JP5281241B2 - Base material with transparent colored film and coating liquid for forming transparent colored film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a base with a transparent colored film featuring high adhesion with a base, mar resistance, degree of film hardness, etc. and also, outstanding smoothness of film surface, light resistance, contrast, display performance, etc. <P>SOLUTION: The base with a transparent colored film is composed of a base and a transparent colored film formed on one surface or both surfaces of the base. The transparent colored film contains a matrix component, a pigment particle covered with an inorganic oxide or a resin as a colorant and/or a metallic fine particle. The colorant content of the colored film ranges from 0.1 to 50 wt.%. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention is excellent in adhesion to a substrate, scratch resistance, film hardness, etc., and also has a transparent colored film substrate having excellent film surface smoothness, light resistance, contrast, display performance, and the like, and the transparency The present invention relates to a coating solution for forming a transparent colored film having excellent stability, which can be suitably used for forming a colored film.

  In order to prevent reflection on the surface of a substrate such as glass, plastic sheet, plastic lens, and various display devices, it is known to form an antireflection film on the surface. For example, a coating of a low refractive index material such as fluororesin or magnesium fluoride is formed on the surface of a glass or plastic substrate by a coating method, a vapor deposition method, a CVD method or the like, or a low refractive index fine particle such as a silica fine particle. There has been known a method of forming an antireflection coating by applying a coating solution containing a liquid to a substrate surface (for example, see JP-A-7-133105). Further, in order to impart antistatic performance and electromagnetic wave shielding performance to the base material, a conductive film containing metal fine particles and conductive oxide fine particles is also formed.

  Even when such an antireflection film or conductive film is provided, a hard coat film may be formed between the substrate and the antireflection film and / or the conductive film in order to improve the scratch resistance. ing.

Further, when a filter is provided on the outer surface of the display device to improve the contrast, a glass film is used. In order to give a desired filter characteristic, the glass film made of metal alkoxide has an average particle diameter of 3 to 300 nm. The inclusion of a dye is disclosed. (Japanese Patent Laid-Open No. 05-178623)
Japanese Patent Application Laid-Open No. 2005-181952 uses a colored film in which an appropriate amount of a dye or a pigment is added to a protective film that can be provided on a polarizing plate in order to make a liquid crystal display device with high contrast and high display quality. Is disclosed.

However, a conventional colored film has no affinity with a matrix component (sometimes referred to as a binder component) depending on a coloring agent such as a pigment (dye) or a pigment or metal fine particles, and dispersibility is insufficient. Transparency and haze are not always satisfactory, and contrast is not satisfactory. In addition, adhesion to the substrate or other coatings that may be provided simultaneously, scratch resistance, film strength, etc. are not always sufficient. That wasn't true. Moreover, there was a problem that the light resistance was insufficient and the coloration faded over time.
JP-A-7-133105 JP 05-178623 A JP 2005-181952 A

  The present invention is excellent in adhesion to a substrate, scratch resistance, hardness and the like, and has transparency, and has a transparent colored film substrate having smoothness, light resistance, and contrast on the film surface, and the transparency It aims at providing the coating liquid for transparent colored film formation for forming a colored film.

As a result of intensive studies to solve the above-mentioned problems, the present inventors are excellent in adhesion to the substrate, scratch resistance, film hardness, etc. by coating the colorant particles with an inorganic oxide or resin, and The present invention has been completed by finding that a colored film having transparency and excellent light resistance and contrast can be formed.
[1] consisting of a base material and a transparent colored film formed on one or both sides of the base material,
The transparent colored film comprises a matrix component and pigment particles and / or metal fine particles coated with an inorganic oxide or resin as a colorant, and the content of the colorant in the colored film is 0.1. A substrate with a transparent colored film, characterized by being in the range of ˜50% by weight.
[2] The transparent colored film-coated substrate according to [1], wherein the colorant is 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 or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
[3] The substrate with a transparent colored film according to [1] or [2], wherein the colorant is surface-treated with an organosilicon compound represented by the following formula (2).
X-R-Si (OR) ₃ (2)
(In the formula, R represents an organic group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group. X represents a γ-glycidoxy group or a (meth) acryloyl group.)
[4] The substrate with a transparent colored film according to [1] to [3], wherein the transparent colored film further contains a dye as a colorant.
[5] The transparent colored film is
The light transmittance (I) at least at a wavelength of 560 to 620 nm is 40 to 98%, or the light transmittance (II) at a wavelength of 450 to 500 nm is in the range of 40 to 98%. A substrate with a transparent colored film.
[6] The transparent colored film-coated substrate according to [1] to [5], which is further provided with another coating of the transparent colored film.
[7] A matrix-forming component and pigment particles and / or metal fine particles coated with an inorganic oxide or a resin as a colorant, and the total concentration of the matrix-forming component and the colorant is 0. A coating solution for forming a transparent colored film which is in the range of 5 to 60% by weight and contains the colorant in the transparent colored film so that the solid content is 0.1 to 50% by weight.
[8] The coating solution for forming a transparent colored film according to [7], wherein the colorant is 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 or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
[9] The coating solution for forming a transparent colored film according to [7] or [8], wherein the colorant is further surface-treated with an organosilicon compound represented by the following formula (2):
X-R-Si (OR) ₃ (2)
(In the formula, R represents an organic group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group. X- represents a γ-glycidoxy group or a (meth) acryloyl group.)
[10] The coating solution for forming a transparent colored film according to [7] to [9], further comprising a dye as a colorant.

