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WO2013118442A1 - Laminé à film fin - Google Patents

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Publication number
WO2013118442A1
WO2013118442A1 PCT/JP2013/000383 JP2013000383W WO2013118442A1 WO 2013118442 A1 WO2013118442 A1 WO 2013118442A1 JP 2013000383 W JP2013000383 W JP 2013000383W WO 2013118442 A1 WO2013118442 A1 WO 2013118442A1
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WIPO (PCT)
Prior art keywords
thin film
group
layer
metal
compound
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Ceased
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PCT/JP2013/000383
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English (en)
Japanese (ja)
Inventor
大幹 芝田
和久 熊澤
木村　信夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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Priority to CN201380007697.9A priority Critical patent/CN104093560B/zh
Priority to JP2013557403A priority patent/JP5911182B2/ja
Priority to KR1020147021492A priority patent/KR101563451B1/ko
Publication of WO2013118442A1 publication Critical patent/WO2013118442A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0843—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0875—Antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0881—Titanium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0887—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc

Definitions

  • 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.
  • 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.
  • ITO indium tin oxide
  • a method of forming a thin film laminate for controlling the reflectance between a plastic substrate and a transparent conductive film is employed.
  • 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.
  • 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.
  • Patent Document 3 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.
  • Patent Document 4 An organic-inorganic composite having excellent adhesion to the substrate and moisture resistance has been developed (Patent Document 4).
  • Patent Document 8 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.
  • 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.
  • 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.
  • the first layer contains a condensate of an organosilicon compound and an organic polymer compound as a first layer
  • 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.
  • 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.
  • 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 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 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 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.
  • 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.
  • 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
  • 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.
  • 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.
  • each X may be the same or different when (4-n) is 2 or more.
  • 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.
  • 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.
  • a thin film laminate can be produced on a resin substrate by an inexpensive wet process.
  • 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.
  • 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. .
  • the surface of the first layer 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.
  • 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.
  • a transparent conductive film such as ITO
  • it is also useful as a transparent conductive film for a touch panel or the like.
  • 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.
  • 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
  • gas barrier properties can also be improved.
  • 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.
  • the adhesion with the substrate resin film is also good.
  • 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.
  • 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.
  • FIG. 1 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.
  • 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.
  • each X may be the same or different when (4-n) is 2 or more.
  • 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,
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • these substrates may be provided with a waterproof layer containing a polyvinylidene chloride polymer for the purpose of improving so-called dimensional stability.
  • a thin film made of an organic compound and / or an inorganic compound may be provided for the purpose of gas barrier.
  • the inorganic compound include silica, alumina, talc, vermiculite, kaolinite, mica, and synthetic mica.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m, preferably 3 to 500 ⁇ m.
  • 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 ⁇ m to 10 ⁇ m. If the thickness is less than 500 nm, the surface unevenness of the substrate tends to be affected, and if it exceeds 10 ⁇ m, the substrate tends to warp and the flexibility becomes poor.
  • the organosilicon compound is represented by the following formula (I).
  • R n SiX 4-n (I)
  • 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 may be the same or different, and when (4-n) is 2 or more, each X may be the same or different.
  • 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.
  • 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.
  • hydrocarbon group or “group consisting of a hydrocarbon polymer” may contain an oxygen atom, a nitrogen atom, or a silicon atom.
  • linear or branched alkyl group having 1 to 10 carbon atoms examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and n-pentyl.
  • 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.
  • cycloalkyl group having 3 to 8 carbon atoms examples 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.
  • 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.
  • 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 is a C3-C8 alkenyl group having a carbon-carbon double bond at any one or more positions and having a cyclic portion.
  • 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.
  • alkynyl group examples 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.
  • cycloalkylalkyl group examples 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.
  • arylalkyl group examples 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.
  • arylalkenyl group examples 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.
  • -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
  • hydrocarbon group having an oxygen atom examples 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.
  • 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; ⁇ -methylglycidyl group, ⁇ -ethylglycidyl group, ⁇ -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
  • 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).
  • R ′′ represents a hydrogen atom or an alkyl group, and each R ′′ may be the same as or different from each other.
  • alkyl group and aryl group for R ′′ include the same groups as those exemplified for R above.
  • 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.
  • hydrocarbon having a silicon atom examples 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.
  • 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.).
  • n 1 or 2
  • each R may be the same or different.
  • these can be used individually by 1 type or in combination of 2 or more types.
  • X represents a hydroxyl group or a hydrolyzable group.
  • 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.
  • Examples of 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.
  • the raw material organosilicon compounds include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethylsilane.
  • 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, ⁇ -ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) acrylamide; Lil, styren
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • f is the valence of M.
  • This onium salt is a compound that releases a Lewis acid by receiving light.
  • 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.
  • 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.
