JP5931009B2 - Method for producing surface-treated metal oxide particles, coating liquid for forming transparent film containing the particles, and substrate with transparent film - Google Patents

Description

  The present invention is highly dispersible in the matrix component, and the resulting film has high strength, and is excellent in scratch strength, water resistance, water repellency, fingerprint non-adhesion, chemical resistance, heat resistance, moisture resistance, etc. The present invention relates to a method for producing surface-treated metal oxide particles that can be suitably used for forming an antireflection film, a hard coat film, and the like, a coating liquid for forming a transparent film containing the fine particles, and a substrate with a transparent film.

  Conventionally, it has been known to form a hard coat film on the surface of a substrate in order to improve the scratch resistance of the substrate surface such as glass, plastic sheet, plastic lens, etc. An organic resin is used as such a hard coat film. A film or an inorganic film is formed on the surface of glass or plastic. Furthermore, it is practiced to further improve the scratch resistance by blending resin particles or inorganic particles such as silica in an organic resin film or an inorganic film.

  In addition, in order to prevent reflection of the surface of a substrate such as glass, plastic sheet, plastic lens, etc., it is known to form an antireflection film on the surface. For example, by a coating method, a vapor deposition method, a CVD method, A film of a low refractive index substance such as fluororesin or magnesium fluoride is formed on the surface of a glass or plastic substrate, or a coating liquid containing low refractive index fine particles such as silica fine particles is applied to the substrate surface. A method of forming an antireflection coating is known (see, for example, Patent Document 1 (Japanese Patent Laid-Open No. 7-133105)). At this time, in order to improve the antireflection performance, it is also known to form a high refractive index film containing fine particles of high refractive index under the antireflection coating.

  In recent years, in addition to transparency, haze, etc., in addition to scratch resistance, hardness, scratch strength, etc., such transparent coatings have water resistance, water repellency, fingerprint non-adhesion, chemical resistance, heat resistance, moisture resistance, etc. There is a demand for a transparent coating that is simultaneously superior in properties and the like.

  The present applicants treated with a matrix made of a fluorine-containing compound and a specific silane coupling agent (not containing a fluoro group) as a transparent film having a low refractive index and excellent strength, hardness, scratch resistance, abrasion resistance, etc. The use of such hollow silica fine particles. (Patent Document 2, JP 2006-348267 A)

  In addition, the applicant of the present application, as a transparent film excellent in chemical resistance against acids and alkalis, is a perfluoro group-containing (meth) acrylic ester resin and a specific silane coupling agent (may contain a fluoro group). And the use of hollow silica-based fine particles treated with the above. (Patent Document 3, Japanese Patent Application Laid-Open No. 2006-291077)

JP-A-7-133105 JP 2006-348267 A JP 2006-291077 A

However, the thing of patent document 1 was insufficient in water repellency and fingerprint non-adhesiveness. In Patent Document 2, although excellent in chemical resistance, water repellency, fingerprint non-adhesiveness, etc., the scratch resistance, strength, scratch strength, etc. are not always sufficient.

  In view of such problems, the present inventors have conducted further intensive studies. As a result, the metal oxide particles surface-treated simultaneously with a silane coupling agent containing a fluoro group and a silane coupling agent not containing a fluoro group are: Dispersibility in matrix components is good, and the resulting transparent film has water resistance, water repellency, fingerprint non-adhesion, chemical resistance, heat resistance, moisture resistance, etc. in addition to scratch resistance, hardness, scratch strength, etc. The inventors have found that the present invention is superior and have completed the present invention.

The configuration of the present invention is as follows.
[1] In a metal oxide particle dispersion, a silane coupling agent (A) represented by the following formula (1), methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxy Silane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxy Propyltrimethoxy Lan, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltri Ethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylooxy Propyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxy Syrah Perfluorooctylethyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxy At least one silane coupling agent (B) selected from the group consisting of silane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, and methyltrichlorosilane,
The ratio (M ₁ / M ₂ ) of the number of moles (M ₁ ) of the silane coupling agent (A) to the number of moles (M ₂ ) of the silane coupling agent (B ) is 0.16 to 1.51 . A mixing step of mixing so as to be in a range;
A aging step of adding water and ammonia to the dispersion obtained by the mixing step and heating at 40 to 100 ° C.,
The silane coupling agent (A) and the silane coupling agent The total number of moles of (B) (M _SC) the moles of said water ratio _{(M H2O) (M H2O /} M SC) is 9.67～ In the range of 58.01 ,
The method for producing surface-treated metal oxide particles, wherein a ratio (M _HC / M _SC ) of the total number of moles to the number of moles of ammonia (M _HC ) is in the range of 0.07 to 0.16. .
RnSiX _4-n (1)
(However, R: fluoro group-containing hydrocarbon group, X: alkoxy group having 1 to 4 carbon atoms, hydroxyl group, halogen or hydrogen, n: an integer of 1 to 3)

[2] A coating solution for forming a transparent film, comprising the surface-treated metal oxide particles obtained by the method of [1], a matrix-forming component, and a dispersion medium.
[3] Polyfunctional (meth) acrylic, wherein the matrix forming component has a functional group selected from a hydroxyl group, an amino group, a carboxyl group, a sulfo group, a vinyl group, a urethane group, an epoxy group, a (meth) acryloyl group, and a CF ₂ group The coating liquid for forming a transparent film according to [2], which is one or more organic resins selected from acid ester resins.
[4] It comprises a substrate and a transparent coating formed on the substrate, and the transparent coating comprises the surface-treated metal oxide particles obtained by the method of [1] and a matrix component. A substrate with a transparent coating characterized by
[5] Polyfunctional (meth) acrylic acid in which the matrix component has a functional group selected from hydroxyl group, amino group, carboxyl group, sulfo group, vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF ₂ group [4] The substrate with a transparent coating, which is one or more organic resins selected from ester resins.
[6] The substrate with a transparent coating according to [4] or [5], wherein the transparent coating is in an outermost layer, and another coating is provided between the substrate and the transparent coating.

  According to the present invention, the surface treatment is performed with a silane coupling agent in which a silane coupling agent containing a fluoro group and a silane coupling agent not containing a fluoro group are mixed at a predetermined ratio, so that dispersibility and bonding to a matrix component are achieved. A method for producing surface-treated metal oxide particles having excellent properties, a coating solution for forming a transparent film having excellent stability including the fine particles, and water resistance, water repellency, fingerprint non-adhesion, chemical resistance, etc. A substrate with a transparent coating excellent in hardness and scratch resistance can be provided.

Hereinafter, first, the manufacturing method of the surface treatment metal oxide particle concerning this invention is demonstrated concretely.
Method for producing surface-treated metal oxide particles The production method of the present invention performs surface treatment by adding a specific combination of silane coupling agents to a metal oxide particle dispersion.

Metal Oxide Particles As the metal oxide particles used in the present invention, known metal oxide particles conventionally used for transparent coatings can be used.

The metal oxide particles can be appropriately selected and used depending on the application. For example, the metal oxide fine particles used for the antireflection film are usually metal oxide fine particles having a refractive index of 1.45 or less, preferably 1.40 or less. used, specifically SiO _2, fine particles coated with metal oxides having a SiO ₂ or conductive thereto, having a cavity inside thereof. As the SiO ₂ particles having a cavity inside, silica-based fine particles having a cavity inside disclosed in JP-A-2001-233611 filed by the applicant of the present application can be suitably employed.