According to the present invention, pigment particles coated with an inorganic oxide or a resin that absorbs in the wavelength range of 560 to 620 nm or the wavelength range of 450 to 500 nm, where the emission spectrum of RGB tends to overlap as a colorant on the transparent colored film, and / or Because it contains fine metal particles, and if necessary, pigment particles and / or fine metal particles that have been surface-treated with a specific organosilicon compound, the colorant is uniformly dispersed in the transparent colored film. With low light transmittance, high light transmittance in other wavelength regions, excellent adhesion to the substrate, scratch resistance, hardness, etc. and transparency, film surface smoothness, light resistance, A substrate with a transparent colored film having excellent contrast and a coating liquid for forming a transparent colored film for forming the transparent colored film can be provided.

  In addition, since the transparent colored film-coated substrate has high transmission definition and excellent contrast, it can be suitably used for a display device or the like.

Hereinafter, the transparent colored film-coated substrate according to the present invention will be described.
The base material with a transparent colored film The base material with a transparent colored film according to the present invention comprises a base material and a transparent colored film formed on one or both surfaces of the base material.

Substrate As the substrate used in the present invention, known materials can be used without particular limitation, and glass, polycarbonate, acrylic resin, PET, TAC, cyclopoleolefin, norbornene and other plastic sheets, plastic films Etc., and plastic panels. Among these, a resin-based substrate can be preferably used.
Transparent colored film The transparent colored film contains a matrix component and pigment particles and / or metal fine particles coated with an inorganic oxide or resin as a colorant.
(i) Matrix component As the matrix component, a conventionally known matrix component can be used, and a resin matrix is preferable.

  As such a resin matrix, any of known thermosetting resins, thermoplastic resins, ultraviolet curing and the like as coating resins can be employed. Specifically, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubber and other thermoplastic resins, urethane resins, melamines Resins, butyral resins, silicone resins, phenol resins, epoxy resins, unsaturated polyester resins and the like can be mentioned. Further, it may be a copolymer or modified body of two or more of these resins.

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 curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.
(ii) Colorant As the colorant used in the present invention, a conventionally known pigment, or a metal fine particle coated with an inorganic oxide or resin is used. Examples of the pigment include inorganic materials such as titanium white, bengara, yellow lead, and cobalt blue. Pigments, azo yellow pigments (benzidine yellow, carmine FB, etc.), red pigments, condensation pigments (perylene, perinone, dioxazine, thioindigo, isoindolinone, quinophthalone, quinacrobone, quinacridone, etc.), phthalocyanine pigments (phthalocyanine blue, etc.), etc. Is mentioned.

Such pigments preferably have an average particle size in the range of 5 to 500 nm, more preferably 10 to 200 nm.
It is difficult to obtain a pigment having a small average particle diameter, and even if it is obtained, the stability becomes insufficient when used in a coating solution, and the resulting transparent colored film has good adhesion and resistance to the substrate. Abrasion, hardness and transparency may be insufficient. If the average particle diameter of the pigment is too large, irregularities are generated on the surface of the film and light is scattered, and light is also scattered inside, and transparency (sometimes referred to as transmission sharpness) may be lowered. When the particle diameter of the pigment exceeds 500 nm, the particle diameter may be adjusted to the above range by pulverization or the like.

  As the metal fine particles, particles having characteristic absorption in the visible light region are preferably used. Specific examples include metal fine particles such as Ag, Au, Pd, Pt, Ru, Cu, and Nd, and alloy fine particles containing these. .

  The metal fine particles preferably have an average particle diameter in the range of 1 to 200 nm, more preferably 2 to 100 nm. It is difficult to obtain metal fine particles having an average particle size smaller than the lower limit, and even if it is obtained, the stability of the substrate is insufficient when used in a coating solution, and the resulting transparent colored film substrate is obtained. Adhesion, scratch resistance, hardness and transparency may be insufficient. Even if the average particle diameter of the metal fine particles is too large, light scattering may occur on the surface and inside of the film, and the transmission line brightness may decrease.

Such pigments and metal fine particles are coated with an inorganic oxide or resin.
As the inorganic _{oxide, SiO 2, TiO 2, ZrO} 2, SnO 2, CeO 2, ZnO 2, Fe 2 O 5 , and mixtures or composite oxides thereof.

  Also, as the resin, polyester resin, polycarbonate resin, polyamide resin, polyphenylene oxide resin, acrylic resin, vinyl chloride resin, fluororesin, vinyl acetate resin, silicone rubber and other thermoplastic resins, urethane resin, melamine resin, butyral resin, Silicone resin, phenol resin, epoxy resin, unsaturated polyester resin and the like can be mentioned.

  The amount of the inorganic oxide or resin covering the pigment and the metal fine particles is preferably in the range of 1 to 100% by weight, more preferably 5 to 50% by weight as a solid content with respect to the pigment and the metal fine particles.

  When the amount of the inorganic oxide or resin to be coated is small, the effect of improving the stability is insufficient, and when used in the coating liquid, the dispersibility and stability are low, which may cause agglomeration. The adhesion of the colored film to the substrate, scratch resistance, hardness and transparency may be insufficient.

