TWI465532B - Coating material for forming transparent coating film and a substrate with a transparent coating film - Google Patents

Description

Transparent film forming coating and substrate with transparent film

The present invention relates to a coating material for forming a transparent film which can be used for forming a transparent film such as an antireflection property or a hard coating function which has at least two or more functions by applying one coating at a time, and is formed using the transparent film. A substrate formed with a coating and having a transparent film.

In order to improve the scratch resistance of the surface of a substrate such as a glass, a plastic sheet, or a plastic lens, it is known that a hard coat film is formed on the surface of the substrate, and such a hard coat film is formed to form an organic resin film or an inorganic film. On the surface of glass or plastic. Further, inorganic particles such as resin particles or cerium oxide are blended in the organic resin film or the inorganic film to further improve scratch resistance.

Further, it is known to prevent reflection of the surface of a substrate such as glass, a plastic sheet or a plastic lens, and to form an antireflection film on the surface thereof. For example, it is known to use a coating method, a vapor deposition method, a CVD method, or the like. A film of a material having a low refractive index of a fluorine-containing resin or magnesium fluoride is formed on a surface of a substrate of glass or plastic, or a coating liquid containing low refractive index fine particles such as cerium oxide fine particles is applied onto a surface of a substrate to form a film. A method of anti-reflection film (for example, Patent Document 1 (JP-A-7-133105)).

At this time, it is known that a high refractive index film containing fine particles having a high refractive index or the like is formed on the lower layer of the antireflection film in order to improve the antireflection performance. Further, in order to impart antistatic properties and electromagnetic wave shielding properties to the substrate, a conductive coating film containing conductive oxide fine particles or metal fine particles is also formed. For example, a cathode ray tube, a fluorescent display tube, a liquid crystal display panel For the purpose of antistatic and antireflection of the surface of the transparent substrate of the display panel, etc., the surface of the display forms a transparent film having antistatic properties and antireflection properties.

In particular, in recent years, it has been used to laminate such various functional films. For example, a hard coat film is formed on a substrate to form a conductive film or a high refractive index film to form an antireflection film.

However, each film is composed of a coating coating, drying, and hardening as needed. Therefore, there are many steps in forming the multilayer film, and the adhesion between the films is insufficient, or productivity, economy, etc. problem.

In addition, the inventors of the present invention have proposed to use a conductive particle having a small average particle diameter and a small particle diameter and a low refractive index which is large in particle diameter, as disclosed in Japanese Laid-Open Patent Publication No. 2003-12965. The coating liquid of two kinds of fine particles having different particle ratios is obtained, and the conductive film having antireflection properties is formed by coating once.

(Patent Document 1) Japanese Patent Publication No. 7-133105

(Patent Document 2) JP-A-2003-12965

Heretofore, in order to simplify the steps or to reduce the thickness of the film itself, a transparent film having two or more functions has been sought only by applying the coating once.

In the coating liquid of the above-mentioned Patent Document 2, since it is a mixture of two types of fine particles, only one layer is formed, and antireflection performance and antistatic performance may not be sufficient. Further, adhesion of a plastic or the like to a substrate may occur. Low, and the strength of the film is insufficient.

In view of such a problem, the inventors of the present invention have found that, in the film formed by coating, if a fine particle layer is formed in the form of the above completely separated, and only the coating material is applied once, it can be formed. A transparent film having two or more functions.

Then, as a result of further research, it was found that the surface was hydrophobized with a specific organic cerium compound, and the metal oxide fine particles having a specific surface charge amount were combined with the hydrophobic matrix forming component so that the metal oxide fine particles did not The film was uniformly dispersed in the transparent film, and a layer was formed on the upper portion of the transparent film. That is, it was found that the film can be formed at one time to form a film having two or more functions, and finally the present invention has been completed.

[1] A coating material for forming a transparent film, which comprises the following:

(A) Metal oxide fine particles (a) whose surface is surface-treated with an organic cerium compound represented by the following formula (1) and/or a multifunctional acrylate resin having a hydrophobic functional group, and a surface charge amount (Q) _A ) in the range of 5 to 80 μ eq/g; R _n -SiX _4-n (1) (wherein, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different from each other. X : alkoxy group having 1 to 4 carbon atoms, stanol group, halogen, hydrogen, n: an integer of 0 to 3)

(B) a matrix-forming component comprising an organic hydrazine compound represented by the following formula (2) or a hydrolyzate thereof, a hydrolyzed polycondensate, and/or a polyfunctional (meth) acrylate resin having a hydrophobic functional group the hydrophobic matrix forming component _{composed; R n '-SiX 4-n} ' (2) ( wherein, R is a 1 to 10 carbon atoms, non-substituted or substituted hydrocarbon group, may be the same or different from each other .X: carbon Alkoxy groups of 1 to 4, stanol groups, halogens, hydrogen, n': an integer from 1 to 3)

(C) a polar solvent; characterized in that the concentration (C _PA ) of the solid content of the metal oxide fine particles (a) is in the range of 0.1 to 20% by weight, and the concentration of the solid component as the matrix forming component (C) (C) _M ) is in the range of 1 to 50% by weight.

[2] The coating material for forming a transparent film according to [1], wherein the matrix-forming component contains a hydrophobic matrix, and an organic hydrazine compound represented by the following formula (3) or a hydrolyzate thereof, hydrolyzed poly a hydrophilic matrix-forming component composed of a condensate or a polyfunctional (meth) acrylate resin having a hydrophilic functional group; SiX ₄ (3) (wherein X: alkoxy group having 1 to 4 carbon atoms, stanol Base, halogen, hydrogen)

Concentration (C _MA) formed in the solid component of the points as the hydrophilic matrix and the concentration (C _MB) of forming the solid component of the points as the hydrophobic matrix concentration ratio _{(C MA) / (C MB} ) is a range of 0.01 to 1.

[3] The coating material for forming a transparent film according to [1] or [2], wherein the metal oxide fine particles (a) have an average particle diameter in the range of 5 to 500 nm.

[4] The coating material for forming a transparent film according to any one of [1] to [3], further comprising metal oxide fine particles (BB) having a surface charge amount (Q _B ) in the range of 25 to 100 μ eq/g The difference between the surface charge amount (Q _B ) of the metal oxide fine particles (b) and the surface charge amount (Q _A ) of the metal oxide fine particles (a) (Q _B )-(Q _A ) is 20 to 95 μ eq The range of /g.

[5] The coating material for forming a transparent film according to any one of [1] to [4] wherein the concentration (C _PB ) of the solid content of the metal oxide fine particles (b) is in the range of 0.1 to 20% by weight. .

[6] The coating material for forming a transparent film according to [4], wherein the metal oxide fine particles (b) have an average particle diameter in the range of 5 to 500 nm.

[7] The coating material for forming a transparent film according to the above [1], wherein the hydrophilic functional group is at least one selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, a sulfo group, and a glycidyl group, and the hydrophobic The functional group is one or more selected from the group consisting of a (meth)acryl fluorenyl group, an alkyl group, a phenyl group, a urethane group, and a CF ₂ group.

[8] A substrate with a transparent film attached to a substrate to form a transparent film with a transparent film, characterized in that the transparent film has a surface charge amount (Q _A ) of 5 to 80 μ eq. The hydrophobic metal oxide fine particles (a) in the /g range are composed of a matrix component; the metal oxide fine particles (a) are deposited in a layer formed on the upper portion of the transparent film, and the content of the metal oxide fine particles (a) in the transparent film is (W _PA ) is in the range of 0.2 to 90% by weight; the content of the matrix component (W _M ) is in the range of 10 to 99.8% by weight; the matrix component is selected from the hydrolysis of the organic cerium compound represented by the following formula (4) A hydrophobic matrix component of a polycondensate and/or a polyfunctional (meth) acrylate resin having a hydrophobic functional group.

R _n -SiX _4-n (4) (wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms which may be the same or different from each other. X: alkoxy group having 1 to 4 carbon atoms, stanol Base, halogen, hydrogen, n: an integer from 0 to 3)

[9] The substrate having a transparent film according to [8], wherein the matrix component is composed of a hydrophobic matrix component and a hydrophilic matrix component, and the hydrophilic matrix component is represented by the following formula (3) Hydrolyzed polycondensate of an organic hydrazine compound and/or polyfunctional (meth) acrylate resin having a hydrophilic functional group; SiX ₄ (3) (wherein X: alkoxy group having 1 to 4 carbon atoms, stanol Base, halogen, hydrogen)

The content ratio (W _MA ) of the solid content of the hydrophilic matrix component (W _MA ) to the content of the solid component (W _MB ) as the hydrophobic matrix component (W _MA )/(W _MB ) is in the range of 0.01 to 1.

[10] The substrate having a transparent film as in [8] or [9], wherein the transparent film further contains metal oxide fine particles (b), and the surface charge amount of the metal oxide fine particles (b) (Q _B ) in the range of 25 to 100 μ eq/g; and the difference between the surface charge amount (Q _B ) of the metal oxide fine particles (b) and the surface charge amount (Q _A ) of the metal oxide fine particles (a) (Q _B ) - (Q _A ) is in the range of 20 to 95 μ eq/g; the metal oxide fine particles (b) are deposited on a layer formed on the surface of the substrate, or dispersed in a layer composed of the aforementioned metal oxide fine particles (a) Made between the surface of the substrate.

