JP5546239B2 - Base material with hard coat film and coating liquid for forming hard coat film - Google Patents

Description

  The present invention relates to a base material with a hard coat film excellent in antiblocking properties (the hard coat films do not adhere to each other) and a coating liquid used for forming the hard coat film.

  It is known that a hard coat film is formed on the surface of the base material in order to improve the scratch resistance of the surface of the base material such as glass, plastic sheet, plastic lens, resin film, and display device front plate. An organic resin film or an inorganic film is formed as a coat film on the surface of glass, plastic or the like. Furthermore, it is practiced to further improve the scratch resistance by blending resin particles or inorganic particles such as silica in an organic resin film or an inorganic film. In some cases, a resin base material with a hard coat film is attached to a display device front plate or the like.

  However, when a substrate with a transparent coating is wound up at the time of production or when a substrate with a transparent coating is laminated after production, the substrates with a transparent coating adhere to each other, and then During processing, there was a problem that peeling was difficult during use.

  For this reason, the present inventors thought that antiblocking property may improve by providing unevenness in the hard coat film.

Patent Document 1 (Japanese Patent Laid-Open No. 2009-35614) discloses a curable resin composition for a hard coat layer containing reactive inorganic fine particles A and organic silicone fine particles B. In Patent Document 1, in order to prevent adhesion between mirror surfaces, a reactive inorganic fine particle A in which a surface excellent in dispersibility and binding property to a binder component is coated with an organic component, and the reactive inorganic fine particle A are separated. The organic silicone fine particles B containing organic groups containing organic groups tend to be mixed, and the organic silicone fine particles B are distributed on the surface of the hard coat layer due to the volume exclusion effect of the reactive inorganic fine particles A, thereby forming irregularities on the surface. It is disclosed.

  In order to impart antiglare properties to the hard coat film, it is possible to provide irregularities in Patent Document 2 (Japanese Patent Laid-Open No. 2007-76055), Patent Document 3 (Japanese Patent Laid-Open No. 2009-169409), and Patent Document. 4 (Japanese Patent Laid-Open No. 2008-163205) and the like.

JP 2009-35614 A JP 2007-76055 A JP 2009-169409 JP 2008-163205 A

However, the organic silicone fine particles B containing an organic group disclosed in Patent Document 1 have a high dispersibility in many organic resin binder components (matrix components), and in order to obtain the above volume exclusion effect, a large amount of reactive inorganic fine particles A are used. If not used, the effect of preventing adhesion could not be obtained sufficiently. Further, when a large amount of the reactive inorganic fine particles A are used, the adhesion to the substrate and the scratch resistance may be lowered. Further, depending on the particle size and content of the organic silicone fine particles B, the transparency of the film may be remarkably insufficient.

  Note that Patent Documents 2 to 4 focus on antiglare properties, and the purpose of the present invention to suppress the adhesion of the substrate with a transparent coating is not recognized at all.

  For this reason, there has been a demand for the emergence of a substrate with a hard coat film that is excellent in anti-blocking properties, and has excellent adhesion to the substrate, transparency, scratch resistance, scratch strength, pencil hardness, and the like.

  Under these circumstances, the present inventors include metal oxide fine particles that are hydrophilic and have no compatibility with the matrix component and have a refractive index of both. By adjusting to a specific range, a convex portion having a specific height can be formed on the surface of the hard coat film, and the above-mentioned problems such as transparency, scratch resistance and strength can be solved. As a result, the present invention has been completed.

The configuration of the present invention is as follows.
[1] a substrate;
It consists of a hard coat film composed of hydrophilic metal oxide particles (A) and a hydrophobic matrix component (M) formed on a substrate,
The refractive index (n _PA ) of the hydrophilic metal oxide particles (A) is in the range of 1.45 to 1.70,
The refractive index (n _M ) of the hydrophobic matrix component (M) is in the range of 1.45 to 1.70, and the refractive index difference between the refractive index (n _PA ) and the refractive index (n _M ) is 0.02 or less, A hard coat in which at least a part of the hydrophilic metal oxide particles (A) are present on the surface of the hard coat film by forming a convex portion, and the height of the convex portion (H convex) is in the range of 50 nm to 1 μm. Substrate with film.
[2] The base material with a hard coat film according to [1], wherein a difference in refractive index between the refractive index (n _B ) of the base material and the refractive index (n _H ) of the hard coat film is 0.04 or less.
[3] The substrate with a hard coat film according to [1] or [2], wherein the hydrophilic metal oxide particles (A) have an average particle diameter (D _A ) in the range of 80 nm to 3 μm.
[4] The hydrophilic metal oxide particles (A) are composed of silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, phosphorus-doped tin oxide, tin-doped indium oxide, and complex oxides and mixtures thereof. [1] to [3] A substrate with a hard coat film.
[5] The substrate with a hard coat film according to [1] to [4], wherein the hydrophobic matrix component (M) is a hydrophobic organic resin matrix component.
[6] The hydrophobic organic resin matrix component is selected from polyfunctional (meth) acrylic acid ester resins having a hydrophobic functional group such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF ₂ group, etc. [5] A substrate with a hard coat film, which is at least a seed.
[7] The hydrophobic organic resin matrix component is pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl One or more polyfunctional (meth) selected from metechlylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, and urethane acrylate [5] or [6] A substrate with a hard coat film, which is an acrylic ester resin.
[8] The substrate with a hard coat film according to [1] to [7], further comprising hydrophobic metal oxide particles (B) having an average particle diameter in the range of 5 to 200 nm.
[9] The hydrophobic metal oxide particles (B) are silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, phosphorus-doped tin oxide, tin-doped indium oxide, and complex oxides and mixtures thereof. The base material with a hard coat film according to [8], wherein the metal oxide particles (B) comprising the material 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)
[10] The substrate with a hard coat film according to [1] to [9], wherein the thickness of the hard coat film is in the range of 0.5 to 20 μm.
[11] A hydrophilic metal oxide particle (A) having a refractive index (n _PA ) in the range of 1.45 to 1.70, and a refractive index (n _M ) after curing of 1.45 to 1.70. A coating liquid for forming a hard coat film comprising a hydrophobic matrix-forming component in an area and an organic dispersion medium, and having a refractive index difference between a refractive index (n _PA ) and a refractive index (n _M ) of 0.02 or less.
[12] The coating solution for forming a hard coat film according to [11], wherein the hydrophilic metal oxide particles (A) have an average particle diameter (D _A ) in the range of 80 nm to 3 μm.
[13] The hydrophilic metal oxide particles (A) are composed of silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, phosphorus-doped tin oxide, tin-doped indium oxide, and composite oxides and mixtures thereof. [11] or [12] is a coating liquid for forming a hard coat film.
[14] The coating liquid for forming a hard coat film according to [10] to [13], wherein the hydrophobic matrix forming component is a hydrophobic organic resin matrix forming component.
[15] The hydrophobic organic resin matrix component is selected from polyfunctional (meth) acrylic acid ester resins having a hydrophobic functional group such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF ₂ group, etc. [14] The coating liquid for forming a hard coat film, which is a species or more.
[16] The hydrophobic organic resin matrix component is pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl Methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate It is one or more polyfunctional (meth) acrylic ester resin selected from acrylate and urethane acrylate [14] A hard coat film-forming coating solution of [15].
[17] The coating liquid for forming a hard coat film according to [11] to [16], further comprising hydrophobic metal oxide particles (B) having an average particle diameter in the range of 5 to 300 nm.
[18] The hydrophobic metal oxide particles (B) are silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, phosphorus-doped tin oxide, tin-doped indium oxide, and complex oxides and mixtures thereof. The coating liquid for forming a hard coat film according to [17], wherein the metal oxide particles (B) made of the above 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)