  Even if the amount of the inorganic oxide or resin to be coated is too large, the dispersibility and stability are not further improved, and thus the adhesion of the transparent colored film obtained to the base material, scratch resistance, hardness and Transparency is not further improved.

  The method for coating the pigment or the metal fine particle with the inorganic oxide is not particularly limited as long as the surface of the pigment or the metal fine particle can be coated with the inorganic oxide, and a conventionally known method can be adopted.

  For example, when a pigment is coated with an inorganic oxide, a predetermined amount of a metal salt aqueous solution or a mixed metal salt aqueous solution to be used as a precursor of the inorganic oxide is added to the pigment particle dispersion, followed by hydrolysis and precipitation. Accordingly, it can be coated by aging, washing, drying, firing, and the like.

  In addition, when the pigment is coated with silica, in addition to the above method, a silica solution obtained by dealkalizing alkali silicate is added to the pigment particle dispersion, and aging, washing, drying, firing, etc. are performed as necessary. Can be coated.

  Further, when the metal fine particles are coated with an inorganic oxide, the metal alkoxide can be coated with an acid, an alkali, and the like after oxidization and then aging, washing, drying, firing, and the like.

The method for coating the pigment or metal fine particle with the resin is not particularly limited as long as the surface of the pigment or metal fine particle can be coated with the resin, and a conventionally known method can be employed.
For example, a predetermined amount of resin (emulsion) is mixed with an alcohol dispersion of pigments or fine metal particles, and coating is usually performed by heating and stirring at 40 to 60 ° C.

As a specific example, coating can be performed by mixing 1,6-hexanediol diacrylate in a 2-propanol dispersion of gold fine particles and stirring with heating.
Furthermore, the colorant used in the present invention is preferably such that the pigment coated with the inorganic oxide or resin is 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 or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3, 3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltrioxy Silane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltri Excisilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylooxy Propyltrimethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane , Γ- (meth) acrylooxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ- Examples include aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, and the like, and mixtures thereof. (When treated with an organosilicon compound, hydrolyzed residues are present, contributing to improved dispersibility)
When using a tetrafunctional organosilicon compound (n = 0) among the organosilicon compounds represented by the formula (1), the weight ratio between the tetrafunctional organosilicon compound and pigment particles coated with an inorganic oxide or resin (Weight of organosilicon compound converted to SiO ₂ / weight of coating particle) varies depending on the average particle diameter of pigment particles and the type of coating layer, but is in the range of 1 to 100% by weight, more preferably 5 to 50% by weight. Preferably there is. When the weight ratio is small, the dispersibility and stability of the coating solution may be insufficient, and the adhesion of the resulting transparent colored film to the substrate, scratch resistance, hardness and transparency may be insufficient. May be. Even if the weight ratio is increased, the dispersibility and stability are not further improved, and the adhesion, scratch resistance, hardness, and transparency of the obtained transparent colored film to the base material are further improved. Nor.

Of the organosilicon compounds represented by the formula (1), organosilicon compounds other than tetrafunctional (n = 1, 2,
When 3) is used, the weight ratio of the organosilicon compound other than tetrafunctional to pigment particles coated with an inorganic oxide or resin (weight of organosilicon compound converted to SiO ₂ / weight of coated particles) is the average of the pigment particles Although it varies depending on the particle diameter and the kind of the coating layer, it is preferably in the range of 5 to 80%, more preferably 10 to 50%.

  When the weight ratio is small, dispersibility and stability may be insufficient, and therefore, the adhesion of the transparent colored film obtained to the substrate, scratch resistance, hardness and transparency are insufficient. Sometimes. Even if the weight ratio is too large, dispersibility and stability are not further improved, and adhesion of the transparent colored film obtained to the substrate, scratch resistance, hardness and transparency are further improved. Nor.

In particular, the colorant is preferably surface-treated with a trifunctional organosilicon compound represented by the following formula (2).
X-R-Si (OR) ₃ (2)
(In the formula, R represents an organic group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group. X- represents a γ-glycidoxy group and a (meth) acryloyl group).
Specifically, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ -(Meth) acryloxymethyltrimethoxysilane, γ- (meth) acryloxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane , Γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) acrylooxy Examples include cyclopropyltrimethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, and the like.

  When the surface treatment is performed with such a trifunctional organosilicon compound, when a resin matrix, particularly an ultraviolet curable resin matrix is used as a matrix component, the bonding between the colorant and the matrix is promoted, and the scratch resistance and hardness are increased. Will improve.

  The content of such a colorant in the transparent colored film varies depending on the type of the colorant, the thickness of the colored film, the type of other coating provided as necessary, etc. It is preferable that it is in the range of 0.5% to 40% by weight.

  When the content of the colorant in the transparent color film is small, the absorption peak of the colorant is not clear and sufficient contrast may not be obtained. Moreover, even if there is too much content of a coloring agent, although it changes with film thickness, the light transmittance may fall and a permeation | transmission clarity may become inadequate.

  As the colorant, a pigment or metal fine particles which are directly surface-treated with the above-mentioned organosilicon compound can be used. However, since the organosilicon compound has low reactivity with the pigment or metal fine particles, it is sufficiently dispersed. The surface treatment effects such as properties and stability cannot be obtained sufficiently. However, if it is coated with the inorganic oxide or resin, the hydrolyzate of the organosilicon compound and the —OH group of the coated inorganic oxide or resin are likely to react, and a sufficient surface treatment effect is obtained. A colorant having excellent dispersibility and stability can be obtained, and thus the transparent colored film obtained has excellent adhesion to the substrate, scratch resistance, hardness and transparency, and excellent smoothness of the film surface. ing.

