WO2015129616A1 - Aqueous composition, manufacturing method therefor, hard coat film, laminate film, transparent conductive film, and touch panel - Google Patents
Aqueous composition, manufacturing method therefor, hard coat film, laminate film, transparent conductive film, and touch panel Download PDFInfo
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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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- 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
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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
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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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
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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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
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- 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
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- 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
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- 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
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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
- 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
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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
- 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
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- 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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Abstract
The present invention comprises: an aqueous composition and a manufacturing method therefor; a hard coat film formed using the aqueous composition; a laminate film; a transparent conductive film; and a touch panel. The present invention includes inorganic microparticles which have, on the surface thereof, a metal chelate compound and either a bifunctional alkoxysilane or a hydrolysate thereof, and the zeta potential of the inorganic microparticles is 0-20 mV.
Description
本発明は、水性組成物、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に関する。具体的には、本発明は、金属キレート化合物と、2官能アルコキシシランによって表面修飾された無機微粒子を含む水性組成物であって、修飾された無機微粒子のゼータ電位が一定値以下である水性組成物に関する。また、本発明は、前記水性組成物から形成されたハードコートフィルム及びその利用に関する。
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. Specifically, 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. Related to things. Moreover, this invention relates to the hard coat film formed from the said aqueous composition, and its utilization.
近年、液晶ディスプレイ、プラズマディスプレイ、タッチパネルディスプレイ等の表示装置が急速に普及している。これらの表示装置の部材表面は、製造中、様々な物と接触するため傷が付きやすい。傷がつくと透過率が下がったり、傷自体が見えてしまったりする場合がある。このため、表示装置の表面には高い耐傷性や耐衝撃性が求められている。
In recent years, 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.
表示装置の部材表面に高い耐傷性や耐衝撃性を持たせるために、表示装置の表層には、ハードコート層が設けられることが多い。ハードコート層は、多官能アクリル重合性モノマーやオリゴマーを含む材料に紫外線や電子線などを照射することによって硬化させたり、アルコキシシランの加水分解物を縮合させて硬化させたりすることによって形成される。
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. .
例えば、特許文献1には、所定の構造式で示されるシラン化合物の加水分解物、酸化チタン系複合微粒子、不飽和もしくは飽和の多価カルボン酸またはそれらの酸無水物、および熱硬化性触媒を含有する塗料組成物を用いて、ハードコート層を形成することが開示されている。
特許文献2には、2~4官能のアルコキシシラン、金属酸化物微粒子、および金属キレートを含有するハードコーティング組成物を用いて、ハードコート層を形成することが開示されている。
特許文献3には、ジルコニアコロイド粒子、酢酸およびβ-ジケトン等から選択される分散剤、および3~4官能のアルコキシシランの加水分解物を含有するハードコート組成物を用いて、ハードコート層を形成することが開示されている。 For example, 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 β-diketone, and the like, and a hydrolyzate of a tri- to tetra-functional alkoxysilane. It is disclosed to form.
特許文献2には、2~4官能のアルコキシシラン、金属酸化物微粒子、および金属キレートを含有するハードコーティング組成物を用いて、ハードコート層を形成することが開示されている。
特許文献3には、ジルコニアコロイド粒子、酢酸およびβ-ジケトン等から選択される分散剤、および3~4官能のアルコキシシランの加水分解物を含有するハードコート組成物を用いて、ハードコート層を形成することが開示されている。 For example, 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 β-diketone, and the like, and a hydrolyzate of a tri- to tetra-functional alkoxysilane. It is disclosed to form.
特許文献4には、ルチル型チタニアゾル、ジルコニアゾル、アルミ系触媒、および有機ケイ素化合物を含有するハードコート液を用いて、ハードコート層を形成することが開示されている。
また、特許文献5には、アルコキシシランの加水分解物を縮合させて硬化させて得られるハードコート層であって、無機微粒子を含むハードコート層が開示されている。特許文献5では、ハードコート層を形成する組成物中に無機微粒子を安定して分散させるために、表面処理を施した無機微粒子とアルコキシシランを特定のpH条件下で加熱反応させている。 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.
Further, Patent Document 5 discloses a hard coat layer obtained by condensing and curing an alkoxysilane hydrolyzate and containing inorganic fine particles. In Patent Document 5, in order to stably disperse the inorganic fine particles in the composition for forming the hard coat layer, the inorganic fine particles subjected to the surface treatment and the alkoxysilane are heated and reacted under specific pH conditions.
また、特許文献5には、アルコキシシランの加水分解物を縮合させて硬化させて得られるハードコート層であって、無機微粒子を含むハードコート層が開示されている。特許文献5では、ハードコート層を形成する組成物中に無機微粒子を安定して分散させるために、表面処理を施した無機微粒子とアルコキシシランを特定のpH条件下で加熱反応させている。 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.
Further, Patent Document 5 discloses a hard coat layer obtained by condensing and curing an alkoxysilane hydrolyzate and containing inorganic fine particles. In Patent Document 5, in order to stably disperse the inorganic fine particles in the composition for forming the hard coat layer, the inorganic fine particles subjected to the surface treatment and the alkoxysilane are heated and reacted under specific pH conditions.
従来技術では、ハードコート層形成用組成物中に無機微粒子を安定的に分散させるために、分散剤を用いたり、無機微粒子に表面処理を施したりすることが行われていた。しかしながら、分散剤を用いた場合は、長時間の分散処理が必要となり、また、無機微粒子に表面処理を施す場合は、複雑な製造工程を経ることが必要となるため、ハードコート層形成用組成物やハードコート層の生産効率が上がらないという問題があった。
In the prior art, in order to stably disperse the inorganic fine particles in the composition for forming the hard coat layer, a dispersant is used or surface treatment is performed on the inorganic fine particles. However, when a dispersant is used, a long-time dispersion treatment is required, and when surface treatment is performed on inorganic fine particles, it is necessary to go through a complicated manufacturing process. There was a problem that the production efficiency of goods and hard coat layers did not increase.
また、従来技術では、ハードコート層形成用組成物中における無機微粒子の分散性が十分ではないため、ハードコート層の屈折率を一定値以上に高めることや、その屈折率を自在に調節することが困難であった。また、透明導電層の抵抗を下げるためには、透明導電層の膜厚を上げる必要があるが、特定の膜厚の透明導電層に合わせて光学調整を行うと、他の膜厚の透明導電層を積層した場合に透明導電層のパターン見え(骨見え)を低減することができず、様々な膜厚の透明導電層に対応できないという問題があった。
Further, in the prior art, since the dispersibility of the inorganic fine particles in the composition for forming the hard coat layer is not sufficient, 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. Moreover, in order to reduce the resistance of the transparent conductive layer, it is necessary to increase the film thickness of the transparent conductive layer. When the layers are stacked, the pattern appearance (bone appearance) of the transparent conductive layer cannot be reduced, and there is a problem that the transparent conductive layer having various film thicknesses cannot be handled.
さらに、従来のハードコート層を、透明導電層を有する積層フィルムに用いた場合、透明導電層を積層する際によく用いられるアルカリ溶液によってハードコート層が溶解し、ヘイズ値が上昇するという問題もあった。
Furthermore, when the conventional hard coat layer is used for a laminated film having a transparent conductive layer, 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.
ハードコート層を形成するには、一般的に、基材/易接着層/ハードコート層と積層させるが、基材、易接着層、およびハードコート層の屈折率はそれぞれ異なるので、各層間で光が反射し、干渉縞が見えることがある。それを防ぐために、各層の屈折率と膜厚を正確に調整する必要があるが、膜厚は数nmオーダーでの微調整が必要であり、塗布精度が求められる。また、易接着層が薄膜になるため密着がとりにくい、等の問題がある。
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.
そこで本発明者らは、このような従来技術の課題を解決するために、ハードコート層形成用組成物において、簡便な方法で無機微粒子の安定性を高めることを目的として検討を進めた。また、本発明者らは、屈折率が十分に高いハードコート層を製造することを目的として検討を進めた。さらに、本発明者らは、得られるハードコート層のアルカリ耐性を高めることについても検討を行った。
Therefore, in order to solve the problems of the prior art, 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. In addition, the present inventors have made studies for the purpose of producing a hard coat layer having a sufficiently high refractive index. Furthermore, the present inventors have also studied to increase the alkali resistance of the obtained hard coat layer.
一般的には、無機微粒子のゼータ電位は絶対値が大きい方が分散性が高く、ゼータ電位が0に近くなるほど凝集しやすいと考えられている。即ち、無機微粒子表面を金属キレート化合物および2官能アルコキシシランで修飾すると、ゼータ電位が0に近くなるので、分散性が低くなると思われていた。しかし、本発明者が鋭意検討した結果、無機微粒子の表面を金属キレート化合物と2官能アルコキシシランとによって修飾すると、無機微粒子表面の電荷の変化が小さくなり、液安定性が上昇すること、すなわち溶液のpH変化や他の添加物を添加しても凝集しにくくなり、溶液が安定になることを見出した。本発明者らはさらに、この水性組成物を用いて形成したハードコートフィルムは、高い屈折率を有し、アルカリ耐性及び接着性に優れることを見出した。さらに本発明者は、上記の構成を有する水性組成物からハードコート層を形成した場合、様々な膜厚のITO導電膜を積層した場合であっても骨見えを低減できることを見出した。本発明はこれらの知見に基づいて完成したものである。
具体的に、本発明は、以下の構成を有する。 In general, it is considered that 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. It was found that even when a change in pH or other additives was added, aggregation was difficult to occur and the solution became stable. Furthermore, 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.
具体的に、本発明は、以下の構成を有する。 In general, it is considered that 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. It was found that even when a change in pH or other additives was added, aggregation was difficult to occur and the solution became stable. Furthermore, 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.
<1> 金属キレート化合物と、2官能アルコキシシランまたはその加水分解物とを表面に有する無機微粒子を含み、無機微粒子のゼータ電位が0~20mVである、水性組成物。
<2> 金属キレート化合物の中心金属の電気陰性度は1.3~1.9であり、水酸基または加水分解性基を有する、<1> に記載の水性組成物。
<3> 金属キレート化合物は、アルミニウムキレート化合物、チタンキレート化合物、およびジルコニウムキレート化合物のうち少なくとも1種を含む、<1> または<2>に記載の水性組成物。
<4> 無機微粒子の25℃における屈折率が1.8以上である、<1> ~<3>のいずれかに記載の水性組成物。
<5> 無機微粒子が、ジルコニアまたはチタニアからなる微粒子である、<1> ~<4>のいずれかに記載の水性組成物。
<6> 無機微粒子および金属キレート化合物を混合し、水性混合物を得る工程と、
水性混合物に2官能アルコキシシランまたはその加水分解物を混合する工程と、
2官能アルコキシシランまたはその加水分解物を混合する工程の後に、さらに、3官能アルコキシシランもしくはその加水分解物、および/または4官能アルコキシシランもしくはその加水分解物と、硬化促進剤とを混合する工程を含む、水性組成物の製造方法。
<7> 水性混合物を得る工程では、無機微粒子及び金属キレート化合物を1時間以上反応させる、<6> に記載の水性組成物の製造方法。
<8> <6>または<7>に記載の製造方法により製造された水性組成物。
<9> <1> ~<5> および<8>のいずれかに記載の水性組成物を硬化することにより形成されるハードコートフィルム。
<10> 25℃における屈折率が1.6~2.3である、<9>に記載のハードコートフィルム。
<11> 基材フィルムと、基材フィルムの上に形成された<9> または<10> に記載のハードコートフィルムとを有する、積層フィルム。
<12> 基材フィルムの一方の面上に易接着層とハードコートフィルムとを有し、25℃における、易接着層の屈折率と基材フィルムの屈折率の屈折率の差、およびハードコートフィルムの屈折率と基材フィルムの屈折率の差が、ともに0.1以下である、<11> に記載の積層フィルム。
<13> 基材フィルムの一方の面上に易接着層、光学調整層およびハードコートフィルムをこの順に有する、<11>または<12>に記載の積層フィルム。
<14> 光学調整層の25℃における屈折率が1.60~1.90である、<13>に記載の積層フィルム。
<15> <11>~<14>のいずれかに記載の積層フィルムと透明電極層とを有する透明導電性フィルム。
<16> <15>に記載の透明導電性フィルムを有するタッチパネル。 <1> 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.
<2> The aqueous composition according to <1>, wherein the metal chelate compound has an electronegativity of 1.3 to 1.9 and has a hydroxyl group or a hydrolyzable group.
<3> The aqueous composition according to <1> or <2>, wherein 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.
<8> An aqueous composition produced by the production method according to <6> or <7>.
<9> A hard coat film formed by curing the aqueous composition according to any one of <1> to <5> and <8>.
<10> 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. The laminated film according to <11>, wherein the difference between the refractive index of the film and the refractive index of the base film is 0.1 or less.
<13> The laminated film according to <11> or <12>, having an easy-adhesion layer, an optical adjustment layer, and a hard coat film in this order on one surface of the base film.
<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>.
<2> 金属キレート化合物の中心金属の電気陰性度は1.3~1.9であり、水酸基または加水分解性基を有する、<1> に記載の水性組成物。
<3> 金属キレート化合物は、アルミニウムキレート化合物、チタンキレート化合物、およびジルコニウムキレート化合物のうち少なくとも1種を含む、<1> または<2>に記載の水性組成物。
<4> 無機微粒子の25℃における屈折率が1.8以上である、<1> ~<3>のいずれかに記載の水性組成物。
<5> 無機微粒子が、ジルコニアまたはチタニアからなる微粒子である、<1> ~<4>のいずれかに記載の水性組成物。
<6> 無機微粒子および金属キレート化合物を混合し、水性混合物を得る工程と、
水性混合物に2官能アルコキシシランまたはその加水分解物を混合する工程と、
2官能アルコキシシランまたはその加水分解物を混合する工程の後に、さらに、3官能アルコキシシランもしくはその加水分解物、および/または4官能アルコキシシランもしくはその加水分解物と、硬化促進剤とを混合する工程を含む、水性組成物の製造方法。
<7> 水性混合物を得る工程では、無機微粒子及び金属キレート化合物を1時間以上反応させる、<6> に記載の水性組成物の製造方法。
<8> <6>または<7>に記載の製造方法により製造された水性組成物。
<9> <1> ~<5> および<8>のいずれかに記載の水性組成物を硬化することにより形成されるハードコートフィルム。
<10> 25℃における屈折率が1.6~2.3である、<9>に記載のハードコートフィルム。
<11> 基材フィルムと、基材フィルムの上に形成された<9> または<10> に記載のハードコートフィルムとを有する、積層フィルム。
<12> 基材フィルムの一方の面上に易接着層とハードコートフィルムとを有し、25℃における、易接着層の屈折率と基材フィルムの屈折率の屈折率の差、およびハードコートフィルムの屈折率と基材フィルムの屈折率の差が、ともに0.1以下である、<11> に記載の積層フィルム。
<13> 基材フィルムの一方の面上に易接着層、光学調整層およびハードコートフィルムをこの順に有する、<11>または<12>に記載の積層フィルム。
<14> 光学調整層の25℃における屈折率が1.60~1.90である、<13>に記載の積層フィルム。
<15> <11>~<14>のいずれかに記載の積層フィルムと透明電極層とを有する透明導電性フィルム。
<16> <15>に記載の透明導電性フィルムを有するタッチパネル。 <1> 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.
<2> The aqueous composition according to <1>, wherein the metal chelate compound has an electronegativity of 1.3 to 1.9 and has a hydroxyl group or a hydrolyzable group.
<3> The aqueous composition according to <1> or <2>, wherein 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.
<8> An aqueous composition produced by the production method according to <6> or <7>.
<9> A hard coat film formed by curing the aqueous composition according to any one of <1> to <5> and <8>.
<10> 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. The laminated film according to <11>, wherein the difference between the refractive index of the film and the refractive index of the base film is 0.1 or less.
<13> The laminated film according to <11> or <12>, having an easy-adhesion layer, an optical adjustment layer, and a hard coat film in this order on one surface of the base film.
<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>.
本発明によれば、水性組成物中に無機微粒子を安定的に分散させることが可能となる。また、本発明では、無機微粒子を安定的に分散させるために複雑な製造工程を経る必要がなく、且つ有機溶剤を必要としないため、水性組成物及びハードコートフィルムの生産効率を高めることができる。
According to the present invention, 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. .
以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、代表的な実施形態や具体例に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。なお、本明細書において「~」を用いて表される数値範囲は「~」前後に記載される数値を下限値及び上限値として含む範囲を意味する。
Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, 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.
