step for curing the energy ray-curable component in the gas barrier material obtained in step (1) and modifying the layer to form a gas barrier layer.
Therefore, in the step (2), the plasma ion implantation process may be performed after the energy beam curing process is performed, and conversely, the energy beam curing process may be performed after the plasma ion implantation process is performed. The energy beam curing process may be further performed after the energy beam curing process is performed and the plasma ion implantation process is performed.
In addition, although an energy beam hardening process and a plasma ion implantation process may be implemented simultaneously, it is more preferable to implement a plasma ion implantation process after performing an energy beam hardening process from the point of gas barrier property.

(1) Energy beam curing process The energy beam curing process is a process for curing an energy beam curing component by irradiating energy beams such as ultraviolet rays and electron beams.
Here, as the type of energy rays, ultraviolet rays are preferable because the irradiation device and the like are relatively simple and relatively small.
Accordingly, a xenon lamp, a pulse xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like can be used as such an ultraviolet ray source.
The amount of energy ray irradiation varies depending on the type of energy ray. For example, when curing with ultraviolet rays, a dose amount in the range of 50 to 1000 mJ / cm ² is preferable, and 70 to 800 mJ / cm ² . The dose within the range is more preferable, and the dose within the range of 100 to 500 mJ / cm ² is more preferable.

(2) Plasma ion implantation treatment The plasma ion implantation treatment is a treatment for modifying the layer containing the silicon-containing polymer and energy ray-curable component obtained in step (1) to exhibit excellent gas barrier properties. is there. By this plasma ion implantation treatment, the surface layer of the obtained gas barrier layer has a dense structure as compared with the inside of the layer, and exhibits high barrier properties.
The plasma ion implantation process generates plasma in an atmosphere containing a plasma generation gas such as a rare gas, and applies negative high voltage pulses to apply ions (positive ions) in the plasma to the surface of the layer. It is a method of injection.

Also, among plasma ion implantation processes, a method of injecting ions present in plasma generated using an external electric field into the layer, or a negative high voltage pulse applied to the layer without using an external electric field A method in which ions existing in a plasma generated only by an electric field due to is implanted into the layer is preferable.

Further, when ions in plasma are implanted, a known plasma ion implantation apparatus can be used.

The ion species to be implanted is not particularly limited, but ions of rare gases such as argon, helium, neon, krypton, and xenon; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur Ions of alkane gases such as methane, ethane, propane, butane, pentane and hexane; ions of alkenes such as ethylene, propylene, butene and pentene; and ions of alkadiene gases such as pentadiene and butadiene Ions: Ions of alkyne gases such as acetylene and methylacetylene; Ions of aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene; Cycloalkane gases such as cyclopropane and cyclohexane Ion; cyclopentene, cyclo Ion cycloalkenes based gas such as cyclohexene; gold, silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, a conductive metal such as aluminum ion; silane (SiH ₄₎ Or an ion of an organosilicon compound.

Among these, at least selected from the group consisting of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton, because it can be more easily injected and a gas barrier layer having excellent gas barrier properties can be obtained. One kind of ion is preferred.
Note that the ion species implanted into the polysilazane compound, that is, the ion implantation gas also has a function as a plasma generation gas.

Further, it is preferable that the pressure of the vacuum chamber during ion implantation, that is, the plasma ion implantation pressure is set to a value within the range of 0.01 to 1 Pa.
The reason for this is that when the plasma ion implantation pressure is in such a range, ions can be implanted easily and efficiently uniformly, and a gas barrier layer having excellent bending resistance and gas barrier properties can be obtained. This is because it can be formed efficiently.
Therefore, the plasma ion implantation pressure is more preferably set to a value within the range of 0.02 to 0.8 Pa, and further preferably set to a value within the range of 0.03 to 0.6 Pa.

The applied voltage (high voltage pulse / negative voltage) at the time of ion implantation is preferably set to a value in the range of −1 kV to −50 kV.
The reason for this is that if ion implantation is performed with such an applied voltage greater than −1 kV, the ion implantation amount (dose amount) may be insufficient, and a desired gas barrier property may not be obtained. is there.
On the other hand, if ion implantation is performed with an applied voltage smaller than −50 kV, the film is charged during ion implantation, and defects such as coloring of the film may occur, and a desired gas barrier property may not be obtained. Because there is.
Therefore, the applied voltage at the time of ion implantation is more preferably set to a value within the range of −1 kV to −15 kV, and further preferably set to a value within the range of −5 kV to −8 kV.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the description of the following examples without any particular reason. *

[Example 1]
1. Production of gas barrier laminate (1) Step 1
A polyethylene terephthalate film (manufactured by Mitsubishi Plastics, “PET38 T-100”, thickness 38 μm, hereinafter referred to as “PET film”) was prepared as a substrate.
Next, as a silicon-containing polymer, a coating agent (“AZNL110-20” manufactured by AZ Electronic Materials, solid content concentration 20%) containing perhydropolysilazane (indicated as PHPS in the table) as a main component 500 20 parts by weight of pentaerythritol triacrylate (indicated as PETRA in the table) as an energy ray curable component (ultraviolet ray curable component) with respect to parts by weight (that is, solid content concentration of 100 parts by weight) As an agent, Irgacure 127 (manufactured by BASF) was added at a ratio of 0.6 part by weight to prepare a gas barrier layer forming coating solution (solid content concentration: 33% by weight).
Next, a gas barrier layer forming coating solution was applied onto the PET film, and further heated at 120 ° C. for 2 minutes to form a layer containing a silicon-containing polymer and an energy ray-curable component.

