JP6450531B2 - Manufacturing method of substrate with antireflection film - Google Patents

Description

  The present invention provides a hard coat film having high hardness even when the base material is a resin base material, and has no cracks even when the thickness is reduced, and curling is suppressed. The present invention relates to a base material with an antireflection film comprising an antireflection film having excellent properties, transparency and haze as well as an antireflection film, and a coating liquid for forming an antireflection film that can be suitably used for forming an antireflection 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 (Japanese Patent Laid-Open No. 2010-077409 (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 (Japanese Patent Laid-Open No. 2010-126675 (Patent Document 12)).

Japanese Patent Laid-Open No. 3-163172 JP-A-6-336558 Japanese Patent Application Laid-Open No. 6-049251 JP 2000-143230 A JP 2010-037534 A JP 2010-077409 A JP 2012-072288 A JP 2013-010864 A JP 2013-133444 A JP 2013-136222 A JP 2009-035595 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 display devices, mobile phones, organic EL televisions, and the like.

Moreover, when using it for a display apparatus etc. simultaneously, the antireflection performance is calculated | required.
However, since the film thickness of the antireflection film is usually a thin film of 50 to 300 nm, it is difficult to obtain an antireflection film excellent in hardness and scratch resistance particularly when the substrate is a resin.

  As a result of intensive studies to meet such demands, the present inventors have formed a hard coat film having desired characteristics on the substrate, and then formed an antireflection film on the hard coat film. We tried to solve this problem with a two-layer structure.

  First, regarding the hard coat film, it was considered 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 cracks and shrinkage due to drying during the formation of the hard coat film are large as well as the stability of the coating liquid for forming the hard coat film. As a result of further diligent studies to solve such problems, as a dispersion sol medium at the time of preparing the coating liquid for forming the hard coat film, by using an ultraviolet curable resin monomer instead of the conventional solvent, the final It has been found that the proportion of typical resin can be reduced.

  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 if 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. Even if the coating solution for forming a hard coat film is applied thickly, It has been found that the shrinkage of the film is small, there are no cracks, curling is suppressed, and the hardness of the film is remarkably improved.

  Further, for the antireflection film provided on such a hard coat film, a silica-based hollow fine particle having a small average particle diameter is used, and a matrix forming component similar to that for forming a hard coat film is included as a matrix forming component. It has been found that even if a thin antireflection film is provided, the improved hardness of the hard coat film can be maintained, and the present invention has been completed.

[1] A base material with an antireflection film in which a hard coat film and an antireflection film are formed on a base material,
The hard coat film comprises surface-treated metal oxide fine particles having an average particle diameter in the range of 5 to 300 nm and a matrix component (M _H ),
(i) The content (W _PH ) of the surface-treated metal oxide fine particles (P) as a solid content is in the range of 50 to 90% by weight,
(ii) The content (W _RH ) of the matrix component (M _H ) as a solid content is in the range of 10 to 50% by weight,
(iii) the content (W _RH) and the content (W _PH) and the ratio of _{(W RH) / (W PH} ) is in the range of 0.12 to 1.0,
(iv) The average film thickness (T _H ) is in the range of 1 to 100 μm,
The antireflection film is from a silica-based hollow particles (A) and the matrix component (M _L),
(a) The content of silica-based hollow fine particles (A) (W _PLA ) is in the range of 5 to 80% by weight,
(b) The content (W _ML ) of the matrix component (M _L ) is in the range of 20 to 95% by weight,
(c) The thickness (T _L ) of the antireflection film is in the range of 80 to 200 nm,
(d) The silica-based hollow fine particles (A) have an average particle diameter (Dpa) in the range of 10 to 45 nm,
(e) The ratio of the average particle diameter (Dpa) and the anti-reflection film having a film thickness of the silica-based hollow particles _{(A) (T L) (} Dpa) / (T L) is in the range of from 0.05 to 0.56 A base material with an antireflection film, characterized in that it exists.

[2] The substrate with an antireflection film according to [1], wherein the refractive index of the silica-based hollow fine particles (A) is in the range of 1.10 to 1.40.
[3] The antireflection film further includes silica-based fine particles (B) (hollow fine particles, silica fine particles, and chain particles thereof) having an average particle diameter (Dpb) in the range of 4 to 17 nm. The ratio (Dpb) / (Dpa) of the average particle size (Dpb) of B) to the average particle size (Dpa) of the silica-based hollow fine particles (A) is in the range of 0.1 to 0.4 [1] or [2] A substrate with an antireflection film.
[4] The total content of the silica-based hollow fine particles (A) and the silica-based fine particles (B) in the antireflection film is in the range of 5 to 80% by weight, and the silica-based fine particles (B) in all the fine particles The base material with an antireflection film according to [3], wherein the ratio is 30% by weight or less.

[5] The antireflection film-coated substrate according to [1] to [4], wherein the surface-treated metal oxide fine particles (P) 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 antireflection film-coated base of [1] to [5], wherein the silica-based hollow fine particles (A) and the silica-based fine particles (B) are surface-treated with an organosilicon compound represented by the following formula (2): Wood.
R _n -SiX _4-n (2)
(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)

[7] The substrate with an antireflection film according to any one of [1] to [6], wherein the matrix component (M _H ) comprises a dispersing organic resin (A) and a curing organic resin (B).
[8] the matrix component (M _L) is an organic resin matrix component [1] - antireflection film substrate with [7].
[9] The matrix component (M _L) antireflective film substrate with [8] contained in the dispersion for organic resin (A) and / or curing an organic resin (B).
[10] 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. [8] or [9] A substrate with an antireflection film, which is a mold resin monomer or oligomer.
[11] At least one functional group of the organic resin for dispersion (A) and the organic resin for curing (B) selected from a (meth) acrylate group, a urethane (meth) acrylate group, and an epoxy-modified (meth) acrylate group [10] A substrate with an antireflection film as a seed.
[12] The substrate with antireflection film according to [1] to [11], wherein the spherical coefficient of the surface-treated metal oxide fine particles (P) is in the range of 0.2 to 1.0.

[13] The substrate with antireflection film according to [1] to [12], wherein an interface (bonding surface) between the hard coat film and the antireflection film is corrugated.
[14] The substrate with antireflection film according to [1] to [13], wherein the substrate is at least one resin substrate selected from acrylic, polycarbonate, cycloolefin polymer (COP), PET, and TAC.
[15] The substrate with antireflection film according to [1] to [14], wherein the pencil hardness is 5H or more.
[16] (A) a surface-treated metal oxide fine particle and a matrix-forming form; (i) a content (W _PH ) of the surface-treated metal oxide fine particle is in the range of 50 to 90% by weight; ii) is in the range content as solids (W _RH) of 10 to 50% by weight of the matrix component (M _H), solid and concentration (C _PH) is a hard coat film formed in 45 to 85 wt% After applying and drying the coating liquid on the substrate surface to form a hard coat film,
(B) It consists of silica-based hollow fine particles (A), a matrix-forming component and a solvent, and the silica-based hollow fine particles (A) have an average particle diameter (Dpa) in the range of 10 to 45 nm, and the total solid content concentration is 1 to It is in the range of 10% by weight, the concentration of the silica-based hollow fine particles (A) is in the range of 0.25 to 9% by weight as the solid content, and the concentration of the matrix forming component is 0.75 to 9.5% as the solid content. % Antireflection film-forming coating solution is applied to the surface of the hard coat film and dried to form an antireflection film-coated substrate.

[17] The method for producing a substrate with an antireflection film according to [16], wherein the curling property of the hard coat film is 5 mm or less when measured under the following conditions;
A coating liquid for forming a hard coat film was applied on a TAC film substrate having a thickness of 14 cm × 25 cm × 40 μm (thickness) so that a hard coat film having a thickness of 12 μm could be formed, and allowed to stand for 20 hours. The height from the flat plate at the apex of the substrate which was cut into a size of 10 cm, placed on a flat plate with the coating surface down, and curled (curved) and floated.
[18] After applying the coating liquid for forming a hard coat film, the shrinkage ratio of the coating film when dried is 25% or less, the shrinkage ratio of the coating film when cured is 10% or less, and the total shrinkage [16] and [17], wherein the rate is 35% or less.
[19] The process for producing a substrate with an antireflection film according to [16], wherein the silica-based hollow fine particles (A) have a refractive index in the range of 1.10 to 1.40.
[20] Further, silica-based fine particles (B) having an average particle size (Dpb) in the range of 4 to 17 nm are included, and the average particle size (Dpb) of the silica-based fine particles (B) and the silica-based hollow fine particles (A) [16] The method for producing a substrate with an antireflection film according to [16], wherein the ratio (Dpb) / (Dpa) to the average particle diameter (Dpa) is in the range of 0.1 to 0.4.
[21] The production of a substrate with an antireflection film according to [20], wherein the silica-based hollow fine particles (A) and the silica-based fine particles (B) are surface-treated with an organosilicon compound represented by the following formula (3): Method.
_{R n -SiX 4-n (3} )
(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)

[22] The method for producing a substrate with an antireflection film according to [16], wherein the matrix forming component is an organic resin matrix forming component.
[23] The method for producing a substrate with an antireflection film according to [22], wherein the matrix-forming component contains an organic resin for dispersion (A) and / or an organic resin for curing (B).
[24] 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. [23] A method for producing a substrate with an antireflection film, which is a mold resin monomer or oligomer.
[25] At least one functional group of the organic resin for dispersion (A) and the organic resin for curing (B) selected from a (meth) acrylate group, a urethane (meth) acrylate group, and an epoxy-modified (meth) acrylate group The method for producing a substrate with an antireflection film according to claim 23 or 24, wherein the method is a seed.
[26] With an antireflection film according to [16], wherein the coating liquid for forming a hard coat film is applied and dried, the coating liquid for forming an antireflective film is applied, dried, and then simultaneously cured by ultraviolet irradiation. A method for producing a substrate.

  According to the present invention, even if the substrate is a resin substrate, the hardness is high, and even if it is a film thickness, there is no crack, curling is suppressed, excellent hardness, scratch resistance, transparency, haze and antireflection performance It is possible to provide a base material with an antireflection film that is excellent in performance.

Hereinafter, first, the substrate with antireflection film according to the present invention will be described.
The base material with an antireflection film according to the present invention is a base material with an antireflection film in which a hard coat film and an antireflection film are sequentially formed on the base material.
[Base material]
As the base material used in the present invention, a resin base material is used.
The resin substrate is preferably at least one transparent resin substrate selected from PET, TAC, acrylic, polycarbonate, and cycloolefin polymer (COP).

  These resin base materials have high adhesion to the hard coat film, and in combination with the hard coat film and the antireflection film, the antireflection film has excellent hardness, scratch resistance, transparency, haze and antireflection performance. A substrate with a film can be obtained.

[Hard coat film]
The hard coat film of the present invention comprises surface-treated metal oxide fine particles (P) and a matrix component (M _H ).

Surface-treated metal oxide fine particles (P )
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 10 to 200 nm.
The average particle diameter of the metal oxide fine particles is less than the above lower limit, although depending on the presence or absence of the surface treatment described later, the metal oxide fine particles may aggregate, the haze of the hard coat 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 hard coat film may be deteriorated or the transparency may be lowered depending on the content of the metal oxide fine particles.

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. Cracks may occur in the film. 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 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 hard coat film having high compatibility with the resin (B) and improved dispersibility, and uniform and excellent adhesion to the substrate can be obtained.

In addition, since the bondability with each resin that is a matrix forming component is improved, a hard coat film with 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.

  When 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 hard coat film is hazeed or the adhesion to the substrate and the hardness are insufficient. There is. 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 substituting the solvent with alcohol is added, and a necessary amount of the 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.
The content (W _PH ) of the surface-treated metal oxide fine particles in the hard coat film 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 (W _PH ) of the surface-treated metal oxide fine particles in the hard coat film is in the above range, a hard coat film with high hardness and less shrinkage, dense and free from cracks even with a thick film can be obtained. .

When the content (W _PH ) of the surface-treated metal oxide fine particles is small, the amount of resin increases, so that densification may be insufficient or the hardness of the hard coat film may be lowered. Also, the surface of the hard coating film is smoothed, and the adhesion (bonding) with the antireflection film provided on the hard coating film is insufficient, or the hardness of the finally obtained antireflection film is insufficient. There is a case.

