WO2015129616A1 - Composition aqueuse ainsi que procédé de fabrication de celle-ci, film de revêtement dur, film stratifié, film conducteur transparent, et panneau tactile - Google Patents

Composition aqueuse ainsi que procédé de fabrication de celle-ci, film de revêtement dur, film stratifié, film conducteur transparent, et panneau tactile Download PDF

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WO2015129616A1
WO2015129616A1 PCT/JP2015/055011 JP2015055011W WO2015129616A1 WO 2015129616 A1 WO2015129616 A1 WO 2015129616A1 JP 2015055011 W JP2015055011 W JP 2015055011W WO 2015129616 A1 WO2015129616 A1 WO 2015129616A1
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film
hard coat
aqueous composition
fine particles
inorganic fine
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English (en)
Japanese (ja)
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亜矢 中山
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富士フイルム株式会社
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    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the present invention relates to an aqueous composition, a production method thereof, a hard coat film, a laminated film, a transparent conductive film, and a touch panel.
  • the present invention is an aqueous composition containing a metal chelate compound and inorganic fine particles surface-modified with a bifunctional alkoxysilane, wherein the zeta potential of the modified inorganic fine particles is a certain value or less.
  • this invention relates to the hard coat film formed from the said aqueous composition, and its utilization.
  • display devices such as a liquid crystal display, a plasma display, and a touch panel display are rapidly spreading.
  • the surface of the members of these display devices is easily damaged because they come into contact with various objects during manufacture. If scratches are present, the transmittance may decrease or the scratches may be visible. For this reason, the surface of a display device is required to have high scratch resistance and impact resistance.
  • a hard coat layer is often provided on the surface layer of the display device in order to give the surface of the display device high scratch resistance and impact resistance.
  • the hard coat layer is formed by curing a material containing a polyfunctional acrylic polymerizable monomer or oligomer by irradiating ultraviolet rays or electron beams, or by condensing a hydrolyzate of alkoxysilane and curing the material. .
  • Patent Document 1 discloses a hydrolyzate of a silane compound represented by a predetermined structural formula, titanium oxide composite fine particles, an unsaturated or saturated polyvalent carboxylic acid or acid anhydride thereof, and a thermosetting catalyst. It is disclosed that a hard coat layer is formed using a coating composition containing the coating composition.
  • Patent Document 2 discloses forming a hard coat layer using a hard coating composition containing a bi- to tetra-functional alkoxysilane, metal oxide fine particles, and a metal chelate.
  • Patent Document 3 discloses a hard coat layer using a hard coat composition containing a zirconia colloidal particle, a dispersant selected from acetic acid and ⁇ -diketone, and the like, and a hydrolyzate of a tri- to tetra-functional alkoxysilane. It is disclosed to form.
  • Patent Document 4 discloses forming a hard coat layer using a hard coat liquid containing a rutile type titania sol, a zirconia sol, an aluminum catalyst, and an organosilicon compound.
  • Patent Document 5 discloses a hard coat layer obtained by condensing and curing an alkoxysilane hydrolyzate and containing inorganic fine particles.
  • the inorganic fine particles subjected to the surface treatment and the alkoxysilane are heated and reacted under specific pH conditions.
  • the refractive index of the hard coat layer can be increased to a certain value or the refractive index can be freely adjusted. It was difficult.
  • the hard coat layer is dissolved by an alkaline solution often used when laminating the transparent conductive layer, and the haze value is increased. there were.
  • a hard coat layer In order to form a hard coat layer, it is generally laminated with a base material / an easy adhesive layer / a hard coat layer, but the refractive indexes of the base material, the easy adhesive layer, and the hard coat layer are different from each other. Light may be reflected and interference fringes may be visible. In order to prevent this, it is necessary to accurately adjust the refractive index and film thickness of each layer, but the film thickness needs to be finely adjusted on the order of several nm, and coating accuracy is required. In addition, since the easy-adhesion layer is a thin film, there are problems such as difficulty in adhesion.
  • the present inventors proceeded with studies for the purpose of improving the stability of inorganic fine particles by a simple method in the composition for forming a hard coat layer.
  • the present inventors have made studies for the purpose of producing a hard coat layer having a sufficiently high refractive index.
  • the present inventors have also studied to increase the alkali resistance of the obtained hard coat layer.
  • the zeta potential of the inorganic fine particles has higher dispersibility when the absolute value is larger, and the zeta potential is more likely to aggregate as the zeta potential approaches 0. That is, when the surface of the inorganic fine particles was modified with a metal chelate compound and a bifunctional alkoxysilane, the zeta potential was close to 0, and thus the dispersibility was thought to be low. However, as a result of intensive studies by the present inventors, when the surface of the inorganic fine particles is modified with a metal chelate compound and a bifunctional alkoxysilane, the change in charge on the surface of the inorganic fine particles is reduced, and the liquid stability is increased.
  • the present inventors have found that a hard coat film formed using this aqueous composition has a high refractive index and is excellent in alkali resistance and adhesiveness. Furthermore, the present inventor has found that when a hard coat layer is formed from the aqueous composition having the above-described configuration, bone appearance can be reduced even when ITO conductive films having various thicknesses are laminated.
  • the present invention has been completed based on these findings. Specifically, the present invention has the following configuration.
  • aqueous composition comprising inorganic fine particles having a metal chelate compound and a bifunctional alkoxysilane or a hydrolyzate thereof on the surface, wherein the inorganic fine particles have a zeta potential of 0 to 20 mV.
  • the metal chelate compound has an electronegativity of 1.3 to 1.9 and has a hydroxyl group or a hydrolyzable group.
  • the metal chelate compound includes at least one of an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound.
  • ⁇ 4> The aqueous composition according to any one of ⁇ 1> to ⁇ 3>, wherein the inorganic fine particles have a refractive index of 1.8 or more at 25 ° C.
  • ⁇ 5> The aqueous composition according to any one of ⁇ 1> to ⁇ 4>, wherein the inorganic fine particles are fine particles composed of zirconia or titania.
  • ⁇ 6> Mixing inorganic fine particles and a metal chelate compound to obtain an aqueous mixture; Mixing a bifunctional alkoxysilane or a hydrolyzate thereof with an aqueous mixture; After the step of mixing the bifunctional alkoxysilane or the hydrolyzate thereof, a step of further mixing the trifunctional alkoxysilane or the hydrolyzate thereof and / or the tetrafunctional alkoxysilane or the hydrolyzate thereof with a curing accelerator.
  • a method for producing an aqueous composition comprising: ⁇ 7> The method for producing an aqueous composition according to ⁇ 6>, wherein in the step of obtaining the aqueous mixture, the inorganic fine particles and the metal chelate compound are reacted for 1 hour or more.