In the present invention, it comprises a substrate, a hard coat film comprising hydrophilic metal oxide particles and a hydrophobic matrix component formed on the substrate, and at least a part of the hydrophilic metal oxide particles (A). However, it is excellent in anti-blocking property (the hard coat films do not adhere to each other) because the hard coat film surface is formed with convex portions. In addition, since the refractive index difference between the refractive index (n _PA ) of the hydrophilic metal oxide particles (A) and the refractive index (n _M ) of the hydrophobic matrix component is small, the hydrophilic metal oxide particles (A) Even if it is larger than the optical wavelength, it is not visually recognized. For this reason, the base material with a hard-coat film excellent in transparency, haze, etc. and the coating liquid used for formation of this hard-coat film can be provided.

The cross-sectional schematic diagram of the base material with a hard coat film concerning this invention is shown.

Hereinafter, first, the substrate with a hard coat film according to the present invention will be described.
The substrate with a hard coat film according to the base material with a hard coat film present invention comprises a substrate, a hard coat film made of formed on a substrate the hydrophilic metal oxide particles (A) and the hydrophobic matrix components Consists of.

Substrate As the substrate used in the present invention, conventionally known glass, polycarbonate, acrylic resin, plastic sheets such as PET and TAC, plastic films, plastic panels, etc. can be used. A triacetyl cellulose (TAC) substrate that requires alkalinity, a polyolefin resin substrate such as PET, a polyvinyl alcohol resin substrate, a polyether sulfone resin substrate, and the like are preferably used.

  The base material used in the present invention preferably has a refractive index in the range of 1.45 to 1.70.

  When the refractive index of the base material is in the above range, the refractive index of the matrix component and the hydrophilic metal oxide particles, which will be described later, are also in the same range, and the refractive index difference of the hard coat film with the base material is within the above range. A hard coat film that can be adjusted to be small, has excellent transparency and haze, and has excellent hard coat properties without interference fringes can be obtained.

Hard Coat Film The hard coat film is composed of a hydrophobic matrix component and hydrophilic metal oxide particles (A). Thus, by comprising a hydrophobic matrix component and hydrophilic metal oxide particles, the hydrophilic metal oxide particles (A) are exposed on the hard coat surface to form specific convex portions.
(i) hydrophilic metal oxide particles (A)
The hydrophilic metal oxide particles (A) in the hard coat film are not uniformly dispersed in the hard coat film, but are unevenly distributed in the upper layer, forming a convex portion having a predetermined height on the surface. .

  For this reason, the hard coat film exhibits an excellent anti-blocking property. Here, the anti-blocking property is generally when the resin film is overlaid (blocked) at the time of production or use of the resin film or the like. In some cases), they may adhere to each other to such an extent that they are difficult to peel off, and this means a property of alleviating this adhesion.

The average particle diameter of the hydrophilic metal oxide particles (A) is 80 nm to 3 μm, and further 250 nm to 2 nm.
It is preferable to be in the range of μm. If the average particle size is small, the height of the convex portion (H convex) becomes insufficient, and sufficient antiblocking properties may not be obtained. Hydrophilic metal oxide particles (A)
Even if the average particle diameter is too large, the haze of the hard coat film may be deteriorated, the transparency may be lowered, and the hard coat film may be damaged by friction or the like.

  The average particle diameter can be obtained as an average value by taking a transmission electron micrograph (TEM) and measuring the particle diameter of 100 particles.

The hydrophilic metal oxide particles (A) used in the present invention are composed of silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, phosphorus-doped tin oxide, tin-doped indium oxide, and composite oxides and mixtures thereof. It is preferable that Since these hydrophilic metal oxide particles (A) are poorly miscible with the hydrophobic matrix component, they are not dispersed in the matrix.

  In particular, particles containing silica as a main component can be suitably used for reasons such as being easy to obtain spherical particles and excellent transparency. In addition, the particle | grains which have a silica as a main component mean the particle | grains whose silica content in a particle | grain is 50 weight% or more at least.

The refractive index (n _PA ) of the hydrophilic metal oxide particles (A) is 1.45 to 1.70, and further 1.49.
It is preferable to be in the range of ˜1.65.

If the refractive index (n _PA ) of the hydrophilic metal oxide particles (A) is in the above range, refraction with a hydrophobic matrix component having a refractive index (n _M ) in the range of 1.45 to 1.70, which will be described later. Since the rate difference can be adjusted to be small and light scattering can be suppressed, the hydrophilic metal oxide particles (A) on the surface are not visually recognized, and a hard coat film excellent in haze and transparency can be obtained. Can do.

The hydrophilic metal oxide particles (A) used in the present invention are not particularly limited as long as they have an average particle diameter and a refractive index within the above ranges. For example, JP-A 61-168528 filed by the applicant of the present application. Such as silica particles, titania particles, composite oxide particles, etc. disclosed in JP-A No. 62-275005, JP-A 61-168503, JP-A 61-168520, JP-A 61-174103, and the like. It can manufacture according to a manufacturing method.

The refractive index of the hydrophilic metal oxide particles (A) is adjusted by complex oxidation of two or more kinds of oxides blended so as to have a desired refractive index, except for a single component having a desired refractive index. It can be prepared as physical particles (including surface treatment with an organosilicon compound described later).

The hydrophilic metal oxide particles (A) used in the present invention are not necessarily required because they are hydrophilic as they are, but they are evenly dispersed in the matrix by lowering the affinity with the hydrophobic matrix component. The surface treatment may be performed with an organosilicon compound represented by the following formula (2) so that a convex portion having a predetermined height can be formed on the surface of the transparent coating.

SiX ₄ (2)
(Where X is an alkoxy group having 1 to 4 carbon atoms)
Examples of the organosilicon compound represented by the formula (2) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

When the hydrophilic metal oxide particles (A) are surface-treated with such a tetrafunctional organosilicon compound, they are appropriately dispersed in the hydrophobic matrix-forming component in the coating solution, applied onto the substrate, and dried. In this case, the hydrophilic metal oxide particles (A) form convex portions having a desired height on the surface of the hard coat film, and a substrate with a hard coat film having excellent antiblocking properties can be obtained.