In the present invention, a desired dye can be used as needed together with the pigment particles and / or metal fine particles coated with the inorganic oxide or resin.
Examples of the dye include dyes such as cyan, magenta, and yellow.

Examples of cyan dyes include anthraquinone dyes, azo dyes, and triphenylmethane dyes. Such a dye can be used so that the light transmittance described later falls within a predetermined range.

The transparent colored film of the present invention may contain conventionally known metal oxide fine particles in addition to the colorant.
The metal oxide fine particles vary depending on the purpose other than the improvement of contrast, which is the purpose of providing a colored film, and the improvement of display performance. For example, the coating having antireflection performance usually has a refractive index of 1.45 or less, Conventionally known fine particles having a particle size of 1.40 or less are used. Specific examples thereof include SiO ₂ , SiO ₂ particles having cavities therein, or particles coated with a conductive metal oxide.

Examples of the metal oxide fine particles used in the hard coat film include ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ , chain particles in which these particles are connected in a chain, Conventionally known fine particles such as silica-based fine particles having a refractive index of 1.45 or less can be mentioned.

The metal oxide fine particles used for the high refractive index film are usually fine particles having a refractive index of 1.60 or more, more preferably 1.80 or more. Specifically, ZrO ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO. ₂ , Al ₂
O ₃ , SnO ₂ , antimony-doped tin oxide, tin-doped indium oxide, tin oxide-doped phosphorus (
Conventionally known fine particles such as PTO).

The metal oxide fine particles used for the conductive film are usually Sb ₂ O ₅ , SnO ₂ , antimony-doped tin oxide, tin-doped indium oxide, tin oxide-doped phosphorus (PTO), or silica-based whose surface is coated with these conductive materials. Conventionally known fine particles such as fine particles or silica-based fine particles having cavities inside may be mentioned.

  Such metal oxide fine particles are preferably surface-treated in the same manner as the colorant described above. The average particle size of the metal oxide fine particles is preferably in the range of 1 to 500 nm, more preferably 5 to 200 nm. Those having an average particle size smaller than the lower limit of the above range are difficult to obtain, and even if obtained, the stability may be low and agglomerate. Even if the average particle size is increased, irregularities are likely to occur on the surface of the film, which may cause light scattering and a decrease in film hardness.

  The content of the metal oxide fine particles or the surface-treated metal oxide fine particles in the transparent colored film varies depending on the purpose of use or the type of the metal oxide fine particles, but is 10 to 90% by weight, more preferably 20 to 20% as a solid content. It is preferably in the range of 70% by weight.

  The film thickness of the transparent colored film formed in the present invention is preferably in the range of 20 to 10,000 nm, more preferably 80 to 5000 nm. If the transparent colored film is thin, sufficient coloring may not be obtained even if a colorant is added, and the contrast may not be improved. On the other hand, if the film thickness is too thick, the light transmittance may be too low and the transmission definition may be insufficient.

The transparent colored film formed in the present invention has at least a light transmittance (I) of 40 to 98% at a wavelength of 560 to 620 nm, or a light transmittance (II) of 40 to 98% at a wavelength of 450 to 500 nm.
It is preferable that it exists in.

When the light transmittance (I) at a wavelength of 560 to 620 nm is less than 40%, the transmission sharpness may be insufficient. When the light transmittance (I) at a wavelength of 560 to 620 nm exceeds 98%,
In some cases, the absorption peak is small, and the light in the overlapping portions of the RGB emission spectra cannot be canceled sufficiently, and sufficient contrast cannot be obtained. In addition, the more preferable range of the light transmittance (I) is 50% to 80%.

  Further, when the light transmittance (II) at a wavelength of 450 to 500 nm is less than 40%, the transmission sharpness may be insufficient. When the light transmittance (II) at a wavelength of 450 to 500 nm exceeds 98%, the absorption peak is small and the absorption peak is small, and the light at the overlapping portion of the RGB emission spectrum cannot be sufficiently canceled and sufficient contrast may not be obtained. . A more preferable range of the light transmittance (II) is 50% to 80%.

In addition, the light transmittance of this invention can be measured using JASCO Corporation U-Vest560.
Other coatings The base material with a transparent colored film of the present invention may be provided with a coating other than the transparent colored film formed on one side or both sides of the base material.

  For example, (1) a transparent colored film may be provided on a substrate, and a low refractive index antireflection film may be provided on the transparent colored film. (2) a hard coat layer may be provided on the substrate, A transparent colored film may be provided on the hard coat layer. (3) A hard coat layer is provided on the substrate, a transparent colored film is provided on the hard coat layer, and the refractive index is low on the transparent colored film. An antireflective film with a rate may be provided.

  In addition, it is important that the transparent coloring film provided in the lower layer of the antireflection film has a low refractive index, and the refractive index difference is preferably 0.02 or more, more preferably 0.03 or more. It is preferable.

