WO2015152171A1

WO2015152171A1 - Coating liquid for forming transparent coating and method for producing said coating liquid, organic resin-dispersed sol, and substrate with transparent coating and method for producing said substrate

Info

Publication number: WO2015152171A1
Application number: PCT/JP2015/059981
Authority: WO
Inventors: 夕子箱嶋; 政幸松田; 良村口; 平井　俊晴
Original assignee: 日揮触媒化成株式会社
Priority date: 2014-03-31
Filing date: 2015-03-30
Publication date: 2015-10-08
Also published as: CN106164190A; TWI670335B; TW201546197A; KR20160138972A; KR102379944B1; CN106164190B

Abstract

The present invention provides a high-strength transparent coating that has high strength in the case of a resin substrate, and, in the case of a thick film, causes little film contraction, does not give rise to cracks, and suppresses curling. Provided is a coating liquid for forming a transparent coating, said coating liquid including metal oxide particles having an average particle size in the range of 5-300 nm and having a matrix-forming component, wherein the matrix-forming component comprises a first organic resin having at most two functional groups and a second organic resin having at least three functional groups, the concentration (C_P) of the metal oxide particles as solid content is 45-90 wt%, the concentration (C_R) of the matrix-forming component as solid content is 10-50 wt%, the total solid content concentration (C_T) is at least 60 wt%, and the ratio (C_R/C_P) of the concentration (C_R) to the concentration (C_P) is in the range of 0.11-1.0.

Description

Coating liquid for forming transparent film and method for producing the same, organic resin dispersed 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 substrate with a transparent film. In particular, the present invention relates to a coating solution that is suitable for forming a transparent film having high hardness even when the substrate is a resin substrate, and having no cracks even when the substrate is a thick film.

Conventionally, in order to improve the scratch resistance of glass, plastic sheets, plastic lenses, etc., a transparent film having a hard coat function is provided on the surface of the base material. An organic resin film or an inorganic film is used as such a transparent film. In order to further improve the scratch resistance, it is known to mix inorganic particles such as resin particles and silica in the transparent film.

However, when the particles are dispersed in the coating liquid for forming the transparent film, the particles having low affinity for the matrix forming component and the dispersion medium are aggregated. For this reason, the stability of the coating solution is lowered, and in addition to the transparency and haze of the resulting transparent film, the scratch resistance, strength, scratch strength and the like may be insufficient.

In order to prevent this, it is known that the particles are surface-treated with a silane coupling agent. In addition, it is known that particles are coated with a resin by a mechanochemical method, a graft polymerization method, or the like to increase the affinity with a matrix component or a dispersion medium. (JP-A-3-163172 (Patent Document 1), JP-A-6-336558 (Patent Document 2), JP-A-6-49251 (Patent Document 3), JP-A 2000-143230 (Patent Document) 4))

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

In addition, a dispersion of metal oxide particles having an average secondary particle size of the order of micrometers using an organic solvent such as ethers, esters, and ketones as a dispersion medium is heat-treated, and then an acrylic resin is added thereto. It is known to mechanochemical treatment. Thereby, resin can be uniformly coated on each metal oxide particle. At this time, the dispersion of the metal oxide particles coated with the resin can be increased to a solid concentration of 50% by weight (Japanese Patent Laid-Open No. 2010-077409 (Patent Document 6)).

In addition, a (meth) acrylate resin having an aromatic ring is added to an organic solvent dispersion of metal oxide particles that has been heat-treated in advance, and then the resin is uniformly coated on individual particles by mechanochemical treatment. it can. The resin-coated particles are uniformly dispersed in a low molecular weight resin having a high affinity with the resin-coated particles, and then the organic solvent is removed. Thereby, the resin-coated particles are highly dispersed without being cured, and a composition having excellent stability can be obtained. A curing agent is added to the composition, applied, and cured without drying. Thereby, a transparent film with small shrinkage can be formed thickly. This transparent film is dense and excellent in transparency, haze, scratch resistance, etc. (Japanese Patent Laid-Open No. 2012-72288 (Patent Document 7)).

Furthermore, an organic resin is obtained from a coating containing a (meth) acrylate resin having a fluorene skeleton having an average molecular weight in a specific range, a (meth) acrylate resin having a fluorene skeleton, and (meth) acrylate resin-coated particles. A high-concentration paint can be prepared by removing with a rotary evaporator. When such a paint is used, a thick optical film having excellent hardness can be obtained (Japanese Patent Laid-Open No. 2013-10864 (Patent Document 8)).

Further, when an acrylate having a functional group number of 4 or more, an acrylate resin having a functional group number of 2 or 3, an irregularly shaped particle (a particle having a spherical coefficient in a predetermined range or a chain particle), and a coating material containing a dispersion medium are used, Curling is suppressed even with a thin substrate, and a transparent film excellent in adhesion to the substrate, hardness, scratch resistance, etc. can be obtained (Japanese Patent Laid-Open No. 2013-133444 (Patent Document 9)).

Also, unevenness is formed on the film surface by using a coating liquid for forming a hard coat film composed of metal oxide particles treated with a surfactant having an ethylene oxide-modified skeleton, a hydrophobic matrix forming component, and an organic dispersion medium. And anti-blocking properties are known to improve (Japanese Patent Laid-Open No. 2013-136222 (Patent Document 10)). It also discloses blending hydrophobic particles surface-treated with an organosilicon compound so as to improve the film hardness.

In addition, by using a coating liquid containing metal oxide particles coated with a polymer silane coupling agent and having a surface charge amount within a predetermined range, a hydrophobic organic resin matrix forming component and a dispersion medium, the alkali resistance is excellent. Thus, a hard coat film having excellent adhesion to the substrate, scratch resistance, hardness and the like can be formed (Japanese Patent Laid-Open No. 2009-35595 (Patent Document 11)).

In addition, using a resin having a trifunctional or higher functional group and a bifunctional organic resin monomer or a silicone resin monomer and a monofunctional silicone resin can reduce bleed-out and has excellent water and oil repellency. It is known that a transparent film excellent in wiping properties such as magic can be formed (Japanese Patent Laid-Open No. 2010-126675 (Patent Document 12)).

Japanese Patent Laid-Open No. 3-163172 JP-A-6-336558 JP-A-6-49251 JP 2000-143230 A JP 2010-37534 A JP 2010-077409 A JP 2012-72288 A JP 2013-10864 A JP 2013-133444 A JP 2013-136222 A JP 2009-35595 A JP 2010-126675 A

However, in the conventional mechanochemical method and graft polymerization method described in Patent Documents 1 to 4, it is difficult to uniformly coat the resin on individual particles, and the resin is coated on several or more aggregated particles. The In such resin-coated particles, the resin may be dissolved in the solvent of the coating solution. Therefore, the obtained transparent film has problems such as a decrease in transparency, an increase in haze, and a decrease in scratch resistance.

Patent Document 6 discloses a dispersion sol of resin-coated metal oxide particles containing an organic solvent, and its concentration is in the range of approximately 1 to 60% by weight as a solid content. When the concentration of the coating solution exceeds 60% by weight, the stability is lowered, and there is a case where it aggregates and settles. In addition, a resin component is added as a matrix-forming component together with an organic solvent when preparing a coating solution, but there is a limit to the film thickness of the resulting film.

Further, a transparent film having a film thickness of 4 μm and a pencil hardness exceeding 4H cannot be obtained (Patent Document 6), and a transparent film having a film thickness of 35 μm and a pencil hardness exceeding 3H cannot be obtained (Patent Document 7). Even a transparent film containing 50% by weight or more cannot exceed 4H (Patent Document 12).

Further, as in Patent Document 9, a transparent film having a pencil hardness of 5H or more has not been obtained even if irregularly shaped particles are used.
In recent years, even when a resin substrate is used in various display devices, a transparent film having a pencil hardness comparable to that of a glass substrate has been demanded.

The present inventors thought that the hardness can be increased by decreasing the resin ratio and increasing the particle ratio. However, simply increasing the ratio of the particles has a problem that cracking and shrinkage due to drying during film formation are large as well as stability of the coating solution. Therefore, it has been found that the final resin ratio can be reduced by using an ultraviolet curable resin monomer instead of a conventional solvent as a dispersion sol medium at the time of preparing the coating liquid.

A stable organic resin dispersion is prepared by preparing an organic dispersion medium dispersion of metal oxide particles surface-treated with a predetermined amount of an organosilicon compound, and replacing the organic dispersion medium with an ultraviolet curable resin monomer having a small number of functional groups. It was found that (sometimes referred to as an organic resin dispersion sol) can be obtained. And when this is mixed with an ultraviolet curable resin monomer having 3 or more functional groups to form a coating solution, the ratio of the resin can be reduced, and even when the coating solution is applied thickly, the shrinkage of the transparent film is small. It was also found that there was no crack, curling was suppressed, and the hardness of the film was significantly improved.

That is, the coating liquid for forming a transparent film of the present invention contains metal oxide particles having an average particle diameter in the range of 5 to 300 nm and a matrix-forming component, and the concentration of the metal oxide particles as a solid content ( C _P ) is 45 to 90% by weight, the concentration (C _R ) as a solid content of the matrix forming component is 10 to 50% by weight, the total solid content concentration (C _T ) is 60% by weight or more, and the concentration (C _R) ) And concentration (C _P ) ratio (C _R / C _P ) is in the range of 0.11 to 1.0, and the matrix-forming component and the first organic resin having 2 or less functional groups and 3 It is comprised with the 2nd organic resin which has the above functional group. Furthermore, the first organic resin and the second organic resin are ultraviolet curable resin monomers or oligomers. In addition, (meth) acrylate groups, urethane acrylate groups, and epoxy-modified acrylate groups are suitable as functional groups of the first organic resin and the second organic resin. The metal oxide particles are preferably surface treated with an organosilicon compound.

Further, the method for producing a coating liquid of the present invention comprises a step of preparing a dispersion containing metal oxide particles having an average particle diameter in the range of 5 to 300 nm and an organic dispersion medium, and at least a part of the organic dispersion medium. A step of substituting with a first organic resin having not more than one functional group and a step of mixing a second organic resin having not less than three functional groups. In particular, it is suitable as a method for producing the above coating solution.

The substrate with a transparent coating of the present invention is a substrate on which a transparent coating by the above-described coating solution is provided. The transparent coating comprises metal oxide particles having an average particle size of 5 to 300 nm and a matrix component. The solid content of metal oxide particles (W _P ) is 45 to 90% by weight, the content of the matrix component as solids (W _R ) is 10 to 50% by weight, The content ratio (W _R / W _P ) is 0.11 to 1.0, and the average film thickness (T) is 1 to 100 μm. Further, an antireflection layer is provided on the transparent coating. Antireflective layer comprises a silica-based hollow particles and the matrix component (M _L), the content of the silica-based hollow particles (W _PLA) is 5 to 80 wt%, 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 silica-based hollow particles is 10 to 45 nm, and the silica-based hollow The ratio (D _PA / T _L ) between the average particle diameter (D _PA ) of the particles and the thickness (T _L ) of the antireflection layer is 0.05 to 0.56.

According to the coating solution of the present invention, even a thick film has a small film shrinkage, no cracks, curling is suppressed, and a transparent film having high hardness can be formed.

Hereinafter, first, the coating liquid for forming a transparent film according to the present invention will be described.
[Coating solution for forming transparent film]
The coating liquid according to the present invention contains metal oxide particles having an average particle diameter of 5 to 300 nm and a matrix forming component. In the coating solution, metal oxide particles are present as a solid content at a concentration (C _P ) of 45 to 90% by weight. In particular, a range of 48 to 80% by weight is preferable. The coating solution contains a matrix-forming component as a solid content at a concentration (C _R ) of 10 to 50% by weight. In particular, it is preferably in the range of 15 to 40% by weight. At this time, the total solid content concentration (C _T ) of the coating solution is 60% by weight or more. More than 60% by weight is particularly suitable, and more preferably 63% by weight or more.

If the concentration (C _P ) of the metal oxide particles in the coating solution is low, the film shrinks greatly, so that a thick film is likely to crack. Moreover, densification is not sufficient and a transparent coating film with high hardness cannot be obtained. On the contrary, when the concentration (C _P ) is high, the surface unevenness of the transparent film becomes large. Therefore, external scattering occurs, the haze of the film is deteriorated, and the transparency is lowered. Furthermore, the film is not sufficiently densified, 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 solution is too low, the concentration (C _P ) of the metal oxide particles is increased, the haze of the film is deteriorated as described above, and the transparency is lowered. Furthermore, the densification of the film may be insufficient, and the scratch resistance of the transparent film and the adhesion to the substrate will be insufficient. Even if the concentration (C _R ) of the matrix-forming component is too high, the film shrinks more than when a large amount of metal oxide particles are blended, and cracks tend to occur when the film is thick.
Further, the concentration ratio (C _R / C _P ) between the concentration of the matrix forming component (C _R ) and the concentration of the metal oxide particles (C _P ) is set to 0.11 to 1.0. The range of 0.18 to 0.8 is particularly preferable. When the concentration ratio (C _R / C _P ) is low, since the concentration (C _P ) as the solid content of the metal oxide particles is high, the surface unevenness of the transparent coating becomes large. For this reason, the haze of the film is deteriorated due to external scattering, and the transparency is easily lowered. Furthermore, the densification of the film may be insufficient, and the scratch resistance of the transparent coating and the adhesion to the substrate will be insufficient. On the other hand, if the concentration ratio is too high, the shrinkage of the film increases, and cracks are likely to occur in a thick film. Further, the transparent film is not sufficiently densified, 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 2 or less functional groups and stably disperses the metal oxide particles. The second organic resin is an organic resin having three or more functional groups, and is necessary for increasing the hardness of the coating film. Further, the content of the first organic resin (A) in the matrix-forming component as a solid content is 1 to 80% by weight. In particular, it is preferably in the range of 5 to 60% by weight. If the content of the first organic resin (A) is too small, it is difficult to uniformly disperse the metal oxide particles without agglomerating. A transparent film obtained from such a coating solution has low surface smoothness and insufficient densification. On the other hand, if the content of the first organic resin (A) is too large, the second organic resin (B) is small, so that the denseness of the transparent film is not sufficient and good hardness cannot be obtained. The second organic resin in the matrix-forming component is set so that the total concentration (C _R ) with the first organic resin is in the above range.

The ratio (C _RA / C _P ) between the concentration (C _RA ) of the first organic resin in the matrix-forming component and the concentration (C _P ) of the metal oxide particles is 0.17 to 1.11. In particular, the range of 0.19 to 0.89 is preferable. If it exists in this range, even if there are many metal oxide particles, shrinkage | contraction of a film | membrane is small, a film thickness can be increased, and the crack generation can also be suppressed. The finally obtained transparent film is highly dense and therefore has a high hardness.
Such a coating solution is prepared as follows.

[Method for preparing coating solution for forming transparent film]
Step (a)
First, metal oxide particles having an average particle diameter in the range 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, but is usually in the range of 30 to 50% by weight as a solid content. If the concentration is low, the amount of solvent substitution increases and it is not efficient. When the concentration is high, the metal oxide particles aggregate. Or even if it does not aggregate, a viscosity will rise and it will be difficult to obtain stability. At this time, the metal oxide particles are preferably surface-treated with an organosilicon compound.