  Further, when the refractive index of the metal oxide particles used is high, the refractive index of the hydrophilic metal oxide particles (A) can be adjusted to be low by such surface treatment.

The surface treatment of the hydrophilic metal oxide particles (A) can employ a conventionally known method.For example, a predetermined amount of the organosilicon compound is added to the alcohol dispersion of the hydrophilic metal oxide particles (A),
Water is added thereto, and if necessary, an acid or alkali is added as a catalyst for hydrolysis of the organosilicon compound to hydrolyze the organosilicon compound. The amount of the organosilicon compound used at this time depends on the size of the hydrophilic metal oxide particles (A), but is approximately 2 to 50% by weight of the hydrophilic metal oxide particles (A) as SiO ₂ , and further 5 It is preferably in the range of ˜20% by weight.

The particle refractive index used in the present invention was measured by the following method using Series A and AA manufactured by CARGILL as the standard refractive liquid.
(1) The metal oxide particle dispersion is taken in an evaporator and the dispersion medium is evaporated.
(2) This is dried at 80 ° C. for 12 hours to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.
(4) The operation of (3) is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is defined as the refractive index of the metal oxide particles.

(ii) Hydrophobic metal oxide particles (B)
In the present invention, it is preferable to further contain hydrophobic metal oxide particles (B). Hydrophobic metal oxide particles (B) are not directly involved in the convex part of the hard coat film, but are used to adjust the adhesion between the hard coat film and the substrate, film strength, film hardness, refractive index of the transparent film, etc. Contribute.

The average particle size of the hydrophobic metal oxide particles (B) is 5 to 200 nm, more preferably 10 to 150 nm.
It is preferable that it exists in the range. When the hydrophobic metal oxide particles (B) are smaller than the above range, it is difficult to obtain them, and even if they are obtained, they tend to aggregate regardless of their affinity with the hydrophobic matrix component. If the average particle size of the hydrophobic metal oxide particles (B) is too large, the adhesion to the substrate may be insufficient, or the transparency of the hard coat film may be insufficient. Depending on the film thickness, the formation of surface irregularities may be hindered.

  Such hydrophobic metal oxide particles (B) have an average particle size in the above range, are surface treated with an organosilicon compound represented by the following formula (1), and are hydrophilic except that the range of the average particle size is different. The same particles as the conductive metal oxide particles (A) are used.

  Such hydrophobic metal oxide particles (B) are desirably 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)
Since such an organosilicon compound has at least one hydrocarbon group, it has a high affinity with the hydrophobic matrix component used in the present invention, and the hydrophobic metal oxide particles (B) are unevenly distributed in the matrix. It is possible to obtain a base material with a hard coat film that can be dispersed without any improvement and has improved adhesion to the base material, scratch resistance and the like.

Examples of the organosilicon compound represented by the formula (1) 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-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycid Xymethyltrioxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth)
Acryloxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltrioxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane, γ- ( Meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyl Trimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ- Aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, etc. It is done.

The surface treatment of the hydrophobic metal oxide particles (B) can be performed in the same manner as the surface treatment of the hydrophilic metal oxide particles (A) except that the organosilicon compound is different. A predetermined amount of the organosilicon compound is added to the alcohol dispersion, and water is added thereto. If necessary, an acid or alkali is added as a catalyst for hydrolysis of the organosilicon compound to hydrolyze the organosilicon compound.

The amount of the organosilicon compound used at this time depends on the size of the metal oxide particles (B), but it is approximately 2 to 50% by weight of the metal oxide particles (B) as R _n —SiO 2 _{(4-n) / 2.} %, More preferably in the range of 5 to 20% by weight.

(iii) Hydrophobic matrix component As the hydrophobic matrix component contained in the hard coat film, a hydrophobic organic resin matrix component is used.

  As the hydrophobic organic resin matrix component, specifically, any of thermosetting resins and thermoplastic resins known as coating resins can be employed. For example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubber and other thermoplastic resins, urethane resins, melamine resins , Silicon resins, butyral resins, reactive silicone resins, phenol resins, epoxy resins, unsaturated polyester resins, fluororesins, thermosetting resins such as thermosetting acrylic resins, and light or electron beam curable resins. Further, it may be a copolymer or modified body of two or more of these resins.

  These resins may be emulsion resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.

Among them, the hydrophobic organic resin matrix component is selected from polyfunctional (meth) acrylic ester resins having a hydrophobic functional group such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF ₂ group, etc. It is preferable that it is a seed or more. More specifically, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate Rate, urethane acrylate, and the like and mixtures thereof are preferably used.

  When such a hydrophobic organic resin matrix component is used, the above-described hydrophilic metal oxide particles (A) are present in the form of protrusions on the hard coat film surface, and the above-described metal oxide particles (B) are aggregated. Without being dispersed, it is uniformly dispersed in the hard coat film, has anti-blocking properties, and has water repellency, so it has excellent water resistance, no fingerprint adhesion, adhesion to the substrate, hardness, resistance A base material with a hard coat film having excellent scratch resistance and the like can be obtained.

The refractive index (n _M ) of the hydrophobic matrix component is 1.45 to 1.70, more preferably 1.49 to
It is preferable to be in the range of 1.65. If the refractive index (n _M ) of the hydrophobic matrix component is in the above range, the refractive index (n) of the hydrophilic metal oxide particles (A) having a refractive index (n _PA ) in the range of 1.45 to 1.70. _PA )) can be adjusted to be small, and light scattering can be suppressed, so that a hard coat film excellent in haze and transparency can be obtained.

  In addition, the adjustment of the refractive index of the hydrophobic matrix component can be used by blending a plurality of matrix components so as to obtain a desired refractive index, except when the refractive index is a single component and a desired refractive index.

The difference in refractive index between the refractive index (n _PA ) of the hydrophilic metal oxide particles (A) and the refractive index (n _M ) of the hydrophobic matrix component is preferably 0.02 or less, more preferably 0.01 or less. When the refractive index difference is small, a hard coat film excellent in haze and transparency can be obtained even when the average particle diameter of the hydrophilic metal oxide particles (A) is particularly large.

In the present invention, when the hydrophobic metal oxide particles (B) are included, the refractive index (n _M ) of the hydrophobic matrix component means the refractive index including the hydrophobic metal oxide particles (B). The refractive index (n _M ) of the hydrophobic matrix component, the refractive index of the hydrophobic metal oxide particles (B) and the blending ratio of each component can be obtained by calculation.

(iv) Configuration of hard coat film The content of the hydrophilic metal oxide particles (A) in the hard coat film depends on the film thickness of the hard coat film, the average particle diameter of the hydrophilic metal oxide particles (A), etc. Although it is different, it is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.

If the content of the hydrophilic metal oxide particles (A) is small, depending on the thickness of the hard coat film, sufficient anti-blocking properties are obtained due to the low density of the protrusions formed on the hard coat film surface. It may not be possible. Even if the content of the hydrophilic metal oxide particles (A) is too large, the haze of the hard coat film may be deteriorated or the transparency may be lowered.