A conventionally known hard coat layer can be provided as the hard coat layer. Specifically, Zr which can be suitably used for the matrix component, preferably a hard coat layer.
O ₂ , TiO ₂ , Sb ₂ O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ , chain particles in which these particles are linked in a chain, or silica-based fine particles having a refractive index of 1.45 or less, etc. A hard coat layer composed of conventionally known metal oxide fine particles is preferred.

  As the matrix component, any of known thermosetting resins, thermoplastic resins, and the like as coating resins can be employed. For example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, Thermoplastic acrylic resin, vinyl chloride resin, fluororesin, vinyl acetate resin, silicone rubber and other thermoplastic resins, urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester Examples thereof include thermosetting resins such as resins and thermosetting acrylic resins. Further, it may be a copolymer or modified body of two or more of these resins.

  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 curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.

The thickness of the hard coat layer is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 10 μm.
As the antireflection film, a conventionally known antireflection film can be provided. Specifically, the matrix component, preferably the refractive index that can be suitably used for the matrix component and the above-described antireflection film is 1.45 or less, and Is a conventionally known fine particle of 1.40 or less, specifically, SiO ₂ , SiO ₂ having a cavity inside, or a fine particle coated with a conductive metal oxide, or a conventionally known low refractive index An antireflection film composed of a rate component is preferred.
As the matrix component of the antireflection film, the same matrix component as that for the hard coat layer can be used.

It is also possible to use a polycondensate of a hydrolyzable organosilicon compound as the matrix component.
The thickness of the antireflection film is usually in the range of 50 to 300 nm, further 80 to 200 nm, and the refractive index is usually in the range of 1.35 to 1.45, although it varies depending on the refractive index of the lower layer.

In addition, the base material with a transparent colored film of the present invention may be provided with a transparent colored film on the base material on the opposite side of the colored film provided with the other film, or on the opposite side provided with the other film. A transparent colored film may be provided on the substrate. In this case, in general, a colorant may be mixed in the adhesive layer in order to adhere to a glass substrate or a polarizing plate.
Next, the coating liquid for forming a transparent colored film according to the present invention will be described.

The coating liquid for forming a transparent colored film according to the present invention comprises a matrix-forming component and pigment particles and / or metal fine particles coated with an inorganic oxide or resin as a colorant. The total concentration of the solid content is in the range of 0.5 to 60% by weight as a solid content, and the colorant is contained in the transparent colored film so as to be 0.1 to 50% by weight as the solid content. It is a feature.
Matrix-forming component As the matrix-forming component, the resin having the matrix property described above is used.
Specifically, any of known thermosetting resins, thermoplastic resins, ultraviolet curable resins, and the like can be employed as coating resins. For example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylenes can be used. Examples include oxide resins, acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubber resins, urethane resins, melamine resins, butyral resins, silicone resins, phenol resins, epoxy resins, and unsaturated polyester resins. Further, it may be a copolymer or modified body of two or more of these resins.

  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 curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.

The concentration of such a matrix-forming component in the coating solution for forming a transparent colored film is preferably in the range of 0.1 to 60% by weight, more preferably 0.5 to 50% by weight as the solid content.
When the concentration of the matrix-forming component in the coating liquid for forming the transparent colored film is less than 0.1% by weight as the solid content, the film thickness of the obtained transparent colored film may be less than 20 nm, and the predetermined light The transmittance may not be obtained, and it may be necessary to apply repeatedly to obtain a predetermined light transmittance.
If the concentration of the matrix-forming component in the coating liquid for forming the transparent colored film exceeds 60% by weight as the solid content, the stability of the coating liquid becomes insufficient and unevenness occurs in the resulting transparent colored film, or the substrate Adhesiveness, scratch resistance, hardness, transparency and the like may be insufficient.

The same colorant as described above is used as the colorant.
It is preferable that the density | concentration of the coloring agent in the coating material for transparent colored film formation exists in the range of 0.1 to 60 weight% as solid content, and also 0.5 to 50 weight%. If the concentration of the colorant is low, a predetermined light transmittance may not be obtained. Even if the concentration of the colorant is too high, the coating solution may be insufficiently stable, resulting in unevenness and agglomeration in the transparent colored film, adhesion to the substrate, scratch resistance, hardness, and transparency. Etc. may be insufficient. The colorant is preferably contained in the transparent colored film so that the solid content is 0.1 to 50% by weight, more preferably 0.2 to 40% by weight.

Polymerization initiator The coating liquid for forming a transparent colored film of the present invention may contain a polymerization initiator.
The polymerization initiator is not particularly limited as long as the matrix-forming component can be polymerized and cured, and can be appropriately selected depending on the resin, and conventionally known polymerization initiators can be used.

  For example, in addition to polymerization initiators such as acylphosphine oxides, acetophenones, propiophenones, benzyls, benzoins, benzophenones, and thioxanthones, cationic photopolymerization initiators and the like can be mentioned.

The concentration of the polymerization initiator in the coating for forming a transparent film varies depending on the type of the matrix-forming component, but when the matrix-forming component and the polymerization initiator are solids, 0.1 to 20% by weight of the matrix-forming component, Is preferably in the range of 0.5 to 10% by weight. If the content of the polymerization initiator is low, the coating film may be insufficiently cured. If it is too high, the coating stability may be insufficient, or the resulting transparent film may have insufficient hardness. Sometimes.
The dispersion medium is not particularly limited as long as it can dissolve or disperse the matrix-forming component and, if necessary, the polymerization initiator and uniformly disperse the colorant, and a conventionally known solvent can be used.