Step (b)
Then, the organic dispersion medium in the dispersion is replaced with a first organic resin having 2 or less functional groups. There is no restriction | limiting in particular in the substitution method of a solvent, A conventionally well-known method is employable. For example, a rotary evaporator method or an evaporator method can be employed. At this time, you may carry out under pressure reduction and also heating as needed.

The ratio of replacing the organic dispersion medium with the first organic resin is performed so that the concentration of the organic dispersion medium in the coating liquid finally obtained through the step (c) described later is less than 40% by weight. In particular, it is preferably less than 35% by weight.
If a large amount of the organic dispersion medium remains, the total solid content concentration (C _T ) of the coating solution decreases, and thus the shrinkage from application of the coating solution to drying increases. For this reason, when a thick film, particularly a film having a thickness of 10 μm or more is obtained, cracks are likely to occur during shrinkage, and curling properties are increased.

Step (c)
Next, the 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 ) as a matrix forming component is 15 to 50% by weight. To do.

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

Hereinafter, the metal oxide particles and matrix forming components contained in the coating solution will be described in detail.
Metal oxide particles It is preferable to use metal oxide particles derived from a metal oxide sol. For example, conventionally known silica sol, zirconia sol, titania sol, alumina sol, antimony pentoxide sol, antimony doped tin oxide (ATO), phosphorus doped tin oxide (PTO), indium doped tin oxide (ITO) and the like can be mentioned.

The average particle size of the metal oxide particles is suitably 5 to 300 nm. The range of 5 to 200 nm is particularly preferable. When the average particle diameter of the metal oxide particles is less than 5 nm, the metal oxide particles are likely to aggregate although depending on the presence or absence of a surface treatment described later. When agglomerated, the haze of the transparent film deteriorates and the transparency is lowered. Even if the average particle diameter exceeds 300 nm, although depending on the content of the metal oxide particles, the haze of the transparent film is deteriorated or the transparency is lowered. Further, the transparent film may be damaged by friction or the like.

The spherical coefficient of the metal oxide particles is suitably 0.2 to 1.0. In particular, 0.4 to 1.0 is preferable. When the spherical coefficient is small, the dispersibility in the coating solution is insufficient and the metal oxide particles may aggregate. For this reason, adhesion to the substrate, scratch strength, etc. are insufficient, and cracks may occur in the resulting transparent film. Here, the spherical coefficient is represented by “(average short diameter perpendicular to the longest diameter at the midpoint of the longest diameter; D _S ) / (average particle longest diameter of the particle; D _L )”.
From a photograph taken with a transmission electron microscope (TEM), the shortest diameter orthogonal to the midpoint of the longest diameter and the longest diameter was measured for 100 particles, and the average value of the shortest diameter (D _S ) and the average value of the longest diameter The spherical coefficient can be obtained as a ratio to (D _L ).

Moreover, it is preferable to surface-treat a metal oxide particle with the organosilicon compound represented by following formula (1).
R _n -SiX _{_4-n} ···· formula (1)
In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. X represents an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, or hydrogen, and n represents an integer of 1 to 3. Examples of the substituent include an epoxy group, an alkoxy group, a (meth) acryloyloxy group, a mercapto group, a halogen atom, an amino group, and a phenylamino group.

The surface treatment amount of the metal oxide particles is suitably 0.1 to 50 parts by weight with respect to 100 parts by weight of the metal oxide particles, with the organosilicon compound being R _n —SiO 2 _{(4-n) / 2} . The range of 1 to 40 parts by weight is particularly preferable. When the surface treatment amount is small, the dispersibility of the metal oxide particles is insufficient. For this reason, haze is generated in the obtained transparent film, and the adhesion and hardness with the substrate are not sufficient. Even if the surface treatment amount is too large, the dispersibility is not further improved, and an unreacted surface treatment agent may remain. Then, the high density filling of metal oxide particles is hindered, and the hardness and adhesion are insufficient.

As a surface treatment method, a conventionally known method can be adopted. For example, when the metal oxide sol is a water-dispersed sol, an organosol obtained by solvent substitution with alcohol is added, and a necessary amount of the aforementioned hydrolyzable organosilicon compound is added to the sol and heated as necessary. Examples include a method of hydrolyzing an organosilicon compound by adding an acid or an alkali as a decomposition catalyst. After the hydrolysis, it is preferable to replace the dispersion medium containing water or by-products with an organic dispersion medium described later.

Examples of the organosilicon compound represented by the formula (1) include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldi Ethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoro Propyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyl Rutrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ -(Meth) acrylooxymethyltrimethoxysilane, γ- (meth) acryloxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane , Γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxy Silane, butyltri Ethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) ) Γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane , Γ- (meth) acrylooxypropyldimethoxysilane, γ- (meth) acryloxypropyldiethoxysilane, and the like, and mixtures thereof.

In particular, an organosilicon compound having a substituted hydrocarbon group having a (meth) acrylate group as a substituent as R is preferable. When the surface treatment is performed with such an organosilicon 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 having a uniform and excellent adhesion to the substrate can be obtained.

In addition, since the bondability with each resin which is a matrix forming component is improved, a transparent film with further improved hardness can be obtained.
As organosilicon compounds having a substituted hydrocarbon group with a (meth) acrylate group as a substituent as R, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriexisilane, γ -(Meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane Γ- (meth) acrylooxypropyldimethoxysilane, γ- (meth) acryloxypropyldiethoxysilane, and the like.

Matrix-forming component In the coating liquid for forming a transparent film according to the present invention, as a matrix-forming component, a first organic resin (A) having 2 or less functional groups and a second organic resin having 3 or more functional groups. Of the organic resin (B). The first organic resin and the second organic resin are preferably UV curable resin monomers or oligomers. When a monomer or oligomer of an ultraviolet curable resin having three or more functional groups is used as the second organic resin, the number of functional groups is three or more, so polyethylene terephthalate (PET) or triacetyl cellulose (TAC) It is easy to combine with a resin base material such as, and has excellent adhesion to the base material. Moreover, since it couple | bonds together as a matrix formation component, the transparent film excellent in hardness is obtained. In particular, the second organic resin preferably has at least one functional group selected from a (meth) acrylate group, a urethane acrylate group, and an alkylene oxide-modified acrylate group. When having such a functional group, the bond with the resin substrate is further strengthened, and high adhesion to the substrate can be obtained. In addition, a transparent coating with higher hardness can be obtained.

It is preferable to use an ultraviolet curable resin monomer or oligomer having 1 to 2 functional groups for the first organic resin. When the number of functional groups is 1-2, the viscosity of the organic resin is low, and when the organic dispersion medium dispersion of metal oxide particles is replaced with a solvent, the increase in viscosity is small even when the concentration of the organic resin is increased. It can be used suitably. That is, the metal oxide particles can be stably dispersed by the first organic resin, and an organic resin dispersion of metal oxide particles that is stable at a high concentration can be obtained.

The molecular weight (polystyrene equivalent molecular weight) of the monomer or oligomer of the ultraviolet curable resin is suitably 5,000 or less. In particular, 4,500 or less is preferable. If the molecular weight is too large, the viscosity of the resin is high, and when used as the first organic resin, when the organic dispersion medium dispersion of metal oxide particles is replaced with the dispersion medium, the viscosity of the dispersion increases and the concentration increases. There are cases where it is not possible. Therefore, it becomes difficult to form a thick film, to suppress shrinkage during film formation, to suppress cracks, to suppress curling, and to form a transparent film having excellent hardness. When used as the first organic resin, 1,000 or less is particularly preferable. Further, when used as the second organic resin, the hardness of the resin is lowered, and thus the hardness of the transparent film is hardly exhibited.

When 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 is a hydroxyl group (OH group), an ether group, It preferably contains at least one selected from an amino group, a carboxyl group, and a sulfo group. When the surface treatment amount of the metal oxide particles is in the above range, a hydrophilic group (OH group) remains on the particle surface. Therefore, when the first organic resin has these groups, the affinity with the metal oxide particles is high, and the organic dispersion medium dispersion of the metal oxide particles is solvent-substituted in the coating liquid preparation step (b) described above. In this case, the metal oxide particles can be uniformly dispersed without agglomeration.
When the surface treatment amount of the metal oxide particles is in the range of 5 to 50 parts by weight, the first organic resin has any functional group such as a hydroxyl group, an ether group, an amino group, a carboxyl group, and a sulfo group. Although it is preferable not to have it, you may have these functional groups.

Below, the ultraviolet curable resin which can be used suitably for a 1st organic resin is illustrated.
Having a monofunctional (meth) acrylate group; butoxyethyl acrylate, methoxypolyethylene glycol acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2 -Hydroxybutyl acrylate, ethylene glycol diglycidyl ether acrylate, polyethylene glycol diglycidyl ether acrylate, dipropylene glycol diglycidyl ether acrylate, polypropylene glycol diglycidyl ether acrylate, 1,6-hexanediol diglycidyl ether acrylate, 2-ethylhexyl Glycidyl ether acrylate, pentaerythritol Polyglycidyl ether acrylate, neopentyl glycol diglycidyl ether acrylate, ethoxylated bisphenol A methacrylate, propoxylated bisphenol A diglycidyl ether acrylate, O-phthalic acid diglycidyl ether acrylate, cyclohexanedimethanol diglycidyl ether acrylate, pt-butyl Phenyl glycidyl ether acrylate, O-phenylphenol glycidyl ether acrylate, 2-hydroxy-3-phenoxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2 ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, n- Stealure methacrylate , N-butoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, 2-hydroxy -3-acryloyloxypropyl methacrylate.
Monofunctional (meth) acrylic acid monomer or oligomer; methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxytetrahydrophthalic acid, 2-acryloyloxyhexahydrophthalic acid, 2-acryloyloxypropylphthalic acid, 2- Acryloyloxypropyltetraphthalic acid, 2-acryloyloxypropylhexaphthalic acid, methacryloyloxyethyl succinic acid, methacryloyloxytetrahydrophthalic acid, methacryloyloxyethyltetrahydrophthalic acid, methacryloyloxyethylhexahydrophthalic acid, methacryloyloxypropylphthalic acid, methacryloyl Oxypropyltetraphthalic acid, methacryloyloxypropylhexaphthalic acid.

Having a monofunctional alkylene oxide modified (meth) acrylate group; methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 monoacrylate, methoxypolyethylene glycol # 600 monoacrylate, methoxypolyethylene glycol # 1000 monoacrylate, methoxytripropylene glycol acrylate, Phenoxyethylene glycol acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ethoxylated α-phenylphenol propyl acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, methoxy Triethylene glycol methacrylate, methoxy tripropylene glycol dimethacrylate, ethoxylated 2-ethylhexyl methacrylate, butoxy diethylene glycol methacrylate, butoxy diethylene glycol dimethacrylate, polyethylene glycol-modified stearyl methacrylate, phenoxy ethylene glycol methacrylate, phenoxy diethylene glycol methacrylate, phenoxyethyl methacrylate.

Those having an alkylene oxide-modified (meth) acrylate group are represented by the following formula (2) as disclosed in JP-A-2005-92198.
_{^{[CH 2 = C (R 1}} ) COO (R 2 O) n] m R 3 ··· Equation (2)
In the formula, 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-glycolic (meth) acrylate or oligomer thereof; neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1.9-nonanediol diacrylate, isononanediol diacrylate, 1,10-decanediol Dimethacrylate, glycerin dimethacrylate, dimethylol-tricyclodecane diacrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] full orange acrylate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl Acid phosphate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, neopentyl Call dimethacrylate, glycerol dimethacrylate acrylate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxy ethyl acid phosphate.
Those having a bifunctional alkoxylated bisphenol A (meth) acrylate group; ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate.

Product names having bifunctional urethane acrylate groups (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.
Those having a bifunctional ethylene oxide-modified (meth) acrylate group; tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, polytetramethylene glycol # 650 diacrylate, polyethylene polypropylene glycol diacrylate, dioxane glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 400 dimethacrylate Over DOO, polyethylene glycol # 600 dimethacrylate, polyethylene glycol # 1000 dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene polypropylene glycol diacrylate, glycol acrylates such as ethylene glycol dimethacrylate.

The organic resin which has a specific functional group among the monomer or oligomer of the above-mentioned ultraviolet curable resin is shown below.
Having OH group; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-methacryloyloxyethyl acid phosphate 2-acryloyloxyethyl acid phosphate, glycerine methyacrylate, 2-hydroxy-3-methacrylpropyl acrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-3-phenoxypropyl acrylate.

Those having an ether group; methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 monoacrylate, methoxypolyethylene glycol # 600 monoacrylate, methoxypolyethylene glycol # 1000 monoacrylate, motooxytripropylene glycol acrylate, phenoxyethylene glycol acrylate, phenoxydiethylene glycol acrylate 2-hydroxy-3-phenoxypropyl acrylate, ethoxylated α-phenylphenol propyl acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, metho Citripropylene glycol methacrylate, ethoxylated 2-ethylhexyl methacrylate, butoxydiethylene glycol methacrylate, butoxydiethylene glycol methacrylate, polyethylene glycol modified stearyl methacrylate, phenoxyethylene glycol methacrylate, phenoxydiethylene glycol methacrylate, phenoxyethyl methacrylate, tripropylene glycol diacrylate, polypropylene glycol di Acrylate, polyethylene glycol # 200 diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, polytetramethylene glycol # 650 diacrylate, polyethylene polypropylene glycol diacrylate Rate, dioxane glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, polyethylene glycol # 1000 dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene polypropylene glycol diacrylate, ethylene glycol dimethacrylate.

Those having an amino group; dimethylaminoethyl methacrylate, dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, diethylaminoethyl methacrylate.
Those having an amide group; dimethylacrylamide, acryloylmorpholine, dimethylaminopropylacrylamide, isopropylacrylamide, diethylacrylamide, and hydroxyethylacrylamide.
Having a carboxyl group; methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxytetrahydrophthalic acid, 2-acryloyloxyhexahydrophthalic acid, 2-acryloyloxypropylphthalic acid, 2-acryloyloxypropyltetraphthalic acid 2-acryloyloxypropylhexaphthalic acid, methacryloyloxyethylsuccinic acid, methacryloyloxytetrahydrophthalic acid, methacryloyloxyethyltetrahydrophthalic acid, methacryloyloxyethylhexahydrophthalic acid, methacryloyloxypropylphthalic acid, methacryloyloxypropyltetraphthalic acid, Methacryloyloxypropyl hexaphthalic acid.

No functional group; 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, neopentyl Glycol dimethacrylate, glycerin dimethacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, isononanediol diacrylate, 1,10-decanediol dimethacrylate, glycerol dimethacrylate, Dimethylol-tricyclodecane diacrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] full orange acrylate, dimethylol-tricyclodecane diacrylate, methyl methacrylate, ethyl methacrylate n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, n- stearyl Arles methacrylate.

Next, an example of a monomer or oligomer of an ultraviolet curable resin having three or more functional groups that can be suitably used for the second organic resin.
Trifunctional acrylate resin; pentaerythritol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate.
Trifunctional urethane acrylate resin; pentaerythritol hexamethylene diisocyanate urethane prepolymer.
Epoxy group-containing trifunctional acrylate resin; cresol novolac type epoxy acrylate, bisphenol A diglycidyl ether acrylic acid adduct.
Trifunctional (meth) acrylate resin; trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol trimethacrylate, propoxylated pentaerythritol trimethacrylate.