  • the hard coat film according to ⁇ 9>, wherein the refractive index at 25 ° C. is 1.6 to 2.3.
  • the laminated film which has a ⁇ 11> base film and the hard coat film as described in ⁇ 9> or ⁇ 10> formed on the base film.
  • ⁇ 12> A difference between the refractive index of the easy-adhesion layer and the refractive index of the base film at 25 ° C., and the hard coat at 25 ° C.
  • ⁇ 14> The laminated film according to ⁇ 13>, wherein the optical adjustment layer has a refractive index of 1.60 to 1.90 at 25 ° C.
  • ⁇ 15> A transparent conductive film comprising the laminated film according to any one of ⁇ 11> to ⁇ 14> and a transparent electrode layer.
  • ⁇ 16> A touch panel having the transparent conductive film according to ⁇ 15>.
  • inorganic fine particles can be stably dispersed in an aqueous composition. Further, in the present invention, it is not necessary to go through a complicated manufacturing process in order to stably disperse the inorganic fine particles, and an organic solvent is not required, so that the production efficiency of the aqueous composition and the hard coat film can be increased. .
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the present invention relates to an aqueous composition comprising inorganic fine particles having a metal chelate compound and a bifunctional alkoxysilane or a hydrolyzate thereof on the surface, wherein the inorganic fine particles have a zeta potential of 0 to 20 mV.
  • the zeta potential of the inorganic fine particles in the aqueous composition of the present invention is 0 to 20 mV.
  • aggregation of the inorganic fine particles in the aqueous composition can be prevented by configuring the aqueous composition as described above and setting the zeta potential of the inorganic fine particles to 0 to 20 mV.
  • the refractive index of the hard coat film obtained by curing the aqueous composition can be sufficiently increased.
  • it becomes possible to adjust a hard coat film to the same refractive index as a base material or an easily bonding layer it becomes easy to adjust the film thickness of a hard coat layer and an easily bonding layer.
  • it becomes easy to increase the film thickness of an easily bonding layer it becomes easy to obtain high adhesiveness.
  • the aqueous composition of the present invention is used, a hard coat layer having strong alkali resistance can be obtained. Thereby, when laminating
  • the zeta potential is an index for evaluating the particle dispersibility / aggregation, interaction, and surface modification.
  • the absolute value of the zeta potential is large, the repulsive force between the particles increases, so that the dispersibility tends to be improved.
  • the dispersibility of the particles can also be determined.
  • the zeta potential can be measured using a known method, and the zeta potential is measured at a temperature of 25 ° C. and a pH of 6, for example, using DT1200 (manufactured by RUFUTO).
  • the zeta potential of the inorganic fine particles in the aqueous composition may be 0 to 20 mV, preferably 0 to 18 mV, and more preferably 0 to 15 mV.
  • the zeta potential of the inorganic fine particles being within the above range means that the surface of the inorganic fine particles in the aqueous composition is modified in a good state. Thereby, the stability of the inorganic fine particles in the aqueous solution when a pH change of the aqueous solution or other additives is added can be enhanced, and aggregation of the inorganic fine particles can be prevented.
  • the aqueous composition described above forms, for example, a hard coat layer by coating and curing on a support. That is, the aqueous composition of the present invention can be an aqueous composition for forming a hard coat layer.
  • the aqueous composition concerning embodiment of this invention contains water as a main component of a solvent, 90 mass% or more is preferable and, as for content of the water in a solvent, 95 mass% or more is more preferable. Since the aqueous composition of the present invention does not substantially use an organic solvent, what evaporates when the aqueous composition is applied and dried is mainly a water component. For this reason, compared with the case where an organic solvent is used, the load to an environment can be reduced significantly. Furthermore, since there is no volatilization of the organic solvent in the manufacturing process, manufacturing suitability can be improved.
  • the aqueous composition of the present invention contains inorganic fine particles.
  • the ratio of the inorganic fine particles to the total solid content in the aqueous composition is preferably 10% by volume or more, more preferably 14% by volume or more, and more preferably 20% by volume or more.
  • the proportion of inorganic fine particles is preferably 60% by volume or less, more preferably 55% by volume or less, and further preferably 50% by volume or less.
  • the ratio of the inorganic fine particles to the total solid content in the aqueous composition is preferably 10% by mass or more, more preferably 14% by mass or more, and more preferably 20% by mass or more. preferable.
  • the proportion of inorganic fine particles is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less.
  • two or more kinds of inorganic fine particles may be used in combination, and in this case, the total amount of all kinds used is within the above range.
  • the inorganic fine particles transparent and insulating metal oxide fine particles are preferably used because they are used directly below the transparent conductive film.
  • the refractive index of the inorganic fine particles is preferably 1.8 or more.
  • a refractive index shows the value in 25 degreeC.
  • the metal oxide fine particles include fine particles made of zirconia or titania. Zirconia and titania are preferable because they exhibit a high refractive index, and titania is particularly preferably used.
  • titania titanium oxide
  • examples of titania (titanium oxide) that can be used in the embodiment of the present invention include “TTO-55, 51, S, M, D” series ⁇ above, Ishihara Sangyo Co., Ltd. ⁇ ; “JR” series, “ JA “series ⁇ above, Teika Co., Ltd. ⁇ , rutile-type titania such as SRD-W ⁇ above, Sakai Chemical Industry Co., Ltd. ⁇ and the like.
  • the average particle size of the inorganic fine particles is preferably 1 to 30 nm, and more preferably 1 to 20 nm.
  • the average particle diameter of the inorganic fine particles may be obtained from a photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom, which is taken as the average particle size (average primary particle size).
  • the average particle diameter in this specification can be calculated by measuring the projected area of 300 or more particles and obtaining the equivalent circle diameter.
  • the metal chelate compound that can be used in the present invention can be represented by the following general formula (2).
  • M is selected from the group consisting of Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ga, Sr, Zr, Nb, Cd, In, Hf, Ta, and Tl.
  • R 3 represents one or more organic groups selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an acetylacetonate group, and an alkylacetoacetate group.
  • Y represents the valence of the atom M and is an integer of 2 to 5.
  • M is selected from the group consisting of Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ga, Sr, Zr, Nb, Cd, In, Hf, Ta, and Tl.
  • One or more kinds of atoms may be used. That is, the electronegativity of the metal contained in the metal chelate compound that can be used in the present invention is preferably 1.3 to 1.9. Among them, it is preferably one or more atoms selected from the group consisting of Al, Ti, Zr, and Nb, more preferably one or more atoms selected from the group consisting of Al, Ti, and Zr, Particularly preferred is Al.