  Specifically, alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; acetic acid Esters such as methyl ester, ethyl acetate, butyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone Ketones such as acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone and the like. Among these, a solvent having a carbonyl group can be preferably used.

  When a solvent having a carbonyl group is contained, the surface-treated pigment particles and / or metal fine particles are uniformly dispersed, and the stability of the paint is good, and the uniformity, adhesion to the substrate, strength, etc. are excellent. A transparent film having irregularities can be formed with good reproducibility.

These may be used singly or in combination of two or more. In the present invention, it is preferable to use a mixture of two or more solvents having different boiling points.
Metal oxide fine particles The coating material for forming a transparent colored film of the present invention may contain metal oxide fine particles in addition to the colorant.

As the metal oxide fine particles, the above-described metal oxide fine particles or surface-treated metal oxide fine particles can be used.
The content of the metal oxide fine particles or the surface-treated metal oxide fine particles in the paint for forming a transparent colored film is in the range of 0.1 to 50% by weight, further 0.2 to 40% by weight as the solid content. It is preferable. If the concentration of metal oxide fine particles (including those that have been surface-treated) is low, the intrinsic properties, high refractive index function, low refractive index function, conductivity function, hard coat function, etc. of the metal oxide particles cannot be sufficiently exhibited. If the amount is too large, it may be necessary to reduce the colorant, and a sufficient colorant addition effect may not be obtained.

  When such a coating solution for forming a transparent colored film is applied to a substrate by a known method such as a dipping method, a spray method, a spinner method, or a roll coating method, and dried, and the matrix forming component is a thermosetting resin After being cured, in the case of a thermoplastic resin, a transparent colored film can be formed by further heat treatment at a temperature lower than the softening point of the substrate, if necessary.

  When the substrate with a transparent colored film has another coating, if the other coating is a hard coat layer, apply a coating for forming a hard coat layer on the substrate, dry, and cure as necessary. Then, the transparent colored film-forming coating solution is applied, dried and cured to obtain a substrate with a transparent colored film.

  When the other coating is an antireflection film, the transparent colored film forming coating solution is applied, dried, cured as necessary, and then coated with an antireflection film forming coating and dried. It can be cured to obtain a substrate with a transparent colored film.

  It is also possible to impart adhesiveness to the transparent colored film. In this case, dip the coating liquid for forming the transparent colored film on the base material or on the opposite base material provided with other coatings. When the matrix forming component is a thermosetting resin, it is applied to a substrate by a well-known method such as the spray method, spray method, spinner method, roll coating method, etc., pasted on another substrate, and then dried as necessary. After being cured, in the case of a thermoplastic resin, a transparent colored film can be formed by further heat treatment at a temperature lower than the softening point of the substrate, if necessary.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of coating liquid (1) for forming transparent colored film As a pigment particle, quinacridone pigment dispersion (manufactured by Mikuni Dye Co., Ltd .: Himicron K Violet 13718S, solid content concentration 10% by weight, water dispersion medium) 100 g of SiO ₂ concentration 5 50% by weight of silicic acid solution was added and mixed and stirred in a 50 ° C. bath for 1 hour to obtain a colorant (CH-1) dispersion having a solid content of 8.3% by weight. 24.1 g of the obtained colorant (CH-1) dispersion, 28 g of an acrylic UV curable resin (Dainippon Ink Co., Ltd .: Unidec V5500), and 47.9 g of IPA / butyl cellosolve = 9/1 mixed solution were mixed. The mixture was stirred to prepare a coating solution (1) for forming a transparent colored film having a solid content concentration of 30% by weight (the colorant (CH-1) content in the solid content was 6.7% by weight).
Production of transparent colored film-coated substrate (F-1) The transparent colored film forming coating solution (1) was applied to a TAC film (thickness: 80 μm, refractive index: 1.49, substrate transmittance of 88%). After coating by a coater method and drying at 80 ° C. for 1 minute, a high pressure mercury lamp (80 W / cm) was irradiated and cured at 200 mJ / cm ² to prepare a transparent colored film-coated substrate (F-1). The film thickness at this time was 5 μm.

About the obtained substrate with transparent colored film (F-1), the contrast, light transmittance, reflectance, haze, surface resistance, pencil hardness, scratch resistance and adhesion were evaluated by the following methods and evaluation criteria. The results are shown in the table.

The light transmittance is measured by measuring the light transmittance at the absorption peak wavelength using a spectrophotometer (Nippon Bunko U-vest560), and the difference from the light transmittance of only the base material at the same wavelength is measured with a transparent colored film (F- The light transmittance was 1). The reflectance was measured by using a spectrophotometer (U-vest560 manufactured by JASCO Corporation) to measure the minimum reflectance in the visible light region. The haze was measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.).

The surface resistance was measured with a surface resistance meter (manufactured by Mitsubishi Chemical Corporation: Hiresta).
A substrate with contrast transparent colored film (F-1) is attached to a liquid crystal monitor (Mitsubishi Electric: Diamondcrysta RDTISILM), and the standard below the appearance of red, green, yellow and black compared to the case where only the substrate is attached. It was evaluated with. Looks very vivid: ◎
Visible ： ○
Somewhat vivid: △
Almost the same as the case of only the base material: ×
Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.

