JP2015193756A - Organic resin dispersed sol, coating liquid for formation of transparent film, method of producing coating liquid for formation of transparent film and substrate with transparent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating liquid for formation of a transparent film suitable for formation of a transparent film which is high in hardness even in cases of resin substrates and free of cracks even in cases involving thick films and is suppressed in curling.SOLUTION: A coating liquid for formation of a transparent film comprises a fine particle of surface treatment metal oxide of an average particle size of 5-300 nm and a matrix formation ingredient, and the matrix formation ingredient consists of an organic resin (A) for dispersion and an organic resin (B) for hardening. The concentration (C) of the fine particle of surface treatment metal oxide, based on the solid content, is 45-90 wt.%; the concentration (C) of the matrix formation ingredient, based on the solid content, is 15-50 wt.%; the total solid concentration (C) is 60 wt.% or higher; and the ratio (C)/(C) of the concentration (C) to the concentration (C) is 0.12-1.0.

Description

  The present invention provides a coating solution for forming a transparent coating that can be suitably used for forming a transparent coating that has a high hardness even when the substrate is a resin substrate and has no cracks even when it is a film thickness, and curling is suppressed. The present invention relates to a method for producing a coating liquid for forming a transparent film and a substrate with a transparent film.

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

  However, when fine particles are dispersed in a coating solution for forming a transparent coating to form a transparent coating, if the affinity between the matrix-forming component or the dispersion medium and the particles is low, the particles aggregate or the stability of the coating solution decreases. However, in addition to the transparency and haze of the resulting transparent film, the scratch resistance, strength, scratch strength, etc. may be insufficient.

  For this reason, it is known that the particles are surface-treated with a silane coupling agent in order to improve the dispersibility of the particles to prevent aggregation and to improve the stability of the coating solution. In addition, a resin is coated on the particles 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 a composite particle having an organic component including an aromatic skeleton and a bond structure to an aromatic skeleton in which four or more atoms are linked on the surface of inorganic fine particles. Is excellent in dispersibility, and it is disclosed that when a resin composition comprising such composite particles and a resin component is used, a cured product excellent in heat resistance and mechanical strength can be obtained. At this time, it is described that the composite particles are mixed with heat and / or a photocurable resin, an initiator and a dispersion medium, and then the solvent is deaerated with an evaporator or the like to prepare a resin composition. It is disclosed that it is preferable to degas under reduced pressure under heating at 100 ° C. or lower, and that the solvent is preferably degassed in the presence of a high-boiling component.

  The present applicant added an acrylic resin to an organic solvent dispersion in which ethers, esters, and ketones of metal oxide particles having an average secondary particle size of the order of μm, which had been heat-treated in advance, were used as a dispersion medium, When the mechanochemical treatment is performed, the resin can be uniformly coated on the individual metal oxide particles, and a high concentration resin-coated metal oxide particle dispersion liquid having a solid content concentration of about 50% by weight using an organic solvent as a dispersion medium is obtained. It is disclosed that it is obtained. JP 2010-077409 A (Patent Document 6)

  Furthermore, the present applicant added a (meth) acrylate resin having an aromatic ring to an organic solvent dispersion of metal oxide particles that had been heat-treated in advance, and then the resin was uniformly applied to the individual particles after mechanochemical treatment. Next, when dispersed in a low molecular weight resin having high affinity with the resin-coated particles, and uniformly dispersed, the organic solvent is removed, and the resin-coated particles are highly dispersed without curing. A resin-coated metal oxide particle resin dispersion composition having excellent properties can be obtained. When a curing agent is added to the composition, applied, and cured without drying, a thick film can be formed with little shrinkage. It is disclosed that a transparent film excellent in transparency, haze, scratch resistance and the like can be obtained (Japanese Patent Laid-Open No. 2012-72288 (Patent Document 7)).

  The applicant of the present invention is a paint composed of a (meth) acrylate resin not 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. It is disclosed that a high-concentration paint can be prepared by removing an organic solvent with a rotary evaporator, and that an optical thin film having a thick film and excellent hardness can be obtained by using such a paint (Japanese Patent Laid-Open No. 2013). -10864 publication (patent document 8)).

  In addition, the applicant of the present invention provides a paint comprising an acrylate having 4 or more functional groups, an acrylate resin having 2 to 3 functional groups, particles having a spherical coefficient in a predetermined range or irregular particles that are chain particles, and a dispersion medium. Discloses that curling is suppressed even with a thin substrate, and a transparent film excellent in adhesion to the substrate, hardness, scratch resistance and the like can be obtained (Japanese Patent Laid-Open No. 2013-133444). Gazette (patent document 9)).

  The present applicant uses a coating liquid for forming a hard coat film composed of metal oxide fine particles treated with a surfactant having an ethylene oxide-modified skeleton, a hydrophobic matrix forming component, and an organic dispersion medium. It is disclosed that the anti-blocking property is improved. At this time, it is also disclosed that the hardness is improved when hydrophobic particles surface-treated with an organosilicon compound are blended (Japanese Patent Laid-Open No. 2013-136222 (Patent Document 10)).

  In addition, the applicant of the present invention provides a coating liquid for forming a hard coat film containing a metal oxide particle having a surface charge amount in a predetermined range and a dispersion medium coated with a hydrophobic organic resin matrix-forming component and a polymer silane coupling agent. When used, it is disclosed that it is possible to form a hard coat film that is excellent in alkali resistance, and also excellent in adhesion to a substrate, scratch resistance, hardness, and the like (Japanese Patent Laid-Open No. 2009-35595 (Patent Document 11). )).

  Further, the present applicant can reduce bleed-out by using a resin having a functional group of 3 or more and a bifunctional organic resin monomer or a silicone resin monomer and a monofunctional silicone resin, and is water and oil repellent. It is disclosed that a transparent film excellent in wiping properties such as fingerprints and magic can be formed. (Unexamined-Japanese-Patent 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 conventional mechanochemical methods and graft polymerization methods as 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. In the obtained resin-coated particles, the resin may be dissolved in the solvent of the coating solution. For this reason, the obtained transparent film has problems such as a decrease in transparency, an increase in haze, and a decrease in scratch resistance.

  Furthermore, the resin-coated metal oxide particle-dispersed sol disclosed in Patent Document 5 contains an organic solvent, and a coating solution having a concentration in the range of approximately 1 to 60% by weight as a solid content is stable when the concentration exceeds 60% by weight. In some cases, the properties deteriorated and aggregated and settled. 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.

  In addition, the substrate with a transparent coating obtained in Patent Document 5 has no pencil hardness exceeding 4H when the film thickness is 4 μm, and the substrate with a transparent coating obtained in Patent Document 6 has a film thickness of 35 μm. No pencil hardness exceeding 3H was obtained, and even in Patent Document 12, even if the surface-treated particles were blended in the film at 50% by weight or even 70% by weight, the pencil hardness was not improved. Nothing over 4H has been obtained.

Further, in Patent Document 9, a transparent film having a pencil hardness of 5 or higher is not obtained even when irregularly shaped particles are used.
In recent years, there has been a demand for a transparent film having a pencil hardness comparable to that obtained when glass is used as a base material even when a resin base material is used in various marking devices, mobile phones, organic EL televisions, and the like.

  As a result of diligent investigations to meet such demands, the present inventors have 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. As a result of further intensive studies to solve these problems, the final resin ratio was obtained 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. As a result, the present invention has been completed.

  Then, an organic dispersion medium dispersion of silica fine particles surface-treated with a predetermined amount with an organosilicon compound is prepared, and the organic dispersion medium is replaced with an ultraviolet curable resin monomer having a small number of functional groups, whereby a stable organic resin dispersion (organic It was found that a resin dispersion sol may 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. Further, the inventors have found that there is no crack, curling is suppressed, and the hardness of the film is remarkably improved, thereby completing the present invention.

[1] It consists of surface-treated metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm and a matrix-forming component, and the matrix-forming component consists of an organic resin for dispersion (A) and an organic resin for curing (B). The concentration (C _P ) as the solid content of the surface-treated metal oxide fine particles is in the range of 45 to 90% by weight, and the concentration (C _R ) as the solid content of the matrix forming component is in the range of 15 to 50% by weight. There, the total solids concentration (C _T) is not less than 60% by weight, the concentration (C _R) and the concentration (C _P) and the ratio _{(C R) / (C P} ) is from 0.12 to 1.0 A coating liquid for forming a transparent film, characterized by being in the range.
[2] The dispersing organic resin (A) is an ultraviolet curable resin monomer or oligomer having 1 to 2 functional groups, and the curing organic resin (B) is an ultraviolet curable having 3 or more functional groups. A coating solution for forming a transparent film according to [1], which is a mold resin monomer or oligomer.
[3] The functional group of the dispersing organic resin (A) and the curing organic resin (B) is at least one selected from an acrylate group, a (meth) acrylate group, a urethane acrylate group, and an epoxy-modified acrylate group. [2] The coating liquid for forming a transparent film according to the above.
[4] The coating liquid for forming a transparent film according to [1] to [3], wherein the molecular weight of the organic resin for dispersion (A) and the organic resin for curing (B) is 5,000 or less.

[5] The coating solution for forming a transparent film according to [1] to [4], wherein the surface-treated metal oxide fine 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 from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
[6] The coating liquid for forming a transparent film according to [5], wherein R of the organosilicon compound is an organosilicon compound having at least one substituted hydrocarbon group having a (meth) acrylate group as a substituent.
[7] The surface treatment amount of the surface-treated metal oxide fine particles is in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the metal oxide fine particles and the organosilicon compound as R _n —SiO _{4 -n / 2.} [6] A coating liquid for forming a transparent film.
[8] When the surface treatment amount of the surface-treated metal oxide fine particles is in the range of 0.1 to 5 parts by weight, the dispersing organic resin (A) is a hydroxyl group (OH group) or an ether group (—O— group). , [1] to [7], a coating solution for forming a transparent film, which is an organic resin having at least one of amino group, carboxyl group and sulfo group.
[9] The coating solution for forming a transparent film according to [1] to [8], wherein the spherical coefficient of the surface-treated metal oxide fine particles is in the range of 0.2 to 1.0.

