WO2013118442A1 - Thin-film laminate - Google Patents

Description

Thin film laminate

The present invention relates to a thin film laminate, and more particularly, to a thin film laminate in which a metal oxide thin film or a gas barrier film is laminated on an organic-inorganic composite thin film whose surface has been mineralized.
This application claims priority to Japanese Patent Application No. 2012-025024 filed on February 8, 2012 and Japanese Patent Application No. 2012-086540 filed on April 5, 2012. The contents are incorporated here.

It is well known to produce an antireflection film or a transparent conductive film by forming a thin film laminate on a plastic substrate. In particular, a transparent conductive film for a capacitive touch panel represented by a smartphone is caused by a large difference in refractive index between a plastic substrate and indium tin oxide (ITO) used for the transparent conductive film. Visibility due to the difference in reflectance is a problem.
As a solution, a method of forming a thin film laminate for controlling the reflectance between a plastic substrate and a transparent conductive film is employed.
As a material used for the thin film laminate, a high refractive material and a low refractive material are required as compared with a plastic substrate, and an inorganic compound such as a metal oxide is used.
Each film thickness of the thin film laminate needs to be 200 nm or less in order to control the reflectance, and the film thickness and surface roughness need to be controlled in nanometer order.
Further, since the thin film laminate is an inorganic compound, adhesion with a plastic substrate is also a problem.
As a method for forming a thin film laminate, a sputtering method, a vacuum deposition method, a plasma CVD method, and the like are generally used because they have an advantage that the film thickness can be easily controlled on the nanometer order.
However, this is a process that requires a large-scale apparatus and a vacuum system, has a low formation speed, and is expensive.
On the other hand, it has also been proposed to form a thin film laminate by a sol-gel method (Patent Documents 1, 2, etc.). According to this method, it is said that since it is produced by a normal wet coating, it can be manufactured at a high speed and the cost is low.
In addition to the above technique, the present inventors irradiate the organosilicon compound with ultraviolet light in the presence of the photosensitive compound, so that the surface has a very high hardness, and the inner and back sides have an appropriate hardness. In addition, an organic-inorganic composite having excellent adhesion to the substrate is developed (see Patent Document 3), and further, by adding an ultraviolet curable compound thereto, the surface has a very high hardness. An organic-inorganic composite having excellent adhesion to the substrate and moisture resistance has been developed (Patent Document 4).

In addition, as a packaging material for filling and packaging foods and beverages, chemical products, miscellaneous goods, and protective films for precision equipment, oxygen gas is used to prevent deterioration, alteration, and discoloration of the contents to be packed and protected. The property of blocking and preventing permeation of water vapor, that is, the gas barrier property is required, and various gas barrier laminates have been developed conventionally.
In recent years, as a film having particularly high gas barrier properties and transparency, a gas barrier laminate having a gas barrier layer made of a thin film of an inorganic oxide such as silicon oxide or aluminum oxide on the surface of a base film made of a resin film has been developed. Developed and proposed.
However, since these inorganic oxide barrier layers such as silicon oxide and aluminum oxide are simply heated and vaporized, and the particles are deposited and deposited on the base film. There were gaps called crystal grain boundaries between the inorganic oxide particles, and the gas barrier properties were not satisfactory.
Therefore, in order to improve the gas barrier performance, a gas barrier formed by applying and drying a composition containing a hydrolytic condensate such as Si alkoxide on a thin film of an inorganic oxide such as silicon oxide or aluminum oxide. Have been proposed (Patent Documents 5, 6, 7, etc.).
Recently, a composition containing a hydrolytic condensate of Si alkoxide and a water-soluble polymer compound is applied and dried on a base film made of a resin film to form a first layer thin film. On top of the gas barrier laminate (Patent Document 8) in which a second inorganic compound layer is formed by a plasma CVD method or the like, or on a base film made of a resin film, a hydrolytic condensate of metal alkoxide and water-insoluble A gas barrier laminate (Patent Document 9) or the like in which a thin film is formed by applying and drying a composition containing conductive resin fine particles has also been proposed.

WO2005 / 081065 pamphlet WO2006 / 087986 pamphlet WO 2006/088079 pamphlet WO2008 / 069217 pamphlet JP-A-8-302043 Japanese Patent Laid-Open No. 10-244613 Japanese Patent No. 2790054 JP 2008-29934 A JP 2009-269217 A

Conventionally, forming a thin film laminate by a sol-gel method has the following problems.
(Problem 1) Adhesion failure occurs when a metal oxide sol is coated on a plastic substrate.
(Problem 2) When the film thickness is 200 nm or less, particularly 50 nm or less, the film thickness becomes non-uniform. This may be caused by uneven coating liquid film due to high-speed drying. However, when the film thickness is 50 nm or less, uneven film thickness occurs due to non-uniform wettability with the substrate surface. When unevenness of the film thickness occurs, particularly in the case of a film having a high refractive index, interference fringes become uneven and visibility is deteriorated.
(Problem 3) In order to obtain a film having a high refractive index by the sol-gel method, a high temperature is required, and the base plastic does not have.
(Problem 4) In order to adjust the refractive index, it is necessary to change the film material to be coated each time.
(Problem 5) The surface roughness of the thin film laminate deteriorates.

Moreover, in order to have a higher gas barrier property, the laminated inorganic compound layer needs to have a dense structure, and stress is generated at the interface between the inorganic compound layer having a dense structure and the resin film, resulting in poor adhesion. There was a thing.
Therefore, an object of the present invention is to provide an intermediate film for satisfactorily laminating a metal oxide thin film or a gas barrier film by the sol-gel method on a substrate.

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the first layer contains a condensate of an organosilicon compound and an organic polymer compound as a first layer, and the second layer is a metal oxide. A layer in which the condensate of the organosilicon compound is concentrated on the interface side with the thin film or the gas barrier film, and the concentration of carbon atoms in the concentrated layer is a 300 nm depth from the interface between the first layer and the second layer. An organic-inorganic composite thin film that is 20% or more less than the concentration of carbon atoms in a single layer is laminated, and a film thickness of 200 nm or less formed by the sol-gel method is formed on the organic-inorganic composite thin film. It was found that the above problems can be solved by producing a metal oxide thin film or a gas barrier film having a thickness of 500 nm or less as the second layer, and the present invention has been completed.

That is, the present invention
(1) In the thin film laminate formed in the order of the first layer and the second layer on the resin substrate,
The first layer is
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And when (4-n) is 2 or more, each X may be the same or different.) A condensate of an organosilicon compound represented by b) and a film thickness containing an organic polymer compound An organic-inorganic composite thin film of 500 nm or more,
The second layer
a) A metal oxide thin film having a film thickness of 200 nm or less formed by the sol-gel method, and the following formula: film thickness variation [%] = 100 × (standard deviation of film thickness) / (average film thickness)
Or a metal oxide thin film having a thickness variation of less than 10%, or
b) a gas barrier film having a film thickness of 500 nm or less,
The first layer has a layer on which the condensate of the organosilicon compound represented by formula (I) is concentrated on the interface side with the second layer, and the concentration of carbon atoms in the concentrated layer is the same as that of the first layer. A thin film stack characterized by being 20% or less less than the concentration of carbon atoms in the first layer having a depth of 300 nm from the interface with the second layer,
(2) The concentration of carbon atoms in the concentrated layer of the first layer is 40% or more lower than the concentration of carbon atoms in the first layer having a depth of 300 nm from the interface between the first layer and the second layer. The thin film laminate according to (1) above,
(3) The thin film laminate according to (1) above, wherein the average surface roughness Ra is 1 nm or less,
(4) The first layer further contains a metal compound having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead. The thin film laminate according to (1) above,
(5) The metal oxide thin film of the second layer is a metal oxide thin film having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead. The thin film laminate according to (1), characterized in that:
(6) The thin film stack according to (5), wherein the metal element is a metal element selected from the group consisting of titanium, zirconium, indium, tin, tantalum, zinc, tungsten, and lead,
(7) The thin film laminate according to (6) above, wherein the metal element is a metal element selected from the group consisting of titanium and zirconium,
(8) The metal oxide thin film of the second layer is a layer whose refractive index can be changed from 1.6 to 2.1 by irradiating electromagnetic waves. Thin film laminates,
(9) The thin film laminate according to (7) or (8) above, wherein the second layer metal oxide thin film is an amorphous titanium oxide thin film,
(10) The second layer metal oxide thin film formed by the sol-gel method has a total of 2 or more hydrolyzable groups and / or hydroxyl groups, a metal compound having 2 or more hydrolyzable groups and / or hydroxyl groups. From a thin film forming composition obtained by adding a predetermined amount of water to an organic solvent solution containing at least one selected from the group consisting of metal chelate compounds, metal organic acid salts, and partial hydrolysis products thereof The thin film laminate according to (1) above, which is a thin film formed,
(11) The thin film laminate according to (1), wherein a third layer having a refractive index smaller than that of the second layer and having a thickness of 200 nm or less is formed on the metal oxide thin film of the second layer. ,
(12) The thin film laminate according to (11), wherein the third layer is a thin film containing SiO ₂ formed by a sol-gel method,
(13) The thin film laminate according to (1) above, wherein the thin film laminate is a substrate for forming a transparent conductive film,
(14) A metal oxide or metal nitride in which the gas barrier film of the second layer has a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead The thin film laminate according to (1) above, which is a thin film made of a metal carbide or a composite thereof,
(15) The thin film laminate according to (1) above, wherein the water vapor permeability is 1 × 10 ⁻¹ g / m ² · day or less, and
(16) The thin film laminate according to (1) above, wherein the water vapor permeability is 1 × 10 ⁻² g / m ² · day or less.

The present invention also provides:
(17) The method for producing a thin film laminate according to the above (1), comprising the following steps 1 to 3;
(Step 1) As a first layer on the resin substrate,
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And each X may be the same or different when (4-n) is 2 or more.)
b) forming an organic-inorganic composite thin film containing an organic polymer compound;
(Step 2) Plasma treatment or UV ozone treatment of the surface of the first layer,
(Step 3) A step of forming the second layer on the surface of the first layer by the following method a) or b).
a) A step of forming a metal oxide thin film by a sol-gel method.
b) forming a gas barrier film by sputtering, vacuum deposition, ion plating or plasma CVD;
(18) A metal having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead as a component of the first layer in (Step 1) The method for producing a thin film laminate according to (17) above, comprising a compound, and
(19) The method for producing a thin film laminate according to the above (17), wherein electromagnetic waves are irradiated during or after the formation of the second layer in step a) of step 3.