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.

No streak injury is found: ◎
Slight flaws are observed: ○
Many streak wounds are found: △
The entire surface of the film is scraped: ×
Adhesive transparency Colored film-coated substrate (F-1) surface is made of 11 parallel scratches with a knife at intervals of 1 mm in length and width to make 100 squares, and cellophane tape (registered trademark) is adhered to it Then, the number of cells remaining without peeling when the cellophane tape was peeled was evaluated according to the following criteria. Number of remaining cells: 95 or more: ◎
Number of remaining squares 90-94: ○
Number of remaining squares: 85 to 89: Δ
Number of remaining squares: 84 or less: ×
[Example 2]
Preparation of coating liquid for forming transparent colored film (2) 100 g of a colorant (CH-1) dispersion prepared in the same manner as in Example 1 was added to γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-5103). , 100%) 0.42 g,
The mixture was stirred for 1 hour in a 50 ° C. bath to obtain a colorant (CH-2) dispersion having a solid content of 8.7% by weight.
22.9 g of the obtained colorant (CH-2) dispersion, 28 g of an acrylic ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidec V5500), and 49.1 g of a mixed solution of IPA / butyl cellosolve = 9/1. After mixing and stirring, a coating solution (2) for forming a transparent colored film having a solid content concentration of 30% by weight (6.7% by weight of the colorant (CH-2) in the solid content) was prepared.
Production of transparent colored film-coated substrate (F-2) In Example 1, the transparent colored film-coated substrate (F-2) was used except that the transparent colored film-forming coating solution (2) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (F-2) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 3]
Preparation of coating liquid for forming transparent colored film (3) As pigment particles, 100 g of phthalocyanine pigment dispersion (manufactured by Mikuni Dye Co., Ltd .: Himicron K Blue 5007A, solid concentration 8 wt%, water dispersion medium) and acrylic resin (Japan) Kagaku: 1.6 hexanediol diacrylate) 4 g and IPA 50 g were added and mixed and stirred in a 50 ° C. bath for 1 hour to obtain a colorant (CH-3) dispersion having a solid content concentration of 7.8 wt%. . 38.5 g of the obtained colorant (CH-3), 7 g of an acrylic ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidec V5500) and 54.5 g of a mixed solution of IPA / butyl cellosolve = 9/1 were mixed and stirred. A transparent colored film forming coating solution (3) having a solid content of 10% by weight (colorant (CH-3) content in the solid content of 30% by weight) was prepared.
Production of transparent colored film-coated substrate (F-3) In Example 1, the transparent colored film-coated substrate (F-3) was used except that the transparent colored film-forming coating solution (3) was used. Was prepared. The film thickness at this time was 0.1 μm.
The obtained transparent colored film-coated substrate (F-3) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 4]
Preparation of coating liquid (4) for forming transparent colored film Colorant (CH-2) dispersion 2 having a solid content concentration of 8.7% by weight prepared in the same manner as in Example 2.
2.9 g, antimony pentoxide particle dispersion (catalyst conversion: ELCOM V-4521, solid content concentration 30% by weight, IPA dispersion medium, average particle size 20 nm) and acrylic UV curable resin (Dainippon Ink Co., Ltd.) (Manufactured by: Unidec V5500) 19 g and IPA / butyl cellosolve = 9
/ 2 1 g of the mixed solution is mixed and stirred, and a transparent colored film having a solid content of 30% by weight (colorant (CH-2) 6.7% by weight, Sb ₂ O ₅ concentration 30% by weight in the solid) A forming coating solution (4) was prepared.
Production of transparent colored film-coated substrate (F-4) In Example 1, the transparent colored film-coated substrate (F-4) was used except that the transparent colored film-forming coating solution (4) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (F-4) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 5]
Preparation of coating solution for forming transparent colored film (5) Gold fine particle dispersion (catalyst conversion: CG-001, solid content concentration 10% by weight, water dispersion medium, average particle size 2 nm) in 100 g of SiO ₂ 50 g of 5% by weight silicic acid solution was added and mixed and stirred in a 50 ° C. bath for 1 hour to obtain a colorant (CH-5) dispersion having a solid content of 8.3% by weight. 48.2 g of the obtained colorant (CH-5) dispersion and an acrylic UV curable resin (manufactured by Dainippon Ink Co., Ltd .:
UNIDEC V5500) 26g and IPA / butyl cellosolve = 9/1 mixed solution 25.8g
Were mixed and stirred to prepare a transparent colored film-forming coating solution (5) having a solid content concentration of 30% by weight (colorant (CH-5) content in solid content: 13.4% by weight).
Production of transparent colored film-coated substrate (F-5) In Example 1, the transparent colored film-coated substrate (F-5) was used except that the transparent colored film-forming coating solution (5) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (F-4) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 6]
Preparation of coating liquid (6) for forming transparent colored film Gold fine particle dispersion (catalyst conversion: CS-001, solid content concentration: 10% by weight, water dispersion medium, average particle diameter: 6 nm) in 100 g of SiO ₂ 50 g of a 5% strength by weight silicic acid solution was added and mixed and stirred in a 50 ° C. bath for 1 hour, and then γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KB)
M-403 (100 wt%) 0.42 g was added, and the mixture was further stirred for 1 hour in a 50 ° C. bath to obtain a colorant (CH-6) dispersion having a solid content concentration of 8.6 wt%. 34.9 g of the resulting colorant (CH-6) dispersion, 5 g of an acrylic ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidec V5500), and 60.1 g of a mixed solution of IPA / butyl cellosolve = 9/1 were mixed. The mixture was stirred to prepare a coating solution (6) for forming a transparent colored film having a solid content concentration of 10% by weight (colorant (CH-6) content in the solid content of 30% by weight).
Production of transparent colored film-coated substrate (F-6) In Example 1, the transparent colored film-coated substrate (F-6) was used except that the transparent colored film-forming coating solution (6) was used. Was prepared. The film thickness at this time was 0.1 μm.
The obtained transparent colored film-coated substrate (F-6) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 7]
Production of transparent colored film-coated substrate (F-7) Transparent colored film-coated substrate (F-4) prepared in the same manner as in Example 4 (refractive index of colored film = 1.53)
) Above, anti-reflective coating solution (catalyst conversion: ELCOM P-5013, consisting of hollow silica particles (average particle size 50 nm) and UV curable acrylic resin, solid content concentration 2.5 wt%) After coating by a coater method and drying at 80 ° C. for 1 minute, a high pressure mercury lamp (80 W / cm) was irradiated and cured at 200 mJ / cm ² to prepare a transparent colored film-coated substrate (F-7). At this time, the thickness of the antireflection film was 0.1 μm, and the refractive index was 1.40.

