TW201546197A - Coating liquid for forming transparent coating film and method for producing the same, organic resin dispersant sol, and substrate with transparent coating film and method for producing the same - Google Patents

Abstract

The present invention provides a transparent coating film with high stiffness even be a resin substrate, and with less shrinkage even be a thick film which, has no crack suppressed curling, and high stiffness. A coating liquid for forming the transparent coating film comprises metal oxide particles have an average particle size in a range of 5 to 300 nm and a matrix formation component, the matrix formation component consisting of a first organic resin having 2 or less functional groups, and a second organic resin having 3 or more functional groups, the concentration (CP) of the metal oxide particles as solid component is 45 to 90 mass%, the concentration (CR) of matrix formation component as solid component is 10 to 50 mass%, the concentration (CT) of total solid component is 60 mass% or more, and the ratio of concentration (CR) and concentration (CP), (CR/Cp) is in the range of 0.11 to 1.0.

Description

Coating liquid for forming transparent film, method for producing the same, organic resin dispersion sol, substrate with transparent film, and method for producing the same

The present invention relates to a coating liquid for forming a transparent film and a method for producing the same. In particular, it is a coating liquid suitable for forming a transparent film which is high in hardness even when the substrate is a resin substrate, and which has no crack even when it is a thick film and which has suppressed curl.

Conventionally, in order to improve the scratch resistance of glass, plastic sheets, plastic lenses, and the like, a transparent film having a hard coating function is provided on the surface of the substrate. An organic resin film or an inorganic film is used for such a transparent film. In order to further improve the scratch resistance, it is known that inorganic particles such as resin particles and cerium oxide are blended in the transparent film.

However, when particles are dispersed in the coating liquid for forming a transparent film, particles having low affinity for the matrix forming component and the dispersion medium are aggregated. Therefore, the stability of the coating liquid may be lowered, and Not only the transparency, haze, and the like of the obtained transparent film, but also scratch resistance, strength, scratch resistance, and the like are insufficient.

In order to prevent the above, it is known to subject the particles to a surface treatment with a decane coupling agent. Further, it is known that the particles are coated with a resin by a mechanochemical method or a graft polymerization method to improve the affinity with a matrix component or a dispersion medium. (Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin (Patent Document 4)).

Further, Japanese Patent Publication No. 2010-37534 (Patent Document 5) discloses a composite of an organic component having a structure in which an aromatic skeleton and four or more atoms are bonded to an aromatic skeleton on the surface of an inorganic particle. particle. It is disclosed that such a composite particle is excellent in dispersibility, and a cured product excellent in heat resistance and mechanical strength can be obtained by a resin composition containing the composite particle and the resin component. Further, it is described that the composite particles are mixed with a resin and a starter in a dispersion medium, and then the solvent is degassed by an evaporator or the like to prepare a resin composition. At this time, it was revealed that the solvent was degassed under heating at 100 ° C or lower, under reduced pressure, and the solvent was degassed in the presence of high-boiling components.

Further, it is known that an organic solvent of an ether, an ester or a ketone is a dispersion liquid of metal oxide particles having an average secondary particle diameter of a micron-sized dispersion medium, and an acrylic resin is added thereto, and then Mechanochemical treatment. Thereby, each metal oxide particle can be uniformly coated with a resin. At this time, the metal oxide particles coated with the resin The dispersion can be made to have a high concentration until the solid content concentration is 50% by weight (JP-A-2010-077409 (Patent Document 6)).

Further, a (meth) acrylate-based resin having an aromatic ring is added to the organic solvent dispersion of the metal oxide particles which have been heat-treated in advance, and then, in the case of mechanochemical treatment, each particle can be uniformly coated. Resin. The coating resin-coated particles are dispersed in a low molecular weight resin having high affinity with the coating resin-coated particles, and then the organic solvent is removed. Thereby, it is possible to obtain a composition in which the resin-coated particles are not hardened and are highly dispersed and have excellent stability. A hardener is added to the composition and applied, and it is hardened without drying. Thereby, a thick transparent film having a small shrinkage can be formed. The transparent film is dense, and is excellent in transparency, haze, and scratch resistance (JP-A-2012-72288 (Patent Document 7)).

Further, it is composed of a (meth)acrylate resin having an anthracene skeleton having an average molecular weight of a specific range, a (meth)acrylate resin having an anthracene skeleton, and a coated (meth)acrylate resin. The coating uses a rotary evaporator to remove the organic resin, thereby modulating the high concentration of the coating. When such a coating material is used, a thick optical film having excellent hardness can be obtained (JP-A-2013-10864 (Patent Document 8)).

Further, when an acrylate having a functional group number of 4 or more and an acrylate resin having a number of functional groups of 2 or 3, a special-shaped particle (particles having a spherical coefficient of a specified range or a chain particle), and a dispersion medium are used, Even in the case of a thin substrate, a transparent film which is excellent in adhesion to a substrate, hardness, scratch resistance, and the like can be obtained (JP-A-2013-133444 (Patent Document 9)).

Further, a coating liquid for forming a hard coat film comprising a metal oxide particle treated with a surfactant having a skeleton modified with ethylene oxide, a hydrophobic matrix-forming component, and an organic dispersion medium is known. Concavities and convexities are formed on the surface of the film to improve the anti-caking property (Japanese Laid-Open Patent Publication No. 2013-136222 (Patent Document 10)). Moreover, it has also been revealed that the surface-treated hydrophobic particles are formulated using an organic cerium compound to increase the film hardness.

Further, by using a coating liquid containing a metal oxide particle, a hydrophobic organic resin matrix-forming component, and a dispersion medium having a surface charge amount of the coated polymer decane coupling agent in a predetermined range, it is possible to form an alkali resistance excellent and to a substrate. A hard coat film which is excellent in adhesion, scratch resistance, hardness, and the like (JP-A-2009-35595 (Patent Document 11)).

Further, it is known that when a coating material composed of a resin having a functional group having three or more functional groups, a bifunctional organic resin monomer or an anthracene resin monomer, and a monofunctional fluorene resin is used, it is possible to form a coating which can reduce bleeding and water repellency. A transparent film which is excellent in oil repellency and the like, and which has excellent wiping properties such as fingerprints and marks, etc. (Japanese Laid-Open Patent Publication No. 2010-126675 (Patent Document 12)).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 3-163172

[Patent Document 2] Japanese Patent Laid-Open No. Hei 6-336558

[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-49251

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-143230

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2010-37534

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-077409

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2012-72288

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2013-10864

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2013-133444

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2013-136222

[Patent Document 11] Japanese Patent Laid-Open Publication No. 2009-35595

[Patent Document 12] Japanese Patent Laid-Open Publication No. 2010-126675

However, in the conventional mechanochemical method, graft polymerization method, and the like of Patent Documents 1 to 4, it is difficult to uniformly coat the respective particles, and a plurality of aggregated particles are coated with the resin. As described above, in the resin-coated particles, the resin may be dissolved in the solvent of the coating liquid. Therefore, the obtained transparent film has problems such as low transparency, increased haze, and low scratch resistance.

Further, Patent Document 6 discloses a dispersion sol of metal oxide particles coated with a resin containing an organic solvent, and the concentration thereof is in the range of approximately 1 to 60% by weight in terms of solid content. When the concentration of the coating liquid is more than 60% by weight, stability may be lowered and aggregation may occur due to aggregation. Further, when the coating liquid is used, a resin component is added as a matrix forming component together with the organic solvent, but there is a limit in the film thickness of the obtained film.

Further, a transparent film having a film thickness of 4 μm and a pencil hardness of more than 4H cannot be obtained (Patent Document 6), and a pencil having a film thickness of 35 μm cannot be obtained. The transparent film having a hardness of more than 3H (Patent Document 7) cannot be made larger than 4H even if it is a transparent film of 50% by weight or more of the surface-treated particles (Patent Document 12).

Further, as disclosed in Patent Document 9, a transparent film having a pencil hardness of 5H or more cannot be obtained even if a special-shaped particle is used.

In recent years, in the case of using a resin substrate for various display devices, a transparent film having a pencil hardness similar to that of a glass substrate is still required.

The inventors believe that the hardness can be increased by increasing the proportion of the particles while increasing the proportion of the particles. However, the ratio of the particles is increased, and the stability of the coating liquid is lower than that of the original, and cracking is caused by drying during film formation, and the shrinkage is large. At this time, it was found that by using a UV curable resin monomer instead of a conventional solvent as a medium for dispersing the sol at the time of preparation of the coating liquid, the final resin ratio can be reduced.

Thus, it has been found that an organic dispersion medium dispersion of metal oxide particles subjected to a specified amount of surface treatment with an organic cerium compound is prepared, and the organic dispersion medium is substituted with an ultraviolet curing resin monomer having a small number of functional groups, that is, A stable organic resin dispersion (sometimes referred to as an organic resin dispersion sol) can be obtained. Then, it has been found that when the ultraviolet curable resin monomer having a functional group number of 3 or more is mixed as a coating liquid, the resin ratio can be reduced, and even if a thick coating liquid is applied, the shrinkage of the transparent film is small and cracking is not caused. The curl is suppressed and the hardness of the film is particularly improved.

That is, the coating liquid for forming a transparent film of the present invention includes metal oxide particles having an average particle diameter of 5 to 300 nm and a matrix forming component, wherein the metal oxide particles have a solid content (C _p ) of 45 To 90% by weight, the matrix forming component has a solid content (C _R ) of 10 to 50% by weight, a total solid content concentration (C _T ) of 60% by weight or more, and a concentration (C _R ) and concentration (C _P The ratio (C _R /C _P ) is in the range of 0.11 to 1.0, and the matrix-forming component contains a first organic resin having two or less functional groups and a second organic resin having three or more functional groups. Further, the first organic resin and the second organic resin are ultraviolet curable resin monomers or oligomers. Further, the functional groups of the first organic resin and the second organic resin are preferably a (meth) acrylate group, an amine acrylate group, or an epoxy group-modified acrylate group. The metal oxide particles are preferably surface-treated with an organic cerium compound.

Further, the method for producing a coating liquid of the present invention comprises the steps of: preparing a dispersion liquid containing metal oxide particles having an average particle diameter of 5 to 300 nm and an organic dispersion medium; and at least a part of the organic dispersion medium having 2 or less a step of substituting a first organic resin of a functional group; and a step of mixing a second organic resin having three or more functional groups. In particular, it is suitable as a method of producing the above coating liquid.

Further, the substrate with a transparent film of the present invention is a substrate provided on the surface by the above-mentioned coating liquid transparent film, and the transparent film contains metal oxide particles having an average particle diameter of 5 to 300 nm and a matrix component, wherein The metal oxide particles have a solid content (W _p ) of 45 to 90% by weight, and the matrix component has a solid content (W _R ) of 10 to 50% by weight, and the content ratio (W _R /W _P ) is from 0.11 to 1.0, and the average film thickness (T) is from 1 to 100 μm. Further, an antireflection layer is provided on the transparent film. The antireflection layer contains cerium oxide-based hollow particles and a matrix component (M _L ), and the content of the cerium oxide-based hollow particles (W _PLA ) is 5 to 80% by weight, and the content of the matrix component (M _L ) (W _ML ) The thickness (T _L ) of the antireflection layer is 80 to 200 nm, the average particle diameter (D _PA ) of the cerium oxide-based hollow particles is 10 to 45 nm, and the average particle diameter of the cerium oxide-based hollow particles is 20 to 95% by weight ( The ratio of D _PA ) to the thickness (T _L ) of the antireflection layer (D _PA /T _L ) is 0.05 to 0.56.

According to the coating liquid of the present invention, it is possible to form a transparent film which has a small shrinkage of the film even when it is a thick film, and which has no cracking, is suppressed in curl, and has high hardness.

Hereinafter, the coating liquid for forming a transparent film of the present invention will be described first.

[Coating liquid for forming a transparent film]

The coating liquid of the present invention includes metal oxide particles having an average particle diameter in the range of 5 to 300 nm and a matrix forming component. The metal oxide particles in the coating liquid are present as a solid component at a concentration (C _P ) of 45 to 90% by weight. In particular, a range of 48 to 80% by weight is preferred. Further, in the coating liquid, the matrix-forming component is present as a solid component at a concentration (C _R ) of 10 to 50% by weight. In particular, a range of 15 to 40% by weight is preferred. At this time, the total solid content concentration (C _T ) of the coating liquid is 60% by weight or more. It is particularly preferably more than 60% by weight and more preferably 63% by weight or more.

When the concentration (C _P ) of the metal oxide particles in the coating liquid is low, the shrinkage of the film is increased, and cracking is likely to occur in the thick film. Further, the densification is insufficient, and a transparent film having a high hardness cannot be obtained. Conversely, when the concentration (C _P ) is high, the surface unevenness of the transparent film is increased. Therefore, external scattering occurs, and the haze of the film is deteriorated, and the transparency is lowered. Further, the densification of the film is insufficient, and the scratch resistance of the transparent film and the adhesion to the substrate are insufficient.

When the concentration (C _R ) of the matrix-forming component in the coating liquid is too low, the concentration (C _P ) of the metal oxide particles becomes high, and as described above, the haze of the film is deteriorated and the transparency is lowered. Further, the densification of the film may be insufficient, and the scratch resistance of the transparent film and the adhesion to the substrate may be insufficient. Even when the concentration (C _R ) of the matrix-forming component is too high, the shrinkage of the film is increased as compared with the case of blending a plurality of metal oxide particles, and cracking is likely to occur when a thick film is formed.

Further, the concentration of the concentration (C _R) matrix forming component of the metal oxide particles (C _P) ratio (C _R / C _P) is set to 0.11 to 1.0. In particular, the range of 0.18 to 0.8 is preferred. When the concentration ratio is low, the concentration of the metal oxide particles represented by the solid content is high, and the surface unevenness of the transparent film is increased. Therefore, the haze of the film due to external scattering is likely to be deteriorated, and the transparency is lowered. Further, the densification of the film may be insufficient, and the scratch resistance of the transparent film and the adhesion to the substrate may be insufficient. On the other hand, when the concentration ratio is too high, the shrinkage of the film becomes large, and cracking easily occurs in a thick film. Further, the densification of the transparent film is insufficient, and good hardness cannot be obtained.

The matrix forming component is composed of a first organic resin (A) and a second organic resin (B). The first organic resin is an organic resin having two or less functional groups, and the metal oxide particles are stably dispersed. The second organic resin is an organic resin having three or more functional groups, which is required to increase the hardness of the coating film. Further, the content of the first organic resin (A) in the matrix-forming component as a solid component is from 1 to 80% by weight. In particular, a range of 5 to 60% by weight is preferred. When the content of the first organic resin (A) is too small, it is difficult for the metal oxide particles to aggregate without being uniformly dispersed. The transparent film obtained from such a coating liquid has a low surface smoothness and is insufficient in densification. On the other hand, when the content of the first organic resin (A) is too large, the second organic resin (B) is small, and the denseness of the transparent film is insufficient, and good hardness cannot be obtained. The second organic resin in the matrix-forming component is set such that the total concentration (C _R ) of the first organic resin (A) is in the above range.

The ratio (C _RA /C _P ) of the concentration (C _RA ) of the first organic resin (A) to the concentration (C _P ) of the metal oxide particles in the matrix-forming component is from 0.17 to 1.11. In particular, the range of 0.19 to 0.89 is preferred. When it is in this range, even if there are many metal oxide particles, shrinkage of a film can be made small and thick, and it can suppress the occurrence of a crack. The resulting transparent film has high density and therefore high hardness.

Such a coating liquid was prepared in the following manner.

[Method of Preparing Coating Liquid for Forming Transparent Film]

Step (a)

First, metal oxide particles having an average particle diameter of 5 to 300 nm are dispersed in an organic dispersion medium to prepare an organic dispersion. The concentration of the metal oxide particles in the organic dispersion is not particularly limited, and is usually in the range of 30 to 50% by weight in terms of solid content. When the concentration is low, the amount of solvent substitution increases. Adding is not efficient. When the concentration is high, the metal oxide particles aggregate. Or, even if it does not aggregate, the viscosity will rise and it will become difficult to obtain stability. At this time, the metal oxide particles are desirably surface-treated with an organic cerium compound.

Step (b)

Then, the organic dispersion medium in the dispersion is substituted with a first organic resin having two or less functional groups. The method of substituting the solvent is not particularly limited, and a conventionally known method can be employed. For example, a rotary evaporator method, an evaporation can method, or the like can be employed. At this time, it can also be carried out under reduced pressure and under heating as needed.

The ratio of the organic dispersion medium to the first organic resin is such that the concentration of the organic dispersion medium in the coating liquid finally obtained by the step (c) described later is less than 40% by weight. In particular, it is preferably set to less than 35% by weight.

When too much organic dispersion medium remains, the total solid content concentration (CT) of the coating liquid becomes low, and the shrinkage after application of the coating liquid to drying becomes large. Therefore, in the case of a thick film, in particular, when a thick film of 10 μm or more is obtained, cracking is likely to occur at the time of shrinkage, and curling property is also increased.