(1) When laminating a metal oxide film as the second layer According to the present invention, a thin film laminate can be produced on a resin substrate by an inexpensive wet process. In particular, a first layer having a layer on which the condensate of the organosilicon compound is concentrated is formed, and the surface is very smooth and has a high wettability surface. An inexpensive sol-gel method can be applied to the two layers, and the coated second layer has the advantage that the film thickness is uniform and smooth, and has excellent optical characteristics such as no interference fringes and other irregularities. Yes. In addition, the metal oxide film formed by the organic silicon condensate of the first layer and the sol-gel method of the second layer has high durability because it provides strong adhesion between inorganic substances. .
In particular, when the surface of the first layer is subjected to plasma treatment or UV ozone treatment before forming the second layer, the surface becomes a structure closer to SiO ₂ and the contact angle of water is 20 ° or less (10 ° or less). Since it has high wettability, the affinity with the hydrophilic sol particles formed by the sol-gel method is improved, the film thickness of the second layer becomes more uniform, and the adhesion is also improved.
In addition, since the refractive index can be changed from 1.6 to 2.1 by irradiating electromagnetic waves on the second layer, a film that could not be obtained without high-temperature firing by the sol-gel method can be formed. The sol-gel method can be applied to a resin substrate.
An antireflection function can be imparted by forming a third layer having a low refractive index on the second layer. In addition, when electromagnetic waves are irradiated when forming the second layer, the surface of the second layer becomes 20 ° or less (10 ° or less) in terms of the water contact angle, the thickness of the third layer can be made uniform, and the adhesion is improved. To do.
Further, by forming a transparent conductive film such as ITO on the second and third layers, it is also useful as a transparent conductive film for a touch panel or the like.
In addition, it can be used as a base film for various uses such as a base film for coating a photocatalyst, a scattering prevention film, and a base film for heat ray cut.

(2) When a gas barrier film is stacked as the second layer
The first layer formed according to the present invention is an organic-inorganic composite thin film, and a condensed layer of a condensate of an organosilicon compound is formed on the surface, so that an inorganic compound gas barrier layer laminated thereon In addition to excellent adhesion, gas barrier properties can also be improved. Further, the average surface roughness (Ra) is as smooth as 1 nm or less and has no protrusions, so that it exhibits a stable gas barrier property. This surface smoothness is attributed to the fact that the condensed layer of the condensate of the organosilicon compound formed on the surface of the first layer is very smooth. Moreover, since many organic resin components of the organic-inorganic composite thin film exist on the resin film substrate side of the first layer, the adhesion with the substrate resin film is also good.
Further, after the first layer is formed, the surface of the first layer is subjected to plasma treatment or UV ozone treatment, whereby the surface of the condensed layer of the organosilicon compound condensate formed on the surface of the first layer is changed to silicon oxide. In addition, the adhesion of the inorganic compound laminated thereon to the gas barrier layer is further strengthened, and the gas barrier property is also improved.
Since the gas barrier laminate of the present invention has high transparency, good gas barrier properties, and excellent durability, it is used for various image display devices, electronic display element substrates, solar cell substrates, and the like. be able to.

It is a figure which shows the ESCA analysis result of the element of the thin film laminated body obtained in Example 1 when the integrated irradiation amount of an ultraviolet-ray is 0 mJ / cm < ² >. It is a figure which shows the ESCA analysis result of the element of the thin film laminated body obtained in Example 1 when the integrated irradiation amount of an ultraviolet-ray is 500 mJ / cm < ² >. It is a figure which shows the ESCA analysis result of the element of the thin film laminated body obtained in Example 1 when the integrated irradiation amount of an ultraviolet-ray is 1000 mJ / cm < ² >. It is a figure which shows the ESCA analysis result of the element of the thin film laminated body obtained in Example 1 when the integrated irradiation amount of an ultraviolet-ray is 2000 mJ / cm < ² >. It is a photograph which shows the adhesiveness of the surface of the laminated body of Example 2 and a comparative example. It is a photograph by the AFM (atomic force microscope) of the surface of the laminated body of Example 2 and a comparative example. It is a figure which shows the ESCA analysis result of the surface of the laminated body of Example 2. FIG. It is a figure which shows the ESCA analysis result of the surface of the laminated body of a comparative example. It is the photograph which took the cross section of the thin film laminated body of Example 3 with the transmission electron microscope. It is the photograph which took the cross section of the thin film laminated body of Example 4 with the transmission electron microscope.

The thin film laminate of the present invention has a structure in which the following layers A) resin substrate, B) first layer and C) second layer are laminated in the order of A), B) and C) on at least one surface of the resin substrate. Consists of. The thin film laminate of the present invention further includes a case where one or more other layers are laminated on the second layer.
A) Resin substrate B) First layer a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And when (4-n) is 2 or more, each X may be the same or different.) A condensate of an organosilicon compound represented by b) and a film thickness containing an organic polymer compound 500 nm or more, having a layer in which the condensate of the organosilicon compound represented by the formula (I) is concentrated on the interface side with the second layer,
Organic / inorganic composite thin film in which the concentration of carbon atoms in the concentrated layer is 20% or less less than the concentration of carbon atoms in the first layer at a depth of 300 nm from the interface between the first layer and the second layer C) Second layer a) A film thickness of 200 nm or less formed by the sol-gel method, and the following formula:
Variation in film thickness [%] = 100 x (standard deviation of film thickness) / (average film thickness)
A metal oxide thin film having a thickness variation of less than 10%, or b) a gas barrier film having a thickness of 500 nm or less

The thin film laminate can be produced by the following steps 1 to 3.
(Step 1) As a first layer on the resin substrate,
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And each X may be the same or different when (4-n) is 2 or more.)
b) forming an organic-inorganic composite thin film containing an organic polymer compound;
(Step 2) Plasma treatment or UV ozone treatment of the surface of the first layer,
(Step 3) forming a second layer on the surface of the first layer by the method a) or b) below,
a) A step of forming a metal oxide thin film by a sol-gel method.
b) forming a gas barrier film by sputtering, vacuum deposition, ion plating or plasma CVD;
(Step 4) A step of further forming a metal oxide thin film or the like on the surface of the second layer as required by a sol-gel method.
This will be described in detail below.

1) Resin Base The resin base used in the present invention is not limited as long as the laminate of the present invention can be formed. For example, polyimide bases such as polyamideimide, polyetherimide, polyimide, and polyaminobismaleimide Resins: Polyester resins such as polyethylene terephthalate and polyethylene 2,6-naphthalate; Epoxy resins such as phenolic epoxy resins, alcoholic epoxy resins, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins; polyether ether ketone, poly Polyether resins such as ether ketone, polyether nitrile, and polyether sulfone; Cellulosic resins such as cellulose triacetate, cellulose diacetate, and nitrocellulose; Polystyrene, syndiotactic polymer Polystyrene resins such as restyrene; polyolefin resins such as homopolymers or copolymers of olefins such as ethylene, propylene, butene; cycloolefin resins such as norbornene resins; nylon 6, nylon 12, copolymer nylon, etc. Polyamide resin; Polyvinyl alcohol resin such as ethylene-polyvinyl alcohol copolymer; Ethylene-tetrafluoroethylene copolymer, Polytrifluoroethylene chloride, Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, Polyfluoride Fluorine resins such as vinyl and perfluoroethylene-perfluoropropylene-perfluorovinyl ether copolymers; polycarbonate, polyvinyl butyrate resin, polyarylate resin, and the like.

Further, as a resin, a resin composition made of an acrylic compound having a radical reactive unsaturated compound, a resin composition made of a mercapto compound having an acrylic compound and a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, poly A photocurable resin such as a resin composition obtained by dissolving an oligomer such as ether acrylate in a polyfunctional acrylate monomer, a mixture thereof, or the like can be used.

The size and shape of the substrate are not particularly limited, and any flat plate, three-dimensional object, film, or the like can be used, but a film-like one is preferable.

In addition, these substrates may be provided with a waterproof layer containing a polyvinylidene chloride polymer for the purpose of improving so-called dimensional stability. Furthermore, a thin film made of an organic compound and / or an inorganic compound may be provided for the purpose of gas barrier. Examples of the inorganic compound include silica, alumina, talc, vermiculite, kaolinite, mica, and synthetic mica. Examples of the organic compound include polyvinyl alcohol and polyethylene-vinyl alcohol copolymer.
Various organic and / or inorganic additives may be added to the substrate for the purpose of imparting other functions. Furthermore, a coated article can also be used as a substrate.

The film-like substrate may be made of an unstretched film or may be made of a stretched film.
Examples of the resin substrate include a single layer film and a laminated film obtained by laminating two or more layers by means such as laminating or coating.

The film-like resin substrate can be produced by a conventionally known general method. For example, a substrate made of an unstretched film that is substantially amorphous and not oriented can be produced by melting a material resin with an extruder, extruding it with an annular die or a T die, and quenching. In addition, a substrate made of an unstretched film is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the like. A substrate made of a stretched film can be produced by stretching in a direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.
The thickness of the film-like resin substrate is not particularly limited, but is usually 1 to 1000 μm, preferably 3 to 500 μm.

2) 1st layer Although the organic-inorganic composite thin film of this invention contains the condensate of an organic silicon compound, and an organic polymer compound as an essential component, it may contain a metal compound, a photoinitiator, etc. in addition to this. Good. The organic / inorganic composite thin film is usually 500 nm or more, preferably 1 μm to 10 μm. If the thickness is less than 500 nm, the surface unevenness of the substrate tends to be affected, and if it exceeds 10 μm, the substrate tends to warp and the flexibility becomes poor.

2-1) Condensate of organosilicon compound The organosilicon compound is represented by the following formula (I).
R _n SiX _4-n (I)
In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, and X represents a hydroxyl group or a hydrolyzable group. n represents 1 or 2, and when n is 2, each R may be the same or different, and when (4-n) is 2 or more, each X may be the same or different.

Here, examples of the “organic group in which a carbon atom is directly bonded to Si” represented by R include a hydrocarbon group which may be substituted, a group composed of a polymer of a hydrocarbon which may be substituted, and the like. Can do.
The hydrocarbon group in the above “optionally substituted hydrocarbon group” and “group consisting of an optionally substituted hydrocarbon polymer” is usually a hydrocarbon group having 1 to 30 carbon atoms, for example, , Alkyl group, cycloalkyl group, cycloalkylalkyl group, alkenyl group, alkynyl group, aryl group, arylalkyl group, arylalkenyl group and the like. Of these, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, and a carbon number of 3 are preferable. 8 to 8 cycloalkenyl groups.