[10] A method for producing a coating liquid for forming a transparent film, comprising the following steps (a) and (b):
(A) a step of replacing part or all of the organic dispersion medium of the organic dispersion medium dispersion of the surface-treated metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm with the organic resin for dispersion (A);
(B) A step of mixing the curing organic resin (B).
[11] The dispersion medium organic resin (A) is an ultraviolet curable resin monomer or oligomer having 1 to 2 functional groups, and the curable organic resin (B) is an ultraviolet light having 3 or more functional groups. [10] A coating solution for forming a transparent film, which is a curable resin monomer or oligomer.
[12] The functional group of the organic resin for dispersion (A) and the organic resin for curing (B) is at least one selected from an acrylate group, a (meth) acrylate group, a urethane acrylate group, and an epoxy-modified acrylate group. [10] The method for producing a coating liquid for forming a transparent film according to [11].
[13] The concentration (C _P ) as a solid content of the surface-treated metal oxide fine particles is in the range of 45 to 90% by weight, and the organic resin for dispersion medium (A) as the matrix-forming component and the curing organic The concentration (C _R ) of the resin (B) as the total solid content is in the range of 15 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) and the ratio _{(C R) / (C P} ) is [10] the method for producing a transparent film-forming coating liquid to [12] in the range of 0.12 to 1.0.

[14] A surface-treated metal oxide fine particle having an average particle diameter in the range of 5 to 300 nm and a matrix component, and the content (W _P ) as a solid content of the surface-treated metal oxide fine particle is 50 to 90% by weight. in the range of the content of the solid content of the matrix component (W _R) is in the range of 10 to 50 wt%, the ratio (W _R) between the content (W _R) and the content (W _P) / (W _P ) is in the range of 0.12 to 1.0, and the average film thickness (T) is in the range of 1 to 100 μm.
[15] The substrate with a transparent coating according to [14], wherein the matrix component comprises the organic resin for dispersion (A) and the organic resin for curing (B).
[16] The substrate with a transparent film according to [14] or [15], wherein the spherical coefficient of the surface-treated metal oxide fine particles is in the range of 0.2 to 1.0.
[17] The substrate with a transparent coating according to [14] to [16], wherein the substrate is at least one resin substrate selected from acrylic, polycarbonate, cycloolefin polymer (COP), PET, and TAC.
[18] The substrate with a transparent coating according to [14] to [17], wherein the pencil hardness is 5H or more.
[19] The substrate with a transparent coating according to [14] to [18], which has a curling characteristic of 5 mm or less, measured under the following conditions;
A coating solution for forming a transparent film is applied on a TAC film substrate having a thickness of 14 cm × 25 cm × 40 μm (thickness) so that a transparent film having a thickness of 12 μm can be formed, and is allowed to stand for 20 hours, and then the film is 10 cm × 10 cm in size. The height from the flat plate at the apex of the base material that was cut into two pieces, placed on a flat plate with the coating surface down, and curled (curved) and floated.

[20] A transparent film-coated base according to [14] to [19], wherein the coating liquid for forming a transparent film according to [1] to [9] is applied onto a substrate, dried, and then cured. Wood.
[21] After applying the coating liquid for forming a transparent film, the shrinkage ratio of the coating film when dried is 25% or less, and then the shrinkage ratio of the coating film when cured is 10% or less. The base material with a transparent film according to [20], in which the shrinkage ratio is 35% or less.
[22] Surface-treated metal oxide fine particles having an average particle size in the range of 5 to 300 nm are dispersed in the dispersing organic resin (A) or the dispersing organic resin (A) and the organic dispersion medium. Concentration (C _PS ) of solid particles as a solid content is in the range of 45 to 90% by weight, and concentration (C _RS ) as a solid content of the organic resin for dispersion (A) is in the range of 15 to 50% by weight An organic resin dispersion sol of surface-treated metal oxide fine particles, wherein the total solid content concentration (C _TS ) is 60% by weight or more.
[23] The organic resin dispersion sol of surface-treated metal oxide fine particles according to [22], wherein the dispersing organic resin (A) is an ultraviolet curable resin monomer or oligomer having 1 to 2 functional groups.
[24] The organic resin dispersion sol of surface-treated metal oxide fine particles according to [22] or [23], wherein the organic resin for dispersion (A) has a molecular weight of 5,000 or less.

  According to the present invention, a coating liquid for forming a transparent film that can form a transparent film having a small film shrinkage, no cracks, curling is suppressed, and the film hardness is greatly improved, even for a thick film, and the coating The manufacturing method of a liquid and the base material with a transparent film formed using this coating liquid can be provided.

Hereinafter, first, the coating liquid for forming a transparent film according to the present invention will be described.
[Transparent coating solution]
The coating liquid for forming a transparent film according to the present invention contains surface-treated metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm and a matrix forming component.

Surface-treated metal oxide fine particles As the metal oxide fine particles used in the present invention, metal oxide fine particles derived from a metal oxide sol are preferably used.
As the metal oxide sol, a conventionally known sol can be used, for example, silica sol, zirconia sol, titania sol, alumina sol, antimony pentoxide sol, antimony doped tin oxide (ATO), phosphorus doped tin oxide (PTO), indium doped. Examples thereof include tin oxide (ITO).

The average particle diameter of the metal oxide fine particles is preferably in the range of 5 to 300 nm, more preferably 5 to 200 nm.
The average particle diameter of the metal oxide fine particles is less than the above lower limit, although it varies depending on the presence or absence of the surface treatment described later, the metal oxide fine particles may agglomerate, the haze of the transparent coating film may deteriorate, or the transparency May decrease. Even if the average particle diameter of the metal oxide fine particles exceeds the above range, the haze of the obtained transparent coating may be deteriorated or the transparency may be lowered, although depending on the content of the metal oxide fine particles, the friction may be further reduced. May damage the transparent coating.

The metal oxide fine particles preferably have a spherical coefficient in the range of 0.2 to 1.0, more preferably 0.4 to 1.0.
If the spherical coefficient of the metal oxide fine particles is small, the dispersibility in the coating solution is insufficient and may aggregate, resulting in insufficient adhesion to the substrate, scratch strength, etc. May crack. Here, the spherical coefficient is represented by the following equation.
Spherical coefficient = (D _S ) / (D _L )
(However, (D _L ) is the average longest diameter of the particles, and (D _S ) is the average short diameter perpendicular to the longest diameter at the midpoint of the longest diameter)

The spherical coefficient is measured by taking a transmission electron micrograph (TEM), measuring the longest diameter and the shortest axis perpendicular to the midpoint of the longest diameter for 100 particles, and calculating the average value of the shortest diameter (D _S ). And the average value of the longest diameter (D _L ).
The metal oxide fine particles are preferably surface-treated with an organosilicon compound represented by the following formula (1).
_{R n -SiX 4-n (1} )
However, in formula, R is a C1-C10 unsubstituted or substituted hydrocarbon group, Comprising: You may mutually be same or different. X: An alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, hydrogen, n: an integer of 1 to 3 is shown. 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.

  For example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-g Sidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) Acryloxymethyltriexylsilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- ( (Meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluoroo Cutylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, γ- (meth) acrylooxypropyldimethoxysilane, γ -(Meth) acrylooxypropyldiethoxysilane and the like and mixtures thereof.

The organosilicon compound used in the present invention is preferably an organosilicon compound in which R has at least one substituted hydrocarbon group having a (meth) acrylate group as a substituent.
When R has a substituted hydrocarbon group having a (meth) acrylate group as a substituent, the surface-treated metal oxide fine particles, an ultraviolet curable organic resin for dispersion (A), and an ultraviolet curable organic for curing A transparent film having high compatibility with the resin (B), improved dispersibility, and 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.
Examples of organosilicon compounds having a substituted hydrocarbon group in which R has a (meth) acrylate group as a substituent include γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethylsilane. Excisilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylooxy Preferable examples include propyltriethoxysilane, γ- (meth) acrylooxypropyldimethoxysilane, γ- (meth) acrylooxypropyldiethoxysilane, and the like.

The surface treatment amount of the surface-treated metal oxide fine particles is 0.1 to 50 parts by weight, further 1 to 40 parts by weight, based on 100 parts by weight of the metal oxide fine particles and the organosilicon compound as R _n —SiO _{4 -n / 2.} It is preferable to be in the range of parts.

  If the amount of surface treatment is small, the dispersibility of the surface-treated metal oxide fine particles is insufficient and easily aggregated, and the resulting transparent film may be hazed, or the adhesion and hardness with the substrate may be insufficient. is there. Even if the amount of surface treatment is too much, dispersibility is not further improved, and unreacted surface treatment agent may remain, which inhibits high-density filling of surface-treated metal oxide fine particles, and hardness and adhesion May be insufficient.

As a method for producing the surface-treated metal oxide fine particles, a conventionally known method can be employed. 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 use the dispersion medium containing water or by-products after replacing the solvent with an organic dispersion medium described later.

Matrix-forming component In the coating solution for forming a transparent film according to the present invention, the organic resin for dispersion (A) and the organic resin for curing (B) are used as the matrix-forming component.
Both the dispersing organic resin (A) and the curing organic resin (B) 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 ATC and excellent hardness. In addition, a substrate with a transparent coating can be produced by a highly productive winding method (roll to roll).

Organic resin for dispersion (A) and organic resin for curing (B)
The dispersing organic resin (A) and the curing organic resin (B) are preferably monomers or oligomers of an ultraviolet curable resin.
When used as a dispersing organic resin (A), UV-curable resin monomers or oligomers can stably disperse the surface-treated metal oxide fine particles, and the surface-treated metal oxide is stable at a high concentration. A fine-particle organic resin dispersion can be obtained.

In addition, when an oligomer of an ultraviolet curable resin is used as the curable organic resin (B), a transparent film having higher hardness can be obtained.
The monomer or oligomer of the ultraviolet curable resin preferably has at least one functional group selected from an acrylate group, a (meth) acrylate group, a urethane acrylate group, and an alkylene oxide-modified acrylate group.

  When having such a functional group, it is easily bonded to a resin base material such as PET or TAC, and has excellent adhesion to the base material. Moreover, since it mutually couple | bonds as a matrix formation component, the transparent film excellent in hardness can be obtained.