(水性組成物)
本発明は、金属キレート化合物と、2官能アルコキシシランまたはその加水分解物とを表面に有する無機微粒子を含み、無機微粒子のゼータ電位が0~20mVである水性組成物に関する。また、本発明の水性組成物中の無機微粒子のゼータ電位は0~20mVである。本発明は水性組成物の構成を上記のようにし、かつ無機微粒子のゼータ電位を0~20mVとすることにより、水性組成物中における無機微粒子の凝集を防ぐことができる。さらに、水性組成物を硬化して得られるハードコートフィルムの屈折率を十分に高めることができる。また、本発明によれば、ハードコートフィルムを基材や易接着層と同じ屈折率に調整することが可能となるので、ハードコート層と易接着層の膜厚を調整し易くなる。そして、易接着層の膜厚を厚くし易くなることから、高い接着性を得やすくなる。またITO導電膜等の膜厚を変更しても、骨見えを低減することが可能となった。さらに、本発明の水性組成物を用いれば、アルカリ耐性の強いハードコート層を得ることができる。これにより、ハードコート層の上に透明電極層を積層する際にハードコート層がアルカリ溶液で溶解してしまうことを防ぐことができ、ヘイズ値の上昇を抑えることができる。 (Aqueous composition)
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. In the present invention, 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. Furthermore, the refractive index of the hard coat film obtained by curing the aqueous composition can be sufficiently increased. Moreover, according to this invention, since 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. And since it becomes easy to increase the film thickness of an easily bonding layer, it becomes easy to obtain high adhesiveness. Further, even if the film thickness of the ITO conductive film or the like is changed, the bone appearance can be reduced. Furthermore, if the aqueous composition of the present invention is used, a hard coat layer having strong alkali resistance can be obtained. Thereby, when laminating | stacking a transparent electrode layer on a hard-coat layer, it can prevent that a hard-coat layer melt | dissolves with an alkaline solution, and can suppress the raise of a haze value.
本発明は、金属キレート化合物と、2官能アルコキシシランまたはその加水分解物とを表面に有する無機微粒子を含み、無機微粒子のゼータ電位が0~20mVである水性組成物に関する。また、本発明の水性組成物中の無機微粒子のゼータ電位は0~20mVである。本発明は水性組成物の構成を上記のようにし、かつ無機微粒子のゼータ電位を0~20mVとすることにより、水性組成物中における無機微粒子の凝集を防ぐことができる。さらに、水性組成物を硬化して得られるハードコートフィルムの屈折率を十分に高めることができる。また、本発明によれば、ハードコートフィルムを基材や易接着層と同じ屈折率に調整することが可能となるので、ハードコート層と易接着層の膜厚を調整し易くなる。そして、易接着層の膜厚を厚くし易くなることから、高い接着性を得やすくなる。またITO導電膜等の膜厚を変更しても、骨見えを低減することが可能となった。さらに、本発明の水性組成物を用いれば、アルカリ耐性の強いハードコート層を得ることができる。これにより、ハードコート層の上に透明電極層を積層する際にハードコート層がアルカリ溶液で溶解してしまうことを防ぐことができ、ヘイズ値の上昇を抑えることができる。 (Aqueous composition)
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. In the present invention, 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. Furthermore, the refractive index of the hard coat film obtained by curing the aqueous composition can be sufficiently increased. Moreover, according to this invention, since 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. And since it becomes easy to increase the film thickness of an easily bonding layer, it becomes easy to obtain high adhesiveness. Further, even if the film thickness of the ITO conductive film or the like is changed, the bone appearance can be reduced. Furthermore, if the aqueous composition of the present invention is used, a hard coat layer having strong alkali resistance can be obtained. Thereby, when laminating | stacking a transparent electrode layer on a hard-coat layer, it can prevent that a hard-coat layer melt | dissolves with an alkaline solution, and can suppress the raise of a haze value.
ここで、ゼータ電位とは、粒子の分散・凝集性、相互作用、表面改質を評価する上での指標となるものである。ゼータ電位の絶対値が大きいと、粒子同士の反発する力が大きくなるので、分散性がよくなる傾向にある。例えば、表面が改質されていない粒子のゼータ電位と表面が改質された粒子のゼータ電位を比較したとき、表面が改質された粒子のゼータ電位の方が高くなると、粒子の分散性が向上したと言える。これにより、粒子の分散性等を判断することもできる。なお、ゼータ電位は、公知の方法を用いて測定することができ、ゼータ電位は、例えば、DT1200((株)RUFUTO製)を用いて、温度25℃、pH6において測定される。
Here, the zeta potential is an index for evaluating the particle dispersibility / aggregation, interaction, and surface modification. When the absolute value of the zeta potential is large, the repulsive force between the particles increases, so that the dispersibility tends to be improved. For example, when comparing the zeta potential of particles whose surface is not modified with the zeta potential of particles whose surface is modified, if the zeta potential of particles whose surface is modified is higher, the dispersibility of the particles It can be said that it has improved. Thereby, 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).
水性組成物中における無機微粒子のゼータ電位は0~20mVであればよく、0~18mVであることが好ましく、0~15mVであることがさらに好ましい。無機微粒子のゼータ電位が上記範囲内であることは、水性組成物中における無機微粒子の表面が良好な状態で修飾されていることを意味する。これにより、水溶液のpH変化や他の添加物を添加した際の、無機微粒子の水溶液中での安定性を高めることができ、かつ無機微粒子の凝集を防ぐことができる。
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.
上述した水性組成物は、例えば支持体上に塗布し硬化させることによってハードコート層を形成する。すなわち、本発明の水性組成物はハードコート層形成用の水性組成物とすることができる。
また、本発明の実施形態にかかる水性組成物は、溶媒の主成分として水を含み、溶媒中の水の含有量は90質量%以上が好ましく、95質量%以上がより好ましい。本発明の水性組成物は、実質的に有機溶剤を用いていないため、水性組成物を塗布し乾燥させる際に蒸発するものは、主に水成分となる。このため、有機溶剤を用いた場合と比較して、環境への負荷を大幅に低減することができる。さらに、製造工程において、有機溶媒の揮散等がないため、製造適正を高めることができる。 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.
Moreover, 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.
また、本発明の実施形態にかかる水性組成物は、溶媒の主成分として水を含み、溶媒中の水の含有量は90質量%以上が好ましく、95質量%以上がより好ましい。本発明の水性組成物は、実質的に有機溶剤を用いていないため、水性組成物を塗布し乾燥させる際に蒸発するものは、主に水成分となる。このため、有機溶剤を用いた場合と比較して、環境への負荷を大幅に低減することができる。さらに、製造工程において、有機溶媒の揮散等がないため、製造適正を高めることができる。 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.
Moreover, 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.
(無機微粒子)
本発明の水性組成物は、無機微粒子を含む。水性組成物中の全固形分に対して無機微粒子が占める割合は、10体積%以上であることが好ましく、14体積%以上であることがより好ましく、20体積%以上であることがより好ましい。また、無機微粒子が占める割合は、60体積%以下であることが好ましく、55体積%以下であることがより好ましく、50体積%以下であることがさらに好ましい。
また、水性組成物中の全固形分に対して無機微粒子が占める割合は、10質量%以上であることが好ましく、14質量%以上であることがより好ましく、20質量%以上であることがより好ましい。また、無機微粒子が占める割合は、60質量%以下であることが好ましく、55質量%以下であることがより好ましく、50質量%以下であることがさらに好ましい。 なお、無機微粒子は2種以上を併用してもよく、その場合は使用した全種類の合計量が上記範囲内となる。無機微粒子が占める割合を上記範囲内とすることにより、水性組成物中における無機微粒子の分散性を高めることができる。さらに、高硬度であって、耐傷性および耐衝撃性に優れたハードコート層を形成することができる。 (Inorganic fine particles)
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.
Further, 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. In addition, 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. By setting the proportion of the inorganic fine particles within the above range, the dispersibility of the inorganic fine particles in the aqueous composition can be improved. Furthermore, a hard coat layer having high hardness and excellent scratch resistance and impact resistance can be formed.
本発明の水性組成物は、無機微粒子を含む。水性組成物中の全固形分に対して無機微粒子が占める割合は、10体積%以上であることが好ましく、14体積%以上であることがより好ましく、20体積%以上であることがより好ましい。また、無機微粒子が占める割合は、60体積%以下であることが好ましく、55体積%以下であることがより好ましく、50体積%以下であることがさらに好ましい。
また、水性組成物中の全固形分に対して無機微粒子が占める割合は、10質量%以上であることが好ましく、14質量%以上であることがより好ましく、20質量%以上であることがより好ましい。また、無機微粒子が占める割合は、60質量%以下であることが好ましく、55質量%以下であることがより好ましく、50質量%以下であることがさらに好ましい。 なお、無機微粒子は2種以上を併用してもよく、その場合は使用した全種類の合計量が上記範囲内となる。無機微粒子が占める割合を上記範囲内とすることにより、水性組成物中における無機微粒子の分散性を高めることができる。さらに、高硬度であって、耐傷性および耐衝撃性に優れたハードコート層を形成することができる。 (Inorganic fine particles)
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.
Further, 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. In addition, 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. By setting the proportion of the inorganic fine particles within the above range, the dispersibility of the inorganic fine particles in the aqueous composition can be improved. Furthermore, a hard coat layer having high hardness and excellent scratch resistance and impact resistance can be formed.
無機微粒子としては、透明導電膜の直下に用いられるため透明で絶縁性の金属酸化物微粒子等が好ましく用いられる。また、屈折率の高いハードコート層を形成するために、無機微粒子の屈折率は1.8以上であることが好ましい。
なお、本明細書において屈折率は25℃における値を示す。 As the inorganic fine particles, transparent and insulating metal oxide fine particles are preferably used because they are used directly below the transparent conductive film. In order to form a hard coat layer having a high refractive index, the refractive index of the inorganic fine particles is preferably 1.8 or more.
In addition, in this specification, a refractive index shows the value in 25 degreeC.
なお、本明細書において屈折率は25℃における値を示す。 As the inorganic fine particles, transparent and insulating metal oxide fine particles are preferably used because they are used directly below the transparent conductive film. In order to form a hard coat layer having a high refractive index, the refractive index of the inorganic fine particles is preferably 1.8 or more.
In addition, in this specification, a refractive index shows the value in 25 degreeC.
本発明の実施形態では、金属酸化物微粒子の具体例として、ジルコニアやチタニアからなる微粒子を挙げることができる。ジルコニアやチタニアは高い屈折率を示すため好ましく、特に、チタニアは好ましく用いられる。
In the embodiment of the present invention, specific examples of 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.
本発明の実施形態で用いることができるチタニア(酸化チタン)としては、例えば、"TTO-55、51、S、M、D"シリーズ{以上、石原産業(株)};"JR"シリーズ、"JA"シリーズ{以上、テイカ(株)}、SRD-W等のルチル型チタニア{以上、堺化学工業(株)}等が挙げられる。
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.
無機微粒子の平均粒子径は、1~30nmであることが好ましく、1~20nmであることがより好ましい。無機微粒子の平均粒子径を上記範囲内とすることにより、水性組成物のヘイズ値を下げることができる。また、ハードコート層の透明性を高めることができ、屈折率を層内で均一に制御することも可能となる。
ここで、無機微粒子の平均粒子径は、分散した粒子を透過型電子顕微鏡により観察し、得られた写真から求めてもよい。粒子の投影面積を求め、そこから円相当径を求め平均粒子径(平均一次粒子径)とする。本明細書における平均粒子径は、300個以上の粒子について投影面積を測定して、円相当径を求めて算出することができる。 The average particle size of the inorganic fine particles is preferably 1 to 30 nm, and more preferably 1 to 20 nm. By setting the average particle size of the inorganic fine particles within the above range, the haze value of the aqueous composition can be lowered. Further, the transparency of the hard coat layer can be enhanced, and the refractive index can be uniformly controlled in the layer.
Here, 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.
ここで、無機微粒子の平均粒子径は、分散した粒子を透過型電子顕微鏡により観察し、得られた写真から求めてもよい。粒子の投影面積を求め、そこから円相当径を求め平均粒子径(平均一次粒子径)とする。本明細書における平均粒子径は、300個以上の粒子について投影面積を測定して、円相当径を求めて算出することができる。 The average particle size of the inorganic fine particles is preferably 1 to 30 nm, and more preferably 1 to 20 nm. By setting the average particle size of the inorganic fine particles within the above range, the haze value of the aqueous composition can be lowered. Further, the transparency of the hard coat layer can be enhanced, and the refractive index can be uniformly controlled in the layer.
Here, 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.
(金属キレート化合物)
本発明に用いることができる金属キレート化合物は、下記一般式(2)で表すことができる。
M(OR3)y (2)
ここで、式中、Mは、Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ga、Sr、Zr、Nb、Cd、In、Hf、Ta及びTlからなる群より選ばれる1種以上の原子である。R3は水素原子、炭素数1~4のアルキル基、フェニル基、アセチルアセトナート基、およびアルキルアセトアセテート基からなる群より選ばれる1種以上の有機基を表す。また、yは原子Mの価数を表し、2~5の整数である。 (Metal chelate compound)
The metal chelate compound that can be used in the present invention can be represented by the following general formula (2).
M (OR 3 ) y (2)
Here, in the formula, 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 atoms. 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.
本発明に用いることができる金属キレート化合物は、下記一般式(2)で表すことができる。
M(OR3)y (2)
ここで、式中、Mは、Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ga、Sr、Zr、Nb、Cd、In、Hf、Ta及びTlからなる群より選ばれる1種以上の原子である。R3は水素原子、炭素数1~4のアルキル基、フェニル基、アセチルアセトナート基、およびアルキルアセトアセテート基からなる群より選ばれる1種以上の有機基を表す。また、yは原子Mの価数を表し、2~5の整数である。 (Metal chelate compound)
The metal chelate compound that can be used in the present invention can be represented by the following general formula (2).
M (OR 3 ) y (2)
Here, in the formula, 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 atoms. 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.
一般式(2)の、Mは、Mg、Al、Sc、Ti、V、Cr、Mn、Fe、Co、Ga、Sr、Zr、Nb、Cd、In、Hf、Ta及びTlからなる群より選ばれる1種以上の原子であればよい。すなわち、本発明に用いることができる金属キレート化合物に含まれる金属の電気陰性度は、1.3~1.9であることが好ましい。
中でも、Al、Ti、Zr、及びNbからなる群より選ばれる1種以上の原子であることが好ましく、Al、Ti及びZrからなる群より選ばれる1種以上の原子であることがより好ましく、Alであることが特に好ましい。すなわち、金属キレート化合物は、アルミニウムキレート化合物、チタンキレート化合物及びジルコニウムキレート化合物のうち少なくとも1種を含むことが好ましく、アルミニウムキレート化合物であることが特に好ましい。なお、金属キレート化合物としては、上記の化合物を1種で用いてもよく、複数種を組み合わせて用いてもよい。
なお、電気陰性度は、Paulingの電気陰性度の値を参照することができる。 In the 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. 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. That is, it is preferable that 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. In addition, as a metal chelate compound, said compound may be used by 1 type and may be used in combination of multiple types.
For the electronegativity, the value of Pauling's electronegativity can be referred to.
中でも、Al、Ti、Zr、及びNbからなる群より選ばれる1種以上の原子であることが好ましく、Al、Ti及びZrからなる群より選ばれる1種以上の原子であることがより好ましく、Alであることが特に好ましい。すなわち、金属キレート化合物は、アルミニウムキレート化合物、チタンキレート化合物及びジルコニウムキレート化合物のうち少なくとも1種を含むことが好ましく、アルミニウムキレート化合物であることが特に好ましい。なお、金属キレート化合物としては、上記の化合物を1種で用いてもよく、複数種を組み合わせて用いてもよい。
なお、電気陰性度は、Paulingの電気陰性度の値を参照することができる。 In the 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. 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. That is, it is preferable that 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. In addition, as a metal chelate compound, said compound may be used by 1 type and may be used in combination of multiple types.
For the electronegativity, the value of Pauling's electronegativity can be referred to.
R3は、水素原子、炭素数1~4のアルキル基、フェニル基、アセチルアセトナート基、またはアルキルアセトアセテート基であり、例えば水素原子、メチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、sec-ブチル基、tert-ブチル基、フェニル基、アセチルアセトナート基、メチルアセトアセテート基、エチルアセトアセテート基などが挙げられる。
なお、本発明では、金属キレート化合物は、水酸基又は加水分解性基を有する金属キレート錯体であることが好ましい。すなわち、R3のうち少なくとも1つは、水素原子またはアルキル基であることが好ましい。 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. For example, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group Group, n-butyl group, sec-butyl group, tert-butyl group, phenyl group, acetylacetonate group, methylacetoacetate group, ethylacetoacetate group and the like.
In the present invention, 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.
なお、本発明では、金属キレート化合物は、水酸基又は加水分解性基を有する金属キレート錯体であることが好ましい。すなわち、R3のうち少なくとも1つは、水素原子またはアルキル基であることが好ましい。 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. For example, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group Group, n-butyl group, sec-butyl group, tert-butyl group, phenyl group, acetylacetonate group, methylacetoacetate group, ethylacetoacetate group and the like.