The “hydrocarbon group” or “group consisting of a hydrocarbon polymer” may contain an oxygen atom, a nitrogen atom, or a silicon atom.

Examples of the “linear or branched alkyl group having 1 to 10 carbon atoms” include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and n-pentyl. Group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl group and the like. Examples of the long chain alkyl group having more than 10 carbon atoms include lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.

Examples of the “cycloalkyl group having 3 to 8 carbon atoms” include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like.

“Straight or branched alkenyl group having 2 to 10 carbon atoms” means a straight or branched alkenyl group having 2 to 10 carbon atoms having a carbon-carbon double bond at any one or more positions. For example, an ethenyl group, a prop-1-en-1-yl group, a prop-2-en-1-yl group, a prop-1-en-2-yl group, a but-1-en-1-yl group, But-2-en-1-yl group, but-3-en-1-yl group, but-1-en-2-yl group, but-3-en-2-yl group, penta-1-ene- 1-yl group, penta-4-en-1-yl group, penta-1-en-2-yl group, penta-4-en-2-yl group, 3-methyl-but-1-ene-1- Yl group, hexa-1-en-1-yl group, hexa-5-en-1-yl group, hepta-1-en-1-yl group, hepta-6 En-1-yl group, oct-1-en-1-yl group, oct-7-en-1-yl group, buta-1,3-dien-1-yl, and the like.

The “C3-C8 cycloalkenyl group” means a C3-C8 alkenyl group having a carbon-carbon double bond at any one or more positions and having a cyclic portion. And cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, and 3-cyclohexen-1-yl group.

Examples of the “alkynyl group” include ethynyl group, prop-1-yn-1-yl group, prop-2-yn-1-yl group, but-1-in-1-yl group, but-3-yne -1-yl group, penta-1-in-1-yl group, penta-4-in-1-yl group, hexa-1-in-1-yl group, hexa-5-in-1-yl group, Examples include hepta-1-in-1-yl group, octa-1-in-1-yl group, and octa-7-in-1-yl group.
Examples of the “cycloalkylalkyl group” include a cyclopropylmethyl group, a cyclopropylpropyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylethyl group, a cycloheptylmethyl group, and the like.

Examples of the “arylalkyl group” include a C _6-10 aryl C _1-8 alkyl group such as a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, and a 5-phenyl group. -N-pentyl group, 8-phenyl-n-octyl group, naphthylmethyl group and the like can be mentioned.
Examples of the “arylalkenyl group” include a styryl group, a 3-phenyl-prop-1-en-1-yl group, and a 3-phenyl-prop-2-ene as a C _6-10 aryl C _2-8 alkenyl group. -1-yl group, 4-phenyl-but-1-en-1-yl group, 4-phenyl-but-3-en-1-yl group, 5-phenyl-pent-1-en-1-yl group 5-phenyl-pent-4-en-1-yl group, 8-phenyl-oct-1-en-1-yl group, 8-phenyl-oct-7-en-1-yl group, naphthylethenyl group, etc. Can be mentioned.

Examples of the “hydrocarbon group having an oxygen atom” include a group having an oxirane ring (epoxy group) such as an alkoxyalkyl group, an epoxy group, an epoxyalkyl group, a glycidoxyalkyl group, an acryloxymethyl group, a methacryloxymethyl group, etc. Is mentioned.

Here, the “alkoxyalkyl group” is usually a C1-6 alkoxy C1-6 alkyl group, and examples thereof include a methoxymethyl group, a 2-methoxyethyl group, and a 3-ethoxy-n-propyl group.
The “epoxyalkyl group” is preferably a linear or branched epoxyalkyl group having 3 to 10 carbon atoms, such as a glycidyl group, a glycidylmethyl group, a 2-glycidylethyl group, a 3-glycidylpropyl group, or a 4-glycidylbutyl group. Alkyl groups containing linear epoxy groups such as 3,4-epoxybutyl group, 4,5-epoxypentyl group, 5,6-epoxyhexyl group;
β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, 2-glycidylpropyl group, 2-glycidylbutyl group, 3-glycidylbutyl group, 2-methyl-3-glycidylpropyl group, 3-methyl- 2-glycidylpropyl group, 3-methyl-3,4-epoxybutyl group, 3-ethyl-3,4-epoxybutyl group, 4-methyl-4,5-epoxypentyl group, 5-methyl-5,6- Examples thereof include an alkyl group containing a branched epoxy group such as an epoxy hexyl group.
Examples of the “glycidoxyalkyl group” include glycidoxymethyl group and glycidoxypropyl group.

As the “hydrocarbon group having a nitrogen atom”, a group having —NR ′ ₂ (wherein R ′ represents a hydrogen atom, an alkyl group or an aryl group, and each R ′ may be the same as or different from each other). Or a group having —N═CR ″ ₂ (wherein R ″ represents a hydrogen atom or an alkyl group, and each R ″ may be the same as or different from each other). Examples of the alkyl group and aryl group for R ″ include the same groups as those exemplified for R above.

For example, the group having —NR ′ ₂ includes a —CH ₂ —NH ₂ group, a —C ₃ H ₆ —NH ₂ group, a —CH ₂ —NH—CH ₃ group, and the like. -N = Examples of the group having a _{CR '' 2, -CH 2 -N} = CH-CH 3 _{group, -CH 2 -N = C (CH} 3) 2 _{group, -C 2 H 4 -N = CH} -CH ₃ groups etc. are mentioned.

Examples of the “hydrocarbon having a silicon atom” include groups containing a polymer such as polysiloxane, polyvinylsilane, polyacrylsilane and the like.

Examples of the above-mentioned “optionally substituted” substituent include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a methacryloxy group. Examples of the halogen atom, alkyl group, alkenyl group and aryl group are the same as those in R.

Among the above groups, the group that is decomposed by irradiation with light having a wavelength of 350 nm or less includes a vinyl group, a group having an oxirane ring, —NR ′ ₂ (wherein R ′ represents a hydrogen atom, an alkyl group, or an aryl group). And each R ′ may be the same or different from each other, or —N═CR ″ ₂ (wherein R ″ represents a hydrogen atom or an alkyl group, and each R ″ is the same as each other). But may be different.).

In formula (I), n represents 1 or 2, and n = 1 is particularly preferable. When n is 2, each R may be the same or different. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

In the formula (I), X represents a hydroxyl group or a hydrolyzable group. When (4-n) in formula (I) is 2 or more, each X may be the same or different. Here, the hydrolyzable group is, for example, a group that can be hydrolyzed to form a silanol group by heating at 25 ° C. to 100 ° C. in the presence of non-catalyst and excess water, siloxane condensation Means a group capable of forming a product, and specific examples thereof include an alkoxy group, an acyloxy group, a halogen group, an isocyanate group, and the like, including an alkoxy group having 1 to 4 carbon atoms or a group having 1 to 6 carbon atoms. An acyloxy group is preferred.

Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. As the acyloxy group having 1 to 6 carbon atoms, Examples thereof include an acetyloxy group and a benzoyloxy group. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the isocyanate group include an isocyanate group bonded to an alkyl group, an isocyanate group bonded to a cycloalkyl group, an isocyanate group bonded to an aryl group, an isocyanate group bonded to an alkyl group substituted with a cycloalkyl group, and an aryl group. And an isocyanate group bonded to the alkyl group.

Specifically, the raw material organosilicon compounds include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethylsilane. Methoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyldimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, Dibutyldimethoxysilane, vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxy Tanmethoxy) propyltrimethoxysilane, oxacyclohexyltrimethoxysilane, methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, methyl-triglycidyloxysilane, methyltris (3-methyl-3- Oxetanemethoxy) silane, vinyltrichlorosilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropi Methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1 , 3-Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane. These can be used alone or in combination of two or more.

Examples of the “group consisting of a hydrocarbon polymer” include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylic acid esters such as acrylates; carboxylic acids such as (meth) acrylic acid, itaconic acid and fumaric acid and acid anhydrides such as maleic anhydride; epoxy compounds such as glycidyl (meth) acrylate; diethylaminoethyl (meth) Amino compounds such as acrylate and aminoethyl vinyl ether; Amide compounds such as (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) acrylamide; Lil, styrene, alpha-methyl styrene, vinyl chloride, vinyl acetate, a vinyl polymer obtained by copolymerizing a vinyl compound selected from vinyl propionate.
In addition, the condensate of the organosilicon compound used as the main component in the organic-inorganic composite thin film of the present invention means a product obtained by further condensing the organosilicon compound and / or the condensate thereof.
The blending ratio of the organosilicon compound condensate is 2 to 98% by mass, preferably 5 to 50% by mass, based on the solid content of the whole organic-inorganic composite. If the ratio of the organosilicon compound condensate increases, the adhesion of the substrate to the resin becomes worse, and conversely if it decreases, it becomes difficult to form a concentrated layer.

2-2) Organic polymer compound The organic polymer compound of the present invention is not particularly limited, but preferably has a functional group that causes a polymerization reaction upon irradiation with ultraviolet rays in the presence of a photopolymerization initiator. A compound or resin is polymerized by irradiation with ultraviolet rays in the presence of a photopolymerization initiator. Examples thereof include those obtained by polymerizing a (meth) acrylate compound, an epoxy resin, a vinyl compound excluding the acrylate compound, and the like. The number of functional groups is not particularly limited as long as it is 1 or more.

The raw material acrylate compounds include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, polycarbonate diacrylate, and tripropylene Examples include glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and siloxane polymer having a (meth) acryloyloxy group. Polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy poly (meth) acrylate, more preferably polyurea It is down (meth) acrylate.
The molecular weight is not limited as long as it dissolves in the organic-inorganic composite-forming composition, but is usually 500 to 50,000, preferably 1,000 to 10,000 as a weight average molecular weight.

Polyester (meth) acrylate is obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends with acrylic acid, obtained by condensation of polyvalent carboxylic acid and polyhydric alcohol. Alternatively, it can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with acrylic acid.

Polyurethane (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol and diisocyanate and an acrylate monomer having a hydroxyl group. Examples of the polyol include polyester polyol, polyether polyol, and polycarbonate diol. .

The epoxy (meth) acrylate can be obtained by, for example, an esterification reaction between an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin and acrylic acid.