  In the present invention, when the surface treatment amount of the surface-treated metal oxide fine particles is in the range of 0.1 to 5 parts by weight, further 0.1 to 3 parts by weight, the dispersing organic resin (A) is a hydroxyl group (OH Group), an ether group, an amino group, a carboxyl group, and a sulfo group, and an organic resin having at least one of them is preferable.

  When the organic resin for dispersion (A) is a resin having these functional groups, when the surface treatment amount of the surface-treated metal oxide fine particles is in the above range, hydrophilic groups (OH groups) remain on the particle surface. In the step (a) of preparing the coating liquid for forming a transparent film according to the present invention, which will be described later, the surface-treated metal oxide fine particles have high affinity with the dispersing organic resin (A) having the functional group. When the organic dispersion medium of the organic dispersion medium dispersion is replaced with the dispersing organic resin (A), the surface-treated metal oxide fine particles are dispersed uniformly without aggregation of the surface-treated metal oxide fine particles. (A) A dispersion can be obtained.

  Further, when the surface treatment amount of the surface-treated metal oxide fine particles is in the range of 5 to 50 parts by weight, the organic resin for dispersion (A) is preferably an organic resin having no functional group, but the functional group It may be an organic resin.

  The dispersing organic resin (A) is preferably a monomer or oligomer of an ultraviolet curable resin having 1 to 2 functional groups. When the number of functional groups is 1 to 2, the viscosity of the organic resin is low. Even when the concentration of the organic resin is increased when replacing the organic dispersion medium in the organic dispersion medium dispersion of the surface-treated metal oxide fine particles, the increase in viscosity is small and the organic dispersion medium can be suitably used.

As a monomer or oligomer of an ultraviolet curable resin having one functional 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 Glucol 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 Recall diglycidyl ether acrylate, ethoxylated bisphenol A methacrylate, propoxylated bisphenol A diglycidyl ether acrylate, O-phthalic acid diglycidyl ether acrylate, cyclohexanedimethanol diglycidyl ether acrylate, pt-butylphenyl 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-stearyl methacrylate, n-butoxyethyl methacrylate 2-hydroxyethyl ester Monofunctional such as tacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, 2-hydroxy-3-acryloyloxypropyl methacrylate Having a (meth) acrylate group of
Methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-acryloyloxytetrahydrophthalic acid, 2-acryloyloxyhexahydrophthalic acid, 2-acryloyloxypropylphthalic acid, 2-acryloyloxypropyltetraphthalic acid, 2-acryloyloxypropyl Hexaphthalic acid, methacryloyloxyethyl succinic acid, methacryloyloxy tetrahydrophthalic acid, methacryloyloxyethyl tetrahydrophthalic acid, methacryloyloxyethyl hexahydrophthalic acid, methacryloyloxypropyl phthalic acid, methacryloyloxypropyl tetraphthalic acid, methacryloyloxypropyl hexaphthalate Monofunctional (meth) acrylic acid monomers or oligomers such as acids,
I can get lost.

  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, methoxypolyethylene glycol methacrylate, methoxytripropylene glycol Those having monofunctional ethylene oxide (EO) modified acrylate groups such as methacrylate, ethoxylated 2-ethylhexyl methacrylate, butoxydiethylene glycol methacrylate, butoxydiethylene glycol methacrylate, polyethylene glycol modified stearyl methacrylate, phenoxyethylene glycol methacrylate, phenoxydiethylene glycol methacrylate, phenoxyethyl methacrylate Can be given.

As a monomer or oligomer of a bifunctional UV curable resin,
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, 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 glycol dimethacrylate, glycerin dimethacrylate acrylate, 2-methyl Non-glycolic (meth) acrylates or oligomers thereof such as tacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate,
Those having a bifunctional alkoxylated bisphenol A (meth) acrylate group such as ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate,
Bifunctional urethane such as NK Oligo U-200PA, UA-W2, UA-W2A, UA-122P, UA-160TP, UA-2235PE, UA-4200, UA-4400, UA-7000, U-2HA, U-2PPA Having an 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, polyethylene glycol # 600 dimethacrylate, poly Bifunctional ethylene oxide modified (meth) acrylate such as glycol acrylates such as Tylene glycol # 1000 dimethacrylate, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene polypropylene glycol diacrylate, ethylene glycol dimethacrylate And those having a group.

Among the organic resins having each functional group described above, an organic resin having 1 or 2 functional groups can be selected and used.
Among the monomers or oligomers of this UV curable resin,
Those having an OH group are 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 mediacrylate, 2-hydroxy-3-methacrylpropyl acrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-3-phenoxypropyl acrylate, etc. ,
Those having an ether group are 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 diacrylate , Polyethylene glycol # 200 diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, polytetramethylene glycol # 650 diacrylate, polyethylene polypropylene glycol diacrylate Relate, 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, etc.
Those having an amino group are dimethylaminoethyl methacrylate, dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, diethylaminoethyl methacrylate and the like,
Those having an amide group are dimethylacrylamide, acryloylmorpholine, dimethylaminopropylacrylamide, isopropylacrylamide, diethylacrylamide, hydroxyethylacrylamide and the like,
Those having a carboxyl group are methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxytetrahydrophthalic acid, 2-acryloyloxyhexahydrophthalic acid, 2-acryloyloxypropylphthalic acid, 2-acryloyloxypropyltetraphthalate. Acid, 2-acryloyloxypropylhexaphthalic acid, methacryloyloxyethylsuccinic acid, methacryloyloxytetrahydrophthalic acid, methacryloyloxyethyltetrahydrophthalic acid, methacryloyloxyethylhexahydrophthalic acid, methacryloyloxypropylphthalic acid, methacryloyloxypropyltetraphthalic acid , Methacryloyloxypropyl hexaphthalic acid.

  Those having no functional group are 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, glycerin diacrylate Methacrylate, dimethylol-tricyclodecane diacrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] full orange acrylate, dimethylol-tricyclodecane diacrylate, methyl methacrylate, ethyl methacrylate DOO, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, n stearyl Arles methacrylate.

  The curing organic resin (B) is preferably a monomer or oligomer of an ultraviolet curable resin having three or more functional groups. If the number of functional groups is three or more, a resin group such as PET or TAC is used. It is easy to bond with the material and has excellent adhesion to the substrate. Moreover, since it mutually couple | bonds as a matrix formation component, the transparent film excellent in hardness can be obtained.

As a monomer or oligomer of an ultraviolet curable resin having three or more functional groups,
Trifunctional acrylate resins such as pentaerythritol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trifunctional urethane acrylate resins such as pentaerythritol hexamethylene diisocyanate urethane prepolymer, cresol Epoxy group-containing trifunctional acrylate resin such as novolak type epoxy acrylate, bisphenol A diglycidyl ether acrylic acid adduct, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin tri Methacrylate, ethoxylated pentaerythritol Trimethacrylate, trifunctional (meth) acrylate resins such as propoxylated pentaerythritol trimethacrylate,
Those having a trifunctional urethane acrylate group such as NK oligo UA-31F, UA-7100, UA-32P,
Having a trifunctional (caprolactone-modified) isocyanurate acrylate group such as tris- (2-acryloxyethyl) isocyanurate, caprolactone-modified tris- (2-acryloxyethyl) isocyanurate,
Trifunctional epoxy-modified acrylate groups such as ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, propoxylated trimethylolpropane triacrylate, exciminated dipentaerythritol polyacrylate, propoxylated dipentaerythritol polyacrylate, etc. thing,
Tetrafunctional (meth) acrylate resins such as pentaerythritol tetraacrylate,
Epoxy group-containing tetrafunctional (meth) acrylate resins such as ethoxylated pentaerythritol tetraacrylate and propoxylated pentaerythritol tetraacrylate,
Hexafunctional a (meth) acrylate resins such as dipentaerythritol hexaacrylate,
Epoxy group-containing hexafunctional (meth) acrylate resins such as excitated dipentaerythritol polyacrylate and propoxylated dipentaerythritol polyacrylate,
4-functional urethane (meth) acrylate oligomer resin, 6-functional urethane (meth) acrylate oligomer resin, 8-functional urethane (meth) acrylate oligomer resin, 9-functional urethane (meth) acrylate oligomer resin, 10-functional urethane (meth) Examples thereof include acrylate oligomer resin, 12-functional urethane (meth) acrylate oligomer resin, and 15-functional urethane (meth) acrylate oligomer resin. As urethane (meth) acrylate resins, commercially available NK oligos UA-33H, UA-6LR, UA-8LR, UA-12LR, U-10PA, U-10HA, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.) Etc.) can also be suitably used.

  Furthermore, 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 are listed, and examples of such resins include NK Oligo EA-6320, EA-6340. EA-7120, EA-7140, EA-7420 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can also be suitably used.

  Among acrylate resins having 4 or more functional groups, acrylate resins having 6 to 12 functional groups can be suitably used because they have a high curling suppression effect and excellent hardness.

Furthermore, the molecular weight (polystyrene equivalent molecular weight) of the monomer or oligomer of the organic resin is preferably 5,000 or less, and more preferably 4,500 or less.
When the molecular weight of the monomer or oligomer of the organic resin is too large, the viscosity of the resin is high, and when used as a dispersion organic resin (A), the organic dispersion medium dispersion of the surface-treated metal oxide fine particles is used as the dispersion medium organic resin ( When the organic dispersion medium or part of it is replaced with (A), the viscosity of the dispersion becomes high and it may not be possible to increase the concentration. For this reason, thick film formation, shrinkage suppression during film formation, crack suppression In some cases, it is difficult to form a transparent film excellent in curling suppression and hardness. Further, when used as the curable organic resin (B), the hardness of the resin is lowered, so that it may be difficult to express the hardness.

Organic dispersion medium The coating liquid concerning this invention may contain the organic dispersion medium as needed. A conventionally well-known organic dispersion medium is mentioned as an organic dispersion medium. The organic dispersion medium in the coating liquid for forming the transparent film is used when the organic dispersion medium of the surface-treated metal oxide fine particles is replaced with the organic resin for dispersion (A) in the method for preparing the coating liquid for forming the transparent film described later. In addition to the remaining organic dispersion medium and the like, it may be added for viscosity adjustment in view of the handling properties of the coating liquid. Further, the dispersion medium for dilution contained in the resins (A) and (B) is also included here.