In the present invention, 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.
金属キレート錯体は、金属アルコキシド又は金属キレート化合物にキレート化剤を反応させることにより容易に得ることができる。キレート化剤の例としては、アセチルアセトン、ベンゾイルアセトン、ジベンゾイルメタンなどのβ-ジケトン、アセト酢酸エチル、ベンゾイル酢酸エチルなどのβ-ケト酸エステルなどを用いることができる。
The metal chelate complex can be easily obtained by reacting a metal alkoxide or a metal chelate compound with a chelating agent. Examples of chelating agents that can be used include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane, and β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.
アルミニウムアルコキシド又はアルミニウムキレート化合物の例としては、アルミニウム(III)n-ブトキサイド、アルミニウム(III)sec-ブトキサイド、アルミニウム(III)tert-ブトキサイド、アルミニウム(III)エトキサイド、アルミニウム(III)イソプロポキサイド、アルミニウム(III)sec-ブトキサイドビス(エチルアセトアセテート)、アルミニウム(III)ジ-sec-ブトキサイドエチルアセトアセテート、アルミニウム(III)2,4-ペンタンジオネート、アルミニウム(III)フェノキサイド、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート、アルミニウムエチルアセトアセテート・ジイソプロピレートなどが挙げられる。
Examples of 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.
チタンアルコキシド又はチタンキレート化合物の例としては、チタン(IV)n-ブトキサイド、チタン(IV)メトキサイド、チタン(IV)エトキサイド、チタン(IV)n-プロポキサイド、チタン(IV)iso-プロポキサイド、チタン(IV)tert-ブトキサイド、チタン(IV)iso-ブトキサイド、チタン(IV)メトキシプロポキサイド、チタン(IV)ジ-n-ブトキサイド(ビス-2,4-ペンタジオネート)、チタン(IV)ジ-iso-プロポキサイド(ビス-2,4-ペンタジオネート)、チタン(IV)ジ-iso-プロポキサイドビス(エチルアセトアセテート)、チタン(IV)エチルアセトアセテートトリ-iso-プロポキシド、チタン(IV)メチルフェノキサイド等が挙げられる。
Examples of 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.
ジルコニウムアルコキシド又はジルコニウムキレート化合物の例としては、ジルコニウム(IV)エトキサイド、ジルコニウム(IV)-iso-プロポキサイド、ジルコニウム(IV)n-プロポキサイド、ジルコニウム(IV)n-ブトキサイド、ジルコニウム(IV)tert-ブトキサイド、ジルコニウム(IV)アセチルアセトナート、ジルコニウム(IV)ジn-ブトキサイド(ビス-2,4-ペンタンジオネート)等が挙げられる。
Examples of zirconium alkoxides or zirconium chelate compounds 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.
本発明の実施形態で用いる金属キレート錯体の具体的な例としては、アルミニウムエチルアセトアセテート・ジイソプロピレート、アルミニウムトリス(エチルアセトアセテート)、アルミニウムアルキルアセトアセテート・ジイソプロピレート、アルミニウムモノアセチルアセテートビス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)等のアルミニウムキレート化合物、ジルコニウムテトラアセチルアセトナート、ジルコニウムトリブトキシアセチルアセトナート、ジルコニウムアセチルアセトナートビス(エチルアセトアセテート)、チタンアセチルアセトナート、チタンオキシアセチルアセトナート、チタンジイソプロポキサイドビス(エチルアセトアセテート)、プロパンジオキシチタンビス(エチルアセトアセテート)が挙げられる。中でも、アルミニウムキレート化合物であるアルミニウムエチルアセトアセテート・ジイソプロピレート、アルミニウムアルキルアセトアセテート・ジイソプロピレートが特に好ましい。市販品としては、アルミキレートM、ALCH(川研ファインケミカル(株)製)などが挙げられる。
Specific examples of the 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. Of these, 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.).
上述した無機微粒子に対して、金属キレート化合物は0.5~25質量%混合することが好ましく、2.5~10質量%混合することがより好ましい。無機微粒子に対して、上記の範囲で金属キレート化合物を混合することにより、無機微粒子の分散安定性を高めることができる。
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.
(アルコキシシラン)
本発明の水性組成物には、2官能アルコキシシランまたはその加水分解物が含まれ、さらに必要に応じて、3官能アルコキシシラン及び4官能アルコキシシランの少なくとも一方が含まれていてもよい。3官能アルコキシシラン及び4官能アルコキシシランは加水分解物であってもよい。3官能アルコキシシラン及び4官能アルコキシシランの少なくとも一方が含まれている場合、本発明の水性組成物には、2官能アルコキシシランと、3官能アルコキシシラン又は4官能アルコキシシランが含まれてもよいし、2官能アルコキシシラン、3官能アルコキシシラン及び4官能アルコキシシランの全てが含まれてもよい。また、水性組成物中では、上記のアルコキシシランがシロキサン結合でつながった縮合物(ポリアルコキシシラン)として存在していてもよい。 (Alkoxysilane)
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. When at least one of trifunctional alkoxysilane and tetrafunctional alkoxysilane is contained, the aqueous composition of the present invention may contain bifunctional alkoxysilane and trifunctional alkoxysilane or tetrafunctional alkoxysilane. All of bifunctional alkoxysilane, trifunctional alkoxysilane, and tetrafunctional alkoxysilane may be included. Further, in the aqueous composition, the above alkoxysilane may exist as a condensate (polyalkoxysilane) connected by a siloxane bond.
本発明の水性組成物には、2官能アルコキシシランまたはその加水分解物が含まれ、さらに必要に応じて、3官能アルコキシシラン及び4官能アルコキシシランの少なくとも一方が含まれていてもよい。3官能アルコキシシラン及び4官能アルコキシシランは加水分解物であってもよい。3官能アルコキシシラン及び4官能アルコキシシランの少なくとも一方が含まれている場合、本発明の水性組成物には、2官能アルコキシシランと、3官能アルコキシシラン又は4官能アルコキシシランが含まれてもよいし、2官能アルコキシシラン、3官能アルコキシシラン及び4官能アルコキシシランの全てが含まれてもよい。また、水性組成物中では、上記のアルコキシシランがシロキサン結合でつながった縮合物(ポリアルコキシシラン)として存在していてもよい。 (Alkoxysilane)
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. When at least one of trifunctional alkoxysilane and tetrafunctional alkoxysilane is contained, the aqueous composition of the present invention may contain bifunctional alkoxysilane and trifunctional alkoxysilane or tetrafunctional alkoxysilane. All of bifunctional alkoxysilane, trifunctional alkoxysilane, and tetrafunctional alkoxysilane may be included. Further, in the aqueous composition, the above alkoxysilane may exist as a condensate (polyalkoxysilane) connected by a siloxane bond.
本発明に用いることができる2~4官能アルコキシシランは、下記一般式(1)で表すことができる。
Si(OR1)x(R2)4-x (1)
ここで、式中、R1は水素原子、炭素数1~4のアルキル基又はフェニル基を表し、R2はアミノ基を含まない炭素数が1~15の有機基を表す。また、xは、2~4の整数を表し、xが2のときは2官能アルコキシシラン、xが3のときは3官能アルコキシシラン、xが4のときは4官能アルコキシシランを表す。 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)
Here, in the formula, R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and 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.
Si(OR1)x(R2)4-x (1)
ここで、式中、R1は水素原子、炭素数1~4のアルキル基又はフェニル基を表し、R2はアミノ基を含まない炭素数が1~15の有機基を表す。また、xは、2~4の整数を表し、xが2のときは2官能アルコキシシラン、xが3のときは3官能アルコキシシラン、xが4のときは4官能アルコキシシランを表す。 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)
Here, in the formula, R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and 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.
一般式(1)において、R1は水素原子、炭素数1~4のアルキル基又はフェニル基を表す。炭素数を4以下とすることにより、酸性水と混ぜたときのアルコキシシランの加水分解速度が遅くなりすぎることがなく、均一な水溶液にするまでの溶解に要する時間を短くすることができる。R1としては、例えば水素原子、メチル基、エチル基、n-プロピル基、iso-プロピル基、フェニル基などを挙げることができる。これらのうち好ましいのは、メチル基、エチル基である。これにより、ハードコート層を製造する際の製造効率を高めることができる。
In the general formula (1), R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. By setting the number of carbon atoms to 4 or less, the hydrolysis rate of alkoxysilane when mixed with acidic water does not become too slow, and the time required for dissolution until a uniform aqueous solution can be shortened. Examples of R 1 include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and a phenyl group. Among these, 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.
また、一般式(1)において、R2はアミノ基を含まない炭素数が1~15の有機基を表す。すなわち一般式(1)で表されるアルコキシシランは、アミノ基を官能基として含まない。これは、R2がアミノ基を有する場合は、4官能アルコキシシランと混合して加水分解すると、生成するシラノール同士で脱水縮合が促進されてしまい、水性組成物が不安定となるためである。
In the general formula (1), 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.
一般式(1)のR2は、炭素数が1~15の範囲であるような分子鎖長をもつ有機基であれば良い。炭素数を15以下とすることにより、ハードコート層を形成した際の柔軟性が過度に大きくならず、十分な硬度を得ることができる。また、R2の炭素数を上記範囲内とすることにより、脆性がより改善されたハードコート層を得ることができる。また、支持体等の他のフィルムとハードコート層の接着性を高めることができる。
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. 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.
さらに、R2で示す有機基は、酸素、窒素、硫黄などのヘテロ原子を有しても良い。有機基がヘテロ原子をもつことにより、他のフィルムとの接着性をより向上させることができる。
Furthermore, the organic group represented by R 2 may have a heteroatom such as oxygen, nitrogen, or sulfur. When the organic group has a hetero atom, the adhesion to other films can be further improved.
これら一般式(1)の具体例を以下に示す。
x=4のものとしては、テトラメトキシシラン、テトラエトキシシラン、テトラ-n-プロポキシシラン、テトラ-iso-プロポキシシラン、テトラ-n-ブトキシシラン、テトラフェノキシシランなどを挙げることができる。市販品としては、KBE-04(信越化学工業(株)製)などが挙げられる。 Specific examples of these general formulas (1) are shown below.
Examples of x = 4 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, and tetraphenoxysilane. Examples of commercially available products include KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.).
x=4のものとしては、テトラメトキシシラン、テトラエトキシシラン、テトラ-n-プロポキシシラン、テトラ-iso-プロポキシシラン、テトラ-n-ブトキシシラン、テトラフェノキシシランなどを挙げることができる。市販品としては、KBE-04(信越化学工業(株)製)などが挙げられる。 Specific examples of these general formulas (1) are shown below.
Examples of x = 4 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, and tetraphenoxysilane. Examples of commercially available products include KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.).
x=3のものとしては、ビニルトリメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-アクリロキシプロピルトリメトキシシラン、3-クロロプロピルトリメトキシシラン、3-ウレイドプロピルトリメトキシシラン、プロピルトリメトキシシラン、フェニルトリメトキシシラン、ビニルトリエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリエトキシシラン、3-クロロプロピルトリエトキシシラン、3-ウレイドプロピルトリエトキシシラン、メチルトリエトキシシラン、メチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリメトキシシラン、プロピルトリエトキシシラン、プロピルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリメトキシシランを挙げることができる。中でも、メチルトリエトキシシラン、メチルトリメトキシシランは特に好ましく用いられる。市販品としては、KBE-13(信越化学工業(株)製)などが挙げられる。
As x = 3, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, propyltrimethoxy Silane, phenyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-ureidopropyltriethoxysilane, methyltriethoxysilane , Methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, phenyl It can be mentioned silane. Of these, methyltriethoxysilane and methyltrimethoxysilane are particularly preferably used. Examples of commercially available products include KBE-13 (manufactured by Shin-Etsu Chemical Co., Ltd.).
x=2のものとしては、ジメチルジメトキシシラン、ジメチルジエトキシシラン、メチルフェニルジメトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジ-n-プロピルジメトキシシラン、ジ-n-プロピルジエトキシシラン、ジ-iso-プロピルジメトキシシラン、ジ-iso-プロピルジエトキシシラン、ジフェニルジメトキシシランなどを挙げることができる。市販品としては、KBE-22(信越化学工業(株)製)などが挙げられる。
As x = 2, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di- Examples thereof include iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, and diphenyldimethoxysilane. Examples of commercially available products include KBE-22 (manufactured by Shin-Etsu Chemical Co., Ltd.).
本発明では、2官能アルコキシシラン又は3官能アルコキシシランは、エポキシ基を含有することが好ましい。エポキシ基含有2官能アルコキシシラン又は3官能アルコキシシランは、1分子中に1つ以上エポキシ基を有するものであればよく、エポキシ基の数は特に限定されない。なお、エポキシ基含有2官能アルコキシシラン及びエポキシ基含有3官能アルコキシシランは、エポキシ基の他に、さらに、アルキル基、ウレタン基、ウレア基、エステル基、ヒドロキシ基など基を有していても良い。エポキシ基を含有することで、アルカリ耐性の強いハードコート層を形成することができる。
In the present invention, 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. . By containing an epoxy group, a hard coat layer having strong alkali resistance can be formed.
本発明の実施形態で用いるエポキシ基含有2官能アルコキシシラン及びエポキシ基含有3官能アルコキシシランとしては、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルメチルジメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルメチルジエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン等を挙げることができる。市販品としては、KBE-403(信越化学工業(株)製)、KBE-402(信越化学工業(株)製)などが挙げられる。
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). Ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. 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.
水性組成物中の全固形分に対して2~4官能アルコキシシランが占める割合は、40~90体積%であることが好ましく、45~86体積%であることがより好ましく、50~80体積%であることがさらに好ましい。アルコキシシランの含有率を上記範囲内とすることにより、ハードコート層を形成した際の硬度を高めることができる。さらに、ハードコート層の膜厚を厚くすることが可能となり、所望の厚みを有するハードコート層を容易に形成することができる。
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. By setting the content of alkoxysilane within the above range, the hardness when the hard coat layer is formed can be increased. Furthermore, it is possible to increase the thickness of the hard coat layer, and a hard coat layer having a desired thickness can be easily formed.
2官能アルコキシシランの含有率は、上記した無機微粒子に対して5~150質量%であることが好ましく、10~100質量%であることがより好ましく、30~80質量%であることがさらに好ましい。2官能アルコキシシランの含有率を上記範囲内とすることにより、水性組成物中の無機微粒子のゼータ電位を所望の範囲内とすることができ、無機微粒子の分散性を高めることができる。
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. . By setting the content of the bifunctional alkoxysilane within the above range, 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.
また、3官能アルコキシシランと4官能アルコキシシランの混合比はモル比で100:0~65:35であることが好ましく、90:10~85:15であることがより好ましい。エポキシ基含有アルコキシシランとエポキシ基非含有アルコキシシランの混合比を上記の範囲内とすることにより、水性組成物の経時安定性を高めることができる。
Further, 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. By setting the mixing ratio of the epoxy group-containing alkoxysilane and the epoxy group-free alkoxysilane within the above range, the temporal stability of the aqueous composition can be enhanced.
水性組成物には、上述したアルコキシシランの他に、公知の硬化性樹脂を添加してもよい。公知の硬化性樹脂としては、熱硬化性樹脂や活性化エネルギー線重合樹脂を挙げることができる。
熱硬化性樹脂は熱を加えることにより硬化する樹脂である。熱硬化性樹脂としてはメラミン樹脂、ウレタン樹脂、エポキシ樹脂等のプレポリマーの架橋反応を利用するものがある。熱硬化性樹脂としては、カルボキシル(-COOH)基および/またはヒドロキシル(-OH)基を含有するポリエステル樹脂、エポキシ樹脂、ポリアクリレート樹脂、ポリメタクリレート樹脂、ポリアミド樹脂、フルオロ樹脂、ポリイミド樹脂、ポリウレタン樹脂およびアルキド樹脂等を挙げることができる。 In addition to the alkoxysilane described above, a known curable resin may be added to the aqueous composition. Known curable resins include thermosetting resins and activated energy ray polymerization resins.
A 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.
熱硬化性樹脂は熱を加えることにより硬化する樹脂である。熱硬化性樹脂としてはメラミン樹脂、ウレタン樹脂、エポキシ樹脂等のプレポリマーの架橋反応を利用するものがある。熱硬化性樹脂としては、カルボキシル(-COOH)基および/またはヒドロキシル(-OH)基を含有するポリエステル樹脂、エポキシ樹脂、ポリアクリレート樹脂、ポリメタクリレート樹脂、ポリアミド樹脂、フルオロ樹脂、ポリイミド樹脂、ポリウレタン樹脂およびアルキド樹脂等を挙げることができる。 In addition to the alkoxysilane described above, a known curable resin may be added to the aqueous composition. Known curable resins include thermosetting resins and activated energy ray polymerization resins.
A 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.