Examples of commercially available urethane (meth) acrylates used in the present invention include trade names manufactured by Arakawa Chemical Industries, Ltd .: Beam Sets 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM-90, EM92, Sannopco Corporation product name: Photomer 6008, 6210, Shin-Nakamura Chemical Co., Ltd. product name: NK Oligo U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA, U-324A, U-4H, U-6H, trade names manufactured by Toa Gosei Co., Ltd .: Aronix M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, trade names manufactured by Kyoeisha Chemical Co., Ltd .: AH -600, AT606, UA-306H, manufactured by Nippon Kayaku Co., Ltd. Trade names: Kayarad UX-2201, UX- 301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Product names: Purple light UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV -7000, UV-7600B, UV-2010B, manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB, UN -3320HC, UN-3320HS, H-61, HDP-M20, manufactured by Daicel UC Corporation, trade names: Ebecryl IV 6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866 , 5129, 6602, 8301 or the like.

Examples of vinyl compounds other than the above acrylate compounds include N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl acetate, styrene, and unsaturated polyester. Epoxy resins include hydrogenated bisphenol A diglycidyl ether, 3,4 -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) And methyl) adipate.
The blending ratio of the organic polymer compound is usually 2 to 98% by mass, preferably 50 to 95% by mass, based on the solid content of the whole organic-inorganic composite.

2-3) Photopolymerization initiator The photopolymerization initiator used in the present invention includes (a) a compound that generates a cationic species by light irradiation and (b) a compound that generates an active radical species by light irradiation. Can do.
As a compound that generates a cationic species by light irradiation, for example, an onium salt having a structure represented by the following formula (II) can be given as a preferred example.
[R ¹ _a R ² _b R ³ _c R ⁴ _d W] ^{+ e} [ML _{e + f} ] ^−e (II)
(In the formula (II), the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N≡N—, and R ¹ , R ² , R ³ and R ⁴ are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. M is , A metal or metalloid constituting the central atom of the halide complex [ML _{e + f} ], for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. L is a halogen atom such as F, Cl, Br, etc., e is the net charge of the halide complex ion, and f is the valence of M. )
This onium salt is a compound that releases a Lewis acid by receiving light.

Specific examples of the anion (ML _{e + f} ) in the above formula (II) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarce. Nate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.
An onium salt having an anion represented by the formula [ML _f (OH) ⁻ ] can also be used. Further, perchlorate ion (ClO ₄ ⁻ ), trifluoromethanesulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, trinitrobenzenesulfonate anion, trinitrotoluenesulfone The onium salt which has other anions, such as an acid anion, may be sufficient. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the compound that generates active radical species by light irradiation include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde. Fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1 -(4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, N-tone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. .

The amount of the photopolymerization initiator used in the present invention is preferably 0.01 to 20% by mass based on the solid content of the ultraviolet curable compound as the raw material for the organic polymer compound, preferably 0.1 to 10%. More preferred is mass%.

In the present invention, a sensitizer can be added as necessary. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p- Isoamyl dimethylaminobenzoate, N, N-dimethylbenzylamine, 4,4′-bis (diethylamino) benzophenone, and the like can be used.

2-4) Metal Compound The metal compound used in the present invention includes a metal compound having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead. Is mentioned.
Among these, titanium, zirconium, aluminum, and tin are preferable as the metal element, and titanium is particularly preferable. These may be used alone or in combination of two or more.

The metal compound in the present invention removes the carbon component of the concentrated layer of the organosilicon compound represented by the formula (I) formed on the interface side between the first layer and the second layer, regardless of the mechanism. It is a compound that can be Specific examples include compounds that absorb and excite light having a wavelength of 350 nm or less.
When the first layer is formed, the carbon component on the surface side of the concentrated layer of the organosilicon compound represented by formula (I) can be removed by the action of light having a wavelength of 350 nm or less irradiated from the surface side.

Here, the light having a wavelength of 350 nm or less is light using a light source having light of any wavelength of 350 nm or less, preferably a light source having light of any wavelength of 350 nm or less as a main component. It means light made of

The metal compound of the present invention is at least one selected from the group consisting of metal chelate compounds, organic acid metal salts, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. It is a seed compound, preferably a hydrolyzate and / or a condensate, and particularly preferably a hydrolyzate and / or a condensate of a metal chelate compound.
Examples of the compound derived from these include compounds obtained by further condensing a condensate of a metal chelate compound. Such a metal compound and / or a derivative thereof may be chemically bonded to the above-described organosilicon compound, may be dispersed in a non-bonded state, or may be a mixed state thereof.

The metal chelate compound is preferably a metal chelate compound having a hydroxyl group or a hydrolyzable group, and more preferably a metal chelate compound having two or more hydroxyl groups or hydrolyzable groups. The metal chelate compound is preferably a β-ketocarbonyl compound, a β-ketoester compound, or an α-hydroxyester compound. Specifically, methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, acetoacetate β-ketoesters such as n-butyl, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane Β-diketones such as -2,4-dione, nonane-2,4-dione and 5-methyl-hexane-2,4-dione; compounds coordinated with hydroxycarboxylic acids such as glycolic acid and lactic acid Can be mentioned.

The organic acid metal salt is a compound composed of a salt obtained from a metal ion and an organic acid. Examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and benzoic acid; sulfonic acid, sulfinic acid, thiophenol, and the like. Organic compounds exhibiting acidity such as phenolic compounds; enol compounds; oxime compounds; imide compounds; aromatic sulfonamides;

Further, the metal compound having two or more hydroxyl groups or hydrolyzable groups excludes the metal chelate compound and the organic acid metal salt, and examples thereof include metal hydroxides and metal alcoholates.

Examples of the hydrolyzable group in the metal compound of the present invention include an alkoxy group, an acyloxy group, a halogen group, and an isocyanate group, and an alkoxy group having 1 to 4 carbon atoms and an acyloxy group having 1 to 4 carbon atoms are preferable. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the total of hydroxyl groups and hydrolyzable groups is 2 or more.

The hydrolyzate and / or condensate of the metal chelate compound is preferably one obtained by hydrolyzing with 5 to 100 mol of water with respect to 1 mol of the metal chelate compound. More preferably, it is hydrolyzed by use.

The hydrolyzate and / or condensate of the organic acid metal salt is preferably hydrolyzed with 5 to 100 mol of water per 1 mol of the organic acid metal salt. More preferably, it is hydrolyzed with water.

As a hydrolyzate and / or condensate of a metal compound having two or more hydroxyl groups or hydrolyzable groups, 0.5 mol or more is used per 1 mol of a metal compound having two or more hydroxyl groups or hydrolyzable groups. It is preferably hydrolyzed using water, more preferably hydrolyzed using 0.5 to 2 mol of water.

The compounding amount of the metal compound used in the present invention depends on its kind, but generally 0.01 to 0.5 molar equivalent of metal atoms in the metal compound with respect to Si in the organosilicon compound, It is preferably 0.05 to 0.2 molar equivalent.

2-5) Method for producing first layer (organic-inorganic composite thin film) (preparation of solution for forming organic-inorganic composite thin film)
The solution for forming the organic-inorganic composite thin film in the present invention comprises an organosilicon compound and / or a condensate thereof, a raw material of an organic polymer compound and a photopolymerization initiator, and, if necessary, a metal compound, water and / or a solvent. It is prepared by mixing other components such as

Specifically, for example, a metal compound is mixed in a solvent, a predetermined amount of water is added, (partial) hydrolysis is performed, and then an organosilicon compound is added (partial) to be hydrolyzed. On the other hand, the raw material of the organic polymer compound is dissolved in a solvent, a photopolymerization initiator is added, and then both solutions are mixed. These four components can be mixed at the same time, and the method of mixing the organosilicon compound and the metal compound, after mixing the organosilicon compound and the metal compound, adding water (partially), A method of mixing separately (partially) hydrolyzed organosilicon compounds and metal compounds can be mentioned. It is not always necessary to add water or a solvent, but it is preferable to add (partly) a hydrolyzate by adding water. The amount of the predetermined amount of water depends on the type of the metal compound. For example, when the metal compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, the amount of water is 0.5 with respect to 1 mol of the metal compound. It is preferable to use at least mol of water, and more preferably 0.5 to 2 mol of water. When the metal compound is a metal chelate compound or an organic acid metal salt, it is preferable to use 5 to 100 mol of water with respect to 1 mol of the metal chelate compound or organic acid metal salt, and 5 to 20 mol of water is used. It is more preferable.

As the condensate of the organosilicon compound of the present invention, a product obtained by (partially) hydrolyzing an organosilicon compound using a known silanol condensation catalyst may be used.

The composition for forming an organic-inorganic composite thin film in the present invention preferably contains water and / or a solvent in addition to the above components.
The solvent to be used is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane and cyclopentane. Ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethyl sulfoxide And the like; alcohols such as methanol and ethanol; and polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate. These solvents can be used alone or in combination of two or more.

Also, tetrafunctional silane and colloidal silica can be added for the purpose of improving the hardness of the resulting coating film. Examples of the tetrafunctional silane include tetraaminosilane, tetrachlorosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrabenzyloxysilane, tetraphenoxysilane, tetra (meth) acryloxysilane, tetrakis [2 -(Meth) acryloxyethoxy] silane, tetrakis (2-vinyloxyethoxy) silane, tetraglycidyloxysilane, tetrakis (2-vinyloxybutoxy) silane, tetrakis (3-methyl-3-oxetanemethoxy) silane be able to. Examples of the colloidal silica include water-dispersed colloidal silica and organic solvent-dispersed colloidal silica such as methanol or isopropyl alcohol.

In addition, fillers can be added and dispersed separately in order to develop various properties such as coloring, thickening the coating film, preventing UV transmission to the substrate, imparting corrosion resistance, and heat resistance. is there. Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments, and particulate and fibrous or scale-like metals and alloys other than pigments, and oxides, hydroxides, carbides, nitrides thereof, and the like. Examples thereof include sulfides. Specific examples of this filler include particulate, fibrous or scale-like iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, Manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, carbonic acid Magnesium, Barium sulfate, Bentonite, Mica, Zinc green, Chromium green, Cobalt green, Viridian, Guinea green, Cobalt chrome green, Shale green, Green earth, Manganese green, Pigment green, Ultramarine, Bitumen, Rock ultramarine, Cobalt blue, Cerulean Blue, copper borate, molybdenum blue, copper sulfide, koval Purple, Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Lead Sulfide, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium red, chrome vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, sulfuric acid Examples thereof include lead, graphite, bone black, diamond black, thermostatic black, vegetable black, potassium titanate whisker, and molybdenum disulfide.

In addition, known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium coupling agents, dyes, dispersants, thickeners, leveling agents, etc. These additives can also be added.

As a solid content in the solution for forming an organic-inorganic composite in the present invention (an organosilicon compound and / or a condensate thereof, a raw material of an organic polymer compound, and a metal compound component and a photopolymerization initiator as required), The content is preferably 1 to 98% by mass, and more preferably 10 to 60% by mass. The organic polymer compound is 2 to 98% by mass, preferably 50 to 95% by mass, more preferably 60 to 95%, based on the total mass of the solid content in the organic / inorganic composite forming solution. The condensate thereof is 2 to 98% by mass, preferably 5 to 50, more preferably 5 to 40% by mass.