[11] The substrate with a transparent film according to any one of [8] to [10] wherein the metal oxide fine particles (a) have an average particle diameter in the range of 5 to 500 nm, and the metal oxide particles are as described above. The average particle diameter of (b) is in the range of 5 to 500 nm.

[12] The substrate having a transparent film according to any one of [8], wherein the hydrophilic functional group is at least one selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, and a sulfo group, and The hydrophobic functional group is one or more selected from the group consisting of a (meth) acrylonitrile group, an alkyl group, a phenyl group, a urethane group, and a CF ₂ group.

According to the present invention, it is possible to provide a coating material for forming a transparent film and a substrate having a transparent film by forming at least two layers which are separated into upper and lower functional layers by one application.

Further, since the transparent film can be obtained by one application, the step can be greatly shortened and the yield can be improved, and the obtained transparent film can be excellent in adhesion.

(The best form for implementing the invention)

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

Transparent film forming coating

The coating material for forming a transparent film of the present invention comprises a metal oxide fine particle (a) having a specific surface charge amount, a matrix forming component and a polar solvent.

Hydrophobic metal oxide particles (a)

The metal oxide fine particles (a) to be used in the present invention are not particularly limited as long as they have hydrophobicity, and conventionally known hydrophobic metal oxide fine particles can be used, but the surface charge amount (Q _A ) is 5 to 80. μ eq/g, further preferably in the range of 7 to 50 μ eq/g. In this range, in combination with a matrix component to be described later, it is possible to deviate from the upper layer when the film is formed.

The surface charge amount (Q _A ) of the metal oxide fine particles (a) may be small due to excessive hydrophobicity, and the metal oxide fine particles (a) may agglomerate in the coating, and may not form uniform on the upper portion of the film. The situation of the layer.

When the surface charge amount (Q _A ) of the metal oxide fine particles (a) is too high, the metal oxide fine particles (a) do not tend to be present in the upper layer but are dispersed in the film when the film is formed.

The metal oxide fine particles (a) are treated as described below, and the metal oxide fine particles are surface-treated with an organic cerium compound and/or a resin.

The metal oxide fine particles can be appropriately selected and used depending on the application. For example, the metal oxide fine particles used for the antireflection film generally have a refractive index of 1.45 or less, and further, 1.40 or less of fine particles can be used. Specifically, for example, SiO ₂ , SiO ₂ having pores therein, or particles coated with a conductive metal oxide or the like.

Examples of the metal oxide fine particles used in the cured film include ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ or chain-like particles in which the particles are chain-linked, or the foregoing The cerium oxide-based fine particles having a refractive index of 1.45 or less.

The metal oxide fine particles used in the high refractive index film generally have a refractive index of 1.60 or more, and further preferably 1.80 or more fine particles, and specific examples thereof include ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , and Al ₂ O _{3 .} , SnO ₂ , antimony-doped tin oxide, tin-doped indium oxide, doped tin oxide-phosphorus (PTO), and the like.

The metal oxide fine particles used for the conductive film are generally, for example, Sb ₂ O ₅ , SnO ₂ , tin oxide doped with antimony, indium oxide doped with tin, phosphorus doped with tin oxide (PTO), or The conductive material covers the cerium oxide-based fine particles on the surface or the cerium oxide-based fine particles having pores therein.

The metal oxide fine particles (a) are surface-treated by the above-mentioned metal oxide fine particles by an organic cerium compound represented by the following formula (1) and/or a multifunctional acrylate resin having a hydrophobic functional group.

R _n -SiX _4-n (1) (wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms which may be the same or different from each other. X: alkoxy group having 1 to 4 carbon atoms, stanol Base, halogen, hydrogen, n: an integer from 0 to 3)

The organic hydrazine compound represented by the formula (1) may, for example, be tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane, methyl trimethoxy decane or dimethyl. Dimethoxy decane, phenyl trimethoxy decane, diphenyl dimethoxy decane, methyl triethoxy decane, dimethyl diethoxy decane, phenyl triethoxy decane, diphenyl Diethoxy decane, isobutyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (β-methoxyethoxy) decane, 3, 3, 3 -trifluoropropyltrimethoxydecane, methyl-3,3,3-trifluoropropyldimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ -glycidoxymethyltrimethoxydecane, γ-glycidoxymethyltriethoxydecane, γ-glycidoxyethyltrimethoxydecane, γ-glycidoxypropyl B Triethoxy decane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, Γ-glycidoxypropyltriethoxyhydrazine , γ-(β-glycidoxyethoxy)propyltrimethoxydecane, γ-(meth)acryloxymethyltrimethoxydecane, γ-(methyl)propene fluorenyl Triethoxy decane, γ-(meth) propylene methoxyethyl trimethoxy decane, γ-(meth) propylene oxiranyl ethyl Triethoxy decane, γ-(meth) propylene methoxy propyl trimethoxy decane, γ-(meth) propylene methoxy propyl trimethoxy decane, γ-(methyl) propylene decyloxy Propyltriethoxydecane, γ-(meth)acryloxypropyltriethoxydecane, butyltrimethoxydecane, isobutyltriethoxydecane, hexyltriethoxydecane, octyl Triethoxy decane, decyl triethoxy decane, butyl triethoxy decane, isobutyl triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, decyl III Ethoxy decane, 3-ureido isopropyl propyl triethoxy decane, perfluorooctylethyl trimethoxy decane, perfluorooctyl ethyl triethoxy decane, perfluorooctyl ethyl three Isopropoxydecane, trifluoropropyltrimethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldimethoxydecane, N-β(aminoethyl)γ-amine Propyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-hydrothiopropyltrimethoxydecane, trimethylstanol, methyltrichlorodecane, and the like.

Examples of the hydrophobic polyfunctional acrylate resin include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetraacrylate, and di-trimethylolpropane tetra ( Methyl) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Isodecyl ester, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate , urethane acrylate, and the like.

When an organic cerium compound is used, the ratio of the amount of the metal oxide particles (the weight of the organic cerium compound/metal oxide fine particles) depends on the metal oxide particles. The average particle size varies, but is preferably from 0.001 to 2, more preferably from 0.005 to 1.5.

When a polyfunctional acrylate resin having the above hydrophobicity is used, the ratio of the amount to the metal oxide fine particles (the weight of the solid component of the polyfunctional acrylate resin having the above hydrophobicity / the weight of the metal oxide fine particles) is oxidized by metal The average particle diameter of the particles varies, but is preferably from 0.01 to 2, more preferably from 0.05 to 1.5.

When the surface of the organic ruthenium compound or the polyfunctional acrylate resin is treated in such a weight ratio, metal oxide particles having the specific surface charge amount described above can be obtained, and the dispersibility and stability in a polar solvent are high, and the film can be obtained. The upper portion forms a uniform layer.

Further, when the weight ratio is small, the dispersibility and stability in a polar solvent are low, and the stability of the coating material is insufficient, and the film may be whitened when the film is formed. If the aforementioned weight ratio is too high, the surface charge amount of the metal oxide fine particles (a) becomes 5 μq /g or less, and the metal oxide fine particles (a) may agglomerate in the coating due to excessively high hydrophobicity. There is a case where a uniform layer is not formed on the upper portion of the film.

In the present specification, the arrangement of the metal oxide fine particles (a) on the upper portion of the film means that only metal particles are present on the surface of the film and the vicinity thereof, and the so-called metal oxide particles are arranged on the lower portion of the film, which means only on the surface of the substrate. There are metal particles in the vicinity.

In the transparent film of the present invention, the metal oxide fine particles (a) are biased on the upper portion of the transparent film, but in this case, the metal oxide fine particles (a) may be formed into a plurality of layers, or may be formed as a single layer, or may be present in a plurality of layers. Upper part.

The method for measuring the surface charge amount of the metal oxide fine particles (a) described above is a surface potential titrator (Mutek pcd-03) using 0.001 N poly-diallyldimethylammonium chloride. The dispersion of the microparticles was titrated to determine the surface charge amount ( μ eq/g) per unit weight (gram) of each particle.

The metal oxide fine particles (a) have an average particle diameter of from 5 to 500 nm, more preferably from 10 to 100 nm.

When the average particle diameter of the metal oxide fine particles (a) is small, it is difficult to obtain the bulk thereof, and the average particle diameter of the metal oxide fine particles (a) is high, and the haze value at the time of coating the film is high, and may not be used. Comes as an optical film.

The metal oxide fine particles (a) used in the present invention are not particularly limited as long as they are subjected to the above surface treatment, and are preferably prepared by the following methods, for example.

In the case of the organic ruthenium compound, a specific amount of the above organic ruthenium compound is added to the alcohol dispersion of the metal oxide fine particles described above, and water is added thereto, and an acid or a base is added as a catalyst for hydrolysis of the organic ruthenium compound to hydrolyze the organic矽 compound. Alternatively, in the case of a hydrophobic polyfunctional acrylate resin, the polyfunctional acrylate resin having the aforementioned hydrophobicity is polymerized to coat the surface of the particles of the metal oxide fine particles (a) by heat or a polymerization initiator. As the polymerization initiator, a general radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator may be used, and a radical polymerization initiator is preferred, and for example, it is preferably an acetophenone or a benzoate. A polymerization initiator such as a thioselenone system.

Then, an organic solvent dispersion of the metal oxide fine particles (a) can be obtained by substituting an organic solvent. The organic solvent is preferably a polar solvent described later.

The solid content (C _PA ) in the coating material for forming a transparent film of such a metal oxide fine particle (a) is from 0.1 to 20% by weight, more preferably from 0.2 to 15% by weight.