Examples of the metal oxide fine particles used for the hard coat film include ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ , chain particles in which these particles are connected in a chain, Examples thereof include silica-based fine particles having a refractive index of 1.45 or less.

The metal oxide fine particles used for the high refractive index film are usually fine particles having a refractive index of 1.60 or more, more preferably 1.80 or more, specifically ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO. ₂ , Al ₂ O ₃ , SnO ₂ , antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), tin oxide-doped phosphorus (PTO), and the like.

The metal oxide fine particles used for the conductive film are usually Sb ₂ O ₅ , SnO ₂ , antimony-doped tin oxide, tin-doped indium oxide, tin oxide-doped phosphorus (PTO), or silica-based whose surface is coated with these conductive materials. Examples thereof include fine particles or silica-based fine particles having cavities therein.

  The average particle diameter of the metal oxide particles is not particularly limited and is appropriately selected depending on the application, but is preferably in the range of about 5 to 300 nm, more preferably 7 to 200 nm. As a dispersion medium for the metal oxide particle dispersion, water and / or alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), and butanol are usually used. The concentration of the metal oxide particle dispersion is preferably from 0.5 to 40% by weight, more preferably from 1 to 30% by weight, as the solid content concentration.

Silane Coupling Agent In the present invention, a silane coupling agent (A) represented by the following formula (1) and a silane coupling agent (B) represented by the following formula (2) are used.
_{R n SiX 4-n ······ (} 1)
(However, R: fluoro group-containing hydrocarbon group, X: alkoxy group having 1 to 4 carbon atoms, hydroxyl group, halogen or hydrogen, n: an integer of 1 to 3)
_{R n SiX 4-n ······ (} 2)
(However, R: C1-C4 methacryloyloxy group, acryloyloxy group, epoxy group (glycid group), vinyl group, urethane group, X: C1-C4 alkoxy group, hydroxyl group, halogen or hydrogen, n: an integer of 1 to 3)

  Specific examples of the silane coupling agent (A) represented by the formula (1) include trifluoropropyltrimethoxysilane, methyltrifluoropropyldimethoxysilane, perfluorooctylethyltriisopropoxysilane, and tridecafluoro. Examples include octyltriethoxysilane, heptadecatrifluorodecyltrimethoxysilane, and heptadecatrifluorodecyltripropoxysilane.

  Specific examples of the silane coupling agent (B) represented by the formula (2) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, β- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycid Xylpropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acryl Rooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- Meth) acryloxyethyl oxyethyl triethoxysilane, .gamma. (meth) acryloxypropyl trimethoxysilane, .gamma. (meth) acryloxypropyl trimethoxy silane, 3-ureido-isopropyl triethoxysilane, and the like.

  The silane coupling agent (A) represented by the formula (1) has effects such as water repellency, fingerprint adhesion prevention, and magic wiping improvement, and the silane coupling agent (B) represented by the formula (2). Has an effect of improving film hardness, scratch resistance, and the like, and combining these exhibits an effect of improving stain resistance, scratch resistance, chemical resistance, and the like.

  Particularly preferred combinations of silane coupling agents (A) and (B) include heptadecafluorotrimethoxysilane, heptadecatrifluorodecyltripropoxysilane, etc., and γ- (meth) acrylooxypropyltriethoxysilane. It is.

Moles (M ₁₎ and the number of moles (M ₂₎ and the molar ratio of the silane coupling agent represented by the formula (2) (B) of the silane coupling agent represented by the formula (1) (A) ( M ₁ / M ₂ ) is preferably in the range of 0.16 to 1.51 .

When the molar ratio (M ₁ ) / (M ₂ ) is small, the amount of the silane coupling agent (A) is too small, and the water resistance of the transparent coating using the metal oxide particles obtained by the surface treatment, Water repellency, fingerprint non-adhesion, and chemical resistance may be insufficient.

If the molar ratio (M ₁ / M ₂ ) exceeds 1.51 , the bondability with the matrix component becomes poor, or the scratch resistance, hardness, and scratch strength of the transparent film obtained by using the surface-treated metal oxide particles. May be insufficient.

  When the silane coupling agent of n = 1 in the above formula (1) is used as the silane coupling agent (A), the silane coupling of n = 1 in the above formula (2) is used as the silane coupling agent (B). It is desirable to use an agent. Similarly, when the former is n = 2, the latter is preferably n = 2. Further, when the former is n = 3, it is desirable to use a silane coupling agent with n = 3 for the latter.

  In this way, when the silane coupling agent having the same n is used, the hydrolysis characteristics are approximated. Therefore, the silane coupling agent (A) and the silane coupling agent (B) uniformly bonded in a form close to the blending ratio are obtained. It can be formed on the surface.

  In particular, the combination of the silane coupling agent of n = 1 in the formula (1) as the silane coupling agent (A) and the silane coupling agent of n = 1 in the formula (2) as the silane coupling agent (B) Are preferably used. In this case, the surface treatment effect of the metal oxide particles of the present invention is high because it is more easily hydrolyzed than the silane coupling agent having n of 2 to 3, and has excellent binding properties with the metal oxide particles. The coating solution for forming a transparent film using surface-treated metal oxide particles has excellent stability, and the transparent film has excellent water resistance, water repellency, fingerprint non-adhesion, and chemical resistance, as well as scratch resistance, hardness, and scratch. Excellent strength.

A mixed alcohol solution of the silane coupling agent (A) and the silane coupling agent (B) is prepared and mixed with the metal oxide particle dispersion.
The amount of the silane coupling agent added (total of (A) and (B)) is 1 to 50% by weight in terms of the content of the surface-treated metal oxide particles obtained, expressed as R _n SiO _{4 -n / 2.} Is preferably in the range of 2 to 30% by weight.

  When the addition amount of the silane coupling agent is small, the dispersibility to the matrix component is deteriorated and the binding property to the matrix component is also deteriorated. When the amount of the silane coupling agent added is too large, the ratio of the metal oxide particles is low, and desired metal oxide characteristics such as conductivity and refractive index may be impaired.

  The concentration of the silane coupling agent in the silane coupling agent mixed alcohol solution is not particularly limited, and is preferably in the range of 1 to 50% by weight in view of handling and the like. As the solvent, those described above are used, and preferably the same as the solvent constituting the metal oxide particle dispersion.

  The concentration of the metal oxide particle dispersion after mixing the silane coupling agent (including the mixed alcohol solution of the silane coupling agent) should be in the range of 5 to 45% by weight, more preferably 10 to 40% by weight as the solid content concentration. Is preferred. If the concentration of the metal oxide particle dispersion is small, the amount of the silane coupling agent to be used is also small, so the surface treatment may not be possible with a predetermined amount of the silane coupling agent. The metal oxide particles tend to agglomerate and each particle cannot be uniformly surface-treated, or the dispersibility of the resulting surface-treated metal oxide particles in the matrix component may be insufficient. The effects of the invention may not be sufficiently obtained.

Further, in the metal oxide particle dispersion, there is water for hydrolysis of the silane coupling agent. The number of moles of water (M _H2O ), the silane coupling agent (A), and the silane coupling agent (B) The molar ratio (M _H2O / M _SC ) to the total number of moles (M _SC ) is preferably in the range of 9.67 to 58.01 .

If the molar ratio (M _H2O ) / (M _SC ) is small, the silane coupling agent is difficult to hydrolyze, so that a sufficient surface treatment effect may not be obtained. The molar ratio (M _H2O ) / (M _SC ) is If it is too large, the silane coupling agent is hydrolyzed too quickly, so that a hydrolyzate that does not bind to the surface is left, and a sufficient surface treatment effect may not be obtained.