Step (c)

Then, a second organic resin having three or more functional groups is mixed in the dispersion liquid containing the first organic resin obtained in the step (b). The mixing amount of the second organic resin is set so that the total amount of the first organic resin and the second organic resin, that is, the solid content concentration (C _R ) expressed by the matrix forming component is 15 to 50% by weight.

In the coating liquid for forming a transparent film obtained in this manner, the metal oxide particles have a solid content (C _P ) of 45 to 90% by weight and a total solid content concentration (C _T ) of 60% by weight or more. The ratio of the concentration (C _R ) to the concentration (C _P ) (C _R /C _P ) is in the range of 0.11 to 1.0. In particular, it is preferably more than 60% by weight, more preferably 63% by weight or more. At this time, a photopolymerization initiator may be added as needed. Further, after the step (c), in the case where the total solid content concentration is too high, an organic dispersion medium may be added in order to adjust the viscosity of the coating liquid.

Hereinafter, the metal oxide particles and the matrix forming component contained in the coating liquid will be described in detail.

Metal oxide particles

It is preferred to use metal oxide particles derived from a metal oxide sol. For example, conventionally known cerium oxide sol, zirconia sol, titanium oxide sol, alumina sol, cerium oxide sol, cerium-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), indium-doped tin oxide ( ITO) and so on.

The average particle diameter of the metal oxide particles is suitably from 5 to 300 nm. In particular, a range of 5 to 200 nm is preferred. When the average particle diameter of the metal oxide particles is less than 5 nm, depending on the presence or absence of the surface treatment described later, the metal oxide particles are likely to aggregate. When agglutination occurs, the haze of the transparent film is deteriorated and the transparency is lowered. Even if the average particle diameter is more than 300 nm, the haze of the transparent film is deteriorated or the transparency is lowered depending on the content of the metal oxide particles. Furthermore, there is a case where the transparent film such as friction is damaged.

The spherical coefficient of the metal oxide particles is suitably from 0.2 to 1.0. In particular, 0.4 to 1.0 is preferred. If the spherical coefficient is small, the dispersibility in the coating liquid may be insufficient, and the metal oxide particles may aggregate. Therefore, the adhesion to the substrate, the scratch resistance, and the like are insufficient, and the obtained transparent film may be cracked. Here, the spherical coefficient is expressed by "(the average short diameter perpendicular to the longest diameter at the midpoint of the longest diameter; D _S ) / (the average longest diameter of the particles; D _L )".

A photograph taken by a transmission electron microscope (TEM), which measures the longest diameter of 100 particles and the short diameter perpendicular to the midpoint of the longest diameter as the average value of the short diameter (D _S ) and the average of the longest diameter ( The ratio of D _L ) can be obtained as a spherical coefficient.

Further, it is preferred that the metal oxide particles are surface-treated with an organic ruthenium compound represented by the following formula (1).

R _n -SiX _4-n . . . . Formula 1)

However, in the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, and hydrogen, and n represents an integer of 1 to 3. The substituent is, for example, an epoxy group, an alkoxy group, a (meth)acryloxy group, a thiol group, a halogen atom, an amine group, a phenylamine group or the like.

The surface treatment amount of the metal oxide particles is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the metal oxide particles, and the organic ruthenium compound is R _n -SiO _(4-n)/2 . In particular, a range of from 1 to 40 parts by weight is preferred. When the amount of surface treatment is too small, the dispersibility of the metal oxide particles is insufficient. Therefore, the obtained transparent film may be fogged or may have insufficient adhesion to the substrate and hardness. Even if the amount of surface treatment is too large, the dispersibility is not further improved, but an unreacted surface treatment agent remains. As a result, the high-density filling of the metal oxide particles is inhibited, and the hardness and adhesion are insufficient.

The method of surface treatment can be carried out by conventional methods. For example, when the metal oxide sol is a water-dispersible sol, the organosol which is substituted with an alcohol as a solvent is added with a required amount of the hydrolyzable organic ruthenium compound, and if necessary, heating or addition of an acid or a base is used for hydrolysis. Catalyst, a method of hydrolyzing an organic hydrazine compound. After the hydrolysis, it is preferred to replace the dispersion medium solvent containing water or by-products with an organic dispersion medium to be described later.

The organic hydrazine compound represented by the formula (1) is, for example, methyltrimethoxydecane, dimethyldimethoxydecane, phenyltrimethoxydecane, diphenyldimethoxydecane, methyltriethyl Oxy decane, dimethyl diethoxy decane, phenyl triethoxy decane, diphenyl diethoxy decane, isobutyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy Base decane, vinyl stilbene (β-methoxyethoxy) decane, 3,3,3-trifluoropropyltrimethoxydecane, methyl-3,3,3-trifluoropropyldimethoxy Decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxymethyltrimethoxydecane, γ-glycidoxymethyltriethoxydecane , γ-glycidoxyethyltrimethoxydecane, γ-glycidoxyethyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxy Propyltriethoxydecane, γ-(β-glycidoxyethoxy)propyltrimethoxydecane, γ-(meth)acryloxymethyltrimethoxydecane, γ-( Methyl) propylene methoxymethyl triethoxy decane, γ-(methyl) Enterenyloxyethyltrimethoxydecane, γ-(meth)acryloxyethyltriethoxydecane, γ-(meth)acryloxypropyltrimethoxydecane, γ-(A) Base) Isomethoxypropyltriethoxydecane, butyltrimethoxydecane, isobutyltriethoxydecane, hexyltriethoxydecane,octyltriethoxydecane,decyltriethoxydecane , butyl triethoxy decane, 3-ureido isopropyl propyl triethoxy decane, perfluorooctyl ethyl trimethoxy decane, perfluorooctyl ethyl triethoxy decane, perfluorooctane Ethyltriisopropoxydecane, trifluoropropyltrimethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldimethoxydecane, N-β (aminoethyl) γ-Aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-thiolpropyltrimethoxydecane, trimethylstanol, methyltrichloro Decane, γ-(meth)acryloxypropyldimethoxydecane, γ-(meth)acryloxypropyldiethoxydecane, and the like, and mixtures thereof.

In particular, an organic ruthenium compound having a substituted hydrocarbon group having a (meth) acrylate group as a substituent as R is preferred. When the surface treatment is carried out with such an organic cerium compound, the compatibility between the metal oxide particles and the ultraviolet curable organic resin is increased, and the dispersibility is improved. Therefore, a transparent film which is uniform and excellent in adhesion to a substrate can be obtained.

Further, since the bonding property of each resin to the matrix forming component is improved, a transparent film having a higher hardness can be obtained.

An organic ruthenium compound having a substituted hydrocarbon group substituted with a (meth) acrylate group as R, for example, γ-(meth) propylene methoxymethyl trimethoxy decane, γ-(meth) propylene oxime Methyl triethoxy decane, γ-(meth) propylene methoxyethyl trimethoxy decane, γ-(methyl) propylene oxiranyloxyethyl triethoxy decane, γ-(methyl) Propylene methoxypropyltrimethoxydecane, γ-(meth)acryloxypropyltriethoxydecane, γ-(methyl)propyl Ethylidene propyl dimethoxy decane, γ-(meth) propylene methoxy propyl diethoxy decane, and the like.

Matrix forming component

In the coating liquid for forming a transparent film of the present invention, the matrix forming component contains a first organic resin (A) having two or less functional groups and a second organic resin (B) having three or more functional groups. The first organic resin and the second organic resin are preferably ultraviolet curable resin monomers or oligomers. When a monomer or oligomer of an ultraviolet curable resin having three or more functional groups is used for the second organic resin, the number of functional groups is three or more, and it is easy to be combined with polyethylene terephthalate (PET). The resin substrate such as cellulose triacetate (TAC) is bonded to each other and has excellent adhesion to the substrate. Further, by bonding to each other as a matrix forming component, a transparent film excellent in hardness can be obtained. In particular, the second organic resin is preferably one having at least one functional group selected from the group consisting of a (meth) acrylate group, an amine acrylate group, and an alkylene oxide-modified acrylate group. When such a functional group is provided, the bond to the resin substrate is stronger, and high adhesion to the substrate can be obtained. Moreover, a transparent film of higher hardness can be obtained.

Among the first organic resins, it is preferred to use an ultraviolet curable resin monomer or oligomer having 1 to 2 functions. When the number of the functional groups is from 1 to 2, the viscosity of the organic resin is low, and when the organic dispersion medium dispersion of the metal oxide particles is substituted with a solvent, even if the organic resin is increased in concentration, the increase in viscosity is small, and thus it can be suitably used. In other words, the metal oxide particles can be stably dispersed by the first organic resin to obtain an organic resin dispersion of metal oxide particles having a high concentration and stability.

The molecular weight (polystyrene-equivalent molecular weight) of the ultraviolet curable resin monomer or oligomer is suitably 5,000 or less. In particular, it is preferably 4,500 or less. When the molecular weight is too large, the viscosity of the resin is high, and when the first organic resin is used, when the organic dispersion medium dispersion of the metal oxide particles is subjected to solvent substitution, the viscosity of the dispersion becomes high, and the concentration may not be increased. Therefore, formation of a thick film, suppression of shrinkage at the time of film formation, suppression of cracking, suppression of curl, and formation of a transparent film excellent in hardness become difficult. In the case of using as the first organic resin, it is particularly preferably 1000 or less. Further, when the second organic resin is used, the hardness of the resin is lowered, and it becomes difficult to visualize the hardness of the transparent film.

Further, in the case where the surface treatment amount of the metal oxide particles is in the range of 0.1 to 5 parts by weight, particularly 0.1 to 3 parts by weight, the first organic resin contains a group selected from a hydroxyl group (OH group), an ether group, an amine group, a carboxyl group, At least one of the sulfonic acid groups is preferred. When the surface treatment amount of the metal oxide particles is in the above range, a hydrophilic group (OH group) remains on the surface of the particles. Therefore, when the first organic resin has such a group, the affinity with the metal oxide particles is high, and in the coating liquid preparation step (b), when the organic dispersion medium dispersion of the metal oxide particles is subjected to solvent substitution. The metal oxide particles can be uniformly dispersed without being aggregated.

Further, in the case where the surface treatment amount of the metal oxide particles is in the range of 5 to 50 parts by weight, the first organic resin preferably has no functional group of any of a hydroxyl group, an ether group, an amine group, a carboxyl group, and a sulfonic acid group. It is also possible to have these functional groups.

Hereinafter, an example which can be suitably used for the first organic resin is exemplified. UV curable resin.

A compound having a monofunctional (meth) acrylate group; butoxyethyl acrylate, methoxy polyethylene glycol acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate , 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, ethylene glycol diepoxypropyl ether acrylate, polyethylene glycol diepoxypropyl ether acrylate, two Propylene glycol diepoxypropyl ether acrylate, polypropylene glycol diepoxypropyl ether acrylate, 1,6-hexanediol diepoxypropyl ether acrylate, 2-ethylhexyl epoxy propyl ether acrylate, Pentaerythritol polyepoxypropyl ether acrylate, neopentyl glycol diepoxypropyl ether acrylate, ethoxylated bisphenol A methacrylate, propoxylated bisphenol A diglycidyl ether acrylate, Di-epoxypropyl ether phthalate acrylate, cyclohexane dimethanol diglycidyl ether acrylate, p-butyl butyl epoxide propyl acrylate, o-phenylphenol epoxy propyl Ether acrylate, 2-hydroxy-3-phenoxypropyl acrylate, methyl methacrylate, ethyl methacrylate, A N-butyl acrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, n-stearyl methacrylate, n-butoxy methacrylate Ethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, glycidyl methacrylate, 2-methylpropenyloxyethyl acid Phosphate, 2-propenyloxyethyl acid phosphate, 2-hydroxy-3-propenyloxypropyl methacrylate.

a monofunctional (meth)acrylic monomer or oligomer; methacrylic acid, 2-propenyloxyethyl succinic acid, 2-propenyloxytetrahydrophthalic acid, 2-acryloxy 6 Hydrogen phthalic acid, 2-propenyloxypropyl phthalate Formic acid, 2-propenyloxypropyltetrahydrophthalic acid, 2-propenyloxypropyl hexahydrophthalic acid, methacryloxyethyl succinic acid, methacryloxy group Hydrogen phthalic acid, methacryloxyethyltetrahydrophthalic acid, methacryloxyethylhexahydrophthalic acid, methacryloxypropyl phthalate, A Acryl methoxy propyl tetrahydrophthalic acid, methacryloxypropyl hexahydrophthalic acid.

a monofunctional alkylene oxide-modified acrylate base; methoxy triethylene glycol acrylate, methoxy polyethylene glycol #400 monoacrylate, methoxy polyethylene glycol #600 monoacrylate, Methoxy polyethylene glycol #1000 monoacrylate, methoxy tripropylene glycol acrylate, phenoxy ethylene glycol acrylate, phenoxy diethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl Acrylate, ethoxylated alpha-phenylphenol propyl acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate Ester, methoxy polyethylene glycol methacrylate, methoxytripropylene glycol methacrylate, ethoxylated 2-ethylhexyl methacrylate, butoxydiethylene glycol methacrylate, butoxy Diethylene glycol methacrylate, polyethylene glycol modified stearyl methacrylate, phenoxy ethylene glycol methacrylate, phenoxy diethylene glycol methacrylate, benzyl methacrylate Oxyethyl ester.

In addition, the alkylene oxide-modified acrylate group is represented by the following formula (2) as shown in JP-A-2005-92198. [CH ₂ =C(R ¹ )COO(R ² O) _n ] _m R ³ . . . In the formula (2), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group, and R ³ is a hydrocarbon residue. m is 1 or more, and n is 1 or more. m corresponds to the number of functional groups.

Bifunctional non-glycol (meth) acrylate or oligomer thereof; neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, different Decanediol diacrylate, 1,10-nonanediol dimethacrylate, glycerol dimethacrylate, dimethylol tricyclodecane diacrylate, 9,9-bis [4-( 2-hydroxyethoxy)phenyl]anthracene diacrylate, 2-methylpropenyloxyethyl acid phosphate, 2-propenyloxyethyl acid phosphate, 1,4-butanediol Dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-nonanediol dimethacrylate, neopentyl glycol Methacrylate, glycerol dimethacrylate, 2-methylpropenyloxyethyl acid phosphate, 2-propenyloxyethyl acid phosphate.

Bifunctional alkoxylated bisphenol A (meth) acrylate base; ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated double Phenol A dimethacrylate.

Product name of bifunctional amine ester acrylate group (manufactured by Shin-Nakamura Chemical Co., Ltd.); NK OLIGO U-200PA, UA-W2, UA-W2A, UA-122P, UA-160TP, UA-2235PE, UA- 4200, UA-4400, UA-7000, U-2HA, U-2PPA.

Bifunctional ethylene oxide modified (meth) acrylate base; tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol #200 diacrylate, polypropylene glycol #400 diacrylate, poly Propylene glycol #700 diacrylate, polybutylene glycol #650 diacrylate, polyethyl propylene glycol diacrylate, two Alkylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol #200二Methacrylate, polyethylene glycol #400 dimethacrylate, polyethylene glycol #600 dimethacrylate, polyethylene glycol #1000 dimethacrylate, tripropylene glycol dimethacrylate, poly A diol-based acrylate such as propylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylidene polypropylene glycol diacrylate or ethylene glycol dimethacrylate.

Among the above ultraviolet curable monomers or oligomers, an organic resin having a specific functional group is shown below.

OH group; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy methacrylate Butyl ester, 2-methylpropenyloxyethyl acid phosphate, 2-propenyloxyethyl acid phosphate, glycerol dimethacrylate, 2-hydroxy-3-methacrylic acid Propyl acrylate, 2-hydroxy-1,3-dimethylpropenyloxypropane, 2-hydroxy-3-phenoxypropyl acrylate.

Having an ether group; methoxy triethylene glycol acrylate, methoxy polyethylene glycol #400 monoacrylate, methoxy polyethylene glycol #600 monoacrylate, methoxy polyethylene glycol #1000 Monoacrylate, methoxytripropylene glycol acrylate, phenoxyethylene glycol acrylate, phenoxy diethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ethoxylated α-phenyl Phenol propyl acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, methoxy polyethylene glycol Acrylate, methoxytripropylene glycol methacrylate, ethoxylated 2-ethylhexyl methacrylate, butoxydiethylene glycol methacrylate, butoxydiethylene glycol methacrylate, Polyethylene glycol modified stearyl methacrylate, phenoxyethylene glycol methacrylate, phenoxy diethylene glycol methacrylate, phenoxyethyl methacrylate, tripropylene glycol diacrylate , polypropylene glycol diacrylate, polyethylene glycol #200 diacrylate, polypropylene glycol #400 diacrylate, polypropylene Glycol #700 diacrylate, polybutylene glycol #650 diacrylate, polyethylidene polypropylene glycol diacrylate, two Alkylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol #200二Methacrylate, polyethylene glycol #400 dimethacrylate, polyethylene glycol #600 dimethacrylate, polyethylene glycol #1000 dimethacrylate, tripropylene glycol dimethacrylate, poly Propylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylidene polypropylene glycol diacrylate, ethylene glycol dimethacrylate.