Even if the content (W _PH ) of the surface-treated metal oxide fine particles in the hard coat film is too large, the wavy irregularities on the surface become too large and haze deteriorates due to external scattering, and the transparency is In some cases, the film density decreases, and the film densification decreases, resulting in insufficient scratch resistance and adhesion to the substrate.

Even if the content (W _PH ) of the surface-treated metal oxide fine particles in the hard coat film is too large, the wavy irregularities on the surface become too large and haze deteriorates due to external scattering, and the transparency is In some cases, the film density decreases, and the film densification decreases, resulting in insufficient scratch resistance and adhesion to the substrate.

Matrix component (M _H )
The matrix component (M _H ) constituting the hard coat film is composed of an organic resin for dispersion (A) and an organic resin for curing (B). In the hard coat film, these monomers or oligomers are polymerized and cured.

Both the dispersing organic resin (A) and the curing organic resin (B) are preferably ultraviolet curable resins, and the dispersing organic resin (A) and the curing organic resin (B) described later are used.
When these organic resins are ultraviolet curable resins, a hard coat film having excellent adhesion to a resin substrate such as PET or ATC and excellent hardness can be obtained.

Organic resin for dispersion (A) and organic resin for curing (B)
The dispersing organic resin (A) and the curable organic resin (B) are preferably ultraviolet curable resins.
The dispersing organic resin (A) is for stably dispersing the surface-treated metal oxide fine particles, and the curing organic resin (B) is for increasing the hardness of the coating film.
When UV curable resin is used as the organic resin for dispersion (A), the surface-treated metal oxide fine particles can be stably dispersed, and the organic resin dispersion of the surface-treated metal oxide fine particles can be stably dispersed at a high concentration. Can be obtained.

Furthermore, a hard coat film having higher hardness can be obtained by combining the curable organic resin (B).
The ultraviolet curable resin preferably has at least one functional group selected from a (meth) acrylate group, a urethane (meth) acrylate group, and an alkylene oxide-modified (meth) 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. Further, since they are bonded to each other as matrix forming components, a hard coat film having excellent hardness can be obtained.

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

As an ultraviolet curable resin with 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 such as acid,
I can get lost.

  Monofunctional alkylene oxide-modified (meth) acrylate groups having 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, Butoxy polyethylene glycol methacrylate, methoxy tripropylene glycol dimethacrylate, ethoxylated 2-ethylhexyl methacrylate, butoxy diethylene glycol methacrylate, butoxy diethylene glycol dimethacrylate, polyethylene glycol-modified stearyl methacrylate, phenoxy ethylene glycol methacrylate, phenoxy diethylene glycol methacrylate, phenoxyethyl methacrylate.

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

As 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 Monomers or oligomers having two (meth) acrylate groups such as tacryloyloxyethyl acid phosphate and 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 a (meth) acrylate group,
Tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, polytetramethylene glycol # 650 diacrylate, polyethylene polypropylene glycol diacrylate, dioxane Glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 400 dimethacrylate, 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.
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, glycerin 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.

  As the curable organic resin (B), it is preferable to use an ultraviolet curable resin having three or more functional groups. However, when the number of functional groups is three or more, it is bonded to a resin substrate such as PET or TAC. It is easy and has excellent adhesion to the substrate. Also, a hard coat film having excellent hardness can be obtained because they are bonded to each other as a matrix forming component.

As 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 (meth) acrylate group such as NK oligo UA-31F, UA-7100, UA-32P,
Having a trifunctional (caprolactone-modified) isocyanurate (meth) acrylate group such as tris- (2-acryloxyethyl) isocyanurate, caprolactone-modified tris- (2-acryloxyethyl) isocyanurate,
Trifunctional epoxy-modified (meth) acrylates such as ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, propoxylated trimethylolpropane triacrylate, excited dipentaerythritol polyacrylate, propoxylated dipentaerythritol polyacrylate Having a group,
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,
Tetrafunctional urethane (meth) acrylate oligomer resin,
Hexafunctional urethane (meth) acrylate oligomer resin,
Octafunctional urethane (meth) acrylate oligomer resin,
9-functional urethane (meth) acrylate oligomer resin,
10-functional urethane (meth) acrylate oligomer resin,
12-functional urethane (meth) acrylate oligomer resin,
A 15-functional urethane (meth) acrylate oligomer resin and the like can be mentioned. 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, a tetrafunctional or higher functional (meth) acrylate resin containing an epoxy group such as a cresol novolac type epoxy acrylate, a bisphenol A diglycidyl ether acrylic acid adduct, and the like are listed. Examples of such a resin 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 (meth) acrylate resins having 4 or more functional groups, (meth) acrylate resins having 6 to 12 functional groups can be suitably used because they have a high curling suppression effect and excellent hardness.

  In the present invention, when the surface-treated metal oxide fine particles have a surface treatment amount of 0.1 to 5 parts by weight, particularly 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. Surface treatment in which the surface-treated metal oxide fine particles are uniformly dispersed without agglomeration when preparing a coating liquid for forming a hard coat film. An organic resin (A) dispersion for dispersing metal oxide fine particles 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 matrix component is composed of the dispersing organic resin (A) and the curing organic resin (B). The content of the dispersing organic resin (A) in the matrix component as a solid content is 1 to 80 wt. %, More preferably in the range of 5 to 60% by weight.

If the content of the organic resin for dispersion (A) in the matrix component (M _H ) component is small, the smoothness of the hard coat film surface is lowered or the densification is insufficient, and haze, hardness, scratch resistance, Adhesiveness with a substrate may be insufficient.

When the content of the organic resin (A) for dispersion in the matrix component (M _H ) is large, the curing resin (B) is reduced on the other hand, the hard coat film is low in density, and the hardness is insufficient. There is.
The content (W _RH ) of the matrix component as a solid content in the hard coat film is preferably in the range of 10 to 50% by weight, more preferably 15 to 40% by weight.

The surface of the hard coat film (interface with the antireflection film described later) preferably has wavy irregularities.
The wavy unevenness is considered to be formed by the surface-treated metal oxide fine particles present in the surface layer of the hard coat film used by blending with the hard coat film. A tendency to depend is observed.

  In the present invention, since the surface-treated metal oxide fine particles (P) in the hard coat film are relatively large and the matrix component is small, the hard coat film is not flattened during the curing of the matrix, and forms a wavy surface and hardens. It depends on the type of matrix components to be combined.

  If there are few matrix components in the hard coat film, the surface irregularities will become too large, haze of the film may deteriorate due to external scattering, transparency may decrease, and the number of particles will increase. Insufficient densification of the coating film may result in insufficient adhesion to the substrate, scratch resistance, and hardness.

Even if there is too much matrix component (M _H ) in the hard coat film, the wavy irregularities on the surface become too large, haze may deteriorate due to external scattering, and transparency may be lowered. Adhesion with the material may be insufficient. In addition, since the film shrinks greatly, when it is thick (approximately 10 μm or more), curling may occur, cracks may be generated in some cases, and the hardness may be insufficient due to low density.

The ratio (W _RH ) / (W _PH ) between the content (W _RH ) of the matrix component in the hard coat film and the content (W _PH ) of the surface-treated metal oxide fine particles is 0.12 to 1.0, Is preferably in the range of 0.18 to 0.8.

When the ratio (W _RH ) / (W _PH ) is small, the content (W _PH ) as the solid content of the surface-treated metal oxide fine particles is high, and the wavy unevenness on the surface of the hard coat film may become too large. The haze of the film may be deteriorated due to external scattering or the transparency may be lowered, and further the film may be insufficiently densified, and the adhesion between the obtained hard coat film and the substrate is insufficient. In addition, the scratch resistance of the finally obtained substrate with an antireflection film may be insufficient.

Even if the ratio (W _RH ) / (W _PH ) is too large, the shrinkage of the film increases, and cracks may occur when the film is thick. In addition, the hard coat film is insufficiently densified, and thus the hardness may be insufficient.

The wavy unevenness is preferably in the range of 1 to 10 nm, more preferably 1 to 5 nm, as the surface roughness (Ra).
Since the surface-treated metal oxide fine particles (P) having the composition ratio as described above and the matrix component (M _H ) are combined, a hard coat film having wavy irregularities with a predetermined surface roughness is formed. With such a surface roughness, when an antireflection film is formed, the bonding area is increased, so that a coated substrate with high adhesion, excellent hardness, and scratch resistance can be obtained. Since the smoothness of the prevention film is not hindered, the adverse effect of the haze of the film due to external scattering is small, and the transparency is not lowered.

The surface roughness (Ra) can be measured with an atomic force microscope (AFM) (manufactured by Bruker, Inc .: Dimension 3100).
Next, the average thickness (T _H ) of the hard coat film is preferably in the range of 1 to 100 μm, more preferably 12 to 80 μm.

If the average film thickness (T _H ) is within this range, a hard coat film with high hardness and curling suppression can be formed on the resin substrate by using the coating liquid of the present invention.
The average thickness (T _H ) of the hard coat film was taken from a transmission electron micrograph (TEM) of the cross section of the hard coat film, and the bottom portion immediately below the top of the convex portion of the upper surface of the hard coat film in the surface irregularities. The distance between them (T convex) and the distance (T concave) between the deepest part of the concave part adjacent to the convex part and the bottom part directly below (T concave) are obtained and obtained as an average value. In addition, it is preferable that the number of unevenness | corrugations to measure is 10 sets or more at regular intervals.

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

  A coating liquid for forming a hard coat film, which will be described later, is applied on a TAC film substrate having a thickness of 14 cm × 25 cm × 40 μm (thickness) so that a hard coat film having a thickness of 12 μm can be formed. The height from the flat plate at the apex of the base material cut to a size of 10 cm × 10 cm, placed on a flat plate with the coating surface down, and curled (curved).

In the case where a conventional hard coat film is formed on a resin substrate, it is difficult to achieve curling characteristics and hardness as in the present invention.
Such a hard coat film is formed by applying a coating liquid for forming a hard coat film 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 are cured by an ordinary method such as ultraviolet irradiation. .

  In addition, the coating liquid for forming a hard coat film may be applied and dried, and the coating liquid for forming an antireflection film described later may be applied and dried, and then cured simultaneously by irradiation with ultraviolet rays. A substrate with an antireflection film excellent in properties and the like can be obtained.

After the coating liquid for forming a hard coat film having a predetermined configuration is applied, the shrinkage ratio (1) of the coating film when dried is 25% or less, and 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

For the formation of the hard coat film, a hard coat film forming coating solution is used.
The coating liquid for forming a hard coat film contains the surface-treated metal oxide fine particles (P) and a matrix forming component (M _H ).
The matrix forming component (M _H ) is a monomer or oligomer of an organic resin that constitutes the matrix component. The molecular weight (polystyrene equivalent molecular weight) of this monomer or oligomer is preferably 5,000 or less, 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 a part thereof is replaced with (A), the viscosity of the dispersion becomes high and it may not be possible to increase the concentration.Therefore, it becomes difficult to form a thick film or shrinkage during film formation. Occurrence, cracking, or curling of the coated substrate itself may result in failure to obtain a desired substrate with an antireflection film. 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.

  The coating liquid for forming a hard coat film may contain an organic dispersion medium as necessary. A conventionally well-known organic dispersion medium is mentioned as an organic dispersion medium. The organic dispersion medium in the hard coat film forming coating liquid is used when the organic dispersion medium of the surface-treated metal oxide fine particles is replaced with the dispersing organic resin (A) at the time of preparing the hard coat film forming coating liquid. In addition to the remaining organic dispersion medium and the like, in view of the handling properties of the coating liquid, it may be added for viscosity adjustment. 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 hard coat film forming coating solution 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.

  If the organic dispersion medium has a low boiling point, the coating film will dry quickly, resulting in insufficient densification or a non-uniform film thickness, resulting in insufficient hardness of the resulting hard coat film. There is.

When the organic dispersion medium has a high boiling point, the organic dispersion medium may remain, the film shrinks insufficiently, and the resulting hard coat film may have insufficient hardness.
A coating liquid contains a photoinitiator 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.
The concentration (C _PH ) of the surface-treated metal oxide fine particles in the coating liquid for forming a hard coat film as a solid content is preferably in the range of 45 to 85% by weight, more preferably 45 to 80% by weight.