活性エネルギー線重合性樹脂は、多官能モノマーと重合開始剤を含む塗布液を塗布し、多官能モノマーを活性エネルギー線により重合させることで形成される。モノマーが有する官能基としては、重合性不飽和二重結合基を挙げることができる。重合性不飽和二重結合の例としては、アクリレート基、メタクリレート基、ビニル基を挙げることができる。反応性の観点よりアクリレート基が好ましく用いられる。
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. Examples of the functional group possessed by the monomer include a polymerizable unsaturated double bond group. Examples of 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.
活性エネルギー線としては、放射線、ガンマー線、アルファー線、電子線、紫外線等を用いることができるが、紫外線(UV)が好ましく用いられる。UV硬化性樹脂としては、アクリレート系モノマーからなるアクリル樹脂や、エポキシ系あるいはウレタン樹脂等を挙げることができる。
As the active energy ray, radiation, gamma ray, alpha ray, electron beam, ultraviolet ray and the like can be used, and ultraviolet ray (UV) is preferably used. Examples of the UV curable resin include an acrylic resin made of an acrylate monomer, an epoxy resin, and a urethane resin.
(硬化促進剤)
本発明の水性組成物は、硬化促進剤をさらに含むことが好ましい。硬化促進剤は、水溶性であることが好ましい。本発明の実施形態で用いる硬化促進剤は、水性組成物中で、シラノールの脱水縮合を促してシロキサン結合の形成を促進させる働きをする。硬化促進剤は、水溶性の無機酸、有機酸、有機酸塩、無機酸塩、金属アルコキシド、金属錯体を用いることができる。金属錯体としては、Al、Mg、Mn、Ti、Cu、Co、Zn、Hf及びZrよりなる金属錯体が好ましく、これらを併用することもできる。 (Curing accelerator)
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. As the curing accelerator, a water-soluble inorganic acid, organic acid, organic acid salt, inorganic acid salt, metal alkoxide, or metal complex can be used. As 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.
本発明の水性組成物は、硬化促進剤をさらに含むことが好ましい。硬化促進剤は、水溶性であることが好ましい。本発明の実施形態で用いる硬化促進剤は、水性組成物中で、シラノールの脱水縮合を促してシロキサン結合の形成を促進させる働きをする。硬化促進剤は、水溶性の無機酸、有機酸、有機酸塩、無機酸塩、金属アルコキシド、金属錯体を用いることができる。金属錯体としては、Al、Mg、Mn、Ti、Cu、Co、Zn、Hf及びZrよりなる金属錯体が好ましく、これらを併用することもできる。 (Curing accelerator)
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. As the curing accelerator, a water-soluble inorganic acid, organic acid, organic acid salt, inorganic acid salt, metal alkoxide, or metal complex can be used. As 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.
無機酸としては、ホウ酸、リン酸、塩酸、硝酸、硫酸が挙げられ、有機酸としては、酢酸、蟻酸、シュウ酸、クエン酸、リンゴ酸、アスコルビン酸が挙げられる。有機酸塩としては、酢酸アルミ、シュウ酸アルミ、酢酸亜鉛、シュウ酸亜鉛、酢酸マグネシウム、シュウ酸マグネシウム、酢酸ジルコニウム、シュウ酸ジルコニウムが挙げられ、無機酸塩としては、塩化アルミ、硫酸アルミ、硝酸アルミ、塩化亜鉛、硫酸亜鉛、硝酸亜鉛、塩化マグネシウム、硫酸マグネシウム、硝酸マグネシウム、塩化ジルコニウム、硫酸ジルコニウム、硝酸ジルコニウムが挙げられる。金属アルコキシドとしては、アルミニウムアルコキシド、チタンアルコキシド、ジルコニウムアルコキシドが挙げられる。金属錯体としては、エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトリス(エチルアセトアセテート)、アルキルアセトアセテートアルミニウムジイソプロピレート、アルミニウムモノアセチルアセテートビス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)等のアルミニウムキレート化合物、エチルアセトアセテートマグネシウムモノイソプロピレート、マグネシウムビス(エチルアセトアセテート)、アルキルアセトアセテートマグネシウムモノイソプロピレート、マグネシウムビス(アセチルアセトネート)等のマグネシウムキレート化合物、ジルコニウムテトラアセチルアセトナート、ジルコニウムトリブトキシアセチルアセトナート、ジルコニウムアセチルアセトナートビス(エチルアセトアセテート)、マンガンアセチルアセトナート、コバルトアセチルアセトナート、銅アセチルアセトナート、チタンアセチルアセトナート、チタンオキシアセチルアセトナートが挙げられる。これらのうち、好ましくは、アルミニウムトリス(アセチルアセトネート)、アルミニウムトリス(エチルアセトアセテート)、マグネシウムビス(アセチルアセトネート)、マグネシウムビス(エチルアセトアセテート)、ジルコニウムテトラアセチルアセトナートであり、保存安定性、入手容易さを考慮すると、アルミニウムキレート錯体であるアルミニウムトリス(アセチルアセトネート)、アルミニウムトリス(エチルアセトアセテート)、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネートが特に好ましい。市販品としては、アルミキレートA(W)、アルミキレートD(川研ファインケミカル(株)製)などが挙げられる。
Examples of the inorganic acid include boric acid, phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid, and 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. Examples of the metal alkoxide include aluminum alkoxide, titanium alkoxide, and zirconium alkoxide. Examples of metal complexes 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, magnesium 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. Of these, 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.
硬化促進剤の添加量は、3官能アルコキシシランおよび/または4官能アルコキシシランの全量に対して5~60質量%であることが好ましく、10~50質量%であることがより好ましく、30~45質量%であることがさらに好ましい。硬化促進剤の添加量を上記下限値以上含むことにより、ハードコート層を形成した際に優れたアルカリ耐性を得ることができる。また、上記上限値以下とすることにより、水性水溶液中の分散性を良好とすることができる。
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%. By including 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. Moreover, the dispersibility in aqueous solution can be made favorable by setting it as the said upper limit or less.
(その他の添加剤)
本発明の水性組成物には、ハードコートフィルムの平滑性を向上させて塗膜表面の摩擦を軽減する目的で界面活性剤を添加しても良い。また、顔料や染料、その他微粒子等を分散させることによってハードコートフィルムを着色しても良い。さらに、耐候性を向上させる目的で紫外線吸収剤や酸化防止剤等を添加しても良い。 (Other additives)
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. Further, the hard coat film may be colored by dispersing pigments, dyes, and other fine particles. Furthermore, for the purpose of improving the weather resistance, an ultraviolet absorber, an antioxidant or the like may be added.
本発明の水性組成物には、ハードコートフィルムの平滑性を向上させて塗膜表面の摩擦を軽減する目的で界面活性剤を添加しても良い。また、顔料や染料、その他微粒子等を分散させることによってハードコートフィルムを着色しても良い。さらに、耐候性を向上させる目的で紫外線吸収剤や酸化防止剤等を添加しても良い。 (Other additives)
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. Further, the hard coat film may be colored by dispersing pigments, dyes, and other fine particles. Furthermore, for the purpose of improving the weather resistance, an ultraviolet absorber, an antioxidant or the like may be added.
(界面活性剤)
本発明の水性組成物には、塗布性をより向上させる観点から、各種の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。 (Surfactant)
Various surfactants may be added to the aqueous composition of the present invention from the viewpoint of further improving coatability. As the surfactant, 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.
本発明の水性組成物には、塗布性をより向上させる観点から、各種の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。 (Surfactant)
Various surfactants may be added to the aqueous composition of the present invention from the viewpoint of further improving coatability. As the surfactant, 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.
フッ素系界面活性剤としては、例えば、メガファックF171、同F172、同F173、同F176、同F177、同F141、同F142、同F143、同F144、同R30、同F437、同F475、同F479、同F482、同F554、同F780、同F781(以上、DIC(株)製)、フロラードFC430、同FC431、同FC171(以上、住友スリーエム(株)製)、サーフロンS-382、同SC-101、同SC-103、同SC-104、同SC-105、同SC1068、同SC-381、同SC-383、同S393、同KH-40(以上、旭硝子(株)製)、PF636、PF656、PF6320、PF6520、PF7002(OMNOVA社製)等が挙げられる。
Examples of the fluorosurfactant 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.
ノニオン系界面活性剤として具体的には、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート(例えば、グリセロールプロポキシレート、グリセリンエトキシレート等)、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル(BASF社製のプルロニックL10、L31、L61、L62、10R5、17R2、25R2、テトロニック304、701、704、901、904、150R1、パイオニン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-6120-X(竹本油脂(株)製)、ソルスパース20000(日本ルーブリゾール(株)製)、ナロアクティーCL-95、HN-100(三洋化成工業(株)製)等が挙げられる。
Specific examples of 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 -6120-X (manufactured by Takemoto Yushi Co., Ltd.), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NAROACTY CL-95, HN-100 (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
カチオン系界面活性剤として具体的には、フタロシアニン誘導体(商品名:EFKA-745、森下産業(株)製)、オルガノシロキサンポリマーKP341(信越化学工業(株)製)、(メタ)アクリル酸系(共)重合体ポリフローNo.75、No.90、No.95(共栄社化学(株)製)、W001(裕商(株)製)等が挙げられる。
アニオン系界面活性剤として具体的には、W004、W005、W017(裕商(株)社製)、サンデッドBL(三洋化成工業(株)製)等が挙げられる。 Specific examples of the cationic surfactant 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.
アニオン系界面活性剤として具体的には、W004、W005、W017(裕商(株)社製)、サンデッドBL(三洋化成工業(株)製)等が挙げられる。 Specific examples of the cationic surfactant 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.
シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング(株)製「トーレシリコーンDC3PA」、「トーレシリコーンSH7PA」、「トーレシリコーンDC11PA」,「トーレシリコーンSH21PA」,「トーレシリコーンSH28PA」、「トーレシリコーンSH29PA」、「トーレシリコーンSH30PA」、「トーレシリコーンSH8400」、モメンティブ・パフォーマンス・マテリアルズ社製「TSF-4440」、「TSF-4300」、「TSF-4445」、「TSF-4460」、「TSF-4452」、信越シリコーン株式会社製「KP341」、「KF6001」、「KF6002」、ビックケミー社製「BYK307」、「BYK323」、「BYK330」等が挙げられる。
界面活性剤は、1種のみを用いてもよいし、2種類以上を組み合わせてもよい。
界面活性剤の添加量は、水性組成物の全質量に対して、0.001質量%~2.0質量%が好ましく、より好ましくは0.005質量%~1.0質量%である。 Examples of the silicone surfactant 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. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the aqueous composition.
界面活性剤は、1種のみを用いてもよいし、2種類以上を組み合わせてもよい。
界面活性剤の添加量は、水性組成物の全質量に対して、0.001質量%~2.0質量%が好ましく、より好ましくは0.005質量%~1.0質量%である。 Examples of the silicone surfactant 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. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the aqueous composition.
(ハードコートフィルム)
ハードコートフィルム(ハードコート層)は、上述した水性組成物を支持体に塗布して乾燥することにより、形成される。本願明細書において、支持体の上にハードコートフィルムを積層したものを積層フィルムという。なお、積層フィルムにおいては、ハードコートフィルムと支持体との密着力を高めるため、ハードコート層と支持体の間に、易接着層を設けることが好ましい。 (Hard coat film)
The hard coat film (hard coat layer) is formed by applying the aqueous composition described above to a support and drying it. In this specification, what laminated | stacked the hard-coat film on the support body is called laminated | multilayer film. In addition, in a 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.
ハードコートフィルム(ハードコート層)は、上述した水性組成物を支持体に塗布して乾燥することにより、形成される。本願明細書において、支持体の上にハードコートフィルムを積層したものを積層フィルムという。なお、積層フィルムにおいては、ハードコートフィルムと支持体との密着力を高めるため、ハードコート層と支持体の間に、易接着層を設けることが好ましい。 (Hard coat film)
The hard coat film (hard coat layer) is formed by applying the aqueous composition described above to a support and drying it. In this specification, what laminated | stacked the hard-coat film on the support body is called laminated | multilayer film. In addition, in a 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.
ハードコートフィルムの厚みは、水性組成物の塗布量や固形分濃度を調整することにより制御することができる。得られるハードコートフィルムの硬度の観点からは、厚みは、0.3~12μmの範囲で一定であることがより好ましい。厚みが0.3μm未満であると十分な硬度が発現せずにハードコートフィルムとしての機能が得られないことがあり、12μmよりも大きいとハードコートフィルムの内部応力が大きくなってカール等の変形が生じてしまう場合がある。より好ましい厚みの範囲は、0.5~10μmである。
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 μm. If the thickness is less than 0.3 μm, 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 μm, 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 μm.
本発明のハードコートフィルムのヘイズ値は、1.0%以下であることが好ましく、0.7%以下であることがより好ましく、0.4%以下であることがさらに好ましい。本発明では、水性組成物中の無機微粒子のゼータ電位を所定の範囲とすることにより、高屈折率を有する無機微粒子を含有した場合であっても、ヘイズ値の低いハードコート層を形成することができる。
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. In the present invention, by setting the zeta potential of the inorganic fine particles in the aqueous composition within a predetermined range, 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.
本発明では、ハードコートフィルムの屈折率は、1.60~2.40であることが好ましく、1.60~2.30であることがより好ましく、1.80~2.30であることがさらに好ましく、1.95~2.20であることが特に好ましい。
ハードコートフィルムは、その上に透明電極層を積層することでタッチパネルとすることができる。透明電極層には、一般的にITO(インジウム・錫酸化物)が用いられており、その電極パターンはITO導電膜をパターニングすることにより作成される。ハードコートフィルムと透明電極層は接するように積層されても良く、ハードコートフィルムと透明電極の間に光学調整層等の調整層を積層しても良い。光学調整層は、各層間の屈折率の差を調整するために設けられる。なお、光学調整層は、ハードコート層と同様の塗布液から形成することができる。
ITOの屈折率は約2.0程度であり、支持基板であるポリエステルフィルムの屈折率約1.6程度と比べると大きい。したがって、ITOが有るところと無いところとでは、外光による反射強度が異なるため、ITOのパターンが見えてしまい、表示品位を著しく劣化させることになる。この現象をITO骨見えという。
しかし、ハードコート層の屈折率を上記範囲内とすることにより、ハードコート層に透明電極層等を積層してタッチパネルとした際に、透明電極の骨見えを抑制することができる。すなわち、本発明のハードコート層は、支持体としてポリエステルフィルムを用い、ITO導電膜を積層してタッチパネル用の積層フィルムを構成する場合に、特に好ましく用いられる。
なお、ハードコート層等の各層の屈折率は、例えば、シリコンウエハー上に各層を2μmの膜厚になるように塗布した後、プリズムカプラーSPA-4000(SAIRONTECHNOLOGY社製)により測定することができる。 In the present invention, 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. In general, ITO (indium tin oxide) is used for the transparent electrode layer, and 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.
However, by setting 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. That is, 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 μm.
ハードコートフィルムは、その上に透明電極層を積層することでタッチパネルとすることができる。透明電極層には、一般的にITO(インジウム・錫酸化物)が用いられており、その電極パターンはITO導電膜をパターニングすることにより作成される。ハードコートフィルムと透明電極層は接するように積層されても良く、ハードコートフィルムと透明電極の間に光学調整層等の調整層を積層しても良い。光学調整層は、各層間の屈折率の差を調整するために設けられる。なお、光学調整層は、ハードコート層と同様の塗布液から形成することができる。
ITOの屈折率は約2.0程度であり、支持基板であるポリエステルフィルムの屈折率約1.6程度と比べると大きい。したがって、ITOが有るところと無いところとでは、外光による反射強度が異なるため、ITOのパターンが見えてしまい、表示品位を著しく劣化させることになる。この現象をITO骨見えという。
しかし、ハードコート層の屈折率を上記範囲内とすることにより、ハードコート層に透明電極層等を積層してタッチパネルとした際に、透明電極の骨見えを抑制することができる。すなわち、本発明のハードコート層は、支持体としてポリエステルフィルムを用い、ITO導電膜を積層してタッチパネル用の積層フィルムを構成する場合に、特に好ましく用いられる。
なお、ハードコート層等の各層の屈折率は、例えば、シリコンウエハー上に各層を2μmの膜厚になるように塗布した後、プリズムカプラーSPA-4000(SAIRONTECHNOLOGY社製)により測定することができる。 In the present invention, 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. In general, ITO (indium tin oxide) is used for the transparent electrode layer, and 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.
However, by setting 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. That is, 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 μm.