Furthermore, a catalyst for hydrolysis of the silane coupling agent can be used in the metal oxide particle dispersion mixed with the silane coupling agent, if necessary.
Examples of the catalyst for hydrolysis include ammonia, sodium hydroxide, potassium hydroxide, tetramethylammonium hydrite, tetrapropylammonium hydrite, tetrabutylammonium hydrate, triethanolamine, triethylamine, nitric acid, hydrochloric acid, acetic acid and the like. .

The molar ratio (M _HC / M _SC ) between the number of moles of hydrolysis catalyst (M _HC ) and the total number of moles of silane coupling agent (M _SC ) is in the range of 0.07 to 0.16. Is preferred .

When the molar ratio (M _HC ) / (M _SC ) is small, depending on the type of silane coupling agent, hydrolysis cannot be promoted, so that sufficient surface treatment cannot be performed, and the molar ratio (M _HC ) / ( If M _SC ) is too large, hydrolyzate that does not bind to the surface of the metal oxide particles increases, and a sufficient surface treatment effect may not be obtained.

  The metal oxide particle dispersion mixed with the silane coupling agent is subjected to surface treatment of the metal oxide by hydrolyzing the silane coupling agent while stirring. At this time, it is preferable to age | cure | ripen under a 40-100 degreeC heating.

  If the hydrolysis and aging temperature is low, the hydrolysis of the silane coupling agent having a fluoro group-containing hydrocarbon group becomes slow, and if the aging temperature is too high, the hydrolysis becomes too fast and the surface of the metal oxide particles In some cases, the hydrolyzate that does not bind to the surface increases, and a sufficient surface treatment effect cannot be obtained.

The obtained surface-treated metal oxide particle dispersion can be used as it is for a transparent film or the like, but it can also be used by washing with an ultrafiltration membrane method or the like and substituting with a desired organic solvent.
Examples of organic solvents include alcohols such as methyl alcohol, ethyl alcohol, propanol, and 2-propanol (IPA) isopropyl glycol; esters such as acetic acid methyl ester, ethyl acetate, and butyl acetate; diethyl ether, ethylene glycol monomethyl ether, ethylene Ethers such as glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetoacetate, methyl cellosolve, ethyl Cellosolve, butyl cellosolve, toluene, cyclohexanone, isophoro Are preferred.
The size of the metal oxide particles after the treatment is not substantially changed.

Transparent Film Forming Coating Liquid The transparent film forming coating liquid according to the present invention contains the surface-treated metal oxide particles and a dispersion medium.

(i) Surface-treated metal oxide fine particles The surface-treated metal oxide fine particles obtained by the above production method are used in the coating liquid for forming a transparent film of the present invention.

(ii) Matrix-forming component As the matrix-forming component, an organic resin-based matrix-forming component, a silicone-based matrix-forming component, or the like is used.

  Examples of organic resin matrix forming components include polyfunctional (meth) acrylic acid ester resins having functional groups such as hydroxyl, amino, carboxyl, and sulfo groups. Specifically, pentaerythritol triacrylate, diethylaminomethyl methacrylate, It may be dimethylaminomethyl methacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, methoxytriethylene glycol dimethacrylate, butoxydiethylene glycol methacrylate and mixtures thereof, or a copolymer or modified body of two or more of these resins. .

Examples of the organic resin matrix forming component include polyfunctional (meth) acrylic acid ester resins having functional groups such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF ₂ group, and the like. Is pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl Metecrylate, isodecyl metecrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooct Le methacrylate, trifluoroethyl methacrylate, urethane acrylate and the like and mixtures thereof.

  Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, a silicone-based (sol-gel) matrix forming component, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-tri Fluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyl Rutrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxy Silane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acrylooxypropyl Trimethoxysilane, γ- (meth) acrylooxypropyltrimethoxysilane Lan, γ- (meth) acrylooxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxy Silane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxy Silane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxy Sisilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane and the like, and partial hydrolysis thereof Products and hydrolyzed polycondensates.

  Among them, in the present invention, the organic resin-based matrix-forming component described above can be suitably used because it has excellent affinity with the surface-treated metal oxide particles, dispersibility, and binding properties with the surface-treated metal oxide particles. .

As described above, since the surface-treated metal oxide particles combine a specific silane coupling agent (A) and (B), the matrix-forming component is a specific silane coupling agent (A) and (B). It is desirable that the bonding with the organic group of the silane coupling agent is promoted, so that in the organic resin matrix, an organic resin having a CF ₂ group is combined with another resin. It is desirable to use it.

  In the present invention, a catalyst for polycondensation of the organic resin matrix forming component may be included as necessary. Moreover, when using a silicone type matrix formation component, a hydrolysis and a polycondensation catalyst may be contained.

(iii) Dispersion medium The dispersion medium used in the present invention is not particularly limited as long as it can dissolve or disperse the matrix-forming component and, if necessary, the polymerization initiator and uniformly disperse the surface-treated metal oxide fine particles. A conventionally known solvent can be used.

  Specifically, alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; acetic acid Esters such as methyl ester, ethyl acetate, butyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone Ketones such as acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone and the like.

These may be used alone or in combination of two or more.
The concentration of the coating solution for forming the transparent film is not particularly limited, but the total solid concentration of the surface-treated metal oxide fine particles and the matrix-forming component is in the range of 0.5 to 40% by weight, more preferably 1 to 30% by weight. Preferably there is.

  If the total solid content concentration is small, the formed transparent film becomes thin, and the resulting transparent film may have insufficient adhesion, strength, scratch resistance, and the like. In addition, sufficient antireflection performance may not be obtained. Even if the total solid content concentration is too high, the viscosity of the paint increases, the stability of the coating solution decreases or the applicability decreases, the uniformity of the resulting transparent film, the adhesion to the substrate, the strength, etc. May be insufficient.

The concentration of the surface-treated metal oxide fine particles (in terms of solid content) in the coating solution for forming a transparent film is preferably 0.1 to 36% by weight, more preferably 0.2 to 32% by weight.
When the concentration of the surface-treated metal oxide fine particles is low, the amount of particles in the obtained transparent coating is small, so that the scratch resistance, antireflection performance due to the characteristics of the particles (scratch resistance, refractive index, conductivity, etc.), The antistatic performance and the like may be insufficient. If the concentration of the surface-treated metal oxide fine particles is too high, the amount of particles in the resulting transparent coating is too large, and adhesion to the substrate, transparency, scratch resistance, etc. may be insufficient.

The concentration of the matrix-forming component in the coating solution for forming a transparent film is preferably in the range of 0.4 to 38% by weight, more preferably 0.8 to 35% by weight as the solid content.
If the concentration of the matrix-forming component in the coating liquid for forming a transparent film is low, the film thickness of the transparent film may be reduced, and adhesion to the substrate, transparency, scratch resistance, etc. may be insufficient. If the concentration of the matrix-forming component is too high, the resulting transparent film may have insufficient scratch resistance, antireflection performance, antistatic performance, and the like.

  The above-mentioned coating liquid for forming a transparent film is applied to a substrate by a known method such as a dipping method, a spray method, a spinner method, a roll coating method, a bar coating method, a gravure printing method, or a micro gravure printing method, dried, and then irradiated with ultraviolet rays. A transparent film can be formed by curing by conventional methods such as irradiation and heat treatment.