  • 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%.
  • a sensitizer can be added as necessary.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ -ketocarbonyl compound, a ⁇ -ketoester compound, or an ⁇ -hydroxyester compound.
  • methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, acetoacetate ⁇ -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 ⁇ -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.
  • 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;
  • 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.
  • hydrolyzable group in the metal compound of the present invention examples 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.
  • 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.
  • 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.
  • 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
  • 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.
  • the raw material of the organic polymer compound is dissolved in a solvent, a photopolymerization initiator is added, and then both solutions are mixed.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the concentration of carbon atoms means the molar concentration of carbon atoms when (total metal atoms + oxygen atoms + carbon atoms) is 100%.
  • 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.
  • the silicon concentration increases as the carbon concentration decreases.
  • step (C) may be omitted.
  • step (C) Method of performing step (C) By performing this method, R in formula (I) may not be selected.
  • 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.
  • the film thickness to be formed is not particularly limited and is, for example, about 0.1 to 200 ⁇ m.
  • 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.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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
  • the irradiation amount of UV is usually 1 J / cm 2 or more, preferably 1 ⁇ 100000J / cm 2, more preferably 10 ⁇ 100000J
  • 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.
  • the treatments have been used mainly for the purpose of cleaning dirt derived from organic substances on inorganic compounds such as glass.
  • 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.
  • the second layer is a metal oxide thin film or a gas barrier 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.
  • the metal oxide is preferably amorphous.
  • 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.
  • Metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total is a hydrolyzable group and / or hydroxyl group.
  • a compound represented by the formula (III) can be preferably exemplified.
  • R a M 2 (Y) b (III)
  • M 2 represents a metal atom, preferably a metal atom of Groups 13 to 15 of the periodic table.
  • At least one selected from the group consisting of silicon, germanium, tin, lead, titanium, zirconium, aluminum, indium, tantalum, tungsten and zinc can be exemplified.
  • 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.
  • R represents a hydrogen atom or an organic group which may have a hydrolyzable group.
  • 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.
  • the organic group include an alkyl group, an alkenyl group, and an aryl group.
  • R is an organic group, the carbon number thereof is not particularly limited, but is usually 1 to 20, preferably 1 to 12.
  • R examples 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 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.
  • 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, t
  • tetramethoxysilane, tetraethoxysilane, titanium tetrapropoxide, zirconium tetrapropoxide, and zirconium tetrabutoxide are more preferable.
  • 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.
  • 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
  • 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; ⁇ -diketones such as acetylacetone, benzoylacetone and hexafluoroacetylacetone; ⁇ -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
  • 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.
  • the obtained metal chelate compound can be isolated, it can be subjected to the subsequent hydrolysis and polycondensation reaction as it is.
  • 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.
  • organic acids examples 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.
  • 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.
  • Partial hydrolysis product of the compounds of 3-1) to 3-3) 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. .
  • 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,
  • 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.
  • halogenated hydrocarbons such as carbon chloride, dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and bromobenzene.
  • organic solvents can be used singly or in combination of two or more.
  • 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 ⁇ -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.
  • a metal chelate compound having a total of 2 or more hydrolyzable groups and / or hydroxyl groups when used as the metal compound or the like, it preferably has 2 or more total hydrolyzable groups and / or hydroxyl groups, and ⁇ -
  • a metal chelate compound having a diketone or hydroxycarboxylic acid as a ligand when 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.
  • 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.
  • a metal chelate compound having a total of 2 or more hydrolyzable groups and / or hydroxyl groups when 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.
  • 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.
  • water used for the preparation of the metal oxide thin film forming composition examples 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 ⁇ S / cm or less is particularly preferred.
  • the water added to the metal oxide thin film-forming composition is preferably diluted with an organic solvent.
  • 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.
  • water and the organic solvent 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.
  • 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.
  • an organic solvent solution such as a metal compound
  • the time for stirring the whole volume is usually several minutes to several tens of hours.
  • 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.
  • 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.
  • 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.
  • the dropping of water 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.
  • 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.
  • Transparent means a state with high transmittance in visible light.
  • the particle diameter for obtaining high transmittance in visible light is preferably in the range of 1 to 50 nm.
  • 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.
  • 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 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.
  • those having a property of absorbing ultraviolet light having a wavelength of 350 nm or less, preferably 250 to 350 nm are preferable.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a film made of silicon oxide can be formed by using, for example, an organic solvent solution containing a silicon compound as an evaporant.
  • a metal oxide thin film can be laminated by a sol-gel method as in the second layer.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 hydrolyze
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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 ⁇ m.
  • 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%.
  • 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 ⁇ m square range was measured. The surface roughness was determined from the measured shape image data (FIG. 6).
  • 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.

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TW201334969A (zh) 2013-09-01
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TW201333055A (zh) 2013-08-16
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KR101563451B1 (ko) 2015-10-26
JP5911182B2 (ja) 2016-04-27

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