When the solid content concentration (C _PH ) is within the above range, the shrinkage of the film is small, the generation of cracks is suppressed even when the film is thick, and a dense hard coat film can be formed, and predetermined irregularities are formed. Can do.

The concentration (C _RH ) as a solid content of the matrix forming component in the hard coat film forming coating solution is preferably in the range of 15 to 50% by weight, more preferably 15 to 40% by weight.
If the concentration (C _RH ) of the matrix-forming component in the coating liquid for forming a hard coat film is within this range, predetermined irregularities can be formed, the haze of the film is not deteriorated by external scattering, and the transparency is lowered. In addition, a hard coat film having high density and high hardness can be formed, and the hard coat film obtained is excellent in scratch resistance and adhesion to a substrate.
It 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. Within this range, it is possible to obtain an organic resin (A) dispersion for dispersing predetermined surface-treated metal oxide fine particles when preparing a coating solution for forming a hard coat film, and smoothness, denseness, haze, A hard coat film excellent in hardness, scratch resistance, adhesion and the like can be formed.

The curable organic resin (B) in the matrix-forming component is used so that the total concentration (C _RH ) with the organic resin for dispersion (A) is in the above range.
Concentration of Concentration (C _RH) and surface-treated metal oxide fine particles of the above-described matrix-forming component (C _PH) ratio of _{(C RH) / (C PH} ) is from 0.12 to 1.0, more 0.18 It is preferable to be in the range of ~ 0.8.

When the ratio (C _RH ) / (C _PH ) is within this range, desired surface irregularities can be formed on the hard coat film, and haze of the film is not deteriorated or transparency is not deteriorated by external scattering. In addition, a dense hard coat film excellent in scratch resistance and adhesion to the substrate can be formed.

The concentration of dispersing organic resin in the matrix-forming component (A) (C _RHA), the ratio of the surface-treated metal oxide fine particles _{(C PH) (C RHA)} / (C PH) is 0.17 to 1. 11, preferably 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 hard coat film has high density, and therefore has high hardness.

Such a coating liquid for forming a hard coat film is
(A) After 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) It is prepared by mixing a curing organic resin (B).

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 is generated in the obtained hard coat film, or the film is not sufficiently 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 as follows. The organic dispersion medium (B) is mixed as described later, and the concentration of the organic dispersion medium in the coating liquid for forming a hard coat film finally obtained is 40% by weight. To less than 35% by weight.

If a large amount of the organic dispersion medium remains, the total solid concentration (C _TH ) of the coating liquid for forming the hard coat film will be low, and the shrinkage from applying the coating liquid to drying will be large. When a thick film having a thickness of 10 μm or more is obtained, cracks may occur during shrinkage or curling properties may increase.

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 _RH ) 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 coating liquid for forming a hard coat film 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.

[Antireflection film]
It is formed antireflection film on the hard coat layer, the antireflection film is formed of a silica-based hollow particles (A) and the matrix component (M _L).
Silica-based hollow fine particles (A)
As silica-based hollow fine particles (A), silica-based fine particles having cavities therein disclosed in Japanese Patent Application Laid-Open Nos. 2001-233611 and 2003-192994 filed by the applicant of the present application have a low refractive index and a colloidal region. These fine particles are excellent in dispersibility and can be suitably used.

The average particle diameter (Dpa) of the silica-based hollow fine particles (A) used in the present invention is preferably in the range of 10 to 45 nm, more preferably 15 to 40 nm.
When the average particle diameter (DpA) of the silica-based hollow fine particles (A) is less than 10 nm, there are cavities inside, but the ratio of the cavities is small and the refractive index is not sufficiently low (refractive index is 1. 40) or more), the antireflection performance tends to be insufficient, and the silica-based hollow fine particles (A) are arranged in multiple layers due to the relationship with the film thickness (T _L ) described later. There are cases where the layers are regularly (aggregated) and the reflectivity becomes insufficient and the strength of the film becomes insufficient.

  When the average particle diameter (DpA) of the silica-based hollow fine particles (A) exceeds 45 nm, the adhesion to the lower hard coat film may be lowered and the hardness of the obtained base material with an antireflection film may be lowered. The reason for this is not necessarily clear, but when the average particle diameter (DpA) of the silica-based hollow fine particles (A) becomes too large, the underlying hard coat film has the aforementioned irregularities, and the irregularities This is considered to be because the size exceeds the size, and the adhesion with the antireflection film cannot be performed.

The refractive index of the silica-based hollow fine particles (A) is preferably in the range of 1.10 to 1.40, more preferably 1.10 to 1.35.
It is difficult to obtain silica-based hollow fine particles (A) having a refractive index of less than 1.10. When the refractive index exceeds 1.40, although it depends on the refractive index of the substrate or the lower layer film (hard coat film), antireflection is achieved. The performance may be insufficient, or the light contrast may be insufficient due to the high reflectance of the antireflection film.

The ratio (Dpa) / (T _L ) between the film thickness (T _L ) of the antireflection coating and the average particle diameter (Dpa) of the silica-based hollow fine particles (A) is 0.05 to 0.56, and It is preferable to be in the range of 1 to 0.45.
When the ratio (Dpa) / (T _L ) is less than 0.05, the refractive index of the particles does not become low as described above. Therefore, the refractive index of the antireflection film is high and the function as an antireflection film is not good. May be sufficient.
When the ratio (Dpa) / (T _L ) exceeds 0.56, the strength of the particles is lowered or the smoothness of the antireflection film surface is lowered, so that the desired film strength and film hardness cannot be obtained. There is.

Silica-based fine particles (B)
In the present invention, in addition to the silica-based hollow fine particles (A), it is preferable to include silica-based fine particles (B) having an average particle diameter (Dpb) in the range of 4 to 17 nm.
Examples of such silica-based fine particles (B) include silica sol, silica-based hollow fine particles, and chain silica-based fine particles in which these are connected in a chain.

  When the average particle diameter (Dpb) of the silica-based fine particles (B) is less than 4 nm, it is difficult to obtain the particles themselves, and even if they are obtained, they are aggregated during the surface treatment to form a uniform dispersion or coating solution. In some cases, the smoothness of the surface of the antireflection film is deteriorated, and sufficient film strength and film hardness may not be obtained because particles in the film are not densely packed.

  If the average particle diameter (Dpb) of the silica-based fine particles (B) exceeds 17 nm, the silica-based hollow fine particles (A) may not enter the particle gaps, and the silica-based hollow fine particles (A) may be randomly arranged or Aggregation may result in insufficient reflectivity and insufficient film strength.

The preferable average particle diameter (Dpb) of the silica-based fine particles (B) is in the range of 4 to 12 nm.
The refractive index of the silica-based fine particles (B) is 1.15 to 1.46, preferably 1.15 to 1.40.

  The ratio (Dpb) / (Dpa) of the average particle size (Dpb) of the silica-based fine particles (B) to the average particle size (Dpa) of the silica-based hollow fine particles (A) is 0.1 to 0.4, further 0 It is preferable to be in the range of .1 to 0.35.

  When (Dpb) / (Dpa) is less than 0.1, the silica-based hollow fine particles (A) may be agglomerated or the arrangement may be irregular, resulting in insufficient reflectivity and increased film strength. It may be insufficient.

  When (Dpb) / (Dpa) exceeds 0.4, the silica-based hollow fine particles (A) may be irregularly arranged or aggregated because they do not enter the particle gaps of the silica-based hollow fine particles (A). In some cases, the reflectivity becomes insufficient and the strength of the film becomes insufficient.

  In the present invention, the average particle diameter of the silica-based hollow fine particles (A) and the silica-based fine particles (B) is obtained by taking a transmission electron micrograph (TEM), measuring the particle diameter of 100 particles, did.

The silica-based hollow fine particles (A) and the silica-based fine particles (B) used in the present invention are preferably surface-treated with an organosilicon compound represented by the following formula (2).
R _n -SiX _4-n (2)
(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)

  Examples of the organosilicon compound represented by the formula (2) include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and diphenyl. Diethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoro Propyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriexylsilane, γ-glycidoxyethyltrimethoxysilane, γ -Guri Sidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- ( β-Glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltrioxysilane, γ- (meth) acrylooxyethyltrimethoxysilane , Γ- (meth) acrylooxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane Ethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, Butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3 -Ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-amino Propylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Emissions, .gamma.-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, and the like.

In the present invention, it is preferable that the surface treatment is performed with the organic silicon compound of n = 0 in the formula (2), and then the surface treatment is performed with any of the organic silicon compounds of n = 1, 2, or 3.
Examples of the organic silicon compound with n = 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

  The surface treatment of the silica-based hollow fine particles (A) and the silica-based fine particles (B) can employ a conventionally known method.For example, a predetermined amount of the organosilicon compound is added to an alcohol dispersion of these silica-based particles, Water is added thereto, and if necessary, hydrolysis is carried out by adding an acid or alkali as a catalyst for hydrolysis.

At this time, the weight ratio of the _{R n -SiX (4-n)} / 2 of the amount of the silica-based particles and an organic silicon compound of the organosilicon compound _{(R n -SiX (4-n} ) / 2 wt / silica-based particles Is preferably in the range of 0.01 to 0.5, more preferably 0.02 to 0.25.

  When the weight ratio is less than 0.01, the affinity for the matrix-forming component or the dispersion medium in the coating solution for forming an antireflection film, which will be described later, is low and the stability is insufficient, and the coating solution is uniformly dispersed. In some cases, silica-based particles may agglomerate, the strength and scratch resistance of the antireflection film may be reduced, and the haze value and reflectance may be increased.

Even if the weight ratio exceeds 0.5, the dispersibility is not further improved, the refractive index is increased, and the cost is reduced only by increasing the expensive organosilicon compound.
Subsequently, the organic solvent dispersion liquid of the silica-type particle | grains surface-treated by substituting with an organic solvent as needed can be obtained. As the organic solvent, it is preferable to use the same organic solvent as the coating liquid for forming an antireflection film described later.

The content of the silica-based hollow fine particles (A) in the antireflection film is preferably in the range of 5 to 80% by weight, more preferably 10 to 75% by weight.
When the content of silica-based hollow fine particles (A) in the antireflection film is less than 5% by weight, adhesion to the hard coat film, film strength, surface flatness, scratch resistance, scratch strength, etc. are insufficient. In addition, since the refractive index of the antireflection film cannot be further reduced, the effect of further improving the antireflection performance may be insufficient.

  If the content of silica-based hollow fine particles (A) in the antireflection film exceeds 80% by weight, there are too many particles, resulting in insufficient film strength, scratch resistance, scratch strength, etc., and antireflection The haze value of the film may increase.

  Even when the silica-based fine particles (B) are blended and used in the antireflection film, the total content of the silica-based hollow fine particles (A) and the silica-based fine particles (B) in the antireflection film is 5 to 80% by weight, Is preferably used in a range of 10 to 75% by weight.

When the silica-based fine particles (B) are used, the ratio of the silica-based fine particles (B) in the total silica-based particles is preferably 30% by weight, more preferably 20% by weight or less.
When the proportion of silica-based fine particles (B) exceeds 30% by weight, the number of silica-based fine particles (B) that do not enter the gap between the silica-based hollow fine particles (A) increases, and the silica-based hollow fine particles (A) are irregular. In some cases, the reflectance may be insufficient and the strength of the film may be insufficient.

When the silica-based fine particles (B) are contained in the above range, the silica-based hollow fine particles (B) are present in the interstices of the silica-based hollow fine particles (A) in the surface portion of the antireflection film, and the surface is flattened. Thus, an antireflection film excellent in scratch resistance and scratch strength can be obtained.
Further, when the silica-based fine particles (B) are surface-treated with the organosilicon compound, an antireflection film excellent in water resistance, water repellency, antifouling property and the like can be obtained.

Matrix component (M _L)
The matrix component of the antireflective film (M _L), the organic resin matrix component is used.
Examples of the organic resin-based matrix component include known thermosetting resins, thermoplastic resins, electron beam curable resins, and the like as coating resins.