  • a metal chelate compound contains at least 1 sort (s) among an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound, and it is especially preferable that it is an aluminum chelate compound.
  • said compound may be used by 1 type and may be used in combination of multiple types.
  • the electronegativity the value of Pauling's electronegativity can be referred to.
  • R 3 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an acetylacetonate group, or an alkylacetoacetate group.
  • the metal chelate compound is preferably a metal chelate complex having a hydroxyl group or a hydrolyzable group. That is, at least one of R 3 is preferably a hydrogen atom or an alkyl group.
  • the metal chelate complex can be easily obtained by reacting a metal alkoxide or a metal chelate compound with a chelating agent.
  • chelating agents include ⁇ -diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane, and ⁇ -keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.
  • aluminum alkoxides or aluminum chelate compounds include aluminum (III) n-butoxide, aluminum (III) sec-butoxide, aluminum (III) tert-butoxide, aluminum (III) ethoxide, aluminum (III) isopropoxide, aluminum (III) sec-butoxide bis (ethyl acetoacetate), aluminum (III) di-sec-butoxide ethyl acetoacetate, aluminum (III) 2,4-pentandionate, aluminum (III) phenoxide, aluminum bisethyl aceto Acetate monoacetylacetonate, aluminum ethyl acetoacetate diisopropylate and the like can be mentioned.
  • titanium alkoxides or titanium chelate compounds include titanium (IV) n-butoxide, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) n-propoxide, titanium (IV) iso-propoxide, titanium (IV ) Tert-butoxide, titanium (IV) iso-butoxide, titanium (IV) methoxypropoxide, titanium (IV) di-n-butoxide (bis-2,4-pentadionate), titanium (IV) di-iso -Propoxide (bis-2,4-pentadionate), titanium (IV) di-iso-propoxide bis (ethyl acetoacetate), titanium (IV) ethyl acetoacetate tri-iso-propoxide, titanium (IV) And methyl phenoxide.
  • zirconium alkoxides or zirconium chelate compounds examples include zirconium (IV) ethoxide, zirconium (IV) -iso-propoxide, zirconium (IV) n-propoxide, zirconium (IV) n-butoxide, zirconium (IV) tert-butoxide, Zirconium (IV) acetylacetonate, zirconium (IV) di-n-butoxide (bis-2,4-pentanedionate) and the like can be mentioned.
  • metal chelate complex used in the embodiment of the present invention include aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), aluminum alkyl acetoacetate diisopropylate, aluminum monoacetyl acetate bis ( Ethyl chelate compounds such as ethyl acetoacetate), aluminum tris (acetylacetonate), zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium acetylacetonate bis (ethylacetoacetate), titanium acetylacetonate, titanium oxyacetyl Acetonate, titanium diisopropoxide bis (ethyl acetoacetate), propanedioxytitanium bis (eth Acetoacetate) can be mentioned.
  • aluminum ethyl acetoacetate diisopropylate and aluminum alkyl acetoacetate diisopropylate which are aluminum chelate compounds, are particularly preferred.
  • Examples of commercially available products include aluminum chelate M and ALCH (manufactured by Kawaken Fine Chemical Co., Ltd.).
  • the metal chelate compound is preferably mixed in an amount of 0.5 to 25% by mass, more preferably 2.5 to 10% by mass, based on the inorganic fine particles described above. By mixing the metal chelate compound within the above range with respect to the inorganic fine particles, the dispersion stability of the inorganic fine particles can be enhanced.
  • the aqueous composition of the present invention contains bifunctional alkoxysilane or a hydrolyzate thereof, and may further contain at least one of trifunctional alkoxysilane and tetrafunctional alkoxysilane as necessary.
  • the trifunctional alkoxysilane and the tetrafunctional alkoxysilane may be hydrolysates.
  • the aqueous composition of the present invention may contain bifunctional alkoxysilane and trifunctional alkoxysilane or tetrafunctional alkoxysilane.
  • bifunctional alkoxysilane, trifunctional alkoxysilane, and tetrafunctional alkoxysilane may be included.
  • the above alkoxysilane may exist as a condensate (polyalkoxysilane) connected by a siloxane bond.
  • the bi- to tetra-functional alkoxysilane that can be used in the present invention can be represented by the following general formula (1).
  • Si (OR 1 ) x (R 2 ) 4-x (1)
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group
  • R 2 represents an organic group having 1 to 15 carbon atoms that does not contain an amino group.
  • X represents an integer of 2 to 4, when x is 2, it represents a bifunctional alkoxysilane, when x is 3, it represents a trifunctional alkoxysilane, and when x is 4, it represents a tetrafunctional alkoxysilane.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
  • R 1 includes a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and a phenyl group.
  • a methyl group and an ethyl group are preferable. Thereby, the manufacturing efficiency at the time of manufacturing a hard-coat layer can be improved.
  • R 2 represents an organic group having 1 to 15 carbon atoms that does not contain an amino group. That is, the alkoxysilane represented by the general formula (1) does not contain an amino group as a functional group. This is because when R 2 has an amino group, when it is mixed with a tetrafunctional alkoxysilane and hydrolyzed, dehydration condensation is promoted between the produced silanols, and the aqueous composition becomes unstable.
  • R 2 in the general formula (1) may be an organic group having a molecular chain length in the range of 1 to 15 carbon atoms.
  • the number of carbon atoms By setting the number of carbon atoms to 15 or less, the flexibility when the hard coat layer is formed is not excessively increased, and sufficient hardness can be obtained. Further, by setting the carbon number of R 2 within the above range, a hard coat layer with improved brittleness can be obtained. Moreover, the adhesiveness of other films, such as a support body, and a hard-coat layer can be improved.
  • the organic group represented by R 2 may have a heteroatom such as oxygen, nitrogen, or sulfur.
  • the organic group has a hetero atom, the adhesion to other films can be further improved.
  • Examples of commercially available products include KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the bifunctional alkoxysilane or the trifunctional alkoxysilane preferably contains an epoxy group.
  • the epoxy group-containing bifunctional alkoxysilane or trifunctional alkoxysilane only needs to have one or more epoxy groups in one molecule, and the number of epoxy groups is not particularly limited.
  • the epoxy group-containing bifunctional alkoxysilane and the epoxy group-containing trifunctional alkoxysilane may further have groups such as an alkyl group, a urethane group, a urea group, an ester group, and a hydroxy group in addition to the epoxy group. .
  • a hard coat layer having strong alkali resistance can be formed.
  • Examples of the epoxy group-containing bifunctional alkoxysilane and epoxy group-containing trifunctional alkoxysilane used in the embodiment of the present invention include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl).