An amine group; dimethylaminoethyl methacrylate, dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, diethylaminoethyl methacrylate.

Having a guanamine group; dimethyl methacrylate, propylene decyl morpholine, dimethylaminopropyl acrylamide, isopropyl acrylamide, diethyl acrylamide, hydroxyethyl acrylamide .

Having a carboxyl group; methacrylic acid, 2-propenyloxyethyl succinic acid, 2-propylene decyloxytetrahydro phthalic acid, 2-propylene decyloxy hexahydro phthalic acid, 2-propylene oxy oxy propylene Phthalic acid, 2-propenyloxypropyl tetrahydrogen Phthalic acid, 2-propenyloxypropyl hexahydrophthalic acid, methacryloxyethyl succinic acid, methacryloxytetrahydrophthalic acid, methacryloxyethylidene Hydrogen phthalic acid, methacryloxyethyl hexahydrophthalic acid, methacryloxypropyl phthalic acid, methacryloxypropyltetracarboxylic acid, methacryloxy group Propyl hexaphthalic acid.

Without functional groups; 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-fluorene Diol dimethacrylate, neopentyl glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9- Decanediol diacrylate, isodecanediol diacrylate, 1,10-nonanediol dimethacrylate, glycerol dimethacrylate, dimethylol tricyclodecane diacrylate, 9 , 9-bis[4-(2-hydroxyethoxy)phenyl]phosphonium diacrylate, dimethylol tricyclodecane diacrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid N-butyl ester, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, n-stearyl methacrylate.

Then, a monomer or oligomer suitable for using an ultraviolet curable resin having three or more functional groups as a second organic resin is exemplified.

3-functional acrylate resin; neopentyl alcohol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate.

3-functional amine ester acrylate resin; neopentyl alcohol hexamethylene diisocyanate amine ester prepolymer.

A trifunctional acrylate resin containing an epoxy group; a cresol novolac type epoxy acrylate, a bisphenol A diglycidyl ether acrylic acid addition product.

3-functional (meth) acrylate resin; trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, ethoxylated Glycerol trimethacrylate, ethoxylated neopentyl alcohol trimethacrylate, propoxypentaerythritol trimethacrylate.

A 3-functional product name having an amine ester acrylate group (manufactured by Shin-Nakamura Chemical Co., Ltd.); NK OLIGO UA-31F, UA-7100, UA-32P.

3-functional (caprolactone-modified) isocyanate acrylate base; ginseng-(2-propenyloxyethyl)isocyanate, caprolactone modified tris-(2- Propylene oxiranyl ethyl) iso-cyanate.

3-functional epoxide-modified acrylate base; ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, propoxylated trimethylolpropane triacrylate, succinyl pentoxide Polyacrylate, propylene pentaerythritol polyacrylate.

4-functional (meth) acrylate resin; neopentyl alcohol tetraacrylate.

An epoxy group-containing tetrafunctional (meth) acrylate resin; ethoxylated pentaerythritol tetraacrylate, propoxypentaerythritol tetraacrylate.

6-functional (meth) acrylate resin; dipentaerythritol hexaacrylate.

A 6-functional (meth) acrylate resin containing an epoxy group; bis-pentaerythritol polyacrylate, propylene pentaerythritol polyacrylate.

In addition to these, for example, a tetrafunctional amine ester (meth)acrylic acid Ester oligomer resin, 6-functional amine ester (meth) acrylate oligomer resin, 8-functional amine ester (meth) acrylate oligomer resin, 9-functional amine ester (meth) acrylate Polymer resin, 10-functional amine ester (meth) acrylate oligomer resin, 12-functional amine ester (meth) acrylate oligomer resin, 15-functional amine ester (meth) acrylate oligomer Resin, etc. As such an amine ester (meth) acrylate oligomer resin, there are NK OLIGO UA-33H, UA-6LR, UA-8LR, UA-12LR, U-10PA, U-10HA, UA-1100H (Xinzhongcun) Chemical (share) system, etc. are commercially available.

Other epoxy group-containing tetrafunctional or higher acrylate resins such as cresol novolac type epoxy acrylate and bisphenol A diglycidyl ether acrylic acid addition product. As such a resin, NK OLIGO EA-6320, EA-6340, EA-7120, EA-7140, EA-7420 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like are available. In particular, an acrylate resin having a functional group number of 6 to 12 is excellent in the effect of suppressing curl and excellent in hardness, and is most suitable as a second organic resin.

Organic dispersion medium

An organic dispersion medium may be added to the coating liquid as needed. The concentration of the organic dispersion medium in the coating liquid is suitably set to be less than 40% by weight. In particular, it is preferably less than 35% by weight. In addition, the organic dispersion medium in the coating liquid is not limited to the organic dispersion medium remaining when the organic dispersion medium of the metal oxide particles in the preparation method of the coating liquid for forming a transparent film is replaced by the first organic resin. In view of the handleability of the coating liquid, those added for adjusting the viscosity may also be included. Further, the dispersion medium for dilution contained in the first organic resin or the second organic resin is also the same.

A conventionally known material can be used in the organic dispersion medium. For example, alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, and the like; glycols such as ethylene glycol and hexanediol; Diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether An ether such as propylene glycol monoethyl ether; propyl acetate, isobutyl acetate, butyl acetate, isoamyl acetate, amyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, acetate ring Esters of hexyl ester, ethylene glycol monoacetate, etc.; acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, A Ketones such as pentyl ketone, diisobutyl ketone, isophorone, acetoacetone, acetamidine acetate; toluene, xylene, and the like. Among them, alcohols, ethers, esters, and ketones are preferable, and the dispersibility of the metal oxide particles and the solubility of the organic resin are improved.

Further, the organic dispersion medium has a boiling point of 56.12 to 200 ° C, and further preferably 56.12 to 180 ° C.

When the boiling point of the organic dispersion medium is low, the drying of the coating film is fast, the densification tends to be insufficient, and the film thickness tends to be uneven. Therefore, the hardness of the obtained transparent film becomes insufficient.

When the boiling point of the organic dispersion medium is high, the organic dispersion medium remains, the shrinkage of the film becomes insufficient, and the hardness of the obtained transparent film becomes insufficient.

Polymerization initiator

A photopolymerization initiator may be added to the coating liquid as needed. The polymerization initiator is preferably used in an amount of from 2 to 20% by weight based on the solid content of the organic resin. %, more preferably in the range of 4 to 16% by weight. As a polymerization initiator, a conventional one can be used. For example, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, bis(2,6-dimethoxybenzylidene) 2,4,4-trimethylpentylphosphine oxide , 2-hydroxy-methyl-2-methyl-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclo Hexyl-1 phenyl-ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, and the like.

[Organic Resin Dispersed Sol]

The organic resin-dispersed sol of the present invention is a sol obtained by dispersing metal oxide particles having an average particle diameter of 5 to 300 nm in a first organic resin or an organic dispersion medium having two or less functional groups and a first organic resin. . The organic resin dispersion sol was used to prepare a coating liquid for a transparent film. The metal oxide particles are desirably subjected to surface treatment with an organic ruthenium compound such as a decane coupling agent.

The first organic resin is preferably an ultraviolet curable resin having two or less functional groups. Since the viscosity of the organic resin having a 1-2 function is low, the viscosity of the organic resin dispersion sol of the metal oxide particles can be increased. The first organic resin functions as a resin for dispersing metal oxide particles.

Further, the first organic resin is preferably a monomer or oligomer of an ultraviolet curable resin. In the case of a monomer of an ultraviolet curable resin, an organic resin dispersion sol of stable metal oxide particles can be formed at a high concentration.

The molecular weight of the first organic resin (the molecular weight of the converted polystyrene) is suitably 5,000 or less, and particularly preferably 4,500 or less. When the molecular weight is more than 5,000, the viscosity of the sol becomes high, and the concentration of the particles cannot be increased. again Preferably, it is 1000 or less.

A general organic solvent such as an alcohol, an ether, an ester or a ketone can be used for the organic dispersion medium.

The organic resin-dispersed sol of the metal oxide particles preferably has a concentration (C _PS ) of the metal oxide particles represented by a solid content of 45 to 90% by weight, more preferably 45 to 80% by weight. Further, the concentration (C _RS ) of the first organic resin in the sol represented by the solid content is suitably from 10 to 50% by weight. In particular, 15 to 40% by weight is preferred.

At this time, the total solid content concentration (C _TS ) of the sol is 60% by weight or more. More preferably, it is more than 60% by weight, more preferably 65% by weight or more. When the total solid content concentration (C _TS ) is less than 100% by weight, the remaining components are organic dispersion media.

The organic resin dispersion sol which is conventionally not known to have such a composition is stable. The organic resin dispersion sol can be produced in accordance with the steps (a) to (b) of the preparation method of the coating liquid. Since such an organic resin dispersion sol can stably disperse metal oxide particles for a long period of time, the sol can be stored as it is and can be liquefied before the moment to be used.

[Substrate with transparent film]

The coating liquid described above is applied to a substrate to form a transparent film on the substrate. The transparent film is formed of metal oxide particles and a matrix component. Substrate

Preferably, the substrate is selected from the group consisting of polyethylene terephthalate (PET), cellulose triacetate (TAC), acrylic acid, polycarbonate, and cycloolefin polymer (COP). Resin substrate. The resin substrates, and The transparent film formed by the coating liquid is excellent in adhesion, and a substrate having a transparent film excellent in hardness and scratch resistance can be obtained.

Metal oxide particles

It is preferred to use metal oxide particles which have been surface-treated with the aforementioned organic cerium compound. The content (W _P ) of the metal oxide particles in the transparent film represented by the solid content is preferably from 50 to 90% by weight, more preferably from 65 to 85% by weight. When the content (W _P ) is in this range, a transparent film having no unevenness and small shrinkage, and having a small thickness and a small occurrence of cracks and high hardness can be obtained.

When the content (W _P ) is small, the resin is increased, the densification is insufficient, and the hardness of the transparent film is lowered. When the content (W _P ) is too large, the surface unevenness is increased, and the haze of the external scattering is deteriorated, whereby the transparency is lowered, and the densification of the film is further lowered, and the scratch resistance and the adhesion to the substrate are obtained. Become insufficient.

Matrix component

The matrix component is composed of a first organic resin and a second organic resin. In the transparent film, the monomers and oligomers of the resins are cured in a polymerized state. The first organic resin and the second organic resin are preferably ultraviolet curable resins.

When the organic resin is an ultraviolet curable resin, it is excellent in adhesion to a resin substrate such as PET or TAC, and a transparent film having excellent hardness can be obtained. Moreover, the substrate with the transparent film can be produced by a highly productive winding method (roll-to-roll).

The content of the first organic resin in the matrix component expressed as a solid component is from 0.1 to 80% by weight. In particular, a range of 5 to 60% by weight is preferred. If the content of the first organic resin in the matrix component is small, transparent The smoothness of the surface of the film is lowered, or the densification becomes insufficient. Therefore, haze, hardness, scratch resistance, adhesion, and the like become insufficient. When the content of the first organic resin in the matrix component is large, the second organic resin is reduced, the denseness of the transparent film is low, and the hardness is insufficient.

The content (W _R ) of the matrix component in the transparent film as a solid component is preferably from 10 to 50% by weight. More preferably, it is in the range of 15 to 40% by weight. When the content (W _R ) of the matrix component in the transparent film is less than 10% by weight, the haze of the film on the surface is deteriorated, and the haze of the film which is externally scattered is deteriorated to lower the transparency. In addition, as the number of particles increases, the densification of the transparent film becomes insufficient, and the adhesion to the substrate, the scratch resistance, and the hardness become insufficient. On the other hand, when the content (W _R ) is more than 50% by weight, the shrinkage of the film becomes large. Therefore, when it is a thick film (about 10 μm or more), curling and cracking may occur. Moreover, high hardness cannot be obtained because of low density.

The ratio (W _R /W _P ) of the content of the matrix component (W _R ) to the content (W _P ) of the metal oxide particles in the transparent film is preferably from 0.11 to 1.0, more preferably from 0.18 to 0.8. When the ratio (W _R /W _P ) is small, the surface unevenness of the transparent film may become large, and the haze by external scattering may be deteriorated to lower the transparency. Further, the film is insufficiently densified, and a transparent film excellent in scratch resistance and adhesion to a substrate cannot be obtained. Further, when the ratio (W _R /W _P ) is large, the shrinkage of the film becomes large, and cracking may occur when the film is thick. Further, the densification of the transparent film becomes insufficient, so that the hardness may become insufficient.

The average film thickness (T) of the transparent film formed with such a matrix component is suitably from 1 to 100 μm. Especially the range of 12 to 80 μm Better around. In the case of the film thickness in this range, a transparent film having a high hardness and suppressed curl can be formed on the resin substrate.

Here, the average film thickness (T) of the transparent film is a transmission electron microscope photograph (TEM) of the cross section of the film, and the distance from the vertex of the upper surface of the film of the surface unevenness to the bottom of the film is measured (T convex) And the distance (T concave) from the deepest portion of the concave portion adjacent to the convex portion to the bottom portion directly below, and the average value thereof is obtained. Further, it is preferable that the number of unevenness measured is 10 or more sets at regular intervals. Thereby, a transparent film having a pencil hardness of 5H or more and even 6H or more can be formed on the resin substrate. In addition, the base material with a transparent film was measured by the following conditions, and the crimping property was 5 mm or less.

In the method of measuring the curling property, the coating liquid was applied to a TAC film substrate having a coated surface of 14 cm × 25 cm and a thickness of 40 μm so as to form a transparent film having a thickness of 12 μm, and allowed to stand for 20 hours. Then, the film was cut into a size of 10 cm × 10 cm, and the coated surface was placed on the flat plate so as to be curled (bent) to measure the height of the apex of the substrate floating from the flat plate.

In the conventional transparent film formed on a resin substrate, it is difficult to achieve such curl characteristics and hardness. Such a transparent film is formed by applying a coating liquid for forming a transparent film on a resin substrate to form a coating film, drying it, and curing it.

It is preferable to form wavy irregularities on the surface of the transparent film (the interface with an antireflection film to be described later). Since the cerium oxide particles (P) and the matrix component are combined in the above composition ratio, a transparent film having a predetermined surface roughness is formed. When the surface roughness is formed, the joint area is increased when the antireflection film is formed, so that a transparent cover having high adhesion and excellent hardness and scratch resistance can be obtained. The substrate of the film. Further, since the smoothness of the antireflection film is not inhibited, the haze of the film by external scattering is less adversely affected, and the transparency is not lowered.

The wavy irregularities, expressed as surface roughness (Ra), are suitably in the range of 1 to 10 nm, or even 1 to 5 nm. The surface roughness (Ra) can be measured by an atomic force microscope (manufactured by Bruker: Dimension 3100).

The undulating unevenness is thought to occur because the surface-treated cerium oxide particles formulated on the coating liquid are present on the surface layer of the film. Therefore, it is considered that there is a tendency to depend on the content of cerium oxide particles in the transparent film.

According to the transparent film of the present invention, it is considered that since the cerium oxide particles (P) are relatively large and the matrix component is small, the film is hardened into a wave shape without being flattened during curing. This varies depending on the type of the matrix component. When the matrix component is too small, the unevenness of the surface becomes too large, and the haze of the film which is externally scattered deteriorates, and the transparency is lowered. Further, as the number of particles increases, the densification of the film becomes insufficient, and adhesion to the substrate, scratch resistance, and hardness are not obtained. When the amount of the matrix component is too large, the wavy irregularities on the surface become too large, and the transparency is lowered, and the adhesion to the substrate and the scratch resistance may not be obtained. Further, when the shrinkage of the film is increased, it is accompanied by curling or cracking when a thick film (about 10 μm or more) is used. Moreover, the hardness is insufficient due to low compactness.

Further, the coating method can be printed by a conventional method such as a dip coating method, a spray method, a spin method, a roll coating method, a bar coating method, a gravure printing method, or a micro gravure printing method. After printing, it is hardened by ultraviolet irradiation or the like.

After coating the coating liquid according to the present invention, by drying The steps are allowed to dry. In the drying step, the volume shrinkage ratio (a) of the coating film is 25% or less. In particular, it is preferably 20% or less. After drying, the coating film is hardened. The volume shrinkage ratio (b) of the coating film at the time of hardening is set to 10% or less. In particular, it is preferably 5% or less. When the volume shrinkage ratio (a) of the coating film during drying or the volume shrinkage ratio (b) of the coating film at the time of curing is high, cracking occurs in the case of a thick film, and hardness is insufficient due to low density. Further, the total shrinkage ratio (c) at the time of drying and hardening is 35% or less, and particularly preferably 30% or less.