Although the content of the metal compound depends on the kind thereof, generally, the metal atom in the metal compound is 0.01 to 0.5 molar equivalent, preferably 0.8, relative to Si in the organosilicon compound. It is preferably from 05 to 0.2 molar equivalent.
The content of the photopolymerization initiator is preferably 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the solid content of the ultraviolet curable compound as a raw material for the organic polymer compound. Further preferred. If the amount is too small, curing does not proceed sufficiently. If the amount is too large, it remains and affects the film.

(Manufacturing method of organic-inorganic composite thin film)
The following process can be illustrated as an organic-inorganic composite thin film of the present invention. (A) The organic-inorganic composite thin film forming solution described above can be applied to a substrate and dried, and (B) a step of irradiating light containing a wavelength of 350 nm or less. Thereafter, (C) plasma treatment or UV ozone treatment is performed before laminating the second layer.

The element concentration in the depth direction of the organic-inorganic composite thin film of the present invention can be measured by ESCA analysis.
According to ESCA analysis, the organic-inorganic composite thin film of the present invention has a layer in which the condensate of the organosilicon compound represented by formula (I) is concentrated on the interface side with the second layer, and the carbon atoms of the concentrated layer The concentration of is 20% or more, preferably 40% or less less than the concentration of carbon atoms in the first layer having a depth of 300 nm from the surface of the thin film stack.
Here, “the concentration of carbon atoms” means the molar concentration of carbon atoms when (total metal atoms + oxygen atoms + carbon atoms) is 100%. The same applies to the concentrations of other elements.
Further, “the layer in which the condensate of the organosilicon compound is concentrated” is defined by the concentration of carbon atoms by ESCA analysis, but in the concentrated layer, the concentration of silicon is also high.
Therefore, in the present invention, the silicon concentration increases as the carbon concentration decreases.
In order to improve the wettability and adhesiveness by decomposing organic contaminants on the surface of the layer where the condensate of the organosilicon compound is concentrated and the organic group R of the raw material, and changing the surface to a state close to SiO ₂ , It is preferable to carry out.

i) A method of containing 70% by mass or more of a condensate of a compound in which R is a vinyl group in the organosilicon compound represented by the formula (I) By performing this method, the step (C) may be omitted. .
ii) Method of performing step (C) By performing this method, R in formula (I) may not be selected.
iii) Method of increasing the amount of irradiation with light having a wavelength of 350 nm or less
By performing the method, R in formula (I) may not be selected.

As a coating method of the organic / inorganic composite thin film forming solution, a known coating method can be used. For example, dipping method, spray method, bar coating method, roll coating method, spin coating method, curtain coating method, gravure printing method. , Silk screen method, ink jet method and the like. Further, the film thickness to be formed is not particularly limited and is, for example, about 0.1 to 200 μm.

The film formed by applying the organic / inorganic composite thin film forming solution is preferably dried at 40 to 200 ° C. for about 0.5 to 30 minutes, preferably at 60 to 120 ° C. for 1 to 10 minutes. It is more preferable to carry out to the extent.

In the present invention, “light including a wavelength of 350 nm or less” means not only a wavelength of 350 nm or less but also ultraviolet rays having a wavelength longer than 350 nm. This is because the organic polymer compound is a compound or resin having a functional group that undergoes a polymerization reaction upon irradiation with ultraviolet rays in the presence of a photopolymerization initiator, and has a sensitivity at a wavelength exceeding 350 nm, preferably around 365 nm. is there.

Irradiation with light having a wavelength of 350 nm or less can be performed using a known apparatus such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp. The irradiation light is in the range of 150 to 350 nm. Preferably, the light is mainly composed of light having any one of the wavelengths, and more preferably light having any wavelength in the range of 250 to 310 nm. As long as it is sensitive to wavelengths in this range and does not react to light exceeding 350 nm, preferably 310 nm, it is hardly affected by sunlight. Further, the irradiation light amount of the light to be irradiated is, for example, about 0.1 to 100 J / cm ^2, and considering film curing efficiency (relation between irradiation energy and film curing degree), 0.2 to 10 J / cm 2. More preferably, it is about ² .
Note that irradiation with light having a wavelength of 350 nm or less is irradiation using a light source having light of any wavelength of 350 nm or less, preferably a light source having light of any wavelength of 350 nm or less as a main component. Irradiation used, that is, irradiation using a light source having a wavelength of 350 nm or less with the largest component amount.

In the present invention, the plasma treatment is a corona discharge treatment or glow plasma treatment in a nitrogen gas atmosphere or a rare gas atmosphere such as helium or argon.
More specifically, a method of generating plasma by applying a high voltage at a high frequency between parallel plate electrodes in which at least one of the electrode pairs is coated with a dielectric, and holding a base material layer between the electrodes, Or the method of moving this base material layer between these electrodes is mentioned. Plasma processing includes atmospheric pressure plasma processing and vacuum plasma processing, but since the density of active species is higher in atmospheric pressure plasma processing than in vacuum plasma processing, electrode surfaces can be processed at high speed and high efficiency. In addition, since there is no need to use a vacuum during processing, there is an advantage that processing can be performed with a small number of steps.

The atmospheric pressure plasma treatment is performed using an atmospheric pressure plasma generator (for example, atmospheric pressure plasma apparatus S-5000 manufactured by Sakai Semiconductor Co., Ltd., atmospheric pressure plasma surface treatment apparatus RD series manufactured by Sekisui Chemical Co., Ltd.). Can do.

In the present invention, UV ozone treatment means that the thin film is irradiated with UV (ultraviolet rays), oxygen in the air is changed to ozone, and the thin film is modified by the ozone and ultraviolet rays.

The UV light source is not particularly limited as long as oxygen can be changed to ozone by UV irradiation. Examples of the UV light source include a low-pressure mercury lamp. Low pressure mercury lamps generate UV light at 185 nm and 254 nm, and the 185 nm line can convert oxygen to ozone. The illuminance upon irradiation varies depending on the light source used, but generally several tens to several hundreds mW / cm ² are used. Moreover, illumination intensity can be changed by condensing or diffusing. The irradiation time varies depending on the illuminance of the lamp and the type of the untreated layer, but is usually 1 minute to 24 hours. The treatment temperature is usually 10 to 200 ° C. The irradiation amount of UV (i.e., ultraviolet amount) is usually 1 J / cm ² or more, preferably 1 ~ 100000J / cm ^2, more preferably 10 ~ 100000J / cm ^2.

The organic-inorganic composite thin film in the present invention can remove the carbon component on the surface side of the concentrated layer of the organosilicon compound represented by the formula (I) through the plasma treatment and the UV ozone treatment in the step (C), It can be in SiO ₂ form. In this reaction, only the silane compound on the film surface reacts, and the organic polymer compound in the film is hardly affected. As a result, even if the average roughness by AFM measurement is compared before and after the step (C), no change is observed.

Generally, since organic compounds are decomposed by plasma treatment or UV ozone treatment, the treatments have been used mainly for the purpose of cleaning dirt derived from organic substances on inorganic compounds such as glass. In the organic-inorganic composite thin film of the present invention, it can be said that the silane compound concentrated layer on the surface of the film plays a role as a protective layer against plasma treatment and UV ozone treatment.

3) Second layer The second layer is a metal oxide thin film or a gas barrier film.
(Metal oxide thin film)
The metal oxide thin film which is the second layer of the present invention is a metal oxide thin film formed by a sol-gel method.
The metal element of the metal oxide is preferably a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, and lead, and more preferably titanium, zirconium, indium More preferred is a metal element selected from the group consisting of tin, tantalum, zinc, tungsten and lead, and most preferred is a metal element selected from the group consisting of titanium and zirconium.
Furthermore, the metal oxide is preferably amorphous.
In addition, the metal oxide thin film of the present invention may be a metal oxide alone or contains a metal oxide as a main component, and other components for increasing the strength of the film, adjusting characteristics, and imparting functions. It may be a composite metal oxide such as ITO or BaTiO ₃ .
The metal oxide thin film of this invention has favorable adhesiveness with the organic inorganic composite thin film which is a 1st layer.

The method for producing the metal oxide thin film is specifically shown below.
The metal oxide thin film of the present invention includes a metal compound having two or more hydrolyzable groups and / or hydroxyl groups, a metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups, an organic acid metal salt, and It can be prepared using a composition for forming a thin film obtained by adding a predetermined amount of water to at least one organic solvent solution selected from the group consisting of these partial hydrolysis products.

3-1) Metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total The metal compound having two or more hydrolyzable groups and / or hydroxyl groups used in the present invention is a hydrolyzable group and / or hydroxyl group. As long as it is a metal compound having 2 or more in total, a compound represented by the formula (III) can be preferably exemplified.
(R) _a M ² (Y) _b (III)
In the above formula (III), M ² represents a metal atom, preferably a metal atom of Groups 13 to 15 of the periodic table. More specifically, at least one selected from the group consisting of silicon, germanium, tin, lead, titanium, zirconium, aluminum, indium, tantalum, tungsten and zinc can be exemplified. Among these, at least one selected from the group consisting of titanium, zirconium, indium, tin, tantalum, zinc, tungsten and lead is preferable, and at least one selected from the group consisting of titanium and zirconium is more preferable.

The above R represents a hydrogen atom or an organic group which may have a hydrolyzable group.

Here, the hydrolyzable group is a functional group that hydrolyzes upon contact with water, or a functional group that can form a bond with a metal atom via an oxygen atom in the presence of water (the same applies hereinafter).
Specific examples of the hydrolyzable group include a halogen atom, amino group, alkoxyl group, ester group, carboxyl group, phosphoryl group, isocyanate group, cyano group, and epoxy group.
Examples of the organic group include an alkyl group, an alkenyl group, and an aryl group.
When R is an organic group, the carbon number thereof is not particularly limited, but is usually 1 to 20, preferably 1 to 12.