The concentration of the organic dispersion medium in the coating liquid for forming a transparent film is preferably less than 40% by weight, and more preferably less than 35% by weight.
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-methyl acetate Esters such as xylbutyl, 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 can be preferably used in terms of dispersibility of the surface-treated metal oxide fine particles and solubility of the organic resin.
Moreover, it is preferable that the boiling point of an organic dispersion medium exists in the range of 56.12 to 200 degreeC, Furthermore, 56.12 to 180 degreeC.

When the organic dispersion medium has a low boiling point, the coating film dries quickly, so that the densification is insufficient, the film thickness tends to be non-uniform, and the hardness of the resulting transparent film may be insufficient. is there.
When the organic dispersion medium has a high boiling point, the organic dispersion medium may remain, the film shrinks insufficiently, and the resulting transparent film may have insufficient hardness.

Polymerization initiator In this invention, a photoinitiator is included as needed.
As the polymerization initiator, known ones can be used without particular limitation. 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- Examples include cyclohexyl-phenyl-ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.
The amount of the polymerization initiator used is preferably 2 to 20% by weight, more preferably 4 to 16% by weight, based on the solid content concentration of the organic resin.

Composition of coating solution for forming transparent coating The coating solution for forming a transparent coating comprises surface-treated metal oxide fine particles and a matrix forming component.
The concentration (C _P ) as the solid content of the surface-treated metal oxide fine particles in the coating solution for forming a transparent film is preferably in the range of 45 to 85% by weight, more preferably 45 to 80% by weight.

When the concentration of the surface-treated metal oxide fine particles (C _P ) is small, the film shrinks greatly, so that if the film is thick, cracks occur, densification is insufficient, and the resulting transparent film has insufficient hardness. There is a case. If the concentration (C _P ) of the surface-treated metal oxide fine particles is too high, the surface roughness of the transparent coating obtained may increase, and the haze of the film may deteriorate due to external scattering, or the transparency may decrease. Further, the film may be insufficiently densified, and the resulting transparent film may have insufficient scratch resistance and adhesion to the substrate.

The concentration (C _R ) as a solid content of the matrix-forming component in the coating solution for forming a transparent film is preferably 15 to 50% by weight, more preferably 15 to 40% by weight.
If the concentration (C _R ) of the matrix-forming component in the coating solution for forming the transparent coating is too low, the concentration (C _P ) of the surface-treated metal oxide fine particles is increased, and the surface of the transparent coating obtained as described above The unevenness may become large, the haze of the film may deteriorate due to external scattering, the transparency may decrease, and the film may be insufficiently densified, and the scratch resistance of the resulting transparent film In some cases, the adhesion to the substrate is insufficient.

Even if the matrix forming component concentration (C _R ) in the coating solution for forming a transparent film is too high, the film shrinks more than when a large amount of surface-treated metal oxide fine particles are blended. Cracks may occur. Further, when a resin having a small number of functional groups is used as the matrix forming component, the transparent film is insufficiently densified, and thus the hardness may be insufficient.

  The matrix-forming component is composed of the dispersing organic resin (A) and the curing organic resin (B), but the content of the dispersing organic resin (A) in the matrix-forming component as a solid content is 1 to 1. It is preferably in the range of 80% by weight, more preferably 5 to 60% by weight.

  If the content of the organic resin for dispersion (A) in the matrix-forming component is too small, that is, the organic dispersion of the surface-treated metal oxide fine particles in the step (a) at the time of preparing a transparent film-forming coating solution (described later) When the organic dispersion medium in the liquid dispersion is replaced with the organic resin for dispersion (A), the surface-treated metal oxide is uniformly dispersed without aggregation of the surface-treated metal oxide fine particles because the organic resin for dispersion (A) is small. It is difficult to obtain an organic resin (A) dispersion for dispersing fine particles, which may cause gelation at the time of substitution or increase in viscosity, resulting in decreased smoothness or densification of the surface of the resulting transparent film. Insufficient haze, hardness, scratch resistance, adhesion and the like may be insufficient.

  If the content of the organic resin for dispersion (A) in the matrix-forming component is too large, the curing resin (B) is decreased on the one hand, and the resulting transparent film has low denseness and the hardness may be insufficient. is there.

The curing organic resin (B) in the matrix-forming component is used so that the total concentration (C _R ) with the dispersing organic resin (A) falls within the above range.
The ratio (C _R ) / (C _P ) between the concentration (C _R ) of the matrix-forming component and the concentration (C _P ) of the surface-treated metal oxide fine particles is 0.12 to 1.0, more preferably 0.18. It is preferable to be in the range of ~ 0.8.

When the ratio (C _R ) / (C _P ) is low, the concentration (C _P ) as the solid content of the surface-treated metal oxide fine particles may be high, and the surface irregularity of the transparent coating may be increased. The haze of the film may be deteriorated or the transparency may be lowered. Further, the film may be insufficiently densified, and the resulting transparent film has insufficient scratch resistance and insufficient adhesion to the substrate. There is a case.

Even if the ratio (C _R ) / (C _P ) is too large, the shrinkage of the film increases, and cracks may occur when the film is thick. Moreover, the densification of the transparent film becomes insufficient, and thus the hardness may be insufficient.

Concentration (C _RA) of dispersing the organic resin in the matrix-forming component (A), the ratio of the surface-treated metal oxide fine particles _{(C P) (C RA)} / (C P) is from 0.17 to 1.11, preferably It is in the range of 0.19 to 0.89. If it is in this range, even if a large amount of the surface-treated metal oxide is added, the shrinkage of the film is small, a thick film can be formed, and cracking can be suppressed. The finally obtained transparent film is highly dense and therefore has a high hardness.
Such a coating liquid for forming a transparent film according to the present invention is prepared by the following method.

[Preparation method of coating liquid for forming transparent film]
The method for producing a coating liquid for forming a transparent film according to the present invention is characterized by comprising the following steps (a) and (b).
(A) a step of replacing part or all of the organic dispersion medium of the organic dispersion medium dispersion of the surface-treated metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm with the organic resin for dispersion (A);
(B) A step of mixing the curing organic resin (B).

Step (a)
A dispersion is prepared by dispersing the surface-treated metal oxide fine particles in an organic dispersion medium. Then, the organic dispersion medium in the dispersion is replaced with the dispersing organic resin (A).
The concentration of the surface-treated metal oxide fine particles in the organic dispersion medium dispersion is not particularly limited, but is usually in the range of 30 to 50% by weight as the solid content. If the concentration is low, the amount of solvent substitution increases and it is not efficient. Even if the concentration is too high, the metal oxide fine particles may be aggregated or the viscosity may be increased even if the metal oxide fine particles are not aggregated, resulting in insufficient stability. For this reason, haze occurs in the obtained transparent film, or the film becomes insufficiently densified, and thus the hardness may be insufficient.

Next, the solvent is substituted with the dispersing organic resin (A), and the substitution method is not particularly limited, and a conventionally known method can be employed.
For example, methods such as a rotary evaporator method and an evaporator method can be employed. At this time, it can carry out under reduced pressure as needed, and can also carry out under heating.

  The ratio of substitution with the organic resin for dispersion (A) is such that the concentration of the organic dispersion medium in the coating liquid for forming a transparent film finally obtained by mixing the organic resin for curing (B) in the step (b) described later. It is performed so as to be less than 40% by weight, and further 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 for forming a transparent film is lowered, and the shrinkage from application of the coating solution to drying is large, so that a thick film, particularly 10 μm. When the above thick film is obtained, cracks may occur during shrinkage or curling properties may increase.

Step (b)
Next, the curing organic resin (B) is mixed.
The mixing amount of the curing organic resin (B) is such that the total amount of the dispersing organic resin (A) and the dispersing organic resin (B), that is, the solid content concentration (C _R ) as a matrix forming component is within the above range. It is preferable to mix so that it becomes.

In the present invention, the above-described photopolymerization initiator can be added as necessary.
The transparent film-forming coating solution thus obtained has the above-described composition.
When the total solid content concentration is too high, the viscosity can be adjusted and the coating property and the like can be improved by mixing the organic dispersion medium.

[Base material with transparent film]
The substrate with a transparent coating according to the present invention comprises the surface-treated metal oxide fine particles and a matrix component.

The base material used for the substrate present invention, a resin substrate.
The resin substrate is preferably at least one transparent resin substrate selected from PET, TAC, acrylic, polycarbonate, and cycloolefin polymer (COP).
When these resin substrates are used, it is possible to obtain a substrate with a transparent coating excellent in adhesion to the transparent coating formed from the coating solution according to the present invention and excellent in hardness, scratch resistance and the like.

Surface-treated metal oxide fine particles As the surface-treated metal oxide fine particles, the aforementioned surface-treated metal oxide fine particles are preferably used.
The content (W _P ) of the surface-treated metal oxide fine 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.

If the content of the surface-treated metal oxide fine particles in the transparent film is within the above range (W _P ), the transparent film has a high hardness with no irregularities, little shrinkage, dense, crack-free even with a thick film. can get.
When the content (W _P ) of the surface-treated metal oxide fine particles is small, the amount of resin increases, so that the densification may be insufficient or the hardness of the transparent film may be low.
Even if the content (W _P ) of the surface-treated metal oxide fine particles in the transparent coating as a solid content is too large, the surface irregularities may become large and haze may deteriorate due to external scattering, or the transparency may decrease. Further, the densification of the film is further lowered, and the scratch resistance and the adhesion to the substrate may be insufficient.

Matrix component The matrix component comprises the organic resin for dispersion (A) and the organic resin for curing (B). In the transparent film, these monomers or oligomers are polymerized and cured.
The content of the organic resin for dispersion (A) in the matrix component as a solid content is preferably 0.1 to 80% by weight, more preferably 5 to 60% by weight.

  If the content of the organic resin for dispersion (A) in the matrix component is small, the smoothness of the surface of the transparent coating is lowered or densification is insufficient, and haze, hardness, scratch resistance, adhesion, etc. are insufficient. It may become.

When the content of the dispersing organic resin (A) in the matrix component is large, the curing resin (B) is decreased on the other hand, and the denseness of the transparent film may be low and the hardness may be 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 as a solid content in the transparent film is less than 10% by weight, irregularities occur on the surface, and haze of the film deteriorates due to external scattering, or the transparency decreases. In addition, since the number of particles increases, the transparent film is not sufficiently densified, and the adhesion to the substrate, scratch resistance, and hardness may be insufficient.