Product names having trifunctional urethane acrylate groups (manufactured by Shin-Nakamura Chemical Co., Ltd.); NK Oligo UA-31F, UA-7100, UA-32P.
Those having a trifunctional (caprolactone-modified) isocyanurate acrylate group; tris- (2-acryloxyethyl) isocyanurate, caprolactone-modified tris- (2-acryloxyethyl) isocyanurate.
Having trifunctional epoxy-modified acrylate groups; ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, propoxylated trimethylolpropane triacrylate, excitated dipentaerythritol polyacrylate, propoxylated dipentaerythritol polyacrylate .
Tetrafunctional (meth) acrylate resin; pentaerythritol tetraacrylate.
Epoxy group-containing tetrafunctional (meth) acrylate resin; ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate.
Hexafunctional (meth) acrylate resin; dipentaerythritol hexaacrylate.
Epoxy group-containing hexafunctional (meth) acrylate resin; excited dipentaerythritol polyacrylate, propoxylated dipentaerythritol polyacrylate.

In addition, tetrafunctional urethane (meth) acrylate oligomer resin, hexafunctional urethane (meth) acrylate oligomer resin, 8-functional urethane (meth) acrylate oligomer resin, 9-functional urethane (meth) acrylate oligomer resin, 10 Functional urethane (meth) acrylate oligomer resin, 12 functional urethane (meth) acrylate oligomer resin, 15 functional urethane (meth) acrylate oligomer resin and the like can be mentioned. As such urethane (meth) acrylate resin, NK oligo UA-33H, UA-6LR, UA-8LR, UA-12LR, U-10PA, U-10HA, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. Is commercially available.

Other examples include tetrafunctional or higher functional acrylate resins containing epoxy groups such as cresol novolac type epoxy acrylate, bisphenol A diglycidyl ether acrylic acid adduct, and the like. 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 commercially available. In particular, an acrylate resin having 6 to 12 functional groups is most suitable as the second organic resin because it has a high curling suppression effect and excellent hardness.

If necessary, an organic dispersion medium may be added to the organic dispersion medium coating solution. It is suitable that the concentration of the organic dispersion medium in the coating liquid is less than 40% by weight. In particular, it is preferably less than 35% by weight. The organic dispersion medium in the coating liquid is not limited to the organic dispersion medium remaining when replacing the organic dispersion medium of the metal oxide particles with the first organic resin in the method for preparing the coating liquid for forming the transparent film. In view of the handling property of the coating liquid, it may contain a material added for viscosity adjustment. The same applies to the dispersion medium for dilution contained in the first organic resin and the second organic resin.

A conventionally known material can be used for this organic dispersion medium. For example, alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol; glycols such as ethylene glycol and hexylene glycol; diethyl ether, ethylene glycol Ethers such as monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; propyl acetate, isobutyl acetate , Butyl acetate, isopentyl acetate, pentyl acetate, 3-acetic acid Esters such as toxibutyl, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, Ketones such as acetylacetone and acetoacetate; toluene, xylene and the like. Among these, alcohols, ethers, esters, and ketones are suitable, and the dispersibility of the metal oxide particles and the solubility of the organic resin are improved.

The boiling point of the organic dispersion medium is preferably in the range of 56.12 ° C. to 200 ° C., more preferably 56.12 to 180 ° C.
When the organic dispersion medium has a low boiling point, the coating film dries quickly, so that the densification tends to be insufficient and the film thickness tends to be non-uniform. Therefore, the hardness of the obtained transparent film becomes insufficient.
If the organic dispersion medium has a high boiling point, the organic dispersion medium may remain, resulting in insufficient film shrinkage and insufficient hardness of the resulting transparent film.

You may add a photoinitiator to a polymerization initiator coating liquid as needed. The amount of the polymerization initiator used is preferably in the range of 2 to 20% by weight, more preferably 4 to 16% by weight, based on the solid content concentration of the organic resin. Known polymerization initiators can be used. For example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-methyl-2-methyl- Phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl]- And 2-morpholinopropan-1-one.

[Organic resin dispersion sol]
The organic resin dispersion sol of the present invention is obtained by dispersing metal oxide particles having an average particle diameter of 5 to 300 nm in a first organic resin having two or less functional groups, or an organic dispersion medium and a first organic resin. Is a sol. A coating solution for a transparent film is prepared using this organic resin dispersion sol. The metal oxide particles are desirably surface-treated with an organosilicon compound such as a silane coupling agent.

As the first organic resin, an ultraviolet curable resin having 2 or less functional groups is preferable. Since the organic resin having 1 to 2 functional groups has a low viscosity, the increase in the viscosity of the organic dispersion medium sol of metal oxide particles can be reduced. The first organic resin functions as a resin for dispersing metal oxide particles.
The first organic resin is preferably a monomer or oligomer of an ultraviolet curable resin. When the monomer is an ultraviolet curable resin, an organic resin-dispersed sol of metal oxide particles that is stable at a high concentration can be formed.

The molecular weight (polystyrene equivalent molecular weight) of the first organic resin is suitably 5,000 or less. In particular, it is preferably 4,500 or less. When the molecular weight exceeds 5,000, the viscosity of the sol increases and the concentration of particles cannot be increased. More preferably, it is 1,000 or less.
As the organic dispersion medium, general organic solvents such as alcohols, ethers, esters, and ketones can be used.

The organic resin-dispersed sol of metal oxide particles preferably has a concentration (C _PS ) as a solid content of the metal oxide particles in the range of 45 to 90% by weight, more preferably 45 to 80% by weight. The concentration (C _RS ) as the solid content of the first organic resin in the sol is suitably 10 to 50% by weight. In particular, 15 to 40% by weight is preferable.
At this time, the total solid content concentration (C _TS ) of the sol is 60% by weight or more. More than 60% by weight is preferable, and 65% by weight or more is more preferable. When the total solid content (C _TS ) is less than 100% by weight, the remainder is the organic dispersion medium.

It has not been conventionally known that an organic resin dispersed sol having such a composition is stable. This organic resin-dispersed sol can be produced according to steps (a) to (b) of the method for preparing a coating liquid described above. Since such an organic resin dispersion sol can stably disperse metal oxide particles for a long period of time, it can be stored as a sol and can be liquefied immediately before use.

[Base material with transparent film]
The above-mentioned coating solution is applied to the substrate to form a transparent film on the substrate. The transparent coating is formed of metal oxide particles and a matrix component.
The substrate substrate is preferably at least one transparent resin substrate selected from polyethylene terephthalate (PET), triacetyl cellulose (TAC), acrylic, polycarbonate, and cycloolefin polymer (COP). These resin base materials are excellent in adhesion to the transparent film formed by the coating solution described above, and can provide a base material with a transparent film excellent in hardness, scratch resistance and the like.

Metal oxide particles It is preferable to use metal oxide particles that have been surface-treated with the aforementioned organosilicon compound. The content (W _P ) of the metal oxide particles in the transparent coating as a solid content is preferably in the range of 50 to 90% by weight, more preferably 65 to 85% by weight. When the content (W _P ) is within this range, a transparent film having high hardness and no irregularities, little shrinkage, dense and crack-free even with a thick film can be obtained.
When the content (W _P ) is small, the resin is increased, so that densification is not sufficient and the hardness of the transparent film may be lowered. Even if the content (W _P ) is too large, surface irregularities become large, haze may deteriorate due to external scattering, transparency may decrease, and film densification may decrease, scratch resistance, substrate Adhesiveness with the ink becomes insufficient.

Matrix component The matrix component comprises a first organic resin and a second organic resin. In the transparent film, these resins are cured in a polymerized state. Both the first organic resin and the second organic resin are preferably ultraviolet curable resins.
When these organic resins are ultraviolet curable resins, it is possible to obtain a transparent film having excellent adhesion to a resin substrate such as PET or TAC and excellent hardness. Moreover, a substrate with a transparent coating can be produced by a highly productive winding method (roll-to-roll).

The content of the first organic resin in the matrix component as a solid content is 0.1 to 80% by weight. In particular, it is preferably in the range of 5 to 60% by weight. When there is little content of the 1st organic resin in a matrix component, the smoothness of the surface of a transparent film will fall, or densification will become inadequate. For this reason, haze, hardness, scratch resistance, adhesion and the like are insufficient. When the content of the first organic resin in the matrix component is large, the second organic resin is decreased, so that the denseness of the transparent film is low and the hardness is insufficient.

The content (W _R ) of the matrix component as a solid content in the transparent film is preferably in the range of 10 to 50% by weight, more preferably 15 to 40% by weight. When the content (W _R ) of the matrix component in the transparent film as a solid content is less than 10% by weight, irregularities are generated on the surface, haze of the film is deteriorated due to external scattering, and transparency is lowered. In addition, since the number of particles increases, the transparent film becomes insufficiently densified, resulting in insufficient adhesion to the substrate, scratch resistance, and hardness. On the other hand, when the content (W _R ) exceeds 50% by weight, the shrinkage of the film increases. Therefore, curling and cracking occur when the film is thick (approximately 10 μm or more). Moreover, since the denseness is low, high hardness cannot be obtained.

The ratio (W _R / W _P ) between the content (W _R ) of the matrix component in the transparent film and the content (W _P ) of the metal oxide particles is 0.11 to 1.0, more preferably 0.18 to It is preferable to be in the range of 0.8. When this ratio (W _R / W _P ) is small, the surface unevenness of the transparent film may become large, haze of the film deteriorates due to external scattering, and transparency is lowered. Furthermore, the film is not sufficiently densified, and a transparent film having excellent scratch resistance and adhesion to the substrate may not be obtained. Further, when this ratio (W _R / W _P ) is large, the film shrinks, and when the film is thick, cracks may occur. Moreover, the densification of the transparent film becomes insufficient, and thus the hardness may be insufficient.

The average film thickness (T) of the transparent film formed with such a matrix component is suitably 1 to 100 μm. The range of 12 to 80 μm is particularly preferable. If it is the film thickness of this range, the transparent film by which curling was suppressed with high hardness can be formed on a resin base material.

Here, the average film thickness (T) of the transparent film is obtained by taking a transmission electron micrograph (TEM) of the cross section of the film, and the distance between the top of the convex portion on the top surface of the film and the bottom immediately below the surface (T And the distance (T-concave) between the deepest part of the concave part adjacent to the convex part and the bottom part directly underneath (T-concave), and the average value is obtained. In addition, it is preferable that the number of unevenness | corrugations to measure is 10 sets or more at regular intervals. Thereby, a transparent film having a pencil hardness of 5H or more, and further 6H or more can be formed on the resin substrate. Moreover, the substrate with a transparent coating has a curling characteristic measured under the following conditions of 5 mm or less.
The curling characteristic is measured by applying a coating solution on a TAC film substrate having a coating surface of 14 cm × 25 cm and a thickness of 40 μm so that a 12 μm-thick transparent film can be formed, and allowing to stand for 20 hours. Thereafter, the film is cut into a size of 10 cm × 10 cm, placed on a flat plate with the coating surface down, and the height of the apex of the base material that has been curled (curved) and floated is measured.
With a transparent film formed on a conventional resin substrate, it is difficult to achieve such curling characteristics and hardness. Such a transparent coating is formed by applying a coating solution for forming a transparent coating on a resin substrate to form a coating, drying, and curing.

It is preferable that wavy irregularities are formed on the surface of the transparent coating (an interface with an antireflection film described later). Since the silica particles (P) and the matrix component are combined at the composition ratio described above, a transparent film having a predetermined surface roughness is formed. If the surface roughness is present, the bonded area is increased when the antireflection film is formed, so that a coated substrate with high adhesion and excellent hardness and scratch resistance can be obtained. Further, since the smoothness of the antireflection film is not hindered, there is little adverse effect of haze of the film due to external scattering, and transparency is not lowered.
For the wavy irregularities, the surface roughness (Ra) is suitably in the range of 1 to 10 nm, more preferably 1 to 5 nm. The surface roughness (Ra) can be measured with an atomic force microscope (manufactured by Bruker, Inc .: Dimension 3100).
The wavy unevenness is considered to be caused by the presence of surface-treated silica particles blended in the coating solution on the surface layer of the film. Therefore, the tendency depending on the content of silica particles in the transparent coating is recognized.

The transparent coating according to the present invention has a relatively large amount of silica particles (P) and a small amount of matrix components. Therefore, it is considered that the film is cured in a wavy shape without being flattened during curing. This varies depending on the type of matrix component. When there are few matrix components, the surface unevenness | corrugation becomes large too much, the haze of a film | membrane may deteriorate by external scattering, and transparency may fall. Moreover, since the number of particles increases, the film is not sufficiently densified, and adhesion to the substrate, scratch resistance, and hardness may not be obtained. Even if there are too many matrix components, the wavy unevenness of the surface becomes too large and the transparency may be lowered, and the adhesion to the substrate and the scratch resistance may not be obtained. Further, since the shrinkage of the film increases, curling or cracking occurs when the film is thick (approximately 10 μm or more). Moreover, since the denseness is low, the hardness is insufficient.

Also, as a coating method, printing can be performed by a known method such as a dipping method, a spray method, a spinner method, a roll coating method, a bar coating method, a gravure printing method, or a micro gravure printing method. After printing, it is cured by ultraviolet irradiation or the like.

After apply | coating the coating liquid by this invention, it is made to dry by a drying process. The shrinkage ratio (a) of the volume of the coating film in the drying process is set to 25% or less. In particular, it is preferably 20% or less. After drying, the coating film is cured. The shrinkage ratio (b) of the coating film during curing is made 10% or less. In particular, 5% or less is preferable. If the shrinkage ratio (a) of the coating film at the time of drying or the shrinkage ratio (b) of the coating film at the time of curing is high, cracks occur in the case of a thick film, and the hardness is insufficient due to low density. . Furthermore, the total shrinkage (c) at the time of drying and curing is preferably 35% or less, particularly preferably 30% or less.
The shrinkage rate (a), shrinkage rate (b), and shrinkage rate (c) are expressed by the following mathematical formulas (A) to (C).
Shrinkage ratio (a) [%] = (1− (density of coating solution / density of dry film)) × 100 Expression (A)
Shrinkage rate (b) [%] = (1− (density of dried film / density of cured film)) × 100 Expression (B)
Shrinkage ratio (c) [%] = (1− (density of coating solution / density of cured film)) × 100 Expression (C)

[Antireflection layer]
An antireflection layer is formed on the above-described transparent film as necessary. Antireflection layer contains silica-based hollow particles and the matrix component (M _L). Here, the silica-based hollow particles having a small average particle diameter were combined with the same matrix component as the transparent coating. Thereby, the hardness of a transparent film can be maintained even with a thin antireflection layer.

Hereinafter, the silica-based hollow particles and the matrix component constituting the antireflection layer (M _L) is described in detail.
Silica-based hollow particles (A)
Silica-based hollow particles are silica-based particles having cavities inside (disclosed in JP-A-2001-233611 and JP-A-2003-192994), and are particles in a colloidal region having a low refractive index and dispersibility. It is suitable for the antireflection layer.

The average particle diameter (D _PA ) of the silica-based hollow particles is suitably 10 to 45 nm. In particular, 15 to 40 nm is preferable. When the average particle diameter is less than 10 nm, the void ratio is small, so the refractive index of the particles does not decrease (1.4 or less). Therefore, sufficient antireflection performance cannot be obtained. Further, in order to obtain the film thickness (T _L ), the silica-based hollow particles are arranged in a multilayer or irregularly (aggregate). Therefore, not only the reflectance but also the film strength is not improved. When the average particle diameter exceeds 45 nm, the adhesion to the transparent coating is lowered and the hardness of the film-coated 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 size is larger than the unevenness of the transparent coating, the transparent coating cannot be adhered and bonded.