Specific examples of R include a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, and a propyl group; a halogen such as a chloromethyl group, a chloroethyl group, a chloropropyl group, a bromopropyl group, a bromooctyl group, and a trifluoropropyl group. Alkyl group; epoxyalkyl group such as glycidoxypropyl group and epoxycyclohexylethyl group; aminoalkyl group such as aminopropyl group and aminobutyl group; alkenyl group such as vinyl group and allyl group; acryloxypropyl group and methacryloxy group (Meth) acryloxyalkyl groups such as propyl group; aralkyl groups such as benzyl group; aryl groups such as phenyl group and naphthyl group;

Y represents a hydrolyzable group bonded to M ² . Specifically, it contains an alkoxyl group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a pentoxy group; contains a nitrogen atom such as a hydroxyimino group, a hydroxyamino group, an amino group, or a carbamoyl group. A group; an enoxy group such as a propeneoxy group; a halogen atom such as a chlorine atom and a bromine atom; and the like.

A and b each independently represent an integer of 0 to m (m is a valence of a metal atom). However, a + b = m.

The compound represented by the formula (III) is a compound having two or more hydrolyzable groups in the molecule.
Specific examples of the compound represented by the formula (III) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, tetramethoxysilane, Tetraethoxysilane, tetrapropoxysilane, germanium tetramethoxide, germanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, aluminum triethoxide, aluminum tripropoxide, aluminum tributoxide, Tetrachlorosilane, tetrabromosilane, dimethyldichlorosilane, tetrakis (diethylamino) silane, 4-aminobutyltriethoxysilane 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, benzyltrichlorosilane, benzyltriethoxysilane, t-butylphenyldichlorosilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrichlorosilane, 8-bromo Octyltrichlorosilane, 3-bromopropyltrichlorosilane, (3,3,3-trifluoropropyl) dichlorosilane, (3,3,3-trifluoropropyl) trichlorosilane, chloromethyltrichlorosilane, β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, allyltrichlorosilane, allyltriethoxysilane, vinylmethyl Diacetoxysilane, vinylmethylbis (methylethylketoximine) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrichlorosilane, 3-acryloxypropyltrimethoxysilane, etc. Can be mentioned. Among these, tetramethoxysilane, tetraethoxysilane, titanium tetrapropoxide, zirconium tetrapropoxide, and zirconium tetrabutoxide are more preferable.

3-2) Metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups in total The metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups used in the present invention is composed of hydrolyzable groups and / or Alternatively, there is no particular limitation as long as it has two or more hydroxyl groups in total and a metal and a chelate compound are combined. Especially, the chelate compound of the partial hydrolyzate of the metal compound which has a hydrolysable group and / or a hydroxyl group in total 2 or more is preferable.
Here, the metal element in the metal chelate compound is the same as that exemplified in the metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total.

The chelate compound used is not particularly limited as long as it is a ligand capable of forming a chelate by binding to a metal, and may be a neutral ligand or an anion. What is necessary is just to couple | bond with the metal atom at at least one place, and it may be a monodentate ligand or a polydentate ligand. For example, even if it is a bidentate ligand, it does not need to be bound to one metal atom by bidentate.

Specific examples of the chelate ligand include the following. However, it illustrates as a chelate compound which can become a chelate ligand.
Saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; β-diketones such as acetylacetone, benzoylacetone and hexafluoroacetylacetone; Β-ketoesters such as methyl acetate and ethyl acetoacetate; glycols such as ethylene glycol; glycolic acids such as oxyacetic acid; ethylenediaminetetraacetic acid (EDTA) and its sodium salt, ethylenediamine, 1,3-propanediamine, diethylenetriamine, penta Nitrogen-containing compounds such as methyldiethylenetriamine, hexamethyltriethylenetetramine, tris [2- (dimethylamino) ethyl] amine, tri (pyridinylmethyl) amine;

Furancarboxylic acid, thiophenecarboxylic acid, nicotinic acid, isonicotinic acid, phenanthroline, phenanthroline, diphenanthroline, substituted phenanthroline, 2,2 ': 6', 2 "-terpyridine, pyridineimine, bridged aliphatic diamine, 4-4 ' -Di (5-nonyl) -2,2'-bipyridine, bipyridine coordinated with O, S, Se, Te, alkyliminopyridine, alkylbipyridinylamine, alkyl-substituted tripyridine, di (alkylamino) alkylpyridine, Ethylenediaminedipyridine, other heterocyclic compounds;

Sulfur-containing compounds such as mercapto alcohols such as 2-mercaptoethanol; dithiols such as ethanedithiol; mercaptoamines such as 2-mercaptoethylamine; dithioketones such as 2,4-pentanedithione;
These can be used alone or in combination of two or more.

A metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups in total is obtained, for example, by allowing a predetermined amount of a chelate compound to act on a metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total. be able to.
Although the obtained metal chelate compound can be isolated, it can be subjected to the subsequent hydrolysis and polycondensation reaction as it is.

3-3) Organic acid metal salt The metal element of the organic acid metal salt used in the present invention is the same as that exemplified in the metal compound having a total of two or more hydrolyzable groups and / or hydroxyl groups.

Examples of organic acids include carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and benzoic acid; sulfur-containing organic acids such as sulfonic acid, sulfinic acid, and thiophenol; acidic acids such as phenol; enol; oxime; imide; The compound which exhibits is mentioned.

Commercially available organic acid metal salts can be used as they are, but known production methods such as organic acid salts such as alkali metal salts and alkaline earth metal salts of organic acids, metal halides and metal sulfates. In addition, those produced by a method of reacting a metal salt such as a metal nitrate can be used.

3-4) Partial hydrolysis product of the compounds of 3-1) to 3-3) The partial hydrolysis product used in the present invention is a metal compound having a total of 2 or more hydrolyzable groups and / or hydroxyl groups, It is obtained by partial hydrolysis by adding water to at least one selected from the group consisting of metal chelate compounds having a total of 2 or more hydrolyzable groups and / or hydroxyl groups, and organic acid metal salts. .

3-5) Preparation of Metal Oxide Thin Film Forming Composition Specifically, the metal oxide thin film forming composition includes a metal compound having two or more total hydrolyzable groups and / or hydroxyl groups, hydrolyzable groups and In an organic solvent solution of at least one selected from the group consisting of metal chelate compounds having two or more hydroxyl groups in total, organic acid metal salts, and partial hydrolysis products thereof (hereinafter referred to as “metal compounds and the like”). It can be prepared by adding a predetermined amount of water and stirring the whole volume (sol-gel method).

The organic solvent used in the solution of the metal compound or the like is preferably an organic solvent that has high water solubility and does not solidify at a low temperature.

Organic solvents used include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, benzyl alcohol, methylcyclohexanol, ethanediol, propanediol, butanediol, pentanediol, hexylene glycol, octylene Alcohols such as glycol, hexanetriol, 3,5,5-trimethyl-1-hexanol; butyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, benzyl acetate, 3- Methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, butyl propionate, pentyl propionate Esters of; ketones such as acetone, methyl ethyl ketone, pentanone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone; nitriles such as acetonitrile; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole, tetrahydrofuran , Tetrahydropyran, dimethoxyethane, diethoxyethane, dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and other ethers; methylal and other acetals; pentane, hexane, heptane, octane, nonane, decane, dodecane, etc. Aliphatic hydrocarbons: toluene, xylene, ethylbenzene, cumene, MIS Aromatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, etc .; dichloromethane, chloroform, selenium, tetralin, butylbenzene, cymene, diethylbenzene, pentylbenzene, dipentylbenzene, etc. And halogenated hydrocarbons such as carbon chloride, dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and bromobenzene. These organic solvents can be used singly or in combination of two or more.

Among these, alcohols, esters and hydrocarbons are preferable, and butanol, pentanol, hexanol, trimethylhexanol, ethyl acetate, propyl acetate, butyl acetate, pentane, hexane, xylene and the like are particularly preferable.

The amount of the organic solvent used is preferably 10 to 5,000 parts by mass, more preferably 100 to 3,000 parts by mass with respect to 100 parts by mass of the metal compound and the like. In some cases, it may be difficult to control the particle size. On the other hand, when the amount exceeds 5,000 parts by mass, the solution may be too dilute to generate fine particles.

The content of the metal compound in the organic solvent solution containing the metal compound or the like used in the present invention is not particularly limited, but is preferably in the range of 0.1 to 30% by mass in order to produce a dense thin film.

The amount of water used for the preparation of the metal oxide thin film forming composition is not particularly limited, but when using a metal chelate compound having a total of two or more hydrolyzable groups and / or hydroxyl groups as the metal compound or the like, In particular, when a metal chelate compound having a total of 2 or more hydrolyzable groups and / or hydroxyl groups and having a β-ketoester as a ligand is used, the amount is less than 2 mol with respect to 1 mol of the metal chelate compound. It is preferable that it is 0.5 mol or more and less than 2 mol.

Further, when a metal chelate compound having a total of 2 or more hydrolyzable groups and / or hydroxyl groups is used as the metal compound or the like, it preferably has 2 or more total hydrolyzable groups and / or hydroxyl groups, and β- When a metal chelate compound having a diketone or hydroxycarboxylic acid as a ligand is used, a transparent metal oxide dispersion can be obtained by using 2 mol or more of water with respect to 1 mol of the metal chelate compound. it can. Here, the term “transparent” means a state where the transmittance in visible light is high, as described later. By using such a dispersion, a homogeneous and dense metal oxide thin film can be formed.

Further, when a metal chelate compound having a total of 2 or more hydrolyzable groups and / or hydroxyl groups is used as the metal compound or the like, when the metal element is a Ti atom, it is 5 times mol or more with respect to the titanium chelate compound. In addition, by using preferably 10 times mol or more, more preferably 20 times mol or more of water, a dispersion liquid in which fine particles of titanium oxide having a particle diameter of 1 to 20 nm are uniformly dispersed can be obtained.

Examples of water used for the preparation of the metal oxide thin film forming composition include general tap water, distilled water, and ion exchange water. Of these, use of distilled water or ion exchange water is preferred, and use of ion exchange water having an electric conductivity of 2 μS / cm or less is particularly preferred.

The water added to the metal oxide thin film-forming composition is preferably diluted with an organic solvent. As an organic solvent used for diluting water, a solvent having no reactivity with a metal compound and having a freezing point below a temperature at which the metal compound does not react with water and hydrolyze, that is, the freezing point is 0 ° C. In particular, those below −10 ° C. are preferred. Specific examples include those listed as organic solvents used in the organic solvent solution of the metal compound and the like.

The mixing ratio of water and organic solvent is such that the amount of water is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, and even more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the organic solvent. It is. When the proportion of water used exceeds 50 parts by mass, the generated particles may be intensively aggregated.

Further, when water and the organic solvent are uniformly dissolved and mixed, they can be used as they are, but when water and the organic solvent are not uniformly mixed, for example, 1,2-bis- (2- It is preferable to use a surfactant such as sodium ethylhexyloxycarbonyl) -1-ethanesulfonate, polyoxyethylene (6) nonylphenyl ether, or to uniformly disperse by a method such as stirring treatment or ultrasonic treatment.