When the content (W _R ) of the matrix component in the transparent film exceeds 50% by weight, the film shrinks greatly, and curling or cracking occurs when the film is thick (approximately 10 μm or more). May occur, and the hardness may be insufficient due to low density.

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 surface-treated metal oxide fine particles is 0.12 to 1.0, It is preferable to be in the range of 0.18 to 0.8.

When the ratio (W _R ) / (W _P ) is small, the concentration (W _P ) as the solid content of the surface-treated metal oxide fine particles may be high, and the surface unevenness of the transparent coating may be increased. The haze of the transparent film may be deteriorated or the transparency may be lowered. Further, the film may be insufficiently densified, and the resulting transparent film has insufficient scratch resistance and adhesion to the substrate. There is a case.

Even if the ratio (W _R ) / (W _P ) is too large, the shrinkage of the film increases, and cracks may occur when the film is thick. Moreover, the densification of the transparent film becomes insufficient, and thus the hardness may be insufficient.

The average film thickness (T) of the transparent coating is preferably in the range of 1 to 100 μm, more preferably 12 to 80 μm.
If it exists in the film thickness of this range, the hardness which is high on the resin base material and curling was suppressed can be formed by using the coating liquid of this invention.

According to the present invention, even if the resin base material is used, a transparent film having a pencil hardness of 5H or more, and further 6H or more can be formed.
Moreover, the substrate with a transparent coating has a curling characteristic of 5 mm or less as measured under the following conditions.

-Curing characteristics: A coating solution for forming a transparent film was applied on a TAC film substrate having a size of 14 cm x 25 cm x 40 µm (thickness) so that a transparent film having a thickness of 12 µm could be formed, and allowed to stand for 20 hours. The height from the flat plate of the vertex of the base material which cut | disconnected to * 10cm size, set | placed the film on the flat plate with the application surface down, and curled (curved) and floated.

When a conventional transparent film is formed on a resin substrate, it is difficult to achieve curling characteristics and hardness as in the present invention.
Such a transparent film is formed by applying the transparent film-forming coating solution on a resin substrate, drying, and curing.

  Examples of the coating method include well-known methods such as a dipping method, a spray method, a spinner method, a roll coating method, a bar coating method, a gravure printing method, and a micro gravure printing method, and the coating is cured by a conventional method such as ultraviolet irradiation.

After applying the coating liquid for forming a transparent coating film having the predetermined configuration, the shrinkage ratio (1) of the coating film when dried is 25% or less, further 20% or less.
If the shrinkage ratio (1) of the dried coating film is higher than the above range, cracks may occur in the case of a thick film, or the hardness may be insufficient due to low denseness.

After drying, the shrinkage ratio (2) of the coating film when cured is 10% or less, and further 5% or less.
If the shrinkage ratio of the coating film when cured (2) is high, the film shrinks greatly when cured, so cracks may occur in the case of a thick film, or the hardness may be insufficient due to low denseness. is there.

Further, the total shrinkage when dried and cured is preferably 35% or less, more preferably 30% or less.
The shrinkage rate (1) is expressed by the following formula A.
Volume shrinkage (1) (%) = [1− (density of coating solution / density of dry film)] × 100... A
Further, the shrinkage rate (2) is expressed by the following formula B.
Volume shrinkage (2) (%) = [1− (density of dried film / density of cured film)] × 100... B

[Organic resin dispersion sol]
The organic resin-dispersed sol according to the present invention is a sol in which the surface-treated metal oxide fine particles are dispersed in the dispersing organic resin (A) or the dispersing organic resin (A) and an organic dispersion medium.

  The dispersing organic resin (A) is as described above, and is preferably an ultraviolet curable resin having 1 to 2 functional groups. When having 1 to 2 functional groups, the viscosity of the organic resin is low, and the increase in the viscosity of the organic dispersion medium sol of the surface-treated metal oxide fine particles can be reduced.

  Further, as described above, the dispersing organic resin (A) is preferably a monomer or oligomer of an ultraviolet curable resin, and if it is a monomer of an ultraviolet curable resin, the surface-treated metal oxide fine particles are stable at a high concentration. An organic resin dispersion sol can be formed.

  The molecular weight (polystyrene equivalent molecular weight) of the dispersing organic resin (A) is preferably 5,000 or less, more preferably 4,500 or less. When the molecular weight of the dispersing organic resin (A) exceeds 5,000, the sol viscosity becomes high, and the particles may not be dispersed to increase the concentration.

As the organic dispersion medium, normally used organic solvents such as alcohols, ethers, esters and ketones are used as described above.
The organic resin dispersion sol of the surface-treated metal oxide fine particles preferably has a concentration (C _PS ) as a solid content of the surface-treated metal oxide fine particles in the range of 45 to 85% by weight, more preferably 45 to 80% by weight. . The concentration (C _RS ) of the organic resin (A) for dispersion in the organic resin dispersion sol as a solid content is preferably 15 to 50% by weight, more preferably 15 to 40% by weight.

The total solid content concentration (C _TS ) of the organic resin dispersion sol is preferably 60% by weight or more, and more preferably 65% by weight or more. The residue when (C _TS ) is less than 100% by weight is the organic dispersion medium.

A stable organic resin dispersion sol having such a composition has not been conventionally known.
Such an organic resin-dispersed sol of surface-treated metal oxide fine particles can be prepared according to step (a) of the method for producing a coating liquid for forming a transparent film according to the present invention described above.

  Such an organic resin-dispersed sol can be used in the coating liquid for forming the transparent film and can be dispersed stably over a long period of time alone. For example, it can be stored and used as a coating liquid at the time of use, or It can be sent to customers and used as a coating liquid.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of coating solution for transparent film formation (1)
Preparation of surface-treated metal oxide fine particles (1) Silica sol dispersion (manufactured by JGC Catalysts &Chemicals; Cataloid SI-30; average particle size 12 nm, SiO ₂ concentration 40.5% by weight, dispersion medium: isopropanol, particles Refractive index 1.46) 7.48 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO ₂ component 81.2%) was mixed with 100 g of ultrapure water. After adding 1 g and stirring at 50 ° C. for 6 hours, a surface-treated 12 nm silica sol dispersion was obtained (solid content concentration 40.5 wt%).

  Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) by a rotary evaporator to obtain a dispersion of surface-treated metal oxide particles (1) having a solid content concentration of 40.5% by weight.

Surface-treated metal oxide particles (1) 2,500 g of dispersion liquid dimethylol-tricyclodecanediacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, number of functional groups: as organic resin for dispersion (A) 2, molecular weight: 219) 202.5 g was added, a part of the solvent was removed by a rotary evaporator, and the organic resin (A) dispersion for dispersing the surface-treated metal oxide fine particles having a solid content concentration of 76.0% by weight ( 1) was prepared. Step (a)
Hereinafter, the composition of the organic resin dispersion (A) for dispersion in each example and comparative example is shown in the table as an organic resin dispersion sol.

Next, 75.31 g of the organic resin (A) dispersion liquid (1) for dispersing the surface-treated metal oxide fine particles and urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H) as the curing organic resin (B). , Functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000, solid content concentration 100%) 8.32 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g And a photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, 2.37 g of PGME, and 12.50 g of acetone were mixed well to form a coating solution for forming a transparent film having a solid content concentration of 66.1% by weight ( 1) was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (1) is shown in the table.

Preparation of substrate with transparent film (1) Apply coating liquid (1) for forming a transparent film to a TAC film (manufactured by Fuji Film Co., Ltd .: FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51). It was applied by the bar coater method # 16 and dried at 80 ° C. for 120 seconds. The film thickness of the transparent coating was 12 μm.
Next, the substrate (1) with a transparent coating was manufactured by irradiating and curing ultraviolet rays of 300 mJ / cm ^{2 in} an N ₂ atmosphere. The film thickness of the transparent coating was 12 μm.
The following evaluation was performed about the obtained base material with a transparent film.

Shrinkage rate Shrinkage rate was evaluated by the following (1) to (3).
(1) Shrinkage from paint to drying (volume shrinkage (1))
1. The density (specific gravity) of the coating liquid for forming a transparent film is measured.
2. After applying the coating liquid for forming a transparent film so that the film thickness after drying becomes about 10 μm, the film is dried at 80 ° C. for 2 minutes to form a dry film. Next, a portion of the dried film is sampled and the density (specific gravity) is measured.
3. The volume shrinkage (1) is calculated according to the following formula (A).
Volume shrinkage (1) (%) = [1− (density of coating solution / density of dry film)] × 100... A

(2) Shrinkage after drying and UV curing (curing shrinkage (2))
1. The specific gravity of the dry film was (1) -2.
2. A part of the transparent coating after curing is collected, and the density (specific gravity) of the transparent coating is measured.
3. The volume shrinkage (2) is calculated according to the following formula (B).
Volume shrinkage (2) (%) = [1− (density of dried film / density of cured film)] × 100... B

(3) Overall shrinkage (3)
The total volume shrinkage rate (3) is calculated according to the following equation (C).
Volume shrinkage (3) (%) = [1− (density of coating solution / density of cured film)] × 100... C
About the obtained base material (1) with a transparent film, the total light transmittance and haze were measured with the haze meter (made by Suga Test Instruments Co., Ltd.).

Moreover, the refractive index of the transparent film was measured with an ellipsometer (manufactured by ULVAC, EMS-1).
The uncoated TAC film had a total light transmittance of 93.2%, a haze of 0.2%, and a reflectance of light having a wavelength of 550 nm was 6.0%.
Further, the presence or absence of cracks was observed, and curling characteristics, scratch resistance, and pencil hardness were measured by the following methods.

Curling property evaluation 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 was placed with the coated surface down, and the height A of the base material from the floor surface was measured. The results are shown in the table.
Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5600.
Measurement of scratch resistance Using # 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]
Preparation of coating liquid for forming transparent film (2) Organic resin (A) dispersion (1) for dispersion of surface-treated metal oxide fine particles prepared in Example 1 and urethane as curing organic resin (B) 8.88 g of 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 content concentration 100%) and an acrylic silicone leveling agent ( Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g, photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.53 g, PGME 0.21 g and acetone 9.0 g were mixed thoroughly and solid. A coating solution (2) for forming a transparent film having a partial concentration of 70.6% by weight was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (2) is shown in the table.