  Examples of such resins include conventionally used thermoplastic resins such as polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, and silicone rubbers. , Urethane resin, melamine resin, butyral resin, phenolic resin, epoxy resin, unsaturated polyester resin, thermosetting resin such as thermosetting acrylic resin and ultraviolet curable acrylic resin, and ultraviolet curable acrylic resin. Further, it may be a copolymer or modified body of two or more of these resins.

In the present invention, preferably contains a matrix component (M _L) of at least a portion as the hard coating dispersion organic resin used in the film (A) and / or curing an organic resin (B).

  When such an organic resin for dispersion (A) and / or an organic resin for curing (B) is included, when an antireflection film is formed on the hard coat film, a hard coat film containing the same matrix component and A substrate with an antireflection film excellent in hardness, scratch resistance and the like can be obtained because of increased bonding with the antireflection film.

The content of the matrix component in the anti-reflective film (M _L) is 20 to 95% by weight solids, more preferably in the range of 25 to 90 wt%.
The strength of the antireflection film, adhesion to a substrate, scratch resistance, etc. becomes insufficient when the content of the matrix component in the anti-reflective film (M _L) is less than 20% by weight solids .

When the content of the matrix component in the anti-reflective film (M _L) is more than 95 wt% as solid content, due to the low amount of silica-based particles, not a uniform thickness, the surface lacking in flatness, In addition to insufficient scratch resistance, scratch strength and the like, the antireflective performance may be insufficient because the refractive index does not sufficiently decrease.

The film thickness (T _L ) of the antireflection film is preferably in the range of 80 to 200 nm, more preferably 90 to 150 nm.
If the film thickness (T _L ) of the antireflection film is thin, the strength and scratch resistance of the film may be insufficient.

Even if the film thickness (T _L ) of the antireflection film is too thick, cracks are likely to occur in the film, so that the film strength may be insufficient, and the antireflection performance deteriorates due to the film being too thick. There is a case.
When the film thickness (T _L ) of the antireflection film is within the above range, an antireflection film having a low reflectance (bottom reflectance, luminous reflectance) and excellent film hardness can be obtained.

In the present invention, the film thickness (T _L ) of the antireflection film is measured by taking a transmission electron micrograph (TEM) of the cross section of the hard coat film and the antireflection film, and calculating the average of the hard coat film from the total film thickness. Obtained by subtracting the film thickness (T _H ).

  According to the present invention, an antireflection film with an antireflection film having a pencil hardness of 5H or more, or even 6H or more can be formed even when the resin substrate is used. This is derived from the hard coat film provided in the lower layer, and an antireflection film having a pencil hardness as high as that of the hard coat film can be formed.

Next, a method for producing a substrate with an antireflection film according to the present invention will be described.
In the present invention, after (A) the coating liquid for forming a hard coat film is applied to the substrate surface and dried to form a hard coat film, (B) the coating liquid for forming an antireflection film is applied to the surface of the hard coat film. The antireflection film is formed by applying and drying.

The hard film forming coating solution is as described above, and the hard coat film to be formed is also as described above.
As described above, it is desirable that the hard coat film has curling characteristics, and that the shrinkage ratio after coating / drying and curing of the hard coat film forming coating liquid is within a specific range.
An antireflection film-forming coating solution is applied and dried on the hard coat film to form an antireflection film.

Antireflection film-forming coating solution The antireflection film-forming coating solution comprises the silica-based hollow fine particles (A), a matrix-forming component, and a solvent, and the silica-based hollow fine particles (A) have an average particle diameter (Dpa). In the range of 10 to 45 nm, the total solid content concentration is in the range of 1 to 10% by weight, the concentration of the silica-based hollow fine particles (A) is in the range of 0.25 to 9% by weight as the solid content, and matrix formation The component concentration is in the range of 0.75 to 9.5% by weight as solid content.

Matrix-forming component The matrix-forming component used in the coating solution for forming the antireflection film is preferably an organic resin-based matrix-forming component.
As the organic resin matrix-forming component, similar organic resin matrix component and used in the matrix component (M _L) is used.

  Furthermore, it is preferable that the matrix forming component contains the organic resin for dispersion (A) and / or the organic resin for curing (B) used in the coating liquid for forming the hard coat film. The matrix-forming component used in the coating solution for forming the transparent film only needs to contain either one of the organic resin for dispersion (A) and / or the organic resin for curing (B), or both. It may be.

  When such an organic resin for dispersion (A) and / or organic resin for curing (B) is contained, a coating liquid for forming a hard coat film is applied, dried and cured, and then a coating liquid for forming an antireflection film. Applying, drying, and then irradiating with ultraviolet rays, the bond between the hard coat film containing the same matrix component and the antireflection film is increased, or a substrate with an antireflection film excellent in hardness, scratch resistance, etc. is obtained. Can do.

  Further, the dispersing 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 curable resin having 3 or more functional groups. Monomers or oligomers are preferred.

  When the dispersion organic resin (A) is a monomer or oligomer of an ultraviolet curable resin having 1 to 2 functional groups, the antireflection film having a high stability and a smooth surface can be obtained. can get. Furthermore, when the coating liquid for forming the antireflection film contains the curing organic resin (B), the curing organic resin (B), the dispersing organic resin (A) and the curing organic resin (B) contained in the hard coat film are used. And an antireflection film integrated with the hard coat film can be obtained.

  Further, when the curable organic resin (B) is an ultraviolet curable resin monomer or oligomer having three or more functional groups, it easily binds to the curable organic resin (B) contained in the lower hard coat film, It is possible to obtain an antireflection film that is excellent in adhesion to the coating film and integrated with the hard coating film. Moreover, since it couple | bonds together as a matrix formation component, the antireflection film excellent in hardness can be obtained.

Polymerization initiator A polymerization initiator can be used in the coating solution for forming an antireflection film of the present invention, if necessary.
The polymerization initiator is not particularly limited as long as it can polymerize and cure the matrix-forming component, and can be appropriately selected depending on the resin, and conventionally known polymerization initiators can be used.
For example, in addition to polymerization initiators such as acylphosphine oxides, acetophenones, propiophenones, benzyls, benzoins, benzophenones, and thioxanthones, cationic photopolymerization initiators and the like can be mentioned.

  More specifically, the same bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethyl used in the hard coat film forming coating solution. -Pentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like can be used.

  The concentration of the polymerization initiator in the coating solution for forming the antireflection film varies depending on the type of the matrix forming component, but 0.1 to 20% by weight of the matrix forming component when the matrix forming component and the polymerization initiator are solids. Furthermore, it is preferable to be in the range of 0.5 to 10% by weight.

When the content of the polymerization initiator is less than 0.1% by weight of the matrix forming component as a solid content, the antireflection film may be insufficiently cured.
When the content of the polymerization initiator exceeds 20% by weight of the matrix forming component as a solid content, the stability of the coating solution may be insufficient.

The solvent used in the coating solution for forming the solvent antireflective film is particularly limited as long as it can dissolve or disperse the matrix forming component and the polymerization initiator and can uniformly disperse the silica-based hollow fine particles (A) and the silica-based fine particles (B). However, a conventionally known solvent can be used.

  Specifically, alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; glycols such as ethylene glycol and hexylene glycol; Ethers such as diethyl ether, ethylene glycol 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; Purpyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, vinegar Esters such as 3-methoxybutyl, 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 , Ketones such as isophorone, acetylacetone and acetoacetate; toluene, xylene and the like.

The total solid concentration of the coating solution for forming an antireflection film is preferably in the range of 1 to 10% by weight, more preferably 1.5 to 8% by weight.
When the total solid concentration of the coating solution for forming an antireflection film is less than 1% by weight, it is difficult to adjust the film thickness, and coating unevenness and drying unevenness may occur.

  When the total solid concentration of the coating solution for forming the antireflection film exceeds 10% by weight as the solid content, the film thickness of the antireflection film becomes too thick, and sufficient optical characteristics and antireflection performance cannot be obtained. Since it is difficult to control the surface smoothness, the surface smoothness may decrease, and the film strength and film hardness may decrease.

The concentration of the silica-based hollow fine particles (A) in the coating solution for forming the antireflection film is preferably in the range of 0.25 to 9% by weight, more preferably 0.35 to 8% by weight as the solid content.
When the concentration of the silica-based hollow fine particles (A) in the coating solution for forming the antireflection film is less than 0.25% by weight as a solid content, adhesion with the lower hard coat film, film strength, surface flatness, In addition to insufficient scratch resistance, scratch strength, etc., the antireflective performance may be insufficient because the refractive index of the antireflective film cannot be lowered.

  When the concentration of the silica-based hollow fine particles (A) in the coating solution for forming the antireflection film exceeds 9% by weight as a solid content, the film strength, scratch resistance, scratch strength, etc. of the antireflection film obtained when there are too many particles May become insufficient, and the anti-reflection film may have a high haze value.

Even when the silica-based fine particles (B) are used, the total solid concentration of the coating solution for forming an antireflection film is preferably within the above range.
Furthermore, the ratio of the silica-based fine particles (B) in the total silica-based particles is preferably 30% by weight, more preferably 20% by weight or less.

  When silica-based fine particles (B) are contained in such a range, the silica-based hollow fine particles (B) are present in the gaps between the silica-based hollow fine particles (A) in the surface portion of the obtained antireflection film, and the surface is Due to the flattening effect, an antireflection film excellent in scratch resistance and scratch strength can be obtained. In addition, since silica-based fine particles (B) having a refractive index lower than that of the matrix-forming component are used, the refractive index of the antireflection film can be lowered, and an antireflection film having more excellent antireflection performance can be obtained.

The concentration of the matrix forming component in the coating solution for forming an antireflection film as a solid content is preferably in the range of 0.75 to 9.5% by weight, more preferably 0.75 to 8% by weight.
When the concentration of the matrix-forming component in the coating solution for forming the antireflection film is less than 0.75% by weight as the solid content, there are cases where there are too many fine particles relative to the matrix, and the film strength of the antireflection film, scratch resistance, scratches, etc. In addition to insufficient strength and the like, the haze value of the antireflection film may increase.

  If the concentration of the matrix-forming component in the coating solution for forming the anti-reflective film exceeds 9.5% by weight as the solid content, the amount of fine particles may be too small with respect to the matrix, resulting in adhesion to the hard coat film, film strength, surface In addition to insufficient flatness, scratch resistance, scratch strength, etc., the antireflective performance may be insufficient because the refractive index of the antireflective film cannot be lowered.

  The base material with an antireflection film according to the present invention is manufactured by applying the above antireflection film-forming coating solution onto the hard coat film formed on the base material, drying, and then curing. be able to.

  Examples of the coating method of the coating solution for forming the antireflection film include known methods such as a dipping method, a spray method, a spinner method, a roll coating method, a bar coating method, a slit coater printing method, a gravure printing method, and a micro gravure printing method. It is done.

Then, although it is dried, there is no particular limitation as long as the solvent of the coating solution for forming the antireflection film can be substantially removed, and a conventionally known method can be employed.
Usually, it can be dried by heating at a temperature of about 60 to 120 ° C. for several minutes.

Although it hardens | cures after drying, as a hardening method, a hard-coat film | membrane and an antireflection film | membrane can be formed by making it harden | cure using ultraviolet irradiation, heat processing, or these together.
It is also possible to apply and dry the coating liquid for forming a hard coat film, apply and dry the coating liquid for forming an antireflection film, and then simultaneously cure by irradiating with ultraviolet rays.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of coating liquid for hard coat film formation (1)
Preparation of surface-treated metal oxide fine particles (1) Silica sol aqueous dispersion (manufactured by JGC Catalysts &Chemicals; Cataloid SI-50; average particle size 25 nm, SiO ₂ concentration 48.0 wt%, dispersion medium: water, particle refraction) (Rate 1.46) 960 g of cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added to 1000 g and stirred for 30 minutes, and then the ion exchange resin was separated.
Subsequently, 480 g of an anion exchange resin (Mitsubishi Chemical Corporation: SA-20A) was added and stirred for 30 minutes, and then the ion exchange resin was separated.

Next, after adding 480 g of cation exchange resin (Mitsubishi Chemical Corporation: SK-1BH) and stirring for 5 minutes, after agitation at 80 ° C. for 3 hours and cooling to room temperature, the ion exchange resin was separated and concentrated. A 48% by weight silica fine particle (1) aqueous dispersion was prepared.
Subsequently, 2000 g of the silica fine particle (1) aqueous dispersion was replaced with methanol by an ultrafiltration membrane method to prepare a silica fine particle (1) methanol dispersion having a concentration of 40% by weight as SiO ₂ .