A substrate with a transparent coating The substrate with a transparent coating according to the present invention is a substrate with a transparent coating in which a transparent coating is formed on the substrate, and the transparent coating is a surface obtained by the matrix component and the production method. It is characterized by comprising treated metal oxide particles.

(i) Substrate As the substrate used in the present invention, a conventionally known substrate can be used without particular limitation, and glass, polycarbonate, acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC) And plastic sheets such as cyclopolyolefin and norbornene, plastic films, and plastic panels. Among these, a resin base material can be preferably used. Moreover, the base material with a film in which another film was formed on such a base material can also be used. Examples of other coatings include conventionally known primer films, hard coat films, high refractive index films, and conductive films.

(ii) Surface-treated metal oxide fine particles As the surface-treated metal oxide fine particles, the surface-treated metal oxide fine particles obtained by the production method are used.

  The content of the surface-treated metal oxide fine particles in the transparent coating is preferably in the range of 0.2 to 90% by weight, more preferably 0.5 to 80% by weight as the solid content. When the content of the surface-treated metal oxide fine particles is small, the amount of particles in the transparent film is small, so the scratch resistance, antireflection performance, and antistatic properties depending on the particle properties (scratch resistance, refractive index, conductivity, etc.) The performance may be insufficient. If the content of the surface-treated metal oxide fine particles is large, the amount of particles in the transparent coating is too large, and adhesion to the substrate, transparency, scratch resistance, etc. may be insufficient.

(iii) Matrix component As the matrix component, the above-mentioned organic resin matrix component or the hydrolyzed polycondensate of the aforementioned silicone matrix forming component is used. In the present invention, the organic resin matrix component described above can be suitably used because it is excellent in the dispersibility of the surface-treated metal oxide particles and the binding properties with the surface-treated metal oxide particles.

  The content of the matrix component in the transparent coating is preferably in the range of 10 to 99.8% by weight, more preferably 20 to 99.5% by weight as the solid content. When the content of the matrix component is small, the proportion of particles in the film increases, and adhesion to the substrate, transparency, scratch resistance, and the like may be insufficient. If the content of the matrix component is large, the amount of particles in the transparent coating is small, so the scratch resistance, antireflection performance, antistatic performance, etc. due to the properties of the particles (scratch resistance, refractive index, conductivity, etc.) are poor. May be sufficient.

  The film thickness of the transparent film varies depending on the application, but is generally in the range of 30 nm to 12 μm, and more preferably in the range of 70 nm to 10 μm. If the transparent film is thin, the adhesion, strength, etc. of the resulting transparent film may be insufficient, or the antireflection performance, antistatic performance, etc. due to the properties of the particles (refractive index, conductivity, etc.) may be insufficient. is there. Even if the transparent film is too thick, the transparent film may be cracked, or a substrate such as plastic may be curled (curved or warped).

The substrate with a transparent coating according to the present invention can be produced by applying the above-described coating solution for forming a transparent coating on a substrate, drying and curing.
Specifically, the above-described coating liquid for forming a transparent film is formed by a known method such as a dipping method, a spray method, a spinner method, a roll coating method, a bar coating method, a slit coater printing method, a gravure printing method, or a micro gravure printing method. A transparent film can be formed by coating on a base material (if another film is formed, on that film), drying, and curing by an ordinary method such as ultraviolet irradiation or heat treatment.

When manufacturing a substrate with a transparent coating having a string-proof property, a roll coating method, a slit coater printing method, a gravure printing method, and a micro gravure printing method are recommended.
In the substrate with a transparent coating of the present invention, another coating different from the transparent coating can be provided between the substrate and the transparent coating. Examples of other coatings include conventionally known primer films, hard coat films, high refractive index films, conductive films, low refractive index films, antiglare films, infrared shielding films, and ultraviolet shielding films.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[Example 1]
Preparation of coating liquid for forming transparent film (A-1H) As conductive component, antimony pentoxide fine particle dispersed sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ELCOM V-4560, average particle size 20 nm, concentration 30.5% by weight, dispersed Medium: ethanol / methanol / isopropanol = 85.5 / 13.4 / 1.1, particle refractive index 1.64) 44.26 g and dihexaerythritol triacetate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) and 1.85 g. Photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184, dissolved in IPA, solid content concentration 10%) in 1.65 g of 6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate 1.6HX-A) 8.25 g and a transparent coating for hard coating and antistatic by thoroughly mixing 30.99 g of 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve A forming coating solution (A-1H) was prepared.

Preparation of surface-treated metal oxide particles (A-1) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion Medium: isopropanol, particle refractive index 1.30) was used. To 80 g of this sol, 0.82 g of heptadecatrifluorodecyltripropoxysilane (Momentive Performance Materials Co., Ltd. (former name: GE Toshiba Silicone): XC95-A9715) and γ-methacryloxypropyltrimethoxysilane (Shin-Etsu) Chemical Co., Ltd .: KBM-503) 0.82 g was mixed, 2.38 g of ultrapure water and 0.06 g of 29% ammonia water were added, and the mixture was stirred at 50 ° C. for 20 hours to obtain a solid content concentration of 21.0 wt%. A surface-treated metal oxide particle (A-1) -dispersed sol was obtained.

Preparation of coating liquid for transparent film formation (A-1R) 5.95 g of this surface-treated metal oxide particle (1) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 54 g, fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 0.54 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light Acrylate 1.6HX-A) 0.12 g and par Fluorooctyl ethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate FA-108, diluted with MIBK, solid content concentration 10%) 0.50 g dissolved in photoinitiator (Ciba Supality Co., Ltd .: Irgacure 184, IPA) , Solid content concentration 10%) and 0.51 g of an isopropanol and 1/1 (weight ratio) mixed solvent of butyl cellosolve and 91.85 g of a mixed solvent are sufficiently mixed to form a transparent coating for antireflection Use coating solution (A-1R) was prepared.

Preparation of substrate with transparent film (A-1) Coating liquid (A-1H) for forming a transparent film was obtained by using a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%). The film was coated with a bar coater at a reflectance of 5.1%, dried at 70 ° C. for 1 minute, and then cured by irradiation with 400 mJ / cm ² of UV with a high-pressure mercury lamp (80 W / cm). A-1H) was prepared. The film thickness at this time was 5 μm.

Next, a coating solution (A-1R) for forming a transparent coating for preventing reflection was applied to the substrate with a transparent coating (A-1H) with a bar coater and dried at 70 ° C. for 1 minute. The substrate (A-1) with a transparent coating was prepared by irradiating and curing 400 mJ / cm ² ultraviolet light at cm). At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping resistance, resistance of the obtained transparent coated substrate (A-1) The alkalinity was measured and the results are shown in Table 1.

The surface resistance was measured with a surface resistance meter (manufactured by Mitsubishi Oil Chemical Co., Ltd .: LORESTA), the total light transmittance and haze were measured with a haze meter (manufactured by Nippon Denshoku Co., Ltd .: NDH2000), and the reflectance was measured with a spectrophotometer ( Measurement was carried out by JASCO Corporation (Ubest-55).
Further, antiglare property, adhesion, pencil hardness, scratch resistance, magic wiping property, and alkali resistance were evaluated by the following methods and evaluation criteria, and the results are shown in Table 1.