(2) Step 2
Next, the layer obtained in Step 1 was subjected to energy ray curing treatment using a UV light irradiation line (high pressure mercury lamp, line speed, 20 m / min, integrated light quantity 100 mJ / cm ² , peak intensity 1.466 W, number of passes. Twice) to form an energy ray cured layer.

Next, using a plasma ion implantation apparatus (RF power supply: manufactured by JEOL Ltd., RF56000, high voltage pulse power supply: Kurita Seisakusho Co., Ltd., PV-3-HSHV-0835) Plasma ion implantation was performed under the conditions to obtain a gas barrier laminate including the gas barrier layer (thickness: 150 nm) of Example 1.
Chamber internal pressure: 0.2 Pa
Plasma generation gas: Argon gas flow rate: 100 sccm
RF output: 1000W
RF frequency: 1000Hz
RF pulse width: 50 μsec
RF delay: 25nsec
DC voltage: -10kV
DC frequency: 1000Hz
DC pulse width: 5 μsec
DC delay: 50 μsec
Duty ratio: 0.5%
Processing time: 300 sec

2. Evaluation of gas barrier laminate The following evaluation was performed on the gas barrier laminate provided with the obtained gas barrier layer.

(1) Scratch resistance evaluation About the obtained laminated body, the surface hardness in 25 degreeC of a gas barrier layer is measured with a surface hardness measuring apparatus (Nanoindenter, the product made from MTS), and scratch resistance is evaluated as follows. did.
“Good”: 2.0 GPa or more.
“Bad”: Less than 2.0 GPa.

(2) Solvent resistance evaluation The solvent resistance was evaluated by immersing the gas barrier layer in a 10% NaOH aqueous solution at 40 ° C for 90 seconds and evaluating the solvent resistance as follows.
“Good”: No difference in surface hardness.
“Bad”: The surface hardness decreased.

(3) Gas barrier property evaluation About the obtained gas barrier laminated body, using a water vapor permeability measuring device (manufactured by MOCON Co., Ltd., AQUATRAN), the water vapor permeability under conditions of RH 90% and 40 ° C. was measured, and the gas barrier property was obtained. Evaluated.

[Examples 2 to 5]
In Examples 2 to 5, the blending amount of PETRA as an energy ray-curable component was set to 40, 60, 80, and 100 parts by weight with respect to 100 parts by weight of PHPS, respectively, as in Example 1. A gas barrier laminate was prepared and evaluated.

[Example 6]
Example 6 Example 6 uses dipentaerythritol hexaacrylate (denoted as DPHA in the table) as an energy ray-curable component, except that the ratio is 40 parts by weight with respect to 100 parts by weight of PHPS. As in Example 1, a gas barrier laminate was prepared and evaluated.

[Example 7]
In Example 7, Example 1 was used except that pentaerythritol tetraacrylate (denoted as PETA in the table) was used as the energy ray-curable component and the ratio was 40 parts by weight with respect to 100 parts by weight of PHPS. Similarly, a gas barrier laminate was prepared and evaluated.

[Example 8]
In Example 8, except that tricyclodecane dimethanol diacrylate (shown as DCPA in the table) was used as the energy ray-curable component, and the ratio was 40 parts by weight with respect to 100 parts by weight of PHPS. A gas barrier laminate was prepared and evaluated in the same manner as in Example 1.

[Example 9]
In Example 9, a urethane acrylate ultraviolet curable compound (SHIKOH UT-4692, manufactured by Nippon Synthetic Chemical Co., Ltd., indicated as UA in the table) is used as an energy ray curable component, based on 100 parts by weight of PHPS. A gas barrier laminate was prepared and evaluated in the same manner as in Example 1 except that the ratio was 40 parts by weight.

[Comparative Example 1]
In Comparative Example 1, a gas barrier laminate was prepared and evaluated in the same manner as in Example 6 except that PHPS was not used and only 100 parts by weight of DPHA as an energy ray-curable component and a photoinitiator were used.

[Comparative Example 2]
In Comparative Example 2, a gas barrier laminate was prepared and evaluated in the same manner as in Example 7 except that no PHPS was used and only 100 parts by weight of PETA as an energy ray-curable component and a photoinitiator were used.