The refractive index of silica-based hollow particles is suitably 1.10 to 1.40. In particular, 1.10 to 1.35 is preferable. A refractive index of less than 1.10.
The ratio (D _PA / T _L ) between the thickness (T _L ) of the antireflection layer and the average particle diameter (D _PA ) of the silica-based hollow particles is suitably 0.05 to 0.56. Furthermore, the range of 0.1 to 0.45 is preferable. When this ratio is less than 0.05, the refractive index of the particles is not lowered as described above, and the function as an antireflection layer becomes insufficient. When this ratio exceeds 0.56, the strength of the particles is low and the smoothness of the surface of the antireflection layer cannot be obtained. Therefore, it is difficult to obtain desired strength and hardness.

Second silica-based particles (B)
The antireflection layer preferably contains not only silica-based hollow particles (A) but also second silica-based particles (B) having an average particle diameter (D _PB ) of 4 to 17 nm. A particularly preferable average particle diameter (D _PB ) is 4 to 12 nm. Examples of the second silica-based particles include silica sol, silica-based hollow particles, and chain silica-based particles in which these are connected in a chain. The refractive index of the second silica-based particles is 1.15 to 1.46, preferably 1.15 to 1.40.
Particles having an average particle diameter of less than 4 nm are difficult to realize, and even if obtained, it is difficult to form a uniform dispersion or coating solution. For this reason, the smoothness of the antireflection layer surface is poor. Moreover, since the particles in the layer are not densely packed, sufficient strength and hardness cannot be obtained. When the average particle diameter exceeds 17 nm, the silica hollow particles (A) do not enter the interstices, resulting in insufficient reflectivity and insufficient strength.

The ratio (D _PB / D _PA ) between the average particle diameter of the second silica-based particles (B) and the silica-based hollow particles (A) is preferably 0.1 to 0.4. In particular, 0.1 to 0.35 is preferable. When this ratio is less than 0.1, the silica-based hollow particles are aggregated or the arrangement is irregular. As a result, the reflectivity and intensity become insufficient. When this ratio exceeds 0.4, the silica-based hollow particles are irregularly arranged or aggregated because they do not enter the particle gaps of the silica-based hollow particles.
The average particle diameter of each particle was obtained by taking a transmission electron micrograph (TEM), measuring the particle diameter of 100 particles, and setting the average value.

The silica-based hollow particles (A) and the second silica-based particles (B) used here are represented by the formula (1), similarly to the metal oxide particles contained in the coating liquid for forming the transparent film. The surface is preferably treated with an organosilicon compound. When the second silica-based particles are surface-treated with an organosilicon compound, an antireflection layer excellent in water resistance, water repellency, antifouling property and the like is obtained.
In particular, it is preferable to perform surface treatment with an organic silicon compound of formula (1) where n = 0, and then surface treatment with an organosilicon compound of n = 1, 2, 3. Examples of the organic silicon compound with n = 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

Hereinafter, an example of a surface treatment method using an organosilicon compound will be described. Conventionally known methods can be employed.
A predetermined amount of an organosilicon compound is added to an alcohol dispersion of silica-based particles, and water is added thereto. If necessary, hydrolysis is carried out by adding an acid or alkali as a hydrolysis catalyst. At this time, the ratio of the weight of the organosilicon compound as R _n —SiX _{(4-n) / 2} to the weight of the silica-based particles (R _n —SiX _{(4-n) / 2} weight / silica-based particle weight) Is preferably 0.01 to 0.5, more preferably 0.02 to 0.25. When this 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, which will be described later, is low, the stability is insufficient, and the coating liquid is uniform. Cannot be distributed. As a result, silica-based particles may agglomerate, the strength and scratch resistance of the antireflection layer may decrease, and the haze value and reflectance may increase. Even if the weight ratio exceeds 0.5, the dispersibility is not further improved, the refractive index is increased, and the cost is reduced only by increasing the expensive organosilicon compound.

Thereafter, an organic solvent dispersion of silica-based particles that are replaced with an organic solvent as necessary and subjected to surface treatment is prepared. As the organic solvent, it is preferable to use the same organic solvent as the coating liquid for forming the antireflection layer described later. An antireflection layer is formed from the coating solution thus prepared.

The antireflection layer preferably contains 5 to 80% by weight of silica-based hollow particles (A). A content of 10 to 75% by weight is more preferred. When the content is less than 5% by weight, adhesion to the transparent film, strength, surface flatness, scratch resistance, scratch strength, and the like are insufficient. Furthermore, since the refractive index of the antireflection layer cannot be lowered, the antireflection performance cannot be improved. When the content exceeds 80% by weight, there are too many particles, resulting in insufficient film strength, scratch resistance, scratch strength, and the like. Furthermore, the haze value of the antireflection film also increases.

Even when the second silica-based particles (B) are blended in the antireflection layer, the total content of the silica-based hollow particles and the second silica-based particles is 5 to 80% by weight, more preferably 10 to 75% by weight. It is preferable to use so that it may become the range of%. Further, the ratio of the second silica-based particles is preferably 30% by weight or less, more preferably 20% by weight or less, based on the total silica-based particles. When the ratio of the second silica-based particles exceeds 30% by weight, the second silica-based particles (B) that do not fit into the gaps of the silica-based hollow particles (A) increase, and the silica-based hollow particles (A) Are randomly arranged or agglomerated.
When the second silica-based particle (B) is contained in the above-mentioned appropriate range, the second silica-based particle (B) is placed in the gap between the silica-based hollow particles (A) on the surface portion of the antireflection layer. Exists to planarize the surface. Therefore, an antireflection layer excellent in scratch resistance and scratch strength can be obtained.

Matrix component (M _L)
Examples of the matrix component (M _L ) of the antireflection layer include thermosetting resins, thermoplastic resins, and electron beam curable resins, which are organic resins for paints. Polyester resin, polycarbonate resin, polyamide resin, polyphenylene oxide resin, thermoplastic acrylic resin, vinyl chloride resin, fluorine resin, vinyl acetate resin, silicone rubber and other thermoplastic resins, urethane resin, melamine resin, butyral resin, phenol resin, epoxy Conventionally used resins such as resins, unsaturated polyester resins, thermosetting acrylic resins, thermosetting resins such as ultraviolet curable acrylic resins, and ultraviolet curable acrylic resins can be exemplified. Further, two or more types of copolymers or modified products of these resins may be used.

In particular, the matrix component (M _L ) preferably contains at least one of the first organic resin and the second organic resin used in the above-described transparent film. If at least one part of such an organic resin is contained, when the antireflection layer is formed on the transparent film, two films containing the same matrix component are bonded to each other, so that hardness, scratch resistance, etc. An excellent film-coated substrate can be obtained.

The content of the matrix component (M _L ) in the antireflection layer is preferably 20 to 95% by weight, more preferably 25 to 90% by weight as a solid content. When the content of the matrix component (M _L ) is less than 20% by weight, the strength of the antireflection film, adhesion to the substrate, scratch resistance, etc. are insufficient. When the content of the matrix component (M _L) is more than 95 wt%, due to the low amount of silica-based particles, not a uniform thickness, the surface lacking in flatness, scratch resistance, scratch strength etc. Insufficient and low refractive index cannot be obtained. For this reason, the antireflection performance is insufficient.

The thickness (T _L ) of the antireflection layer is suitably from 80 to 200 nm. Furthermore, 90 to 150 nm is preferable. If the layer is thin, strength and scratch resistance are insufficient. Even if the layer is too thick, cracks are likely to occur, resulting in insufficient strength. Also, the layer may be too thick and the antireflection performance may be reduced. When the thickness is in an appropriate range, an antireflection layer having a low reflectance (bottom reflectance, luminous reflectance) and excellent hardness or the like can be obtained. A cross-sectional photograph of the transparent coating and the antireflection layer was taken using a transmission electron microscope (TEM), and the average thickness (T _H ) of the transparent coating was subtracted from the total thickness of the antireflection layer ( _TL). )
Thereby, even if it uses the above-mentioned resin base material, the antireflection layer of pencil hardness 5H or more can be formed. This is derived from the lower transparent coating, and an antireflection layer having pencil hardness comparable to that of the transparent coating can be realized.

Since the coating solution such for forming the coating solution above antireflection layer for the anti-reflective layer forming, a material comprising a silica-based hollow particles (A) contained in the film and based on the matrix component (M _L) include together with a solvent Yes. That is, the coating liquid contains silica-based hollow particles, a matrix forming component, and a solvent. The average particle diameter (D _PA ) of the silica-based hollow particles is in the range of 10 to 45 nm. Matrix-forming component, which is a base of the matrix components described in the anti-reflective layer (M _L), the same organic resin as described above.

Furthermore, it is preferable that the matrix forming component contains at least one of the first organic resin and the second organic resin used in the coating liquid for forming the transparent film. When containing at least one of the first organic resin and the second organic resin, after forming a transparent film, the coating liquid for forming the antireflection film is applied, dried, and irradiated with ultraviolet rays. Since the bond between the transparent coating containing the antireflection layer and the antireflection layer increases, a film-coated substrate having an antireflection layer excellent in hardness, scratch resistance and the like can be obtained.

Furthermore, when the first organic resin ( _AL ) contained in the coating solution for forming the antireflection layer is a monomer or oligomer of an ultraviolet curable resin having 1 to 2 functional groups, An antireflection layer having a high coating solution stability and a smooth surface can be obtained. When this coating liquid contains the second organic resin (B _L ), the second organic resin, the first organic resin and the second organic resin contained in the transparent film are easily combined, and the transparent film And an antireflection layer integrated therewith.

Further, when the second organic resin (B _L ) contained in the coating solution for forming the antireflection layer is an ultraviolet curable resin monomer or oligomer having three or more functional groups, the second transparent resin contained in the lower transparent film It is easy to bond with the second organic resin (B), has excellent adhesion to the transparent film, and the transparent film and the antireflection layer are integrated. Moreover, since it couple | bonds together as a matrix formation component, the antireflection layer excellent in hardness is obtained.

Further, a polymerization initiator can be added to the coating solution for forming the antireflection layer, if necessary. The polymerization initiator is not particularly limited as long as it can polymerize and cure the matrix-forming component, and can be appropriately selected depending on the resin, and conventionally known polymerization initiators can be used. For example, in addition to polymerization initiators such as acylphosphine oxides, acetophenones, propiophenones, benzyls, benzoins, benzophenones, and thioxanthones, cationic photopolymerization initiators and the like can be mentioned. More specifically, the substances exemplified in the coating liquid for forming the transparent film can be used.

The solid content concentration of the polymerization initiator in the coating solution for forming the antireflection film varies depending on the kind of the matrix forming component, but is 0.1 to 20% by weight, more preferably 0.5 to 10% with respect to the matrix forming component. It is preferably in the range of wt%.
When the content of the polymerization initiator is less than 0.1% by weight of the matrix forming component as a solid content, the antireflection layer is not sufficiently cured. If it exceeds 20% by weight of the matrix forming component, the stability of the coating solution becomes insufficient.

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

The total solid concentration of the coating solution is preferably in the range of 1 to 10% by weight, more preferably 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 there is a risk of uneven coating and uneven drying. If the total solid content exceeds 10% by weight, the film thickness of the anti-reflection film becomes too thick, and sufficient optical properties and anti-reflection performance cannot be obtained. There is a risk that strength and hardness may decrease.

The concentration of the silica-based hollow particles (A) in this coating solution is preferably 0.25 to 9% by weight, more preferably 0.35 to 8% by weight as the solid content. When the solid content concentration is less than 0.25% by weight, not only the adhesion with the underlying transparent film, film strength, surface flatness, scratch resistance, scratch strength, etc. are insufficient, but also the antireflection layer. Since the refractive index cannot be lowered, the antireflection performance becomes insufficient. When the solid content concentration exceeds 9% by weight, the amount of particles is too large, and not only the strength, scratch resistance, scratch strength, etc. of the antireflection layer become insufficient, but also the haze value increases.

Even when the second silica-based particles (B) are used, the total solid concentration of the coating solution is preferably 0.25 to 9% by weight. Furthermore, the ratio of the second silica-based particles in all the silica-based particles is preferably 30% by weight, more preferably 20% by weight or less.
When the second silica-based particles are contained in such a range, the second silica-based particles exist in the particle gaps of the silica-based hollow particles in the surface portion of the obtained antireflection layer, and the surface is flattened. Thereby, an antireflection layer excellent in scratch resistance and scratch strength can be obtained. Moreover, since the refractive index of the second silica-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 more excellent antireflection performance can be obtained.

The concentration of the matrix forming component in the coating solution as a solid content is preferably 0.75 to 9.5% by weight, more preferably 0.75 to 8% by weight. When the solid content concentration is less than 0.75% by weight, there are too many particles relative to the matrix, so that not only the strength, scratch resistance, scratch strength, etc. of the antireflection layer become insufficient, but also the antireflection layer, film Increases the haze value. If the solid content concentration exceeds 9.5% by weight, there are too few particles relative to the matrix, so that adhesion to the transparent film, film strength, surface flatness, scratch resistance, scratch strength, etc. are insufficient. In addition, since the refractive index of the antireflection film cannot be lowered, the antireflection performance becomes insufficient.

[Production method of substrate with film having antireflection layer]
Next, a method for producing a film-coated substrate having an antireflection layer will be described. An antireflection layer is formed on the transparent coating formed on the surface of the resin substrate. That is, a coating solution for forming an antireflection layer is applied onto the above-described 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 good curling characteristics.

Examples of the method for applying the coating liquid include the same method as the method for printing the coating liquid for the transparent film. Any method may be used in the drying step as long as the solvent of the coating solution can be substantially removed. Usually, it can be dried by heating at a temperature of 60 to 120 ° C. for several minutes. After drying, it is cured by ultraviolet irradiation, heat treatment, or a combination thereof.
Alternatively, the transparent coating and the antireflection layer may be cured simultaneously. That is, a coating solution for forming a transparent film is applied and dried, and then a coating solution for forming an antireflection layer is applied thereon and dried, and then both coating solutions are cured simultaneously by irradiation with ultraviolet rays.

Hereinafter, examples using silica particles as the metal oxide particles will be specifically described. The transparent film obtained in this example has a function of a hard coat film. In addition, this invention is not limited by these Examples.

[Example 1]
Silica sol dispersion (manufactured by JGC Catalysts &Chemicals; Cataloid SI-30; average particle size 12 nm, SiO ₂ concentration 40.5 wt%, dispersion medium: isopropanol, particle refractive index 1.46) to 100 g of γ-meta 7.48 g of acryloxypropyltrimethoxysilane (Shin-Etsu Silicon Co., Ltd .: KBM-503, SiO ₂ component 81.2%) is mixed, 3.1 g of ultrapure water is added, and the mixture is stirred at 50 ° C. for 6 hours. . As a result, a 12 nm silica sol dispersion (solid content concentration: 40.5 wt%) surface-treated with a silane coupling agent is obtained.
Thereafter, the dispersion medium is replaced with PGME (propylene glycol monomethyl ether) by a rotary evaporator to prepare a dispersion of silica particles (1) having a solid content concentration of 40.5% by weight.

Dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, functional) as a first organic resin in 2500 g of silica particle (1) dispersion (Base number: 2, molecular weight: 219, solid content concentration: 100%) 202.5 g is added. This resin also has two hydrophilic groups. Then, a part of the solvent is removed by a rotary evaporator to prepare an organic resin dispersion (1) of silica particles having a solid content concentration of 76.0% by weight (in the examples, the first organic resin is used for dispersion). The organic resin (A) and the second organic resin are referred to as a curing organic resin (B)).

Preparation of coating liquid (1) Next, 75.31 g of this organic resin dispersion liquid (1) was added with urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, functional group: urethane acrylate, Number of functional groups: 9, molecular weight: 4,000, solid concentration 100%) 8.32 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g and photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, 2.37 g of PGME, and 12.50 g of acetone are mixed to obtain a coating solution (1) for forming a transparent film having a solid content concentration of 66.1% by weight. Table 2 shows the composition of the coating solution (1) obtained.

Preparation of substrate with film (1) Coating solution (1) was applied to TAC film (manufactured by Fuji Film Co., Ltd .: FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51) by bar coater method # 16 And dried at 80 ° C. for 120 seconds. The thickness of the coating film is 12 μm.
Next, under a N ₂ atmosphere, 300 mJ / cm ² ultraviolet rays are irradiated to cure the coating film, and a transparent film is formed on the substrate. The film thickness of the transparent coating is 12 μm. Such a transparent coating functions as a hard coat. The obtained film-coated substrate (1) was evaluated as follows, and the results are shown in Tables 2 and 3.

The shrinkage of the volume from the paint to the drying (shrinkage (a)), the volume shrinkage due to UV curing (shrinkage (b)), and the overall shrinkage (shrinkage (c)) are calculated. First, the density (specific gravity) of the coating solution is measured. After applying the coating solution so that the film thickness after drying becomes about 10 μm, it is dried at 80 ° C. for 2 minutes to form a dry film. A part of the dried film is collected and the density (specific gravity) is measured. The shrinkage rate (a) is calculated by the above-described equation (A). Next, the dried film is irradiated with UV and cured. A part of the cured transparent film is collected, and the density (specific gravity) of the cured film is measured. The shrinkage rate (b) is calculated by the above-described equation (B). Further, the shrinkage rate (c) is calculated by the above-described equation (C).
The total light transmittance and the substrate with a haze film are measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.). Further, the refractive index of the transparent film is measured by an ellipsometer (manufactured by ULVAC, EMS-1). The uncoated TAC film has a total light transmittance of 93.2%, a haze of 0.2%, and a reflectance of light having a wavelength of 550 nm of 6.0%.
To observe the presence or absence of crack crack.
Curling Curling Test Method: A transparent coating film applied to a TAC film having a size of 14 cm × 25 cm is stored for 20 hours. Cut the film to 10 cm × 10 cm size. The film is placed with the coated surface down, and the height A of the base material from the floor surface is measured.
Pencil hardness Measured with a pencil hardness tester according to JIS-K-5600.
Using scratch-resistant # 0000 steel wool, sliding 10 times with a load of 2 kg / cm ² , visually observing the surface of the film, and evaluating according to the following criteria.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×

[Example 2]
7. Preparation of coating solution (2) To 80.38 g of the silica particle organic resin dispersion (1) prepared in Example 1, urethane acrylate (the same NK oligo UA-33H as in Example 1) was used as the curing organic resin. 88 g, 1.00 g of acrylic silicone leveling agent (Disparon NSH-8430HF same as in Example 1), 0.53 g of photopolymerization initiator (Irgacure 184 same as in Example 1), 0.21 g of PGME, and 9.0 g of acetone Are sufficiently mixed to prepare a coating solution (2) having a solid concentration of 70.6% by weight. Table 2 shows the composition of the coating solution (2) obtained.
Preparation of substrate with film (2) A substrate with film (2) is prepared in the same manner as in Example 1 except that the coating solution (2) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 3]
In the same manner as in Example 1, a silica particle (1) dispersion having a solid content concentration of 40.5% by weight is prepared. Add 202.5 g of dimethylol-tricyclodecane diacrylate (the same light acrylate DCP-A as in Example 1) as an organic resin for dispersion to 2500 g of the silica particle (1) dispersion, and remove part of the solvent with a rotary evaporator. Then, an organic resin dispersion (3) of silica particles having a solid content concentration of 85.0% by weight is prepared.

Preparation of coating solution (3) To 99.99 g of this organic resin dispersion (3), 9.90 g of urethane acrylate (the same NK oligo UA-33H) as the curing organic resin, and an acrylic silicone leveling agent 1.00 g (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF), 0.59 g of a photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184), 0.51 g of PGME, and 8.00 g of acetone are mixed thoroughly. A coating solution (3) having a solid concentration of 78.7% by weight is prepared.
Preparation of substrate with film (3) A substrate with film (3) is produced in the same manner as in Example 1 except that the coating solution (3) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 4]
267.7 g of dimethylol-tricyclodecanediacrylate (the same light acrylate DCP-A as in Example 1) as an organic resin for dispersion was added to 2500 g of the silica particle (1) dispersion prepared in Example 1, and a rotary evaporator was added. A part of the solvent is removed to prepare an organic resin dispersion (4) of silica particles having a solid content concentration of 72.1% by weight.

Preparation of coating solution (4) To 66.61 g of this organic resin dispersion (4), 10.98 g of urethane acrylate (NK oligo UA-33H as in Example 1) as an organic resin for curing, and an acrylic silicone leveling agent (Disparone NSH-8430HF same as in Example 1) 1.00 g, photopolymerization initiator (Irgacure 184 same as Example 1) 0.70 g, 8.21 g of PGME and 12.50 g of acetone were mixed thoroughly to obtain a solid content. A coating solution (4) having a concentration of 66.1% by weight is prepared.
Preparation of substrate with film (4) A substrate with film (4) is produced in the same manner as in Example 1 except that the coating solution (4) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 5]
153.0 g of dimethylol-tricyclodecane diacrylate (the same light acrylate DCP-A as in Example 1) was added as an organic resin for dispersion to 2500 g of the silica particle (1) dispersion prepared in Example 1, and the rotary evaporator was added. A part of the solvent is removed to prepare an organic resin dispersion (5) of silica particles having a solid concentration of 72.3% by weight.

Preparation of coating solution (5) 81.94 g of this organic resin dispersion (5), 6.27 g of urethane acrylate (NK oligo, UA-33H same as in Example 1) as an organic resin for curing, and acrylic silicone leveling 1.00g of the same agent (Disparon NSH-8430HF as in Example 1), 0.46g of photopolymerization initiator (Irgacure 184 as in Example 1), 0.33g of PGME and 10.00g of acetone were mixed thoroughly. A coating solution (5) having a partial concentration of 66.1% by weight is prepared.
Preparation of substrate with film (5) A substrate with film (5) is prepared in the same manner as in Example 1 except that the coating solution (5) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 6]
To 2,500 g of the silica particle (1) dispersion prepared in Example 1, 85.8 g of dimethylol-tricyclodecane diacrylate (the same light acrylate DCP-A as in Example 1) as an organic resin for dispersion was added, and the rotary evaporator was added. A part of the solvent is removed to prepare an organic resin dispersion (6) of silica particles having a solid content concentration of 69.0% by weight.

Preparation of coating liquid (6) Next, 75.31 g of this organic resin dispersion (6) was mixed with 12.15 g of urethane acrylate (the same NK oligo, UA-33H) as the curing organic resin, and acrylic silicone. 1.00 g of a leveling agent (disparone NSH-8430HF, the same as in Example 1), 0.50 g of photopolymerization initiator (Irgacure 184, the same as in Example 1), 2.04 g of PGME, and 9.00 g of acetone are mixed thoroughly. Thus, a coating solution (6) having a solid content concentration of 66.1% by weight is obtained.
Preparation of substrate with film (6) A substrate with film (6) is prepared in the same manner as in Example 1 except that the coating solution (6) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 7]
272.1 g of dimethylol-tricyclodecanediacrylate (the same light acrylate DCP-A as in Example), which is an organic resin for dispersion, was added to 2500 g of the dispersion of silica particles (1) prepared in Example 1, and a rotary evaporator was used. A part of the solvent is removed to obtain an organic resin dispersion (7) of silica particles having a solid content concentration of 80.1% by weight.

Preparation of Coating Solution (7) Next, 75.31 g of this organic resin dispersion (7) was mixed with 5.21 g of urethane acrylate (the same NK oligo UA-33H as in Example 1) and acrylic silicone. A system leveling agent (Disparon NSH-8430HF identical to Example 1) 1.00 g, a photopolymerization initiator (Irgacure 184 identical to Example 1) 0.50 g, PGME 5.48 g and acetone 12.50 g were mixed thoroughly. Thus, a coating solution (7) having a solid content concentration of 66.1% by weight is obtained.
Preparation of substrate with film (7) A substrate with film (7) is prepared in the same manner as in Example 1 except that the coating solution (7) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 8]
1,6-hexadiol dimethacrylate as an organic resin for dispersion (manufactured by Sakai Kogyo Co., Ltd .; SR-238F, functional group; acrylate, number of functional groups: 2) , Molecular weight: 226) 202.5 g is added, and a part of the solvent is removed by a rotary evaporator to obtain an organic resin dispersion (8) of silica particles having a solid content concentration of 76.0% by weight.

Preparation of Coating Solution (8) Next, 75.31 g of this organic resin dispersion (8) was added to urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo U-6LPA, functional group: urethane acrylate). , Functional group number: 6, molecular weight: 2,100, solid content concentration 70%) 11.89 g, acrylic silicone leveling agent (dispalon NSH-8430HF identical to Example 1) 1.00 g and photopolymerization initiator (implementation) The same Irgacure 184 as in Example 1) 0.50 g, 0.30 g of PGME and 11.00 g of acetone are mixed well to prepare a coating solution (8) having a solid content concentration of 66.1% by weight.
Preparation of substrate with film (8) A substrate with film (8) is prepared in the same manner as in Example 1 except that the coating solution (8) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 9]
3.74 g of γ-methacrylooxypropyltrimethoxysilane (KBM-503, the same as in Example 1) is mixed with 100 g of silica sol dispersion (the same cataloid SI-30 as in Example 1), and ultrapure water is added to 3 g. Add 1 g and stir at 50 ° C. for 6 hours. As a result, a 12 nm silica sol dispersion (solid content concentration: 40.5 wt%) surface-treated with a silane coupling agent is obtained.
Thereafter, the solvent is replaced in the same manner as in Example 1 to prepare a silica particle (9) dispersion having a solid content concentration of 40.5% by weight.

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 to 2500 g of the silica particle (9) dispersion, and a part of the solvent was removed with a rotary evaporator. By removing, an organic resin dispersion (9) of silica particles having a solid content concentration of 76.0% by weight is obtained.

Preparation of coating solution (9) Next, 75.31 g of this organic resin dispersion (9) was mixed with 8.32 g of urethane acrylate (NK oligo, UA-33H, which is the same as in Example 1) and acrylic resin. 1.00 g of silicone leveling agent (Disparon NSH-8430HF same as in Example 1), 0.50 g of photopolymerization initiator (Irgacure 184 same as in Example 1), 2.37 g of PGME and 12.50 g of acetone are sufficiently mixed. Then, a coating liquid (9) having a solid content concentration of 63.9% by weight is prepared.
Preparation of substrate with film (9) A substrate with film (9) is prepared in the same manner as in Example 1 except that the coating solution (9) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 10]
14.96 g of γ-methacrylooxypropyltrimethoxysilane (KBM-503, the same as in Example 1) was mixed with 100 g of silica sol dispersion (the same catalloid SI-30 as in Example 1), and 3% of ultrapure water was added. Add 1 g and stir at 50 ° C. for 6 hours. As a result, a 12 nm silica sol dispersion (solid content concentration: 40.5 wt%) surface-treated with a silane coupling agent is obtained.
Thereafter, the solvent is replaced in the same manner as in Example 1 to obtain a silica particle (10) dispersion having a solid concentration of 40.5% by weight.

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 to 2500 g of the silica particle (10) dispersion, and a part of the solvent was removed with a rotary evaporator. By removing, an organic resin dispersion (10) of silica particles having a solid content concentration of 76.0% by weight is prepared.

Preparation of Coating Solution (10) Next, 75.31 g of this organic resin dispersion (10) was mixed with 8.32 g of urethane acrylate (NK oligo UA-33H, which is the same as in Example 1) and acrylic silicone. 1.00 g of a leveling agent (Disparon NSH-8430HF identical to Example 1), 0.50 g of a photopolymerization initiator (Irgacure 184 identical to Example 1), 2.37 g of PGME and 12.50 g of acetone were mixed thoroughly. Thus, a coating solution (10) having a solid content concentration of 70.6% by weight is obtained.
Preparation of substrate with film (10) A substrate with film (10) is prepared in the same manner as in Example 1 except that the coating solution (10) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 11]
7.06 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-5103, SiO ₂ component 86.1%) was mixed with 100 g of silica sol dispersion (cataloid SI-30 identical to Example 1). Then, 3.1 g of ultrapure water is added and stirred at 50 ° C. for 6 hours. Thereby, a 12 nm silica sol dispersion surface-treated with a silane coupling agent is obtained (solid content concentration 40.5% by weight).
Thereafter, the solvent was replaced in the same manner as in Example 1 to obtain a silica particle (11) dispersion having a solid concentration of 40.5% by weight.

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 to 2500 g of the silica particle (11) dispersion, and a part of the solvent was removed with a rotary evaporator. Removal of an organic resin dispersion (11) of silica particles having a solid content concentration of 76.0% by weight is obtained.

Preparation of Coating Solution (11) Next, 75.31 g of this organic resin dispersion (11) was mixed with 8.32 g of urethane acrylate (NK oligo UA-33H, which is the same as in Example 1) and acrylic silicone. 1.00 g of a leveling agent (Disparon NSH-8430HF identical to Example 1), 0.50 g of a photopolymerization initiator (Irgacure 184 identical to Example 1), 2.37 g of PGME and 12.50 g of acetone were mixed thoroughly. A coating solution (11) having a solid content concentration of 66.1% by weight is prepared.
Preparation of substrate with film (11) A substrate with film (11) is produced in the same manner as in Example 1 except that the coating solution (11) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 12]
A sodium silicate aqueous solution having a SiO ₂ concentration of 24 wt% (SiO ₂ / Na ₂ O molar ratio: 3.1) 33.4 Kg was diluted with 126.6 Kg of pure water to obtain a sodium silicate aqueous solution having a SiO ₂ concentration of 5 wt%. 160 kg of (pH 11) is prepared. The aqueous solution of sodium silicate is neutralized by adding an aqueous sulfuric acid solution having a concentration of 25% so that the pH of the aqueous solution is 4.5, and is kept at room temperature for 5 hours. Thereby, aging is performed to obtain a silica hydrogel.

This silica hydrogel is sufficiently washed with pure water equivalent to about 120 times the SiO ₂ solid content using a filter equipped with a filter cloth. This silica hydrogel is dispersed in pure water to prepare a dispersion having a SiO ₂ concentration of 3% by weight, and stirred using a powerful stirrer until a fluid slurry is obtained. Ammonia water having a concentration of 15% by weight was added so that the pH of the slurry-like silica hydrogel dispersion was 10.5, and stirring was continued at 95 ° C. for 1 hour to perform the deflocculation operation of the silica hydrogel. Got.