When the concentration (C _PA ) of the metal oxide fine particles (a) is small, even if it is excessively deposited on the upper portion of the film, the amount of particles is small, so the characteristics of the particles (low refractive index or conductivity) may be sometimes caused. Etc.), which causes insufficient anti-reflection performance, antistatic performance, and the like. Further, even if the concentration (C _PA ) of the metal oxide fine particles (a) is too large, the ratio of the particles in the obtained film is too large, and the film mainly disperses the metal oxide fine particles in the entire region in the film, and sometimes A film having two or more functions of the present invention could not be obtained.

Metal oxide particles (b)

The coating material for forming a transparent film of the present invention may contain metal oxide fine particles (a) and may further contain metal oxide fine particles (b).

The metal oxide fine particles (b) are preferably those having a lower hydrophobicity than the metal oxide fine particles (a) contained therein and having a higher surface charge than the metal oxide fine particles (a). Such metal oxide particles form a uniform layer under the film. Thereby, it is also possible to further impart another characteristic to the transparent film.

The surface charge amount (Q _B ) of the metal oxide fine particles (b) is 25 to 100 μ eq/g, more preferably in the range of 30 to 100 μ eq/g.

If the surface charge amount (Q _B ) of the metal oxide fine particles (b) is low, since the surface charge amount is close to the metal oxide fine particles (a), it does not deviate from the lower portion of the film, and the metal oxide fine particles (a) The tendency to be located above the film is mixed, and the effect of the characteristics of the metal oxide fine particles (a), for example, the low refractive index property may be insufficient. If the surface charge amount (Q _B ) of the metal oxide fine particles (b) is too large, it may be close to hydrophilic due to low hydrophobicity, and there may be agglomeration of metal oxide fine particles (b) in the coating, and there is a phenomenon in the film. The lower part does not form a uniform layer.

The difference (Q _B )-(Q _A ) between the surface charge amount (Q _A ) of the metal oxide fine particles (a) and the surface charge amount (Q _B ) of the metal oxide fine particles (b) is 20 to 95 μ eq/g. More preferably in the range of 25 to 85 μ eq/g.

When (Q _B )-(Q _A ) is small, the difference in surface charge amount between the metal oxide fine particles (a) and the metal oxide fine particles (b) is small, and the separation of these fine particles becomes insufficient, and sometimes it is impossible. A film having two or more functions of the present invention is obtained. If (Q _B )-(Q _A ) is large, the metal oxide fine particles (a) will aggregate, and the metal oxide fine particles (b) will also aggregate, and the obtained film will be whitened or adhered to the substrate. Or there may be insufficient strength.

The metal oxide fine particles (b) are the same as the metal oxide fine particles (a) described above, and the metal oxide fine particles are surface-treated. In general, as the metal oxide fine particles, metal oxide fine particles different from the metal oxide fine particles used for the metal oxide fine particles (a) described above are used depending on the purpose. Specifically, for example, the metal oxide fine particles (a) are exemplified. Further, the surface treatment is selected such that the amount of surface charge becomes a specific difference (that is, the surface charge amount of the metal oxide fine particles becomes high). For example, a treatment method in which the hydrophilicity is higher than that of the metal oxide fine particles (a) or the amount of treatment is reduced can be selected.

The metal oxide fine particles (b) have an average particle diameter of from 5 to 500 nm, more preferably from 10 to 100 nm. A person having a small average particle size is difficult to obtain by itself, and if it is too large, there is a case where the stability of the paint is insufficient. Again, got The transparency of the film is lowered, and the film is further whitened.

The solid content (C _PB ) in the coating material for forming a transparent film of the metal oxide fine particles (b) is from 0.1 to 20% by weight, more preferably from 0.2 to 15% by weight. If the concentration (C _PB ) of the metal oxide fine particles (b) is low, even if the metal oxide fine particles (b) are deposited in the lower portion of the film, the effect of adding the metal oxide fine particles (b) is small because the amount of the particles is small. (High refractive index, electrical conductivity, etc., and antireflection performance improvement effect, antistatic performance, etc.) may become insufficient. If the concentration (C _PA ) of the metal oxide fine particles (b) is too large, the ratio of the particles in the obtained film is too large, and is mixed with the metal oxide fine particles (a), or becomes a metal oxide fine particle in the film (b) A film which is dispersed throughout the whole is covered, and a film having two or more functions of the present invention cannot be obtained.

Matrix forming component

In the present invention, in particular, the matrix-forming component may be a matrix-forming component containing an organic hydrazine compound represented by the following formula (2) or a hydrolyzate thereof, a hydrolyzed polycondensate, or a hydrophobic property. A hydrophobic matrix forming component composed of a functional group polyfunctional (meth) acrylate resin.

As the hydrophobic polyoxo-based (sol-gel-based) matrix-forming component, an organic hydrazine compound represented by the following formula (2), a hydrolyzate thereof, or a hydrolyzed polycondensate can be used.

R _n' -SiX _4-n' (2) (wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms which may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, Sulfhydryl, halogen, hydrogen, n': an integer from 1 to 3)

Specifically, among the compounds represented by the above formula (1), for example, n It is 0. Among these, 3,3,3-trifluoropropyltrimethoxydecane, methyl-3,3,3-trifluoropropyldimethoxydecane, and the like, hydrolyzed, and hydrolyzed Condensate.

The hydrophobic organic resin-based matrix-forming component may, for example, be a polyfunctional group having a hydrophobic functional group such as a vinyl group, a urethane group, an epoxy group, a (meth) acryl fluorenyl group or a CF ₂ group. The acrylate resin may specifically be, for example, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetra(a) Acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Oxime ester, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, amine A urethane acrylate or the like and a mixture thereof.

These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curing type, an electron beam curing type, or a thermosetting resin, and may also contain a curing catalyst.

The matrix-forming component used in the present invention preferably contains a hydrophobic matrix-forming component and a hydrophilic matrix-forming component.

The hydrophilic matrix-forming component may, for example, be a hydrophilic matrix-forming component composed of an organic hydrazine compound, a hydrolyzate thereof, a hydrolyzed polycondensate, or a polyfunctional (meth) acrylate resin having a hydrophilic functional group.

SiX ₄ (3) (wherein X: alkoxy group having 1 to 4 carbon atoms, stanol group, halogen, hydrogen)

Specific examples of the organic phosphonium compound represented by the formula (3) include tetramethoxydecane, tetraethoxydecane, tetrapropoxydecane, tetrabutoxydecane, methyltrimethoxydecane, and the like. Hydrolyzate, hydrolyzed polycondensate, and the like.

Further, the hydrophilic organic resin-based matrix-forming component may, for example, be a polyfunctional (meth)acrylate resin having a hydrophilic functional group such as a hydroxyl group (OH group), an amine group, a carboxyl group or a sulfo group, and specifically, for example, For example, pentaerythritol triacrylate having a hydrophilic functional group such as a hydroxyl group (OH group), an amine group, a carboxyl group or a sulfo group, trimethylolpropane tri(meth)acrylate, pentaerythritol tetraacrylate, or di-trihydroxyl In addition to propane tetra(meth)acrylate, dipentaerythritol hexaacrylate, etc., there are still diethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, 2-hydroxy-3 - propylene oxypropyl acrylate, methoxy triethylene glycol dimethacrylate, butoxy diethylene glycol methacrylate and mixtures thereof.

When the hydrophilic matrix-forming component is mixed with the hydrophobic matrix-forming component, the metal oxide fine particles (a) and the metal oxide fine particles (b) are easily separated, and a film having two layers can be easily obtained.

Concentration (C _MA) formed in the solid component of the points as the hydrophilic matrix and the concentration (C _MB) of forming the solid component of the points as the hydrophobic matrix concentration ratio _{(C MA) / (C MB} ) appropriate for the range of 0.01 to 1 More preferably in the range of 0.05 to 0.5.

If the concentration ratio (C _MA ) / (C _MB ) is small, the hydrophilic matrix forming component is small, and substantially becomes close to the hydrophobic matrix forming component, so that the metal oxide fine particles (a) (upper portion) and the metal oxide fine particles The separation effect of (b) (lower part) becomes insufficient. When the concentration ratio (C _MA )/(C _MB ) exceeds 1, the hydrophilic matrix forming component is large, and the metal oxide fine particles (b) having a high surface charge amount may not be excessively deposited in the lower layer.

Polar solvent

As the polar solvent to be used in the present invention, a solvent which dissolves the above-mentioned polyfunctional (meth) acrylate resin while being easily volatilized can be suitably used.

Specific examples thereof include water; alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, diacetone alcohol, mercapto alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexanediol, and isopropanol. ; esters of methyl acetate, ethyl acetate, butyl acetate, etc.; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol An ether such as monomethyl ether, diethylene glycol monoethyl ether or propylene glycol monomethyl ether; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetonyl acetone or ethyl decyl acetate; . These may be used singly or in combination of two or more. Methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone or the like can also be used.

When the metal oxide fine particles (a) and the metal oxide fine particles (b) used as needed, the matrix forming component and the polar solvent are appropriately mixed in a desired amount ratio, the transparent film of the present invention can be prepared. coating.

The coating material for forming a transparent film is applied to a substrate by a known method such as a dipping method, a spray coating method, a spin coating method, a roll coating method, a bar coating method, a gravure printing method, or a micro gravure printing method, and is dried. It is hardened by a usual method such as irradiation or heat treatment to form a transparent film.