The content of the hydrophobic metal oxide particles (B) in the hard coat film is preferably 80% by weight or less, more preferably in the range of 2 to 60% by weight.

By including hydrophobic metal oxide particles (B) in the hard coat film, the hardness and scratch resistance are improved,
The refractive index of the transparent film can be adjusted.

The content of the hydrophobic matrix component in the hard coat film is preferably in the range of 80 to 99.99% by weight, more preferably 90 to 99.9% by weight. When the content of the hydrophobic matrix component in the hard coat film is not within the above range, adhesion to the substrate, hardness, scratch resistance, etc. may be insufficient.

When the hydrophobic metal oxide particles (B) are contained, the content of the hydrophobic matrix component is more desirably 10 to 98.9% by weight, and further desirably 20 to 70% by weight. Therefore, the ratio of the hydrophobic matrix component in the total of the hydrophobic metal oxide particles (B) and the hydrophobic matrix component (ie, the hydrophobic component) is 1 to 87.5% by weight, preferably 2
It is desirable to be in the range of 2 to 70% by weight.

  In addition, the quantitative ratio between the hydrophilic metal oxide particles and the hydrophobic matrix component is desirably 20:80 to 0.01: 99.99, preferably 10:90 to 0.1: 99.9.

  The total amount of the hydrophobic matrix component, the hydrophilic metal oxide particles, and the hydrophobic metal oxide particles does not exceed 100% by weight.

The height of the convex portion (H convex) is preferably in the range of 50 nm to 1 μm, more preferably 60 nm to 0.5 μm. The convex portion is substantially derived from the hydrophilic metal oxide particles (A), and the particles (A) may be exposed on the hard coat film surface or on the particle (B) surface. The hard coat film component may be present as a thin film. A schematic diagram of such a hard coat film is shown in FIG.

  When the height of the convex part (H convex) is small, sufficient anti-blocking properties cannot be obtained, and when the base material with a hard coat film is laminated, the base material with a hard coat film cannot be peeled one by one There is. If the height of the convex portion (H convex) is too large, haze may occur due to light scattering, and the transparency of the hard coat film may be impaired.

  In the present invention, the thickness of the hard coat film is a thickness that does not consider the height of the convex portions of the particles.

  In the present invention, the thickness of the hard coat film is measured by photographing a stylus type step gauge or a transmission electron micrograph (TEM) of a vertical cross section of the hard coat film. The height of the convex portion (H convex) can also be measured by the same method as described above.

  The refractive index of such a hard coat film is preferably 0.04 or less, more preferably 0.03 or less, with respect to the refractive index of the substrate.

  If the difference between the refractive index of the hard coat film and the refractive index of the base material is too large, there is a problem of generating interference fringes.

  Such a hard coat film can be formed by applying, drying and curing a coating liquid for forming a hard coat film according to the present invention which will be described later.

The thickness of the hard coat film is preferably in the range of 0.5 to 20 μm, more preferably 1 to 15 μm. When the thickness of the hard coat film is less than the lower limit of the above range, since the hard coat film is thin, the stress applied to the hard coat film surface cannot be sufficiently absorbed, and the hard coat function is insufficient. When the thickness of the hard coat film exceeds the upper limit of the above range, it becomes difficult to apply the film so that the film thickness becomes uniform or to dry uniformly, and further shrinkage increases, so curling (with hard coat film) The substrate may be curved). Also, the film thickness may be too thick and the transparency may be insufficient. The film thickness does not exceed the size of the hydrophilic metal oxide particles (A) and hydrophobic metal oxide particles (B) used.

Such a hard coat film can be formed by applying, drying and curing a coating liquid for forming a hard coat film according to the present invention which will be described later.

[Coating liquid for forming hard coat film]
The coating liquid for forming a hard coat film according to the present invention comprises the hydrophilic metal oxide particles (A), a hydrophobic matrix forming component, and an organic dispersion medium. If necessary, the metal oxide particles (B) may be included.

The concentration of the hydrophilic metal oxide particles (A) in the coating liquid for forming the particle component hard coat film is 0. As described above, the content of the hydrophilic metal oxide particles (A) in the obtained hard coat film is 0. 01-20% by weight
The solid content in the coating solution is preferably 0.0001 to 12% by weight, more preferably 0.001 to 6% by weight.

The concentration of the metal oxide particles (B) in the coating liquid for forming the hard coat film is such that the content of the metal oxide particles (B) in the resulting hard coat film is 80% by weight or less, preferably 2 as described above. ~ 6
Although used so that it may become 0 weight%, it is preferable that it exists in the range of 48 weight% or less as a solid content of a coating liquid, and also 0.02-36 weight%.

Hydrophobic matrix forming component As the hydrophobic matrix forming component, those constituting the hydrophobic matrix component described above are used. In the case of a thermoplastic resin, the hydrophobic matrix forming component becomes a hydrophobic matrix component as it is, but in the case of a curable resin, the hydrophobic matrix forming component reacts or polymerizes to become a hydrophobic matrix component. For this reason, when using curable resin as a hydrophobic matrix formation component, a catalyst, a polymerization accelerator, etc. may be contained.

  The concentration of the hydrophobic matrix forming component in the hard coat film forming coating solution is preferably in the range of 0.1 to 58% by weight, more preferably 0.2 to 48% by weight, based on the resin. If the hydrophobic matrix forming component in the coating liquid for forming the hard coat film is small, adhesion to the substrate, hardness, scratch resistance, etc. may be insufficient. Tend to be uneven.

Organic dispersion medium The organic dispersion medium used in the present invention can dissolve or disperse the hydrophobic matrix-forming component and, if necessary, the polymerization initiator, and the hydrophilic metal oxide particles (A) described above are dispersed. There is no particular limitation as long as the metal oxide particles (B) to be used can be uniformly dispersed, and a conventionally known solvent can be used. Specifically, alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; methyl acetate , Esters such as ethyl acetate, butyl acetate; 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 Ethers such as ether and propylene glycol monoethyl ether; Acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, ketones such as acetoacetate, toluene, xylene and the like. These may be used alone or in combination of two or more.

  The concentration of the coating solution for forming a hard coat film is preferably in the range of 1 to 60% by weight, more preferably 2 to 40% by weight as the total solid content.

  If the solid content concentration is low, it may be difficult to obtain a hard coat film having a film thickness of 0.5 μm or more by a single application, and if repeated application and drying are repeated, a predetermined convex portion cannot be formed. Sometimes. If the solid content concentration is too high, the viscosity of the coating solution may increase, resulting in a decrease in coating properties, an increase in the haze of the resulting hard coat film, and inadequate scratch resistance.

  A hard coat film is formed by applying such a coating solution to the substrate described above by a known method such as a dipping method, a spray method, a spinner method, a roll coating method, drying, and curing by heat treatment, ultraviolet irradiation, or the like. Can be formed.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.