Silica Fine Particles (1) 7.48 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO ₂ component 81.2%) was mixed with 100 g of methanol dispersion and ultrapure water was added. 3.1 g was added and stirred at 50 ° C. for 6 hours to obtain a surface-treated 25 nm silica sol dispersion (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).
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, and + part of the solvent was removed with 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.

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 are sufficiently mixed to form a coating solution for forming a hard coat film having a solid content concentration of 66.1 wt%. (1) was prepared.
The composition of the obtained coating liquid for forming a hard coat film (1) is shown in the table.

Preparation of silica -based hollow fine particle (A-1) dispersion Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-550, average particle diameter 5 nm, SiO ₂ concentration 20% by weight) 5.0 g and pure water 999.5 g While maintaining this temperature, 1575 g of a sodium silicate aqueous solution having a concentration of 3.0% by weight as SiO ₂ and 1575 g of a sodium aluminate aqueous solution having a concentration of 1.5% by weight as Al ₂ O ₃ were added. Thus, a SiO ₂ .Al ₂ O ₃ primary particle dispersion was obtained. At this time, the molar ratio MO _X / SiO ₂ (A) = 0.25, and the average particle size was 13 nm. Further, the pH of the reaction solution at this time was 12.0.

Next, 8370 g of a 3.0 wt% sodium silicate aqueous solution as SiO ₂ and 2790 g of a 1.5 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were added to disperse the composite oxide fine particles (secondary particles). A liquid was obtained.

At this time, the molar ratio MO _X / SiO ₂ (B) = 0.13, and the average particle size was 30 nm. Further, the pH of the reaction solution at this time was 12.0.
Next, 1,125 g of pure water was added to 500 g of the dispersion of the composite oxide fine particles that had been washed with an ultrafiltration membrane to a solid content concentration of 13 wt%, and concentrated hydrochloric acid (concentration 35.5 wt%) was further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Subsequently, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated and washed to obtain an aqueous dispersion of silica-based hollow fine particles having a solid content concentration of 20% by weight.

  Next, aqueous ammonia is added to the silica-based hollow fine particle dispersion to adjust the pH of the dispersion to 10.5, and after aging at 200 ° C. for 11 hours, the mixture is cooled to room temperature, and a cation exchange resin (Mitsubishi). Chemical Co., Ltd. (Diaion SK1B) 400 g was used for ion exchange for 3 hours, then anion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SA20A) 200 g was used for ion exchange for 3 hours. Using 200 g of ion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SK1B), it was washed by ion exchange at 80 ° C. for 3 hours to obtain silica-based fine particles (A An aqueous dispersion of 1-3-3) was obtained.

  Subsequently, a methanol dispersion of silica-based hollow fine particles (A-1) having a solid content concentration of 20% by weight, in which the solvent was replaced with methanol using an ultrafiltration membrane, was prepared. The average particle diameter and refractive index of the obtained silica-based hollow fine particles (A-1) were measured, and the results are shown in the table.

  Next, 3.7 g of a methacrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added to 100 g of a methanol dispersion of silica-based hollow fine particles (A-1) having a solid content concentration of 20% by weight, and 50 ° C. Then, a MIBK dispersion of silica-based hollow microparticles (A-1) having a solid content concentration of 20.5% by weight, in which the solvent was replaced with MIBK by a rotary evaporator, was prepared. The refractive index of the surface-treated silica-based hollow fine particles (A-1) was measured, and the results are shown in the table.

Preparation of coating solution (1) for forming an antireflection film Dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd.) was added to 8.05 g of a surface-treated silica-based hollow fine particle dispersion (A-1) having a solid content concentration of 20.5% by weight. Product: DPE-6A, solid content concentration 100% by weight) 1.07 g and 1,6-hexanediol diacrylate (manufactured by Sakai Kogyo Co., Ltd .: SR-238F, solid content concentration 100% by weight) 0.12 g and water repellency Reactive silicone oil for chemicals (Shin-Etsu Chemical Co., Ltd .; X-22-174DX, solid content concentration: 100% by weight) and silicone-modified polyurethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; Shikko UT-4314): (Solid content concentration 30 wt%) 0.37 g and photopolymerization initiator (BSF Japan Ltd.): Lucillin TPO, solid content concentration 100 wt%) 0.09 g and isopropyl Alcohol 64.65G, methyl isobutyl ketone 9.60 g, a mixture of isopropyl glycol 16.00 g, solid content concentration of 3.0% by weight of the antireflection film-forming coating liquid (1) was prepared.

Preparation of Substrate with Hard Coat Film (1) A coating liquid for forming a hard coat film (1) was prepared from a TAC film (Fuji Film Co., Ltd .: FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51). ) By a 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 hard coat film was produced by irradiating and curing 300 mJ / cm ² of ultraviolet rays. The film thickness of the hard coat film was 12 μm.
The obtained hard coat film-coated substrate (1) was evaluated as follows, and the results are shown in the table.

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 the hard coat film is measured.
2. The hard coat film forming coating solution is applied so that the film thickness after drying is about 10 μm, and then 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 hard coat film after curing is collected, and the density (specific gravity) of the hard coat film 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

The total light transmittance and haze were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.).
Further, the refractive index of the hard coat 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%.
Furthermore, the presence or absence of cracks was observed, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured by the following methods.

Measurement of surface roughness (Ra) The surface roughness (Ra) was measured at 10 μm × 10 μm with an atomic force microscope (AFM) (manufactured by Bruker, Inc .: Dimension 3100).

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.

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: ×

Preparation of base material with antireflection film (1) After preparing a base material with a hard coat film (1) in the same manner as described above, a coating solution for forming an antireflection film (1) was applied onto the hard coat film by the bar coater method ( After coating with bar # 4) and drying at 80 ° C. for 120 seconds, the substrate (1) with an antireflection film was prepared by irradiating with an ultraviolet ray of 400 mJ / cm ² under an N ₂ atmosphere and curing. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (1) are shown in the table.
The refractive index was measured with an ellipsometer (manufactured by ULVAC, EMS-1).

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

Next, 2940 g of a sodium silicate aqueous solution having a concentration of 3.0% by weight as SiO ₂ and 980 g of a sodium aluminate aqueous solution having a concentration of 1.5% by weight as Al ₂ O ₃ were added to disperse the composite oxide fine particles (secondary particles). A liquid was obtained.

At this time, the molar ratio MO _X / SiO ₂ (B) = 0.13, and the average particle size was 20 nm. Further, the pH of the reaction solution at this time was 12.0.
Next, 1,125 g of pure water was added to 500 g of the dispersion of the composite oxide fine particles that had been washed with an ultrafiltration membrane to a solid content concentration of 13 wt%, and concentrated hydrochloric acid (concentration 35.5 wt%) was further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Subsequently, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated and washed to obtain an aqueous dispersion of silica-based hollow fine particles having a solid content concentration of 20% by weight.

  Next, aqueous ammonia is added to the silica-based hollow fine particle dispersion to adjust the pH of the dispersion to 10.5, and after aging at 200 ° C. for 11 hours, the mixture is cooled to room temperature, and a cation exchange resin (Mitsubishi). Chemical Co., Ltd. (Diaion SK1B) 400 g was used for ion exchange for 3 hours, then anion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SA20A) 200 g was used for ion exchange for 3 hours. Using 200 g of ion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SK1B), it was washed by ion exchange at 80 ° C. for 3 hours to obtain silica-based fine particles (A An aqueous dispersion of -2) was obtained.

  Then, a methanol dispersion of silica-based hollow fine particles (A-2) having a solid content concentration of 20% by weight, in which the solvent was replaced with methanol using an ultrafiltration membrane, was prepared. The average particle diameter and refractive index of the obtained silica-based hollow fine particles (A-2) were measured, and the results are shown in the table. 3.7 g of methacrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) is added to 100 g of a methanol dispersion of silica-based hollow fine particles (A-2) having a solid content concentration of 20% by weight and heated at 50 ° C. After the treatment, a MIBK dispersion of silica-based hollow microparticles (A-2) having a solid content concentration of 20.5 wt%, in which the solvent was replaced with MIBK by a rotary evaporator, was prepared. The refractive index of the surface-treated silica-based hollow fine particles (A-2) was measured, and the results are shown in the table.

Preparation of antireflection film-forming coating liquid (2) In Example 1, the solid content was the same except that the surface-treated silica-based hollow fine particle dispersion (A-2) having a solid content concentration of 20.5% by weight was used. A coating solution (2) for forming an antireflection film having a concentration of 3.0% by weight was prepared.

Preparation of base material with antireflection film (2) In Example 1, after the hard coat film was formed, reflection was conducted in the same manner except that the antireflection film-forming coating liquid (2) having a solid content concentration of 3.0% by weight was used. A substrate (2) with a protective film was produced. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (2) are shown in the table.

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

Subsequently, 1607 g of a sodium silicate aqueous solution having a concentration of 1.5% by weight as SiO ₂ and 535 g of a sodium aluminate aqueous solution having a concentration of 0.5% by weight as Al ₂ O ₃ were added to disperse the composite oxide fine particles (secondary particles). A liquid was obtained.

At this time, the molar ratio MO _X / SiO ₂ (B) = 0.07, and the average particle size was 40 nm. Further, the pH of the reaction solution at this time was 12.0.
Next, 1,125 g of pure water was added to 500 g of the dispersion of the composite oxide fine particles that had been washed with an ultrafiltration membrane to a solid content concentration of 13 wt%, and concentrated hydrochloric acid (concentration 35.5 wt%) was further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Subsequently, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated and washed to obtain an aqueous dispersion of silica-based hollow fine particles having a solid content concentration of 20% by weight.

  Next, aqueous ammonia is added to the silica-based hollow fine particle dispersion to adjust the pH of the dispersion to 10.5, and after aging at 200 ° C. for 11 hours, the mixture is cooled to room temperature, and a cation exchange resin (Mitsubishi). Chemical Co., Ltd. (Diaion SK1B) 400 g was used for ion exchange for 3 hours, then anion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SA20A) 200 g was used for ion exchange for 3 hours. Using 200 g of ion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SK1B), it was washed by ion exchange at 80 ° C. for 3 hours to obtain silica-based fine particles (A -3) was obtained.

  A methanol dispersion of silica-based hollow fine particles (A-3) having a solid content concentration of 20% by weight, in which the solvent was replaced with methanol using an ultrafiltration membrane, was prepared. The average particle diameter and refractive index of the obtained silica-based hollow fine particles (A-3) were measured, and the results are shown in the table.

  3.7 g of a methacrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) is added to 100 g of a methanol dispersion of silica-based hollow fine particles (A-3) having a solid content concentration of 20% by weight and heated at 50 ° C. After the treatment, a MIBK dispersion of silica-based hollow fine particles (A-2) having a solid content concentration of 20.5% by weight, in which the solvent was replaced with MIBK by a rotary evaporator, was prepared. The refractive index of the surface-treated silica-based hollow fine particles (A-3) was measured, and the results are shown in the table.

Preparation of antireflection film-forming coating liquid (3) In Example 1, the solid content was the same except that the surface-treated silica-based hollow fine particle dispersion (A-3) having a solid content concentration of 20.5% by weight was used. A coating solution (3) for forming an antireflection film having a concentration of 3.0% by weight was prepared.

Preparation of base material with antireflection film (3) In Example 1, after the formation of the hard coat film, reflection was conducted in the same manner except that the antireflection film-forming coating solution (3) having a solid content concentration of 3.0% by weight was used. A substrate (3) with a protective film was produced. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of the substrate with antireflection film (3) are shown in the table.
[Example 4]

Preparation of dispersion of silica-based fine particles (B-1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-550, average particle diameter 5 nm, SiO ₂ concentration 20 wt%) 5.0 g and a mixture of 999.5 g of pure water While maintaining the temperature at 80 ° C., 321 g of a sodium silicate aqueous solution having a concentration of 3.0% by weight as SiO ₂ and 321 g of a sodium aluminate aqueous solution having a concentration of 1.5% by weight as Al ₂ O ₃ were added. Thus, a SiO ₂ .Al ₂ O ₃ primary particle dispersion was obtained. At this time, the molar ratio MO _X / SiO ₂ (A) = 0.23, and the average particle size was 7 nm. Further, the pH of the reaction solution at this time was 12.0.