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

At this time, the average particle longest diameter (D _L ) of the silica particles of the silica sol (12) is 48 nm, the average short diameter (D _S ) is 16 nm, and the spherical coefficient is 0.33.
600 g of silica sol (12), 5,955 g of pure water, and 63.3 g of a sodium silicate aqueous solution (SiO ₂ / Na ₂ O molar ratio of 3.1) having a SiO ₂ concentration of 24% by weight were mixed and heated to 87 ° C. Warmed and aged for 0.5 hours. Subsequently, 1,120 g of a silicic acid solution having a SiO ₂ concentration of 3% by weight was added over 14 hours. After cooling to room temperature, the obtained silica sol is concentrated using an ultrafiltration membrane (Asahi Kasei Kogyo Co., Ltd .: SIP-1013) until the SiO ₂ concentration becomes 12% by weight. Further, it is concentrated by a rotary evaporator and filtered through a 44 μm mesh nylon filter to obtain a dispersion (12) of non-spherical silica having a solid concentration of 30% by weight.

Pure water is added to 400 g of this dispersion (12) to a solid content concentration of 20% by weight, and washing is performed at 80 ° C. for 3 hours using 240 g of a cation exchange resin (Mitsubishi Chemical Corporation: Diaion SK1B). Further, this dispersion is solvent-substituted with methanol using an ultrafiltration membrane to prepare a methanol dispersion having a solid concentration of 20% by weight.

7.48 g of a methacrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, γ-methacryloyloxypropyltrimethoxysilane) was added to 100 g of this methanol dispersion, and the mixture was heated and stirred at 50 ° C. for 6 hours. A dispersion of non-spherical silica surface-treated with a silicon compound (solid content concentration 40.5% by weight) is obtained.
Thereafter, the solvent was replaced in the same manner as in Example 1 to obtain a dispersion of non-spherical silica particles (12) having a solid concentration of 40.5% by weight. The average particle longest diameter (D _L ) of the non-spherical silica particles (12) was 50 nm, the average short diameter (D _S ) was 21 nm, and the spherical coefficient (D _S ) / (D _L ) was 0.42.

Preparation of coating liquid (12) To 2500 g of this silica particle (12) dispersion, 202.5 g of dimethylol-tricyclodecanediacrylate (the same light acrylate DCP-A as in Example 1) as an organic resin for dispersion was added, A part of the solvent is removed by a rotary evaporator to obtain an organic resin dispersion (12) of silica particles having a solid concentration of 76.0% by weight.

To 75.31 g of this organic resin dispersion (12), 8.32 g of urethane acrylate (the same NK oligo UA-33H) as in Example 1 and an acrylic silicone leveling agent (same as in Example 1) were added. Of Disparon NSH-8430HF), 1.00 g of photopolymerization initiator (Irgacure 184 same as in Example 1), 2.37 g of PGE and 12.50 g of acetone were mixed thoroughly to obtain a solid content concentration of 66.1% by weight. A coating solution (12) was prepared.
Preparation of substrate with film (12) A substrate with film (12) is prepared in the same manner as in Example 1 except that the coating solution (12) is used. The film thickness of the transparent coating is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 13]
Preparation of substrate with film (13) The coating solution (1) prepared in Example 1 is applied to the substrate using the bar coater method # 20 to prepare the substrate with film (13). The same procedure as in Example 1 is performed except for the coating method. The film thickness of the obtained transparent film is 15 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Example 14]
Preparation of substrate with film (14) The coating solution (1) prepared in Example 1 is applied to the substrate using the bar coater method # 40 to prepare the substrate with film (14). The same procedure as in Example 1 is performed except for the coating method. The film thickness of the obtained transparent film is 30 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Comparative Example 1]
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 to 2500 g of the silica particle (1) dispersion prepared in the same manner as in Example 1. A part of the solvent was removed by a rotary evaporator to prepare an organic resin dispersion (R1) of silica particles having a solid concentration of 76.0% by weight.

Preparation of Coating Solution (R1) Next, 75.31 g of this organic resin dispersion (R1) was further added to dimethylol-tricyclodecane diacrylate (light acrylate DCP-A, the same as in Example 1), which is an organic resin for dispersion. .32 g, 1.00 g of an acrylic silicone leveling agent (Disparon NSH-8430HF identical to Example 1), 0.50 g of a photopolymerization initiator (Irgacure 184 identical to Example 1), 2.37 g of PGME and acetone 12. 50 g is mixed well to prepare a coating solution (R1) having a solid content concentration of 66.1% by weight.
Preparation of substrate with film (R1) A substrate with film (R1) is prepared in the same manner as in Example 1 except that the coating solution (R1) is used. The film thickness of the obtained transparent film is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Comparative Example 2]
202.5 g of urethane acrylate (NK oligo UA-33H, which is the same as in Example 1) was added to 2500 g of the silica particle (1) dispersion prepared in the same manner as in Example 1, and the solvent was removed using a rotary evaporator. A part thereof is removed to prepare an organic resin dispersion (R2) of silica particles having a solid content concentration of 53.3% by weight.

Preparation of coating solution (R2) Next, 82.96 g of this organic resin dispersion (R2) was added to 1.00 g of an acrylic silicone leveling agent (dispalon NSH-8430HF identical to Example 1) and a photopolymerization initiator (Example). 1) Irgacure 184) 0.50 g, PGME 0.13 g and acetone 9.00 g are sufficiently mixed to obtain a coating solution (R2) having a solid content concentration of 51.0% by weight.
Preparation of substrate with film (R2) A substrate with film (R2) is prepared in the same manner as in Example 1 except that the coating solution (R2) is used. The film thickness of the obtained transparent film is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Comparative Example 3]
Preparation of coating liquid for forming transparent film (R3) 69.14 g of silica particle (1) dispersion prepared in the same manner as in Example 1, and dimethylol-tricyclodecane diacrylate (same as in Example 1) as an organic resin for dispersion Light acrylate DCP-A) 5.26 g, curing organic resin urethane acrylate (NK oligo UA-33H same as in Example 1) 4.83 g, acrylic silicone leveling agent (same as in Example 1) Disparone NSH-8430HF) 1.00 g, photopolymerization initiator (Irgacure 184 same as in Example 1) 0.29 g, PGME 6.99 g and acetone 12.50 g were mixed thoroughly to obtain a solid content concentration of 41.4% by weight. A coating solution (R3) is prepared.
Preparation of substrate with film (R3) A substrate with film (R3) is produced in the same manner as in Example 1 except that the coating solution (R3) is used. The film thickness of the obtained transparent film is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

[Comparative Example 4]
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 to 2500 g of silica sol dispersion (cataloid SI-30 as in Example 1), A part of the solvent is removed by a rotary evaporator to obtain an organic resin dispersion (RA4) of silica particles having a solid concentration of 53.3% by weight.

Preparation of Coating Solution (R4) To this organic resin dispersion (RA4) 75.31 g, 7.19 g of urethane acrylate (NK oligo, UA-33H, which is the same as in Example 1) and acrylic silicone type 1.00 g of a leveling agent (Disparon NSH-8430HF identical to that in Example 1), 0.50 g of a photopolymerization initiator (Irgacure 184 identical to Example 1), 0.83 g of PGME, and 8.00 g of acetone were mixed thoroughly. A coating solution (R4) having a solid content concentration of 53.3% by weight is prepared.
Preparation of substrate with film (R4) A substrate with film (R4) is produced in the same manner as in Example 1 except that the coating solution (R4) is used. The film thickness of the obtained transparent film is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 1.

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

[Example 15]
Silica sol aqueous dispersion (manufactured by JGC Catalysts &Chemicals; Cataloid SI-50; average particle size 25 nm, SiO ₂ concentration 48.0 wt%, dispersion medium: water, particle refractive index 1.46) to 1000 g of cation exchange resin 960 g (manufactured by Mitsubishi Chemical Corporation: SK-1BH) is added and stirred for 30 minutes, and then the ion exchange resin is separated. Next, 480 g of an anion exchange resin (Mitsubishi Chemical Corporation: SA-20A) is added and stirred for 30 minutes, and then the ion exchange resin is separated. Next, 480 g of cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) is added, stirred for 5 minutes, aged at 80 ° C. for 3 hours and cooled to room temperature, and then the ion exchange resin is separated. Thereby, a silica sol aqueous dispersion having a concentration of 48% by weight is obtained.
2000 g of this silica sol aqueous dispersion is subjected to solvent substitution with methanol by an ultrafiltration membrane method to produce a silica sol methanol dispersion having a concentration of 40% by weight as SiO ₂ .

To 100 g of this dispersion, 7.48 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon 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. As a result, a 25 nm silica sol dispersion (solid content concentration: 40.5 wt%) surface-treated with a silane coupling agent is obtained.
This dispersion was solvent-substituted with PGME in the same manner as in Example 1 to obtain a silica particle (15) dispersion. To 2500 g of this silica particle (15) dispersion, 202.5 g of dimethylol-tricyclodecane diacrylate (the same light acrylate DCP-A as in Example 1), which is an organic resin for dispersion, was added, and a part of the solvent was removed with a rotary evaporator. Is removed to prepare an organic resin dispersion (15) of silica particles (15) having a solid concentration of 76.0% by weight.

Preparation of coating liquid (15) for forming a hard coat film Next, 75.31 g of this organic resin dispersion (15) was added urethane acrylate (NK oligo UA-33H as in Example 1) as a curing organic resin. 32 g, 1.00 g of an acrylic silicone leveling agent (Disparon NSH-8430HF identical to Example 1), 0.50 g of a photopolymerization initiator (Irgacure 184 identical to Example 1), 2.37 g of PGME and 12.50 g of acetone. Are sufficiently mixed to obtain a coating solution (15) having a solid concentration of 66.1% by weight. The compositions of the coating solution (15) are shown in Tables 4 and 5.

Preparation of Silica-Based Hollow Particle (A15) Dispersion A mixture of 5.0 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-550, average particle diameter 5 nm, SiO ₂ concentration 20 wt%) and 999.5 g of pure water 80 While maintaining this temperature, 1575 g of a 3.0 wt% sodium silicate aqueous solution as SiO ₂ and 1575 g of a 1.5 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were added. , SiO ₂ · Al ₂ O ₃ primary particle dispersion is obtained. At this time, the molar ratio MO _X / SiO ₂ (A) = 0.25, and the average particle size is 13 nm. The pH of the reaction solution is 12.0.
Next, 8370 g of a sodium silicate aqueous solution having a concentration of 3.0% by weight as SiO ₂ and 2790 g of a sodium aluminate aqueous solution having a concentration of 1.5% by weight as Al ₂ O ₃ were added to form composite oxide particles (secondary particles). A dispersion is obtained.

At this time, the molar ratio MO _X / SiO ₂ (B) = 0.13, and the average particle size is 30 nm. The pH of the reaction solution is 12.0.
Next, the dispersion of the composite oxide particles was washed with an ultrafiltration membrane until the solid content concentration became 13% by weight. ) Was dropped to pH 1.0, and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane is separated and washed while adding 10 L of pH 3 hydrochloric acid aqueous solution and 5 L of pure water to prepare an aqueous dispersion of silica-based hollow particles having a solid content concentration of 20% by weight.

Aqueous ammonia was added to this aqueous dispersion to adjust the pH of the dispersion to 10.5, and after aging at 200 ° C. for 11 hours, the mixture was cooled to room temperature, and a cation exchange resin (manufactured by Mitsubishi Chemical Corporation). : Ion exchange for 3 hours using 400 g of Diaion SK1B), ion exchange for 3 hours using 200 g of anion exchange resin (Made by Mitsubishi Chemical Co., Ltd .: Diaion SA20A), and cation exchange resin (Mitsubishi) Using 200 g of Chemical Co., Ltd. (Diaion SK1B), ion exchange is performed at 80 ° C. for 3 hours to perform washing, and an aqueous dispersion of silica-based hollow particles having a solid content concentration of 20% by weight is obtained.

Further, the solvent is replaced with methanol using an ultrafiltration membrane to prepare a methanol dispersion of silica-based hollow particles having a solid concentration of 20% by weight. The average particle diameter and refractive index of the obtained silica-based hollow particles were measured, and the results are shown in the table.
Next, 3.7 g of a methacrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) is added to 100 g of a methanol dispersion of silica-based hollow particles having a solid content concentration of 20% by weight, and heated at 50 ° C. to obtain silica. Surface treatment of the system hollow particles. Further, the solvent is replaced with MIBK by a rotary evaporator, and a MIBK dispersion of silica-based hollow particles (A15) subjected to surface treatment with a solid content concentration of 20.5% by weight is prepared. The refractive index of the silica-based hollow particles (A15) was measured, and the results are shown in the table.

Preparation of coating solution (15 L) for forming antireflection layer To 8.05 g of this silica-based hollow particle (A15) dispersion, dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: DPE-6A, solid content concentration: 100% by weight) ) 1.07 g, 1,6-hexanediol diacrylate (manufactured by Sakai Kogyo Co., Ltd .: SR-238F, solid concentration 100% by weight) and water-repellent reactive silicon oil (Shin-Etsu Chemical Co., Ltd.) ); X-22-174DX, solid content concentration 100 wt%) 0.05 g and silicon-modified polyurethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; purple light UT-4314: solid content concentration 30 wt%) 0.37 g and light 0.09 g of a polymerization initiator (manufactured by BISF Japan Co., Ltd .: Lucillin TPO, solid content concentration 100% by weight), 64.65 g of isopropyl alcohol, methyl isobutene Ketone 9.60 g, a mixture of isopropyl glycol 16.00 g, to prepare solid concentration of 3.0% by weight of the coating solution (15L).

Production of Substrate with Hard Coat Film (15) A substrate with film (15) is produced in the same manner as in Example 1 using the coating liquid (15) for forming a hard coat film. The thickness of the hard coat film is 12 μm.
For the obtained film-coated substrate (15), the total light transmittance and haze, cracks, shrinkage, curling properties, pencil hardness, and scratch resistance are evaluated in the same manner as in Example 1. Furthermore, the surface roughness (Ra) is measured at 10 μm × 10 μm using an atomic force microscope (manufactured by Bruker, Inc .: Dimension-3100). The results are shown in Table 11.

After applying the coating solution (15 L) for forming the antireflection layer on the hard coat film of the base material with antireflection layer forming film (15) by the bar coater method (bar # 4) and drying at 80 ° C. for 120 seconds. Then, an antireflection layer is formed by irradiating and curing an ultraviolet ray of 400 mJ / cm ² in an N ₂ atmosphere. At this time, the thickness of the antireflection layer is 100 nm.
The total light transmittance, haze, reflectance, crack, pencil hardness, and scratch resistance of the film-coated substrate having this antireflection layer are evaluated in the same manner as the substrate with hard coat film (15). The refractive index is measured with an ellipsometer (ULVAC, EMS-1). The results are shown in Table 12.

[Example 16]
Preparation of silica-based hollow particle (A16) dispersion Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-550, average particle diameter 5 nm, SiO ₂ concentration 20% by weight) 5.0 g and a mixture of 999.5 g of pure water 80 While maintaining this temperature, 650 g of a sodium silicate aqueous solution having a concentration of 3.0% by weight as SiO ₂ and 650 g of a sodium aluminate aqueous solution having a concentration of 1.5% by weight as Al ₂ O ₃ were added. , SiO ₂ .Al ₂ O ₃ primary particle dispersion is obtained. At this time, the molar ratio MO _X / SiO ₂ (A) = 0.24, and the average particle size is 13 nm. Further, the pH of the reaction solution at this time is 12.0.