Adhesive hard coat function with anti-reflection coating base material (1) The surface of the substrate (1) with a knife to make 11 parallel scratches at intervals of 1 mm in length and width, make 100 squares, glue cellophane tape to this, Adhesiveness was evaluated by classifying the number of cells remaining without peeling of the coating when the cellophane tape was peeled into the following four stages. The results are shown in Table 1.
Number of remaining squares: ◎
Number of remaining squares 90-99: ○
Number of remaining squares: 85 to 89: Δ
Number of remaining squares: 84 or less: ×

Pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.

The substrate with scratch-resistant transparent coating (1) was rubbed 10 times with standard # 0000 steel wool applied with a load of 100 g / cm ² , and the degree of scratching on the film surface was visually observed.
A sample having no scratches was evaluated as ◎, a sample of less than 10 was evaluated as ◯, a sample of 10 to 20 was evaluated as Δ, and a countless number of scratches was evaluated as ×.

Magic wiping base material with transparent coating (1) Write a 2cm straight line with a Mitsubishi oil marker made by Mitsubishi Pencil Co., Ltd. and wipe it with a wipe made by Nippon Paper Crecia Co., Ltd. The property was observed visually.
What was wiped in 1 time was marked with 、, what was wiped with 2 to 3 times was marked with ○, what was wiped with 4 to 10 times was marked with Δ, and what was not wiped with was marked with ×.

One drop of a 3% strength by weight aqueous sodium hydroxide solution was dropped on the chemical-resistant transparent film-coated substrate (1) and allowed to stand at room temperature for 30 minutes, and the appearance change of the transparent film was visually observed. The case where there was no change in appearance was marked with ◎, the case where there was almost no change in appearance, ○, the case where it was partially whitened or partially eroded, and the case where it was whitened or completely eroded.

[Example 2]
Preparation of surface-treated metal oxide particles (A-2) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion Medium: isopropanol, particle refractive index 1.30) was used. 80 g of this sol was added with 0.49 g of heptadecatrifluorodecyltripropoxysilane (XC95-A9715 manufactured by Momentive Performance Materials Co., Ltd.) and γ-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) 1.15 g was mixed, 2.38 g of ultrapure water and 0.06 g of 29% ammonia water were added, and the mixture was stirred at 50 ° C. for 20 hours, and the surface-treated metal oxide particles (A− 2) A dispersed sol was obtained.

Preparation of coating liquid for forming transparent film (A-2R) 5.95 g of this surface-treated metal oxide particle (A-2) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 0.54 g and fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 0.54 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 0.12 g And perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 0.50 g of photoinitiator (Ciba Specialty Co., Ltd .: Irgacure 184, IPA) A transparent coating for antireflection by thoroughly mixing 0.50 g (solid content concentration 10%) and 91.85 g of a 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve A composition coating solution (A-2R) was prepared.

Preparation of substrate with transparent coating (A-2) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm.

Next, a coating solution (2R) for forming a transparent coating for preventing reflection was applied on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm). The substrate (A-2) with a transparent film was prepared by irradiating with 400 mJ / cm ² ultraviolet rays and curing. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-2) The results are shown in Table 1.

[Example 3]
Preparation of surface-treated metal oxide particles (A-3) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion Medium: isopropanol, particle refractive index 1.30) was used. To 80 g of this sol, 1.31 g of heptadecatrifluorodecyltripropoxysilane (XC95-A9715 manufactured by Momentive Performance Materials Co., Ltd.) and γ-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.33 g was mixed, 2.38 g of ultrapure water and 0.06 g of 29% ammonia water were added, and the mixture was stirred at 50 ° C. for 20 hours, and the surface-treated metal oxide particles (A− 3) A dispersed sol was obtained.

Preparation of coating liquid for forming transparent film (A-3R) 5.95 g of this surface-treated metal oxide particle (A-3) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 0.54 g and fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 0.54 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 0.12 g And perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 0.50 g of photoinitiator (Ciba Specialty Co., Ltd .: Irgacure 184, IPA) A transparent coating for antireflection by thoroughly mixing 0.50 g (solid content concentration 10%) and 91.85 g of a 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve A composition coating solution (A-3R) was prepared.

Preparation of substrate with transparent coating (A-3) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm. Next, a coating solution (A-3R) for forming a transparent coating for an antireflection film was coated on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was cured by irradiating 400 mJ / cm ² ultraviolet rays to prepare a substrate (A-3) with a transparent coating. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light having a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping resistance, resistance of the obtained transparent coated substrate (A-3) The alkalinity was measured and the results are shown in Table 1.

[Example 4]
Preparation of surface-treated metal oxide particles (A-4) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5% by weight, dispersion Medium: isopropanol, particle refractive index 1.30) was used. To 80 g of this sol, 0.41 g of heptadecatrifluorodecyltripropoxysilane (XC95-A9715 manufactured by Momentive Performance Materials Co., Ltd.) and γ-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.41 g was mixed, 2.38 g of ultrapure water and 0.03 g of 29% ammonia water were added, and the mixture was stirred at 50 ° C. for 20 hours, and the surface-treated metal oxide particles (A− 4) A dispersed sol was obtained.

Preparation of coating liquid for forming transparent film (A-4R) 6.10 g of this surface-treated metal oxide particle (A-4) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 0.54 g and fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 0.54 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 0.12 g And perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 0.50 g of photoinitiator (Ciba Specialty Co., Ltd .: Irgacure 184, IPA) To form a transparent coating for anti-reflection by thoroughly mixing 0.50 g of a solid content concentration of 10%) and 91.7 g of a 1: 1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve. A coating solution (A-4R) was prepared.

Preparation of substrate with transparent coating (A-4) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm. Next, a coating solution (4R) for forming a transparent coating for an antireflection film was coated on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm The substrate (A-4) with a transparent coating was prepared by irradiating with 400 mJ / cm ² ultraviolet light and curing. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-4) The results are shown in Table 1.

[Example 5]
Preparation of surface-treated metal oxide particles (A-5) Silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion as low refractive index component Medium: Isopropanol Particle refractive index 1.30) was used. 80 g of this sol was mixed with 2.46 g of heptadecatrifluorodecyltripropoxysilane (XC95-A9715 manufactured by Momentive Performance Materials Co., Ltd.) and γ-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) 2.46 g was mixed, 2.38 g of ultrapure water and 0.18 g of 29% ammonia water were added, and the mixture was stirred at 50 ° C. for 20 hours to obtain surface-treated metal oxide particles (A− 5) A dispersed sol was obtained.

Preparation of coating liquid for forming transparent film (A-5R) 5.32 g of this surface-treated metal oxide particle (4) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 54 g, fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 0.54 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light Acrylate 1.6HX-A) 0.12 g and par Fluorooctyl ethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate FA-108, diluted with MIBK, solid content concentration 10%) 0.50 g dissolved in photoinitiator (Ciba Supality Co., Ltd .: Irgacure 184, IPA) , Solid content concentration 10%) and 0.50 g of isopropanol and butyl cellosolve 1/1 (weight ratio) mixed solvent 92.48 g were mixed thoroughly to obtain a transparent coating for an antireflection film Forming coating solution (A-5R) were prepared.

Preparation of substrate with transparent coating (5) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm. Next, a coating solution (5R) for forming a transparent coating for an antireflection film was applied on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm The substrate (A-5) with a transparent coating was prepared by irradiating with 400 mJ / cm ² ultraviolet light and curing. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-5) The results are shown in Table 1.