Then, the dispersion of the concentration of 3.0 wt% concentration 1.5% by weight of additives to the complex oxide fine particles of an aqueous sodium aluminate solution 410g of the sodium silicate aqueous solution 1231g and for Al ₂ O ₃ SiO ₂ (secondary particles) A liquid was obtained.

At this time, the molar ratio MO _X / SiO ₂ (B) = 0.13, and the average particle size was 14 nm. Further, the pH of the reaction solution at this time was 12.0.
1,125 g of pure water was added to 500 g of a dispersion of fine composite oxide particles having a solid content of 13% by weight washed with an ultrafiltration membrane, and concentrated hydrochloric acid (concentration 35.5% by weight) was added dropwise to adjust the pH to 1. 0.0, and dealumination was performed. Subsequently, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated and washed to obtain an aqueous dispersion of silica-based hollow fine particles having a solid content concentration of 20% by weight.

Next, aqueous ammonia is added to the silica-based hollow fine particle dispersion to adjust the pH of the dispersion to 10.5, and after aging at 200 ° C. for 11 hours, the mixture is cooled to room temperature, and a cation exchange resin (Mitsubishi). Chemical Co., Ltd. (Diaion SK1B) 400 g was used for ion exchange for 3 hours, then anion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SA20A) 200 g was used for ion exchange for 3 hours. Using 200 g of ion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SK1B), it was washed by ion exchange at 80 ° C. for 3 hours to obtain silica-based fine particles having a solid content concentration of 20 wt% and a solid content concentration of 20 wt% (B An aqueous dispersion of -1) was obtained.
Next, a methanol dispersion of silica-based hollow fine particles (B-1) having a solid content concentration of 20% by weight, in which the solvent was replaced with methanol using an ultrafiltration membrane, was prepared. The average particle diameter and refractive index of the obtained silica-based hollow fine particles (B-1) were measured, and the results are shown in the table.

  3.7 g of a methacrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) is added to 100 g of a methanol dispersion of silica-based hollow fine particles (B-1) having a solid content of 20% by weight, and heated at 50 ° C. After the treatment, a MIBK dispersion of silica-based hollow fine particles (B-1) having a solid content concentration of 20.5% by weight, in which the solvent was replaced with MIBK by a rotary evaporator, was prepared. The refractive index of the surface-treated silica-based hollow fine particles (B-1) was measured, and the results are shown in the table.

Preparation of antireflection film-forming coating liquid (4 ) To 7.90 g of a surface-treated silica-based hollow fine particle dispersion (A-3) having a solid concentration of 20.5 and 20% by weight prepared in the same manner as in Example 3, Solid content concentration 20.5 Silica fine particles (B-1) methanol dispersion 0.15 g of 20% by weight, dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: DPE-6A, solid content concentration 100% by weight) 1.07 g, 1,6-hexanediol diacrylate (manufactured by Sakai Kogyo Co., Ltd .: SR-238F, solid concentration 100% by weight) and reactive silicone oil for water repellent material (Shin-Etsu Chemical Co., Ltd.) X-22-174DX, solid content concentration 100% by weight) 0.05 g and silicone-modified polyurethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; purple light UT-4314: solid content concentration 30% by weight) 0.37 g and light 0.09 g of a polymerization initiator (B-S-Japan Co., Ltd.): lucillin TPO, solid content concentration 100% by weight), 64.65 g of isopropyl alcohol, 9.60 g of methyl isobutyl ketone, and 16.00 g of isopropyl glycol are mixed. Thus, an antireflection film-forming coating solution (4) having a solid content concentration of 3.0% by weight was prepared.

Preparation of substrate with antireflection film (4) In Example 1, after the formation of the hard coat film, reflection was performed in the same manner except that the antireflection film-forming coating solution (4) having a solid content concentration of 3.0% by weight was used. A substrate (4) with a protective film was produced. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of the substrate with antireflection film (4) are shown in the table.

[Example 5]
Preparation of silica -based fine particle (B-2) dispersion Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-30, SiO ₂ concentration 40.5 wt%, average particle diameter 23 nm, refractive index 1.46) After adding 960 g of ion exchange resin (Mitsubishi Chemical Corporation: SK-1BH) and stirring for 30 minutes, the ion exchange resin was separated.

After adding 480 g of an anion exchange resin (Mitsubishi Chemical Corporation: SA-20A) and stirring for 30 minutes, the ion exchange resin was separated.
After adding 480 g of cation exchange resin (Mitsubishi Chemical Corporation: SK-1BH) and stirring for 5 minutes, after agitation at 80 ° C. for 3 hours and cooling to room temperature, the ion exchange resin was separated and the concentration was 48 weight. % Silica fine particle (1) aqueous dispersion was prepared.

Subsequently, 2000 g of the silica fine particle (1) aqueous dispersion was replaced with methanol by an ultrafiltration membrane method to prepare a silica-based fine particle (B-2) methanol dispersion having a concentration of 40% by weight as SiO ₂ .

3.7 g of methacrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) is added to 100 g of a methanol dispersion of silica-based fine particles (B-2) having a solid content concentration of 20% by weight, and heat-treated at 50 ° C. Then, a MIBK dispersion of silica-based hollow fine particles (B-2) having a solid content concentration of 20.5% by weight, in which the solvent was replaced with MIBK by a rotary evaporator, was prepared.
The refractive index of the surface-treated silica-based fine particles (B-2) was measured, and the results are shown in the table.

Preparation of antireflection film-forming coating solution (5) In Example 4, instead of a methanol dispersion of silica-based fine particles (B-1) with a solid content concentration of 20.5 wt%, a solid content concentration of 20.5 wt% An antireflection film-forming coating solution (5) having a solid content concentration of 3.0% by weight was prepared in the same manner except that the MIBK dispersion of silica-based hollow fine particles (B-2) was used.

Preparation of substrate with antireflection film (5) In Example 1, after the hard coat film was formed, the reflection was conducted in the same manner except that the antireflection film-forming coating solution (5) having a solid concentration of 3.0% by weight was used. A substrate with a protective film (5) was produced. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (5) are shown in the table.

[Example 6]
Preparation of antireflection film-forming coating solution (6 ) Dispersed in 8.05 g of a surface-treated silica-based hollow fine particle dispersion (A-1) having a solid content concentration of 20.5% by weight prepared in the same manner as in Example 1. As organic resin (A), dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 219) 0.12 g and curing organic resin ( B) 1.07 g of 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%) and water repellency Reactive silicon oil for materials (Shin-Etsu Chemical Co., Ltd .; X-22-174DX, solid content concentration: 100% by weight) and silicone-modified polyurethane acrylate (Nippon Synthetic Chemical Industry Co., Ltd.) ); Purple light UT-4314: solid content concentration 30% by weight) 0.37 g and photopolymerization initiator (BSF Japan Ltd.): Lucirin TPO) 0.09 g, isopropyl alcohol 64.65 g, methyl 9.60 g of isobutyl ketone and 16.00 g of isopropyl glycol were mixed to prepare a coating solution (6) for forming an antireflection film having a solid content concentration of 3.0% by weight.

Preparation of substrate with antireflection film (6) In Example 1, after the hard coat film was formed, the reflection was conducted in the same manner except that the antireflection film-forming coating solution (6) having a solid content concentration of 3.0% by weight was used. A substrate (6) with a protective film was produced. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (6) are shown in the table.

[Example 7]
Preparation of substrate with hard coat film (7) A hard coat film-forming coating solution (1) prepared in the same manner as in Example 1 was prepared using a TAC film (Fuji Film Co., Ltd .: FT-PB40UL-M, thickness). : 40 μm, refractive index: 1.51) by bar coater method # 16 and dried at 80 ° C. for 120 seconds. The film thickness of the hard coat film was 12 μm. The physical properties and the like of the hard coat film are indicated as the same as in Example 1.

Preparation of base material with antireflection film (7) Subsequently, reflection was carried out in the same manner except that the coating liquid (1) for forming an antireflection film having a solid content concentration of 3.0% by weight prepared in the same manner as in Example 1 was used. A base material with a protective film (7) was produced. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, refractive index of the coating, adhesion, pencil hardness, and scratch resistance of this substrate with antireflection film (7) are shown in the table.

[Example 8]
Preparation of Hard Coat Film Forming Coating Liquid (8 ) 80.38 g of the surface-treated metal oxide fine particle dispersion organic resin (A) dispersion liquid (1) prepared in the same manner as in Example 1, and a curing organic resin ( B) urethane acrylate (manufactured by 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%) 8.88 g, acrylic silicone Leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g, photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.53 g, 0.21 g of PGME and 9.0 g of acetone are sufficiently added. By mixing, a coating liquid (8) for forming a hard coat film having a solid content concentration of 70.6% by weight was prepared.
The composition of the obtained coating liquid for forming a hard coat film (8) is shown in the table.

Preparation of base material with hard coat film (8) In Example 1, the base material with hard coat film (8) was similarly applied except that the coating liquid for hard coat film formation (8) was applied by the bar coater method # 16. Manufactured. The film thickness of the transparent coating was 12 μm.

  For the obtained substrate (8) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (8) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film having a solid content of 3.0% by weight was used. A base material (8) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of this substrate with antireflection film (8) are shown in the table.

[Example 9]
Preparation of organic resin (A) dispersion (9) for dispersion of surface-treated metal oxide fine particles Silica sol dispersion (manufactured by JGC Catalysts &Chemicals; Cataloid SI-30; average particle size 12 nm, SiO ₂ concentration 40.5 wt. %, Dispersion medium: isopropanol, particle refractive index 1.46) to 7.48 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO ₂ component 81.2%) ), 3.1 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 6 hours to obtain a surface-treated 12 nm silica sol dispersion (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 ( 9) was prepared.

Preparation of Hard Coat Film Forming Coating Liquid (9) Surface Treatment Metal Oxide Fine Particle Dispersion Organic Resin (A) Dispersion Liquid (9) 79.99g and Curing Organic Resin (B) Urethane Acrylate (Shin Nakamura Chemical) Product: NK Oligo UA-33H, functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000, solid content concentration 100%) and 9.90 g, acrylic silicone leveling agent (Enomoto Kasei Co., Ltd.) 1.00 g of Disparon NSH-8430HF), 0.59 g of a photopolymerization initiator (manufactured by Ciba Japan Co., Ltd .: Irgacure 184), 0.51 g of PGME, and 8.00 g of acetone are mixed thoroughly to obtain a solid content concentration of 78.7. A coating solution (9) for forming a hard coat film with a weight% was prepared.
The composition of the obtained coating liquid for forming a hard coat film (9) is shown in the table.

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

  For the obtained substrate (9) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (9) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film having a solid content of 3.0% by weight was used. A base material (9) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (9) are shown in the table.

[Example 10]
Preparation of coating liquid for forming hard coat film (10) Surface-treated metal oxide particles (1) 2,500 g of dispersion liquid as dimethylol-tricyclodecane diacrylate (Kyoeisha Chemical Co., Ltd .; light acrylate) as organic resin for dispersion (A) 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 having a solid content concentration of 72.1% by weight An organic resin (A) dispersion (10) for dispersing fine particles was prepared.

Next, 66.61 g of the organic resin (A) dispersion liquid (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%) 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 hard coat film having a solid content concentration of 66.1% by weight (10 ) Was prepared.
The composition of the obtained coating liquid for forming a hard coat film (10) is shown in the table.

Preparation of substrate with hard coat film (10) The substrate with hard coat film (10) was prepared in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (10) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film was 12 μm.
For the obtained substrate (4) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflective coating (10) Antireflective coating in the same manner as in Example 1 except that the coating solution for forming an antireflective coating (1) having a solid concentration of 3.0% by weight was used. A base material (10) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (10) are shown in the table.

[Example 11]
Preparation of coating liquid for hard coat film formation (11) 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) 153.0 g was added, a part of the solvent was removed by a rotary evaporator, and the solid content concentration was 72.3% by weight. An organic resin (A) dispersion (10) for dispersing fine particles was prepared.