The shrinkage ratio (a), the shrinkage ratio (b), and the shrinkage ratio (c) are represented by the following mathematical formulas (A) to (C).

Shrinkage ratio (a) [%] = (1 - (density of coating liquid / density of dried film)) × 100... Mathematical formula (A)

Shrinkage ratio (b) [%] = (1 - (density of dried film / density of cured film)) × 100... Mathematical formula (B)

Shrinkage ratio (c) [%] = (1 - (density of coating liquid / density of cured film)) × 100... Mathematical formula (C)

[anti-reflection layer]

An antireflection layer is formed on the transparent film as needed. The antireflection layer contains cerium oxide-based hollow particles and a matrix component (M _L ). Here, the cerium oxide-based hollow particles having a small average particle diameter and the same matrix component as the transparent film are combined. Thereby, the hardness of the transparent film can be maintained even with a thin anti-reflection layer.

Hereinafter, the cerium oxide-based hollow particles and the matrix component (M _L ) constituting the antireflection layer will be described in detail.

Cerium oxide hollow particles (A)

The cerium oxide-based hollow particles are cerium oxide-based particles having a void inside, and the particles in the colloidal region having a low refractive index are excellent in dispersibility, and are disclosed in Japanese Laid-Open Patent Publication No. 2001-233611 and JP-A-2003-192994. Therefore, it is suitable for anti-reflection layer.

The average particle diameter (D _PA ) of the cerium oxide-based hollow particles is suitably from 10 to 45 nm. In particular, 15 to 40 nm is preferred. When the average particle diameter is less than 10 nm, the refractive index of the particles cannot be lowered (1.4 or less) because the ratio of voids is small. Therefore, sufficient antireflection performance cannot be obtained. In order to obtain a film thickness (T _L ), the cerium oxide-based hollow particles are arranged in a plurality of layers or irregularly arranged (aggregated). Therefore, not only the reflectance and the film strength are not improved. When the average particle diameter is more than 45 nm, the adhesion to the transparent film is lowered, and the hardness of the film-attached substrate on which the antireflection layer is formed is also lowered. Although the reason is not clear, it is considered that when the average particle diameter is larger than the unevenness of the transparent film, the transparent film is in close contact with each other and cannot be joined.

The refractive index of the cerium oxide-based hollow particles is suitably from 1.10 to 1.40. In particular, 1.10 to 1.35 is preferred. A refractive index of less than 1.10 is difficult to achieve, and when it is more than 1.40, sufficient antireflection performance cannot be obtained, and the contrast of bright places becomes insufficient.

The ratio (D _PA /T _L ) of the thickness (T _L ) of the antireflection layer to the average particle diameter (D _PA ) of the cerium oxide-based hollow particles is suitably from 0.05 to 0.56. Even a range of 0.1 to 0.45 is preferred. When the ratio is less than 0.05, the refractive index of the particles cannot be lowered as described above, and the function as an antireflection layer becomes insufficient. When the ratio is more than 0.56, the strength of the particles is low, and the surface smoothness of the antireflection layer cannot be obtained. Therefore, it is difficult to obtain desired strength and hardness.

Second cerium oxide-based particles (B)

In the antireflection layer, not only the cerium oxide-based hollow particles (A) but also the second cerium oxide-based particles (B) having an average particle diameter (D _PB ) of 4 to 17 nm are preferable. A particularly preferred average particle size (D _PB ) is 4 to 12 nm. The second cerium oxide-based particles are, for example, cerium oxide sol, cerium oxide-based hollow particles, or chain-connected chain cerium oxide-based particles. The second cerium oxide-based particles have a refractive index of 1.15 to 1.46, preferably 1.15 to 1.40.

It is difficult to realize a particle system having an average particle diameter of less than 4 nm, and it is difficult to obtain a uniform dispersion liquid or a coating liquid even if it is obtained. Therefore, the smoothness of the surface of the antireflection layer is poor. Moreover, the particles in the layer are not densely packed, and sufficient strength and hardness cannot be obtained. When the average particle diameter is more than 17 nm, the particle gap of the cerium oxide-based hollow particles (A) cannot be entered, and the reflectance becomes insufficient and the strength cannot be obtained.

The ratio (D _PB /D _PA ) of the average particle diameter of the second cerium oxide-based particles (B) to the cerium oxide-based hollow particles (A) may be from 0.1 to 0.4. In particular, 0.1 to 0.35 is preferred. When the ratio is less than 0.1, the cerium oxide-based hollow particles are agglomerated or arranged to be irregular. As a result, the reflectance and the strength become insufficient. When the ratio is more than 0.4, the yttrium oxide-based hollow particles are irregularly arranged or aggregated because they cannot enter the particle gap of the yttrium oxide-based hollow particles.

The average particle diameter of each particle was measured by a transmission electron micrograph (TEM), and the particle diameter of 10 particles was measured as an average value.

The cerium oxide-based hollow particles (A) or the second cerium oxide-based particles (B) used herein are coated with the above-described coating film for forming a transparent film. Similarly, the metal oxide particles of the liquid are preferably surface-treated with the organic ruthenium compound represented by the formula (1). When the second cerium oxide-based particles are surface-treated with an organic cerium compound, an antireflection layer excellent in water resistance, water repellency, stain resistance, and the like can be obtained.

In particular, surface treatment is carried out with an organic ruthenium compound of the formula (1) of n = 0, and then any of the organic ruthenium compounds of n = 1, 2, 3 is preferably surface-treated. The organic hydrazine compound having n = 0 is, for example, tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane or the like.

Hereinafter, an example of a surface treatment method by an organic cerium compound will be described. A conventionally known method can be employed.

A predetermined amount of an organic ruthenium compound is added to the alcohol dispersion of the cerium oxide-based particles, and water is added thereto. An acid or a base is added as a hydrolysis catalyst to carry out hydrolysis as needed. At this time, the ratio of the weight of the organic cerium compound represented by R _n -SiX _{(4-n)/2 to} the weight of the cerium oxide-based particles (R _n -SiX _(4-n)/2 weight / cerium oxide-based particles The weight) is preferably from 0.01 to 0.5, even from 0.02 to 0.25. When the weight ratio is less than 0.01, the affinity with the matrix forming component or the dispersion medium in the coating liquid for forming an antireflection film to be described later is low, the stability is insufficient, and the coating liquid cannot be uniformly dispersed. Therefore, the cerium oxide-based particles are aggregated, the strength and scratch resistance of the antireflection layer are lowered, and the haze value and the reflectance are increased. Even if the weight ratio is more than 0.5, the dispersibility cannot be further improved, the refractive index rises, and only the expensive organic ruthenium compound is added, resulting in low economy.

Then, if necessary, it is replaced with an organic solvent to prepare an organic solvent dispersion of the surface-treated cerium oxide-based particles. As the organic solvent, the same organic solvent as the coating liquid for forming an antireflection film to be described later is used. Preferably. An antireflection layer was formed from the coating liquid thus prepared.

In the antireflection layer, it is desirable to contain 5 to 80% by weight of the cerium oxide-based hollow particles (A). The content is preferably from 10 to 75% by weight. When the content is less than 5% by weight, the adhesion to the transparent film, the strength, the surface flatness, the scratch resistance, the scratch resistance, and the like become insufficient. Furthermore, since the refractive index of the antireflection layer cannot be lowered, the antireflection performance cannot be improved. When the content is more than 80% by weight, too many particles cause insufficient film strength, scratch resistance, scratch resistance, and the like. Further, the haze value of the antireflection film also becomes high.

When the second cerium oxide-based particles (B) are blended in the anti-reflection layer, the total content of the cerium oxide-based hollow particles (A) and the second cerium oxide-based particles (B) is 5 to 80% by weight, or even 10 It is preferred to use it in a range of up to 75% by weight. Further, the ratio of the second cerium oxide-based particles is 30% by weight or less of all the cerium oxide-based particles, and preferably 20% by weight or less. When the proportion of the second cerium oxide-based particles is more than 30% by weight, the second cerium oxide-based particles (B) which cannot enter the particle gap of the cerium oxide-based hollow particles (A) increase, and the cerium oxide-based hollow particles (A) may be irregular. Arrange and agglomerate.

When the second cerium oxide-based particles (B) are contained in the above-mentioned appropriate range, the second cerium oxide-based particles (B) are present in the particle gap of the cerium oxide-based hollow particles (A) on the surface of the anti-reflective layer, and the surface is flat. Chemical. Therefore, an antireflection layer excellent in scratch resistance and scratch resistance is obtained.

Matrix component (M _L )

The matrix component (M _L ) as the antireflection layer is, for example, a thermosetting resin, a thermoplastic resin, an electron beam curable resin, or the like which is an organic resin for coating. For example, a thermoplastic resin such as a polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene oxide resin, a thermoplastic acrylic resin, a vinyl chloride resin, a fluororesin, a vinyl acetate resin, or a polyoxyethylene rubber; A thermosetting resin such as an amine ester resin, a melamine resin, a butyral resin, a phenol resin, an epoxy resin, an unsaturated polyester resin, a thermosetting acrylic resin, or an ultraviolet curable acrylic resin; and a conventional ultraviolet curing resin; The resin used. Further, two or more kinds of copolymers or modified bodies of the above resins may be used.

In particular, it is preferred that the matrix component (M _L ) comprises at least one of the first organic resin and the second organic resin used in the transparent film. When such an organic resin is contained in at least one portion, when an antireflection layer is formed on a transparent film, a film-attached substrate excellent in hardness and scratch resistance can be obtained by bonding two films containing the same matrix component.

The content of the matrix component (M _L ) in the antireflection layer is preferably from 20 to 95% by weight, more preferably from 25 to 90% by weight, based on the solid content. When the content of the matrix component (M _L ) is less than 20% by weight, the strength of the antireflection film, the adhesion to the substrate, and the scratch resistance are insufficient. When the content of the matrix component (M _L ) is more than 95% by weight, the amount of the cerium oxide-based particles is small, the film thickness cannot be uniform, the flatness is insufficient on the surface, the scratch resistance and the scratch resistance are insufficient, and the film is not obtained. Low refractive index. Therefore, the anti-reflection performance becomes insufficient.

The thickness (T _L ) of the antireflection layer is suitably from 80 to 200 nm. Even 90 to 150 nm is preferred. If the layer is too thin, strength and scratch resistance become insufficient. Even if the layer is too thick, the strength is insufficient due to the occurrence of cracking. Moreover, if the layer is too thick, the antireflection performance is lowered. When the thickness is within an appropriate range, an antireflection layer having a low reflectance (bottom reflectance, visual reflectance) and excellent hardness can be obtained. Further, a cross-sectional photograph of the transparent film and the antireflection layer was taken using a transmission electron microscope (TEM), and the average film thickness (T _H ) of the transparent film was subtracted from the full thickness to determine the thickness (T _L ) of the antireflection layer. .

Thereby, an antireflection layer having a pencil hardness of 5H or more can be formed even by using the aforementioned resin substrate. This is derived from the underlying transparent film, and an antireflection layer having the same degree of pencil hardness as the transparent film can be realized.

Coating liquid for forming an antireflection layer

The coating liquid for forming the antireflection layer contains a base of the cerium oxide-based hollow particles (A) and the matrix component (M _L ) contained in the film together with the solvent. That is, the coating liquid contains cerium oxide-based hollow particles, a matrix forming component, and a solvent. The average particle diameter (D _PA ) of the cerium oxide-based hollow particles is in the range of 10 to 45 nm. The matrix-forming component is a base of the matrix component (M _L ) described in the antireflection layer, and is the same organic resin as described above.

Further, the matrix forming component preferably contains at least one of the first organic resin and the second organic resin used for the coating liquid for forming a transparent film. When at least one of the first organic resin and the second organic resin is formed, after the transparent film is formed, the coating liquid for forming an anti-reflective film is applied, dried, and irradiated with ultraviolet rays, the transparent film containing the same matrix component is formed. The bonding with the antireflection layer is increased, and a film-attached substrate having an antireflection layer excellent in hardness, scratch resistance, and the like can be obtained.

In addition, when the first organic resin (A _L ) contained in the coating liquid for forming an antireflection layer is an ultraviolet curable resin monomer or oligomer having 1 to 2 functional groups, coating for forming an antireflection layer The stability of the liquid is high, and an antireflection layer having a smooth surface can be obtained. In the case where the coating liquid contains the second organic resin (BL), the second organic resin is easily bonded to the first organic resin and the second organic resin contained in the transparent film, and an antireflection layer integrated with the transparent film can be obtained. .

In addition, when the second organic resin (B _L ) contained in the coating liquid for forming an antireflection layer is an ultraviolet curable resin monomer or oligomer having three or more functional groups, it is easy to be transparent to the lower layer. The second organic resin (B) of the film is bonded, and the adhesion to the transparent film is excellent, and the transparent film is integrated with the antireflection layer. Further, as a matrix forming component by bonding to each other, an antireflection layer excellent in hardness can be obtained.

Further, a polymerization initiator may be added to the coating liquid for forming an antireflection layer as needed. The polymerization initiator may be any one which can polymerize and harden the matrix-forming component, and can be appropriately selected depending on the resin, and a conventional polymerization initiator can be used. For example, in addition to polymerization initiators such as fluorenylphosphine oxides, acetophenones, propiophenones, benzophenones, benzoin, diphenyl ketones, oxazepines, etc., there are also cationic systems. Photopolymerization initiator and the like. Specifically, a material exemplified as a coating liquid for forming a transparent film can be used.

The solid content concentration of the polymerization initiator in the coating liquid for forming an antireflection layer varies depending on the kind of the matrix-forming component, and is preferably 0.1 to 20% by weight, more preferably 0.5 to 5% to the matrix-forming component. A range of 10% by weight.

When the content of the polymerization initiator is less than 0.1% by weight of the matrix-forming component represented by the solid content, the hardening of the antireflection layer becomes insufficient. When it is more than 20% by weight of the matrix-forming component, the stability of the coating liquid becomes insufficient.

The solvent to be used in the coating liquid is not particularly limited as long as it can disperse or dissolve the matrix-forming component, the polymerization initiator, and uniformly disperse the cerium oxide-based hollow particles (A) and the second cerium oxide-based particles (B). A conventionally known solvent can be used. Specifically, water is exemplified in addition to the solvent exemplified as the organic solvent for forming a transparent film.

The coating liquid has a total solid content concentration of preferably from 1 to 10% by weight, more preferably from 1.5 to 8% by weight. When the total solid content concentration is less than 1% by weight, it is difficult to adjust the film thickness, and uneven coating and uneven drying may occur. When the total solid content concentration is more than 10% by weight, the film thickness of the antireflection film becomes too thick, and sufficient optical characteristics and antireflection ability cannot be obtained, and control of the film thickness is difficult, surface smoothness is low, and strength and hardness are likely to be lowered. After that.

The concentration of the cerium oxide-based hollow particles (A) in the coating liquid is preferably 0.25 to 9% by weight, more preferably 0.35 to 8% by weight, based on the solid content, and the solid concentration is less than 0.25% by weight. The adhesion to the underlying transparent film, the film strength, the surface flatness, the scratch resistance, the scratch resistance, and the like are insufficient, and the refractive index of the antireflection layer cannot be lowered, and the antireflection performance is insufficient. When the solid content concentration is more than 9% by weight, not only the particles are too large, but also the strength, scratch resistance, scratch resistance, and the like of the antireflection layer are insufficient, and the haze value is also high.

In the case of using the second cerium oxide-based particles (B), coating The liquid has a total solid content concentration of preferably from 0.25 to 9% by weight. Further, the proportion of the second cerium oxide-based particles in all the cerium oxide-based particles is preferably 30% by weight, and more preferably 20% by weight or less.

When the second cerium oxide-based particles are contained in such a range, the second cerium oxide-based particles are present in the particle gap of the cerium oxide-based hollow particles in the surface portion of the obtained anti-reflective layer to planarize the surface. Thereby, an antireflection layer excellent in scratch resistance and scratch resistance can be obtained. Further, since the refractive index of the second cerium oxide-based particles is lower than that of the matrix-forming component, the refractive index of the antireflection layer can be lowered, and a film having better antireflection performance can be obtained.

The concentration of the matrix-forming component in the coating liquid, which is represented by a solid content, is preferably from 0.75 to 9.5% by weight, more preferably from 0.75 to 8% by weight. When the concentration of the solid component is less than 0.75% by weight, the particle of the matrix is too large, and the strength, scratch resistance, scratch resistance, and the like of the antireflection layer are insufficient, and the haze value of the antireflection layer or the film is also increased. Becomes high. When the solid content concentration is more than 9.5% by weight, the particles of the matrix are too small, and not only the adhesion to the transparent film, the film strength, the surface flatness, the scratch resistance, the scratch resistance, etc., but also the antireflection layer are insufficient. The refractive index cannot be lowered, and the antireflection performance becomes insufficient.