  • Examples of commercially available products include KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.), KBE-402 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
  • the proportion of the bi- to tetra-functional alkoxysilane with respect to the total solid content in the aqueous composition is preferably 40 to 90% by volume, more preferably 45 to 86% by volume, and 50 to 80% by volume. More preferably.
  • the content of the bifunctional alkoxysilane is preferably 5 to 150% by mass, more preferably 10 to 100% by mass, and further preferably 30 to 80% by mass with respect to the inorganic fine particles described above. .
  • the zeta potential of the inorganic fine particles in the aqueous composition can be set within a desired range, and the dispersibility of the inorganic fine particles can be improved.
  • the mixing ratio of the trifunctional alkoxysilane and the tetrafunctional alkoxysilane is preferably 100: 0 to 65:35, more preferably 90:10 to 85:15 in terms of molar ratio.
  • thermosetting resin is a resin that cures when heated.
  • Some thermosetting resins utilize a cross-linking reaction of prepolymers such as melamine resins, urethane resins, and epoxy resins.
  • Thermosetting resins include polyester resins containing carboxyl (—COOH) groups and / or hydroxyl (—OH) groups, epoxy resins, polyacrylate resins, polymethacrylate resins, polyamide resins, fluoro resins, polyimide resins, polyurethane resins. And alkyd resins.
  • the active energy ray polymerizable resin is formed by applying a coating liquid containing a polyfunctional monomer and a polymerization initiator and polymerizing the polyfunctional monomer with active energy rays.
  • the functional group possessed by the monomer include a polymerizable unsaturated double bond group.
  • the polymerizable unsaturated double bond include an acrylate group, a methacrylate group, and a vinyl group. From the viewpoint of reactivity, an acrylate group is preferably used.
  • UV curable resin examples include an acrylic resin made of an acrylate monomer, an epoxy resin, and a urethane resin.
  • the aqueous composition of the present invention preferably further contains a curing accelerator.
  • the curing accelerator is preferably water-soluble.
  • the curing accelerator used in the embodiment of the present invention functions to promote the formation of siloxane bonds by promoting dehydration condensation of silanol in the aqueous composition.
  • a water-soluble inorganic acid, organic acid, organic acid salt, inorganic acid salt, metal alkoxide, or metal complex can be used.
  • the metal complex a metal complex composed of Al, Mg, Mn, Ti, Cu, Co, Zn, Hf and Zr is preferable, and these can be used in combination.
  • Examples of the inorganic acid include boric acid, phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid
  • examples of the organic acid include acetic acid, formic acid, oxalic acid, citric acid, malic acid, and ascorbic acid.
  • Organic acid salts include aluminum acetate, aluminum oxalate, zinc acetate, zinc oxalate, magnesium acetate, magnesium oxalate, zirconium acetate, zirconium oxalate, and inorganic acid salts include aluminum chloride, aluminum sulfate, nitric acid Examples include aluminum, zinc chloride, zinc sulfate, zinc nitrate, magnesium chloride, magnesium sulfate, magnesium nitrate, zirconium chloride, zirconium sulfate, and zirconium nitrate.
  • the metal alkoxide include aluminum alkoxide, titanium alkoxide, and zirconium alkoxide.
  • metal complexes examples include aluminum such as ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetylacetonate), etc.
  • Chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monoisopropylate, magnesium bis (acetylacetonate), zirconium tetraacetylacetonate, zirconium tributoxyacetyl Acetonate, zirconium acetylacetonate bis Ethylacetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate and titanium oxy acetylacetonate.
  • magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monoisopropylate, magnesium bis (acetylacetonate), zirconium tetraacetylacetonate, zir
  • aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), magnesium bis (acetylacetonate), magnesium bis (ethylacetoacetate), and zirconium tetraacetylacetonate are preferred, and storage stability Considering availability, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), and aluminum bisethylacetoacetate monoacetylacetonate, which are aluminum chelate complexes, are particularly preferable.
  • Examples of commercially available products include aluminum chelate A (W), aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.), and the like.
  • the addition amount of the curing accelerator is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and more preferably 30 to 45% with respect to the total amount of trifunctional alkoxysilane and / or tetrafunctional alkoxysilane. More preferably, it is mass%.
  • the addition amount of the curing accelerator more than the above lower limit value, excellent alkali resistance can be obtained when the hard coat layer is formed.
  • the dispersibility in aqueous solution can be made favorable by setting it as the said upper limit or less.
  • a surfactant may be added to the aqueous composition of the present invention for the purpose of improving the smoothness of the hard coat film and reducing the friction of the coating film surface.
  • the hard coat film may be colored by dispersing pigments, dyes, and other fine particles.
  • an ultraviolet absorber, an antioxidant or the like may be added for the purpose of improving the weather resistance.
  • surfactant Various surfactants may be added to the aqueous composition of the present invention from the viewpoint of further improving coatability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Onin D-6512, D-6414, D-6112, D-6115, D-6120, D-6131, D-6108-W, D-6112-W, D-6115-W, D-6115-X, D
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), sanded BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the hard coat film (hard coat layer) is formed by applying the aqueous composition described above to a support and drying it.
  • multilayer film what laminated
  • multilayer film in order to improve the adhesive force of a hard-coat film and a support body, it is preferable to provide an easily bonding layer between a hard-coat layer and a support body.
  • the thickness of the hard coat film can be controlled by adjusting the coating amount and solid content concentration of the aqueous composition. From the viewpoint of the hardness of the obtained hard coat film, the thickness is more preferably constant in the range of 0.3 to 12 ⁇ m. If the thickness is less than 0.3 ⁇ m, sufficient hardness may not be exhibited and the function as a hard coat film may not be obtained. If the thickness is greater than 12 ⁇ m, the internal stress of the hard coat film increases and deformation such as curling occurs. May occur. A more preferable thickness range is 0.5 to 10 ⁇ m.
  • the haze value of the hard coat film of the present invention is preferably 1.0% or less, more preferably 0.7% or less, and further preferably 0.4% or less.
  • a hard coat layer having a low haze value can be formed even when inorganic fine particles having a high refractive index are contained. Can do.
  • the refractive index of the hard coat film is preferably 1.60 to 2.40, more preferably 1.60 to 2.30, and preferably 1.80 to 2.30. More preferred is 1.95 to 2.20.
  • a hard coat film can be made into a touch panel by laminating a transparent electrode layer thereon.
  • ITO indium tin oxide
  • the electrode pattern is formed by patterning an ITO conductive film.
  • the hard coat film and the transparent electrode layer may be laminated so as to contact each other, or an adjustment layer such as an optical adjustment layer may be laminated between the hard coat film and the transparent electrode.
  • the optical adjustment layer is provided to adjust the difference in refractive index between the layers.