[Example 1]
Preparation of dispersion of hydrophilic metal oxide particles (A-1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Spherical slurry 300, average particle size 300 nm, SiO ₂ concentration 20 wt%) was added to 1000 g of ion exchange resin (Mitsubishi). 400 g of Chemical Co., Ltd. (Diaion SK1B) was added, and washing was performed by ion exchange at 80 ° C. for 3 hours. Next, after removing the ion exchange resin, the dispersion was subjected to solvent substitution with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophilic metal oxide particle (A-1) methanol dispersion having a solid concentration of 20% by weight. Was prepared. The average particle diameter and refractive index of the hydrophilic metal oxide particles (A-1) are shown in the table. The particle refractive index was measured by the following method.
Method for Measuring Refractive Index of Particle (1) The dispersion is taken on an evaporator and the dispersion medium is evaporated.
(2) This is dried at 120 ° C. to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.
(4) The operation of (3) is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is used as the refractive index of the fine particles.

Preparation of coating liquid for hard coat film formation (1) Acrylic resin (manufactured by DIC Corporation: 17-824-9, resin concentration: 79.8% by weight, solvent: butyl acetate) and fluorine resin (Kyoeisha Chemical) 20 g of LINK-2A (resin concentration: 100% by weight, manufactured by Co., Ltd.) was diluted with isopropyl alcohol to prepare a resin component (1) for forming a hard coat film having a solid concentration of 30% by weight.

The hard coat film forming resin component (1) (100) is mixed with 1.5 g of a methanol dispersion of hydrophilic metal oxide particles (A-1) having a solid content concentration of 20% by weight. ) Was prepared.

Production of Substrate with Hard Coat Film (1) Coating liquid (1) for forming a hard coat film was prepared by triacetylcellulose (TAC) film (thickness: 80 μm, refractive index: 1.49, total light transmittance: 93. 2%, haze: 0.2%) by a bar coater method (# 18), dried at 80 ° C. for 120 seconds, and then cured by irradiation with 600 mJ / cm ² ultraviolet rays to form a substrate with a hard coat film (1) was produced. At this time, the thickness of the hard coat film was 7 μm.

  The total light transmittance and haze of the obtained hard coat film were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the results are shown in Table 1. The refractive index of the hard coat film was separately formed on a silicon wafer and measured with an ellipsometer (manufactured by SOPRA, ESVG). Further, the height of the convex portion, scratch resistance and anti-blocking property were evaluated, and the results are shown in Table 1. Moreover, the interference fringes were observed and the results are shown in the table.

  In addition, the visibility of particle | grains is reflected in haze, the external appearance evaluation (comprehensive evaluation) combined with the interference fringe is performed on the following reference | standard, and a result is shown in a table | surface.

A part of the base material with antiblocking hard coat film (1) is cut into two pieces, and the other base material with hard coat film (base material + hard coat film) The base material + the hard coat film) were overlapped, the weight was placed so that a load of 10 kg per 1 cm ² was applied, and the difficulty of peeling after being allowed to stand for 24 hours was evaluated according to the following criteria.

Easy peeling: ○
Peeling is slightly difficult: △
Can not be peeled off or difficult: ×
Measurement of scratch resistance Using # 0000 steel wool, sliding 50 times at a load of 500 g / cm ² , visually observing the surface of the film, and evaluating according to the following criteria, the results are shown in the table.

Evaluation criteria:
No streak injury is found: ◎
Slight flaws are observed: ○
Many streak wounds are found: △
The surface has been cut entirely: ×
Reflecting the light of the fluorescent lamp on the surface of the transparent coating with the black background of the substrate with interference fringe hard coat film (1), visually observing the occurrence of a rainbow pattern due to the interference of the light and evaluating it according to the following criteria .

No rainbow pattern is recognized: ◎
A slight rainbow pattern is observed: ○
A rainbow pattern is clearly visible:
Rainbow pattern is clearly recognized: ×
Comprehensive evaluation (or appearance evaluation)
When the transparent film haze is 0.3% or less and the evaluation of interference fringes is ○ or ◎: ◎
When the transparent film haze is 0.3% or less and the evaluation of the interference fringes is Δ: ○
When transparent film haze is 0.3% or less and interference fringe evaluation is x: Δ
When transparent film haze is 0.4% or more: ×
Here, the haze of the transparent coating was defined as the difference between the haze (measured value) of the substrate with the transparent coating and the haze of the substrate.

[Example 2]
Preparation of hard coat film forming coating solution (2 ) 30 g acrylic resin (DIC Corporation: 17-824-9, resin concentration: 79.8 wt%, solvent: butyl acetate) and fluororesin (Kyoeisha Chemical) Co., Ltd .: LINK-2A, resin concentration: 100% by weight) was diluted with isopropyl alcohol to prepare a resin component (2) for forming a hard coat film having a solid content concentration of 30% by weight. To 100 g of this hard coat film forming resin component (2), 1.5 g of a methanol dispersion of hydrophilic metal oxide particles (A-1) having a solid content concentration of 20% by weight prepared in the same manner as in Example 1 was mixed. Thus, a coating liquid (2) for forming a hard coat film was prepared.

Production of Substrate with Hard Coat Film (2) A substrate with hard coat film (2) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (2) was used. At this time, the thickness of the hard coat film was 7 μm.

  The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

[Example 3]
Preparation of dispersion of hydrophobic metal oxide particles (B-1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-30, average particle size 12 nm, SiO ₂ concentration 30
400% of ion exchange resin (Mitsubishi Chemical Corporation: Diaion SK1B) was added to 670 g (weight%), and washing was performed by ion exchange at 80 ° C. for 3 hours. Subsequently, after removing the ion exchange resin, the dispersion was subjected to solvent substitution with methanol by an ultrafiltration membrane method and concentrated to obtain a silica particle (B-1) methanol dispersion having a solid content concentration of 20% by weight.

  Next, 100 g of this methanol dispersion was added with 3.0 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, γ-methacryloxyfluorotrimethoxysilane) and stirred at 50 ° C. for 6 hours for organic stirring. Surface treatment with a silicon compound, and then the dispersion was subjected to solvent substitution with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophobic metal oxide particle (B-1) methanol dispersion having a solid content concentration of 20% by weight. Obtained. The average particle diameter and refractive index of the hydrophobic metal oxide particles (B-1) are shown in the table.

Preparation of Hard Coat Film Forming Coating Liquid (3 ) 100 g of hard coat film forming resin component (2) prepared in the same manner as in Example 2 and having a solid content concentration of 20% by weight is hydrophobic. 150 g of the metal oxide particle (B-1) methanol dispersion was mixed, and then the hydrophilic metal oxide particle (A-1) methanol dispersion 3 having a solid concentration of 20% by weight prepared in the same manner as in Example 1. 0.0 g was mixed to prepare a coating solution (3) for forming a hard coat film.

Production of substrate with hard coat film (3) A substrate with hard coat film (3) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (3) was used. At this time, the thickness of the hard coat film was 5 μm.