[Example 6]
Preparation of surface-treated metal oxide particles (A-6) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion Medium: Isopropanol Particle refractive index 1.30) was used. To 80 g of this sol, 0.82 g of trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-7103) and 0.82 g of γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-403) are added. After mixing, 2.38 g of ultrapure water and 0.06 g of 29% ammonia water were added and stirred at 50 ° C. for 20 hours, and the surface-treated metal oxide particles (A-6) dispersed sol having a solid content concentration of 21.0 wt% Got.

Preparation of coating liquid for forming transparent film (A-6R) 5.95 g of this surface-treated metal oxide particle (A-6) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 0.54 g and fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 0.54 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 0.12 g And perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 0.50 g of photoinitiator (Ciba Specialty Co., Ltd .: Irgacure 184, IPA) A transparent coating for an anti-reflective coating by thoroughly mixing 0.50 g dissolved in a solid content concentration of 10%) and 91.85 g of a 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve A forming coating solution (A-6R) was prepared.

Preparation of substrate with transparent coating (A-6) A coating solution for forming a transparent coating (A-1H) was prepared from a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%). The film was coated with a bar coater at a reflectance of 5.1%, dried at 70 ° C. for 1 minute, and then cured by irradiation with 400 mJ / cm ² of UV with a high-pressure mercury lamp (80 W / cm). 1-1) was prepared. The film thickness at this time was 5 μm.

Next, a coating solution (6R) for forming a transparent coating for an antireflection film was coated on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm ) Was cured by irradiating with 400 mJ / cm ² ultraviolet rays to prepare a substrate with a transparent coating (A-6). At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light having a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-6) The results are shown in Table 1.

[Example 7]
Preparation of surface-treated metal oxide particles (A-7) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion Medium: Isopropanol Particle refractive index 1.30) was used. 80 g of this sol was mixed with 0.82 g of heptadecatrifluorodecyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-7803) and γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-403). 82g was mixed, 2.38g of ultrapure water and 0.06g of 29% ammonia water were added and stirred at 50 ° C for 20 hours, and the surface-treated metal oxide particles (A-7) having a solid content concentration of 21.0% by weight A dispersed sol was obtained.

Preparation of coating liquid for forming transparent film (A-7R) 5.95 g of this surface-treated metal oxide particle (A-7) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 1.08 g and 1.6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate 1.6HX-A) and perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate FA-108) Diluted with MIBK, solid content 10%) 0.50 g photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184, dissolved with IPA, solid content 10%) 0.50 g and 1/1 of isopropanol and butyl cellosolve (Weight ratio) 91.85 g of a mixed solvent was sufficiently mixed to prepare a coating liquid for forming a transparent film (A-7R) for an antireflection film.

Preparation of substrate with transparent coating (A-7) A coating solution for forming a transparent coating (A-1H) is a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%). The film was coated with a bar coater at a reflectance of 5.1%, dried at 70 ° C. for 1 minute, and then cured by irradiation with 400 mJ / cm ² of UV with a high-pressure mercury lamp (80 W / cm). A-1H) was prepared. The film thickness at this time was 5 μm.

Next, a coating solution (7R) for forming a transparent coating for an antireflection film was coated on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm ) Was cured by irradiating with 400 mJ / cm ² ultraviolet rays to prepare a substrate (A-7) with a transparent coating. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-7) The results are shown in Table 1.

[Example 8]
Preparation of surface-treated metal oxide particles (A-8) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 40 nm, concentration 20.5% by weight, dispersion Medium: isopropanol, particle refractive index 1.35) was used. 80 g of this sol was mixed with 0.82 g of heptadecatrifluorodecyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-7803) and γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-403). 82 g was mixed, 2.38 g of ultrapure water and 0.06 g of 29% ammonia water were added, and the mixture was stirred at 50 ° C. for 20 hours, and the surface-treated metal oxide particles (A-8) having a solid content concentration of 21.0 wt% A dispersed sol was obtained.

Preparation of coating liquid for forming transparent film (A-8R) 5.95 g of this surface-treated metal oxide particle (A-8) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 1.08 g and 1.6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate 1.6HX-A) and perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate FA-108) Diluted with MIBK, solid content 10%) 0.50 g photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184, dissolved with IPA, solid content 10%) 0.50 g and 1/1 of isopropanol and butyl cellosolve (Weight ratio) 91.85 g of a mixed solvent was sufficiently mixed to prepare a coating solution (A-8R) for forming a transparent film for an antireflection film.

Preparation of substrate with transparent coating (A-8) Coating solution (1H) for forming a transparent coating was prepared by using a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflection) After coating with a bar coater at a rate of 5.1% and drying at 70 ° C. for 1 minute, the substrate was coated with a transparent coating (A-) by curing with UV irradiation at 400 mJ / cm ² with a high-pressure mercury lamp (80 W / cm). 1H) was prepared. The film thickness at this time was 5 μm.
Next, a coating solution (8R) for forming a transparent coating for an antireflection film was applied on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm The substrate (A-8) with a transparent coating was prepared by irradiating with 400 mJ / cm ² ultraviolet light and curing. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-8) The results are shown in Table 1.

[Example 9]
Preparation of surface-treated metal oxide particles (A-9) Silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 80 nm, concentration 20.5 wt%, dispersion as low refractive index component Medium: isopropanol, particle refractive index 1.25) was used. 80 g of this sol was mixed with 0.82 g of heptadecatrifluorodecyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-7803) and γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-403). 82g was mixed, 2.38g of ultrapure water and 0.06g of 29% ammonia water were added and stirred for 20 hours at 50 ° C, and the surface-treated metal oxide particles (A-9) having a solid content concentration of 21.0% by weight A dispersed sol was obtained.

Preparation of coating liquid for forming transparent film (A-9R) 5.95 g of this surface-treated metal oxide particle (A-9) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 1.08 g and 1.6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 0.12 g were dissolved in photoinitiator (Ciba Specialty Co., Ltd .: Irgacure 184, IPA), (Solid content concentration 10%) 0.50 g and a 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve 91.85 g were mixed thoroughly to prepare a coating solution (A-9R) for forming a transparent film for an antireflection film. Prepared.

Preparation of substrate with transparent coating (A-9) A coating solution (1H) for forming a transparent coating was applied to a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflection) applying the rate 5.1%) with a bar coater, dried for 1 minute at 70 ° C., a high pressure mercury lamp (80W / cm) at 400 mJ / cm ² ultraviolet cured by irradiating the substrate with a transparent film (A- 1H) was prepared. The film thickness at this time was 5 μm.

Next, a coating solution (8R) for forming a transparent coating for an antireflection film was applied on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm The substrate (A-9) with a transparent coating was prepared by curing with UV irradiation at 400 mJ / cm ² . At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-9) The results are shown in Table 1.

[Example 10]
Preparation of coating liquid for forming transparent film (A-10R) 7.14 g of the surface-treated metal oxide particle (A-1) dispersion sol prepared in Example 1 and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light 0.45 g of acrylate DPE-6A) and fluororesin (manufactured by Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 0.45 g and 1.6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate 1.6HX- A) 0.10 g and perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 0.40 g of photoinitiator (manufactured by Ciba Spun Charity Co., Ltd.) : Irgacure 184, dissolved in IPA, solid content concentration 10%) 0.40 g and 1 / 1.0 (weight ratio) mixed solvent of isopropanol and butyl cellosolv were mixed well and anti-reflective. Transparent film-forming coating liquid for film (A-10R) was prepared.

Preparation of substrate with transparent coating (A-10) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm.