When the matrix-forming component is an organic ruthenium compound, an acid or a base may be contained as a hydrolysis catalyst. Further, when the matrix-forming component contains a polyfunctional (meth) acrylate resin, a polymerization initiator may be contained. The polymerization initiator may be a known one, and is not particularly limited, and specifically, for example, the same as the user of the surface treatment described above.

Substrate with transparent film

With the present invention based on the transparent film substrate may be formed of a transparent film of the substrate with a transparent film on a substrate, a transparent film by the surface charge amount (Q _A) μ eq 5 to 80 / g in the range The hydrophobic metal oxide fine particles (a) and the matrix component are formed; the metal oxide fine particles (a) are deposited on the upper layer of the transparent film, and the content (W _PA ) of the metal oxide fine particles (a) in the transparent film is The range of 0.2 to 90% by weight; the content of the matrix component (W _M ) is in the range of 10 to 99.8% by weight. Further, it corresponds to the amount ratio of each component in the transparent film and the amount ratio in the coating liquid.

Substrate

The substrate to be used in the present invention may be any conventionally known one, and is not particularly limited, and examples thereof include glass, polycarbonate, acrylic resin, polyethylene terephthalate (PET), and triethylenesulfonyl cellulose ( TAC), plastic sheets such as cycloolefin and norbornene, plastic films, etc., plastic panels, etc. Among them, a resin-based substrate can be suitably used. also. An adhesive film substrate on which another film is formed may also be used on such a substrate.

Metal oxide particles (a)

The metal oxide fine particles (A) can be used in the same manner as the metal oxide fine particles (A) described above. The content (W _PA ) of the metal oxide fine particles (a) in the transparent film is preferably in the range of 0.2 to 90% by weight, more preferably in the range of 0.5 to 80% by weight.

When the content (W _PA ) of the metal oxide fine particles (a) is small, even if it is excessively deposited on the upper portion of the film, the amount of particles is small, and the particles may have characteristics such as low refractive index, high refractive index, and conductivity. However, functions such as anti-reflection performance and antistatic performance cannot be fully exhibited. In addition, even if the content (W _PA ) of the metal oxide fine particles (a) is too large, the metal oxide fine particles (a) are substantially present in the entire region, and cannot be a transparent film having two or more functions of the present invention. Sometimes, the adhesion to the substrate becomes insufficient.

In the transparent film, the hydrophobic metal oxide fine particles (a) are deposited on the upper layer of the transparent film. Such a state is schematically shown in Fig. 1.

Metal oxide particles (b)

The transparent film of the substrate to which the transparent film of the present invention is attached may further contain metal oxide fine particles (b). The metal oxide fine particles (b) are dispersed in a layer formed in the film or dispersed in the layer composed of the metal oxide fine particles (a) and the surface of the substrate. Such a state is schematically represented in the second, third, and fourth figures. Fig. 2 is an example in which the lower layer of the transparent film is deposited. Fig. 3 is an example in which a layer directly under the layer of the metal oxide fine particles (a) is present, and Fig. 4 is a dispersion without being biased under the layer of the metal oxide fine particles (a).

The metal oxide fine particles (b) can be used in the same manner as the metal oxide fine particles (b) described above.

The content (W _PB ) of the metal oxide fine particles (b) in the transparent film is preferably in the range of 0.1 to 40% by weight, more preferably in the range of 0.2 to 30% by weight. When the content (W _PB ) of the metal oxide fine particles (b) is small, even if it is present in the lower layer of the film, the amount of particles is small, and thus the characteristics of the particles (electric conductivity, high refractive index, low refractive index) may not be sufficiently exhibited. Rate, adhesion to the substrate, etc.). In addition, when the content (W _PB ) of the metal oxide fine particles (b) is too large, it is mixed with the metal oxide fine particles (a) arranged in the upper portion, and the two or more functions of the present invention may not be obtained. Transparent film.

Matrix component

As the matrix component, a polyoxynitride-based (sol-gel) matrix component, an organic resin-based matrix component, or the like can be used.

As the polyoxymethylene base component, a hydrolyzed polycondensate of the same organic hydrazine compound as the above formula (2) can be suitably used. Among these, a hydrolyzed polycondensate such as 3,3,3-trifluoropropyltrimethoxydecane or methyl-3,3,3-trifluoropropyldimethoxydecane may also be suitably used.

In addition, examples of the organic resin-based matrix component include a known thermosetting resin, a thermoplastic resin, an electron beam-curing resin, and the like as a coating resin.

Specifically, it is preferably a polyfunctional (meth) acrylate resin having a hydrophobic functional group. The hydrophobic organic resin-based matrix component may, for example, be a polyfunctional (meth) group having a hydrophobic functional group such as a vinyl group, a urethane group, an epoxy group, a (meth) acryl fluorenyl group or a CF ₂ group. Specific examples of the acrylate resin include the same as those described above.

Further, as such a resin, for example, a polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene oxide resin, a thermoplastic acrylic resin, a vinyl chloride resin, a fluororesin, a vinyl acetate resin, or the like, which have been conventionally used, may be mentioned. Thermoplastic resin such as polyoxymethylene rubber, urethane resin, melamine tree Thermosetting resin such as grease, enamel resin, butyral resin, reactive polyoxyl resin, phenol resin, epoxy resin, unsaturated polyester resin, thermosetting acrylic resin, ultraviolet curable acrylic resin, ultraviolet curing Acrylic resin, etc. Further, a copolymer or a modified body of two or more kinds of resins may be used.

These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curing type, an electron beam curing type, or a thermosetting resin, and may also contain a curing catalyst.

The matrix component used in the present invention preferably contains a hydrophilic matrix component and a hydrophobic matrix component. In particular, in terms of dispersibility and offset property of the metal oxide fine particles (b), it is preferable to contain the metal oxide fine particles (b).

When the matrix component of the polyoxymethylene system is used, it is preferable to use it together with a hydrophilic polyoxo-based (sol-gel-based) matrix component in terms of affinity, and an organic hydrazine represented by the following formula (3) can be used. Hydrolyzed polycondensate of the compound.

R _n -SiX ₄ (3) (wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms which may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a stanol group, Halogen, hydrogen, n: an integer of 0)

Specifically, a hydrolyzed polycondensate of tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane or methyltrimethoxy decane can be suitably used.

Further, the hydrophilic organic resin-based matrix component may, for example, be a polyfunctional group having a hydrophilic functional group such as a hydroxyl group (OH group), an amine group, a carboxyl group or a sulfo group (A) Specific examples of the acrylate resin include the above.

The ratio (W _MA ) / (W _MB ) of the content of the solid component (W _MA ) as the hydrophilic matrix component to the content of the solid component (W _MB ) as the hydrophobic matrix component is preferably in the range of 0.01 to 1. More preferably in the range of 0.05 to 0.5.

When (W _MA )/(W _MB ) is small, the hydrophilic matrix forming component is small, and substantially becomes close to only the hydrophobic matrix forming component, and the metal oxide fine particles (a) (upper portion) and the metal oxide fine particles ( b) The separation effect of the (lower part) becomes insufficient. Even if (W _MA )/(W _MB ) is too large, the hydrophilic matrix is formed in a large amount, and the metal oxide fine particles (b) having a high surface charge amount may not be deposited in the lower layer.

The content (W _MA ) of the hydrophilic matrix component in the transparent film is preferably from 10 to 99.8% by weight, more preferably from 20 to 99.5% by weight. When the content (W _MA ) of the matrix component in the transparent film is small, the proportion of the particles in the film is too large, and substantially the film in which the metal oxide fine particles in the film are dispersed throughout the entire region is not obtained. A membrane of the above function.

Even if the content of the hydrophilic matrix component (W _MA ) in the transparent film is too large, the amount of particles may be small, and the particles may have anti-reflection properties and antistatic properties due to their properties (low refractive index, conductivity, etc.). The situation.

The film thickness of the transparent film of the present invention varies depending on the application, but is preferably in the range of about 30 nm to 12 μm , more preferably in the range of 70 nm to 10 μm . When two or more functions are provided in one layer, it is necessary to have such a thickness.

When the film thickness of the transparent film is less than 30 nm, it is substantially difficult to form a transparent film which is separated into two layers, and the film thickness exceeds 12 μm , and cracks occur in the transparent film, or may be curled on a substrate such as plastic. (bending or warping).

The preferred aspect of the transparent film is as follows.

(1) When the upper portion is a low refractive index antireflection film or an antiglare film, and the lower portion is a hard coating film, a high refractive index film, a conductive film, or the like, the film thickness of the antireflection film portion is preferably 40 nm to 10 μ. m is more preferably in the range of 60 nm to 8 μm .

When the film of the anti-reflection film is thin, it becomes an optical film thickness that deviates from the Fresnel's principle, and sometimes sufficient anti-reflection performance cannot be obtained, and even if the anti-reflection film is too thick, the film shrinks, and the base is weak. The type of material is, for example, a thin PET film or the like, which sometimes causes curling.

At this time, the refractive index of the lower film is preferably in the range of 1.48 to 2.20, and the refractive index of the upper anti-reflecting film portion is preferably in the range of 1.45 or less.

In this case, the transparent film has low reflectivity and anti-glare property, and if the lower layer is a high refractive index film, it has high anti-reflection performance, and when the lower layer contains ruthenium pentoxide particles as the hydrophobic metal oxide fine particles (b) It has high hard coating properties and antistatic properties. It contains antistatic properties and heat ray shielding properties when it contains ATO or ITO particles. It contains UV absorbing properties when it contains titanium oxide.