  • the optical adjustment layer can be formed from the same coating solution as the hard coat layer.
  • the refractive index of ITO is about 2.0, which is larger than the refractive index of about 1.6 of the polyester film that is the support substrate. Therefore, since the reflection intensity due to external light is different between the place where ITO is present and the place where ITO is not present, the ITO pattern can be seen and display quality is remarkably deteriorated. This phenomenon is called ITO bone appearance.
  • the refractive index of the hard coat layer within the above range, it is possible to suppress bone appearance of the transparent electrode when a transparent electrode layer or the like is laminated on the hard coat layer to form a touch panel.
  • the hard coat layer of the present invention is particularly preferably used when a polyester film is used as a support and an ITO conductive film is laminated to form a laminated film for a touch panel.
  • the refractive index of each layer such as a hard coat layer can be measured by, for example, a prism coupler SPA-4000 (manufactured by SAIRONTECHNOLOGY) after coating each layer on a silicon wafer to a thickness of 2 ⁇ m.
  • the above-described hard coat film is preferably formed on a support, and such a laminated film form is also included in the present invention.
  • the hard coat film described above is formed on at least one surface of the polyester film to form a laminated film.
  • the hard coat film of the present invention may be used for a laminated film having other constituent layers. Specific examples include an optical adjustment layer, a gas barrier layer, a transparent electrode layer such as an ITO electrode, a prism layer, an antireflection layer, and the like.
  • the difference between the refractive index of the easy adhesion layer and the refractive index of the polyester film is preferably 0.2 or less, and the optical adjustment is performed.
  • the refractive index of the layer is preferably 1.60 to 1.90, and the refractive index of the hard coat layer is preferably 1.80 to 2.30.
  • the difference between the refractive index of the easy adhesion layer and the refractive index of the polyester film is more preferably 0.1 or less, and further preferably 0.05 or less.
  • the refractive index of the optical adjustment layer is more preferably 1.70 to 1.87, and further preferably 1.80 to 1.85.
  • the laminated film of the present invention by setting the difference between the refractive index of the easy-adhesive layer and the refractive index of the polyester film within the above range, the degree of freedom in setting the film thickness of the easy-adhesive layer increases. Can improve the adhesion.
  • the ITO conductive film was formed on the hard coat film by providing the optical adjustment layer as described above and setting the refractive indexes of the optical adjustment layer and the hard coat layer within the above range. In some cases, the appearance of bone can be prevented.
  • the optical adjustment layer is provided to adjust the difference in refractive index between the layers.
  • a polymer compound formed into a film shape by a melt film forming method or a solution film forming method can be used as the base film as a support on which the hard coat film is laminated.
  • the polymer compound used for the base film is not particularly limited, but polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polyarylates, polyether sulfone, Polycarbonate, polyether ketone, polysulfone, polyphenylene sulfide, polyester liquid crystal polymer, triacetyl cellulose, cellulose derivatives, polypropylene, polyamides, polyimides, polycycloolefins, and the like are preferable.
  • PET, PEN, triacetyl cellulose, and cellulose derivatives are more preferable, and PET and PEN are particularly preferable.
  • These base films are preferably biaxially stretched.
  • Biaxial stretching refers to stretching in both directions by regarding the width direction and the longitudinal direction of the film as uniaxial.
  • the biaxially stretched polyester film has very good mechanical strength because the molecular orientation in the biaxial direction is sufficiently controlled.
  • the draw ratio is not particularly limited, but the draw ratio in one direction is preferably 1.5 to 7 times, more preferably 2 to 5 times.
  • a polyester film that is biaxially stretched at a stretching ratio of 2 to 5 times per uniaxial direction has a very excellent mechanical strength because the molecular orientation is controlled more efficiently and effectively, and the polyester film Suitable as a film.
  • the base film may have a surface subjected to corona treatment or glow treatment. By these treatments, the surface of the base film is hydrophilized, and the wettability of the aqueous composition can be improved, so that the adhesive force with the hard coat film or the adhesive layer can be further increased. .
  • the easy-adhesion layer is appropriately provided on the base film in order to improve the adhesion between the base film and the hard coat film and to increase the adhesion with the hard coat film.
  • the easy-adhesion layer is usually formed by applying a coating liquid composed of a binder, a curing agent, and a surfactant to the surface of the base film on which the hard coat film is provided.
  • Organic or inorganic fine particles may be appropriately added to the easy adhesion layer.
  • the fine particles are not particularly limited, and examples thereof include metal oxides. Specifically, tin oxide, zirconium oxide, zinc oxide, titanium oxide, cerium oxide, niobium oxide and the like are preferable, and these are used alone or in combination of two kinds. You may use the above together.
  • Examples of commercially available products include ET-500W and other ET series, FT-2000 and other FT series, SN-100P and other SN series, FS-10D and other FS series (manufactured by Ishihara Sangyo Co., Ltd.), ZR-30BF (Sakai Chemical Industry) Etc.).
  • the binder used for the easy-adhesion layer is not particularly limited, but is preferably at least one of polyester, polyolefin, polyurethane, acrylic resin, and styrene-butadiene copolymer from the viewpoint of adhesiveness.
  • a binder having water solubility or water dispersibility is particularly preferable from the viewpoint that the load on the environment is small.
  • Examples of commercially available products include Carbodilite V-02-L2 and other Carbodilite series (Nisshinbo Co., Ltd.) Takelac WS-5100 and Takerak WS Series (Mitsui Chemicals).
  • the thickness of the easy-adhesion layer can be adjusted as appropriate by adjusting the coating amount. More preferably, the thickness of the easy-adhesion layer is constant in the range of 0.05 to 5 ⁇ m. If the thickness is less than 0.05 ⁇ m, the adhesion may be insufficient. If the thickness is greater than 5 ⁇ m, it may be difficult to form an adhesive having a uniform thickness, and the amount of solution used may increase. The drying time may take too long and the cost may increase. A more preferable thickness range is 0.1 to 3 ⁇ m. Only one layer may be sufficient as an easily bonding layer, and the aspect which piled up this may be sufficient. When a plurality of easy adhesion layers are stacked, the total thickness of all the easy adhesion layers is regarded as the thickness of the easy adhesion layer.
  • a transparent conductive film can be produced by further laminating a transparent electrode layer on the hard coat film (hard coat layer) of the laminated film described above, and a touch panel can be formed using this transparent conductive film.
  • a transparent electrode layer that can be used for the touch panel of the present invention, any one of indium oxide, zinc oxide, tin oxide, or two or three mixed oxides thereof, and other additives are added. Although various materials can be used depending on the purpose and application, it is not particularly limited. At present, the most reliable and proven material is indium tin oxide (ITO).