(積層フィルム)
本発明は、上述したハードコートフィルムを支持体の上に形成することが好ましく、このような積層フィルムの形態も本発明に含まれる。本発明では、ポリエステルフィルムの少なくとも片面に上述したハードコートフィルムを形成し積層フィルムとすることが好ましい。
本発明のハードコートフィルムは、さらに、他の構成層を有する積層フィルムに用いられてもよい。具体的には、光学調整層、ガスバリア層、ITO電極等の透明電極層、プリズム層、反射防止層等が例示される。中でも、ポリエステルフィルム上に、易接着層、光学調整層及び上述したハードコート層をこの順に形成し、積層フィルムとすることがより好ましい。 (Laminated film)
In the present invention, 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. In the present invention, it is preferable that 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. Especially, it is more preferable to form an easily bonding layer, an optical adjustment layer, and the hard-coat layer mentioned above on the polyester film in this order, and to set it as a laminated film.
本発明は、上述したハードコートフィルムを支持体の上に形成することが好ましく、このような積層フィルムの形態も本発明に含まれる。本発明では、ポリエステルフィルムの少なくとも片面に上述したハードコートフィルムを形成し積層フィルムとすることが好ましい。
本発明のハードコートフィルムは、さらに、他の構成層を有する積層フィルムに用いられてもよい。具体的には、光学調整層、ガスバリア層、ITO電極等の透明電極層、プリズム層、反射防止層等が例示される。中でも、ポリエステルフィルム上に、易接着層、光学調整層及び上述したハードコート層をこの順に形成し、積層フィルムとすることがより好ましい。 (Laminated film)
In the present invention, 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. In the present invention, it is preferable that 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. Especially, it is more preferable to form an easily bonding layer, an optical adjustment layer, and the hard-coat layer mentioned above on the polyester film in this order, and to set it as a laminated film.
ポリエステルフィルム上に、易接着層、光学調整層及びハードコート層を有する積層フィルムにおいては、易接着層の屈折率とポリエステルフィルムの屈折率の差は0.2以下であることが好ましく、光学調整層の屈折率は1.60~1.90であり、ハードコート層の屈折率は1.80~2.30であることが好ましい。
易接着層の屈折率とポリエステルフィルムの屈折率の差は0.1以下であることがより好ましく、0.05以下であることがさらに好ましい。また、光学調整層の屈折率は1.70~1.87であることがより好ましく、1.80~1.85であることがさらに好ましい。このように、本発明の積層フィルムでは、易接着層の屈折率とポリエステルフィルムの屈折率の差を上記範囲内とすることにより、易接着層の膜厚設定の自由度が増すため、各層間の接着性を高めることができる。また、本発明では、上記のように光学調整層を設け、光学調整層とハードコート層の屈折率を上記範囲内とすることにより、ハードコートフィルムの上にITO導電膜の成膜を行った場合に、骨見えが生じることを防ぐことができる。このように、光学調整層は、各層間の屈折率の差を調整するために設けられる。 In the laminated film having the easy adhesion layer, the optical adjustment layer and the hard coat layer on the polyester film, 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. Further, the refractive index of the optical adjustment layer is more preferably 1.70 to 1.87, and further preferably 1.80 to 1.85. Thus, in 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. In the present invention, 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. Thus, the optical adjustment layer is provided to adjust the difference in refractive index between the layers.
易接着層の屈折率とポリエステルフィルムの屈折率の差は0.1以下であることがより好ましく、0.05以下であることがさらに好ましい。また、光学調整層の屈折率は1.70~1.87であることがより好ましく、1.80~1.85であることがさらに好ましい。このように、本発明の積層フィルムでは、易接着層の屈折率とポリエステルフィルムの屈折率の差を上記範囲内とすることにより、易接着層の膜厚設定の自由度が増すため、各層間の接着性を高めることができる。また、本発明では、上記のように光学調整層を設け、光学調整層とハードコート層の屈折率を上記範囲内とすることにより、ハードコートフィルムの上にITO導電膜の成膜を行った場合に、骨見えが生じることを防ぐことができる。このように、光学調整層は、各層間の屈折率の差を調整するために設けられる。 In the laminated film having the easy adhesion layer, the optical adjustment layer and the hard coat layer on the polyester film, 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. Further, the refractive index of the optical adjustment layer is more preferably 1.70 to 1.87, and further preferably 1.80 to 1.85. Thus, in 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. In the present invention, 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. Thus, the optical adjustment layer is provided to adjust the difference in refractive index between the layers.
ハードコートフィルムを積層する支持体としての基材フィルムとしては、高分子化合物を溶融製膜方法や溶液製膜方法によりフィルム形状にしたものを用いることができる。基材フィルムに用いる高分子化合物は特に制限されないが、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート(PBT)、ポリブチレンナフタレート(PBN)、ポリアリレート類、ポリエーテルスルフォン、ポリカーボネート、ポリエーテルケトン、ポリスルフォン、ポリフェニレンサルファイド、ポリエステル系液晶ポリマー、トリアセチルセルロース、セルロース誘導体、ポリプロピレン、ポリアミド類、ポリイミド、ポリシクロオレフィン類等が好ましい。この中でも、PET、PEN、トリアセチルセルロース、セルロース誘導体がより好ましく、PET、PENが特に好ましい。
As the base film as a support on which the hard coat film is laminated, a polymer compound formed into a film shape by a melt film forming method or a solution film forming method can be used. 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. Among these, PET, PEN, triacetyl cellulose, and cellulose derivatives are more preferable, and PET and PEN are particularly preferable.
これらの基材フィルムは、2軸延伸されていることが好ましい。2軸延伸とは、フィルムの幅方向および長手方向をそれぞれ1軸とみなして両方向に延伸させることである。このように2軸延伸されたポリエステルフィルムは、2軸での分子配向が十分に制御されているため非常に優れた機械強度を有する。延伸倍率は特に制限されるものではないが、一方向に対する延伸倍率が1.5~7倍であることが好ましく、より好ましくは2~5倍である。特に、1軸方向あたりの延伸倍率を2~5倍として2軸延伸させたポリエステルフィルムは、分子配向がより効率良くかつ効果的に制御されているので、非常に優れた機械強度を備え、ポリエステルフィルムとして好適である。
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. Thus, 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. In particular, 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.
基材フィルムは、表面がコロナ処理又はグロー処理されたものであってもよい。それらの処理により、基材フィルムの表面が親水化され、水性組成物の塗れ性を改善することができるので、ハードコートフィルムとの密着力または易接着層との密着力をより高めることができる。
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. .
易接着層は、基材フィルムとハードコートフィルムの接着性を向上させ、ハードコートフィルムとの密着力を高めるために基材フィルムに適宜設けられる。易接着層は、通常、バインダーと硬化剤と界面活性剤とからなる塗布液を、基材フィルムのハードコートフィルムが設けられる面に塗布して形成される。易接着層には、有機または無機の微粒子を適宜添加してもよい。微粒子としては、特に限定されないが例えば金属酸化物が挙げられ、具体的には酸化スズ、酸化ジルコニウム、酸化亜鉛、酸化チタン、酸化セリウム、酸化ニオブなどが好ましく、これらを単独で使用、もしくは2種以上を併用してもよい。市販品としては、例えば、ET-500WほかETシリーズ、FT-2000ほかFTシリーズ、SN-100PほかSNシリーズ、FS-10DほかFSシリーズ(石原産業(株)製)、ZR-30BF(堺化学工業(株)製)などが挙げられる。
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.).
易接着層に使用するバインダーは、特に限定されないが、接着性の観点からポリエステル、ポリオレフィン、ポリウレタン、アクリル樹脂、スチレンブタジエン共重合体の少なくともひとつであることが好ましい。また、バインダーは、水溶性または水分散性を持つものが環境への負荷が少ない点で特に好ましい。市販品としては、例えば、カルボジライトV-02-L2ほかカルボジライトシリーズ(日清紡(株)製)タケラックWS-5100ほかタケラックWSシリーズ(三井化学(株)製)などが挙げられる。
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. In addition, 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).
易接着層の厚みは、その塗布量を調節することで適宜調整することができる。易接着層の厚みは、0.05~5μmの範囲で一定であることがより好ましい。厚みが0.05μm未満であると接着性が不十分となることがあり、5μmよりも大きいと均一な厚みの接着性を形成することが難しかったり、さらには、溶液の使用量が増加したり乾燥時間が長くかかりすぎてコストが増大したりすることがある。より好ましい厚みの範囲は、0.1~3μmである。易接着層は、1層のみでもよいし、これを複数重ねた態様であってもよい。複数の易接着層を重ねた場合には、すべての易接着層の厚みの合計を、易接着層の厚みとみなす。
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 μm. If the thickness is less than 0.05 μm, the adhesion may be insufficient. If the thickness is greater than 5 μm, 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 μm. 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.
(タッチパネル)
上述した積層フィルムのハードコートフィルム(ハードコート層)上に、さらに透明電極層を積層することで透明導電性フィルムを製造することができ、この透明導電性フィルムを用いてタッチパネルとすることができる。
本発明のタッチパネルに用いることができる透明電極層としては、酸化インジウム、酸化亜鉛、酸化スズのいずれか、または、それらの2種類もしくは3種類の混合酸化物、さらには、その他添加物が加えられた物などが挙げられるが、目的・用途により種々の材料が使用でき、特に限定されるものではない。現在のところ、最も信頼性が高く、多くの実績のある材料は酸化インジウムスズ(ITO)である。透明電極層の製造方法としては、膜厚の制御が可能であればいかなる成膜方法でもよく、例えば特開2012-206307号公報に記載の方法を用いることができる。 (Touch panel)
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. .
As 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). As a method for producing the transparent electrode layer, 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.
上述した積層フィルムのハードコートフィルム(ハードコート層)上に、さらに透明電極層を積層することで透明導電性フィルムを製造することができ、この透明導電性フィルムを用いてタッチパネルとすることができる。
本発明のタッチパネルに用いることができる透明電極層としては、酸化インジウム、酸化亜鉛、酸化スズのいずれか、または、それらの2種類もしくは3種類の混合酸化物、さらには、その他添加物が加えられた物などが挙げられるが、目的・用途により種々の材料が使用でき、特に限定されるものではない。現在のところ、最も信頼性が高く、多くの実績のある材料は酸化インジウムスズ(ITO)である。透明電極層の製造方法としては、膜厚の制御が可能であればいかなる成膜方法でもよく、例えば特開2012-206307号公報に記載の方法を用いることができる。 (Touch panel)
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. .
As 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). As a method for producing the transparent electrode layer, 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.
本発明のタッチパネルは、液晶ディスプレイ、プラズマディスプレイ、有機ELディスプレイ、CRTディスプレイ、電子ペーパー等の表示装置等に組み込むことで、入力デバイスとして利用することができる。本発明のタッチパネルを利用することで、干渉ムラの発生が抑制され、かつ、良好な色味のタッチパネルとすることができる。
タッチパネルの構成については、抵抗膜型、静電容量型などがあり、静電容量型の入力装置は、単に一枚の基板に透光性導電膜を形成すればよいという利点があるため、静電容量型であることが好ましい。かかる静電容量型の入力装置では、例えば、前記透明電極層として互いに交差する方向に電極パターンを延在させて、指などが接触した際、電極間の静電容量が変化することを検知して入力位置を検出するタイプのものを好ましく用いることができる。このようなタッチパネルの構成については、例えば、特開2010-86684号公報、特開2010-152809号公報、特開2010-257492号公報等の記載を参酌できる。
タッチパネルを構成要素として備えた画像表示装置の構成については、『最新タッチパネル技術』(2009年7月6日発行(株)テクノタイムズ)、三谷雄二監修、“タッチパネルの技術と開発”、シーエムシー出版(2004,12)、FPD International 2009 Forum T-11講演テキストブック、Cypress Semiconductor Corporation アプリケーションノートAN2292等に開示されている構成を適用することができる。
また、タッチパネルを組み込むことができる液晶ディスプレイの構成については、特開2002-48913号公報等の記載も参酌できる。 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. By using the touch panel of the present invention, occurrence of interference unevenness can be suppressed and a touch panel with good color can be obtained.
There are two types of touch panel configurations, such as a resistance film type and a capacitance type. Capacitance type input devices have the advantage of simply forming a light-transmitting conductive film on a single substrate. A capacitance type is preferred. In such 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. Thus, a type that detects the input position can be preferably used. Regarding the configuration of such a touch panel, for example, descriptions in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be referred to.
Regarding the configuration of an image display device equipped with a touch panel as a component, “Latest Touch Panel Technology” (published July 6, 2009, Techno Times), supervised by Yuji Mitani, “Technology and Development of Touch Panels”, CM Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, and the like can be applied.
In addition, regarding the configuration of a liquid crystal display in which a touch panel can be incorporated, description in JP-A-2002-48913 can be referred to.
タッチパネルの構成については、抵抗膜型、静電容量型などがあり、静電容量型の入力装置は、単に一枚の基板に透光性導電膜を形成すればよいという利点があるため、静電容量型であることが好ましい。かかる静電容量型の入力装置では、例えば、前記透明電極層として互いに交差する方向に電極パターンを延在させて、指などが接触した際、電極間の静電容量が変化することを検知して入力位置を検出するタイプのものを好ましく用いることができる。このようなタッチパネルの構成については、例えば、特開2010-86684号公報、特開2010-152809号公報、特開2010-257492号公報等の記載を参酌できる。
タッチパネルを構成要素として備えた画像表示装置の構成については、『最新タッチパネル技術』(2009年7月6日発行(株)テクノタイムズ)、三谷雄二監修、“タッチパネルの技術と開発”、シーエムシー出版(2004,12)、FPD International 2009 Forum T-11講演テキストブック、Cypress Semiconductor Corporation アプリケーションノートAN2292等に開示されている構成を適用することができる。
また、タッチパネルを組み込むことができる液晶ディスプレイの構成については、特開2002-48913号公報等の記載も参酌できる。 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. By using the touch panel of the present invention, occurrence of interference unevenness can be suppressed and a touch panel with good color can be obtained.
There are two types of touch panel configurations, such as a resistance film type and a capacitance type. Capacitance type input devices have the advantage of simply forming a light-transmitting conductive film on a single substrate. A capacitance type is preferred. In such 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. Thus, a type that detects the input position can be preferably used. Regarding the configuration of such a touch panel, for example, descriptions in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be referred to.
Regarding the configuration of an image display device equipped with a touch panel as a component, “Latest Touch Panel Technology” (published July 6, 2009, Techno Times), supervised by Yuji Mitani, “Technology and Development of Touch Panels”, CM Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, and the like can be applied.
In addition, regarding the configuration of a liquid crystal display in which a touch panel can be incorporated, description in JP-A-2002-48913 can be referred to.
(水性組成物及びハードコートフィルムの製造方法)
本発明の水性組成物の製造方法は、無機微粒子及び金属キレート化合物を混合し、水性混合物を得る工程と、水性混合物に2官能アルコキシシランを混合する工程と、2官能アルコキシシランを混合する工程の後に、さらに、3官能アルコキシシランもしくはその加水分解物、および/または4官能アルコキシシランもしくはその加水分解物と、硬化促進剤とを混合する工程を含む。すなわち、本発明の水性組成物の製造方法においては、無機微粒子と金属キレート化合物がまず混合され、その混合液に2官能アルコキシシランが添加される。 (Method for producing aqueous composition and hard coat film)
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.
本発明の水性組成物の製造方法は、無機微粒子及び金属キレート化合物を混合し、水性混合物を得る工程と、水性混合物に2官能アルコキシシランを混合する工程と、2官能アルコキシシランを混合する工程の後に、さらに、3官能アルコキシシランもしくはその加水分解物、および/または4官能アルコキシシランもしくはその加水分解物と、硬化促進剤とを混合する工程を含む。すなわち、本発明の水性組成物の製造方法においては、無機微粒子と金属キレート化合物がまず混合され、その混合液に2官能アルコキシシランが添加される。 (Method for producing aqueous composition and hard coat film)
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.
無機微粒子と金属キレート化合物を混合して混合物を得る工程では、無機微粒子と金属キレート化合物を1時間以上反応させることが好ましい。無機微粒子と金属キレート化合物の反応時間は1時間以上であることが好ましく、2時間以上であることがより好ましい。なお、無機微粒子と金属キレート化合物の反応時間は20時間以下であることが好ましく、15時間以下であることがより好ましく、13時間以下であることがさらに好ましい。
In the step of mixing the inorganic fine particles and the metal chelate compound to obtain a mixture, it is preferable to react the inorganic fine particles and the metal chelate compound for 1 hour or more. 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.
本発明では、このような工程を経て水性組成物を製造することにより、水性組成物中の無機微粒子のゼータ電位を0~20mVとすることができる。これは、無機微粒子と金属キレート化合物を十分に反応させた後に2官能アルコキシシランを加えることにより、無機微粒子の表面を良好な状態に修飾することができるためであると考えられる。このように、無機微粒子の表面に金属キレート化合物と2官能アルコキシシランを順番に結合させることにより、無機微粒子の表面を強固に覆うことが可能となり、この結果、ハードコート層を形成した際に良好なアルカリ耐性を発揮することができる。
また、無機微粒子の表面が修飾されることにより、無機微粒子の分散性が高まり、ヘイズ値が低く、かつ屈折率の高いハードコート層を形成することが可能となる。
なお、3官能アルコキシシランや4官能アルコキシシランは、水性組成物中において、バインダーとして機能し、ハードコート層の強度を高める働きをする。 In the present invention, 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.