(2) When used as a conductive film, the film thickness of the conductive film portion is in the range of 30 nm to 10 μm , more preferably in the range of 60 nm to 8 μm . When the film thickness of the conductive film portion is less than 30 nm, it is difficult to form another film which has been separated from each other in function, and there is a case where the conductivity is insufficient because a sufficient conductive path is not formed.

When the film thickness of the conductive film exceeds 10 μm , the shrinkage of the film becomes large, and if it is a plastic film having a thin substrate, curling may occur.

The surface resistivity of the transparent film having such a conductive film portion is preferably in the range of 10 ³ to 10 ¹³ Ω/□.

When the upper portion is a conductive film, in addition to the case of the above (1), the lower portion has a hard coat property even when no particles are present.

Further, when the lower portion contains titanium oxide particles as the hydrophobic metal oxide fine particles (B), it has ultraviolet absorbing properties, and when low refractive index fine particles are contained, it has low dielectric constant properties.

(3) When used as a high refractive index film, the film thickness of the high refractive index film portion is from 40 nm to 10 μm , more preferably from 60 nm to 8 μm .

When the film thickness of the high refractive index film portion is thin, it is difficult to form another film which has been separated from each other in function, and a layer having a desired refractive index may not be formed depending on the refractive index of particles or substrates having other functions. . When the film of the high refractive index film portion is thick, the shrinkage of the film becomes large, and when the substrate is a thin plastic film or the like, curling may occur.

At this time, the refractive index of the high refractive index film portion is preferably in the range of 1.52 to 2.00, and when the upper portion is the high refractive index film, even if there is no particle in the lower portion, it has hard coatability.

Further, when the lower portion contains ATO or ITO as the hydrophobic metal oxide fine particles (B), it has conductivity, antistatic property, and infrared shielding property; and if it contains ruthenium pentoxide or phosphorus-doped tin oxide, it has Antistatic properties, hard coating properties; such as low refractive index cerium oxide particles or hollow cerium oxide particles, etc., have high hard coating properties, low dielectric properties.

The substrate with a transparent film of the present invention can be produced by applying the above-mentioned coating material for forming a transparent film onto a substrate, drying and curing. The coating method is applied to a substrate by a known method such as a dipping method, a spray coating method, a spin coating method, a roll coating method, a bar coating method, a gravure printing method, or a micro gravure printing method, followed by drying, and thermosetting. In the case of the resin, it is heat-treated and then heat-treated. When the resin is cured by ultraviolet rays, it can be formed by irradiation with ultraviolet rays of about 400 mJ/cm ² to cure it.

Further, in the substrate having the transparent film of the present invention, another film different from the transparent film may be provided between the substrate and the transparent film and/or on the transparent film. The other film may be a conventionally known hard coat film, high refractive index film, conductive film, low refractive index film, antiglare film, infrared shielding film, ultraviolet shielding film, or transparent having the hard coating function of the present invention. A film, a transparent film having a high refractive index, a transparent film having conductivity, and the like.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples.

[Example 1] Modification of coating film for transparent film formation (A-1)

As the cerium oxide-based hollow fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: Sria (transliteration) 1420, average particle diameter: 60 nm, concentration: 20.5 wt%, dispersant: isopropyl alcohol, particle refractive index: 1.30) Low refractive index component. 10 g of perfluorooctylethyltriethoxydecane (100% by Aray 43-158E manufactured by Toray Dow Corning) was mixed with 100 g of the sol, and 10 g of ultrapure water was added thereto, and the mixture was stirred at 40 ° C for 5 hours to obtain a surface-treated second. The cerium oxide-based hollow fine particle-dispersed sol (solid content: 19.3% by weight).

After measuring the surface charge amount of this silicon dioxide-based hollow microparticle dispersion sol of the surface treated, and is 8.3 μ eq / g. 15.5 g of the surface-treated cerium oxide-based hollow fine particle-dispersing sol and 30 g of hexapentaerythritol tris(pentaacrylate) (Japan Chemical Co., Ltd.: KAYARD DPHA) and a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd.) A coating film for forming a transparent film (A-1) was prepared by thoroughly mixing the mixture with an IPA solution and a solid content of 10% by weight of 0.42 g and a 1/1 (by weight) mixed solvent of isopropyl alcohol and methyl isobutyl ketone. .

Modulation of substrate (1) with transparent film

The coating liquid for forming a transparent film (A-1) was applied to a PET film by a bar coater (thickness: 100 μm , refractive index: 1.65, substrate transmittance: 88.0%, haze: 1.0%, reflectance: 5.1%) After drying at 70 ° C for 1 minute, it was irradiated with a high-pressure mercury lamp (80 W/cm) for 1 minute to be hardened to prepare a substrate (1) having a transparent film. At this time, the film thickness of the transparent film 5 μ m. One portion of the transparent film was cut perpendicularly in the longitudinal direction, and the cross section was observed by a transmission electron microscope. Then, a layer having a thickness of the ceria-based hollow fine particles of 100 nm was formed on the upper portion, and only the matrix was present in the lower portion, and the presence of particles was not observed.

The surface resistivity, total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate (1) with a transparent film were measured. The results are shown in Table 1.

The surface resistance was measured by a surface resistance meter (Mitsubishi Olefin Co., Ltd.: LORESTA), and the total light transmittance and haze were measured by a haze meter (Nippon Denshoku Co., Ltd.: NDH2000), and the reflectance was measured. A spectrophotometer (manufactured by JASCO Corporation: Ubest-55) was used for the measurement.

Further, the anti-glare property, the adhesion, and the pencil hardness were evaluated according to the following methods and evaluation criteria, and the results are shown in Table 1.

[anti-glare]

The anti-glare property of the anti-reflective film substrate (1) with a hard-coating function was uniformly applied to the back surface of the substrate by black, and the fluorescent lamp was exposed to a light of 2 m from a 30 W fluorescent lamp to visually confirm the reflection of the fluorescent lamp. Anti-glare properties were evaluated on the following scales. The results are shown in Table 1.

Fluorescent light is not visible at all: ◎

Slightly see the fluorescent light: ○

Although you can see the fluorescent light, the outline is blurred: △

Obviously see the fluorescent lamp: ×

[adhesiveness]

On the surface of the anti-reflection film substrate (1) with a hard coating function, 11 parallel cuts were cut by a blade at intervals of 1 mm in length and width, and 100 grids were formed, and then the celluloid tape was attached.

Then, when the cellophane tape was peeled off, the number of the cells remaining without being peeled off by the film was classified into the following four stages, and the adhesion was evaluated. The results are shown in Table 1.

The number of remaining grids is 100: ◎

The number of remaining eyes is 90 to 99: ○

The number of remaining eyes is 85 to 89: △

The number of remaining eyes is 84 or less: ×

[pencil hardness]

The measurement was carried out by a pencil hardness tester in accordance with the standard of JIS-K-5400.

[Embodiment 2] Modification of coating film for transparent film formation (A-2)

As the cerium oxide-based hollow fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: Sria (transliteration) 1420, average particle diameter: 60 nm, concentration: 20.5 wt%, dispersant: isopropyl alcohol, particle refractive index: 1.30) Low refractive index component. To 100 g of the sol, 7.11 g of ethyl ortho-nonanoate (28.8% of ethyl phthalate 28 SiO ₂ component) was added, and 10 g of ultrapure water was added thereto, and the mixture was stirred at 40 ° C for 5 hours to obtain a surface-treated second. The cerium oxide-based hollow fine particle-dispersed sol (solid content: 19.3% by weight).

The surface charge amount of the surface-treated ceria-based hollow fine particle-dispersed sol was measured and found to be 18.3 μ eq/g. This surface-treated cerium oxide-based hollow fine particle-dispersed sol was 15.5 g, pentaerythritol triacetate (Kyoeisha Chemical Co., Ltd.: PE-3A), 24 g, and diethylaminoethyl methacrylate (total Rongshe Chemical Co., Ltd.: Light Ester DE) 3 g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid concentration 10%) 0.42 g and isopropanol and methyl isobutyl ketone The composite film for forming a transparent film (A-2) was prepared by thoroughly mixing the 1/1 (weight ratio) mixed solvent 54.08 g.

Modulation of substrate (2) with transparent film

The coating film for forming a transparent film (A-2) was applied to a PET film by a bar coater (thickness: 100 μm , refractive index: 1.65, substrate transmittance: 88.0%, haze: 1.0%, reflectance: 5.1%). After drying at 70 ° C for 1 minute, it was irradiated with a high pressure mercury lamp (80 W/cm) for 1 minute to be hardened to prepare a substrate (2) with a transparent film. The film thickness at this time was 5 μm . One part of the transparent film was cut perpendicularly in the longitudinal direction, and the cross section was observed by a transmission electron microscope, and it was found that a layer of ceria-based hollow fine particles having a thickness of 100 nm was formed on the upper portion, and only a matrix was formed in the lower portion, and no particles were observed. presence.

The surface resistance value, the total light transmittance, the haze, the reflectance of the light having a wavelength of 550 nm, the anti-glare property, the adhesion, and the pencil hardness of the obtained substrate (2) with the transparent film were measured, and the results were shown. In Table 1.