The temperature at which water is added to an organic solvent solution such as a metal compound and the whole volume is stirred is usually −100 ° C. to + 200 ° C., preferably −80 ° C. to + 150 ° C. By adding water to an organic solvent solution such as a metal compound and stirring the entire volume, hydrolysis and polycondensation reaction of the metal compound and the like proceed. The time for stirring the whole volume is usually several minutes to several tens of hours.

In this case, in order to control the hydrolysis and polycondensation reaction of the metal compound, the temperature at which water is added to the organic solvent solution such as the metal compound, the temperature at which the entire volume is stirred, and the like can be changed stepwise. For example, the temperature of a solution of a metal compound or the like is cooled to −80 ° C. to −20 ° C., and water (or a mixture of water and an organic solvent) at −10 ° C. to + 20 ° C. is slowly added dropwise with stirring. After completion of the dropwise addition of (or a mixture of water and an organic solvent), a method of gradually raising the temperature of the reaction solution gradually to the boiling point of the solvent to complete the hydrolysis / condensation reaction can be employed. Moreover, the dropping of water (or a mixture of water and an organic solvent) can be divided into a plurality of times, and the dropping temperature of water (or a mixture of water and an organic solvent) can be set to different temperatures. Furthermore, after hydrolyzing a metal compound etc., you may neutralize a reaction liquid with a suitable base.

The metal oxide thin film forming composition obtained as described above is a transparent solution containing a metal oxide precursor.
This metal oxide precursor is a particulate material having an average particle size in the range of 1 to 10 nm, and is a monodisperse dispersoid that is dissolved or uniformly dispersed without agglomeration in an organic solvent. That is, the metal compound or the like is a dispersoid having a metal-oxygen bond that is stably dispersed without aggregation in an organic solvent in the absence of an acid, a base and / or a dispersion stabilizer.

Here, the state of stable dispersion without aggregation means a state in which a dispersoid having a metal-oxygen bond is not condensed and not separated in an organic solvent, preferably transparent and homogeneous. State. Transparent means a state with high transmittance in visible light. Specifically, the spectral transmittance measured under the conditions that the concentration of the dispersoid is 0.5% by weight in terms of oxide, the optical path length of the quartz cell is 1 cm, the control sample is an organic solvent, and the light wavelength is 550 nm. In particular, it refers to a state representing a transmittance of 80 to 100%. Further, the particle diameter for obtaining high transmittance in visible light is preferably in the range of 1 to 50 nm.

In the present invention, the solution obtained above can be used as it is as a composition for forming a metal oxide thin film, or is diluted with an appropriate solvent, or the solvent is distilled off and then redissolved in another solvent. A thing can also be used as a composition for metal oxide thin film formation.

3-6) Production of Metal Oxide Thin Film A metal oxide thin film can be formed by applying or spraying a composition for forming a metal oxide thin film on the first layer and drying the obtained coating film. .

The method for applying or spraying the metal oxide thin film forming composition onto the substrate is not particularly limited, and includes a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, There is no particular limitation as long as it is a method capable of forming a thin film having a smooth surface, such as a silk screen method or an ink jet method.

The obtained coating film is dried usually at 20 to 200 ° C., preferably 20 to 150 ° C. for several minutes to several tens of minutes, whereby a metal oxide thin film can be formed.
The thickness of the metal oxide thin film formed as described above is 200 nm or less, preferably 10 to 100 nm, more preferably 10 to 50 nm, and variation in the film thickness of the following formula [%] = 100 × (film thickness Standard deviation) / (average thickness)
Is less than 10%, preferably less than 6%.

Also, the metal oxide thin film can be made into a super hydrophilic thin film having a smooth surface by cleaning the surface with ozone.

The average surface roughness (Ra) is usually 5 nm or less, preferably 3 nm or less, and most preferably 1 nm or less. A dense monomolecular film capable of forming a nanoscale fine pattern can be efficiently formed on the first thin film having a smooth surface by irradiation with light, ultraviolet light, an electron beam, or the like. *

The metal oxide thin film is preferably sensitive to electromagnetic waves. In particular, those having a property of absorbing ultraviolet light having a wavelength of 350 nm or less, preferably 250 to 350 nm are preferable.
Further, when the metal oxide thin film is at least one selected from the group consisting of titanium and zirconium, an organic substance contained by irradiating electromagnetic waves during or after the formation of the metal oxide thin film As a result, the refractive index of 1.5 to 1.7 before irradiation with electromagnetic waves can be improved to 1.6 to 2.1.
Here, as the electromagnetic wave, those having a wavelength of 350 nm or less are preferable, and ultraviolet light having a wavelength of 250 to 350 nm is preferable.

(Gas barrier film)
The gas barrier film as the second layer of the present invention is not particularly limited as long as it has gas barrier properties such as oxygen and water vapor, but is preferably a thin film of an inorganic compound, and in particular, titanium, zirconium, aluminum, silicon, germanium, Preference is given to thin films of metal oxides, metal nitrides, metal carbides or their composites with a metal element selected from the group consisting of indium, tin, tantalum, zinc, tungsten and lead.
The thickness of the gas barrier film is usually 500 nm or less, preferably 10 to 200 nm. If the film thickness is less than 10 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and the function as a gas barrier material may not be sufficiently achieved. On the other hand, when the film thickness exceeds 500 nm, it is difficult to maintain flexibility in the thin film, and productivity is lowered.
The average surface roughness (Ra) of the gas barrier laminate is usually preferably 1 nm or less. The water vapor permeability is 1 × 10 ⁻¹ g / m ² · day or less, preferably 1 × 10 ⁻² g / m ² · day or less.
A method of forming a gas barrier film made of an inorganic compound on the first layer can be formed by a known method, but a physical method such as a sputtering method, a vacuum evaporation method, an ion plating method, or a spray method. , A chemical method such as a dip method, a thermal CVD method, a plasma CVD method, or the like.
For example, according to the sputtering method, a film made of silicon oxide can be formed by using, for example, a silicon compound sintered in the presence of oxygen gas as a target, and metal silicon as a target. Films can also be formed by reactive sputtering in the presence of oxygen. Further, according to the plasma CVD method, a film made of silicon oxynitride can be formed on a substrate by supplying silane gas together with oxygen gas and nitrogen gas into a chamber in which plasma is generated and reacting them. . Further, according to the thermal CVD method or the like, a film made of silicon oxide can be formed by using, for example, an organic solvent solution containing a silicon compound as an evaporant.
In the present invention, it is particularly preferable to form a film by sputtering, vacuum deposition, ion plating, or plasma CVD.

4) Other layers In the thin film laminate of the present invention, one or more other layers may be laminated on the second layer. For example, a metal oxide thin film can be laminated by a sol-gel method as in the second layer. For example, a layer having a refractive index smaller than that of the second layer can be provided by laminating a SiO ₂ film or the like. Furthermore, ITO (indium tin oxide), SAM (self-integrated film), other functional thin films, and the like can be laminated by a conventionally known method other than the sol-gel method.
5) Others The thin film laminate of the present invention can be used in various shapes such as a film shape, a plate shape, a lens shape, and a bead shape.

Hereinafter, the present invention will be described in detail using examples, but the technical scope of the present invention is not limited to these examples.

1 Preparation of first layer 1-1 Preparation of organic / inorganic composite thin film forming solution 264.7 g of diisopropoxybisacetylacetonate titanium (Nippon Soda, T-50) was added to industrial ethanol (Nippon Alcohol Sales, Sol Mix AP-7) After dissolving in 137.3 g, 51.1 g of ion-exchanged water was added with stirring. The solution was stirred for 2 hours while being heated to 40 ° C. to be hydrolyzed to obtain a hydrolyzate solution [A-1] of a yellow transparent metal compound.
264.8 g of vinyltrimethoxysilane [B-1] (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003) and 190.2 g of 3-methacryloxypropyltrimethoxysilane [B-2] (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) A mixed solution [C-1] ([B-1] / [B-2] = 70/30: mol) was prepared. Next, 453.1 g of [A-1] and 455.0 g of [C-1] were stirred and mixed, and 92.0 g of ion-exchanged water was added and stirred for one day to produce a condensed liquid [D-1].
451.8 g of urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry, UV7600B) was dissolved in 364.1 g of methyl isobutyl ketone. In this solution, 18.1 g of 2-methyl-1- (methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF, Irgacure907) is dissolved as a photopolymerization initiator to obtain a solution [E-1]. It was.
[D-1] 166.1 g and [E-1] 834.0 g were mixed so that the solid content ratio was [D-1] / [E-1] = 10% by mass / 90% by mass, An organic-inorganic composite thin film forming solution [F-1] was prepared.

1-2 Preparation of Organic-Inorganic Composite Thin Film 1-2-1 Preparation of Organic-Inorganic Composite Thin Film (1) The solution for forming the organic-inorganic composite thin film [F-1] was dried at 80 ° C., and the cumulative UV irradiation amount was 473 mJ / cm ^2. Using a micro gravure coater (manufactured by Yasui Seiki Co., Ltd.) under the conditions (made by Eye Graphics, using a high-pressure mercury lamp), a film having a thickness of 5 μm was formed on a PET film (Toyobo Co., Ltd., Cosmo Shine A4300). The coating film surface was subjected to atmospheric pressure plasma treatment to obtain an organic-inorganic composite thin film [X-1]. The contact angle of water on the surface of this coating film was 10 ° or less immediately after the atmospheric pressure plasma treatment.

1-2-2 Preparation of organic / inorganic composite thin film (2) A solution for forming an organic / inorganic composite thin film [F-1] was dried at a temperature of 80 ° C. and an integrated UV irradiation amount of about 200 mJ / cm ² (manufactured by Fusion UV System, “ The film was formed on a PET film (Toyobo Co., Ltd., “Cosmo Shine A1598”) using a gravure coater under the conditions of “H bulb”. Further, this coating film surface was subjected to an atmospheric pressure plasma treatment to obtain an organic-inorganic composite thin film [X-2] having a film thickness of 5 μm.

2 Fabrication of the second layer

[Example 1] In the case of a metal oxide thin film (preparation of a solution for forming a metal oxide thin film)
After dissolving 60.6 g of diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda Co., Ltd., T-50) in 469.7 g of industrial ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., Solmix AP-7), ions were stirred while stirring. 469.7 g of exchange water was added. This solution was stirred for 2 hours while being heated to 40 ° C. and hydrolyzed to obtain a metal oxide thin film forming solution [G-1] of a yellow transparent metal compound.