Next, 2940 g of a sodium silicate aqueous solution having a concentration of 3.0% by weight as SiO ₂ and 980 g of a sodium aluminate aqueous solution having a concentration of 1.5% by weight as Al ₂ O ₃ were added to form composite oxide particles (secondary particles). A dispersion is prepared. At this time, the molar ratio MO _X / SiO ₂ (B) = 0.13, and the average particle size is 20 nm. Further, the pH of the reaction solution at this time is 12.0.
Subsequently, by the same process as in Example 15, dealumination treatment, washing with an ultrafiltration membrane, and washing by ion exchange are performed to obtain an aqueous dispersion of silica-based hollow particles having a solid content concentration of 20% by weight.
Further, through the same process as in Example 15, a MIBK dispersion of silica-based hollow particles (A16) having a solid content concentration of 20.5% by weight and surface-treated is prepared. The refractive index of the silica-based hollow particles (A16) was measured, and the results are shown in the table.

Preparation of coating solution (16 L) for forming an antireflection layer A coating solution (16 L) having a solid concentration of 3.0% by weight was prepared in the same manner as in Example 15 except that this dispersion of silica-based hollow particles (A16) was used. ) Was prepared.
Formation of Antireflection Layer A substrate (16) with a hard coat film is produced in the same manner as in Example 15. An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that the above coating solution (16L) was used. At this time, the thickness of the antireflection layer is 100 nm. The base material (16) with the antireflection layer is evaluated in the same manner as in Example 15.

[Example 17]
Preparation of silica-based hollow particle (A17) dispersion Silica-alumina sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: USBB-120, average particle size 25 nm, SiO ₂ · Al ₂ O ₃ concentration 20% by weight, Al ₂ O in solid content ₍₂ content 27 wt%) A mixture of 100 g and pure water 3900 g was heated to 98 ° C., and while maintaining this temperature, 405 g of a sodium silicate aqueous solution having a concentration of 1.5 wt% as SiO ₂ and Al ₂ O ₃ 405 g of a sodium aluminate aqueous solution having a concentration of 0.5% by weight is added to obtain a SiO ₂ .Al ₂ O ₃ primary particle dispersion. In this case, the molar ratio MO _X / SiO ₂ (A) = 0.2, and the average particle size is 28 nm. Further, the pH of the reaction solution at this time is 12.0.

Next, 1607 g of 1.5 wt% sodium silicate aqueous solution as SiO ₂ and 535 g of 0.5 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were added to disperse the composite oxide particles (secondary particles). Obtain a liquid. At this time, the molar ratio MO _X / SiO ₂ (B) = 0.07, and the average particle size is 40 nm. Further, the pH of the reaction solution at this time is 12.0.
Next, by the same process as in Example 15, dealumination treatment, washing with an ultrafiltration membrane, and washing by ion exchange are performed to produce an aqueous dispersion of silica-based hollow particles having a solid content concentration of 20% by weight.
Further, through the same process as in Example 15, a MIBK dispersion of silica-based hollow particles (A17) having a solid content concentration of 20.5% by weight and surface-treated is prepared. The refractive index of the silica-based hollow particles (A17) was measured, and the results are shown in the table.

Preparation of coating solution (17 L) for forming antireflection layer A coating solution (17 L) having a solid content concentration of 3.0% by weight was prepared in the same manner as in Example 15 except that this dispersion of silica-based hollow particles (A17) was used. ) Was prepared.
Formation of Antireflection Layer A substrate (17) with a hard coat film is produced in the same manner as in Example 15. An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that the above coating solution (17L) was used. At this time, the thickness of the antireflection layer is 100 nm. The substrate (17) with the antireflection layer is evaluated in the same manner as in Example 15.

[Example 18]
Preparation of dispersion of silica-based particles (B18) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-550, average particle diameter 5 nm, SiO ₂ concentration 20% by weight) 5.0 g and a mixture of 999.5 g of pure water at 80 ° C. While maintaining this temperature, 321 g of a 3.0 wt% sodium silicate aqueous solution as SiO ₂ and 321 g of a 1.5 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were added, A SiO ₂ .Al ₂ O ₃ primary particle dispersion was obtained. At this time, the molar ratio MO _X / SiO ₂ (A) = 0.23, and the average particle size was 7 nm. Further, the pH of the reaction solution at this time was 12.0.

Next, 1231 g of a sodium silicate aqueous solution having a concentration of 3.0% by weight as SiO ₂ and 410 g of a sodium aluminate aqueous solution having a concentration of 1.5% by weight as Al ₂ O ₃ were added to disperse the composite oxide particles (secondary particles). A liquid was obtained. At this time, the molar ratio MO _X / SiO ₂ (B) = 0.13, and the average particle size was 14 nm. Further, the pH of the reaction solution at this time was 12.0.
Next, by the same process as in Example 15, dealumination treatment, washing with an ultrafiltration membrane, and washing by ion exchange are performed to produce an aqueous dispersion of silica-based hollow particles having a solid content concentration of 20% by weight.

Next, in the same manner as in Example 15, a methanol dispersion of silica-based hollow particles having a solid content concentration of 20% by weight in which the solvent is replaced with methanol is prepared. The average particle diameter and refractive index of the silica-based hollow particles obtained here are measured, and the results are shown in the table.
Further, according to the same process as in Example 15, a MIBK dispersion of silica-based hollow particles (B18) having a solid content concentration of 20.5% by weight and surface-treated is prepared. The refractive index of the silica-based hollow particles (B18) was measured, and the results are shown in the table.

Preparation of coating solution (18 L) for formation of antireflection layer To 7.90 g of surface-treated silica-based hollow particle dispersion (A17) having a solid content concentration of 20.5% by weight prepared in the same manner as in Example 17, 0.15 g of a silica dispersion of silica-based hollow particles having a concentration of 20.5 wt%, dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: DPE-6A, solid content concentration 100 wt%) 1.07 g and 1,6 -0.12 g of hexanediol diacrylate (manufactured by Sakai Kogyo Co., Ltd .: SR-238F, solid content concentration 100% by weight) and reactive silicone oil for water repellency (Shin-Etsu Chemical Co., Ltd .; X-22-174DX, Photopolymerization started with 0.05 g of solid content concentration (100% by weight) and 0.37 g of silicon-modified polyurethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; Purple light UT-4314: solid content concentration of 30% by weight). (BASF Japan Co., Ltd.): 0.09 g, isopropyl alcohol 64.65 g, methyl isobutyl ketone 9.60 g, and isopropyl glycol 16.00 g were mixed to obtain a solid concentration of 3 Prepare a coating solution (18 L) of 0% by weight.
Formation of Antireflection Layer A substrate (18) having an antireflection layer is produced in the same manner as in Example 15 except that an antireflection layer is formed using this coating solution (18L). At this time, the thickness of the antireflection layer is 100 nm. The substrate (18) with the antireflection layer is evaluated in the same manner as in Example 15.

[Example 19]
Preparation of dispersion of silica-based particles (B19) Cation exchange to 1000 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-30, SiO ₂ concentration 40.5 wt%, average particle diameter 23 nm, refractive index 1.46) 960 g of resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) is added and stirred for 30 minutes, and then the ion exchange resin is separated. Further, washing is performed by anion exchange and cation exchange in the same manner as in Example 15 to obtain an aqueous dispersion of silica-based particles having a concentration of 48% by weight.
Next, the same process (methanol solvent substitution, surface treatment, MIBK solvent substitution) as in Example 15 is carried out to prepare a MIBK dispersion liquid of surface-treated silica-based particles (B19) having a solid content concentration of 20.5% by weight. The refractive index of the silica-based particles (B19) was measured, and the results are shown in the table.

Preparation of coating solution (19 L) for formation of antireflection layer Instead of the methanol dispersion of silica-based particles having a solid content concentration of 20.5 wt% in Example 18, silica-based particles having a solid content concentration of 20.5 wt% ( A coating solution (19 L) having a solid content concentration of 3.0% by weight is prepared in the same manner as in Example 18 except that the MIBK dispersion of B19) is used.
Formation of Antireflection Layer A substrate (19) having an antireflection layer is produced in the same manner as in Example 15 except that the coating solution (19L) is used to form an antireflection layer. At this time, the thickness of the antireflection layer is 100 nm. This base material (19) is evaluated in the same manner as in Example 15.

[Example 20]
Preparation of coating solution (20 L) for formation of antireflection layer To 8.05 g of a surface-treated silica-based hollow particle (A15) dispersion having a solid content concentration of 20.5% by weight prepared in Example 15, an organic resin for dispersion was used. 0.12 g of a certain dimethylol-tricyclodecane diacrylate (the same light acrylate DCP-A as in Example 1), 1.07 g of a urethane acrylate that is a curing organic resin (the same NK oligo UA-33H as in Example 1), Reactive silicone oil for water repellent material (Shin-Etsu Chemical Co., Ltd .; X-22-174DX, solid content concentration: 100% by weight) 0.05 g, and silicon-modified polyurethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; Shikko UT) -4314: solid content concentration 30% by weight) 0.37 g, photopolymerization initiator (BASF Japan KK: Lucillin TPO) 0.09 g and isopropyl alcohol 6 .65G, methyl isobutyl ketone 9.60 g, a mixture of isopropyl glycol 16.00 g, solid content concentration of 3.0% by weight of the coating solution (20L) was prepared.

Formation of Antireflection Layer A substrate (15) with a hard coat film is produced in the same manner as in Example 15. An antireflection layer material (20) is formed on the hard coat film in the same manner as in Example 15 except that this coating solution (20L) is used. At this time, the thickness of the antireflection layer is 100 nm. The base material (20) with the antireflection layer is evaluated in the same manner as in Example 15.

[Example 21]
Preparation of substrate (21) with hard coat film The coating liquid (15) for forming the hard coat film prepared in Example 15 was applied to the TAC film in the same manner as in Example 1, and a hard coat film having a thickness of 12 μm was formed. Formed. The physical properties and the like of the hard coat film are indicated as the same as in Example 15.

Formation of Antireflection Layer Next, an antireflection layer was formed in the same manner except that the coating solution (15) for forming an antireflection layer having a solid content concentration of 3.0% by weight prepared in the same manner as in Example 15 was used. . At this time, the thickness of the antireflection layer was 100 nm. The total light transmittance, haze, reflectance, film refractive index, 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 hard coat film 80.38 g of an organic resin dispersion (15) of silica particles having a solid content concentration of 76.0% by weight prepared in Example 15 was prepared and used for curing. 8.88 g of organic resin urethane acrylate (NK oligo UA-33H same as in Example 1), 1.00 g of acrylic silicone leveling agent (Disparon NSH-8430HF same as in Example 1) and photopolymerization initiator ( The same Irgacure 184 as in Example 1) 0.53 g, 0.21 g of PGME, and 9.0 g of acetone were sufficiently mixed to prepare a coating solution (22) having a solid content concentration of 70.6% by weight. The composition of the coating liquid (22) is shown in the table.

Production of substrate (22) with a hard coat film A substrate (22) with a hard coat film is produced in the same manner as in Example 15 except that this coating solution (22) is used. The thickness of the hard coat film is 12 μm. The obtained film-coated substrate (22) is evaluated in the same manner as in Example 15.

Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that the substrate (22) with a hard coat film of this example was used. The thickness of the antireflection layer was 100 nm. The substrate having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 23]
The substrate (3) with a transparent coating prepared by the coating solution prepared in Example 3 is applied as the substrate (23) with a hard coat film of this example. The film thickness of the hard coat film was 12 μm. This base material with a hard coat film (23) is evaluated in the same manner as in Example 15.

Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material with hard coat film (23) was used. The thickness of the antireflection layer was 100 nm. The substrate (23) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 24]
The substrate with transparent film (4) produced using the coating solution prepared in Example 4 is applied as the substrate with hard coat film (24) of this example. The thickness of the hard coat film is 12 μm. This base material with a hard coat film (24) is evaluated in the same manner as in Example 15.
Formation of Antireflection Film An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material with a hard coat film (24) was used. The thickness of the antireflection layer is 100 nm. The substrate (24) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 25]
The base material with a transparent film (5) produced using the coating liquid prepared in Example 5 is applied as the base material with a hard coat film (25) of this example. The thickness of the hard coat film is 12 μm. This base material with a hard coat film (25) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material with hard coat film (25) was used. The thickness of the antireflection layer is 100 nm. The substrate (25) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 26]
The substrate (6) with a transparent coating produced using the coating solution prepared in Example 6 is applied as the substrate (26) with a hard coat film of this example. The thickness of the hard coat film is 12 μm. This base material with a hard coat film (26) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material (26) with a hard coat film was used. The thickness of the antireflection layer is 100 nm. The substrate (26) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 27]
The substrate with transparent film (7) produced using the coating solution prepared in Example 7 is applied as the substrate with hard coat film (27) of this example. The thickness of the hard coat film is 12 μm. This base material with a hard coat film (27) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material (27) with a hard coat film was used. The thickness of the antireflection layer is 100 nm. The substrate (27) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 28]
The substrate with transparent coating (8) produced using the coating solution prepared in Example 8 is applied as the substrate with hard coat film (28) of this example. The thickness of the hard coat film is 12 μm. This base material with a hard coat film (28) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material (28) with a hard coat film was used. The thickness of the antireflection layer is 100 nm. The substrate (28) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 29]
The base material with a transparent film (9) produced using the coating solution prepared in Example 9 is applied as the base material with a hard coat film (29) of this example. The thickness of the hard coat film is 12 μm. This base material with a hard coat film (29) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material with hard coat film (29) was used. The thickness of the antireflection layer is 100 nm. The substrate (29) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 30]
The base material (10) with a transparent coating produced using the coating solution prepared in Example 10 is applied as the base material (30) with a hard coat film of this example. The thickness of the hard coat film is 12 μm. This base material with a hard coat film (30) is evaluated in the same manner as in Example 15.
Preparation of formation of antireflection layer An antireflection layer was formed on the hard coat film in the same manner as in Example 15 except that this base material with hard coat film (30) was used. The thickness of the antireflection layer is 100 nm. The substrate (30) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 31]
The base material with a transparent film (11) produced using the coating solution prepared in Example 11 is applied as the base material with a hard coat film (31) of this example. The thickness of the hard coat film is 12 μm. This base material with hard coat film (31) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material with hard coat film (31) was used. The thickness of the antireflection layer is 100 nm. The base material (31) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 32]
The substrate (32) with a transparent coating produced using the coating liquid (12) prepared in Example 12 is applied as the substrate (32) with a hard coat film of this example. The thickness of the hard coat film is 12 μm. This base material with hard coat film (32) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material (32) with a hard coat film was used. The thickness of the antireflection layer was 100 nm. The substrate (32) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 33]
The substrate with transparent film (13) produced in Example 13 is applied as the substrate with hard coat film (33) of this example. The thickness of the hard coat film is 15 μm. This base material with hard coat film (33) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material with hard coat film (33) was used. The thickness of the antireflection layer was 100 nm. The base material (33) having this antireflection layer is evaluated in the same manner as in Example 15.

[Example 34]
The substrate with a transparent film (14) produced in Example 14 is applied as the substrate with a hard coat film (34) of this example. The thickness of the hard coat film is 30 μm. This base material with hard coat film (34) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this base material (34) with a hard coat film was used. The thickness of the antireflection layer was 100 nm. The substrate (34) having this antireflection layer is evaluated in the same manner as in Example 15.