Method for producing film-attached substrate having anti-reflection layer

Next, a method of producing a film-attached substrate having an antireflection layer will be described. An antireflection layer is formed on the transparent film formed on the surface of the resin substrate. That is, a coating liquid for forming an antireflection layer is applied onto the transparent film, dried, and then cured to form an antireflection layer. At this time, the resin substrate on which the transparent film is formed has excellent curl characteristics.

The coating method of the coating liquid is, for example, the same method as the printing method of the coating liquid for a transparent film. In the drying step, any method can be used as long as the solvent of the coating liquid can be removed. It is usually dried by heating at a temperature of 60 to 120 ° C for several minutes. After drying, it is irradiated with ultraviolet rays, heat treated, or used together to harden it.

Alternatively, the transparent film and the antireflection layer can be simultaneously hardened. In other words, the coating liquid for forming a transparent film is applied and dried, and then the coating liquid for forming an antireflection layer is applied thereon, dried, and then irradiated with ultraviolet rays to simultaneously cure the two coating liquids.

(Example)

Hereinafter, an example in which cerium oxide particles are used as the metal oxide particles will be specifically described. The transparent film obtained in this example has a function as a hard coat film. Furthermore, the invention is not limited to the embodiments.

[Example 1]

Γ- mixed in yttrium oxide sol dispersion (made by Catalyst Chemical Co., Ltd.; Cataloid SI-30; average particle size 12 nm, SiO ₂ concentration 40.5 wt%, dispersion medium: isopropanol, particle refractive index 1.46) Methyl propylene methoxy propyl trimethoxy decane 7.48 g (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO ₂ component: 81.2%), 3.1 g of ultrapure water was added, and stirred at 50 ° C for 6 hours. Thus, a 12 nm cerium oxide sol dispersion (solid content concentration: 40.5 wt%) surface-treated with a decane coupling agent was obtained.

Then, the dispersion medium was replaced with PGME (propylene glycol monomethyl ether) by a rotary evaporator to prepare a cerium oxide particle (1) dispersion having a solid concentration of 40.5 wt%.

To 2,500 g of the cerium oxide particle (1) dispersion, a dimethylol-tricyclodecane diacrylate as a monomer of the ultraviolet curable resin of the first organic resin (manufactured by Kyoeisha Chemical Co., Ltd.; Light) Acrylate DCP-A, functional group: acrylate, number of functional groups: 2, molecular weight: 219, solid content concentration: 100%) 202.5 g. Further, the resin has two hydrophilic groups. Then, a part of the solvent was removed using a rotary evaporator to prepare an organic resin dispersion (1) of cerium oxide particles having a solid concentration of 76.0% by weight (further, in the examples, the first organic resin was used as an organic resin for dispersion) (A), the second organic resin is used as the organic resin (B) for curing.

Preparation of coating liquid (1)

Then, 75.31 g of the organic resin dispersion (1) was mixed with an amine ester acrylate as an organic resin for curing (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Oligo UA-33H, functional group: amine ester acrylate, functional group) Number of base: 9, molecular weight: 4000, solid content concentration: 100%) 8.32g, acrylic polyfluorene-based leveling agent (manufactured by Nanben Chemical Co., Ltd.; DISPARLON NSH-8430HF) 1.00g, photopolymerization initiator (CHIBA JAPAN) (Production) (Irgacure 184) 0.50 g, PGME 2.37 g, and acetone 12.50 g, and a coating liquid (1) for forming a transparent film having a solid concentration of 66.1% by weight was obtained. The composition of the obtained coating liquid (1) is shown in Table 2.

Fabrication of film-attached substrate (1)

The coating liquid (1) was applied to a TAC film (FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51) by a bar coating method #16, and dried at 80 ° C for 120 seconds. The film thickness of the coating film was 12 μm.

Then, ultraviolet rays of 300 mJ/cm ² were irradiated in an N ₂ atmosphere to cure the coating film, and a transparent film was formed on the substrate, and the film thickness of the transparent film was 12 μm. Such a transparent film system functions as a hard coat film. The obtained film-attached substrate (1) was subjected to the following evaluation, and the results are shown in Table 2 and Table 3.

Shrinkage

The volume shrinkage ratio (shrinkage ratio (a)) from the coating material to dryness, the volume shrinkage ratio (shrinkage ratio (b)) by UV curing, and the overall shrinkage ratio (shrinkage ratio (c)) were calculated. First, the density (specific gravity) of the coating liquid was measured. The coating liquid was applied by coating with a coating film so as to have a film thickness after drying of about 10 μm, and then dried at 80 ° C for 2 minutes to prepare a dried film. A part of the dried film was collected, and the density (specific gravity) was measured. The shrinkage ratio (a) was calculated by the above formula (A). Then, the dried film was subjected to UV irradiation to harden it. A part of the cured transparent film was collected, and the density (specific gravity) of the cured film was measured. The shrinkage ratio (b) was calculated by the above formula (B). Furthermore, the shrinkage ratio (c) was calculated by the above formula (C).

Full light transmittance and haze

The film-attached substrate was measured by a haze meter (manufactured by SUGA Tester Co., Ltd.). Further, the refractive index of the transparent film was measured by an ellipsometer (manufactured by ULVAC, EMS-1). Further, the uncoated TAC film had a total light transmittance of 93.2%, a haze of 0.2%, and a light reflectance of 6.0% at a wavelength of 550 nm.

Crack

Observe the presence or absence of cracks.

Curl

Curl test method: will be applied to a TAC film of 14 cm × 25 cm size The film of the transparent film was stored for 20 hours. The film was cut into a size of 10 cm x 10 cm. The film was placed with the coated surface as below, and the height A of the substrate from the bottom surface was measured.

Pencil hardness

It was measured by a pencil hardness tester in accordance with JIS-K-5600.

Scratch resistance

Using #0000 steel wool, the film was slid 10 times with a load of 2 kg/cm ² , and the surface of the film was visually observed and evaluated by the following criteria.

Evaluation criteria:

Unable to confirm the rib scars: ◎

Slightly confirmed rib scars: ○

Confirmed many rib scars: △

The whole face is cut off: ×

[Embodiment 2]

Preparation of coating liquid (2)

Then, 80.38 g of the organic resin dispersion (1) of the cerium oxide particles prepared in Example 1 was sufficiently mixed with an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as a curing organic resin (8.88 g). 0.02 g of a polyacrylic acid-based leveling agent (DISPARLON NSH-8430HF identical to Example 1), a photopolymerization initiator (Irgacure 184 which is the same as in Example 1), 0.53 g, PGME 0.21 g, and acetone 9.0 g, The coating liquid (2) having a solid content concentration of 70.6% by weight was adjusted. The composition of the obtained coating liquid (2) is shown in Table 2.

Production of film-attached substrate (2)

The same procedure as in Example 1 was carried out except that the coating liquid (2) was used. Film substrate (2). The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Example 3]

In the same manner as in Example 1, a dispersion of cerium oxide particles (1) having a solid concentration of 40.5% by weight was produced. To 2,500 g of the cerium oxide particle (1) dispersion, 202.5 g of dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) as an organic resin for dispersion was added, and rotary evaporation was used. A part of the solvent was removed to prepare an organic resin dispersion (3) of cerium oxide particles having a solid concentration of 85.0% by weight.

Preparation of coating liquid (3)

In the organic resin dispersion (3), 79.99 g, 9.00 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as an organic resin for curing was sufficiently mixed, and a polyacrylic acid-based leveling agent ( Nanben Chemical Co., Ltd.; DISPARLON NSH-8430HF) 1.00 g, photopolymerization initiator (CHIBA JAPAN Co., Ltd.; Irgacure 184) 0.59 g, PGME 0.51 g, and acetone 8.00 g, and the solid content concentration was 78.7 wt%. Coating solution (3).

Production of film-attached substrate (3)

A film-attached substrate (3) was produced in the same manner as in Example 1 except that the coating liquid (3) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Example 4]

To 2,500 g of the cerium oxide particle (1) dispersion prepared in Example 1, dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) as a dispersing organic resin was added. g, use spin A part of the solvent was removed by a rotary evaporator to prepare an organic resin dispersion (4) of cerium oxide particles having a solid concentration of 72.1% by weight.

Preparation of coating liquid (4)

In the 66.61 g of the organic resin dispersion (4), 10.98 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as a curing organic resin was sufficiently mixed, and a polyacrylic acid-based leveling agent ( The same DISPARLON NSH-8430HF) 1.00 g as in Example 1, a photopolymerization initiator (Irgacure 184 same as in Example 1) 0.70 g, PGME 8.21 g, and acetone 12.50 g, and the coating having a solid content concentration of 66.1% by weight was adjusted. Liquid (4).

Production of film-attached substrate (4)

A film-attached substrate (4) was produced in the same manner as in Example 1 except that the coating liquid (4) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Example 5]

To 2500 g of the cerium oxide particle (1) dispersion prepared in Example 1, dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) 153.0 as an organic resin for dispersion was added. g, a part of the solvent was removed using a rotary evaporator to prepare an organic resin dispersion (5) of cerium oxide particles having a solid concentration of 72.3 wt%.

Preparation of coating liquid (5)

81.94 g of the organic resin dispersion liquid (5), 6.27 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1), and a polyacrylic acid-based leveling agent (for the example) 1 identical DISPARLON NSH-8430HF) 1.00 g, photopolymerization initiator (with Example 1 The same Irgacure 184) 0.46 g, PGME 0.33 g, and acetone 10.00 g were thoroughly mixed to prepare a coating liquid (5) having a solid concentration of 66.1% by weight.

Production of film-attached substrate (5)

A film-attached substrate (5) was produced in the same manner as in Example 1 except that the coating liquid (5) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Embodiment 6]

To 2500 g of the cerium oxide particle (1) dispersion prepared in Example 1, dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) was added as a dispersing organic resin 85.8 g. g, a part of the solvent was removed using a rotary evaporator to prepare an organic resin dispersion (6) of cerium oxide particles having a solid concentration of 69.0% by weight.

Preparation of coating liquid (6)

Then, in the 75.31 g of the organic resin dispersion (6), an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as a curing organic resin was sufficiently mixed with 12.15 g of acrylic acid polyfluorene-based leveling. 1.00 g of the same agent (DISPARLON NSH-8430HF as in Example 1), photopolymerization initiator (Irgacure 184 same as in Example 1), 0.50 g, PGME 2.04 g, and acetone 9.00 g, to obtain a solid content concentration of 66.1% by weight. Coating solution (6).

Production of film-attached substrate (6)

A film-attached substrate (6) was produced in the same manner as in Example 1 except that the coating liquid (6) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Embodiment 7]

To 2,500 g of the cerium oxide particle (1) dispersion prepared in Example 1, dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) 272.1 as an organic resin for dispersion was added. g, a part of the solvent was removed using a rotary evaporator to obtain an organic resin dispersion (7) of cerium oxide particles having a solid concentration of 80.1% by weight.

Preparation of coating liquid (7)

Then, in the 75.31 g of the organic resin dispersion (7), 5.21 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as an organic resin for curing was sufficiently mixed, and polyacrylonitrile-based polysilicon was leveled. 1.00 g of the same agent (DISPARLON NSH-8430HF as in Example 1), photopolymerization initiator (Irgacure 184 same as in Example 1), 0.50 g, PGME 5.48 g, and acetone 12.50 g, to give a solid concentration of 66.1% by weight. Coating solution (7).

Production of film-attached substrate (7)

A film-attached substrate (7) was produced in the same manner as in Example 1 except that the coating liquid (7) was used. The film thickness of the transparent film was 12 μm. This film-attached substrate was evaluated in the same manner as in Example 1.

[Embodiment 8]

To 2,500 g of the cerium oxide particle (1) dispersion prepared in Example 1, 1,6-hexanediol dimethacrylate (manufactured by Ba Industrial Co., Ltd.; SR-238F, functional group) was added as an organic resin for dispersion. : acrylate, number of functional groups: 2, molecular weight: 226) 202.5 g, a part of the solvent was removed using a rotary evaporator to obtain an organic resin dispersion (8) of cerium oxide particles having a solid concentration of 76.0% by weight.

Preparation of coating liquid (8)

Then, in the organic resin dispersion (8), 75.31 g, an amine ester acrylate which is an organic resin for curing (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Oligo U-6LPA, functional group: amine ester acrylate, functional group) Number of base: 6, molecular weight: 2100, solid content concentration: 70%) 11.89 g, acrylic polyfluorinated leveling agent (DISPARLON NSH-8430HF identical to Example 1) 1.00 g, photopolymerization initiator (with examples) 1 The same Irgacure 184) 0.50 g, PGME 0.30 g, and acetone 11.00 g were used to prepare a coating liquid (8) having a solid concentration of 66.1% by weight.

Production of film-attached substrate (8)

A film-attached substrate (8) was produced in the same manner as in Example 1 except that the coating liquid (8) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Embodiment 9]

Γ-methacryloxypropyltrimethoxydecane (the same KBM-503 as in Example 1) was mixed with 3.74 g of 100 g of a cerium oxide sol dispersion (the same Cataloid SI-30 as in Example 1). 3.1 g of ultrapure water was added and stirred at 50 ° C for 6 hours. Thus, a 12 nm cerium oxide sol dispersion (solid content concentration: 40.5 wt%) surface-treated with a decane coupling agent was obtained.

Then, in the same manner as in Example 1, solvent substitution was carried out to prepare a dispersion of cerium oxide particles (9) having a solid concentration of 40.5% by weight.

To 2500 g of the cerium oxide particle (9) dispersion, 202.5 g of dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) as an organic resin for dispersion was added, and rotary evaporation was used. Remove a part of the solvent to obtain a solid concentration of 76.0% by weight An organic resin dispersion of cerium oxide particles (9).

Preparation of coating liquid (9)

Then, in the 75.31 g of the organic resin dispersion (9), 8.32 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as an organic resin for curing was sufficiently mixed, and polyacrylonitrile-based polysilicon was leveled. 1.00 g of the same agent (DISPARLON NSH-8430HF as in Example 1), photopolymerization initiator (Irgacure 184 same as in Example 1) 0.50 g, PGME 2.37 g, and acetone 12.50 g, and a solid content concentration of 63.9 wt% was produced. Coating solution (9).

Production of film-attached substrate (9)

A film-attached substrate (9) was produced in the same manner as in Example 1 except that the coating liquid (9) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Embodiment 10]

Into 100 g of a cerium oxide sol dispersion (the same Cataloid SI-30 as in Example 1), 14.96 g of γ-methacryloxypropyltrimethoxydecane (the same KBM-503 as in Example 1) was mixed. 3.1 g of ultrapure water was added and stirred at 50 ° C for 6 hours. Thus, a 12 nm cerium oxide sol dispersion (solid content concentration: 40.5 wt%) surface-treated with a decane coupling agent was obtained.

Then, solvent substitution was carried out in the same manner as in Example 1 to obtain a dispersion of cerium oxide particles (10) having a solid concentration of 40.5% by weight.

To 2500 g of the cerium oxide particle (10) dispersion, 202.5 g of dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) as an organic resin for dispersion was added, and rotary evaporation was used. Remove a portion of the solvent to produce a solids concentration of 76.0% by weight An organic resin dispersion (10) of cerium oxide particles.

Preparation of coating liquid (10)

Then, in the organic resin dispersion (10), 75.31 g, 8.32 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as an organic resin for curing was sufficiently mixed, and polyacrylonitrile-based polysilicon was leveled. 1.00 g of the same agent (DISPARLON NSH-8430HF as in Example 1), photopolymerization initiator (Irgacure 184 same as in Example 1), 0.50 g, PGME 2.37 g, and acetone 12.50 g, to obtain a solid concentration of 70.6 wt%. Coating solution (10).

Production of film-attached substrate (10)

A film-attached substrate (10) was produced in the same manner as in Example 1 except that the coating liquid (10) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Example 11]

Γ-acryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-5103, SiO ₂ component 86.1) was mixed with 100 g of the cerium oxide sol dispersion (the same Cataloid SI-30 as in Example 1). %) 7.06 g, 3.1 g of ultrapure water was added and stirred at 50 ° C for 6 hours. Thus, a 12 nm cerium oxide sol dispersion (solid content concentration: 40.5 wt%) surface-treated with a decane coupling agent was obtained.

Then, solvent substitution was carried out in the same manner as in Example 1 to obtain a dispersion of cerium oxide particles (11) having a solid concentration of 40.5% by weight.

To 2500 g of the cerium oxide particle (11) dispersion, 202.5 g of dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) as an organic resin for dispersion was added, and rotary evaporation was used. A part of the solvent was removed to obtain an organic resin dispersion (11) of cerium oxide particles having a solid concentration of 76.0% by weight.