Preparation of substrate with transparent film (2) In Example 1, a substrate with transparent film (2) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (2) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.
About the obtained base material (2) with a transparent film, shrinkage rate, total light transmittance, and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 3]
Preparation of surface-treated metal oxide fine particles (1) Silica sol dispersion (manufactured by JGC Catalysts &Chemicals; Cataloid SI-30; average particle size 12 nm, SiO ₂ concentration 40.5% by weight, dispersion medium: isopropanol, particles Refractive index 1.46) 7.48 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO ₂ component 81.2%) was mixed with 100 g of ultrapure water. After adding 1 g and stirring at 50 ° C. for 6 hours, a surface-treated 12 nm silica sol dispersion was obtained (solid content concentration 40.5 wt%).

Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) by a rotary evaporator (solid content concentration: 40.5% by weight).
Surface-treated metal oxide particles (1) 2,500 g of dispersion liquid dimethylol-tricyclodecanediacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, number of functional groups: as organic resin for dispersion (A) 2, molecular weight: 219) Add 202.5 g, remove part of the solvent with a rotary evaporator, and disperse organic resin (A) dispersion liquid of surface-treated metal oxide fine particles having a solid content concentration of 85.0% by weight ( 1) was prepared. Step (a)

Preparation of coating liquid for forming transparent film (3) Organic resin (A) for dispersing surface-treated metal oxide fine particles prepared in Example 1 (1) 79.99 g and urethane as curing organic resin (B) 9.90 g of 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 content concentration 100%) and an acrylic silicone leveling agent ( Sugimoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g, photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.59 g, PGME 0.51 g and acetone 8.00 g were mixed thoroughly and solid. A coating solution (3) for forming a transparent film having a partial concentration of 78.7% by weight was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (3) is shown in the table.

Preparation of substrate with transparent film (3) In Example 1, a substrate with transparent film (3) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (3) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  About the obtained base material (3) with a transparent film, shrinkage rate, total light transmittance, and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 4]
Preparation of coating liquid for forming transparent film (4) Surface-treated metal oxide particles (1) 2,500 g of dispersion liquid as dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as a dispersion organic resin (A); Light acrylate DCP -A, functional group: acrylate, functional group number: 2, molecular weight: 219) 267.7 g was added, a part of the solvent was removed by a rotary evaporator, and the surface-treated metal oxide fine particles having a solid content concentration of 72.1% by weight Dispersion organic resin (A) dispersion liquid (4) was prepared. Step (a)

Next, 66.61 g of dispersion-treated organic resin (A) dispersion liquid (4) of surface-treated metal oxide fine particles and urethane acrylate (made by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H) as curing organic resin (B) , Functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000, solid content concentration 100%) 10.98 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF 1.00 g and light Polymerization initiator (manufactured by Ciba Japan Co., Ltd .: Irgacure 184) 0.70 g, 8.21 g of PGME and 12.50 g of acetone were sufficiently mixed to form a coating solution for forming a transparent film having a solid concentration of 66.1% by weight (4) Step (b)
The composition of the obtained coating liquid for forming a transparent film (4) is shown in the table.

Preparation of substrate with transparent film (4) In Example 1, the substrate with transparent film (4) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (4) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.
For the obtained substrate (4) with a transparent coating, the shrinkage rate, the total light transmittance, and the haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 5]
Preparation of coating liquid for forming transparent film (5) Surface-treated metal oxide particles (1) 2,500 ml of dispersion liquid as dimethylol-tricyclodecanediacrylate (Kyoeisha Chemical Co., Ltd.) as dispersion organic resin (A); Light acrylate DCP -A, functional group: acrylate, functional group number: 2, molecular weight: 219) 153.0 g was added, and a part of the solvent was removed by a rotary evaporator, and the surface-treated metal oxide fine particles having a solid content concentration of 72.3% by weight Dispersion organic resin (A) dispersion liquid (5) was prepared. Step (a)

Surface treatment metal oxide fine particle dispersion organic resin (A) 81.94 g dispersion (5) and curing organic resin (B) 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 content concentration 100%) 6.27 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g and light Polymerization initiator (manufactured by Ciba Japan Co., Ltd .: Irgacure 184) 0.46 g, 0.33 g of PGME and 10.00 g of acetone are mixed well to form a coating solution for forming a transparent film having a solid content concentration of 66.1% by weight (5) Was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (5) is shown in the table.

Preparation of substrate with transparent film (5) In Example 1, a substrate with transparent film (5) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (5) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.
At this time, the shrinkage ratio (1) of the coating film during drying and the shrinkage ratio (2) during curing were measured, and the results are shown in the table.

  For the obtained substrate with transparent coating (5), the total light transmittance and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 6]
Preparation of coating liquid for forming transparent film (6) Surface-treated metal oxide particles (1) 2,500 g of dispersion liquid dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as dispersion organic resin (A); Light acrylate DCP -A, functional group: acrylate, functional group number: 2, molecular weight: 219) 85.8 g was added, and a part of the solvent was removed by a rotary evaporator, and the surface-treated metal oxide fine particles having a solid content concentration of 69.0% by weight Dispersion organic resin (A) dispersion liquid (6) was prepared. Step (a)

Next, 75.31 g of the dispersion-treated organic resin (A) dispersion (6) of the surface-treated metal oxide fine particles and urethane acrylate (made by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H) as the curing organic resin (B). , Functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000, solid content concentration 100%) 12.15 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g And a photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, 2.04 g of PGME, and 9.00 g of acetone are thoroughly mixed to form a coating solution for forming a transparent film having a solid content concentration of 66.1% by weight. (6) was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (6) is shown in the table.

Preparation of substrate with transparent film (6) In Example 1, a substrate with transparent film (6) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (6) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  For the obtained substrate (6) with a transparent coating, the shrinkage rate, the total light transmittance, and the haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 7]
Preparation of coating liquid for forming transparent film (7) Surface-treated metal oxide particles (1) 2,500 g of dispersion liquid as dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as dispersion organic resin (A); Light acrylate DCP -A, functional group: acrylate, functional group number: 2, molecular weight: 219) 272.1 g was added, and a part of the solvent was removed with a rotary evaporator, and the surface-treated metal oxide fine particles having a solid content concentration of 80.1% by weight A dispersion organic resin (A) dispersion liquid (7) was prepared. Step (a)

Next, 75.31 g of the organic resin (A) dispersion liquid (7) for dispersing the surface-treated metal oxide fine particles and urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H) as the curing organic resin (B). , Functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000, solid content concentration 100%) 5.21 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g And a photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, 5.48 g of PGME, and 12.50 g of acetone were mixed well to form a coating solution for forming a transparent film having a solid content concentration of 66.1% by weight ( 7) was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (7) is shown in the table.

Preparation of substrate with transparent film (7) A substrate with transparent film (7) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (7) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  For the obtained substrate (7) with a transparent coating, the shrinkage rate, the total light transmittance, and the haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 8]
Preparation of coating liquid for forming transparent film (8) Surface-treated metal oxide particles (1) 1,6-hexadiol dimethacrylate (manufactured by Sakai Kogyo Co., Ltd .; SR-) as dispersion organic resin (A) in 2500 g of dispersion 238F, functional group: acrylate, functional group number: 2, molecular weight: 226) 202.5 g was added, and a part of the solvent was removed by a rotary evaporator to obtain a surface-treated metal oxide fine particle having a solid content concentration of 76.0% by weight. Dispersion organic resin (A) dispersion liquid (8) was prepared. Step (a)

Next, 75.31 g of the dispersion-treated organic resin (A) dispersion (8) of the surface-treated metal oxide fine particles, and urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo U-6LPA) as the curing organic resin (B) , Functional group: urethane acrylate, functional group number: 6, molecular weight: 2,100, solid content concentration 70%) 11.89 g, and acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g And a photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, 0.300 g of PGME, and 11.00 g of acetone were mixed well to form a coating solution for forming a transparent film having a solid content concentration of 66.1% by weight ( 8) was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (8) is shown in the table.

Preparation of substrate with transparent film (8) A substrate with transparent film (8) was produced in the same manner as in Example 1, except that the coating liquid for transparent film formation (8) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  For the obtained substrate with transparent film (8), the shrinkage rate, total light transmittance, and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 9]
Preparation of surface-treated metal oxide fine particles (2) Silica sol dispersion (manufactured by JGC Catalysts &Chemicals; Cataloid SI-30; average particle size 12 nm, SiO ₂ concentration 40.5% by weight, dispersion medium: isopropanol, particles Refractive index 1.46) 3.74 g of γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO ₂ component 81.2%) was mixed with 100 g of ultrapure water. After adding 1 g and stirring at 50 ° C. for 6 hours, a surface-treated 12 nm silica sol dispersion was obtained (solid content concentration 40.5 wt%).

  Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) by a rotary evaporator to obtain a dispersion of surface-treated metal oxide particles (9) having a solid content concentration of 40.5% by weight.

Preparation of coating liquid for forming transparent film (9) Surface-treated metal oxide particles (2) 2,500 g of dispersion liquid as dimethylol-tricyclodecanediacrylate (Kyoeisha Chemical Co., Ltd.) as dispersion organic resin (A); Light acrylate DCP -A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) 202.5 g was added, and a part of the solvent was removed with a rotary evaporator to obtain a solid content concentration of 76.0% by weight. An organic resin (A) dispersion (9) for dispersing the surface-treated metal oxide fine particles was prepared. Step (a)

Next, 75.31 g of the organic resin (A) dispersion (9) for dispersing the surface-treated metal oxide fine particles and urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H) as the curing organic resin (B) , Functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000, solid content concentration 100%) 8.32 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g And a photopolymerization initiator (manufactured by Ciba Japan Co., Ltd .: Irgacure 184), 2.37 g of PGME and 12.50 g of acetone are sufficiently mixed to form a coating solution for forming a transparent film having a solid content concentration of 63.9% by weight ( 9) was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (9) is shown in the table.