  • ITO indium tin oxide
  • any film forming method can be used as long as the film thickness can be controlled. For example, a method described in JP 2012-206307 A can be used.
  • the touch panel of the present invention can be used as an input device by being incorporated in a display device such as a liquid crystal display, a plasma display, an organic EL display, a CRT display, and electronic paper.
  • a display device such as a liquid crystal display, a plasma display, an organic EL display, a CRT display, and electronic paper.
  • occurrence of interference unevenness can be suppressed and a touch panel with good color can be obtained.
  • Capacitance type input devices have the advantage of simply forming a light-transmitting conductive film on a single substrate. A capacitance type is preferred.
  • a capacitance-type input device for example, when the electrode pattern is extended in a direction intersecting each other as the transparent electrode layer and a finger or the like comes into contact, it is detected that the capacitance between the electrodes changes.
  • a type that detects the input position can be preferably used.
  • descriptions in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be referred to.
  • the method for producing an aqueous composition of the present invention comprises a step of mixing inorganic fine particles and a metal chelate compound to obtain an aqueous mixture, a step of mixing a bifunctional alkoxysilane with the aqueous mixture, and a step of mixing bifunctional alkoxysilane. Later, it further includes a step of mixing a trifunctional alkoxysilane or a hydrolyzate thereof and / or a tetrafunctional alkoxysilane or a hydrolyzate thereof with a curing accelerator. That is, in the method for producing an aqueous composition of the present invention, inorganic fine particles and a metal chelate compound are first mixed, and bifunctional alkoxysilane is added to the mixed solution.
  • the reaction time between the inorganic fine particles and the metal chelate compound is preferably 1 hour or longer, and more preferably 2 hours or longer.
  • the reaction time between the inorganic fine particles and the metal chelate compound is preferably 20 hours or shorter, more preferably 15 hours or shorter, and further preferably 13 hours or shorter.
  • the zeta potential of the inorganic fine particles in the aqueous composition can be set to 0 to 20 mV by producing the aqueous composition through such steps. This is presumably because the surface of the inorganic fine particles can be modified to a good state by adding bifunctional alkoxysilane after sufficiently reacting the inorganic fine particles with the metal chelate compound. As described above, by sequentially bonding the metal chelate compound and the bifunctional alkoxysilane to the surface of the inorganic fine particles, it becomes possible to firmly cover the surface of the inorganic fine particles, and as a result, good when a hard coat layer is formed. Can exhibit high alkali resistance.
  • Trifunctional alkoxysilane and tetrafunctional alkoxysilane function as a binder in the aqueous composition and function to increase the strength of the hard coat layer.
  • the pH of the aqueous composition forming the hard coat film is preferably adjusted in advance. For example, before the aqueous composition is applied, it is preferable to add an acidic solution to the aqueous composition and adjust the pH to a desired range.
  • the acidic solution preferably has a pH of 2 to 6, and the aqueous composition is preferably adjusted to have a pH of 2 to 7, preferably 2 to 6.
  • coating process of an aqueous composition may be provided in the middle of the extending process of a polyester film, it is preferable to be provided after an extending process.
  • a known applicator can be used as appropriate for application of the aqueous composition.
  • a spin coater, a roll coater, a bar coater, a curtain coater, etc. can be mentioned.
  • a step of drying the coating solution is provided after the coating step. In the drying step, it is preferable to perform heat drying. In heat drying, heat treatment is preferably performed so that the temperature of the coating film is 120 ° C. or higher, the temperature of the coating film is more preferably 140 ° C. or higher, and further preferably 160 ° C. or higher.
  • the temperature of the coating film is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and further preferably 260 ° C. or lower.
  • the heating time may be 10 seconds to 1 hour, and preferably 10 seconds to 5 minutes.
  • it is sufficient to heat at a heating temperature of about 120 ° C. to 300 ° C., and the heating time is as short as about 10 seconds to 1 hour. For this reason, manufacturing efficiency can be improved and the cost concerning manufacture can be suppressed.
  • the laminated film obtained after the drying step may then be wound up in a roll shape or cut into a sheet shape.
  • a heat treatment process may be provided in the drying process after an application
  • Other display layers may be further laminated on the hard coat film to form a display device such as a touch panel.
  • a method for laminating other constituent layers a conventionally known method can be appropriately selected.
  • Example 1 The following compound was mixed by the following mixing
  • This coating solution was designated as coating solution sample I-1.
  • One side of a PET film (Cosmo Shine A4300, 125 ⁇ m, manufactured by Toyobo Co., Ltd.) was subjected to corona discharge treatment.
  • the coating solution sample I-1 was applied to the surface subjected to the corona discharge treatment and dried at 120 ° C. for 2 minutes to form an easy-adhesion layer having a thickness of 0.1 ⁇ m.
  • An inorganic fine particle solution T-1 was prepared with the following composition.
  • [Inorganic fine particle solution T-1] -100 parts by weight of titania sol (SRD-W, solid content concentration 15% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
  • the inorganic fine particle solution T-1 was prepared by the following method. First, a chelating agent was added to titania sol and stirred for 1 hour or more. When the chelating agent was completely dissolved, 3-glycidoxypropylmethyldiethoxysilane was added thereto and stirred for 1 hour or longer to obtain an inorganic fine particle solution T-1.
  • the zeta potential of the obtained inorganic fine particle solution T-1 was measured as shown in (1) below. The results are shown in the table below.
  • An alkoxysilane hydrolyzate was prepared with the following composition.
  • This preparation solution was designated as a hydrolysis solution A.
  • Hydrolysis solution A Tetraethoxysilane 10.3 parts by mass (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.) ⁇ 20.1 parts by mass of 3-glycidoxypropyltriethoxysilane (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Hydrolysis solution A was prepared by the following method. First, 3-glycidoxypropyltrimethoxysilane was added to this acetic acid aqueous solution while vigorously stirring the acetic acid aqueous solution, and then the stirring was continued for 30 minutes. While this mixture was vigorously stirred, tetraethoxysilane as tetraalkoxysilane was added thereto, and stirring was continued for 1 hour. Next, the curing catalyst was added thereto, and stirring was continued for 1 hour to completely dissolve it.
  • a coating solution for forming a hard coat layer was prepared with the following composition. This coating solution was designated as coating solution sample H-1.
  • This coating solution was designated as coating solution sample H-1.
  • Inorganic fine particle solution T-1 25.4 parts by mass Hydrolyzate A 25.0 parts by mass Surfactant 2.4 parts by mass (Naroacty CL-95, 1% by mass aqueous solution, manufactured by Sanyo Chemical Industries Co., Ltd.) ) ⁇ 47.2 parts by mass of water
  • Coating solution sample H-1 was prepared by the following method. Hydrolyzate A was added to inorganic fine particle solution T-1 and stirred for 30 minutes. A surfactant and water were sequentially added to this mixed solution to prepare a coating solution sample H-1.