Surface treatment metal oxide fine particle dispersion organic resin (A) 81.94 g dispersion (10) 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 hard coat film having a solid concentration of 66.1% by weight (11 ) Was prepared.
The composition of the obtained coating liquid for forming a hard coat film (11) is shown in the table.

Preparation of base material with hard coat film (11) In Example 1, the base material with hard coat film (11) was the same as in Example 1, except that the coating liquid for forming a hard coat film (11) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film 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 (11) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate (11) with antireflection film Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film having a solid content of 3.0% by weight was used. A base material (11) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (11) are shown in the table.

[Example 12]
Preparation of coating liquid for forming hard coat film (12) 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) 85.8 g was added, and a part of the solvent was removed with a rotary evaporator to obtain a solid-treated metal oxide having a solid content concentration of 69.0% by weight. An organic resin (A) dispersion (6) for dispersing fine particles was prepared.

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 sufficiently mixed to form a hard coat film having a solid concentration of 66.1% by weight. Liquid (12) was prepared.
The composition of the obtained coating liquid for forming a hard coat film (12) is shown in the table.

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

  For the obtained substrate (12) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (12) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film having a solid concentration of 3.0% by weight was used. A base material (12) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of the substrate with antireflection film (12) are shown in the table.

[Example 13]
Preparation of coating liquid for forming hard coat film (13) Surface-treated metal oxide particles (1) 2,500 ml of dispersion liquid as dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as a dispersion organic resin (A); 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 by a rotary evaporator to obtain a surface-treated metal oxide having a solid content concentration of 80.1% by weight. An organic resin (A) dispersion (7) for dispersing fine particles was prepared.

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 are thoroughly mixed to form a coating solution for forming a hard coat film having a solid content concentration of 66.1% by weight. (13) was prepared.
The composition of the obtained coating liquid for forming a hard coat film (13) is shown in the table.

Preparation of base material with hard coat film (13) In Example 1, the base material with hard coat film (13) was prepared in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (13) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film was 12 μm.

  For the obtained substrate (13) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (13) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film having a solid content of 3.0% by weight was used. A base material (13) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, refractive index of the coating, adhesion, pencil hardness, and scratch resistance of this substrate with antireflection film (13) are shown in the table.

[Example 14]
Preparation of coating liquid for forming hard coat film (14) Surface treated metal oxide particles (1) 1,6-hexadiol dimethacrylate (manufactured by Sakai Kogyo Co., Ltd.) 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 part of the solvent was removed with 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 (14) was prepared.

Next, 75.31 g of the dispersion-treated organic resin (A) dispersion (14) 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 are thoroughly mixed to form a coating solution for forming a hard coat film having a solid content concentration of 66.1% by weight. (14) was prepared.
The composition of the obtained coating liquid for forming a hard coat film (14) is shown in the table.

Preparation of base material with hard coat film (14) In Example 1, the base material with hard coat film (14) was similarly applied except that the coating liquid for forming a hard coat film (14) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film was 12 μm.

  For the obtained substrate (14) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (14) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film with a solid content concentration of 3.0% by weight was used. A base material (14) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (14) are shown in the table.

[Example 15]
Preparation of surface-treated metal oxide fine particles (15) 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 (15) having a solid content concentration of 40.5% by weight.

Preparation of coating liquid for forming hard coat film (15) Surface-treated metal oxide particles (15) Dispersed in 2500 g of organic resin (A) for dimethylol-tricyclodecane diacrylate (Kyoeisha Chemical Co., Ltd .; light acrylate) 202.5 g of DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) was added, and a part of the solvent was removed by a rotary evaporator to obtain a solid content concentration of 76.0% by weight. An organic resin (A) dispersion (15) for dispersing the surface-treated metal oxide fine particles was prepared.

Subsequently, 75.31 g of the dispersion-treated organic resin (A) dispersion (15) 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%) 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 hard coat film having a solid content concentration of 63.9% by weight. (15) was prepared.
The composition of the obtained coating liquid for forming a hard coat film (15) is shown in the table.

Preparation of substrate with hard coat film (15) In Example 1, the substrate with hard coat film (15) was prepared in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (15) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film was 12 μm.

  For the obtained substrate (14) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (15) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film with a solid content of 3.0% by weight was used. A base material (15) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (15) are shown in the table.

[Example 16]
Preparation of surface-treated metal oxide fine particles (16) 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) 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 (16) having a solid content concentration of 40.5% by weight.

Preparation of Hard Coat Film Forming Coating Liquid (16) Surface Treatment Metal Oxide Particles (16) Dispersion 2500g as Dispersion Organic Resin (A) Dimethylol-Tricyclodecane Diacrylate (Kyoeisha Chemical Co., Ltd .; Light Acrylate) 202.5 g of DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) was added, and a part of the solvent was removed by a rotary evaporator to obtain a solid content concentration of 76.0% by weight. An organic resin (A) dispersion (16) for dispersing the surface-treated metal oxide fine particles was prepared. Step (a)

Next, 75.31 g of the organic resin (A) dispersion liquid (16) 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 thoroughly mixed to form a coating solution for forming a hard coat film having a solid content concentration of 70.6% by weight. (16) was prepared.
The composition of the obtained coating liquid for forming a hard coat film (16) is shown in the table.

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

  For the obtained substrate (16) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (16) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film having a solid content concentration of 3.0% by weight was used. A base material (16) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (16) are shown in the table.

[Example 17]
Preparation of surface-treated metal oxide fine particles (17) 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 (17) having a solid content concentration of 40.5% by weight.

Preparation of coating liquid for forming hard coat film (17) Surface-treated metal oxide particles (4) Dispersed in 2500 g of dimethylol-tricyclodecane diacrylate (Kyoeisha Chemical Co., Ltd.) as dispersion organic resin (A); Light acrylate 202.5 g of DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) was added, and a part of the solvent was removed by a rotary evaporator to obtain a solid content concentration of 76.0% by weight. An organic resin (A) dispersion (17) for dispersing the surface-treated metal oxide fine particles was prepared. Step (a)

Surface treatment metal oxide fine particle dispersion organic resin (A) 75.31 g of dispersion liquid (17) and curing organic resin (B) as 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 (manufactured by 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 hard coat film having a solid content concentration of 66.1% by weight (17 ) Was prepared.
The composition of the obtained coating liquid for forming a hard coat film (17) is shown in the table.

Preparation of substrate with hard coat film (17) The substrate with hard coat film (17) was prepared in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (17) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film was 12 μm.

  For the obtained substrate (17) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (17) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film having a solid content concentration of 3.0% by weight was used. A base material (17) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (17) are shown in the table.

[Example 18]
Preparation of surface-treated metal oxide fine particles (18 ) 33.4 kg of 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, and was aged by maintaining at room temperature for 5 hours to prepare a silica hydrogel.

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.
Silica hydrogel was dispersed in pure water to prepare a dispersion having a SiO ₂ concentration of 3% by weight, and stirred using a powerful stirrer until a fluid slurry 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 (18) 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 (18) was 48 nm, the average short diameter (D _S ) was 16 nm, and the spherical coefficient was 0.33.
600 g of silica sol (18) was mixed with 5,955 g of pure water and 63.3 g of an aqueous sodium silicate solution having a SiO ₂ concentration of 24 wt% (SiO ₂ / Na ₂ O molar ratio: 3.1), 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 (18) dispersion composed of non-spherical silica having a solid content concentration of 30% by weight.

  Pure water is added to 400 g of the dispersion of metal oxide fine particles (18) having a concentration of 30% by weight to obtain a solid concentration of 20% by weight, and 240 g of a 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.

  7.48 g of a methacrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, γ-methacryloyloxypropyltrimethoxysilane) was added to 100 g of this methanol dispersion, and the mixture was heated and stirred at 50 ° C. for 6 hours to form a solid. A metal oxide fine particle (18) 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 (18) 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 Hard Coat Film Forming Coating Liquid (18) Surface-treated metal oxide fine particles (18) with a solid content concentration of 40.5% by weight (18) Dispersed as an organic resin (A) for dimethylol-tricyclodecane diacrylate (A) 202.5 g of Kyoeisha Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, functional group number: 2, molecular weight: 219, solid content concentration 100%) is added, and a part of the solvent is removed with a rotary evaporator. Thus, an organic resin (A) dispersion liquid (18) for dispersing surface-treated metal oxide fine particles having a solid content concentration of 76.0% by weight was prepared. Step (a)

75.31 g of organic resin (A) dispersion liquid (18) for dispersion of surface-treated metal oxide fine particles, and urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, functional as a curing organic resin (B) 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 (manufactured by Ciba Japan Co., Ltd .: Irgacure 184) 0.50 g, 2.37 g of PGE and 12.50 g of acetone were sufficiently mixed to form a coating solution for forming a hard coat film having a solid content concentration of 66.1 wt% (18 ) Was prepared.
The composition of the resulting coating liquid for forming a hard coat film (18) is shown in the table.

Preparation of substrate with hard coat film (18) In Example 1, the substrate with hard coat film (18) was prepared in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (18) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film was 12 μm.

  For the obtained substrate (18) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (18) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film having a solid content of 3.0% by weight was prepared. A base material (18) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (18) are shown in the table.

[Example 19]
Preparation of substrate with hard coat film (19) The substrate with hard coat film (19) was prepared in the same manner as in Example 1, except that the coating liquid for hard coat film formation (1) was applied by the bar coater method # 20. Manufactured. The film thickness of the hard coat film 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.
With respect to the obtained base material with a hard coat film (19), 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (19) Antireflection film was prepared in the same manner as in Example 1 except that coating solution (1) for forming an antireflection film having a solid content of 3.0% by weight was prepared. A base material (19) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of this substrate with antireflection film (19) are shown in the table.

[Example 20]
Preparation of base material with hard coat film (20) In Example 1, the base material with hard coat film (20) was prepared in the same manner as in Example 1, except that the coating liquid for hard coat film formation (1) was applied by the bar coater method # 40. Manufactured. The film thickness of the hard coat film was 30 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 (20) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (20) Antireflection film was prepared in the same manner as in Example 1 except that the coating solution for forming an antireflection film (1) having a solid content of 3.0% by weight was used. A base material (20) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of this substrate with antireflection film (20) are shown in the table.

[Comparative Example 1]
Preparation of silica-based hollow fine particle (RA-1) dispersion
100 g of silica / alumina sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: USBB-120, average particle size 25 nm, SiO ₂ · Al ₂ O ₃ concentration 20 wt%, solid content Al ₂ O ₃ content 27 wt%) 3900 g was added and heated to 98 ° C. While maintaining this temperature, 1750 g of a sodium silicate aqueous solution having a concentration of 1.5% by weight as SiO ₂ and an aqueous solution of sodium aluminate having a concentration of 0.5% by weight as Al ₂ O ₃ 1750 g was added to obtain a SiO ₂ .Al ₂ O ₃ primary particle dispersion (average particle size 35 nm). The MO _X / SiO ₂ molar ratio (A) at this time was 0.2. Further, the pH of the reaction solution at this time was 12.0.

Next, 6,300 g of a 1.5 wt% sodium silicate aqueous solution as SiO ₂ and 2,100 g of a 0.5 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were added to form composite oxide fine particles (2). A dispersion of (secondary particles) (average particle size 50 nm) was obtained.

The MO _X / SiO ₂ molar ratio (B) at this time was 0.07. Further, the pH of the reaction solution at this time was 12.0.
Next, 1,125 g of pure water was added to 500 g of the dispersion of composite oxide fine particles (2) having a solid concentration of 13 wt% by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (concentration 35.5 wt%). Was dropped to pH 1.0, and dealumination was performed. Subsequently, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated and washed to obtain an aqueous dispersion of silica-based hollow fine particles having a solid content concentration of 20% by weight.

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

  Next, a silica-based hollow fine particle (RA-1) methanol dispersion having a solid content concentration of 20% by weight was prepared by replacing the solvent with methanol using an ultrafiltration membrane. The average particle diameter and refractive index of the obtained silica-based hollow fine particles (RA-1) were measured, and the results are shown in the table.

  Add 3 g of acrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103) to 100 g of methanol dispersion of silica-based hollow fine particles (RA-1) with a solid content of 20% by weight, and heat-treat at 50 ° C. Then, a methanol dispersion of silica-based hollow fine particles (RA-1) having a solid content concentration of 20.5% by weight, in which the solvent was replaced with MIBK by a rotary evaporator, was prepared. The refractive index of the surface-treated silica-based hollow fine particles (RA-1) was measured, and the results are shown in the table.