Preparation of substrate with transparent film (9) In Example 1, a substrate with transparent film (9) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (9) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  About the obtained base material (9) with a transparent film, shrinkage rate, total light transmittance, and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 10]
Preparation of surface-treated metal oxide fine particles (3) Silica sol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .; Cataloid SI-30; average particle size 12 nm, SiO ₂ concentration 40.5% by weight, dispersion medium: isopropanol, particles (Refractive index 1.46) 14.96 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO ₂ component 81.2%) was mixed with 100 g of ultrapure water. After adding 1 g and stirring at 50 ° C. for 6 hours, a surface-treated 12 nm silica sol dispersion was obtained (solid content concentration 40.5 wt%).

  Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) by a rotary evaporator to obtain a dispersion of surface-treated metal oxide particles (10) having a solid content concentration of 40.5% by weight.

Preparation of coating liquid for forming transparent film (10) Surface treated metal oxide particles (3) 2,500 g of dispersion liquid dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as dispersion organic resin (A); Light acrylate DCP -A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) 202.5 g was added, and a part of the solvent was removed with a rotary evaporator to obtain a solid content concentration of 76.0% by weight. An organic resin (A) dispersion liquid (10) for dispersing surface-treated metal oxide fine particles was prepared. Step (a)

Next, 75.31 g of the organic resin (A) dispersion (10) for dispersing the surface-treated metal oxide fine particles and urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H) as the curing organic resin (B) , Functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000, solid content concentration 100%) 8.32 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g And a photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, 2.37 g of PGME, and 12.50 g of acetone are sufficiently mixed to form a coating solution for forming a transparent film having a solid content concentration of 70.6% by weight ( 10) was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (10) is shown in the table.

Preparation of substrate with transparent coating (10) A substrate with transparent coating (10) was produced in the same manner as in Example 1, except that the coating solution for forming a transparent coating (10) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  For the obtained substrate (10) with a transparent coating, the shrinkage rate, total light transmittance, and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 11]
Preparation of surface-treated metal oxide fine particles (4) Silica sol dispersion (manufactured by JGC Catalysts &Chemicals; Cataloid SI-30; average particle size 12 nm, SiO ₂ concentration 40.5% by weight, dispersion medium: isopropanol, particles 7.06 g of γ-acryloxypropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd .: KBM-5103, SiO ₂ component 86.1%) was mixed with 100 g of refractive index 1.46), and 3.1 g of ultrapure water was added. Then, a 12 nm silica sol dispersion surface-treated by stirring at 50 ° C. for 6 hours was obtained (solid content concentration 40.5 wt%).

  Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) by a rotary evaporator to obtain a dispersion of surface-treated metal oxide particles (11) having a solid content concentration of 40.5% by weight.

Preparation of coating liquid for forming transparent film (11) Surface-treated metal oxide particles (4) 2,500 g of dispersion liquid as dimethylol-tricyclodecane diacrylate (Kyoeisha Chemical Co., Ltd.) as dispersion organic resin (A); -A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) 202.5 g was added, and a part of the solvent was removed with a rotary evaporator to obtain a solid content concentration of 76.0% by weight. An organic resin (A) dispersion (11) for dispersing surface-treated metal oxide fine particles was prepared. Step (a)

Surface treatment metal oxide fine particle dispersion organic resin (A) dispersion (11) 75.31 g and curing organic resin (B) 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 content concentration 100%) 8.32 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g and light Polymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, 2.37 g of PGME, and 12.50 g of acetone were mixed well to form a coating solution for forming a transparent film having a solid concentration of 66.1 wt% (11) Was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (11) is shown in the table.

Preparation of substrate with transparent film (11) In Example 1, a substrate with transparent film (11) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (11) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  For the obtained substrate (11) with a transparent coating, the shrinkage rate, the total light transmittance, and the haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 12]
Preparation of surface-treated metal oxide fine particles (5 ) 33.4 Kg of a sodium silicate aqueous solution (SiO ₂ / Na ₂ O molar ratio: 3.1) having a SiO ₂ concentration of 24% by weight was diluted with 126.6 Kg of pure water, 160 kg of an aqueous sodium silicate solution (pH 11) having a SiO ₂ concentration of 5% by weight was prepared. The aqueous solution of sodium silicate was neutralized by adding an aqueous sulfuric acid solution having a sulfuric acid concentration of 25% so that the pH of the aqueous solution of sodium silicate was 4.5.

This silica hydrogel was 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 was dispersed in pure water to prepare a dispersion having a SiO ₂ concentration of 3% by weight, and the mixture was stirred using a powerful stirrer until a fluid slurry was 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.

After the obtained silica sol was stabilized by heating at 150 ° C. for 1 hour, the silica sol was made to have an SiO ₂ concentration of 13% by weight using an ultrafiltration membrane (Asahi Kasei Kogyo Co., Ltd .: SIP-1013). Then, it was concentrated with a rotary evaporator and filtered through a 44 μm mesh nylon filter to prepare a silica sol (5) 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 (5) was 48 nm, the average short diameter (D _S ) was 16 nm, and the spherical coefficient was 0.33.
600 g of silica sol (5) was mixed with 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 wt%, and the temperature was raised to 87 ° C. And aged for 0.5 hour. 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 was concentrated using an ultrafiltration membrane (Asahi Kasei Kogyo Co., Ltd .: SIP-1013) until the SiO ₂ concentration became 12% by weight, and then concentrated on a rotary evaporator. Then, the mixture was filtered through a 44 μm mesh nylon filter to obtain a metal oxide fine particle (5) dispersion composed of non-spherical silica having a solid concentration of 30% by weight.

  Pure water is added to 400 g of a dispersion of metal oxide fine particles (5) having a concentration of 30% by weight to obtain a solid concentration of 20% by weight, and 240 g of cation exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SK1B) is used. Washing was performed by ion exchange at 3 ° C. for 3 hours, and this dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain a methanol dispersion having a solid content concentration of 20% by weight.

  To 100 g of this methanol dispersion, 7.48 g of a methacrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, γ-methacryloxyfluorotrimethoxysilane) is added, and the mixture is heated and stirred at 50 ° C. for 6 hours to form a solid. A metal oxide fine particle (5) dispersion composed of non-spherical silica surface-treated with an organosilicon compound having a partial concentration of 40.5% by weight was prepared.

The solvent was replaced with PGME by a rotary evaporator to obtain a PGME dispersion of surface-treated metal oxide fine particles (5) made of non-spherical silica having a solid concentration of 40.5% by weight.
The average particle longest diameter (D _L ) of the obtained surface-treated metal oxide fine particles (5) is 50 nm, the average short diameter (D _S ) is 21 nm, and the spherical coefficient (D _S ) / (D _L ) is 0. 42.

Preparation of coating solution for forming transparent film (12) Surface-treated metal oxide fine particles (5) with a solid content of 40.5% by weight (5) Dimethylol-tricyclodecane diacrylate (Kyoeisha) as an organic resin for dispersion (A) Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) 202.5 g was added, and a part of the solvent was removed with a rotary evaporator. An organic resin (A) dispersion (12) for dispersing surface-treated metal oxide fine particles having a solid content concentration of 76.0% by weight was prepared. Step (a)

Surface treatment metal oxide fine particle dispersion organic resin (A) dispersion liquid (12) 75.31 g and curing organic resin (B) 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 content concentration 100%) 8.32 g, acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g and light Polymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, 2.37 g of PGE, and 12.50 g of acetone are mixed well to form a coating solution for forming a transparent film having a solid concentration of 66.1% by weight (12) Was prepared. Step (b)
The composition of the obtained coating liquid for forming a transparent film (12) is shown in the table.

Preparation of substrate with transparent film (12) In Example 1, the substrate with transparent film (12) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (12) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  For the obtained substrate with transparent film (12), the shrinkage rate, the total light transmittance, and the haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Example 13]
Preparation of transparent film-coated substrate (13) A transparent film-coated substrate (13) was produced in the same manner as in Example 1, except that the coating liquid (1) for forming a transparent film was coated by the bar coater method # 20. . The film thickness of the transparent coating was 15 μm.

At this time, the shrinkage ratio (1) of the coating film during drying and the shrinkage ratio (2) during curing were measured, and the results are shown in the table.
For the obtained substrate with transparent coating (13), the total light transmittance and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Example 14
Preparation of substrate with transparent film (14) A substrate with transparent film (14) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (1) was applied by the bar coater method # 40. . The film thickness of the transparent coating was 30 μm.

  For the obtained substrate with transparent film (14), the shrinkage rate, total light transmittance, and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Comparative Example 1]
Preparation of coating solution (R1) for forming a transparent film The surface-treated metal oxide particles (1) having a solid concentration of 40.5% by weight prepared in the same manner as in Example 1 (1) Dispersed as an organic resin (A) in 2500 g 202.5 g of dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) was added, and the rotary evaporator was added. A part of the solvent was removed to prepare an organic resin (A) dispersion (R1) for dispersing the surface-treated metal oxide fine particles having a solid content concentration of 76.0% by weight. Step (a)

Next, 75.31 g of the organic resin (A) dispersion liquid (R1) for dispersing the surface-treated metal oxide fine particles, and dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as the organic resin for dispersion (A); Light acrylate DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) 8.32 g, and acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1 .00 g, 0.50 g of photopolymerization initiator (manufactured by Ciba Japan Co., Ltd .: Irgacure 184), 2.37 g of PGME and 12.50 g of acetone are sufficiently mixed to form a transparent film having a solid content concentration of 66.1% by weight. A liquid (R1) was prepared. Step (b)
The composition of the obtained coating solution for forming a transparent film (R1) is shown in the table.

Preparation of substrate with transparent coating (R1) In Example 1, a substrate with transparent coating (R1) was produced in the same manner as in Example 1, except that the coating solution for transparent coating formation (R1) was applied by the bar coater method (# 16). The film thickness of the transparent coating was 12 μm.