  • This coating liquid sample H-1 was applied on the easy-adhesion layer formed on the PET film by a bar coating method, dried by heating at 150 ° C. for 2 minutes to form a hard coating layer having a thickness of 1.0 ⁇ m. And a laminated film was obtained.
  • the resulting laminated film was evaluated for alkali resistance as shown in (3) below. The results are shown in the table below.
  • Example 2 instead of preparing and using the inorganic fine particle solution T-1 in Example 1, it was the same as in Example 1 except that the inorganic fine particle solutions T-2 to T-4 were prepared and used with the following composition. A laminated film was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in the following table.
  • Chelating agent 1.0 part by mass (aluminum bisethyl acetoacetate / monoacetylacetonate, 75% by mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.) -10.0 parts by mass of 3-glycidoxypropylmethyldiethoxysilane (KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • a titania fine particle is reacted with a metal chelate and a bifunctional alkoxysilane to have a zeta potential of 20 mV or less, and a stable aqueous composition is obtained. Furthermore, since it has an epoxy group-containing bifunctional alkoxysilane on the surface, it can be bonded to an alkoxysilane existing as a binder via an epoxy group, and thus exhibits high alkali resistance.
  • Comparative Example 1 Although a relatively stable aqueous composition was obtained by reacting titania fine particles with metal chelate, alkali resistance cannot be obtained because it does not contain bifunctional alkoxysilane. Furthermore, in Comparative Example 2, acetylacetone was reacted with titania particles. However, since acetylacetone is only coordinated with titania, acetylacetone gradually dissociates, and the aqueous composition gels, thereby evaluating alkali resistance. could not.
  • Examples 3 to 5-2 Coating liquid sample I-1 and coating liquid sample H-1 were applied in the same manner as in Example 1 so that the film thicknesses shown in the following table were obtained, to obtain a laminated film. .
  • the refractive index of each layer was measured at 25 ° C. using a prism coupler SPA-4000 (manufactured by SAIRONTECHNOLOGY) after coating each layer on a silicon wafer to a thickness of 2 ⁇ m.
  • the obtained laminated film was evaluated for interference fringes and adhesiveness as shown in the following (4) and (5). These results are shown in the table below.
  • Interference fringes Place the resulting laminated film on a black background and observe the rainbow-colored interference pattern appearing on the coating surface from a distance of about 50 cm from the laminated film using a three-wavelength fluorescent lamp. did.
  • the interference fringes were evaluated according to the following evaluation criteria. A: Interference fringes are not visible B: Interference fringes are slightly visible but not noticeable C: Interference fringes are clearly visible Evaluation ranks A and B are acceptable in practice.
  • coating solution sample I-2 The following compounds were mixed in the following composition to prepare a coating solution for forming an easy adhesion layer.
  • This coating solution was designated as coating solution sample I-2.
  • Example 2 In the same manner as in Example 1, the coating solution sample I-2 was applied, and an easy-adhesion layer having a thickness of 88 nm was formed on the PET film.
  • a coating solution for forming a hard coat layer was prepared with the following composition.
  • This coating solution was designated as coating solution sample H-2.
  • Coating solution sample H-2 was prepared by the following method. First, 3-glycidoxypropyltrimethoxysilane was added to this acetic acid aqueous solution while vigorously stirring the acetic acid aqueous solution, and then the stirring was continued for 30 minutes. While stirring this mixed solution vigorously, tetramethoxysilane as tetraalkoxysilane was added thereto, and then the stirring was continued for 1 hour. Next, the silica solution was added here, and stirring was continued for 30 minutes after that. Next, the curing catalyst was added thereto, and stirring was continued for 1 hour to completely dissolve it. A surfactant and water were sequentially added thereto to prepare a coating solution sample H-2.
  • This coating solution sample H-2 was applied on the easy-adhesion layer formed on the PET film by a bar coating method, dried by heating at 150 ° C. for 2 minutes to form a hard coating layer having a thickness of 1.0 ⁇ m. And a laminated film was obtained.
  • Examples 3 to 5 are optically excellent films having no interference fringes because the refractive indexes of the respective layers are the same. Moreover, it turns out that PET film, an easily bonding layer, and a hard-coat layer have favorable adhesiveness. Among them, in Examples 3 and 4, since the easy-adhesion layer has a sufficient thickness, the PET film, the easy-adhesion layer and the hard coat layer have good adhesiveness. On the other hand, in Example 5-2, since the thickness of the easy-adhesion layer was 60 nm or less, the adhesiveness was lowered as compared with Examples 3 to 5.
  • the refractive index of a hard coat layer using a general organic resin or silica particles is about 1.45 to 1.50.
  • the film thickness of the easy-adhesion layer needs to be relatively thin as 89 nm as in Comparative Example 4, but it is sufficient. The optical properties cannot be exhibited.
  • the difference between the refractive index of the easy adhesion layer and the refractive index of the PET film is suppressed to 0.05 or less, and the film thickness of the easy adhesion layer is set to 100 nm or more.
  • An excellent hard coat film can be obtained due to the adhesion of the adhesive layer and the hard coat layer.
  • Example 6 In the same manner as in Example 3, an easy adhesion layer having a thickness of 150 nm was formed on the PET film.
  • a coating solution for forming the optical adjustment layer was prepared with the following composition.
  • This coating solution was designated as coating solution sample K-1.
  • [Coating liquid sample K-1] ⁇ 23 parts by weight of titania sol (SRD-W, solid concentration 15% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
  • Hydrolyzed liquid A 7.5 parts by mass Surfactant 2.3 parts by mass (Naroacty CL-95, 1% by mass aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.) ⁇ 65.9 parts by weight of water
  • Coating solution sample K-1 was prepared in the same manner as coating solution sample H-1.
  • the coating liquid sample K-1 was applied on the easy-adhesion layer formed on the PET film by a bar coating method, heated at 150 ° C. for 2 minutes and dried to form an optical adjustment layer having a thickness of 77 nm.
  • a coating solution for forming a hard coat layer was prepared with the following composition. This coating solution was designated as coating solution sample H-3.
  • coating solution sample H-3 ⁇ 86 parts by mass of titania sol (SRD-W, solid content 15% by mass, manufactured by Sakai Chemical Industry Co., Ltd.) ⁇ 0.9 parts by mass of chelating agent (aluminum ethyl acetoacetate / diisopropylate, 75% by mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.) ⁇ 4.3 parts by mass of 3-glycidoxypropylmethyldiethoxysilane (KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.) Hydrolyzate A 0.9 parts by mass Surfactant 2.3 parts by mass (Naroacty CL-95, 1% by mass aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.) ⁇ 5.6 parts by weight of water
  • Coating solution sample H-3 was prepared in the same manner as coating solution sample H-1, and coated on the optical adjustment layer to form a hard coat layer having a thickness of 1.0 ⁇ m.