  The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

[Example 4]
Preparation of dispersion of hydrophilic metal oxide particles (A-2 ) 1111 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Spherica slurry 120, average particle size 120 nm, SiO ₂ concentration 18% by weight) was added to ion exchange resin (Mitsubishi Chemical). Washing was performed by adding 400 g of Diaion SK1B (made by Co., Ltd.) and performing ion exchange at 80 ° C. for 3 hours. Next, after removing the ion exchange resin, the dispersion was subjected to solvent substitution with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophilic metal oxide particle (A-2) methanol dispersion having a solid concentration of 20% by weight. Got.

  The average particle diameter and refractive index of the hydrophilic metal oxide particles (A-2) are shown in the table.

Preparation of Hard Coat Film Forming Coating Liquid (4) Prepared in the same manner as in Example 3 to 100 g of hard coat film forming resin component (2) having a solid content concentration of 30% by weight prepared in the same manner as in Example 2. 150 g of hydrophobic metal oxide particles (B-1) methanol dispersion liquid with a solid content concentration of 20% by weight were mixed, and then hydrophilic metal oxide particles (A-2) methanol dispersion liquid 9 with a solid content concentration of 20 wt% were mixed. 0.0 g was mixed to prepare a hard coat film forming coating solution (4).

Production of Substrate with Hard Coat Film (4) A substrate with hard coat film (4) was produced in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (4) was used. At this time, the thickness of the hard coat film was 5 μm.

  The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

[Example 5]
Preparation of dispersion of hydrophilic metal oxide particles (A-3 ) 200 g of silica particle powder (manufactured by JGC Catalysts & Chemicals Co., Ltd .: silica microbead P-500, average particle size 1.6 μm) was dispersed in 800 g of pure water. , And ion exchange resin (Mitsubishi Chemical (
Co., Ltd .: Diaion SK1B) was added and washed by ion exchange at 80 ° C. for 3 hours. Next, after removing the ion exchange resin, the dispersion was subjected to solvent substitution with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophilic metal oxide particle (A-3) methanol dispersion having a solid concentration of 20% by weight. Got. The average particle diameter and refractive index of the hydrophilic metal oxide particles (A-3) are shown in the table.

Preparation of Hard Coat Film Forming Coating Liquid (5) Prepared in the same manner as in Example 3 to 100 g of hard coat film forming resin component (2) having a solid content concentration of 30% by weight prepared in the same manner as in Example 2. 150 g of hydrophobic metal oxide particles (B-1) methanol dispersion with a solid content concentration of 20% by weight were mixed, and then hydrophilic metal oxide particles (A-3) methanol dispersion with a solid content concentration of 20% by weight were mixed. .9 g was mixed to prepare a hard coat film forming coating solution (5).

Production of Substrate with Hard Coat Film (5) A substrate with hard coat film (5) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (5) was used. At this time, the thickness of the hard coat film was 5 μm.

  The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

[Example 6]
Preparation of dispersion of hydrophilic metal oxide particles (A-4) Silica / alumina sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: USBB-120, average particle size 25 nm, SiO ₂ / Al ₂ O ₃ concentration 20% by weight, solid content medium content of Al ₂ O ₃ 27 wt%) was heated to 95 ° C. pure water was added to 546g to 14 g, while maintaining this temperature, sodium as SiO ₂ concentration of 1.5 wt% silicate solution 8270g and Al ₂ An aqueous solution of sodium aluminate having a concentration of 0.5% by weight as O ₃ was added to obtain a dispersion of SiO ₂ · Al ₂ O ₃ composite oxide fine particles (average particle size 100 nm). The Al ₂ O ₃ / SiO ₂ molar ratio at this time is 0.2
It was 9. Further, the pH of the reaction solution at this time was 12.0. Subsequently, it was washed with an ultrafiltration membrane to obtain composite oxide fine particles (A-4-1) having a solid content concentration of 5% by weight.

To 150 g of the composite oxide fine particles (A-4-1), 1330 g of pure water was added and heated to 95 ° C. While maintaining this temperature, 8990 g of an aqueous sodium silicate solution having a concentration of 1.5% by weight as SiO ₂ and Al _{2 were} added. An aqueous solution of sodium aluminate having a concentration of 0.5% by weight as O ₃ was added to obtain a dispersion of SiO ₂ · Al ₂ O ₃ composite oxide fine particles (average particle size 300 nm). At this time, the Al ₂ O ₃ / SiO ₂ molar ratio was 0.30. Also, the pH of the reaction solution at this time
Was 12.0. Subsequently, it was washed with an ultrafiltration membrane to obtain a composite oxide fine particle (A-4-2) dispersion having a solid content concentration of 5% by weight.

To 4000 g of the composite oxide fine particle (A-4-2) dispersion with a solid content concentration of 5% by weight, an ion exchange resin (
400 g of Mitsubishi Chemical Co., Ltd. (Diaion SK1B) was added and washed by ion exchange at 80 ° C. for 3 hours. Next, after removing the ion exchange resin, the dispersion was subjected to solvent replacement with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophilic metal oxide particle (A-4) methanol dispersion having a solid concentration of 20% by weight. Was prepared. The average particle diameter and refractive index of the hydrophilic metal oxide particles (A-4) are shown in the table.
Preparation of dispersion of hydrophobic metal oxide particles (B-2) Silica / alumina sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: USBB-120, average particle size 25 nm, SiO ₂ · Al ₂ O ₃ concentration 20% by weight, solid content Middle Al ₂ O ₃ content 27 wt%) 1000
400 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SK1B) was added to g, and ion exchange was performed at 80 ° C. for 3 hours for washing. Next, after removing the ion exchange resin, the dispersion is solvent-replaced with methanol by the ultrafiltration membrane method and concentrated to prepare a composite oxide fine particle (B-2) methanol dispersion having a solid content concentration of 20% by weight. did.

  Next, 100 g of this methanol dispersion was added with 3.0 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, γ-methacryloxyfluorotrimethoxysilane) and stirred at 50 ° C. for 6 hours for organic stirring. Surface treatment with a silicon compound, and then the dispersion was subjected to solvent replacement with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophobic metal oxide particle (B-2) methanol dispersion having a solid content concentration of 20% by weight. Obtained. The average particle diameter and refractive index of the hydrophobic metal oxide particles (B-2) are shown in the table.

Preparation of Hard Coat Film Forming Coating Liquid (6) Acrylic resin (DIC Corporation: 17-824-9, resin concentration: 79.8 wt%, solvent: butyl acetate) was diluted with isopropyl alcohol. A resin component (3) for forming a hard coat film having a solid content concentration of 30% by weight was prepared.

100 g of the resin component (3) for forming a hard coat film with a solid content concentration of 30% by weight is mixed with 100 g of a hydrophobic metal oxide particle (B-2) methanol dispersion with a solid content concentration of 20% by weight. A coating solution (6) for forming a hard coat film was prepared by mixing 2.5 g of a methanol dispersion of hydrophilic metal oxide particles (A-4) having a partial concentration of 20% by weight.