[Example 3] Modification of coating film for transparent film formation (A-3)

A cerium oxide-based hollow fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.): Sriah 1420-120, an average particle diameter of 120 nm, a concentration of 20.5 wt%, a dispersing agent: isopropyl alcohol, and a particle refractive index of 1.20 ) as a low refractive index component. To 100 g of the sol, 7.11 g of ethyl ortho-nonanoate (28.8% of ethyl phthalate 28 SiO ₂ component) was added, and 10 g of ultrapure water was added thereto, and the mixture was stirred at 40 ° C for 5 hours to obtain a surface-treated second. The cerium oxide-based hollow fine particle-dispersed sol (solid content: 19.3%).

The surface charge amount of this surface-treated ceria-based hollow fine particle-dispersed sol was measured and found to be 15.3 μ eq/g. 15.5 g of this surface-treated cerium oxide-based hollow fine particle-dispersed sol, perfluoroethyl acrylate (Kyoeisha Chemical Co., Ltd.: FA-108), 24 g, diethylaminoethyl methacrylate ( Gongrongshe Chemical Co., Ltd.: Light Ester DE) 3 g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid concentration: 10%) 0.42 g and isopropanol and methyl isobutyl 57.08 g of a 1/1 (by weight) mixed solvent of the ketone was sufficiently mixed to prepare a coating film (A-3) for forming a transparent film.

Modulation of substrate (3) with transparent film

The coating liquid for forming a transparent film (A-3) was applied to a PET film by a bar coater (thickness: 100 μm, refractive index: 1.65, substrate transmittance: 88.0%, haze: 1.0%, reflectance: 5.1%). After drying at 70 ° C for 1 minute, it was irradiated with a high pressure mercury lamp (80 W/cm) for 1 minute to be hardened to prepare a substrate (3) with a transparent film. The film thickness at this time was 5 μm . One portion of the transparent film was cut perpendicularly in the longitudinal direction, and the cross section was observed by a transmission electron microscope. It was found that a layer of ceria-based hollow fine particles having a thickness of 120 nm was formed on the upper portion, and only a matrix was formed in the lower portion, and no particles were observed. presence.

The surface resistance value, total light transmittance, haze, reflectance of light having a wavelength of 550 nm, anti-glare property, adhesion, and pencil hardness of the obtained substrate (3) with a transparent film were measured, and the results were shown. In Table 1.

[Example 4] Modification of coating film for transparent film formation (A-4)

As the conductive component, a ruthenium pentoxide fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: ELCOM V-4560, an average particle diameter of 20 nm, a concentration of 30.5 wt%, a dispersing agent: isopropyl alcohol, and a particle refractive index of 1.60) was used. Into 100 g of the sol, 1.88 g of γ-methylpropenyloxypropyltrimethoxydecane (81.2% of KBM-503 SiO ₂ component manufactured by Shin-Etsu Silicone Co., Ltd.) was added, and 10 g of ultrapure water was added thereto, and the mixture was stirred at 40 ° C for 5 hours. A surface treated pentoxide pentoxide fine particle sol (solid fraction 28.6%) was obtained.

The surface charge amount of this surface-treated pentoxide pentoxide fine particle sol was measured and found to be 45.3 μ eq/g. The surface-treated cerium oxide microparticles dispersed sol 17.48 g, dierythritol triacetate (Kyoeisha Chemical Co., Ltd.: DPE-6A) 22.5 g, hydroxy-containing acrylate (Kyoeisha Chemical Co., Ltd.) (Unit): MMH-40 propylene glycol monomethyl ether dispersion solid fraction 40%) 6.25 g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid concentration 10%) 0.42 g and isopropanol 53.35 g of a mixed solvent of 1/1 (weight ratio) of methyl isobutyl ketone was sufficiently mixed to prepare a coating material (A-4) for forming a transparent film.

Modulation of anti-reflection forming coating liquid (A-4R)

As the cerium oxide-based hollow fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: Sria (transliteration) 1420, average particle diameter: 60 nm, concentration: 20.5 wt%, dispersant: isopropyl alcohol, particle refractive index: 1.30) Low refractive index component. The sol was diluted with isopropanol to a solid content of 5% by weight of a dispersion of 33 g and an ultraviolet curable resin (manufactured by Dainippon Ink (Unisex): Unidic 17-824-9, solid concentration: 78.9%), light-emitting Starting agent (Cure 184, manufactured by Chiba Specialty Co., Ltd., dissolved in IPA, solid concentration: 10%), 0.42 g, and 65.46 g of a mixed solvent of isopropyl alcohol and butyl cellosolve in a ratio of 1/1 (by weight) were prepared to sufficiently react. A coating material for forming a reflective film (A-4R).

Modulation of substrate (4-1) with transparent film

The coating film for forming a transparent film (A-4) was applied to a PET film by a bar coater (thickness: 100 μm , refractive index: 1.65, substrate transmittance: 88.0%, haze: 1.0%, reflectance: 5.1%). After drying at 70 ° C for 1 minute, it was irradiated with a high pressure mercury lamp (80 W/cm) for 1 minute to be hardened to prepare a substrate (4-1) having a transparent film. The film thickness at this time was 5 μm . One of the transparent films was cut perpendicularly in the longitudinal direction, and the cross section was observed by a transmission electron microscope. It was found that a layer having a thickness of 150 nm of pentoxide particles was formed on the upper portion, and only the matrix was present in the lower portion, and the presence of particles was not observed.

The surface resistance value, the total light transmittance, the haze, the reflectance of the light having a wavelength of 550 nm, the anti-glare property, the adhesion, and the pencil hardness of the obtained substrate (4-1) with a transparent film were measured. The results are shown in Table 1.

Modulation of substrate (4-2) with transparent film

Then, the anti-reflective film-forming coating material (A-4R) was applied to a substrate (4-1) having a transparent film by a bar coater, and dried at 70 ° C for 1 minute, and then irradiated with a high-pressure mercury lamp (80 W/cm). ) hardened in 1 minute to prepare a substrate (4-2) to which a transparent film was attached. The film thickness of the antireflection film at this time was 100 nm.

The surface resistance value, the total light transmittance, the haze, the reflectance of the light having a wavelength of 550 nm, the anti-glare property, the adhesion, and the pencil hardness of the obtained substrate (4-2) with a transparent film were measured. The results are shown in Table 1.

[Example 5] Modification of coating film for transparent film formation (A-5)

As the high refractive index particles, a titanium oxide fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: OPTLAK 1137Z, an average particle diameter of 20 nm, a concentration of 30.5 wt%, a dispersing agent: methanol, and a particle refractive index of 2.10) was used. Into 100 g of sol, 1.86 g of γ-acryloxypropyltrimethoxydecane (81.9% of KBM-503 SiO ₂ component manufactured by Shin-Etsu Silicone Co., Ltd.) was added, and 10 g of ultrapure water was added thereto, and the mixture was stirred at 40 ° C for 5 hours to obtain a The surface treated titanium oxide fine particle dispersed sol (solid content 28.6%). After the measurement of this surface charge amount of surface treated particulate titanium oxide-dispersed sol, it is 19.5 μ eq / g.

The surface-treated titanium oxide fine particles dispersed sol 17.48 g, dierythritol triacetate (Kyoeisha Chemical Co., Ltd.: DPE-6A) 22.5 g, hydroxy-containing acrylate (Kyoeisha Chemical ( Share): MMH-40 propylene glycol monomethyl ether dispersion solid fraction 40%) 6.25g, photoinitiator (Irgacure 184 made by Ciba Specialty, dissolved in IPA, solid concentration 10%) 0.42g and isopropanol Methyl isobutyl ketone 1/1 (by weight) mixed solvent 53.35g for charging The coating material for transparent film formation (A-5) was prepared by mixing.

Modulation of substrate (5-1) with transparent film

The coating film for forming a transparent film (A-5) was applied to a PET film (100 μm thick, refractive index 1.65, substrate transmittance: 88.0%, haze 1.0%, and reflectance: 5.1%) by a bar coater. After drying at 70 ° C for 1 minute, it was irradiated with a high pressure mercury lamp (80 W/cm) for 1 minute to be hardened to prepare a substrate (5) with a transparent film. The film thickness at this time was 5 μm . One of the transparent films was cut perpendicularly in the longitudinal direction, and the cross section was observed by a transmission electron microscope. It was found that a layer having a thickness of 80 nm of titanium oxide fine particles was formed on the upper portion, and only the matrix was present in the lower portion, and the presence of particles was not observed.

The surface resistance value, the total light transmittance, the haze, the reflectance of the light having a wavelength of 550 nm, the anti-glare property, the adhesion, and the pencil hardness of the obtained substrate (5-1) with a transparent film were measured. The results are shown in Table 1.

Modulation of substrate (5-2) with transparent film

Then, the antireflection-forming coating material (A-4R) prepared in the same manner as in Example 4 was applied to a substrate (5-1) having a transparent film by a bar coater, and dried at 70 ° C for 1 minute. The high-pressure mercury lamp (80 W/cm) was irradiated for 1 minute to be hardened to prepare a substrate (5-2) to which a transparent film was attached. The film thickness of the antireflection film at this time was 100 nm.

The surface resistance value, the total light transmittance, the haze, the reflectance of the light having a wavelength of 550 nm, the anti-glare property, the adhesion, and the pencil hardness of the obtained substrate (5-2) having the transparent film were measured. The results are shown in Table 1.