Next, a coating solution (A-10R) for forming a transparent coating for an antireflection film was applied to the substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm) was cured by irradiating with 400 mJ / cm ² ultraviolet rays to prepare a substrate (10) with a transparent coating. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-10) The results are shown in Table 1.

[Example 11]
Preparation of coating liquid for forming transparent film (A-11R) 4.76 g of the surface-treated metal oxide particle (A-1) dispersion sol prepared in Example 1 and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light 0.68 g of acrylate DPE-6A) and 0.68 g of fluororesin (manufactured by Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) and 1.6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate 1.6HX- A) 0.14 g and perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 0.60 g of photoinitiator (Ciba Spun Charity Co., Ltd.) : Irgacure 184, dissolved in IPA, solid content concentration 10%) 0.60 g, and 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve 92.54 g were mixed thoroughly to prevent reflection Transparent film-forming coating liquid for film (A-11R) was prepared.

Preparation of substrate with transparent coating (A-11) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm. Next, a coating solution (11R) for forming a transparent coating for an antireflection film was applied on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then a high-pressure mercury lamp (80 W / cm The substrate (A-11) with a transparent coating was prepared by irradiating with 400 mJ / cm ² ultraviolet light and curing. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-11) The results are shown in Table 1.

[Example 12]
Preparation of surface-treated metal oxide particles (A-12) Silica-based fine particle-dispersed sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: OSCAL1132, average particle size 12 nm, concentration 30% by weight, dispersion medium: methanol, particle refractive index 1.46) Was used. To 80 g of this sol, 1.2 g of heptadecatrifluorodecyltripropoxysilane (Momentive Performance Materials Co., Ltd .: XC95-A9715) and γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-503) ) Mixing 1.2 g, adding 3.5 g of ultrapure water and 0.09 g of 29% ammonia water, stirring the mixture at 50 ° C. for 20 hours, and treating the surface-treated metal oxide particles (A -12) A dispersed sol was obtained.

Preparation of coating liquid for forming transparent film (A-12) 20 g of this surface-treated metal oxide particle (A-12) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 5 g, fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 10.5 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 2.4 g and par Fluorooctyl ethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 6 g of photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184, dissolved with IPA, solid (Concentration 10%) 9.6 g and 1/14 (by weight) mixed solvent of isopropanol and butyl cellosolv, 43.4 g of mixed solvent are thoroughly mixed to form a transparent coating for a hard coat film (A-12) was prepared.

Preparation of substrate with transparent film (A-12) Coating liquid (A-12) for forming a transparent film was prepared by using a TAC film (thickness 80 μm, refractive index 1.49, substrate transmittance 88.0%, Haze 0.2%). , With a bar coater, and dried at 70 ° C. for 1 minute, and then cured by irradiation with 400 mJ / cm ² of UV with a high-pressure mercury lamp (80 W / cm). 12) was prepared. The film thickness at this time was 5 μm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-12) The results are shown in Table 1.

[ Reference Example 13 ]
Preparation of surface-treated metal oxide particles (A-13) ATO fine particle dispersed sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ELCOM V-3501, average particle diameter of 8 nm, concentration of 20.5% by weight ) as an antistatic high refractive index component Dispersion medium: ethanol Particle refractive index 1.75) was used. 100 g of this sol was mixed with 1.02 g of heptadecatrifluorodecyltripropoxysilane (Momentive Performance Materials Co., Ltd .: XC95-A9715) and γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-503) ) 1.02 g was mixed, 2.05 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 20 hours to obtain a surface-treated metal oxide particle (A-13) dispersion sol having a solid content concentration of 21.4% by weight. .

Preparation of coating liquid for forming transparent film (A-13) 56.1 g of this surface-treated metal oxide particle (A-13) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 3.5 g, fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 3.5 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light Acrylate 1.6HX-A) 0.8 g And perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 2.0 g of photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184, IPA) In this case, the solid content concentration is 10%) and the coating solution for forming a transparent film for a hard coat film is sufficiently mixed with 3.2 g of isopropanol and 6.6 g of a mixed solvent of isopropanol and butyl cellosolve (1/1 by weight). Liquid and (A-13) was prepared.

Preparation of substrate with transparent coating (A-13) Coating solution (A-13) for forming transparent coating was prepared from a TAC film (thickness 80 μm, refractive index 1.49, substrate transmittance 88.0%, Haze 0.2% reflection) After coating with a bar coater at a rate of 4.8% and drying at 70 ° C. for 1 minute, the substrate was coated with a transparent coating (A-) by curing with UV irradiation at 400 mJ / cm ² with a high-pressure mercury lamp (80 W / cm). 13) was prepared. The film thickness at this time was 5 μm.

  Surface resistance, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-13) The results are shown in Table 1.

[ Reference Example 14 ]
Preparation of surface-treated metal oxide particles (A-14) As conductive component, antimony pentoxide fine particle dispersion sol (manufactured by Catalytic Chemical Industry Co., Ltd .: ELCOM V-4560, average particle diameter 20 nm, concentration 30.5% by weight, dispersion Medium: Ethanol / methanol / isopropanol = 85.5 / 13.4 / 1.1 Particle refractive index 1.64). To 100 g of this sol, 1.52 g of heptadecatrifluorodecyltripropoxysilane (Momentive Performance Materials Co., Ltd .: XC95-A9715) and γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-503) 1.52 g was mixed, 3.05 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 20 hours to obtain a surface-treated metal oxide particle (A-14) dispersion sol having a solid content concentration of 31.2% by weight. .

Preparation of coating liquid for forming transparent film (A-14) 28.85 g of this surface-treated metal oxide particle (A-14) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 9.18 g and fluorine resin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 9.18 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 2.1 g And perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 5.3 g of photoinitiator (manufactured by Ciba Specialty Co., Ltd .: Irgacure 184, IPA) 8.4 g dissolved in a solid content concentration of 10%) and 37.0 g of a mixed solvent of isopropanol and butyl cellosolve 1/1 (weight ratio) was thoroughly mixed to form a transparent coating for a hard coat film Forming coating solution (A-14) was prepared.

Preparation of substrate with transparent coating (A-14) Coating solution (A-14) for forming a transparent coating was prepared by using a TAC film (thickness 80 μm, refractive index 1.49, substrate transmittance 88.0%, Haze 0.2% reflection) After coating with a bar coater at a rate of 4.8% and drying at 70 ° C. for 1 minute, the substrate was coated with a transparent coating (A-) by curing with UV irradiation at 400 mJ / cm ² with a high-pressure mercury lamp (80 W / cm). 14) was prepared. The film thickness at this time was 5 μm.

  Surface resistance value, total light transmittance, haze, reflectance of light having a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (A-14) The results are shown in Table 1.

[Comparative Example 1]
Preparation of surface-treated metal oxide particles (R-1) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion Medium: Isopropanol Particle refractive index 1.30) was used. 80 g of this sol was mixed with 1.64 g of heptadecatrifluorodecyltripropoxysilane (manufactured by Momentive Performance Materials Co., Ltd .: XC95-A9715), and 2.38 g of ultrapure water and 0.06 g of 29% ammonia water were added. The mixture was added and stirred at 50 ° C. for 20 hours to obtain a surface-treated metal oxide particle (R-1) dispersed sol having a solid content concentration of 21.0% by weight.