[Comparative Example 5]
Preparation of silica-based hollow particle (RA5) dispersion silica-alumina sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: USBB-120, average particle size 25 nm, SiO ₂ · Al ₂ O ₃ concentration 20 wt%, solid content Al ₂ O ₃ content 27 wt%) 100 g of pure water 3900 g was added and heated to 98 ° C. While maintaining this temperature, 1750 g of a sodium silicate aqueous solution with a concentration of 1.5 wt% as SiO ₂ and Al ₂ O ₃ By adding 1750 g of an aqueous solution of sodium aluminate having a concentration of 0.5% by weight, a SiO ₂ · Al ₂ O ₃ primary particle dispersion (average particle size 35 nm) is obtained. At this time, the MO _X / SiO ₂ molar ratio (A) is 0.2, and the pH of the reaction solution is 12.0.
Next, 6,300 g of a 1.5 wt% sodium silicate aqueous solution as SiO ₂ and 2,100 g of a 0.5 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were added to form composite oxide particles (two Secondary particle) dispersion. At this time, the MO _X / SiO ₂ molar ratio (B) is 0.07, the pH of the reaction solution is 12.0, and the average particle size is 50 nm.

Next, a methanol dispersion of silica-based hollow particles having a solid concentration of 20% by weight is produced through the same process as in Example 15. The average particle diameter and refractive index of the obtained silica-based hollow particles were measured, and the results are shown in the table.
3 g of an acrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103) is added to 100 g of this methanol dispersion and heated at 50 ° C. for surface treatment. Further, the solvent is replaced with MIBK by a rotary evaporator to prepare a dispersion of silica-based hollow particles (RA5) having a solid content concentration of 20.5% by weight. The refractive index of the surface-treated silica-based hollow particles (RA5) was measured, and the results are shown in the table.

Preparation of coating solution (R5L) for formation of antireflection film Solid content concentration was the same as in Example 15 except that a surface-treated silica-based hollow particle (RA5) dispersion having a solid content concentration of 20.5% by weight was used. A 3.0 wt% coating solution (R5L) is prepared.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that this coating solution (R5L) is used. At this time, the thickness of the antireflection layer is 100 nm. The base material (R5) having the base material with the antireflection layer was evaluated in the same manner as in Example 15.

[Comparative Example 6]
Preparation of base material with hard coat film (R6) The coating liquid (15) for forming the hard coat film prepared in Example 15 is diluted with PGME to a solid content concentration of 30% by weight. This was applied to a TAC film (manufactured by Fuji Film Co., Ltd .: FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51) by the bar coater method # 3 and dried at 80 ° C. for 120 seconds. Next, it is cured by irradiating with 300 mJ / cm ² of ultraviolet light in an N ₂ atmosphere to produce a base material with a hard coat film (R6). The thickness of the hard coat film is 1 μm. The obtained base material with a hard coat film (R6) is evaluated in the same manner as in Example 15.
Formation of antireflection film Next, an antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that the base material with hard coat film (R6) was used. At this time, the thickness of the antireflection layer is 100 nm. The base material with the antireflection layer is evaluated in the same manner as in Example 15.

[Comparative Example 7]
Preparation of coating liquid (R7) for forming a hard coat film To 2500 g of the surface-treated silica sol dispersion prepared in Example 15 and having a solid concentration of 40.5% by weight, dimethylol-tricyclodecanedi, an organic resin for dispersion, was used. 202.5 g of acrylate (the same light acrylate DCP-A as in Example 1) was added, a part of the solvent was removed by a rotary evaporator, and organic particles of surface-treated silica particles having a solid content concentration of 76.0% by weight were obtained. A resin dispersion (RA7) is prepared.

To 75.31 g of this organic resin dispersion (RA7), 8.32 g of dimethylol-tricyclodecane diacrylate (the same light acrylate DCP-A as in Example 1) as an organic resin for dispersion, and an acrylic silicone leveling agent ( Sugimoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g, photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, PGME 2.37 g and acetone 12.50 g were mixed thoroughly. A coating solution (R7) having a solid content concentration of 66.1% by weight is prepared. Here, the organic resin for dispersion is added again instead of the organic resin for curing. The composition of the resulting coating solution (R7) is shown in the table.

Production of Substrate with Hard Coat Film (R7) A substrate with film (R7) is produced in the same manner as in Example 15 except that the coating liquid (R7) for forming a hard coat film is used. The thickness of the hard coat film is 12 μm. The obtained film-coated substrate (R7) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that the above-mentioned base material with hard coat film (R7) was used. The thickness of the antireflection layer is 100 nm. The film-coated substrate having this antireflection layer is evaluated in the same manner as in Example 15.

[Comparative Example 8]
Preparation of coating liquid (R8) for forming a hard coat film To 2500 g of a surface-treated silica sol dispersion having a solid content of 40.5% by weight prepared in Example 15, urethane acrylate (Example 1) was used. 202.5 g of the same NK oligo UA-33H), a part of the solvent was removed by a rotary evaporator, and the surface-treated silica particle organic resin dispersion (RB8) having a solid content concentration of 53.3% by weight To prepare.
To 82.96 g of this organic resin dispersion (RB8), 1.00 g of an acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) and a photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, PGME 0.13 g, and acetone 9.00 g are sufficiently mixed to prepare a coating solution (R8) having a solid content concentration of 51.0% by weight. The composition of the coating liquid (R8) obtained for forming the hard coat film is shown in the table.

Production of Substrate with Hard Coat Film (R8) A substrate with film (R8) is produced in the same manner as in Example 15 except that the coating liquid (R8) for forming a hard coat film is used. The thickness of the hard coat film is 12 μm. The obtained film-coated substrate (R8) is evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that the base material with hard coat film (R8) described above was used. The thickness of the antireflection layer is 100 nm. The film-coated substrate (R8) having this antireflection layer was evaluated in the same manner as in Example 15.

[Comparative Example 9]
Preparation of coating solution (R9) for forming a hard coat film To 69.14 g of the surface-treated silica sol dispersion prepared in Example 15 and having a solid content concentration of 40.5 wt%, dimethylol-tricyclo, which is an organic resin for dispersion, was added. 5.26 g decanediacrylate (same light acrylate DCP-A as in Example 1), 4.83 g of urethane acrylate (NK oligo UA-33H as in Example 1), an acrylic silicone type 1.00 g of a leveling agent (Tsubakimoto Kasei Co., Ltd .; Disparon NSH-8430HF), 0.29 g of a photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184), 6.99 g of PGME, and 12.50 g of acetone are simultaneously supplied. Mix well to prepare a coating solution (R9) having a solid content concentration of 41.4% by weight. The composition of the obtained coating solution (R9) for forming the hard coat film is shown in the table.

Production of substrate with hard coat film (R9) A substrate with film (R9) is produced in the same manner as in Example 15 except that this coating solution (R9) is used. The thickness of the hard coat film is 12 μm. The obtained film-coated substrate (R9) was evaluated in the same manner as in Example 15.
Formation of Antireflection Layer An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that the above-mentioned base material with hard coat film (R9) was used. The thickness of the antireflection layer is 100 nm. The substrate with film (R9) having this antireflection layer is evaluated in the same manner as in Example 15.

[Comparative Example 10]
Preparation of coating solution (R10) for hard coat film formation Silica sol dispersion (cataloid SI-30 same as in Example 1) was dispersed in 2500 g of dimethylol-tricyclodecane diacrylate (same as in Example 1) as an organic resin for dispersion. 202.5 g of light acrylate DCP-A) is added, and a part of the solvent is removed by a rotary evaporator to obtain an organic resin dispersion (R10) of silica particles having a solid concentration of 53.3% by weight.
To this organic resin dispersion (R10) 75.31 g, 7.19 g of urethane acrylate (NK oligo UA-33H, which is the same as in Example 1) as an organic resin for curing, and acrylic silicone leveling agent (same as in Example 1). 1.00 g of Disparon NSH-8430HF), 0.50 g of a photopolymerization initiator (Irgacure 184 as in Example 1), 0.83 g of PGME and 8.00 g of acetone were mixed thoroughly to obtain a solid content of 53. A 3% by weight coating solution (R10) is prepared. The composition of the coating solution (R10) obtained is shown in the table.

Production of base material with hard coat film (R10) A base material with hard coat film (R10) is produced in the same manner as in Example 15 except that this coating solution (R10) is used. The thickness of the hard coat film is 12 μm. The obtained film-coated substrate (R10) is evaluated in the same manner as in Example 15.
An antireflection layer is formed on the hard coat film in the same manner as in Example 15 except that the base material (R10) with an antireflection layer is used. The thickness of the antireflection layer is 100 nm. The film-coated substrate having this antireflection layer is evaluated in the same manner as in Example 15.

[Comparative Example 11]
Formation of Antireflective Layer The coating solution for forming an antireflective film having a solid content concentration of 3.0% by weight (15 L) prepared in Example 15 was applied to the TAC film used in Example 15 by the bar coater method # 4. After drying at 80 ° C. for 120 seconds, the substrate was cured by irradiation with ultraviolet rays of 600 mJ / cm ² in an N ₂ atmosphere to prepare a base material (R11) with an antireflection layer. Therefore, no hard coat film is provided, and the antireflection layer is formed directly on the substrate. The thickness of the antireflection layer is 100 nm. The base material (R11) with the antireflection layer is evaluated in the same manner as in Example 15.

[Example 35]
Preparation of base material with hard coat film (35) This example has a configuration in which an antireflection layer is not provided in Example 15, and Examples 1 to 14 differ from the thickness of the base material and the particle size of metal oxide particles. Etc. are different. The coating liquid (15) for forming the hard coat film prepared in Example 15 was applied to the TAC film used in Example 15 by the bar coater method # 16, dried at 80 ° C. for 120 seconds, and then in an N ₂ atmosphere. Then, the substrate (35) with a hard coat film is prepared by irradiating and curing ultraviolet rays of 300 mJ / cm ² . The thickness of the hard coat film is 12 μm. This film-coated substrate is evaluated in the same manner as in Example 15.

Claims

A coating liquid for forming a transparent film comprising metal oxide particles having an average particle diameter in the range of 5 to 300 nm and a matrix-forming component, wherein the concentration (C P ) of the metal oxide particles as a solid content is 45 To 90% by weight, the concentration (C R ) of the matrix-forming component as a solid content is 10 to 50% by weight, the total solid content concentration (C T ) is 60% by weight or more, and the concentration (C R ) And concentration (C P ) ratio (C R / C P ) is 0.11 to 1.0, and the matrix-forming component and the first organic resin having 2 or less functional groups and 3 or more A coating liquid comprising a second organic resin having a functional group of
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 functional group of the first organic resin and the second organic resin is at least one selected from a (meth) acrylate group, a urethane acrylate group, and an epoxy-modified acrylate group. The coating solution as described in 1.
4. The coating solution according to claim 1, wherein the metal oxide particles are surface-treated with an organosilicon compound represented by the following formula (1).
R n -SiX 4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen and hydrogen, and n is an integer of 1 to 3.)
The coating liquid according to claim 4, wherein R of the organosilicon compound is a substituted hydrocarbon group having a (meth) acrylate group as a substituent.
The metal oxide particles are surface-treated with 0.1 to 50 parts by weight of an organosilicon compound as R n —SiO 2 (4-n) / 2 with respect to 100 parts by weight of the metal oxide particles. The coating liquid according to claim 4 or 5.
When the surface treatment amount of the metal oxide particles is in the range of 0.1 to 5 parts by weight, the first organic resin contains at least one of a hydroxyl group, an ether group, an amino group, a carboxyl group, and a sulfo group. The coating solution according to claim 6.
The coating solution 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.
Preparing a dispersion containing metal oxide particles having an average particle diameter in the range of 5 to 300 nm and an organic dispersion medium;
Replacing at least a portion of the organic dispersion medium with a first organic resin having two or less functional groups;
And a step of mixing a second organic resin having three or more functional groups.
10. 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 second organic resin is an ultraviolet curable resin monomer or oligomer, and the functional group of the first organic resin and the second organic resin is a (meth) acrylate group, a urethane acrylate group, or an epoxy-modified acrylate group. The method for producing a coating liquid according to claim 9 or 10, which is at least one selected.
A substrate with a transparent coating, wherein a transparent coating is formed on the substrate using the coating solution according to any one of claims 1 to 8 or the coating solution obtained by the production method according to claims 9 to 11. ,
The transparent coating comprises metal oxide particles having an average particle size of 5 to 300 nm and a matrix component,
The content (W P ) of the metal oxide particles as a solid content is 50 to 90% by weight, the content (W R ) of the matrix component as a solid content is 10 to 50% by weight, and the content A substrate with a transparent coating, wherein the ratio (W R / W P ) is 0.11 to 1.0 and the average film thickness (T) is 1 to 100 μm.
The substrate with a transparent coating according to claim 12, wherein the substrate is at least one resin substrate selected from acrylic, polycarbonate, cycloolefin polymer, polyethylene terephthalate, and triacetyl cellulose.
The substrate with a transparent coating according to claim 12 or 13, wherein the transparent coating has a pencil hardness of 5H or more.
The substrate with a transparent coating according to any one of claims 12 to 14, wherein the curling property measured under the following conditions is 5 mm or less;
A coating solution for forming a transparent film is applied on a triacetyl cellulose base material having a coating surface of 14 cm × 25 cm and a thickness of 40 μm so that a transparent film with a thickness of 12 μm is formed. The height from the flat plate at the top of the base material was cut into a size of 10 cm × 10 cm, the film was placed on a flat plate with the coating surface down, and curled (curved).
Applying a coating solution according to any one of claims 1 to 8 or a coating solution obtained by the production method according to claims 9 to 11 on a substrate to produce a coating film; ,
Drying the coating film;
Comprising a step of curing the coating after drying to obtain a transparent coating;
The method for producing a substrate with a transparent coating, wherein the shrinkage rate of the coating film by drying is 25% or less, the shrinkage rate of the coating film by curing is 10% or less, and the total shrinkage rate is 35% or less. .
An organic resin dispersion sol in which metal oxide particles having an average particle diameter of 5 to 300 nm are dispersed in a first organic resin having 2 or less functional groups,
The concentration (C PS ) as the solid content of the metal oxide particles is 45 to 90% by weight, the concentration (C RS ) as the solid content of the first organic resin is 10 to 50% by weight, An organic resin-dispersed sol of metal oxide particles, wherein the solid content concentration (C TS ) is 60% by weight or more.
A substrate with a transparent coating in which an antireflection layer is formed on the transparent coating,
The antireflection layer includes silica-based hollow particles and the matrix component (M L),
The content of the silica-based hollow particles (W PLA ) is 5 to 80% by weight,
The content (W ML ) of the matrix component (M L ) is 20 to 95% by weight,
The antireflection layer has a thickness (T L ) of 80 to 200 nm;
The silica-based hollow particles have an average particle diameter (D PA ) of 10 to 45 nm,
A ratio (D PA / T L ) between an average particle diameter (D PA ) of the silica-based hollow particles and a thickness (T L ) of the antireflection layer is 0.05 to 0.56, The substrate with a transparent coating according to any one of claims 12 to 15.
The antireflection layer includes second silica-based particles having an average particle diameter (D PB ) of 4 to 17 nm, and an average particle diameter ratio (D PB / D PA ) of 0.1 to 0.4 The base material with a transparent film of Claim 18 characterized by these.
The substrate with a transparent coating according to claim 18 or 19, wherein an interface between the transparent coating and the antireflection layer is wavy.