[Embodiment 6] Modification of coating film for transparent film formation (A-6)

As the cerium oxide-based hollow fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: Sria (transliteration) 1420, average particle diameter: 60 nm, concentration: 20.5 wt%, dispersant: isopropyl alcohol, particle refractive index: 1.30) Low refractive index component. 10 g of perfluorooctylethyltriethoxydecane (100% by Aray 43-158E manufactured by Toray Dow Corning) was mixed with 100 g of sol, and 10 g of ultrapure water was added thereto, and the mixture was stirred at 40 ° C for 5 hours to obtain a surface-treated oxidizing agent. The lanthanide hollow fine particle dispersion sol (solid content 19.3 wt%). After measuring the surface charge amount of this silicon dioxide-based hollow microparticle dispersion sol of the surface treated, and is 8.3 μ eq / g. The ATO fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: ELCOM V-3501, average particle diameter: 8 nm, concentration: 19.3% by weight, dispersant: ethanol, particle refractive index: 1.75) was used as an antistatic high refractive index component. To 100 g of the sol, 1.26 g of γ-acryloxypropyltrimethoxydecane (81.2% of KBM-5103 SiO ₂ component manufactured by Shin-Etsu Silicone Co., Ltd.) was added, and 10 g of ultrapure water was added thereto, and the mixture was stirred at 40 ° C for 5 hours to obtain Surface treated ATO microparticle dispersion sol (solids 19.3%). The surface charge amount of this surface-treated ATO fine particle-dispersed sol was measured and found to be 35.8 μeq/g. 15.5 g of the surface-treated cerium oxide-based hollow fine particle-dispersing sol, 31.3 g of the surface-treated ATO fine particle-dispersing sol, and erythritol tris(pentaacrylate) (Nippon Chemical Co., Ltd.: KAYARD DPHA) 27 g With a photoinitiator (Irgacure 184, manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid concentration: 10%), 0.35 g, and 1/1 (by weight) mixed solvent of isopropanol and methyl isobutyl ketone 26.05 g The coating film for forming a transparent film (A-6) was prepared by thoroughly mixing.

Modulation of substrate (6) with transparent film

The coating film for forming a transparent film (A-6) was applied to a TAC film by a bar coater (thickness: 80 μm , refractive index: 1.48, substrate transmittance: 88.0%, haze: 0.0%, reflectance: 4.8%). After drying at 70 ° C for 1 minute, it was irradiated with a high pressure mercury lamp (80 W/cm) for 1 minute to be hardened to prepare a substrate (6) with a transparent film. The film thickness at this time was 5 μm . One part of the transparent film was cut perpendicularly in the longitudinal direction, and the cross section was observed by a transmission electron microscope, and it was found that a layer having a thickness of 100 nm of titanium oxide fine particles was formed on the upper portion, and the lower ATO fine particles were in the form shown in FIG. Present in the matrix.

The surface resistance value, the total light transmittance, the haze, the reflectance of the light having a wavelength of 550 nm, the anti-glare property, the adhesion, and the pencil hardness of the obtained substrate (6) with a transparent film were measured, and the results were shown. In Table 1.

[Embodiment 7] Modification of coating film for transparent film formation (A-7)

As the cerium oxide-based hollow fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: Sria (transliteration) 1420, average particle diameter: 60 nm, concentration: 20.5 wt%, dispersant: isopropyl alcohol, particle refractive index: 1.30) Low refractive index component. 10 g of tridecyl methacrylate (Light Ester TD, manufactured by Kyoeisha Chemical Co., Ltd.) was mixed with 100 g of the sol, and stirred at 50 ° C for 24 hours to obtain a surface-treated cerium oxide hollow fine particle dispersion sol (solid form) 27.7%). After measuring the surface charge amount of this silicon dioxide-based hollow microparticle dispersion sol of the surface treated, and is 5.3 μ eq / g. The ruthenium pentoxide fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: ELCOM V-4560, average particle diameter: 20 nm, concentration: 30.5 wt%, dispersant: isopropanol, particle refractive index: 1.60) was used as an antistatic high refractive index. ingredient. Γ-glycidoxypropyltrimethoxydecane 1.44 g (86.8% of AY43-026 SiO ₂ component manufactured by Toray Dow Corning) was mixed with 100 g of the sol diluted with isopropanol to 100%, and 10 g of ultrapure water was added. The mixture was stirred at 40 ° C for 5 hours to obtain a surface-treated cerium oxide microparticle-dispersed sol (solid content: 19.5%). The surface charge amount of this surface-treated pentoxide pentoxide fine particle sol was measured and found to be 35.3 μ eq/g.

10.8 g of the surface-treated cerium oxide-based hollow fine particle-dispersing sol, 30 g of the surface-treated ATO fine particle-dispersing sol, and hexaerythritol tris(pentaacrylate) (Nippon Chemical Co., Ltd.: KAYARAD DPHA) 27 g 0.39 g with a photoinitiator (Irgacure 184, manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid concentration: 10%) and 1/1 (by weight) mixed solvent of isopropyl alcohol and methyl isobutyl ketone 31.9 g The coating film for forming a transparent film (A-7) was prepared by thoroughly mixing.

Modulation of substrate (7) with transparent film

The coating film for forming a transparent film (A-7) was applied to a PET film (100 μm thick, refractive index: 1.65, substrate transmittance: 88.0%, haze 1.0%, reflectance: 5.1%) by a bar coater. After drying at 70 ° C for 1 minute, it was irradiated with a high pressure mercury lamp (80 W/cm) for 1 minute to be hardened to prepare a substrate (7) with a transparent film. The film thickness at this time was 5 μm . One part of the transparent film was cut perpendicularly in the longitudinal direction, and the cross section was observed by a transmission electron microscope, and it was found that a layer having a thickness of 100 nm in the upper portion of the ceria hollow fine particles was formed, and the lower part was a layer of ruthenium pentoxide particles. The morphology shown is present in the matrix.

The surface resistance value, the total light transmittance, the haze, the reflectance of the light having a wavelength of 550 nm, the anti-glare property, the adhesion, and the pencil hardness of the obtained substrate (7) with a transparent film were measured, and the results were shown. In Table 1.

[Comparative Example 1] Modification of coating film for transparent film formation (R-1)

As the cerium oxide-based hollow fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: Sria (transliteration) 1420, average particle diameter: 60 nm, concentration: 20.5 wt%, dispersant: isopropyl alcohol, particle refractive index: 1.30) Low refractive index component. Into 100 g of the sol, 32.69 g of vinyl decane (62.7% of KBE-1003 SiO ₂ component manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and 10 g of ultrapure water was added thereto, and the mixture was stirred at 40 ° C for 5 hours to obtain surface-treated cerium oxide hollow particles. Dispersed sol (solids 28.4%). The surface charge amount of this surface-treated ceria-based hollow fine particle-dispersed sol was measured and found to be 3.3 μ eq/g. 10.54 g of this surface-treated cerium oxide-based hollow fine particle-dispersed sol, pentaerythritol triacetate (Kyoeisha Chemical Co., Ltd.: PE-3A), 24 g, diethylaminoethyl methacrylate (total Rongshe Chemical Co., Ltd.: Light Ester DE) 3g, photoinitiator (Irgacure 184 made by Ciba Specialty, dissolved in IPA, solid concentration 10%) 0.42g and isopropanol and methyl isobutyl ketone The composite film for forming a transparent film (R-1) was prepared by sufficiently mixing 62.04 g of a 1/1 (weight ratio) mixed solvent.

Modulation of substrate (R-1) with transparent film

The coating film for forming a transparent film (R-1) was applied to a PET film by a bar coater (thickness: 100 μm , refractive index: 1.65, substrate transmittance: 88.0%, haze: 1.0%, reflectance: 5.1%). After drying at 70 ° C for 1 minute, it was irradiated with a high pressure mercury lamp (80 W/cm) for 1 minute to be hardened to prepare a substrate (R-1) having a transparent film. The film thickness at this time was 5 μm . One of the transparent films was cut perpendicularly in the longitudinal direction, and the cross section was observed by a transmission electron microscope, and it was found that the ceria-based hollow fine particles were uniformly dispersed in the film. The surface resistance value, the total light transmittance, the haze, the reflectance of the light having a wavelength of 550 nm, the anti-glare property, the adhesion, and the pencil hardness of the obtained substrate (R-1) having the transparent film were measured. Shown in Table 1.

[Comparative Example 2] Modification of coating film for transparent film formation (R-2)

As the conductive component, a ruthenium pentoxide fine particle dispersion sol (manufactured by Catalyst Chemical Co., Ltd.: ELCOM V-4560, an average particle diameter of 20 nm, a concentration of 30.5 wt%, a dispersing agent: isopropyl alcohol, and a particle refractive index of 1.60) was used. Into 100 g of this sol, 37.57 g of γ-methylpropenyloxypropyltrimethoxydecane (81.2% of KBM-503 SiO ₂ component manufactured by Shin-Etsu Silicone Co., Ltd.) was mixed, and 10 g of ultrapure water was added thereto, and the mixture was stirred at 40 ° C for 5 hours. A surface treated pentoxide pentoxide fine particle sol (solid fraction 42.1%) was obtained. This surface treatment was measured after the surface charge amount of an antimony pentoxide sol particle dispersion, is 5.5 μ eq / g. The surface-treated cerium oxide microparticles dispersed sol 11.88 g, dierythritol triacetate (Kyoeisha Chemical Co., Ltd.: DPE-6A) 22.5 g, hydroxy-containing acrylate (Kyoeisha Chemical Co., Ltd.) (Unit): MMH-40 propylene glycol monomethyl ether dispersion solid fraction 40%) 6.25 g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid concentration 10%) 0.42 g and isopropanol 58.95 g of a mixed solvent of 1/1 (weight ratio) of methyl isobutyl ketone was thoroughly mixed to prepare a coating material for transparent film formation (R-2).