Further, by modifying the surface of the inorganic fine particles, the dispersibility of the inorganic fine particles is enhanced, and a hard coat layer having a low haze value and a high refractive index can be formed.
Trifunctional alkoxysilane and tetrafunctional alkoxysilane function as a binder in the aqueous composition and function to increase the strength of the hard coat layer.
また、無機微粒子の表面が修飾されることにより、無機微粒子の分散性が高まり、ヘイズ値が低く、かつ屈折率の高いハードコート層を形成することが可能となる。
なお、3官能アルコキシシランや4官能アルコキシシランは、水性組成物中において、バインダーとして機能し、ハードコート層の強度を高める働きをする。 In the present invention, 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.
Further, by modifying the surface of the inorganic fine particles, the dispersibility of the inorganic fine particles is enhanced, and a hard coat layer having a low haze value and a high refractive index can be formed.
Trifunctional alkoxysilane and tetrafunctional alkoxysilane function as a binder in the aqueous composition and function to increase the strength of the hard coat layer.
ハードコートフィルムを形成する水性組成物のpHはあらかじめ調整されていることが好ましい。例えば、水性組成物が塗布される前に、水性組成物に酸性溶液を添加し、pHを所望の範囲となるように調節することが好ましい。酸性溶液は、pHが2~6であることが好ましく、水性組成物のpHは2~7、好ましくは2~6となるように調整されることが好ましい。
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.
水性組成物の塗布工程は、ポリエステルフィルムの延伸工程の途中に設けられても良いが、延伸工程の後に設けられることが好ましい。水性組成物の塗布は公知の塗布機を適宜用いることができる。例えば、スピンコータ、ロールコータ、バーコータ、カーテンコータ等を挙げることができる。
塗布工程の後には、塗布液を乾燥させる工程が設けられる。乾燥工程では、加熱乾燥を行うことが好ましい。加熱乾燥では、塗布膜の温度が120℃以上となるように加熱処理を行うことが好ましく、塗布膜の温度は140℃以上であることがより好ましく、160℃以上であることがさらに好ましい。また、塗布膜の温度は、300℃以下であることが好ましく、280℃以下であることがより好ましく、260℃以下であることがさらに好ましい。加熱処理温度を上記範囲内とすることにより、塗布膜を十分に硬化することができ、かつ、ハードコート層に変形が起こることを防ぐことができる。なお、加熱時間は、10秒~1時間であればよく、10秒~5分であることが好ましい。本発明では、加熱工程では、120℃~300℃の程度の加熱温度で加熱すれば十分であり、加熱時間も10秒~1時間程度と短時間である。このため、製造効率を高めることができ、製造にかかるコストを抑制することができる。 Although the application | 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. For example, 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. By setting the heat treatment temperature within the above range, the coating film can be sufficiently cured, and deformation of the hard coat layer can be prevented. The heating time may be 10 seconds to 1 hour, and preferably 10 seconds to 5 minutes. In the present invention, in the heating step, 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.
塗布工程の後には、塗布液を乾燥させる工程が設けられる。乾燥工程では、加熱乾燥を行うことが好ましい。加熱乾燥では、塗布膜の温度が120℃以上となるように加熱処理を行うことが好ましく、塗布膜の温度は140℃以上であることがより好ましく、160℃以上であることがさらに好ましい。また、塗布膜の温度は、300℃以下であることが好ましく、280℃以下であることがより好ましく、260℃以下であることがさらに好ましい。加熱処理温度を上記範囲内とすることにより、塗布膜を十分に硬化することができ、かつ、ハードコート層に変形が起こることを防ぐことができる。なお、加熱時間は、10秒~1時間であればよく、10秒~5分であることが好ましい。本発明では、加熱工程では、120℃~300℃の程度の加熱温度で加熱すれば十分であり、加熱時間も10秒~1時間程度と短時間である。このため、製造効率を高めることができ、製造にかかるコストを抑制することができる。 Although the application | 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. For example, 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. By setting the heat treatment temperature within the above range, the coating film can be sufficiently cured, and deformation of the hard coat layer can be prevented. The heating time may be 10 seconds to 1 hour, and preferably 10 seconds to 5 minutes. In the present invention, in the heating step, 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.
乾燥工程の後に得られた積層フィルムは、その後ロール状に巻き取られても良く、シート状にカットされても良い。なお、加熱処理工程は、塗布工程の後の乾燥工程に設けられてもよく、ロール状に巻き取られた後に加熱処理工程を設けてもよい。
The laminated film obtained after the drying step may then be wound up in a roll shape or cut into a sheet shape. In addition, a heat treatment process may be provided in the drying process after an application | coating process, and may be provided in a heat treatment process, after winding up in roll shape.
ハードコートフィルムの上には、さらに、他の構成層を積層してタッチパネル等の表示装置を形成しても良い。他の構成層の積層方法としては、各々、従来の公知の方法を適宜選択できる。
Other display layers may be further laminated on the hard coat film to form a display device such as a touch panel. As a method for laminating other constituent layers, a conventionally known method can be appropriately selected.
以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。
Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
(実施例1)
下記の化合物を下記の配合で混合し、易接着層を形成する塗布液を調製した。この塗布液を塗布液サンプルI-1とした。[塗布液サンプルI-1]
・酸化ジルコニウム分散液 11.8質量部
(SZR-W、固形分濃度30質量%、堺化学工業(株)製)
・タケラックWS-5100 3.7質量部
(固形分濃度30質量%、三井化学(株)製)
・カルボジライトV-02-L2 5.5質量部
(固形分濃度40質量%、日清紡(株)製)
・界面活性剤 2.2質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・界面活性剤 2.2質量部
(サンデットBL、固形分濃度43質量%、三洋化成工業(株)製)
・水 74.6質量部 Example 1
The following compound was mixed by the following mixing | blending, and the coating liquid which forms an easily bonding layer was prepared. This coating solution was designated as coating solution sample I-1. [Coating liquid sample I-1]
・ Zirconium oxide dispersion 11.8 parts by mass (SZR-W, solid content concentration 30% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
・ Takelac WS-5100 3.7 parts by mass (solid content concentration 30% by mass, manufactured by Mitsui Chemicals, Inc.)
・ Carbodilite V-02-L2 5.5 parts by mass (solid content: 40% by mass, manufactured by Nisshinbo Co., Ltd.)
・ Surfactant 2.2 parts by mass (Naroacty CL-95, 1% by weight aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.)
・ Surfactant 2.2 parts by mass (Sandet BL, solid content concentration 43% by mass, manufactured by Sanyo Chemical Industries, Ltd.)
・ 74.6 parts by mass of water
下記の化合物を下記の配合で混合し、易接着層を形成する塗布液を調製した。この塗布液を塗布液サンプルI-1とした。[塗布液サンプルI-1]
・酸化ジルコニウム分散液 11.8質量部
(SZR-W、固形分濃度30質量%、堺化学工業(株)製)
・タケラックWS-5100 3.7質量部
(固形分濃度30質量%、三井化学(株)製)
・カルボジライトV-02-L2 5.5質量部
(固形分濃度40質量%、日清紡(株)製)
・界面活性剤 2.2質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・界面活性剤 2.2質量部
(サンデットBL、固形分濃度43質量%、三洋化成工業(株)製)
・水 74.6質量部 Example 1
The following compound was mixed by the following mixing | blending, and the coating liquid which forms an easily bonding layer was prepared. This coating solution was designated as coating solution sample I-1. [Coating liquid sample I-1]
・ Zirconium oxide dispersion 11.8 parts by mass (SZR-W, solid content concentration 30% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
・ Takelac WS-5100 3.7 parts by mass (solid content concentration 30% by mass, manufactured by Mitsui Chemicals, Inc.)
・ Carbodilite V-02-L2 5.5 parts by mass (solid content: 40% by mass, manufactured by Nisshinbo Co., Ltd.)
・ Surfactant 2.2 parts by mass (Naroacty CL-95, 1% by weight aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.)
・ Surfactant 2.2 parts by mass (Sandet BL, solid content concentration 43% by mass, manufactured by Sanyo Chemical Industries, Ltd.)
・ 74.6 parts by mass of water
PETフィルム(コスモシャインA4300、 125μm、東洋紡(株)製)の一方の面にコロナ放電処理を施した。このコロナ放電処理を施した面に、上記の塗布液サンプルI-1を塗布し120℃で2分乾燥させて、厚みが0.1μmの易接着層を形成した。
One side of a PET film (Cosmo Shine A4300, 125 μm, 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 μm.
下記の配合で無機微粒子溶液T-1を調製した。
[無機微粒子溶液T-1]
・チタニアゾル 100質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 1.0質量部
(アルミニウムエチルアセトアセテート・ジイソプロピレート、75質量%イソプロピルアルコール(IPA)溶液、川研ファインケミカル(株)製)
・3-グリシドキシプロピルメチルジエトキシシラン 10.0質量部
(KBE-402、信越化学工業(株)製) 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.)
Chelating agent 1.0 part by mass (aluminum ethyl acetoacetate / diisopropylate, 75% by mass isopropyl alcohol (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.)
[無機微粒子溶液T-1]
・チタニアゾル 100質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 1.0質量部
(アルミニウムエチルアセトアセテート・ジイソプロピレート、75質量%イソプロピルアルコール(IPA)溶液、川研ファインケミカル(株)製)
・3-グリシドキシプロピルメチルジエトキシシラン 10.0質量部
(KBE-402、信越化学工業(株)製) 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.)
Chelating agent 1.0 part by mass (aluminum ethyl acetoacetate / diisopropylate, 75% by mass isopropyl alcohol (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.)
無機微粒子溶液T-1は、以下の方法で調製した。まず、チタニアゾルにキレート剤を添加し、1時間以上攪拌した。キレート剤が完全に溶解したら、ここに3-グリシドキシプロピルメチルジエトキシシランを添加して1時間以上攪拌し、無機微粒子溶液T-1を得た。
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.
得られた無機微粒子溶液T-1について、下記(1)に示すようにゼータ電位を測定した。結果は、下記表に示す。
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.
(1)ゼータ電位測定
無機微粒子溶液T-1について、DT1200((株)RUFUTO製)を用いて、温度25℃、pH6においてゼータ電位を測定した。 (1) Zeta potential measurement With respect to the inorganic fine particle solution T-1, the zeta potential was measured at a temperature of 25 ° C and a pH of 6 using DT1200 (manufactured by RUFUTO).
無機微粒子溶液T-1について、DT1200((株)RUFUTO製)を用いて、温度25℃、pH6においてゼータ電位を測定した。 (1) Zeta potential measurement With respect to the inorganic fine particle solution T-1, the zeta potential was measured at a temperature of 25 ° C and a pH of 6 using DT1200 (manufactured by RUFUTO).
以下の配合で、アルコキシシランの加水分解液を調製した。この調製液を加水分解液Aとした。
[加水分解液A]
・テトラエトキシシラン 10.3質量部
(KBE-04、信越化学工業(株)製)
・3-グリシドキシプロピルトリエトキシシラン 20.1質量部
(KBE-403、信越化学工業(株)製)
・酢酸水溶液(酢酸濃度=1質量%) 60.4質量部
・硬化触媒 9.2質量部
(アルミキレートD、75%質量IPA溶液、川研ファインケミカル(株)製) 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.)
Acetic acid aqueous solution (acetic acid concentration = 1% by mass) 60.4 parts by mass Curing catalyst 9.2 parts by mass (aluminum chelate D, 75% mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.)
[加水分解液A]
・テトラエトキシシラン 10.3質量部
(KBE-04、信越化学工業(株)製)
・3-グリシドキシプロピルトリエトキシシラン 20.1質量部
(KBE-403、信越化学工業(株)製)
・酢酸水溶液(酢酸濃度=1質量%) 60.4質量部
・硬化触媒 9.2質量部
(アルミキレートD、75%質量IPA溶液、川研ファインケミカル(株)製) 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.)
Acetic acid aqueous solution (acetic acid concentration = 1% by mass) 60.4 parts by mass Curing catalyst 9.2 parts by mass (aluminum chelate D, 75% mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.)
加水分解液Aは、以下の方法で調製した。まず、酢酸水溶液を激しく攪拌しながら、3-グリシドキシプロピルトリメトキシシランを、この酢酸水溶液中に添加し、その後30分攪拌を続けた。この混合液を強く攪拌しながら、ここにテトラアルコキシシランとしてのテトラエトキシシランを添加し、その後1時間攪拌を続けた。次に、ここに硬化触媒を添加し、1時間攪拌を続けて完全に溶解させた。
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.
以下の配合で、ハードコート層を形成する塗布液を調製した。この塗布液を塗布液サンプルH-1とした。
[塗布液サンプルH-1]
・無機微粒子溶液T-1 25.4質量部
・加水分解液A 25.0質量部
・界面活性剤 2.4質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・水 47.2質量部 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.
[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
[塗布液サンプルH-1]
・無機微粒子溶液T-1 25.4質量部
・加水分解液A 25.0質量部
・界面活性剤 2.4質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・水 47.2質量部 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.
[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
塗布液サンプルH-1は、以下の方法で調製した。無機微粒子溶液T-1に加水分解液Aを添加し、30分攪拌した。この混合液に界面活性剤と水を順次添加し、塗布液サンプルH-1を調製した。
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.
得られた塗布液サンプルについて、下記(2)に示すように液安定性を評価した。結果は、下記表に示す。
The liquid stability of the obtained coating solution sample was evaluated as shown in (2) below. The results are shown in the table below.
(2)液安定性
調製した塗布液サンプルを室温で放置し、液の安定性を目視にて確認し、以下の基準で評価した。A:塗布液サンプルが調製後3日以上ゲル化しない
B:調製後1日以上、3日未満でゲル化
C:調製後1日未満でゲル化 (2) Liquid stability The prepared coating liquid sample was allowed to stand at room temperature, and the stability of the liquid was visually confirmed and evaluated according to the following criteria. A: The coating liquid sample does not gel for 3 days or more after preparation B: Gelates for 1 day or more and less than 3 days after preparation C: Gelation for less than 1 day after preparation
調製した塗布液サンプルを室温で放置し、液の安定性を目視にて確認し、以下の基準で評価した。A:塗布液サンプルが調製後3日以上ゲル化しない
B:調製後1日以上、3日未満でゲル化
C:調製後1日未満でゲル化 (2) Liquid stability The prepared coating liquid sample was allowed to stand at room temperature, and the stability of the liquid was visually confirmed and evaluated according to the following criteria. A: The coating liquid sample does not gel for 3 days or more after preparation B: Gelates for 1 day or more and less than 3 days after preparation C: Gelation for less than 1 day after preparation
この塗布液サンプルH-1を上記PETフィルム上に形成した易接着層の上にバーコート法により塗布し、150℃で2分間加熱して乾燥し、厚さ1.0μmのハードコート層を形成し、積層フィルムを得た。
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 μm. And a laminated film was obtained.
得られた積層フィルムについて、下記(3)に示すようにアルカリ耐性を評価した。結果は、下記表に示す。
The resulting laminated film was evaluated for alkali resistance as shown in (3) below. The results are shown in the table below.
(3)アルカリ耐性
5質量%のNaOH水溶液に30℃にて10分間、積層フィルムを浸漬させ、この浸漬前後のヘイズ値を測定した。ヘイズの測定には、日本電色工業(株)製のヘイズ測定機NDH5000を用いた。ヘイズ値の上昇を下記表に示し、以下の基準で評価した。
A:ヘイズ値の上昇が0.1以下
B:0.1より大きく0.5以下
C:0.5よりも大きい (3) Alkali resistance The laminated film was immersed in a 5% by mass NaOH aqueous solution at 30 ° C. for 10 minutes, and the haze values before and after this immersion were measured. A haze measuring machine NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. was used for haze measurement. The increase in haze value is shown in the table below and evaluated according to the following criteria.
A: Increase in haze value is 0.1 or less B: greater than 0.1 and 0.5 or less C: greater than 0.5
5質量%のNaOH水溶液に30℃にて10分間、積層フィルムを浸漬させ、この浸漬前後のヘイズ値を測定した。ヘイズの測定には、日本電色工業(株)製のヘイズ測定機NDH5000を用いた。ヘイズ値の上昇を下記表に示し、以下の基準で評価した。
A:ヘイズ値の上昇が0.1以下
B:0.1より大きく0.5以下
C:0.5よりも大きい (3) Alkali resistance The laminated film was immersed in a 5% by mass NaOH aqueous solution at 30 ° C. for 10 minutes, and the haze values before and after this immersion were measured. A haze measuring machine NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. was used for haze measurement. The increase in haze value is shown in the table below and evaluated according to the following criteria.