(Production of metal oxide thin film)
Using a micro gravure coater (manufactured by Yasui Seiki Co., Ltd.), the metal oxide thin film forming solution [G-1] is deposited on the organic-inorganic composite thin film [X-1] at a drying temperature of 80 ° C. A metal oxide thin film having an amorphous structure was formed to obtain a highly transparent thin film laminate [Y-1] having a total light transmittance of 92% and a haze ratio of 0.5%.

(UV irradiation)
The thin film laminate [Y-1] was irradiated with ultraviolet rays using a conveyor type UV lamp (manufactured by Eye Graphics, high pressure mercury lamp). The integrated irradiation amount was changed by fixing the peak illuminance of ultraviolet rays and increasing the number of exposures. The metal oxide thin film had an amorphous structure even after the ultraviolet irradiation, and the transparency of the thin film laminate [Y-1] did not change. Further, the contact angle of water on the surface of the laminate immediately after the ultraviolet irradiation was 10 ° or less.

(Measurement of refractive index)
A spectroscopic ellipsometer (manufactured by JA Woollam, M-2000D) was used to measure the refractive index of the thin film laminate produced in Example 1 before and after UV irradiation. The results are shown in Table 1.

　

　

(Measurement of surface roughness)
Using AFM (manufactured by SII Nanotechnology, SPI-3800N, SPA400 unit), the surface roughness of the thin film laminate produced in Example 1 before and after UV irradiation was measured. The results are shown in Table 2.

(Analysis of composition in film)
Using ESCA, the composition analysis before and after ultraviolet irradiation of the thin film laminate produced in Example 1 was performed. The results are shown in FIGS.
From this result, the concentration of carbon atoms in the concentrated layer of the condensate of the organosilicon compound at a depth of 50 nm from the film surface is 20% or more compared to the concentration of carbon atoms in the first layer at a depth of 400 nm from the film surface. There were few.

　同じ薄膜積層体について、第１層と第２層との界面から３００ｎｍにある第１層の炭素原子の濃度と、有機ケイ素化合物の縮合物の濃縮層の炭素原子の濃度との比較を示す。

For the same thin film laminate, a comparison is made between the concentration of carbon atoms in the first layer at 300 nm from the interface between the first layer and the second layer and the concentration of carbon atoms in the concentrated layer of the condensate of the organosilicon compound.

 

 

(Evaluation of film thickness uniformity)
The thin film laminate [Y-1] is cut into a size of 30 cm × 30 cm, and further divided into 36 pieces each having a size of 5 cm × 5 cm, and each is formed into a film with a spectroscopic ellipsometer (manufactured by JA Woollam, M-2000D). Thickness measurement was performed. The results are shown in Table 4. Table 4 shows the film thickness for each section divided into six sections in the vertical and horizontal directions.
As a result, the average film thickness was 32.8 nm, and the variation in film thickness represented by the following formula was 5.4%.
Variation in film thickness [%] = 100 x (standard deviation of film thickness) / (average film thickness)

 

 

Example 2 Gas Barrier Film A silicon oxynitride thin film having a thickness of 50 nm was formed on the organic-inorganic composite thin film “X-2” by reactive sputtering using a Si target.

[Comparative example]
(Preparation of organic polymer thin film forming solution)
A urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry, “purple light UV7600B”) was dissolved in methyl isobutyl ketone so as to be 40% by mass. In this solution, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173) as a photopolymerization initiator was dissolved to 4% by mass with respect to the solid content of the urethane acrylate oligomer, An organic polymer thin film forming solution [F-2] was prepared.

(Formation of organic polymer thin film)
The organic polymer thin film forming solution “F-2” was subjected to PET film (Toyo) using a gravure coater under the conditions of a drying temperature of 80 ° C. and an integrated UV irradiation amount of about 473 mJ / cm ² (manufactured by Eye Graphics, high-pressure mercury lamp). An organic polymer thin film [X-3] was obtained on a “Cosmo Shine A4300” (spun product) film having a thickness of 7 μm.

(Formation of gas barrier layer)
A silicon oxynitride thin film having a thickness of 50 nm was formed on the organic polymer thin film [X-3] by reactive sputtering using a Si target.

Evaluation method (measurement of water vapor permeability)
In accordance with JIS K7129-C, the water vapor permeability was measured under conditions of a temperature of 40 ° C. and a humidity of 90%.

(Evaluation of adhesion)
In accordance with JIS K5600, the grids were made by making 11 cuts at 1 mm intervals vertically and horizontally into the coating film to make 100 grids. Cellotape (registered trademark) was affixed to each sample, and the tape was peeled off after being rubbed several times with the belly of the finger, and evaluated by the number of grids remaining without peeling off the coating film (FIG. 5).

(Evaluation of surface roughness)
The average surface roughness of the thin film was measured with an AFM (atomic force microscope) using SPI3800N and SPA400 units (both manufactured by SII Nanotechnology). An SN-AF01 cantilever was used for AFM measurement, and a 10 μm square range was measured. The surface roughness was determined from the measured shape image data (FIG. 6).

(Elemental analysis in film)
The distribution of elements in the depth direction in the film was analyzed using ESCA (Quantum 2000, manufactured by ULVAC-PHI). The film was etched by Ar sputtering, and the content of carbon atoms, oxygen atoms, silicon atoms, and nitrogen atoms in the film was measured with an X-ray photoelectron analyzer (XPS) (FIGS. 7 and 8). The carbon atom concentration at a depth of 300 nm from the interface between the first layer and the second layer is 90%, and the carbon atom concentration of the concentrated layer of the organosilicon compound of the first layer is 60 nm (from the surface of the film, as shown in FIG. Interface), depths of 90 nm and 100 nm were 3%, 41% and 53%, respectively. This value is 3, 46, 59, assuming that the carbon atom concentration at a depth of 300 nm from the interface is 100, and is 20% or less less than the carbon atom concentration at a depth of 300 nm from the interface.

[Examples 3 and 4]
(TEM observation of thin film laminate)
A thin film laminate produced by changing only the thickness of the second layer to be laminated by the same method as in Example 1 and Example 2 was used to obtain a transmission electron microscope (FE-TEM, HF-2000 manufactured by Hitachi, Ltd., acceleration voltage). 200 kV), and the cross-sectional observation was measured (FIGS. 9 and 10). On the first layer side of the interface between the first layer and the second layer, a layer in which the condensation product of the organosilicon compound is concentrated is observed. It is also observed that the surface of the second layer is very smooth.

Claims (19)

In the thin film laminate formed in the order of the first layer and the second layer on the resin substrate,
The first layer is
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And when (4-n) is 2 or more, each X may be the same or different.) A condensate of an organosilicon compound represented by b) and a film thickness containing an organic polymer compound An organic-inorganic composite thin film of 500 nm or more,
The second layer
a) a metal oxide thin film having a thickness of 200 nm or less formed by a sol-gel method, and the following formula:
Variation in film thickness [%] = 100 x (standard deviation of film thickness) / (average film thickness)
Or a metal oxide thin film having a thickness variation of less than 10%, or
b) a gas barrier film having a film thickness of 500 nm or less,
The first layer has a layer on which the condensate of the organosilicon compound represented by formula (I) is concentrated on the interface side with the second layer, and the concentration of carbon atoms in the concentrated layer is the same as that of the first layer. A thin film laminated body characterized by being 20% or less less than the concentration of carbon atoms in the first layer having a depth of 300 nm from the interface with the second layer. The concentration of carbon atoms in the concentrated layer of the first layer is 40% or more lower than the concentration of carbon atoms in the first layer having a depth of 300 nm from the interface between the first layer and the second layer. Item 2. The thin film laminate according to Item 1. The thin film laminate according to claim 1, wherein the average surface roughness Ra is 1 nm or less. The first layer further contains a metal compound having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead. 1. The thin film laminate according to 1. The metal oxide thin film of the second layer is a metal oxide thin film having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead. The thin film laminate according to claim 1, wherein 6. The thin film laminate according to claim 5, wherein the metal element is a metal element selected from the group consisting of titanium, zirconium, indium, tin, tantalum, zinc, tungsten and lead. The thin film laminate according to claim 6, wherein the metal element is a metal element selected from the group consisting of titanium and zirconium. 8. The thin film laminate according to claim 7, wherein the metal oxide thin film of the second layer is a layer whose refractive index can be changed from 1.6 to 2.1 by irradiation with electromagnetic waves. . 9. The thin film laminate according to claim 7, wherein the second metal oxide thin film is an amorphous titanium oxide thin film. The metal oxide thin film of the second layer formed by the sol-gel method has a total of two or more hydrolyzable groups and / or hydroxyl groups, and a metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups in total. Formed from a composition for forming a thin film obtained by adding a predetermined amount of water to an organic solvent solution containing at least one selected from the group consisting of metal organic acid salts, and partial hydrolysis products thereof. The thin film laminate according to claim 1, wherein the thin film laminate is a thin film. The thin film laminate according to claim 1, wherein a third layer having a refractive index smaller than that of the second layer and having a thickness of 200 nm or less is formed on the metal oxide thin film of the second layer. The thin film stack according to claim 11, wherein the third layer is a thin film containing SiO ₂ formed by a sol-gel method. The thin film laminate according to claim 1, wherein the thin film laminate is a substrate for forming a transparent conductive film. Metal oxide, metal nitride, metal carbide in which the gas barrier film of the second layer has a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead Or it is a thin film which consists of those composites, The thin film laminated body of Claim 1 characterized by the above-mentioned. ^2. The thin film laminate according to claim 1, wherein the water vapor permeability is 1 × 10 ⁻¹ g / m ² · day or less. The thin film laminate according to claim 1, wherein the water vapor permeability is 1 × 10 ⁻² g / m ² · day or less. The method for producing a thin film laminate according to claim 1, comprising the following steps 1 to 3.
(Step 1) As a first layer on the resin substrate,
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And each X may be the same or different when (4-n) is 2 or more.)
b) forming an organic-inorganic composite thin film containing an organic polymer compound;
(Step 2) Plasma treatment or UV ozone treatment of the surface of the first layer,
(Step 3) A step of forming the second layer on the surface of the first layer by the following method a) or b).
a) A step of forming a metal oxide thin film by a sol-gel method.
b) A step of forming a gas barrier film by sputtering, vacuum deposition, ion plating, or plasma CVD. In (Step 1), the composition of the first layer further includes a metal compound having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, and lead. The method for producing a thin film laminate according to claim 17. 18. The method of manufacturing a thin film laminate according to claim 17, wherein the electromagnetic wave is irradiated during or after the formation of the second layer in step a) of step 3.

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