Preparation of coating liquid (11)

Then, in the 75.31 g of the organic resin dispersion (11), 8.32 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as an organic resin for curing was sufficiently mixed, and polyacrylonitrile-based polysilicon was leveled. 1.00 g of the same agent (DISPARLON NSH-8430HF as in Example 1), photopolymerization initiator (Irgacure 184 same as in Example 1), 0.50 g, PGME 2.37 g, and acetone 12.50 g, to obtain a solid concentration of 66.1% by weight. Coating solution (11).

Production of film-attached substrate (11)

A film-attached substrate (11) was produced in the same manner as in Example 1 except that the coating liquid (11) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Embodiment 12]

An aqueous solution of sodium citrate having a SiO ₂ concentration of 24% by weight (SiO ₂ /Na ₂ O molar ratio of 3.1) 33.4 Kg was diluted with pure water 126.6 Kg to prepare an aqueous solution of sodium citrate having a SiO ₂ concentration of 5% by weight ( pH 11) 160 Kg. A 25% sulfuric acid aqueous solution was added to neutralize the pH of the sodium citrate aqueous solution to 4.5, and it was kept at normal temperature for 5 hours. Thereby, the cerium oxide hydrogel was obtained by aging it.

The cerium oxide hydrogel was sufficiently washed with pure water equivalent to about 120 times the solid content of SiO ₂ using a filter cloth coated with a filter cloth, and the cerium oxide hydrogel was dispersed in pure water to prepare SiO _{2 .} The dispersion having a concentration of 3% by weight was stirred with a strong agitator until it became a fluid mud state. A 15% by weight aqueous ammonia solution was added to adjust the pH of the slurry-like cerium oxide hydrogel dispersion to 10.5, and stirring was continued at 95 ° C for 1 hour to carry out a degumming operation of the cerium oxide hydrogel to obtain a cerium oxide sol. .

After the obtained cerium oxide sol was heated at 150 ° C for 1 hour to stabilize it, it was concentrated using an ultrafiltration membrane (made by Asahi Kasei Kogyo Co., Ltd.: SIP-1013) until the SiO ₂ concentration became 13% by weight. Further, the mixture was concentrated using a rotary evaporator, and filtered through a nylon filter of 44 μm mesh to prepare a cerium oxide sol (12) having a SiO ₂ concentration of 30% by weight.

At this time, the cerium oxide particles of the cerium oxide sol (12) had an average particle longest diameter (D _L ) of 48 nm, an average short diameter (D _S ) of 16 nm, and a spherical coefficient of 0.33.

600 g of mixed cerium oxide sol (12), 5955 g of pure water, and 63.3 g of sodium citrate aqueous solution (SiO ₂ /Na ₂ O molar ratio of 3.1) having a SiO ₂ concentration of 24% by weight, and the temperature was raised to 87 ° C, and the mixture was aged for 0.5 hour. . Then, 1120 g of a citric acid solution having a SiO ₂ concentration of 3% by weight was added over 14 hours. After cooling to room temperature, the obtained cerium oxide sol was concentrated using an ultrafiltration membrane (made by Asahi Kasei Kogyo Co., Ltd.: SIP-1013) until the SiO ₂ concentration became 12% by weight. Further, the mixture was filtered through a nylon filter of 44 μm mesh using a rotary evaporator to prepare a dispersion (12) of non-spherical cerium oxide having a solid concentration of 30% by weight.

In the dispersion (12), pure water was added to have a solid concentration of 20% by weight, and 240 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DIAION SK1B) was used, and washed at 80 ° C for 3 hours, and then used. The ultrafiltration membrane was replaced with methanol by the solvent of the dispersion to prepare a methanol dispersion having a solid concentration of 20% by weight.

To 100 g of the methanol dispersion, 7.48 g of a decyl methacrylate coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503, γ-methacryloxypropyltrimethoxydecane) was added, and the mixture was stirred at 50 ° C. After hours, a non-spherical cerium oxide dispersion (solid content concentration: 40.5 wt%) surface-treated with an organic cerium compound was obtained.

Then, in the same manner as in Example 1, solvent substitution was carried out to obtain a dispersion of non-spherical cerium oxide particles (12) having a solid concentration of 40.5% by weight. The non-spherical cerium oxide particles (12) had an average particle longest diameter (D _L ) of 50 nm, an average short diameter (D _S ) of 21 nm, and a spherical coefficient (D _S )/(D _L ) of 0.42.

Preparation of coating liquid (12)

To 2,500 g of the cerium oxide particle (12) dispersion, 202.5 g of dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) as an organic resin for dispersion was added, and rotation was used. The evaporator removed a part of the solvent to prepare an organic resin dispersion (12) of cerium oxide particles having a solid concentration of 76.0% by weight.

75.31 g of the organic resin dispersion (12), and 8.32 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as an organic resin for curing, and a polyacrylic acid-based leveling agent (with In the same manner as in Example 1, the same DISPARLON NSH-8430HF) 1.00 g, a photopolymerization initiator (Irgacure 184 identical to Example 1) 0.50 g, PGME 2.37 g, and acetone 12.50 g were used to prepare a coating liquid having a solid concentration of 66.1% by weight. (12).

Fabrication of film-attached substrate (12)

A film-attached substrate (12) was produced in the same manner as in Example 1 except that the coating liquid (12) was used. The film thickness of the transparent film was 12 μm. The film substrate Evaluation was performed in the same manner as in Example 1.

[Example 13]

Production of film-attached substrate (13)

The coating liquid (1) prepared in Example 1 was applied to a substrate using a bar coating method #20 to prepare a film-attached substrate (13). Except for the coating method, the same procedure as in Example 1 was carried out. The film thickness of the obtained transparent film was 15 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Embodiment 14]

Production of film-attached substrate (14)

The coating liquid (1) prepared in Example 1 was applied to a substrate by a bar coating method #40 to prepare a film-attached substrate (14). Except for the coating method, the same procedure as in Example 1 was carried out. The film thickness of the obtained transparent film was 30 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Comparative Example 1]

In 2500 g of the cerium oxide particle (1) dispersion prepared in the same manner as in Example 1, dimethylol-tricyclodecane diacrylate as a dispersing organic resin was added (the same Light Acrylate as in Example 1) DCP-A) 202.5 g, a part of the solvent was removed using a rotary evaporator, and an organic resin dispersion liquid (R1) of cerium oxide particles having a solid concentration of 76.0% by weight was produced.

Preparation of coating liquid (R1)

Then, 75.31 g of the organic resin dispersion (R1) was further mixed with dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) as an organic resin for dispersion (8.32 g). Acrylic polyfluorene-based leveling agent (the same DISPARLON NSH-8430HF as in Example 1) 1.00 g of a photopolymerization initiator (Irgacure 184 similar to Example 1) 0.50 g, PGME 2.37 g, and acetone 12.50 g were used to prepare a coating liquid (R1) having a solid concentration of 66.1% by weight.

Production of film-attached substrate (R1)

A film-attached substrate (R1) was produced in the same manner as in Example 1 except that the coating liquid (R1) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Comparative Example 2]

To 2500 g of the cerium oxide particle (1) dispersion prepared in the same manner as in Example 1, 202.5 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as a curing organic resin was added and used. A part of the solvent was removed by a rotary evaporator to prepare an organic resin dispersion (R2) of cerium oxide particles having a solid concentration of 53.3 wt%.

Preparation of coating liquid (R2)

Then, in the 82.96 g of the organic resin dispersion (R2), 1.00 g of a polyacrylic acid-based leveling agent (DISPARLON NSH-8430HF similar to that of Example 1) and a photopolymerization initiator (Comparative Example 1) were sufficiently mixed. The same Irgacure 184) 0.50 g, PGME 0.13 g, and acetone 9.00 g were used to obtain a coating liquid (R2) having a solid concentration of 51.0% by weight.

Fabrication of film-attached substrate (R2)

A film-attached substrate (R2) was produced in the same manner as in Example 1 except that the coating liquid (R2) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Comparative Example 3]

Modulation of coating liquid (R3) for forming a transparent film

69.14 g of a cerium oxide particle (1) dispersion prepared in the same manner as in Example 1 and a dimethylol-tricyclodecane diacrylate of an organic resin for dispersion (the same Light Acrylate DCP as in Example 1) A) 5.26 g, an amine ester acrylate of an organic resin for hardening (the same NK Oligo UA-33H as in Example 1) 4.83 g, a polyoxymethylene-based leveling agent (the same DISPARLON NSH-8430HF as in Example 1) 1.00 g, a photopolymerization initiator (Irgacure 184 which is the same as in Example 1), 0.29 g, PGME 6.99 g, and acetone 12.50 g were sufficiently mixed to prepare a coating liquid (R3) having a solid concentration of 41.4% by weight.

Fabrication of film-attached substrate (R3)

A film-attached substrate (R3) was produced in the same manner as in Example 1 except that the coating liquid (R3) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

[Comparative Example 4]

To 2500 g of a cerium oxide sol dispersion (the same Cataloid SI-30 as in Example 1), dimethylol-tricyclodecane diacrylate as a dispersing organic resin was added (the same Light Acrylate DCP as in Example 1) -A) 202.5 g, a part of the solvent was removed using a rotary evaporator to obtain an organic resin dispersion (RA4) of cerium oxide particles having a solid concentration of 53.3% by weight.

Preparation of coating liquid (R4)

In the 75.31 g of the organic resin dispersion (RA4), 7.19 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as an organic resin for curing was sufficiently mixed, and a polyoxymethylene-based leveling agent ( Same as in the first embodiment DISPARLON NSH-8430HF) 1.00 g, a photopolymerization initiator (Irgacure 184 similar to Example 1) 0.50 g, PGME 0.83 g, and acetone 8.00 g were used to prepare a coating liquid (R4) having a solid concentration of 53.3% by weight.

Fabrication of film-attached substrate (R4)

A film-attached substrate (R4) was produced in the same manner as in Example 1 except that the coating liquid (R4) was used. The film thickness of the transparent film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 1.

Hereinafter, an embodiment in which the antireflection layer is formed on the transparent film will be specifically described. A transparent film as a hard coat film will be described in the following examples.

[Example 15]

Adding cation exchange resin to cerium oxide sol dispersion (made by Catalyst Chemical Co., Ltd.; Cataloid SI-50; average particle size 25 nm, SiO ₂ concentration 48.0% by weight, dispersion medium: water, particle refractive index 1.46) 1000 g (Mitsubishi Chemical Co., Ltd.: SK-1BH) 960 g and stirred for 30 minutes, the cation exchange resin was separated. Then, 480 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SA-20A) was added and stirred for 30 minutes, and then the anion exchange resin was separated. Then, 480 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added and stirred for 5 minutes, and then aged at 80 ° C for 3 hours to be cooled to room temperature, and then the cation exchange resin was separated. Thereby, an aqueous dispersion of cerium oxide sol having a concentration of 48% by weight was obtained.

2000 g of this aqueous cerium oxide sol dispersion was replaced with methanol by an ultrafiltration membrane to prepare a cerium oxide sol methanol dispersion having a SiO ₂ concentration of 40% by weight.

Into 100 g of the dispersion, 7.48 g of γ-methylpropenyloxypropyltrimethoxydecane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO ₂ component: 81.2%) was added, and 3.1 g of ultrapure water was added. Stir at 50 ° C for 6 hours. Thereby, a 25 nm cerium oxide sol dispersion (solid content concentration: 40.5 wt%) surface-treated with a decane coupling agent was obtained.

This dispersion was replaced with PGME in the same manner as in Example 1 to obtain a cerium oxide particle (15) dispersion. To the dispersion of the cerium oxide particles (15), 202.5 g of dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) as an organic resin for dispersion was added, and rotary evaporation was used. A part of the solvent was removed to prepare an organic resin dispersion (15) of cerium oxide particles (15) having a solid concentration of 76.0% by weight.

Preparation of coating liquid (15) for forming a hard coating film

Then, in the 75.31 g of the organic resin dispersion (15), 8.32 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as an organic resin for curing was sufficiently mixed, and polyacrylonitrile-based polysilicon was leveled. Agent (with examples 1 same DISPARLON NSH-8430HF) 1.00 g, photopolymerization initiator (Irgacure 184 same as in Example 1) 0.50 g, PGME 2.37 g, and acetone 12.50 g, to obtain a coating liquid having a solid concentration of 66.1% by weight (15) ). The composition of the coating liquid (15) is shown in Tables 4 and 5.

Modulation of cerium oxide hollow particle (A15) dispersion

A mixture of 5.0 g of a cerium oxide sol (manufactured by a cyclization to a catalyst; SI-550, an average particle diameter of 5 nm, a SiO ₂ concentration of 20% by weight) and 999.5 g of pure water was heated to 80 ° C to maintain the temperature. In the case, 1575 g of an aqueous solution of sodium citrate having a concentration of SiO ₂ of 3.0% by weight and 1575 g of an aqueous solution of sodium aluminate having a concentration of 1.5% by weight of Al ₂ O _{3 were} added to obtain SiO ₂ . Al ₂ O ₃ primary particle dispersion. At this time, the molar ratio MO _X /SiO ₂ (A) = 0.25, and the average particle diameter was 13 nm. Further, the pH of the reaction liquid was 12.0.

Then, 8370 g of an aqueous solution of sodium citrate having a concentration of SiO ₂ of 3.0% by weight and 2790 g of an aqueous solution of sodium aluminate having a concentration of 1.5% by weight of Al ₂ O _{3 were} added to obtain dispersion of composite oxide particles (secondary particles). liquid.

At this time, the molar ratio MO _X /SiO ₂ (B) = 0.13, and the average particle diameter was 30 nm. Further, the pH of the reaction liquid was 12.0.

Then, the dispersion liquid of the composite oxide particles was washed with an ultrafiltration membrane to a solid concentration of 13% by weight, and 1125 g of pure water was added to 500 g of the dispersion, and concentrated hydrochloric acid (concentration: 35.5 wt%) was added thereto to form a pH of 1.0. De-aluminum treatment is carried out. Then, while dissolving and washing the dissolved aluminum salt with an ultrafiltration membrane while adding 10 L of a hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, an aqueous dispersion of cerium oxide-based hollow particles having a solid concentration of 20% by weight was produced.

Adding ammonia water to the aqueous dispersion to adjust the pH of the dispersion After 1 hour, it was aged at 200 ° C for 11 hours, cooled to room temperature, and subjected to ion exchange for 3 hours using a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DIAION SK1B), and then anion exchange resin (Mitsubishi Chemical Co., Ltd.) ): 200 g of SA20A) was ion-exchanged for 3 hours, and 200 g of cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DIAION SK1B) was used, and ion exchange was performed at 80 ° C for 3 hours to wash to obtain a solid content concentration of 20% by weight. An aqueous dispersion of cerium oxide hollow particles.

Further, an ultrafiltration membrane was used, and a solvent was substituted for methanol to prepare a methanol dispersion liquid of cerium oxide-based hollow particles having a solid concentration of 20% by weight. The average particle diameter and refractive index of the obtained cerium oxide-based hollow particles were measured, and the results are shown in the table.

Then, 3.7 g of a methacrylic acid decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was added to 100 g of a methanol dispersion of cerium oxide-based hollow particles having a solid concentration of 20% by weight, and heated at 50 ° C. The surface treatment of the cerium oxide-based hollow particles was carried out, and the solvent was replaced with MIBK using a rotary evaporator to prepare a MIBK dispersion of the surface-treated cerium oxide-based hollow particles (A15) having a solid concentration of 20.5% by weight. The refractive index of the cerium oxide-based hollow particles (A15) was measured, and the results are shown in the table.

Preparation of coating liquid for forming anti-reflection layer (15L)

Into 8.05 g of the dispersion of the cerium oxide-based hollow particles (A15), diheptaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.: DPE-6A, solid content concentration: 100% by weight), 1.07 g, was mixed. 1,6-hexanediol diacrylate (manufactured by Ba Industrial Co., Ltd.; SR-238F, solid content concentration: 100% by weight) 0.12 g, reactive eucalyptus for water-repellent materials (Shin-Etsu Chemical Co., Ltd.: X- 22-174DX, solid into Partial concentration: 100% by weight) 0.05 g, hydrazine-modified polyurethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.; Violet UT-4314: solid concentration: 30% by weight) 0.37 g, photopolymerization initiator (BASF JAPAN) Preparation: LUCIRIN TPO, solid content concentration: 100% by weight, 0.09 g, isopropyl alcohol, 64.65 g, methyl isobutyl ketone, 9.60 g, and isopropyl glycol, 16.00 g, to prepare a coating liquid (15 L) having a solid concentration of 3.0% by weight. .

Production of hard coating substrate (15)

The film-attached substrate (15) was produced in the same manner as in Example 1 using the coating liquid (15) for forming a hard coating film. The film thickness of the hard coat film was 12 μm.

The obtained film base material (15) was evaluated for total light transmittance, haze, crack, shrinkage, curling property, pencil hardness, and scratch resistance in the same manner as in Example 1. Further, the surface roughness (Ra) was measured by an atomic force microscope (manufactured by Bruker Co., Ltd.: Dimension-3100) at 10 μm × 10 μm. The results are shown in Table 11.