A: Increase in haze value is 0.1 or less B: greater than 0.1 and 0.5 or less C: greater than 0.5
(実施例2及び比較例1~2)
実施例1において無機微粒子溶液T-1を調製して用いたことに代えて、下記の配合で無機微粒子溶液T-2~T-4を調製して用いたこと以外は実施例1と同様にして積層フィルムを作製し、実施例1と同様に評価した。評価結果は下記表に示す。 (Example 2 and Comparative Examples 1 and 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.
実施例1において無機微粒子溶液T-1を調製して用いたことに代えて、下記の配合で無機微粒子溶液T-2~T-4を調製して用いたこと以外は実施例1と同様にして積層フィルムを作製し、実施例1と同様に評価した。評価結果は下記表に示す。 (Example 2 and Comparative Examples 1 and 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.
[無機微粒子溶液T-2]
・チタニアゾル 100質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 1.0質量部
(アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート、75質量%IPA溶液、川研ファインケミカル(株)製)
・3-グリシドキシプロピルメチルジエトキシシラン 10.0質量部
(KBE-402、信越化学工業(株)製) [Inorganic fine particle solution T-2]
-100 parts by weight of titania sol (SRD-W, solid content concentration 15% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
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.)
・チタニアゾル 100質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 1.0質量部
(アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート、75質量%IPA溶液、川研ファインケミカル(株)製)
・3-グリシドキシプロピルメチルジエトキシシラン 10.0質量部
(KBE-402、信越化学工業(株)製) [Inorganic fine particle solution T-2]
-100 parts by weight of titania sol (SRD-W, solid content concentration 15% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
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.)
[無機微粒子溶液T-3]
・チタニアゾル 100質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 1.0質量部
(アルミニウムエチルアセトアセテート・ジイソプロピレート、75質量%IPA溶液、川研ファインケミカル(株)製)
・水 10.0質量部 [Inorganic fine particle solution T-3]
-100 parts by weight of titania sol (SRD-W, solid content concentration 15% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
Chelating agent 1.0 part by mass (aluminum ethyl acetoacetate / diisopropylate, 75% by mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.)
-10.0 parts by weight of water
・チタニアゾル 100質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 1.0質量部
(アルミニウムエチルアセトアセテート・ジイソプロピレート、75質量%IPA溶液、川研ファインケミカル(株)製)
・水 10.0質量部 [Inorganic fine particle solution T-3]
-100 parts by weight of titania sol (SRD-W, solid content concentration 15% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
Chelating agent 1.0 part by mass (aluminum ethyl acetoacetate / diisopropylate, 75% by mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.)
-10.0 parts by weight of water
[無機微粒子溶液T-4]
・チタニアゾル 75.4質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・アセチルアセトン 0.7質量部
・水 10.0質量部 [Inorganic fine particle solution T-4]
-75.4 parts by mass of titania sol (SRD-W, solid content concentration 15% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
・ Acetylacetone 0.7 mass part ・ Water 10.0 mass part
・チタニアゾル 75.4質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・アセチルアセトン 0.7質量部
・水 10.0質量部 [Inorganic fine particle solution T-4]
-75.4 parts by mass of titania sol (SRD-W, solid content concentration 15% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
・ Acetylacetone 0.7 mass part ・ Water 10.0 mass part
実施例1及び2では、チタニア微粒子に金属キレートと2官能アルコキシシランを反応させることで、20mV以下のゼータ電位を有しており、安定な水性組成物が得られている。さらに、表面にエポキシ基含有2官能アルコキシシランを有することで、バインダーとして存在するアルコキシシランとエポキシ基を介して結合することができるため、高いアルカリ耐性を示している。
In Examples 1 and 2, 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.
一方、比較例1では、チタニア微粒子に金属キレートを反応させることで、比較的安定な水性組成物が得られたものの、2官能アルコキシシランを含まないため、アルカリ耐性を得ることができない。さらに、比較例2では、チタニア粒子にアセチルアセトンを反応させたが、アセチルアセトンはチタニアに配位するだけなので、徐々にアセチルアセトンが解離し、水性組成物がゲル化してしまい、アルカリ耐性を評価することができなかった。
On the other hand, in 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.
以上より、金属キレートと2官能アルコキシシランを反応させた無機微粒子を用いたときのみ、安定な水性組成物を得ることができ、さらにその水性組成物を用いて得たハードコート層はアルカリ耐性を得ることができる。
As described above, only when inorganic fine particles obtained by reacting a metal chelate and a bifunctional alkoxysilane are used, a stable aqueous composition can be obtained, and the hard coat layer obtained using the aqueous composition has alkali resistance. Obtainable.
(実施例3~5-2) 下記表に記載の膜厚となるように、実施例1と同様にして塗布液サンプルI-1、塗布液サンプルH-1を塗布し、積層フィルムを得た。各層の屈折率は、シリコンウエハー上に各層を2μmの膜厚になるように塗布した後、プリズムカプラーSPA-4000(SAIRONTECHNOLOGY社製)により、25℃で測定した。
(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 μm.
得られた積層フィルムについて、下記(4)及び(5)に示すように干渉縞及び接着性を評価した。これらの結果は下記表に示す。
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.
(4)干渉縞
得られた積層フィルムを黒地の上に載せて、三波長蛍光灯を使用してこの積層フィルムから約50cm離れた距離から、塗膜面上に現れる虹色の干渉模様を観察した。干渉縞を下記の評価基準に従って評価した。
A:干渉縞が見えない
B:干渉縞がわずかに見えるが、目立たない
C:干渉縞がはっきりと見える
実用上許容されるのは、評価ランクA、Bである。 (4) 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.
得られた積層フィルムを黒地の上に載せて、三波長蛍光灯を使用してこの積層フィルムから約50cm離れた距離から、塗膜面上に現れる虹色の干渉模様を観察した。干渉縞を下記の評価基準に従って評価した。
A:干渉縞が見えない
B:干渉縞がわずかに見えるが、目立たない
C:干渉縞がはっきりと見える
実用上許容されるのは、評価ランクA、Bである。 (4) 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.
(5)接着性の評価(クロスカットテープ密着試験)
積層フィルムの塗布面にカッターを用いて1mm間隔で縦横それぞれ11本ずつの傷をつけ、100マスのマス目を形成した。この上にセロハン粘着テープ(セロテープ(登録商標)No.405、24mm幅、ニチバン(株)製)を貼って、垂直(90°)方向にすばやく引っ張って剥離した。このとき、剥離したマス目の数によって、PETフィルムと易接着層及びハードコート層との接着性を下記の評価基準に従って評価した。
<評価基準>
A:全く剥離が起こらない。
B:剥離したマス目はゼロであるが、傷部分が僅かに剥離している。
C:剥離したマス目が1マス以上5マス未満であった。
D:剥離したマス目が5マス以上であった。
実用上許容されるのは、評価ランクA~Cに分類されるものである。 (5) Evaluation of adhesion (cross-cut tape adhesion test)
The coated surface of the laminated film was scratched by 11 scratches at 1 mm intervals using a cutter to form 100 squares. A cellophane adhesive tape (cello tape (registered trademark) No. 405, 24 mm width, manufactured by Nichiban Co., Ltd.) was pasted thereon and quickly pulled in the vertical (90 °) direction to peel off. At this time, the adhesiveness between the PET film, the easy-adhesion layer, and the hard coat layer was evaluated according to the following evaluation criteria depending on the number of the peeled cells.
<Evaluation criteria>
A: No peeling occurs.
B: The peeled squares are zero, but the scratches are slightly peeled off.
C: The peeled squares were 1 square or more and less than 5 squares.
D: The peeled squares were 5 squares or more.
What is practically acceptable is classified into the evaluation ranks A to C.
積層フィルムの塗布面にカッターを用いて1mm間隔で縦横それぞれ11本ずつの傷をつけ、100マスのマス目を形成した。この上にセロハン粘着テープ(セロテープ(登録商標)No.405、24mm幅、ニチバン(株)製)を貼って、垂直(90°)方向にすばやく引っ張って剥離した。このとき、剥離したマス目の数によって、PETフィルムと易接着層及びハードコート層との接着性を下記の評価基準に従って評価した。
<評価基準>
A:全く剥離が起こらない。
B:剥離したマス目はゼロであるが、傷部分が僅かに剥離している。
C:剥離したマス目が1マス以上5マス未満であった。
D:剥離したマス目が5マス以上であった。
実用上許容されるのは、評価ランクA~Cに分類されるものである。 (5) Evaluation of adhesion (cross-cut tape adhesion test)
The coated surface of the laminated film was scratched by 11 scratches at 1 mm intervals using a cutter to form 100 squares. A cellophane adhesive tape (cello tape (registered trademark) No. 405, 24 mm width, manufactured by Nichiban Co., Ltd.) was pasted thereon and quickly pulled in the vertical (90 °) direction to peel off. At this time, the adhesiveness between the PET film, the easy-adhesion layer, and the hard coat layer was evaluated according to the following evaluation criteria depending on the number of the peeled cells.
<Evaluation criteria>
A: No peeling occurs.
B: The peeled squares are zero, but the scratches are slightly peeled off.
C: The peeled squares were 1 square or more and less than 5 squares.
D: The peeled squares were 5 squares or more.
What is practically acceptable is classified into the evaluation ranks A to C.
(比較例4)
下記の化合物を以下の配合で混合し、易接着層を形成する塗布液を調製した。この塗布液を塗布液サンプルI-2とした。
[塗布液サンプルI-2]
・酸化ジルコニウム分散液 2.9質量部
(SZR-W、固形分濃度30質量%、堺化学工業(株)製)
・タケラックWS-5100 4.9質量部
(固形分濃度30質量%、三井化学(株)製)
・カルボジライトV-02-L2 7.4質量部
(固形分濃度40質量%、日清紡(株)製)
・界面活性剤 2.2質量部
(ナロアクティーCL-95、三洋化成工業(株)製)
・界面活性剤 2.2質量部
(サンデットBL、固形分濃度43質量%、三洋化成工業(株)製)
・水 80.4質量部 (Comparative Example 4)
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.
[Coating liquid sample I-2]
・ Zirconium oxide dispersion 2.9 parts by mass (SZR-W, solid content concentration 30% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
-Takelac WS-5100 4.9 parts by mass (solid content concentration 30% by mass, manufactured by Mitsui Chemicals, Inc.)
Carbodilite V-02-L2 7.4 parts by mass (solid content concentration 40% by mass, manufactured by Nisshinbo Co., Ltd.)
・ Surfactant 2.2 parts by mass (Naroacty CL-95, manufactured by Sanyo Chemical Industries, Ltd.)
・ Surfactant 2.2 parts by mass (Sandet BL, solid content concentration 43% by mass, manufactured by Sanyo Chemical Industries, Ltd.)
・ 80.4 parts by mass of water
下記の化合物を以下の配合で混合し、易接着層を形成する塗布液を調製した。この塗布液を塗布液サンプルI-2とした。
[塗布液サンプルI-2]
・酸化ジルコニウム分散液 2.9質量部
(SZR-W、固形分濃度30質量%、堺化学工業(株)製)
・タケラックWS-5100 4.9質量部
(固形分濃度30質量%、三井化学(株)製)
・カルボジライトV-02-L2 7.4質量部
(固形分濃度40質量%、日清紡(株)製)
・界面活性剤 2.2質量部
(ナロアクティーCL-95、三洋化成工業(株)製)
・界面活性剤 2.2質量部
(サンデットBL、固形分濃度43質量%、三洋化成工業(株)製)
・水 80.4質量部 (Comparative Example 4)
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.
[Coating liquid sample I-2]
・ Zirconium oxide dispersion 2.9 parts by mass (SZR-W, solid content concentration 30% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
-Takelac WS-5100 4.9 parts by mass (solid content concentration 30% by mass, manufactured by Mitsui Chemicals, Inc.)
Carbodilite V-02-L2 7.4 parts by mass (solid content concentration 40% by mass, manufactured by Nisshinbo Co., Ltd.)
・ Surfactant 2.2 parts by mass (Naroacty CL-95, manufactured by Sanyo Chemical Industries, Ltd.)
・ Surfactant 2.2 parts by mass (Sandet BL, solid content concentration 43% by mass, manufactured by Sanyo Chemical Industries, Ltd.)
・ 80.4 parts by mass of water
実施例1と同様にして、上記塗布液サンプルI-2を塗布し、厚みが88nmの易接着層をPETフィルム上に形成した。
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.
以下の配合で、ハードコート層を形成する塗布液を調製した。この塗布液を塗布液サンプルH-2とした。[塗布液サンプルH-2]
・テトラエトキシシラン 3.9質量部
(KBE-04、信越化学工業(株)製)
・3-グリシドキシプロピルトリエトキシシラン 7.5質量部
(KBE-403、信越化学工業(株)製)
・酢酸水溶液(酢酸濃度=1質量%) 22.5質量部
・シリカ溶液 21.5質量部
(スノーテックスO-33、固形分濃度=33質量%、日産化学工業(株)製)
・硬化触媒 3.0質量部
(アルミキレートD、75質量%IPA溶液、川研ファインケミカル(株)製)
・界面活性剤 2.3質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・水 39.3質量部 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 liquid sample H-2]
Tetraethoxysilane 3.9 parts by mass (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ 7.5 parts by mass of 3-glycidoxypropyltriethoxysilane (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
Acetic acid aqueous solution (acetic acid concentration = 1% by mass) 22.5 parts by mass Silica solution 21.5 parts by mass (Snowtex O-33, solid content concentration = 33% by mass, manufactured by Nissan Chemical Industries, Ltd.)
Curing catalyst 3.0 parts by mass (aluminum chelate D, 75% by mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.)
・ Surfactant 2.3 parts by mass (Naroacty CL-95, 1% by mass aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.)
・ 39.3 parts by mass of water
・テトラエトキシシラン 3.9質量部
(KBE-04、信越化学工業(株)製)
・3-グリシドキシプロピルトリエトキシシラン 7.5質量部
(KBE-403、信越化学工業(株)製)
・酢酸水溶液(酢酸濃度=1質量%) 22.5質量部
・シリカ溶液 21.5質量部
(スノーテックスO-33、固形分濃度=33質量%、日産化学工業(株)製)
・硬化触媒 3.0質量部
(アルミキレートD、75質量%IPA溶液、川研ファインケミカル(株)製)
・界面活性剤 2.3質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・水 39.3質量部 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 liquid sample H-2]
Tetraethoxysilane 3.9 parts by mass (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ 7.5 parts by mass of 3-glycidoxypropyltriethoxysilane (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
Acetic acid aqueous solution (acetic acid concentration = 1% by mass) 22.5 parts by mass Silica solution 21.5 parts by mass (Snowtex O-33, solid content concentration = 33% by mass, manufactured by Nissan Chemical Industries, Ltd.)
Curing catalyst 3.0 parts by mass (aluminum chelate D, 75% by mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.)
・ Surfactant 2.3 parts by mass (Naroacty CL-95, 1% by mass aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.)
・ 39.3 parts by mass of water
塗布液サンプルH-2は、以下の方法で調製した。まず、酢酸水溶液を激しく攪拌しながら、3-グリシドキシプロピルトリメトキシシランを、この酢酸水溶液中に添加し、その後30分攪拌を続けた。この混合液を強く攪拌しながら、ここにテトラアルコキシシランとしてのテトラメトキシシランを添加し、その後1時間攪拌を続けた。次に、ここにシリカ溶液を添加し、その後30分間攪拌を続けた。次に、ここに硬化触媒を添加し、1時間攪拌を続けて完全に溶解させた。ここに界面活性剤と水を順次添加し、塗布液サンプルH-2を調製した。
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.
この塗布液サンプルH-2を上記PETフィルム上に形成した易接着層の上にバーコート法により塗布し、150℃で2分間加熱して乾燥し、厚さ1.0μmのハードコート層を形成し、積層フィルムを得た。
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 μm. And a laminated film was obtained.
得られた積層フィルムについて、上記の(4)及び(5)の評価を実施した。結果は下記表に示す。
Evaluation of (4) and (5) above was performed on the obtained laminated film. The results are shown in the table below.
実施例3~5は、各層の屈折率が同じ値であるため、干渉縞のない光学的に優れたフィルムであることが分かる。また、PETフィルムと易接着層及びハードコート層とが良好な接着性を有することが分かる。中でも、実施例3、4では、十分な厚さの易接着層を持つため、PETフィルムと易接着層及びハードコート層とが良好な接着性を持っている。一方、実施例5-2は易接着層の膜厚が60nm以下であるため、実施例3~5と比較して接着性が低下した。
It can be seen that 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.
また、一般的な有機樹脂やシリカ粒子を用いたハードコート層の屈折率は約1.45~1.50である。ハードコート層の屈折率がこのような値の場合、できる限り干渉縞を減らすためには、比較例4のように易接着層の膜厚を89nmと比較的薄くする必要があるが、十分な光学特性を発揮することができない。
In addition, the refractive index of a hard coat layer using a general organic resin or silica particles is about 1.45 to 1.50. When the refractive index of the hard coat layer is such a value, in order to reduce interference fringes as much as possible, 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.