Production of base material with hard coat film (6) Coating liquid for hard coat film formation (6) was prepared using an acrylic plate (Mitsubishi Rayon Co., Ltd .: # 001).
, Thickness: 3 mm, refractive index: 1.51) by a bar coater method (# 18), dried at 80 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm ² ultraviolet rays to hard coat film A base material (6) was produced. At this time, the thickness of the hard coat film was 4 μm.
The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

[Example 7]
Preparation of dispersion of hydrophilic metal oxide particles (A-5) Solid content obtained by diluting titanium oxide sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: HPW-200C, average particle size 200 nm, TiO ₂ concentration 20% by weight) 270 g of titanium oxide sol with a concentration of 10% by weight
Was adjusted to pH 10 with an aqueous NaOH solution having a concentration of 1% by weight, and the temperature was maintained at 95 ° C.
2800 g of diluted water glass having a SiO ₂ concentration of 1.5% by weight and 6000 g of an aqueous sodium aluminate solution having an Al ₂ O ₃ concentration of 0.5% by weight were continuously added for 40 hours. Thereafter, the sol is cooled to 40 ° C. or lower, pure water is continuously added using an ultrafiltration device, washed thoroughly, and concentrated to a composite oxide fine particle having a solid content concentration of 18% by weight ( A-5) A dispersion was obtained.

To 1111 g of the complex oxide fine particle (A-5) dispersion having a solid content concentration of 18% by weight, an ion exchange resin (
400 g of Mitsubishi Chemical Co., Ltd. (Diaion SK1B) was added and washed by ion exchange at 80 ° C. for 3 hours. Next, after removing the ion exchange resin, the dispersion was subjected to solvent replacement with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophilic metal oxide particle (A-5) methanol dispersion having a solid concentration of 20% by weight. Was prepared. The average particle diameter and refractive index of the hydrophilic metal oxide particles (A-5) are shown in the table.
Preparation of hydrophobic metal oxide particle (B-3) dispersion Titanium oxide fine particle dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: ATOMYBALL- (TZ-R), average particle size 10 nm, solid content concentration 10.0 weight %, TiO ₂ 92 wt% in solid content, ZnO: 8 wt%)
2,000 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: ethyl silicate-A, SiO ₂ 28.8 wt%) was added to 2000 g of a titanium oxide fine particle aqueous dispersion having a solid content concentration of 1.5 wt% obtained by diluting Then, after adding 2000 g of methanol, heat treatment was performed at 50 ° C. for 15 hours. Next, a titanium oxide fine particle (3) methanol dispersion liquid in which the solvent was replaced with methanol using an ultrafiltration membrane and coated with silica having a solid content concentration of 20% by weight was prepared.

  Next, 100 g of this methanol dispersion was added with 3.0 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, γ-methacryloxyfluorotrimethoxysilane) and stirred at 50 ° C. for 6 hours for organic stirring. Surface treatment with a silicon compound, and then the dispersion was subjected to solvent substitution with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophobic metal oxide particle (B-3) methanol dispersion having a solid content concentration of 20% by weight. Obtained. The average particle diameter and refractive index of the hydrophobic metal oxide particles (B-3) are shown in the table.

Preparation of Hard Coat Film Forming Coating Liquid (7) Acrylic resin (Osaka Gas Chemical Co., Ltd .: Ogsol EA-0200, resin concentration: 93.8% by weight, solvent: toluene) was diluted with isopropyl alcohol. A resin component (4) for forming a hard coat film having a solid concentration of 30% by weight was prepared.

100 g of the resin component (4) for forming a hard coat film with a solid content concentration of 30% by weight is mixed with 100 g of a hydrophobic metal oxide particle (B-3) methanol dispersion with a solid content concentration of 20% by weight, and then solids are added. A coating liquid (7) for forming a hard coat film was prepared by mixing 2.5 g of a methanol dispersion of hydrophilic metal oxide particles (A-5) having a partial concentration of 20% by weight.

Production of base material with hard coat film (7) Coating liquid (7) for forming a hard coat film was prepared from PET film ( Toray Industries, Inc .: Lumirror T-6)
0, thickness: 100 μm, refractive index 1.65, substrate transmittance 91.0%, haze 2.0%) by bar coater method (# 18), dried at 80 ° C. for 120 seconds, and then 600 mJ / Cm ²
The base material (7) with a hard coat film was produced by irradiating and curing the ultraviolet ray. At this time, the thickness of the hard coat film was 4 μm.

  The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

[Comparative Example 1]
Preparation of dispersion of hydrophilic metal oxide particles (RA-1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-45P, average particle size 45 nm, SiO ₂ concentration 40 wt%) was added to 500 g of ion exchange resin (Mitsubishi Chemical) Washing was performed by adding 400 g of Diaion SK1B (made by Co., Ltd.) and performing ion exchange at 80 ° C. for 3 hours. Next, after removing the ion exchange resin, the dispersion was subjected to solvent substitution with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophilic metal oxide particle (RA-1) methanol dispersion having a solid content concentration of 20% by weight. Got. The average particle diameter and refractive index of the hydrophilic metal oxide particles (RA-1) are shown in the table.

Preparation of coating liquid for forming a hard coat film (RA-1) In Example 3, a hard coat was similarly applied except that a methanol dispersion of hydrophilic metal oxide particles (RA-1) having a solid content concentration of 20% by weight was used. A coating solution for film formation (RA-1) was prepared.

Production of base material with hard coat film (RA-1) In Example 1, a base material with hard coat film (RA-1) was used in the same manner except that the coating liquid for forming a hard coat film (RA-1) was used. -1) was produced. At this time, the thickness of the hard coat film was 5 μm. The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

[Comparative Example 2]
Preparation of dispersion of hydrophilic metal oxide particles (RA-2 ) 200 g of silica particles (manufactured by JGC Catalysts & Chemicals Co., Ltd .: silica microbead p-1500, average particle size 5 μm) are dispersed in 800 g of pure water, and ions are added thereto. 400 g of an exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SK1B) was added and washed by ion exchange at 80 ° C. for 3 hours.
Next, after removing the ion exchange resin, the dispersion was subjected to solvent replacement with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophilic metal oxide particle (RA-2) methanol dispersion having a solid concentration of 20% by weight. Got.

Preparation of coating liquid for forming a hard coat film (RA-2) In Example 3, a hard coat was similarly applied except that a methanol dispersion of hydrophilic metal oxide particles (RA-2) having a solid content concentration of 20% by weight was used. A coating solution for film formation (RA-2) was prepared.