Preparation of antireflection film-forming coating solution (R1) In Example 1, the solid content concentration was 3 except that a surface-treated silica-based hollow fine particle (RA-1) dispersion with a solid content concentration of 20% by weight was used. A coating solution (R1) for forming an antireflection film of 0.0% by weight was prepared.

Preparation of base material with antireflection film (R1) In Example 1, the base material with antireflection film (R1) was used in the same manner except that the coating solution (R1) for forming an antireflection film having a solid concentration of 3.0% by weight was used. R1) was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of the substrate with antireflection film (R1) are shown in the table.

[Comparative Example 2]
Preparation of base material with hard coat film (R2) The coating liquid for hard coat film formation (1) prepared in the same manner as in Example 1 was diluted with PGME to a solid content concentration of 30% by weight, and TAC film (Fuji Film ( Co., Ltd .: FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51) was applied by the bar coater method # 3 and dried at 80 ° C. for 120 seconds.
Next, the substrate (R2) with a hard coat film was manufactured by irradiating and curing ultraviolet rays of 300 mJ / cm ^{2 in} an N ₂ atmosphere. The film thickness of the hard coat film was 1 μm.

  About the obtained base material (R2) with a hard coat film, 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of base material with antireflection film (R2) Subsequently, reflection was conducted in the same manner except that the coating liquid (1) for forming an antireflection film having a solid content of 3.0% by weight prepared in the same manner as in Example 1 was used. A substrate (R2) with a protective film was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of the substrate with antireflection film (R2) are shown in the table.

[Comparative Example 3]
Preparation of coating liquid for forming hard coat film (R3) Surface-treated metal oxide particles (1) having a solid content concentration of 40.5% by weight prepared in the same manner as in Example 1 (1) Dispersing organic resin (A) 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%) as a rotary A part of the solvent was removed by an evaporator to prepare an organic resin (A) dispersion (R3) for dispersing surface-treated metal oxide fine particles having a solid content concentration of 76.0% by weight.

Next, 75.31 g of an organic resin (A) dispersion (R3) 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 0.000 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 mixed well to form a hard coat film having a solid content concentration of 66.1% by weight. A coating solution (R3) was prepared.
The composition of the obtained coating liquid for forming a hard coat film (R3) is shown in the table.

Preparation of base material with hard coat film (R3) In Example 1, the base material with hard coat film (R3) was applied in the same manner except that the coating liquid for forming a hard coat film (R3) was applied by the bar coater method (# 16). R3) was produced. The film thickness of the hard coat film was 12 μm.

  About the obtained base material with a hard coat film (R3), 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (R3) Subsequently, reflection was conducted in the same manner except that the coating solution (1) for forming an antireflection film having a solid content of 3.0% by weight prepared in the same manner as in Example 1 was used. A base material (R3) with a protective film was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of the substrate with antireflection film (R3) are shown in the table.

[Comparative Example 4]
Preparation of Hard Coat Film Forming Coating Liquid (R4) Surface-treated metal oxide particles (1) having a solid content concentration of 40.5% by weight prepared in the same manner as Example 1 As a 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, A part of the solvent was removed by a rotary evaporator to prepare an organic resin (B) dispersion (R4) for curing the surface-treated metal oxide fine particles having a solid content concentration of 53.3% by weight.

Next, 82.96 g of the organic resin (B) dispersion liquid (R4) 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 mixed well to prepare a hard coat film forming coating solution (R4) having a solid content concentration of 51.0 wt%. did.
The composition of the obtained coating liquid for forming a hard coat film (R4) is shown in the table.

Preparation of base material with hard coat film (R4) In Example 1, the base material with hard coat film (R4) was prepared in the same manner as in Example 1, except that the coating liquid for hard coat film formation (R4) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film 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 hard coat film (R4), 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (R4) Subsequently, reflection was conducted in the same manner except that the coating solution (1) for forming an antireflection film having a solid content of 3.0% by weight prepared in the same manner as in Example 1 was used. A substrate (R4) with a protective film was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, film refractive index, adhesion, pencil hardness, and scratch resistance of the substrate with antireflection film (R4) are shown in the table.

[Comparative Example 5]
Preparation of Hard Coat Film Forming Coating Liquid (R5) 69.14 g of the 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 organic for dispersion Resin (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 And 4.83 g of curable organic resin (B) (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Oligo UA-33H, functional group: urethane acrylate, functional group number: 9, molecular weight: 4,000), and acrylic silicone Leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) 1.00 g, photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184) 0.29 g and PGME 6.9 The g and acetone 12.50g thoroughly mixed solids concentration 41.4 wt% hard coat film-forming coating solution of the (R5) was prepared.
The composition of the obtained coating liquid for forming a hard coat film (R5) is shown in the table.

Preparation of base material with hard coat film (R5) In Example 1, the base material with hard coat film (R5) was prepared in the same manner as in Example 1, except that the hard coat film forming coating solution (R5) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film was 12 μm.

  About the obtained base material with a hard coat film (R5), 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of substrate with antireflection film (R5) Subsequently, reflection was conducted in the same manner except that the coating solution (1) for forming an antireflection film having a solid content of 3.0% by weight prepared in the same manner as in Example 1 was used. A substrate (R5) with a protective film was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of the substrate with antireflection film (R5) are shown in the table.

[Comparative Example 6]
Preparation of coating liquid for hard coat film formation (R6) 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, Dimethylol-tricyclodecane diacrylate (Kyoeisha Chemical Co., Ltd .; light acrylate DCP-A, functional group: acrylate, functional group number: 2, molecular weight), 2500 g of the organic resin (A) for dispersion : 219, solid content concentration 100%) 202.5 g was added, a part of the solvent was removed with a rotary evaporator, and the organic resin for dispersing metal oxide fine particles composed of silica with a solid content concentration of 53.3% by weight (A ) Dispersion (R6) was prepared.

Organic resin (A) dispersion (R6) 75.31 g for dispersion of metal oxide fine particles and organic resin (B) for curing (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 mixed well to prepare a coating solution (R6) for forming a hard coat film having a solid content concentration of 53.3% by weight. did.
The composition of the obtained coating liquid for forming a hard coat film (R6) is shown in the table.

Preparation of base material with hard coat film (R6) In Example 1, the base material with hard coat film (R6) was prepared in the same manner as in Example 1, except that the coating liquid for hard coat film formation (R6) was applied by the bar coater method # 16. Manufactured. The film thickness of the hard coat film was 12 μm.

  About the obtained base material with a hard coat film (R6), 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Preparation of base material with antireflection film (R6) Subsequently, reflection was conducted in the same manner except that the coating liquid (1) for forming an antireflection film having a solid content of 3.0% by weight prepared in the same manner as in Example 1 was used. A substrate (R6) with a protective film was prepared. At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of the substrate with antireflection film (R6) are shown in the table.

[Comparative Example 7]
Preparation of base material with antireflection film (R7) A coating solution (1) for forming an antireflection film having a solid content concentration of 3.0% by weight prepared in the same manner as in Example 1 was prepared using a TAC film (manufactured by Fuji Film Co., Ltd.). : FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51), coated by bar coater method # 4, dried at 80 ° C. for 120 seconds, and then irradiated with ultraviolet rays of 600 mJ / cm ² under N ₂ atmosphere. Irradiated and cured to produce a substrate with antireflection film (R7). At this time, the film thickness of the antireflection film was 100 nm.
The total light transmittance, haze, reflectance, coating refractive index, adhesion, pencil hardness, and scratch resistance of this antireflection film-coated substrate (R7) are shown in the table.

[Comparative Example 8]
Preparation of base material with hard coat film (R8) A coating liquid for hard coat film formation (1) prepared in the same manner as in Example 1 was prepared using a TAC film (Fuji Film Co., Ltd .: FT-PB40UL-M, thickness). : 40 μm, refractive index: 1.51) by bar coater method # 16, dried at 80 ° C. for 120 seconds, and then cured by irradiating with 300 mJ / cm ² ultraviolet ray in N ₂ atmosphere to hard coat film A base material (R8) was produced. The film thickness of the hard coat film was 12 μm.

  For the obtained base material with a hard coat film (R8), 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, and the surface roughness (Ra), curling characteristics, scratch resistance, and pencil hardness were measured, and the results are shown in the table.

Claims (2)

A first matrix-forming component comprising an ultraviolet curable monomer having 1 to 2 (meth) acrylate groups and an ultraviolet curable urethane (meth) acrylate having 3 or more (meth) acrylate groups; Preparing a first coating liquid for forming a hard coat film containing surface-treated metal oxide fine particles having an average particle diameter of 5 to 300 nm and an organic solvent ;
Applying the first coating liquid to a substrate and drying to obtain a first dry film;
Curing the first dry film to obtain a hard coat film having an average film thickness of 12 to 100 μm;
A step of preparing a second coating liquid for forming an antireflection film containing a second matrix-forming component , silica-based hollow fine particles having an average particle diameter of 10 to 45 nm, and a solvent ;
Applying the second coating liquid to the hard coat film and drying to obtain a second dry film;
Curing the second dry film to obtain an antireflection film, and
Wherein the first coating liquid, 45 to 85% by weight of the surface-treated metal oxide fine particles as solid content, the 15 to 40% by weight of the first matrix-forming component as a solid content, 21.3 wt said organic solvent % To less than 40% by weight (however, the total amount of the surface-treated metal oxide fine particles, the first matrix-forming component, and the organic solvent does not exceed 100% by weight) , and the total amount contained in the first coating liquid 65-85% by weight of solids Ri Oh in the surface-treated metal oxide fine particles,
In the surface-treated metal oxide fine particles, the organosilicon compound represented by the following formula (1) is 0.1 to 40 parts by weight as R _n —SiO _{4 -n / 2 with} respect to 100 parts by weight of the metal oxide fine particles. Surface treated,
The second coating liquid contains 0.25 to 9% by weight of the silica-based hollow fine particles as a solid content and 0.75 to 9.5% by weight of the second matrix-forming component as a solid content, method for producing an antireflection film with a substrate concentration is characterized by 1 to 10 wt% der Rukoto.
R _n -SiX _4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n represents an integer of 1 to 3.) A first matrix-forming component comprising an ultraviolet curable monomer having 1 to 2 (meth) acrylate groups and an ultraviolet curable urethane (meth) acrylate having 3 or more (meth) acrylate groups; Preparing a first coating liquid for forming a hard coat film containing surface-treated metal oxide fine particles having an average particle diameter of 5 to 300 nm and an organic solvent ;
Applying the first coating liquid to a substrate and drying to obtain a first dry film;
A step of preparing a second coating liquid for forming an antireflection film containing a second matrix-forming component , silica-based hollow fine particles having an average particle diameter of 10 to 45 nm, and a solvent ;
Applying the second coating liquid to the first dry film and drying to obtain a second dry film on the first dry film;
A step of simultaneously curing the first dry film and the second dry film to obtain an antireflection film on a hard coat film having an average film thickness of 12 to 100 μm,
The first coating solution is 45 to 85% by weight of the surface-treated metal oxide fine particles as a solid content, 15 to 40 % by weight of the first matrix forming component as a solid content, and 21.3% by weight of the organic solvent. More than 40% by weight (however, the total amount of the surface-treated metal oxide fine particles, the matrix forming component, and the organic solvent does not exceed 100% by weight) , and 65 % of the total solid content contained in the first coating solution Ri to 85% by weight Oh in the surface-treated metal oxide fine particles,
In the surface-treated metal oxide fine particles, the organosilicon compound represented by the following formula (1) is 0.1 to 40 parts by weight as R _n —SiO _{4 -n / 2 with} respect to 100 parts by weight of the metal oxide fine particles. Surface treated,
The second coating solution contains the silica-based hollow fine particles in a solid content of 0.25 to 9% by weight, the second matrix-forming component is a solid content of 0.75 to 9.5% by weight, and has a total solid content concentration manufacturing method of the antireflection film-substrate but, wherein 1 to 10 wt% der Rukoto.
R _n -SiX _4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n represents an integer of 1 to 3.)