  • Example 7 The following compound was mixed by the following mixing
  • This coating solution was designated as coating solution sample I-3.
  • the coating liquid sample H-3 was applied on the easy-adhesion layer formed on the PET film by a bar coating method, dried by heating at 150 ° C. for 2 minutes to form a hard coating layer having a thickness of 1.0 ⁇ m. .
  • Example 8 and Example 8-2 In the laminated film of Example 8, an easy-adhesion layer was formed on the PET film using the coating liquid sample I-1 so that the refractive index and film thickness shown in the following table were obtained.
  • a coating liquid sample K-1 was used to form an optical adjustment layer
  • a coating liquid sample H-1 was used to form a hard coat layer on the optical adjustment layer.
  • an easy-adhesion layer was formed on the PET film using the coating liquid sample I-1 so that the refractive index and film thickness shown in the following table were obtained.
  • the coating liquid sample H-1 was used to form a hard coat layer.
  • the easy-adhesion layer and the hard coat layer were formed in the same manner as in Example 1, and the optical adjustment layer was formed in the same manner as in Example 6.
  • the obtained laminated film was subjected to the above (5) adhesive evaluation and the following (6) reflectivity evaluation before and after ITO film formation. These results are shown in the table below.
  • Example 6 to 8-2 the adhesiveness and the reflectance before and after the ITO film formation were satisfactory, and were in a practically acceptable range.
  • Example 6 and 7 by changing the refractive index of the hard coat layer to 2.0, it is possible to obtain an ITO film in which the reflectance change before and after the ITO layer is formed is small and the bones of ITO are not visible. did it.
  • Example 6 by providing an optical adjustment layer and setting the film thickness of the easy-adhesion layer to 100 nm or more, good adhesiveness can also be obtained.
  • the refractive index of the hard coat layer is lower than the refractive index of ITO (about 2.0), but by providing an optical adjustment layer, the difference in reflectance between before and after ITO film formation is 1.0. %.
  • inorganic fine particles can be stably dispersed in an aqueous composition, and a hard coat layer having a sufficiently high refractive index and excellent alkali resistance can be obtained. Further, in the present invention, since it is not necessary to go through a complicated manufacturing process in order to stably disperse the inorganic fine particles, the production efficiency of the aqueous composition and the hard coat layer can be increased, so that it can be used in this industry. High nature.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Theoretical Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Human Computer Interaction (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition aqueuse ainsi qu'un procédé de fabrication de celle-ci, un film de revêtement dur formé à l'aide de ladite composition aqueuse, un film stratifié, un film conducteur transparent, et un panneau tactile, lesquels contiennent des microparticules organiques possédant à leur surface un composé chélaté métallique, un alkoxysilane bifonctionnel ou un hydrolysat de celui-ci. Le potentiel zêta desdites microparticules organiques est compris entre 0 et 20mV.
PCT/JP2015/055011 2014-02-27 2015-02-23 Composition aqueuse ainsi que procédé de fabrication de celle-ci, film de revêtement dur, film stratifié, film conducteur transparent, et panneau tactile WO2015129616A1 (fr)

Applications Claiming Priority (2)

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JP2014-036499 2014-02-27
JP2014036499A JP6204227B2 (ja) 2014-02-27 2014-02-27 水性組成物とその製造方法、ハードコートフィルム、積層フィルム、透明導電性フィルム、およびタッチパネル

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WO2015129616A1 true WO2015129616A1 (fr) 2015-09-03

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
JP2017047685A (ja) * 2015-09-04 2017-03-09 積水化学工業株式会社 光透過性導電フィルム
WO2020085358A1 (fr) * 2018-10-24 2020-04-30 株式会社パイロットコーポレーション Pigment de microcapsule thermochromique réversible pour encre et composition d'encre aqueuse thermochromique réversible l'utilisant
JP7510880B2 (ja) 2018-10-24 2024-07-04 株式会社パイロットコーポレーション インキ用可逆熱変色性マイクロカプセル顔料、およびそれを用いた可逆熱変色性水性インキ組成物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022230864A1 (fr) * 2021-04-28 2022-11-03

Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2004271612A (ja) * 2003-03-05 2004-09-30 Fuji Photo Film Co Ltd 高屈折率層、反射防止膜、偏光板、及びそれを用いた画像表示装置
JP2007536589A (ja) * 2004-05-07 2007-12-13 エシロール アンテルナシオナル （コンパニー ジェネラレ ドプテイク） 偏光性及び耐摩耗性を有する光学器材及びその製造方法
WO2009044879A1 (fr) * 2007-10-03 2009-04-09 Nissan Chemical Industries, Ltd. Sol composite d'oxydes métalliques, composition de revêtement et élément optique
JP2013124283A (ja) * 2011-12-14 2013-06-24 Nippon Paint Co Ltd 修飾シリカ粒子、ハードコーティング用組成物及びハードコーティング膜

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004271612A (ja) * 2003-03-05 2004-09-30 Fuji Photo Film Co Ltd 高屈折率層、反射防止膜、偏光板、及びそれを用いた画像表示装置
JP2007536589A (ja) * 2004-05-07 2007-12-13 エシロール アンテルナシオナル （コンパニー ジェネラレ ドプテイク） 偏光性及び耐摩耗性を有する光学器材及びその製造方法
WO2009044879A1 (fr) * 2007-10-03 2009-04-09 Nissan Chemical Industries, Ltd. Sol composite d'oxydes métalliques, composition de revêtement et élément optique
JP2013124283A (ja) * 2011-12-14 2013-06-24 Nippon Paint Co Ltd 修飾シリカ粒子、ハードコーティング用組成物及びハードコーティング膜

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017047685A (ja) * 2015-09-04 2017-03-09 積水化学工業株式会社 光透過性導電フィルム
WO2020085358A1 (fr) * 2018-10-24 2020-04-30 株式会社パイロットコーポレーション Pigment de microcapsule thermochromique réversible pour encre et composition d'encre aqueuse thermochromique réversible l'utilisant
JP7510880B2 (ja) 2018-10-24 2024-07-04 株式会社パイロットコーポレーション インキ用可逆熱変色性マイクロカプセル顔料、およびそれを用いた可逆熱変色性水性インキ組成物

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JP2015160885A (ja) 2015-09-07
JP6204227B2 (ja) 2017-09-27

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