[Comparative Example 3]
In Comparative Example 3, a gas barrier laminate was prepared and evaluated in the same manner as in Example 1 except that PHPS was not used and only 100 parts by weight of PETRA as an energy ray-curable component and a photoinitiator were used.

[Comparative Example 4]
In Comparative Example 4, a gas barrier laminate was prepared and evaluated in the same manner as in Example 8, except that PHPS was not used and 100 parts by weight of DCPA as an energy ray-curable component and only a photoinitiator were used.

[Comparative Example 5]
In Comparative Example 5, a laminate was prepared and evaluated in the same manner as in Example 2 except that the energy beam curing process was not performed and only the plasma ion implantation process was performed.

[Comparative Example 6]
In Comparative Example 6, a gas barrier laminate was prepared and evaluated in the same manner as in Example 2 except that the plasma ion implantation process was not performed and only the energy beam curing process was performed.

[Comparative Example 7]
In Comparative Example 7, without using an energy beam curable component, using only PHPS, without performing an energy beam curing process, only a plasma ion implantation process was performed, a gas barrier layer was formed, and a laminate was created. evaluated.

[Comparative Example 8]
In Comparative Example 8, a gas barrier layer was formed by using only PHPS without using an energy beam curable component, performing only an energy beam curing process without performing a plasma ion implantation process, creating a laminate, and evaluating it. did.

From Table 1, it was confirmed that the gas barrier laminates of Examples 1 to 9 were excellent in all of gas barrier properties, scratch resistance and solvent resistance.
On the other hand, the laminates of Comparative Examples 1 to 4 containing no silicon-containing polymer have excellent scratch resistance and solvent resistance, but are inferior in gas barrier properties.
Moreover, the laminated body of Comparative Example 5 that has not been subjected to the energy beam curing treatment is inferior in scratch resistance and solvent resistance, although a certain degree of gas barrier property is obtained.
Moreover, the laminated body of the comparative example 6 which has not performed plasma ion implantation processing is inferior in all of gas barrier property, scratch resistance, and solvent resistance.
Moreover, although the laminated body of the comparative example 7 which does not contain an energy-beam curable component and has not performed the energy-beam hardening process is excellent in gas barrier property, it is inferior in abrasion resistance and solvent resistance.
Moreover, the laminated body of the comparative example 8 which does not contain an energy-beam curable component and has not performed plasma ion implantation treatment is inferior in all of gas barrier properties, scratch resistance, and solvent resistance.

As described above in detail, according to the present invention, an energy beam curing process and a plasma ion implantation process are performed on a gas barrier material containing a silicon-containing polymer and an energy beam curable component on at least one surface of a substrate. By forming a gas barrier layer by applying, a gas barrier laminate having excellent gas barrier properties and scratch resistance has been obtained.
Therefore, the gas barrier laminate of the present invention is expected to be effectively used as a plastic film as a substrate for electrode formation in liquid crystal devices and organic electroluminescence devices.

10: Gas barrier layer 12: Base material 50: Gas barrier laminate

Claims (9)

1. A gas barrier laminate having a gas barrier layer on at least one surface of a substrate,
   The gas barrier layer is derived from a gas barrier material comprising a silicon-containing polymer and an energy ray-curable component;
   The gas barrier laminate is characterized in that the gas barrier material is subjected to energy beam curing treatment and plasma ion implantation treatment.
2. The gas barrier laminate according to claim 1, wherein the energy ray curable component is an energy ray curable monomer and / or oligomer.
3. The gas barrier laminate according to claim 1 or 2, wherein the silicon-containing polymer is a polysilazane compound.
4. The gas barrier laminate according to any one of claims 1 to 3, wherein the water vapor permeability is 0.1 g / (m ² · day) or less.
5. The plasma ion implantation process is a plasma ion implantation in which plasma is generated in an atmosphere containing a plasma generating gas and ions in the plasma are implanted into the surface of the treatment layer by applying a negative high voltage pulse. The gas barrier laminate according to any one of claims 1 to 4, wherein:
6. The gas barrier laminate according to any one of claims 1 to 5, wherein the energy ray-curable component is a polyfunctional (meth) acrylate monomer having 3 or more functional groups.
7. The amount of the energy ray-curable component is set to a value in the range of 1 to 500 parts by weight with respect to 100 parts by weight of the silicon-containing polymer. The gas barrier laminate as described.
8. A method for producing a gas barrier laminate having a gas barrier layer on at least one surface of a substrate,
   A method for producing a gas barrier laminate comprising the following steps (1) to (2).
   (1) A step of laminating a gas barrier material containing a silicon-containing polymer and an energy ray curable component on at least one surface of a substrate (2) An energy ray hardening treatment and a plasma ion implantation treatment are performed on the gas barrier material. Step of forming a gas barrier layer by applying
9. 9. The gas barrier laminate according to claim 8, wherein, in the step (2), a gas barrier layer is formed by performing a plasma ion implantation process after performing an energy ray curing process on the gas barrier material. Body manufacturing method.

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