Modulation of substrate (R-2-1) with transparent film

The coating film for forming a transparent film (R-2) was applied to a PET film by a bar coater (thickness: 100 μm, refractive index: 1.65, substrate transmittance: 88.0%, haze: 1.0%, reflectance: 5.1%) at 70 ° C. After drying for 1 minute, the high pressure mercury lamp (80 W/cm) was irradiated for 1 minute to be hardened to prepare a substrate (R-2-1) having a transparent film. The film thickness at this time was 5 μm . One of the transparent films was cut perpendicularly in the longitudinal direction, and after observing the cross section by a transmission electron microscope, it was found that the ruthenium pentoxide particles were uniformly dispersed in the film.

The surface resistance value, total light transmittance, haze, reflectance of light having a wavelength of 550 nm, anti-glare property, adhesion, pencil hardness of the obtained substrate (R-2-1) with a transparent film were measured. The results are shown in Table 1.

Modulation of substrate (R-2-2) with transparent film

Then, in the same manner as in the examples, the antireflection-forming coating material (A-4R) was applied to a substrate (R-2-1) having a transparent film by a bar coater, and dried at 70 ° C for 1 minute. The high pressure mercury lamp (80 W/cm) was irradiated for 1 minute to be hardened to prepare a substrate (R-2-2) having a transparent film. The film thickness at this time was 100 nm.

The surface resistance value, total light transmittance, haze, reflectance of light having a wavelength of 550 nm, anti-glare property, adhesion, pencil hardness of the obtained substrate (R-2-2) with a transparent film were measured. The results are shown in Table 1.

[Comparative Example 3] Modulation of substrate (R-3) with transparent film

The antireflection film-forming coating material (A-4R) prepared in the same manner as in Example 4 was applied to a PET film by a bar coater (thickness: 100 μm , refractive index: 1.65, substrate transmittance: 88.0%, haze) 1.0%, reflectance 5.1%), after drying at 70 ° C for 1 minute, the high pressure mercury lamp (80 W/cm) was irradiated for 1 minute to be hardened to prepare a substrate (R-3) having an antireflection film. The film thickness at this time was 100 μm . One of the transparent films was cut perpendicularly in the longitudinal direction, and the cross section was observed by a transmission electron microscope, and it was found that the ceria-based hollow fine particles were uniformly dispersed in the film.

The surface resistance value, the total light transmittance, the haze, the reflectance of the light having a wavelength of 550 nm, the anti-glare property, the adhesion, and the pencil hardness of the obtained substrate (R-3) with an anti-reflection film were measured. The results are shown in Table 1.

Fig. 1 is a schematic view showing the unevenness of the hydrophobic metal oxide fine particles (a) in the transparent film.

Fig. 2 is a schematic view showing the unevenness of the hydrophobic metal oxide fine particles (a) and the hydrophilic metal oxide fine particles (b) in the transparent film.

Fig. 3 is a schematic view showing the unevenness of the hydrophobic metal oxide fine particles (a) and the hydrophilic metal oxide fine particles (b) in the transparent film.

Fig. 4 is a schematic view showing the unevenness of the hydrophobic metal oxide fine particles (a) and the hydrophilic metal oxide fine particles (b) in the transparent film.

Claims (10)

A coating material for forming a transparent film, comprising: (A) a metal oxide fine particle (a) having an organic ruthenium compound represented by the following formula (1) and/or a polyfunctional acrylate having a hydrophobic functional group; Surface treatment of the resin, and the surface charge amount (Q _A ) is in the range of 5 to 80 μ eq/g; R _n -SiX _4-n (1) (wherein R is an unsubstituted or substituted carbon number of 1 to 10) a hydrocarbon group which may be the same or different from each other; X: an alkoxy group having 1 to 4 carbon atoms, a stanol group, a halogen, a hydrogen, n: an integer of 0 to 3) (B) a matrix-forming component comprising the following formula (2) the organic silicon compound or hydrolyzate of such hydrolysis polycondensation product and / or hydrophobic matrix forming component having the configuration of many hydrophobic functional group-functional (meth) acrylate resin; R _{n '} -SiX _4-n' (2) (wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms which may be the same or different from each other; X: an alkoxy group having 1 to 4 carbon atoms, a decyl alcohol group , halogen, hydrogen, n': an integer from 1 to 3) (C) polar solvent; (D) metal oxide fine particles (b), surface charge amount (Q _B ) of metal oxide fine particles (b) and metal oxidation Surface charge amount of particle (a) (Q _A The difference (Q _B )-(Q _A ) is in the range of 20 to 95 μ eq/g, and the surface charge amount (Q _B ) thereof is in the range of 25 to 100 μ eq/g; characterized by: as a metal oxide The concentration (C _PA ) of the solid content of the fine particles (a) is in the range of 0.1 to 20% by weight, and the concentration (C _M ) of the solid content as the matrix-forming component (B) is in the range of 1 to 50% by weight. The coating material for forming a transparent film according to the first aspect of the invention, wherein the matrix-forming component contains a hydrophobic matrix, and is hydrolyzed and condensed by an organic hydrazine compound represented by the following formula (3) or a hydrolyzate thereof. or having a hydrophilic functional group as many functional (meth) matrix composed of a hydrophilic acrylate resin component; SiX ₄ (3) (in the formula, X: an alkoxy group having 1 to 4 carbon atoms, an alkanol group silicon concentration (C _MA), halogen, hydrogen) form a solid component of the points as the hydrophilic matrix and the concentration (C _MB) of forming the solid component of the points as the hydrophobic matrix concentration ratio _{(C MA) / (C MB} ) 0.01 To the range of 1. The coating material for forming a transparent film according to the first or second aspect of the invention, wherein the metal oxide fine particles (a) have an average particle diameter of 5 to 500 nm. The coating material for forming a transparent film according to the first or second aspect of the invention, wherein the concentration (C _PB ) of the solid content of the metal oxide fine particles (b) is in the range of 0.1 to 20% by weight. The coating material for forming a transparent film according to claim 1 or 2, wherein the metal oxide fine particles (b) have an average particle diameter of 5 to 500 nm. The coating material for forming a transparent film according to the first or second aspect of the invention, wherein the hydrophilic functional group is at least one selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, a sulfo group, and a glycidyl group, and the hydrophobic functional group is used. The group is one or more selected from the group consisting of a (meth) acrylonitrile group, an alkyl group, a phenyl group, a urethane group, and a CF ₂ group. A substrate with a transparent film attached to a substrate to form a transparent film with a transparent film, wherein the transparent film is hydrophobic with a surface charge amount (Q _A ) in the range of 5 to 80 μeq/g. Metal oxide fine particles (a), metal oxide fine particles (b) having a surface charge amount (Q _B ) in the range of 25 to 100 μ eq/g, and matrix components; metal oxide fine particles (a) are partially transparent A layer is formed on the upper portion of the film, and the content (W _PA ) of the metal oxide fine particles (a) in the transparent film is in the range of 0.2 to 90% by weight; the surface charge amount (Q _B ) of the metal oxide fine particles (b) and the metal oxide The difference (Q _B )-(Q _A ) between the surface charge amounts (Q _A ) of the particles (a) is in the range of 20 to 95 μ eq/g; the content of the matrix component (W _M ) is from 10 to 99.8% by weight. The matrix component is selected from the group consisting of a hydrolyzed polycondensate of an organic hydrazine compound represented by the following formula (4) and/or a hydrophobic matrix component R _{n of a} polyfunctional (meth) acrylate resin having a hydrophobic functional group. -SiX _4-n (4) (wherein R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms which may be the same or different from each other; X: an alkoxy group having 1 to 4 carbon atoms, a stanol group, Halogen, hydrogen, n: an integer of 0 to 3); the metal oxide fine particles (b) are deposited on a layer formed on the surface of the substrate, or dispersed in a layer and a substrate composed of the aforementioned metal oxide fine particles (a) Made between the surfaces. The substrate having a transparent film according to the seventh aspect of the invention, wherein the matrix component is composed of a hydrophobic matrix component and a hydrophilic matrix component, and the hydrophilic matrix component is represented by the following formula (3). Hydrolyzed polycondensate of an organic hydrazine compound and/or polyfunctional (meth) acrylate resin having a hydrophilic functional group; SiX ₄ (3) (wherein X: alkoxy group having 1 to 4 carbon atoms, stanol The ratio of the content of the solid component (W _MA ) as the hydrophilic matrix component to the content of the solid component (W _MB ) as the hydrophobic matrix component (W _MA ) / (W _MB ) is 0.01 to The scope of 1. The substrate with a transparent film according to Item 7 or Item 8 of the patent application, wherein the metal oxide fine particles (a) have an average particle diameter in the range of 5 to 500 nm, and the metal oxide fine particles (b) The average particle diameter is in the range of 5 to 500 nm. The substrate having a transparent film, wherein the hydrophilic functional group is one or more selected from the group consisting of a hydroxyl group, an amine group, a carboxyl group, and a sulfo group, and the hydrophobic functional group is the same. The group is one or more selected from the group consisting of a (meth) acrylonitrile group, an alkyl group, a phenyl group, a urethane group, and a CF ₂ group.