Antireflection layer formation

The coating liquid for forming an antireflection layer (15 L) was applied onto the hard coat film of the film-attached substrate (15) by a bar coating method (rod #4), dried at 80 ° C for 120 seconds, and then irradiated under an N ₂ atmosphere. The ultraviolet rays of 400 mJ/cm ² were hardened to form an antireflection layer. The thickness of the antireflection layer at this time was 100 nm.

The total light transmittance, haze, reflectance, crack, pencil hardness, and scratch resistance of the film-attached substrate having the antireflection layer were evaluated in the same manner as the hard coat film substrate (15). Further, the refractive index was measured by an ellipsometer (manufactured by ULVAC, EMS-1). The results are shown in Table 12.

[Example 16]

Modulation of cerium oxide hollow particle (A16) dispersion

A mixture of 5.0 g of a cerium oxide sol (manufactured by a cyclization to a catalyst; SI-550, an average particle diameter of 5 nm, a SiO ₂ concentration of 20% by weight) and 999.5 g of pure water was heated to 80 ° C to maintain the temperature. In the case, 650 g of an aqueous solution of sodium citrate having a concentration of SiO ₂ of 3.0% by weight and 650 g of an aqueous solution of sodium aluminate having a concentration of 1.5% by weight of Al ₂ O _{3 were} added to obtain primary particle dispersion of SiO ₂ and Al ₂ O _{3 .} liquid. At this time, the molar ratio MO _X /SiO ₂ (A) = 0.24, and the average particle diameter was 13 nm. Further, the pH of the reaction liquid at this time was 12.0.

Then, 2940 g of an aqueous solution of sodium citrate having a concentration of SiO ₂ of 3.0% by weight and 980 g of an aqueous solution of sodium aluminate having a concentration of 1.5% by weight of Al ₂ O _{3 were} added to obtain dispersion of composite oxide particles (secondary particles). liquid. At this time, the molar ratio MO _X /SiO ₂ (B) = 0.13, and the average particle diameter was 20 nm. Further, the pH of the reaction liquid at this time was 12.0.

Then, by the same process as in Example 15, the dealuminization treatment, the washing by the ultrafiltration membrane, and the washing by ion exchange were carried out to obtain water of cerium oxide-based hollow particles having a solid concentration of 20% by weight. Dispersions.

Further, the same procedure as in Example 15 was carried out to prepare a MIBK dispersion of surface-treated cerium oxide-based hollow particles (A16) having a solid concentration of 20.5% by weight. The refractive index of the cerium oxide-based hollow particles (A16) was measured, and the results are shown in the table.

Preparation of coating liquid for forming antireflection layer (16L)

A coating liquid (16 L) having a solid concentration of 3.0% by weight was prepared in the same manner as in Example 15 except that the dispersion of the cerium oxide-based hollow particles (A16) was used.

Antireflection layer formation

A hard coat film base material (16) was produced in the same manner as in Example 15. An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the above coating liquid (16 L) was used. The thickness of the antireflection layer at this time was 100 nm. The antireflection layer substrate (16) was evaluated in the same manner as in Example 15.

[Example 17]

Modulation of cerium oxide hollow particle (A17) dispersion

矽 矽 氧化铝 alumina sol (catalyzed into a chemical company: USBB-120, average particle diameter 25nm, SiO ₂ ‧ Al ₂ O ₃ concentration 20% by weight, solid content Al ₂ O ₃ content 27% by weight) A mixture of 100 g and 3900 g of pure water was heated to 98 ° C, and 405 g of an aqueous solution of sodium citrate having a concentration of SiO ₂ of 1.5% by weight and a concentration of 0.5% by weight of Al ₂ O _{3 were} added while maintaining the temperature. 405 g of an aqueous solution of sodium aluminate gave SiO ₂ . Al ₂ O ₃ primary particle dispersion. The molar ratio MO _X /SiO ₂ (A) = 0.2 at this time, and the average particle diameter was 28 nm. Further, the pH of the reaction liquid at this time was 12.0.

Then, 1607 g of an aqueous solution of sodium citrate having a concentration of 1.5% by weight of SiO ₂ and 535 g of an aqueous solution of sodium aluminate having a concentration of 0.5% by weight in terms of Al ₂ O _{3 were} added to obtain composite oxide particles (secondary particles). Dispersion. At this time, the molar ratio MO _X /SiO ₂ (B) = 0.07, and the average particle diameter was 40 nm. Further, the pH of the reaction liquid at this time was 12.0.

Then, by the same process as in Example 15, the aluminum removal treatment, the cleaning by the ultrafiltration membrane, and the ion exchange were carried out to obtain a water dispersion of the cerium oxide-based hollow particles having a solid concentration of 20% by weight. liquid.

Further, a solid component was produced by the same process as in Example 15. A MIBK dispersion of surface-treated cerium oxide-based hollow particles (A17) having a concentration of 20.5 wt%. The refractive index of the cerium oxide-based hollow particles (A17) was measured, and the results are shown in the table.

Preparation of coating liquid for forming antireflection layer (17L)

A coating liquid (17 L) having a solid concentration of 3.0% by weight was prepared in the same manner as in Example 15 except that the dispersion of the cerium oxide-based hollow particles (A17) was used.

Antireflection layer formation

A hard coat film base material (17) was produced in the same manner as in Example 15. An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the above coating liquid (17 L) was used. The thickness of the antireflection layer at this time was 100 nm. The antireflection layer substrate (17) was evaluated in the same manner as in Example 15.

[Embodiment 18]

Modulation of cerium oxide-based particles (B18) dispersion

A mixture of 5.0 g of a cerium oxide sol (manufactured by a cyclization to a catalyst; SI-550, an average particle diameter of 5 nm, a SiO ₂ concentration of 20% by weight) and 999.5 g of pure water was heated to 80 ° C to maintain the temperature. In the case, 321 g of an aqueous solution of sodium citrate having a concentration of SiO ₂ of 3.0% by weight and 321 g of an aqueous solution of sodium aluminate having a concentration of 1.5% by weight of Al ₂ O _{3 were} added to obtain SiO ₂ . Al ₂ O ₃ primary particle dispersion. At this time, the molar ratio MO _X /SiO ₂ (A) = 0.23, and the average particle diameter was 7 nm. Further, the pH of the reaction liquid at this time was 12.0.

Then, 1231 g of an aqueous solution of sodium citrate having a concentration of 3.0% by weight of SiO ₂ and 410 g of an aqueous solution of sodium aluminate having a concentration of 1.5% by weight in terms of Al ₂ O _{3 were} added to obtain composite oxide particles (secondary particles). Dispersion. At this time, the molar ratio MO _X /SiO ₂ (B) = 0.13, and the average particle diameter was 14 nm. Further, the pH of the reaction liquid at this time was 12.0.

Then, by the same process as in Example 15, the aluminum removal treatment, the cleaning by the ultrafiltration membrane, and the ion exchange were carried out to obtain a water dispersion of the cerium oxide-based hollow particles having a solid concentration of 20% by weight. liquid.

Then, in the same manner as in Example 15, a methanol dispersion liquid of cerium oxide-based hollow particles having a solid concentration of 20% by weight in which a solvent was substituted with methanol was prepared. The average particle diameter and refractive index of the cerium oxide-based hollow particles obtained here were measured, and the results are shown in the table.

Further, in the same manner as in Example 15, a MIBK dispersion of surface-treated cerium oxide-based hollow particles (B18) having a solid concentration of 20.5% by weight was produced. The refractive index of the cerium oxide-based hollow particles (B18) was measured, and the results are shown in the table.

Preparation of coating liquid for forming antireflection layer (18L)

In 7.90 g of the surface-treated cerium oxide-based hollow particle dispersion (A17) having a solid concentration of 20.5 wt% prepared in the same manner as in Example 17, a methanol having a solid content concentration of 20.5 wt% of cerium oxide-based hollow particles was mixed. Dispersion 0.15 g, dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.: DPE-6A, solid content concentration: 100% by weight) 1.07 g, 1,6-hexanediol diacrylate (BA industry (Stock) system; SR-238F, solid content concentration: 100% by weight) 0.12g, reactive eucalyptus oil for water repellency material (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-174DX, solid content concentration: 100% by weight) 0.05g , 矽 modified polyurethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.; Violet UT-4314: solid concentration 30% by weight) 0.37g, photopolymerization initiator (BASF JAPAN (Stock) system: LUCIRIN TPO, solid content concentration: 100% by weight; 0.09 g, isopropyl alcohol 64.65 g, methyl isobutyl ketone 9.60 g, and isopropyl glycol 16.00 g, and a coating liquid having a solid concentration of 3.0% by weight was prepared ( 18L).

Antireflection layer formation

A substrate (18) having an antireflection layer was produced in the same manner as in Example 15 except that the coating liquid (18 L) was used to form an antireflection layer. The thickness of the antireflection layer at this time was 100 nm. The antireflection layer substrate (18) was evaluated in the same manner as in Example 15.

[Embodiment 19]

Modulation of cerium oxide-based particles (B19) dispersion

A cation exchange resin (Mitsubishi Chemical Co., Ltd.) was added to 1000 g of a cerium oxide sol (manufactured by Nisko Catalyst Co., Ltd.; Cataloid SI-30, SiO ₂ concentration: 40.5 wt%, average particle diameter: 23 nm, refractive index: 1.46): SK-1BH) 960g and stirred for 30 minutes, then the ion exchange resin was separated. Further, in the same manner as in Example 15, the mixture was washed by anion exchange and cation exchange to obtain a dispersion liquid of cerium oxide-based particles having a concentration of 48% by weight.

Then, the same procedure as in Example 15 (methanol solvent substitution, surface treatment, MIBK solvent substitution) was carried out to prepare a MIBK dispersion of surface-treated cerium oxide-based particles (B19) having a solid concentration of 20.5% by weight. The refractive index of the cerium oxide-based particles (B19) was measured, and the results are shown in the table.

Preparation of coating liquid for forming anti-reflection layer (19L)

The same procedure as in Example 18 except that the MIBK dispersion of the cerium oxide-based particles (B19) having a solid concentration of 20.5% by weight was used instead of the methanol dispersion of the cerium oxide-based particles (B19) having a solid concentration of 20.5% by weight in Example 18. Similarly, a coating liquid (19 L) having a solid concentration of 3.0% by weight was prepared.

Antireflection layer formation

A substrate (19) having an antireflection layer was produced in the same manner as in Example 15 except that the coating liquid (19 L) was used to form an antireflection layer. The thickness of the antireflection layer at this time was 100 nm. The antireflection layer substrate (19) was evaluated in the same manner as in Example 15.

[Example 20]

Preparation of coating liquid for forming anti-reflection layer (20L)

In the 8.05 g of the surface-treated cerium oxide-based hollow particle (A15) dispersion having a solid content concentration of 20.5 wt% prepared in Example 15, dimethylol-tricyclodecane diacrylic acid as a dispersing organic resin was mixed. 0.12 g of an ester (the same Light Acrylate DCP-A as in Example 1), an amine ester acrylate as an organic resin for curing (NK Oligo UA-33H identical to Example 1), 1.07 g, and reactivity for a water-repellent material Oyster sauce (Shin-Etsu Chemical Co., Ltd.: X-22-174DX, solid content concentration: 100% by weight) 0.05 g, yttrium-modified polyurethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.; Violet UT-4314: solid concentration 30 % by weight) 0.37 g, photopolymerization initiator (manufactured by BASF JAPAN: LUCIRIN TPO, solid content concentration: 100% by weight), 0.09 g, isopropyl alcohol, 64.65 g, methyl isobutyl ketone, 9.60 g, and isopropyl glycol, 16.00 g g, and a coating liquid (20 L) having a solid concentration of 3.0% by weight was prepared.

Antireflection layer formation

A hard coat film base material (15) was produced in the same manner as in Example 15. The shape of the hard coat film was the same as in Example 15 except that the coating liquid (20 L) was used. An anti-reflection layer (20). The thickness of the antireflection layer at this time was 100 nm. The antireflection layer substrate (20) was evaluated in the same manner as in Example 15.

[Example 21]

Production of hard coating substrate (21)

The coating liquid (15) for forming a hard coat film prepared in Example 15 was applied to a TAC film in the same manner as in Example 1 to form a hard coat film having a film thickness of 12 μm. The physical property state of the hard coat film and the like are the same as in the fifteenth embodiment.

Antireflection layer formation

Then, an antireflection layer was formed in the same manner as in the coating liquid (15) for forming an antireflection layer having a solid concentration of 3.0% by weight prepared in the same manner as in Example 15. The thickness of the antireflection layer at this time was 100 nm. The total light transmittance, haze, reflectance, refractive index of the film, adhesion, pencil hardness, and scratch resistance of the substrate with the antireflection layer are shown in the table.

[Example 22]

Preparation of coating liquid (22) for forming a hard coating film

80.38 g of an organic resin dispersion (15) having a solid concentration of 76.0% by weight of cerium oxide particles (15) prepared in Example 15 was prepared, and an amine ester acrylate as an organic resin for curing was sufficiently mixed therein (with Example 1). The same NK Oligo UA-33H) 8.88 g, acrylic polyfluorinated leveling agent (DISPARLON NSH-8430HF identical to Example 1) 1.00 g, photopolymerization initiator (Irgacure 184 identical to Example 1) 0.53 g, PGME 0.21 g, and acetone 9.0 g, and a coating liquid (22) having a solid concentration of 70.6 wt% was obtained. The composition of the coating liquid (22) is shown in the table.

Production of hard coating substrate (22)

A hard coat film substrate (22) was produced in the same manner as in Example 15 except that the coating liquid (22) was used. The film thickness of the hard coat film was 12 μm. The obtained film-attached substrate (22) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (22) of the present Example was used. The thickness of the antireflection layer was 100 nm. The substrate provided with the antireflection layer was evaluated in the same manner as in Example 15.

[Example 23]

The transparent film substrate (3) produced by the coating liquid prepared in Example 3 was applied as the hard coat film substrate (23) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (23) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (23) was used. The thickness of the antireflection layer was 100 nm. The substrate (23) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 24]

The transparent film substrate (4) produced by the coating liquid prepared in Example 4 was applied as the hard coat film substrate (24) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (24) was evaluated in the same manner as in Example 15.

Antireflection film formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (24) was used. The thickness of the antireflection layer was 100 nm. The substrate (24) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 25]

The transparent film substrate (5) produced by the coating liquid prepared in Example 5 was applied as the hard coat film substrate (25) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (25) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (25) was used. The thickness of the antireflection layer was 100 nm. The substrate (25) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 26]

The transparent film substrate (6) produced by the coating liquid prepared in Example 6 was applied as the hard coat film substrate (26) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (26) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (26) was used. The thickness of the antireflection layer was 100 nm. The substrate (26) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 27]

The transparent film substrate (7) produced by the coating liquid prepared in Example 7 was applied as the hard coat film substrate (27) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (27) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (27) was used. The thickness of the antireflection layer was 100 nm. The substrate (27) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 28]

The transparent film substrate (8) produced by the coating liquid prepared in Example 8 was applied as the hard coat film substrate (28) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (28) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (28) was used. The thickness of the antireflection layer was 100 nm. The substrate (28) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 29]

The transparent film substrate (9) produced by the coating liquid prepared in Example 9 was applied as the hard coat film substrate (29) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (29) was the same as that of Example 15. to evaluate.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (29) was used. The thickness of the antireflection layer was 100 nm. The substrate (29) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 30]

The transparent film substrate (10) produced by the coating liquid prepared in Example 10 was applied as the hard coat film substrate (30) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (30) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (30) was used. The thickness of the antireflection layer was 100 nm. The substrate (30) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 31]

The transparent film substrate (11) produced by the coating liquid prepared in Example 11 was applied as the hard coat film substrate (31) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (31) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (31) was used. The thickness of the anti-reflection layer is 100 Nm. The substrate (31) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 32]

The transparent film substrate (12) produced by the coating liquid prepared in Example 12 was applied as the hard coat film substrate (32) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (32) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (32) was used. The thickness of the antireflection layer was 100 nm. The substrate (32) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 33]

The transparent film substrate (13) produced by the coating liquid prepared in Example 13 was applied as the hard coat film substrate (33) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (33) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (33) was used. The thickness of the antireflection layer was 100 nm. The substrate (33) having the antireflection layer was evaluated in the same manner as in Example 15.

[Example 34]

The transparent quilt produced by the coating liquid prepared in Example 14 The film substrate (14) was applied as the hard coat film substrate (34) of the present example. The film thickness of the hard coat film was 12 μm. The hard coat film substrate (34) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (34) was used. The thickness of the antireflection layer was 100 nm. The substrate (34) having the antireflection layer was evaluated in the same manner as in Example 15.