  About the obtained base material with a transparent film (R1), shrinkage rate, total light transmittance, and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Comparative Example 2]
Preparation of coating liquid for forming transparent film (R2) Surface-treated metal oxide particles (1) having a solid content of 40.5% by weight prepared in the same manner as in Example 1 (1) Dispersing liquid 2500 g as a curing organic resin (B) Urethane acrylate (Shin Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, functional group: urethane acrylate, functional group number: 9, molecular weight: 4,000, solid content concentration: 100%) 202.5) g is added and rotary A part of the solvent was removed by an evaporator to prepare an organic resin (B) dispersion (R2) for curing the surface-treated metal oxide fine particles having a solid content concentration of 53.3% by weight. Step (a)

Next, 82.96 g of the organic resin (B) dispersion (R2) for curing the surface-treated metal oxide fine particles, an acrylic silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; 1.00 g of 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 were sufficiently mixed to prepare a coating solution (R2) for forming a transparent film having a solid content concentration of 51.0 wt%. Step (b)
The composition of the obtained coating liquid for forming a transparent film (R2) is shown in the table.

Preparation of substrate with transparent coating (R2) A substrate with transparent coating (R2) was produced in the same manner as in Example 1, except that the coating solution for transparent coating formation (R2) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.
At this time, the shrinkage ratio (1) of the coating film during drying and the shrinkage ratio (2) during curing were measured, and the results are shown in the table.

  For the obtained substrate with transparent coating (R2), the total light transmittance and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Comparative Example 3]
Preparation of coating liquid (R3) for forming a transparent film 69.14 g of a surface-treated metal oxide particle (1) dispersion having a solid content concentration of 40.5% by weight prepared in the same manner as in Example 1, and an organic resin for dispersion (A) dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration: 100%) 5.26 g 4.83 g of an organic resin for curing (B) (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000) and acrylic silicone type Leveling agent (Tsubakimoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g, photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.29 g and PGME 6.99 g Acetone 12.50g thoroughly mixed with a solid concentration 41.4% by weight of the transparent film-forming coating liquid (R3) was prepared.
The composition of the obtained coating solution for forming a transparent film (R3) is shown in the table.

Preparation of substrate with transparent coating (R3) A substrate with transparent coating (R3) was produced in the same manner as in Example 1, except that the coating solution for transparent coating formation (R3) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  About the obtained base material with a transparent film (R3), shrinkage rate, total light transmittance, and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

[Comparative Example 4]
Preparation of coating solution (R4) for forming a transparent film Silica sol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .; Cataloid SI-30; average particle size 12 nm, SiO ₂ concentration 40.5% by weight, dispersion medium: isopropanol, particles Dimethylol-tricyclodecane diacrylate (made by Kyoeisha Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 2500 g of an organic resin (A) for dispersion at a refractive index of 1.46) 219, solid content concentration 100%) 202.5 g was added, and a part of the solvent was removed by a rotary evaporator to disperse metal oxide fine particles of silica having a solid content concentration of 53.3% by weight (A). A dispersion (R4) was prepared. Step (a)

75.31 g of organic resin (A) dispersion (R4) for dispersing metal oxide fine particles and organic resin for curing (B) (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%) 7.19 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, 0.83 g of PGME, and 8.00 g of acetone were sufficiently mixed to prepare a coating solution (R4) for forming a transparent film having a solid content concentration of 53.3% by weight. . Step (b)
The composition of the obtained coating solution for forming a transparent film (R4) is shown in the table.

Preparation of substrate with transparent coating (R4) A substrate with transparent coating (R4) was produced in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R4) was applied by the bar coater method # 16. . The film thickness of the transparent coating was 12 μm.

  About the obtained base material (R4) with a transparent film, shrinkage rate, total light transmittance, and haze were measured, and the results are shown in the table. Further, the presence or absence of cracks was observed, curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Claims (24)

Surface-treated metal oxide fine particles having an average particle size in the range of 5 to 300 nm and a matrix-forming component, the matrix-forming component comprising an organic resin for dispersion (A) and an organic resin for curing (B). The concentration (C _P ) as the solid content of the metal oxide fine particles is in the range of 45 to 90% by weight, the concentration (C _R ) as the solid content of the matrix forming component is in the range of 15 to 50% by weight, The solid content concentration (C _T ) is 60% by weight or more, and the ratio (C _R ) / (C _P ) between the concentration (C _R ) and the concentration (C _P ) is in the range of 0.12 to 1.0. A coating solution for forming a transparent film, characterized in that   The dispersing organic resin (A) is an ultraviolet curable resin monomer or oligomer having 1 to 2 functional groups, and the curing organic resin (B) is an ultraviolet curable resin monomer having 3 or more functional groups. The coating solution for forming a transparent film according to claim 1, wherein the coating solution is an oligomer.   The functional group of the organic resin for dispersion (A) and the organic resin for curing (B) is at least one selected from an acrylate group, a (meth) acrylate group, a urethane acrylate group, and an epoxy-modified acrylate group. The coating liquid for forming a transparent film according to claim 2.   The coating liquid for forming a transparent film according to any one of claims 1 to 3, wherein the molecular weight of the dispersing organic resin (A) and the curing organic resin (B) is 5,000 or less. The coating liquid for forming a transparent film according to any one of claims 1 to 4, wherein the surface-treated metal oxide fine 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 from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)   6. The coating liquid for forming a transparent film according to claim 5, wherein R of the organosilicon compound is an organosilicon compound having at least one substituted hydrocarbon group having a (meth) acrylate group as a substituent. The surface treatment amount of the surface-treated metal oxide fine particles is in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the metal oxide fine particles and the organosilicon compound as R _n —SiO _{4 -n / 2.} The coating liquid for forming a transparent film according to claim 6.   When the surface treatment amount of the surface-treated metal oxide fine particles is in the range of 0.1 to 5 parts by weight, the dispersing organic resin (A) is a hydroxyl group (OH group), an ether group (—O— group), an amino group. The coating liquid for forming a transparent film according to any one of claims 1 to 7, which is an organic resin having at least one of benzene, carboxyl group, and sulfo group.   The coating liquid for forming a transparent film according to claim 1, wherein the spherical coefficient of the surface-treated metal oxide fine particles is in the range of 0.2 to 1.0. A method for producing a coating solution for forming a transparent film, comprising the following steps (a) and (b):
(A) a step of replacing part or all of the organic dispersion medium of the organic dispersion medium dispersion of the surface-treated metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm with the organic resin for dispersion (A);
(B) A step of mixing the curing organic resin (B).   The organic resin for dispersion medium (A) is an ultraviolet curable resin monomer or oligomer having 1 to 2 functional groups, and the organic resin for curing (B) is an ultraviolet curable resin having 3 or more functional groups. It is a monomer thru | or oligomer, The coating liquid for transparent film formation of Claim 10 characterized by the above-mentioned.   The functional group of the organic resin for dispersion (A) and the organic resin for curing (B) is at least one selected from an acrylate group, a (meth) acrylate group, a urethane acrylate group, and an epoxy-modified acrylate group. The manufacturing method of the coating liquid for transparent film formation of Claim 10 or 11. The concentration (C _P ) as the solid content of the surface-treated metal oxide fine particles is in the range of 45 to 90% by weight, and the organic resin for dispersion medium (A) and the organic resin for curing (B) as a matrix forming component ) In the range of 15 to 50% by weight as the total solid content (C _R ), the total solid content concentration (C _T ) is 60% by weight or more, and the concentration (C _R ) and concentration (C _P The ratio (C _R ) / (C _P ) to the range of 0.1 to 1.0 is in the range of 0.12 to 1.0, The method for producing a coating liquid for forming a transparent film according to any one of claims 10 to 12 . It consists of surface-treated metal oxide fine particles having a mean particle size in the range of 5 to 300 nm and a matrix component, and the content (W _P ) of the surface-treated metal oxide fine particles as a solid content is in the range of 50 to 90% by weight. Yes, the content (W _R ) of the matrix component as a solid content is in the range of 10 to 50 wt%, and the ratio (W _R ) / (W _P ) of the content (W _R ) and the content (W _P ) ) Is in the range of 0.12 to 1.0, and the average film thickness (T) is in the range of 1 to 100 μm.   The substrate with a transparent coating according to claim 14, wherein the matrix component comprises the organic resin for dispersion (A) and the organic resin for curing (B).   The substrate with a transparent coating according to claim 14 or 15, wherein the surface-treated metal oxide fine particles have a spherical coefficient in the range of 0.2 to 1.0.   The substrate with a transparent coating according to any one of claims 14 to 16, wherein the substrate is at least one resin substrate selected from acrylic, polycarbonate, cycloolefin polymer (COP), PET, and TAC. Wood.   Pencil hardness is 5H or more, The base material with a transparent film in any one of Claims 14-17 characterized by the above-mentioned. The substrate with a transparent coating according to any one of claims 14 to 18, wherein the curling characteristic measured under the following conditions is 5 mm or less;
A coating solution for forming a transparent film is applied on a TAC film substrate having a thickness of 14 cm × 25 cm × 40 μm (thickness) so that a transparent film having a thickness of 12 μm can be formed, and is allowed to stand for 20 hours, and then the film is 10 cm × 10 cm in size. The height from the flat plate at the apex of the base material that was cut into two pieces, placed on a flat plate with the coating surface down, and curled (curved) and floated.   The transparent coating solution according to any one of claims 14 to 19, wherein the transparent coating film forming coating solution according to any one of claims 1 to 9 is applied onto a substrate, dried, and then cured. Base material with coating.   After applying the coating liquid for forming a transparent film, the shrinkage rate of the coating film when dried is 25% or less, and then the shrinkage rate of the coating film when cured is 10% or less, and the total shrinkage rate The substrate with a transparent coating according to claim 20, wherein the content is 35% or less. Surface-treated metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm are dispersed in the organic resin for dispersion (A) or the organic resin for dispersion (A) and the organic dispersion medium. The concentration (C _PS ) as a solid content is in the range of 45 to 90% by weight, and the concentration (C _RS ) as the solid content of the organic resin for dispersion (A) is in the range of 15 to 50% by weight. An organic resin-dispersed sol of surface-treated metal oxide fine particles, wherein the partial concentration (C _TS ) is 60% by weight or more.   23. The organic resin dispersion sol of surface-treated metal oxide fine particles according to claim 22, wherein the organic resin for dispersion (A) is an ultraviolet curable resin monomer or oligomer having 1 to 2 functional groups.   24. The organic resin dispersion sol of surface-treated metal oxide fine particles according to claim 22 or 23, wherein the organic resin for dispersion (A) has a molecular weight of 5,000 or less.