Preparation of coating liquid for transparent film formation (R-1R) 5.95 g of this surface-treated metal oxide particle (R-1) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 1.08 g and 1.6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 0.12 g were dissolved in photoinitiator (Ciba Specialty Co., Ltd .: Irgacure 184, IPA), (Solid content concentration 10%) 0.50 g and a 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve 91.85 g were mixed thoroughly to prepare a coating solution (R-1R) for forming a transparent film for an antireflection film. Prepared.

Preparation of substrate with transparent coating (R-1) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm. Next, a coating solution (R-1R) for forming an antireflection film was applied on a substrate with a transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then with a high pressure mercury lamp (80 W / cm). A substrate with a transparent film (R-1) was prepared by irradiating and curing 400 mJ / cm ² ultraviolet rays. At this time, the film thickness of the antireflection film was 100 nm.

  The surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, and alkali resistance of the obtained transparent film-coated substrate (1) are measured. The results are shown in Table 1.

[Comparative Example 2]
Preparation of coating liquid for forming transparent film (R-2R) 5.95 g of surface-treated metal oxide particle (R-1) dispersion sol prepared in Comparative Example 1 and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) 0.54 g and fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 0.54 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX- A) 0.12 g and perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 0.50 g photoinitiator (manufactured by Ciba Spun Charity) : Irgacure 184, dissolved in IPA, solid content concentration 10%) 0.50 g, and 91.85 g of 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve were mixed well to prevent reflection Transparent film-forming coating liquid of the use of the (R-2R) was prepared.

Preparation of substrate with transparent coating (R-2) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm. Next, an antireflection film-forming coating solution (R-2R) was applied onto the substrate with transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then with a high-pressure mercury lamp (80 W / cm). A substrate with a transparent coating (R-2) was prepared by irradiating and curing 400 mJ / cm ² ultraviolet rays. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (R-2) The results are shown in Table 1.

[Comparative Example 3]
Preparation of surface-treated metal oxide particles (R-3) As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion Medium: Isopropanol Particle refractive index 1.30) was used. 80 g of this sol was mixed with 1.64 g of γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-503), 2.38 g of ultrapure water and 0.06 g of 29% ammonia water were added at 50 ° C. The mixture was stirred for 20 hours to obtain a surface-treated metal oxide particle (R-3) dispersion sol having a solid content concentration of 21.0% by weight.

Preparation of coating liquid for transparent film formation (R-3R) 5.95 g of this surface-treated metal oxide particle (R-3) dispersion sol and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) 1.08 g and 1.6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A) 0.12 g were dissolved in photoinitiator (Ciba Specialty Co., Ltd .: Irgacure 184, IPA), (Solid content concentration 10%) 0.50 g and a 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve 91.85 g were mixed thoroughly to prepare a coating solution (R-3R) for forming an antireflection film. Prepared.

Preparation of substrate with transparent coating (R-3) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm. Next, an antireflection film-forming coating solution (R-3R) was applied onto the substrate with transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then with a high-pressure mercury lamp (80 W / cm). A substrate with a transparent coating (R-3) was prepared by irradiating with 400 mJ / cm ² ultraviolet rays and curing. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (R-3) The results are shown in Table 1.

[Comparative Example 4]
Preparation of coating liquid for transparent film formation (R-4R) 5.95 g of the surface-treated metal oxide particle (R-3) dispersion sol prepared in Comparative Example 1 and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) 0.54 g and fluororesin (Kyoeisha Chemical Co., Ltd .: Fluorite LINC-3A) 0.54 g and 1.6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX- A) 0.12 g and perfluorooctylethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate FA-108, diluted with MIBK, solid content concentration 10%) to 0.50 g photoinitiator (manufactured by Ciba Spun Charity) : Irgacure 184, dissolved in IPA, solid content concentration 10%) 0.50 g, and 91.85 g of 1/1 (weight ratio) mixed solvent of isopropanol and butyl cellosolve were mixed well to prevent reflection Transparent film-forming coating liquid of the use of the (R-4R) was prepared.

Preparation of substrate with transparent coating (R-4) A substrate with transparent coating (A-1H) was prepared in the same manner as in Example 1. The film thickness at this time was 5 μm. Next, an antireflection film-forming coating solution (R-4R) was applied onto the substrate with transparent coating (A-1H) with a bar coater, dried at 70 ° C. for 1 minute, and then with a high-pressure mercury lamp (80 W / cm). A substrate with a transparent coating (R-4) was prepared by irradiating and curing 400 mJ / cm ² ultraviolet rays. At this time, the film thickness of the antireflection film was 100 nm.

  Surface resistance value, total light transmittance, haze, reflectance of light with a wavelength of 550 nm, adhesion, pencil hardness, scratch resistance, magic wiping property, alkali resistance of the obtained substrate with transparent coating (R-4) The results are shown in Table 1.

Claims (2)

In the silica-based particle dispersion, the silane coupling agent (A) represented by the following formula (1) and the silane coupling agent (B) represented by the following formula (2) are mixed with the silane coupling agent ( as the number of moles of a) (M ₁₎ and the silane coupling agent moles of (B) (ratio of _{M 2) (M 1) /} (M 2) is in a range of 0.16 to 1.51 Mixing step to mix with,
A aging step of adding water and ammonia to the dispersion obtained by the mixing step and heating at 40 to 100 ° C.,
The silane coupling agent (A) and the silane coupling agent The total number of moles of (B) (M _SC) the moles of said water ratio _{(M H2O) (M H2O /} M SC) is 9.67～ In the range of 58.01,
The method for producing surface-treated metal oxide particles, wherein a ratio (M _HC / M _SC ) of the total number of moles to the number of moles of ammonia (M _HC ) is in the range of 0.07 to 0.16. .
_{R n SiX 4-n ······ (} 1)
(However, R: fluoro group-containing hydrocarbon group, X: alkoxy group having 1 to 4 carbon atoms, hydroxyl group, halogen or hydrogen, n: an integer of 1 to 3)
_{R n SiX 4-n ······ (} 2)
(However, R: (meth) acryloyloxymethyl group, (meth) acryloyloxyethyl group, (meth) acryloyloxypropyl group, epoxycyclohexylethyl, glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group , Vinyl group, urethane isopropylpropyl group, X: alkoxy group having 1 to 4 carbon atoms, hydroxyl group, halogen or hydrogen, n: an integer of 1 to 3) In the silica-based particle dispersion, a silane coupling agent (A) represented by the following formula (1), vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meta ) Acryloxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxy From orchid, γ- (meth) acrylooxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane At least one silane coupling agent (B) selected from the group consisting of the number of moles (M ₁ ) of the silane coupling agent (A) and the number of moles (M ₂ ) of the silane coupling agent (B). A mixing step of mixing such that the ratio (M ₁ / M ₂ ) is in the range of 0.16 to 1.51;
A aging step of adding water and ammonia to the dispersion obtained by the mixing step and heating at 40 to 100 ° C.,
The silane coupling agent (A) and the silane coupling agent The total number of moles of (B) (M _SC) the moles of said water ratio _{(M H2O) (M H2O /} M SC) is 9.67～ In the range of 58.01,
The method for producing surface-treated metal oxide particles, wherein a ratio (M _HC / M _SC ) of the total number of moles to the number of moles of ammonia (M _HC ) is in the range of 0.07 to 0.16. .
_{R n SiX 4-n ······ (} 1)
(However, R: fluoro group-containing hydrocarbon group, X: alkoxy group having 1 to 4 carbon atoms, hydroxyl group, halogen or hydrogen, n: an integer of 1 to 3)