[Comparative Example 5]

Modulation of cerium oxide hollow particle (RA5) dispersion

矽 矽 氧化铝 alumina sol (catalyzed by Chemical Industry Co., Ltd.: USBB-120, average particle size 25nm, SiO ₂ ‧ Al ₂ O ₃ concentration 20% by weight, solid content Al ₂ O ₃ content 27% by weight) In 100 g, 3900 g of pure water was added and heated to 98 ° C, and while maintaining the temperature, 1750 g of an aqueous solution of sodium citrate having a concentration of SiO ₂ of 1.5% by weight and a concentration of 0.5% by weight of Al ₂ O ₃ were added. 1750 g of an aqueous sodium aluminate solution gave a SiO ₂ ‧ Al ₂ O ₃ primary particle dispersion (average particle diameter: 35 nm). The molar ratio MO _X /SiO ₂ (A) = 0.2 at this time. Further, the pH of the reaction liquid was 12.0.

Then, 6300 g of an aqueous solution of sodium citrate having a SiO ₂ concentration of 1.5% by weight and 2100 g of an aqueous solution of sodium aluminate having an Al ₂ O ₃ concentration of 0.5% by weight were added to obtain a dispersion of composite oxide particles (secondary particles). At this time, the molar ratio MO _X /SiO ₂ (B) = 0.07, the pH of the reaction liquid was 12.0, and the average particle diameter was 50 nm.

Then, methanol dispersion of cerium oxide-based hollow particles having a solid concentration of 20% by weight was produced by the same process as in Example 15. liquid. The average particle diameter and refractive index of the cerium oxide-based hollow particles were measured, and the results are shown in the table.

3 g of an acrylonitrile coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-5103) was added to 100 g of the methanol dispersion, and the surface treatment was carried out by heating at 50 °C. Further, the solvent was replaced with MIBK using a rotary evaporator to prepare a dispersion of cerium oxide-based hollow particles (RA5) having a solid concentration of 20.5% by weight. The refractive index of this surface-treated cerium oxide-based hollow particle (RA5) was measured, and the results are shown in the table.

Preparation of coating liquid for forming anti-reflection film (R5L)

A coating liquid (R5L) having a solid concentration of 3.0% by weight was prepared in the same manner as in Example 15 except that the dispersion of the surface-treated cerium oxide-based hollow particles (RA5) having a solid concentration of 20.5% by weight was used.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the coating liquid (R5L) was used. The thickness of the antireflection layer at this time was 100 nm. The antireflection layer substrate (R5) was evaluated in the same manner as in Example 15.

[Comparative Example 6]

Production of hard coated substrate (R6)

The coating liquid (15) for forming a hard coat film prepared in Example 15 was diluted with PGME to have a solid concentration of 30% by weight. This was applied to a TAC film (Fuji Film Co., Ltd.: FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51) by a bar coating method #3, and dried at 80 ° C for 120 seconds. Then, ultraviolet rays of 300 mJ/cm ² were irradiated and cured in an N ₂ atmosphere to prepare a hard coat film substrate (R6). The obtained hard coat film substrate (R6) was evaluated in the same manner as in Example 15.

Antireflection film formation

Then, an antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the hard coat film substrate (R6) was used. The thickness of the antireflection layer at this time was 100 nm. The antireflection layer substrate was evaluated in the same manner as in Example 15.

[Comparative Example 7]

Preparation of coating liquid (R7) for forming a hard coating film

To 2500 g of the surface-treated cerium oxide sol dispersion having a solid concentration of 40.5% by weight prepared in Example 15, dimethylol-tricyclodecane diacrylate as a dispersing organic resin was added (Example 1) 202.5 g of the same Light Acrylate DCP-A), a part of the solvent was removed using a rotary evaporator, and an organic resin dispersion (RA7) of surface-treated cerium oxide particles having a solid concentration of 76.0% by weight was prepared.

Into 75.31 g of the organic resin dispersion (RA7), dimethylol-tricyclodecane diacrylate (the same Light Acrylate DCP-A as in Example 1) as an organic resin for dispersion was mixed in an amount of 8.32 g, acrylic acid. Polyfluorene-based leveling agent (manufactured by Nanben Chemical Co., Ltd.; DISPARLON NSH-8430HF) 1.00 g, photopolymerization initiator (manufactured by CHIBA JAPAN Co., Ltd.; Irgacure 184) 0.50 g, PGME 2.37 g, and acetone 12.50 g, On the other hand, a coating liquid (R7) having a solid content concentration of 66.1% by weight was prepared. Here, an organic resin for dispersion is further added in place of the organic resin for curing. The composition of the obtained coating liquid (R7) is shown in the table.

Production of hard coated substrate (R7)

A film-attached substrate (R7) was produced in the same manner as in Example 15 except that the coating liquid for forming a hard coating film (R7) was used. The film thickness of the hard coat film was 12 μm. The obtained film-attached substrate (R7) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the above-mentioned hard coat film substrate (R7) was used. The thickness of the antireflection layer was 100 nm. The film-attached substrate having the antireflection layer was evaluated in the same manner as in Example 15.

[Comparative Example 8]

Preparation of coating liquid (R8) for forming a hard coating film

To 2500 g of the surface-treated cerium oxide sol dispersion having a solid concentration of 40.5% by weight prepared in Example 15, an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) was added as a curing organic resin. 202.5 g, a part of the solvent was removed using a rotary evaporator, and an organic resin dispersion (RB8) of surface-treated cerium oxide particles having a solid concentration of 53.3% by weight was prepared.

In the 82.96 g of the organic resin dispersion (RB8), a polyacrylic acid-based leveling agent (manufactured by Nanben Chemical Co., Ltd.; DISPARLON NSH-8430HF) of 1.00 g and a photopolymerization initiator (CHIBA JAPAN) were sufficiently mixed. IrGacure 184) 0.50 g, PGME 0.13 g, and acetone 9.00 g were prepared to prepare a coating liquid (R8) having a solid concentration of 51.0% by weight. The composition of the obtained coating liquid for forming a hard coat film (R8) is shown in the table.

Production of hard coated substrate (R8)

A film-attached substrate (R8) was produced in the same manner as in Example 15 except that the coating liquid for forming a hard coating film (R8) was used. The film thickness of the hard coat film was 12 μm. The obtained film-attached substrate (R8) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the above-mentioned hard coat film substrate (R8) was used. The thickness of the antireflection layer was 100 nm. The film-attached substrate (R8) having the antireflection layer was evaluated in the same manner as in Example 15.

[Comparative Example 9]

Preparation of coating liquid for forming a hard coating film (R9)

In the 69.14 g of the surface-treated cerium oxide sol dispersion having a solid concentration of 40.5% by weight prepared in Example 15, dimethylol-tricyclodecane diacrylate as a dispersing organic resin was simultaneously supplied (and implemented) Example 1 The same Light Acrylate DCP-A) 5.26 g, an amine ester acrylate as an organic resin for curing (the same NK Oligo UA-33H as in Example 1) 4.83 g, and a polyacrylic acid-based leveling agent (Nanben Chemical Co., Ltd.) (Stock) system; DISPARLON NSH-8430HF) 1.00g, photopolymerization initiator (CHIBA JAPAN (Irgacure 184) 0.29g, PGME 6.99g and acetone 12.50g fully mixed to prepare a solid concentration of 41.4 % by weight of coating liquid (R9). The composition of the obtained coating liquid for forming a hard coat film (R9) is shown in the table.

Production of hard coated substrate (R9)

A film-attached substrate (R9) was produced in the same manner as in Example 15 except that the coating liquid (R9) was used. The film thickness of the hard coat film was 12 μm. The resulting film The substrate (R9) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the above-mentioned hard coat film substrate (R9) was used. The thickness of the antireflection layer was 100 nm. The film base material (R9) having the antireflection layer was evaluated in the same manner as in Example 15.

[Comparative Example 10]

Preparation of coating liquid for forming a hard coating film (R10)

To 2500 g of a cerium oxide sol dispersion (the same Cataloid SI-30 as in Example 1), dimethylol-tricyclodecane diacrylate as a dispersing organic resin was added (the same Light Acrylate DCP as in Example 1) -A) 202.5 g, a part of the solvent was removed using a rotary evaporator to obtain an organic resin dispersion (R10) of surface-treated cerium oxide particles having a solid concentration of 53.3% by weight.

In the 75.31 g of the organic resin dispersion (R10), 7.19 g of an amine ester acrylate (the same NK Oligo UA-33H as in Example 1) as an organic resin for curing was sufficiently mixed, and a polyxanthene-based leveling agent ( The same DISPARLON NSH-8430HF) 1.00 g as in Example 1, 0.50 g of a photopolymerization initiator (Irgacure 184 similar to Example 1), 0.83 g of PGME, and 8.00 g of acetone were used to prepare a coating having a solid concentration of 53.3% by weight. Liquid (R10). The composition of the obtained coating liquid (R10) is shown in the table.

Production of hard coated substrate (R10)

A film-attached substrate (R10) was produced in the same manner as in Example 15 except that the coating liquid (R10) was used. The film thickness of the hard coat film was 12 μm. Attached to the income The film substrate (R10) was evaluated in the same manner as in Example 15.

Antireflection layer formation

An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that the film-attached substrate (R10) was used. The thickness of the antireflection layer was 100 nm. The film-attached substrate having the antireflection layer was evaluated in the same manner as in Example 15.

[Comparative Example 11]

Antireflection layer formation

The coating liquid for forming an antireflection layer (15 L) having a solid content concentration of 3.0% by weight prepared in Example 15 was applied to the TAC film used in Example 15 by a bar coating method #4, and dried at 80 ° C for 120 seconds. Thereafter, ultraviolet rays of 600 mJ/cm ² were irradiated and cured in an N ₂ atmosphere to prepare an antireflection layer substrate (R11). Therefore, no hard coat film is provided, and the antireflection layer is formed directly on the substrate. The thickness of the antireflection layer was 100 nm. The antireflection layer substrate (R11) was evaluated in the same manner as in Example 15.

[Example 35]

Production of hard coated substrate (35)

This embodiment is a configuration in which the antireflection layer is not provided in Example 15, and is different from the thickness of the substrate of Examples 1 to 14 and the particle diameter of the metal oxide particles. The coating liquid (15) for forming a hard coat film prepared in Example 15 was applied to the TAC film used in Example 15 by a bar coating method #16, and dried at 80 ° C for 120 seconds, and then in a N ₂ atmosphere. The ultraviolet rays of 300 mJ/cm ² were irradiated and cured to prepare a hard coat film substrate (35). The film thickness of the hard coat film was 12 μm. The film-attached substrate was evaluated in the same manner as in Example 15.

Claims (20)

A coating liquid for forming a transparent film, which comprises metal oxide particles having an average particle diameter of 5 to 300 nm and a matrix forming component, wherein the coating liquid is characterized by a concentration of the metal oxide particles in terms of solid content (C) _p ) is 45 to 90% by weight, the concentration (C _R ) of the matrix-forming component in terms of solid content is 10 to 50% by weight, and the total solid content concentration (C _T ) is 60% by weight or more, and the concentration (C _R ) The ratio (C _R /C _P ) to the concentration (C _P ) is from 0.11 to 1.0, and the matrix-forming component comprises a first organic resin having two or less functional groups and a second organic having three or more functional groups. Resin. The coating liquid according to claim 1, wherein the first organic resin and the second organic resin are ultraviolet curable resin monomers or oligomers. The coating liquid according to the first or second aspect of the invention, wherein the first organic resin and the second organic resin have a functional group selected from the group consisting of (meth) acrylate groups and amine acrylates. At least one of a group and an epoxy group-modified acrylate group. The coating liquid according to any one of the preceding claims, wherein the metal oxide particles are subjected to surface treatment by an organic cerium compound represented by the following formula (1); R _n -SiX _{4 -n} . . . (1) (wherein, wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms which may be the same or different from each other, and X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, or a hydrogen , n represents an integer from 1 to 3.) The coating liquid according to claim 4, wherein the R of the organic hydrazine compound has a substituted hydrocarbon group having a (meth) acrylate group as a substituent. The coating liquid according to Item 4 or 5, wherein the metal oxide particles are 100 parts by weight of R _n -SiO _(4-n)/2 with respect to the metal oxide particles. 0.1 to 50 parts by weight of the organic cerium compound is subjected to surface treatment. The coating liquid according to claim 6, wherein the first organic resin contains a hydroxyl group, an ether group, or an amine group in the case where the surface treatment amount of the metal oxide particles is in the range of 0.1 to 5 parts by weight. At least one of a carboxyl group and a sulfonic acid group. The coating liquid according to any one of claims 1 to 7, further comprising an organic dispersion medium in which the metal oxide particles are dispersed, wherein the concentration of the organic dispersion medium is 40% by weight or less. A method for producing a coating liquid comprising the steps of: preparing a dispersion of metal oxide particles having an average particle diameter of 5 to 300 nm and an organic dispersion medium; and having at least a part of the aforementioned organic dispersion medium a step of substituting a first organic resin of a functional group; and a step of mixing a second organic resin having three or more functional groups. The method for producing a coating liquid according to claim 9, wherein the first organic resin is an ultraviolet curable resin monomer or oligomer. The method for producing a coating liquid according to claim 9 or claim 10, wherein the second organic resin is an ultraviolet curable resin monomer or oligomer, and the first organic resin and the second organic resin The functional group is at least one selected from the group consisting of a (meth) acrylate group, an amine acrylate group, and an epoxy group-modified acrylate group. A substrate with a transparent film, which is a coating liquid according to any one of claims 1 to 8 or a method according to any one of claims 9 to 11. a coating liquid obtained by the production method, wherein a transparent film-attached transparent film is formed on a substrate; wherein the transparent film comprises metal oxide particles having an average particle diameter of 5 to 300 nm and a matrix component; the metal oxide The content (W _p ) of the particles represented by the solid content is 50 to 90% by weight, and the content (W _R ) of the matrix component expressed by the solid content is 10 to 50% by weight, and the content ratio (W _R /W _P ) is From 0.11 to 1.0, the average film thickness (T) is from 1 to 100 μm. The substrate with a transparent film according to claim 12, wherein the substrate is selected from the group consisting of acrylic acid, polycarbonate, cycloolefin polymer, polyethylene terephthalate, and cellulose triacetate. At least one resin substrate. The base material with a transparent film as described in claim 12 or 13, wherein the transparent film has a pencil hardness of 5H or more. The substrate with a transparent film according to any one of claims 12 to 14, which has a curling property of 5 as determined by the following conditions. Mm or less: a coating liquid for forming a transparent film was applied onto a cellulose triacetate substrate having a coated surface of 14 cm × 25 cm and a thickness of 40 μm to form a transparent film having a thickness of 12 μm, and allowed to stand for 20 hours, and then the film was cut. In a size of 10 cm x 10 cm, the film was placed on a flat plate with the coated surface below, and it was curled (curved) while the apex of the floating substrate was at a height from the flat plate. A method for producing a substrate with a transparent film, comprising the steps of applying the coating liquid according to any one of items 1 to 8 or applying the patent scopes 9 to 11 a coating liquid obtained by the production method according to any one of the preceding claims, comprising the steps of: applying a coating film on a substrate to form a coating film; drying the coating film; and drying the coating film to obtain a transparent film In the above, the shrinkage rate of the coating film due to the drying is 25% or less, and the shrinkage ratio of the coating film due to the curing is 10% or less, and the total shrinkage ratio is 35% or less. An organic resin dispersion sol of metal oxide particles, wherein the metal oxide particles having an average particle diameter of 5 to 300 nm are dispersed in a first organic resin having two or less functional groups, wherein the metal oxide is oxidized The concentration (C _PS ) of the particles as a solid component is 45 to 90% by weight, and the concentration (C _RS ) of the first organic resin as a solid component is 10 to 50% by weight, and the total solid concentration (C _{TS )} ) is 60% by weight or more. The substrate with a transparent film according to any one of claims 12 to 15, wherein the transparent film is provided with a transparent film having an antireflection layer formed thereon, wherein the antireflection layer comprises The cerium oxide-based hollow particles and the matrix component (M _L ); the content of the cerium oxide-based hollow particles (W _PLA ) is 5 to 80% by weight; and the content of the matrix component (M _L ) (W _ML ) is 20 to 95% by weight %; the thickness (T _L ) of the antireflection layer is 80 to 200 nm; the average particle diameter (D _PA ) of the cerium oxide-based hollow particles is 10 to 45 nm; and the average particle diameter of the cerium oxide-based hollow particles (D _PA) The ratio (D _PA /T _L ) to the thickness (T _L ) of the aforementioned antireflection layer is 0.05 to 0.56. The substrate with a transparent film according to claim 18, wherein the antireflection layer comprises a second cerium oxide-based particle having an average particle diameter (D _PB ) of 4 to 17 nm, and an average particle diameter ratio ( D _PB /D _PA ) is from 0.1 to 0.4. The substrate with a transparent film according to claim 18, wherein the interface between the transparent film and the antireflection layer is wavy.