Production of base material with hard coat film (RA-2) In Example 1, a base material with hard coat film (RA-2) was used except that the coating liquid for forming a hard coat film (RA-2) was used. -2) was manufactured. At this time, the thickness of the hard coat film was 5 μm. The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

[Comparative Example 3]
Preparation of dispersion of hydrophobic metal oxide particles (RB-1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Spherica slurry 300, average particle size 300 nm, SiO ₂ concentration 20 wt%) was added to 1000 g of ion exchange resin (Mitsubishi Chemical). Washed by ion exchange at 80 ° C. for 3 hours. Next, after removing the ion exchange resin, the dispersion was subjected to solvent substitution with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophilic metal oxide particle (A-1) methanol dispersion having a solid concentration of 20% by weight. Was prepared.

Next, 100 g of this methanol dispersion was added with 3.0 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, γ-methacryloxyfluorotrimethoxysilane) and stirred at 50 ° C. for 6 hours for organic stirring. Surface treatment with a silicon compound, and then the dispersion was subjected to solvent replacement with methanol by an ultrafiltration membrane method and concentrated to obtain a hydrophobic metal oxide particle (RB-1) methanol dispersion having a solid content concentration of 20% by weight. Obtained. The average particle diameter and refractive index of the hydrophobic metal oxide particles (RB-1) are shown in the table. (Note that hydrophilic metal oxide particles are not used)
Preparation of coating liquid for forming a hard coat film (RA-3) In Example 1, a hard coat was similarly applied except that a methanol dispersion of hydrophobic metal oxide particles (RB-1) having a solid content concentration of 20% by weight was used. A film forming coating solution (RA-3) was prepared.

Production of substrate with hard coat film (RA-3) In Example 1, the substrate with hard coat film (RA-3) was prepared in the same manner except that the coating liquid for forming a hard coat film (RA-3) was used. Manufactured. At this time, the thickness of the hard coat film was 5 μm.
The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

[Comparative Example 4]
Preparation of Hard Coat Film Forming Coating Liquid (RA-4) In the same manner as in Example 6, a hard coat film forming resin component (3) having a solid concentration of 30% by weight was prepared.

Example 1 was added to 100 g of the resin component (3) for forming a hard coat film having a solid content concentration of 30% by weight.
A coating solution for forming a hard coat film (RA-4) was prepared by mixing 1.5 g of a methanol dispersion of hydrophilic metal oxide particles (A-1) having a solid content concentration of 20% by weight prepared in the same manner as described above.

Production of base material with hard coat film (RA-4) In Example 1, the base material with hard coat film (RA-4) was used in the same manner except that the coating liquid for forming a hard coat film (RA-4) was used. -4) was produced. At this time, the thickness of the hard coat film was 7 μm. The obtained hard coat film was evaluated for total light transmittance, haze, refractive index, convex height, scratch resistance, anti-blocking property, particle visibility, and interference fringes, and the results are shown in the table.

Claims (10)

A substrate;
It consists of a hard coat film composed of hydrophilic metal oxide particles (A) and a hydrophobic matrix component (M) formed on a substrate,
The refractive index (n _PA ) of the hydrophilic metal oxide particles (A) is in the range of 1.45 to 1.70,
The refractive index (n _M ) of the hydrophobic matrix component (M) is in the range of 1.45 to 1.70, and the refractive index difference between the refractive index (n _PA ) and the refractive index (n _M ) is 0.02 or less. Yes, at least a part of the hydrophilic metal oxide particles (A) are present on the surface of the hard coat film by forming a convex portion, and the height of the convex portion (H convex) is in the range of 50 nm to 1 μm. ,
The hydrophilic metal oxide particles (A) are at least selected from silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, phosphorus-doped tin oxide, tin-doped indium oxide and complex oxides thereof, and mixtures thereof. One kind,
The hydrophobic organic resin matrix component is pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl 1 selected from methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, urethane acrylate It is a polyfunctional (meth) acrylic acid ester resin of more than species,
The weight ratio of the hydrophilic metal oxide particles (A) in the hard coat film to the hydrophobic matrix (M) is in the ratio of 10:90 to 0.1: 99.9,
A base material with a hard coat film, wherein the content of the hydrophilic metal oxide particles (A) in the hard coat film is in the range of 0.01 to 3.0% by weight. Refractive index of the substrate (n _B) and the refractive index of the hard coat layer (n _H) and with a hard coat film substrate according to claim 1, refractive index difference is equal to or is 0.04 or less of . The substrate with a hard coat film according to claim 1 or 2, wherein the hydrophilic metal oxide particles (A) have an average particle diameter (D _A ) in the range of 80 nm to 3 µm. The base material with a hard coat film according to any one of claims 1 to 3 , further comprising hydrophobic metal oxide particles (B) having an average particle diameter in the range of 5 to 200 nm. The hydrophobic metal oxide particle (B) is a metal comprising silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, phosphorus-doped tin oxide, tin-doped indium oxide, and complex oxides thereof, and mixtures thereof The oxide particle (B) is an organosilicon compound represented by the following formula (1), and is in the range of 2 to 50% by weight of the metal oxide particle (B) as R _n —SiX _{(4-n) / 2.} The substrate with a hard coat film according to claim 4 , which has been surface-treated.
_{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) The base material with a hard coat film according to claim 1 , wherein a film thickness of the hard coat film is in a range of 0.5 to 20 μm. The hydrophilic metal oxide particles (A) having a refractive index (n _PA ) in the range of 1.45 to 1.70 and the refractive index (n _M ) after curing are in the range of 1.45 to 1.70. a hydrophobic matrix forming component (M), made of an organic dispersion medium, the refractive index difference between the refractive index (n _PA) and refractive index (n _M) is 0.02 or less,
The weight ratio of the hydrophilic metal oxide particles (A) to the hydrophobic matrix (B) is in the ratio of 10:90 to 0.1: 99.9,
The hydrophilic metal oxide particles (A) are composed of silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, phosphorus-doped tin oxide, tin-doped indium oxide and complex oxides thereof, and mixtures thereof.
The hydrophobic organic resin matrix component is pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl 1 selected from methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, urethane acrylate It is a polyfunctional (meth) acrylic acid ester resin of more than species,
A coating liquid for forming a hard coat film, wherein the content of the hydrophilic metal oxide particles (A) in the obtained hard coat film is in the range of 0.01 to 3.0% by weight. The coating liquid for forming a hard coat film according to claim 7 , wherein the average particle diameter (D _A ) of the hydrophilic metal oxide particles (A) is in the range of 80 nm to 3 µm. The coating liquid for forming a hard coat film according to claim 7 or 8 , further comprising hydrophobic metal oxide particles (B) having an average particle diameter in the range of 5 to 300 nm. The hydrophobic metal oxide particle (B) is a metal comprising silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, phosphorus-doped tin oxide, tin-doped indium oxide, and complex oxides thereof, and mixtures thereof The oxide particle (B) is an organosilicon compound represented by the following formula (1), and is in the range of 2 to 50% by weight of the metal oxide particle (B) as R _n —SiX _{(4-n) / 2.} The coating liquid for forming a hard coat film according to claim 9 , which has been surface-treated.
_{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)

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