以上より、易接着層の屈折率とPETフィルムの屈折率の差を0.05以下に抑え、易接着層の膜厚を100nm以上にすることで、光学特性に優れ、かつ、PETフィルムと易接着層及びハードコート層の接着性により優れたハードコートフィルムを得ることができる。
As described above, 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.
(実施例6)
実施例3と同様にして、厚みが150nmの易接着層をPETフィルム上に形成した。 (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.
実施例3と同様にして、厚みが150nmの易接着層をPETフィルム上に形成した。 (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.
以下の配合で、光学調整層を形成する塗布液を調製した。この塗布液を塗布液サンプルK-1とした。
[塗布液サンプルK-1]
・チタニアゾル 23質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 0.2質量部
(アルミニウムエチルアセトアセテート・ジイソプロピレート、75質量%IPA溶液、川研ファインケミカル(株)製)
・3-グリシドキシプロピルメチルジエトキシシラン 1.1質量部
(KBE-402、信越化学工業(株)製)
・加水分解液A 7.5質量部
・界面活性剤 2.3質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・水 65.9質量部 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.)
Chelating agent 0.2 parts by mass (aluminum ethyl acetoacetate / diisopropylate, 75% by mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.)
・ 1.1 parts by mass of 3-glycidoxypropylmethyldiethoxysilane (KBE-402, manufactured by Shin-Etsu Chemical 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
[塗布液サンプルK-1]
・チタニアゾル 23質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 0.2質量部
(アルミニウムエチルアセトアセテート・ジイソプロピレート、75質量%IPA溶液、川研ファインケミカル(株)製)
・3-グリシドキシプロピルメチルジエトキシシラン 1.1質量部
(KBE-402、信越化学工業(株)製)
・加水分解液A 7.5質量部
・界面活性剤 2.3質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・水 65.9質量部 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.)
Chelating agent 0.2 parts by mass (aluminum ethyl acetoacetate / diisopropylate, 75% by mass IPA solution, manufactured by Kawaken Fine Chemical Co., Ltd.)
・ 1.1 parts by mass of 3-glycidoxypropylmethyldiethoxysilane (KBE-402, manufactured by Shin-Etsu Chemical 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
塗布液サンプルK-1は塗布液サンプルH-1と同様にして調製した。この塗布液サンプルK-1を上記PETフィルム上に形成した易接着層の上にバーコート法により塗布し、150℃で2分間加熱して乾燥し、厚さ77nmの光学調整層を形成した。
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.
以下の配合で、ハードコート層を形成する塗布液を調製した。この塗布液を塗布液サンプルH-3とした。
[塗布液サンプルH-3]
・チタニアゾル 86質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 0.9質量部
(アルミニウムエチルアセトアセテート・ジイソプロピレート、75質量%IPA溶液、川研ファインケミカル(株)製)
・3-グリシドキシプロピルメチルジエトキシシラン 4.3質量部
(KBE-402、信越化学工業(株)製)
・加水分解液A 0.9質量部
・界面活性剤 2.3質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・水 5.6質量部 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
[塗布液サンプルH-3]
・チタニアゾル 86質量部
(SRD-W、固形分濃度15質量%、堺化学工業(株)製)
・キレート剤 0.9質量部
(アルミニウムエチルアセトアセテート・ジイソプロピレート、75質量%IPA溶液、川研ファインケミカル(株)製)
・3-グリシドキシプロピルメチルジエトキシシラン 4.3質量部
(KBE-402、信越化学工業(株)製)
・加水分解液A 0.9質量部
・界面活性剤 2.3質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・水 5.6質量部 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
塗布液サンプルH-3を塗布液サンプルH-1と同様に調製して、光学調整層上に塗布し、厚さ1.0μmのハードコート層を形成した。
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 μm.
(実施例7)
下記の化合物を下記の配合で混合し、易接着層を形成する塗布液を調製した。この塗布液を塗布液サンプルI-3とした。
[塗布液サンプルI-3]
・酸化ジルコニウム分散液 23.0質量部
(SZR-W、固形分濃度30質量%、堺化学工業(株)製)
・タケラックWS-5100 2.1質量部
(固形分濃度30質量%、三井化学(株)製)
・カルボジライトV-02-L2 3.1質量部
(固形分濃度10質量%、日清紡(株)製)
・界面活性剤 2.3質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・界面活性剤 2.3質量部
(サンデットBL、1質量%水溶液、三洋化成工業(株)製)
・水 67.2質量部 (Example 7)
The following compound was mixed by the following mixing | blending, and the coating liquid which forms an easily bonding layer was prepared. This coating solution was designated as coating solution sample I-3.
[Coating liquid sample I-3]
・ Zirconium oxide dispersion 23.0 parts by mass (SZR-W, solid content concentration 30% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
-Takelac WS-5100 2.1 parts by mass (solid content concentration 30% by mass, manufactured by Mitsui Chemicals, Inc.)
Carbodilite V-02-L2 3.1 parts by mass (solid content concentration 10% by mass, manufactured by Nisshinbo Co., Ltd.)
・ Surfactant 2.3 parts by mass (Naroacty CL-95, 1% by mass aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.)
-Surfactant 2.3 parts by mass (Sandet BL, 1% by mass aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.)
・ 67.2 parts by mass of water
下記の化合物を下記の配合で混合し、易接着層を形成する塗布液を調製した。この塗布液を塗布液サンプルI-3とした。
[塗布液サンプルI-3]
・酸化ジルコニウム分散液 23.0質量部
(SZR-W、固形分濃度30質量%、堺化学工業(株)製)
・タケラックWS-5100 2.1質量部
(固形分濃度30質量%、三井化学(株)製)
・カルボジライトV-02-L2 3.1質量部
(固形分濃度10質量%、日清紡(株)製)
・界面活性剤 2.3質量部
(ナロアクティーCL-95、1質量%水溶液、三洋化成工業(株)製)
・界面活性剤 2.3質量部
(サンデットBL、1質量%水溶液、三洋化成工業(株)製)
・水 67.2質量部 (Example 7)
The following compound was mixed by the following mixing | blending, and the coating liquid which forms an easily bonding layer was prepared. This coating solution was designated as coating solution sample I-3.
[Coating liquid sample I-3]
・ Zirconium oxide dispersion 23.0 parts by mass (SZR-W, solid content concentration 30% by mass, manufactured by Sakai Chemical Industry Co., Ltd.)
-Takelac WS-5100 2.1 parts by mass (solid content concentration 30% by mass, manufactured by Mitsui Chemicals, Inc.)
Carbodilite V-02-L2 3.1 parts by mass (solid content concentration 10% by mass, manufactured by Nisshinbo Co., Ltd.)
・ Surfactant 2.3 parts by mass (Naroacty CL-95, 1% by mass aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.)
-Surfactant 2.3 parts by mass (Sandet BL, 1% by mass aqueous solution, manufactured by Sanyo Chemical Industries, Ltd.)
・ 67.2 parts by mass of water
塗布液サンプルI-3を用いて、厚みが76nmの易接着層を実施例1と同様にPETフィルム上に形成した。
Using the coating solution sample I-3, an easy-adhesion layer having a thickness of 76 nm was formed on a PET film in the same manner as in Example 1.
塗布液サンプルH-3を上記PETフィルム上に形成した易接着層の上にバーコート法により塗布し、150℃で2分間加熱して乾燥し、厚さ1.0μmのハードコート層を形成した。
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 μm. .
(実施例8及び実施例8-2)
実施例8の積層フィルムは、下記表に示した屈折率及び膜厚になるように、PETフィルムの上に塗布液サンプルI-1を用いて易接着層を形成し、この易接着層の上に塗布液サンプルK-1を用いて光学調整層を形成し、この光学調整層の上に塗布液サンプルH-1を用いてハードコート層を形成して得た。
実施例8-2の積層フィルムは、下記表に示した屈折率及び膜厚になるように、PETフィルムの上に塗布液サンプルI-1を用いて易接着層を形成し、この易接着層の上に塗布液サンプルH-1を用いてハードコート層を形成して得た。
なお、易接着層及びハードコート層は実施例1と同様にして形成し、光学調整層は実施例6と同様にして形成した。 (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, and a coating liquid sample H-1 was used to form a hard coat layer on the optical adjustment layer.
In the laminated film of Example 8-2, 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.
実施例8の積層フィルムは、下記表に示した屈折率及び膜厚になるように、PETフィルムの上に塗布液サンプルI-1を用いて易接着層を形成し、この易接着層の上に塗布液サンプルK-1を用いて光学調整層を形成し、この光学調整層の上に塗布液サンプルH-1を用いてハードコート層を形成して得た。
実施例8-2の積層フィルムは、下記表に示した屈折率及び膜厚になるように、PETフィルムの上に塗布液サンプルI-1を用いて易接着層を形成し、この易接着層の上に塗布液サンプルH-1を用いてハードコート層を形成して得た。
なお、易接着層及びハードコート層は実施例1と同様にして形成し、光学調整層は実施例6と同様にして形成した。 (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, and a coating liquid sample H-1 was used to form a hard coat layer on the optical adjustment layer.
In the laminated film of Example 8-2, 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.
得られた積層フィルムについて、上記(5)接着性の評価、および下記(6)ITO製膜前後の反射率の評価を実施した。これらの結果は、下記表に示す。
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.
(6)ITO製膜前後の反射率
ハードコート層の上にITOを30nmスパッタ成膜した。紫外可視光分光光度計V-560(日本分光(株)製)を用いて、積層フィルムの5°正反射率を測定した。450~650nmの各波長におけるITO製膜前後の反射率の差の絶対値を平均した値をΔR%として算出した。 (6) Reflectance before and after ITO film formation ITO was deposited on the hard coat layer by sputtering to a thickness of 30 nm. The 5 ° specular reflectance of the laminated film was measured using an ultraviolet-visible light spectrophotometer V-560 (manufactured by JASCO Corporation). A value obtained by averaging the absolute values of the difference in reflectance between before and after the ITO film formation at each wavelength of 450 to 650 nm was calculated as ΔR%.
ハードコート層の上にITOを30nmスパッタ成膜した。紫外可視光分光光度計V-560(日本分光(株)製)を用いて、積層フィルムの5°正反射率を測定した。450~650nmの各波長におけるITO製膜前後の反射率の差の絶対値を平均した値をΔR%として算出した。 (6) Reflectance before and after ITO film formation ITO was deposited on the hard coat layer by sputtering to a thickness of 30 nm. The 5 ° specular reflectance of the laminated film was measured using an ultraviolet-visible light spectrophotometer V-560 (manufactured by JASCO Corporation). A value obtained by averaging the absolute values of the difference in reflectance between before and after the ITO film formation at each wavelength of 450 to 650 nm was calculated as ΔR%.
実施例6~8-2では、接着性およびITO製膜前後の反射率が良好な結果を示し、実用上許容される範囲となった。中でも、実施例6、7では、ハードコート層の屈折率を2.0にすることで、ITO層を製膜した前後の反射率変化が小さく、ITOの骨見えがないITOフィルムを得ることができた。また、実施例6のように、光学調整層を設け、易接着層の膜厚を100nm以上にすることで、良好な接着性も得ることができる。
In Examples 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. In particular, in Examples 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. Further, as in 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.
実施例8では、ハードコート層の屈折率がITOの屈折率(約2.0程度)に比べて低いが、光学調整層を設けることで、ITO製膜前後の反射率の差が1.0%となった。
In Example 8, 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. %.
本発明によれば、水性組成物中に無機微粒子を安定的に分散させることが可能となり、屈折率が十分に高く、かつ優れたアルカリ耐性を有するハードコート層を得ることができる。また、本発明では、無機微粒子を安定的に分散させるために複雑な製造工程を経る必要がないため、水性組成物及びハードコート層の生産効率を高めることができるため、本産業上の利用可能性が高い。
According to the present invention, 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.
Claims (16)
- 金属キレート化合物と、2官能アルコキシシランまたはその加水分解物とを表面に有する無機微粒子を含み、前記無機微粒子のゼータ電位が0~20mVである、水性組成物。
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.
- 前記金属キレート化合物の中心金属の電気陰性度は1.3~1.9であり、
水酸基または加水分解性基を有する、請求項1に記載の水性組成物。
The electronegativity of the central metal of the metal chelate compound is 1.3 to 1.9,
The aqueous composition according to claim 1, which has a hydroxyl group or a hydrolyzable group.
- 前記金属キレート化合物は、アルミニウムキレート化合物、チタンキレート化合物、およびジルコニウムキレート化合物のうち少なくとも1種を含む、請求項1または2に記載の水性組成物。
The aqueous composition according to claim 1 or 2, wherein the metal chelate compound contains at least one of an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound.
- 前記無機微粒子の25℃における屈折率が1.8以上である、請求項1~3のいずれか1項に記載の水性組成物。 The aqueous composition according to any one of claims 1 to 3, wherein the inorganic fine particles have a refractive index of 1.8 or more at 25 ° C.
- 前記無機微粒子が、ジルコニアまたはチタニアからなる微粒子である、請求項1~4のいずれか1項に記載の水性組成物。
The aqueous composition according to any one of claims 1 to 4, wherein the inorganic fine particles are fine particles composed of zirconia or titania.
- 無機微粒子および金属キレート化合物を混合し、水性混合物を得る工程と、
前記水性混合物に、2官能アルコキシシランまたはその加水分解物を混合する工程と、
前記2官能アルコキシシランまたはその加水分解物を混合する工程の後に、さらに、3官能アルコキシシランもしくはその加水分解物、および/または4官能アルコキシシランもしくはその加水分解物と、硬化促進剤とを混合する工程と、
を含む、水性組成物の製造方法。 Mixing an inorganic fine particle and a metal chelate compound to obtain an aqueous mixture;
Mixing the bifunctional alkoxysilane or a hydrolyzate thereof with the aqueous mixture;
After the step of mixing the bifunctional alkoxysilane or the hydrolyzate thereof, the trifunctional alkoxysilane or the hydrolyzate thereof and / or the tetrafunctional alkoxysilane or the hydrolyzate thereof and a curing accelerator are further mixed. Process,
A method for producing an aqueous composition, comprising: - 前記水性混合物を得る工程では、前記無機微粒子及び前記金属キレート化合物を1時間以上反応させる、請求項6に記載の水性組成物の製造方法。
The method for producing an aqueous composition according to claim 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 longer.
- 請求項6または7に記載の製造方法により製造された水性組成物。
An aqueous composition produced by the production method according to claim 6 or 7.
- 請求項1~5および8のいずれか1項に記載の水性組成物を硬化することにより形成されるハードコートフィルム。
A hard coat film formed by curing the aqueous composition according to any one of claims 1 to 5 and 8.
- 25℃における屈折率が1.60~2.30である、請求項9に記載のハードコートフィルム。
The hard coat film according to claim 9, having a refractive index of 1.60 to 2.30 at 25 ° C.
- 基材フィルムと、
前記基材フィルムの上に形成された請求項9または10に記載のハードコートフィルムと、
を有する、積層フィルム。
A base film;
The hard coat film according to claim 9 or 10 formed on the base film,
A laminated film.
- 前記基材フィルムの一方の面上に易接着層と前記ハードコートフィルムと、
を有し、
25℃における、前記易接着層の屈折率と前記基材フィルムの屈折率の差、および前記ハードコートフィルムの屈折率と前記基材フィルムの屈折率の差が、ともに0.1以下である、請求項11に記載の積層フィルム。
An easy-adhesion layer and the hard coat film on one surface of the base film,
Have
At 25 ° C., the difference between the refractive index of the easy adhesion layer and the refractive index of the base film, and the difference between the refractive index of the hard coat film and the refractive index of the base film are both 0.1 or less. The laminated film according to claim 11.
- 前記基材フィルムの一方の面上に易接着層、光学調整層および前記ハードコートフィルムをこの順に有する、請求項11または12に記載の積層フィルム。
The laminated film according to claim 11 or 12, comprising an easy adhesion layer, an optical adjustment layer, and the hard coat film in this order on one surface of the base film.
- 前記光学調整層の25℃における屈折率が1.60~1.90である、請求項13に記載の積層フィルム。
The laminated film according to claim 13, wherein the optical adjustment layer has a refractive index of 1.60 to 1.90 at 25 ° C.
- 請求項11~14のいずれか1項に記載の積層フィルムと、
前記積層フィルムの上に形成された透明電極層と、
を有する透明導電性フィルム。
The laminated film according to any one of claims 11 to 14,
A transparent electrode layer formed on the laminated film;
A transparent conductive film comprising:
- 請求項15に記載の透明導電性フィルムを有するタッチパネル。 A touch panel having the transparent conductive film according to claim 15.
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