The obtained transparent colored film-coated substrate (F-7) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 8]
Production of transparent colored film-coated substrate (F-8) Transparent colored film-coated substrate (F-4) prepared in the same manner as in Example 4 (refractive index of colored film = 1.53)
) A transparent colored film forming coating solution (6) prepared in the same manner as in Example 6 was applied by the bar coater method and dried at 80 ° C. for 1 minute, and then a high pressure mercury lamp (80 W / cm) was applied at 200 mJ. / Cm ² was irradiated and cured to prepare a transparent colored film-coated substrate (F-8). The total film thickness of the transparent colored film at this time was 5.1 μm.
The obtained transparent colored film-coated substrate (F-8) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 9]
Preparation of coating liquid for forming transparent colored film (9) As a pigment particle, quinacridone pigment dispersion (manufactured by Mikuni Dye Co., Ltd .: Himicron K Violet 13718S, solid content concentration 10% by weight, water dispersion medium) 100 g of SiO ₂ concentration 5 6 g of a weight percent silicic acid solution was added and mixed and stirred in a 50 ° C. bath for 1 hour to obtain a colorant (CH-9) dispersion having a solid content concentration of 9.7 g weight percent. 20.6 g of the resulting colorant (CH-9) dispersion, 28 g of an acrylic UV curable resin (Dainippon Ink Co., Ltd .: Unidec V5500), and 51.4 g of IPA / butyl cellosolve = 9/1 mixed solution were mixed. The mixture was stirred to prepare a coating liquid (9) for forming a transparent colored film having a solid content concentration of 30% by weight (colorant (CH-9) content in the solid content: 6.7% by weight). Production of transparent colored film-coated substrate (F-9) In Example 1, the transparent colored film-coated substrate (F-9) was used except that the transparent colored film-forming coating solution (9) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (F-9) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Comparative Example 1]
Manufacture of coating liquid (R1) for forming transparent colored film Antimony pentoxide particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .; ELCOM PC-14, average particle diameter 20 nm, Sb ₂ O ₅ concentration 20% by weight, dispersion medium: Ethyl cellosolve / ethanol weight ratio = 94/6) 200 g of UV curable resin (Dainippon Ink Co., Ltd .: Unidec V5500) 160 g and ethyl cellosolve 640 g were mixed to prepare a transparent colored film forming coating solution (R1). Prepared.
Production of transparent colored film-coated substrate (RF-1) In Example 1, the transparent colored film-coated substrate (RF- 1) was used except that the transparent colored film-forming coating solution (RF-1) was used. 1) was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (RF-1) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Comparative Example 2] (HC thick film blue film, excessive colorant addition)
Preparation of Transparent Colored Film Forming Coating Liquid (R2) A colorant (CH-3) dispersion having a solid content concentration of 7.8% by weight was obtained in the same manner as in Example 3. 76.9 g of the obtained colorant (CH-3) and an acrylic UV curable resin (Dainippon Ink Co., Ltd.)
(Product: Unidec V5500) 2 g and IPA / butyl cellosolve = 9/1 mixed solution 21.1
g was mixed and stirred to prepare a transparent colored film-forming coating solution (R2) having a solid content of 10% by weight (a colorant (CH-3) content of 75% by weight in the solid content).
Production of substrate with transparent colored film (RF-2) Substrate with transparent colored film (RF-2) was produced in the same manner as in Example 1 except that the coating liquid for transparent colored film formation (R2) was used. Was prepared. The film thickness at this time was 0.1 μm.

The obtained transparent colored film-coated substrate (RF-2) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Comparative Example 3]
Preparation of coating liquid (R3) for forming transparent colored film 20 g of quinacridone pigment dispersion (manufactured by Mikuni Dye Co., Ltd .: Himicron K Violet 13718S, solid content concentration 10% by weight, water dispersion medium) as pigment particles and acrylic UV curing 28 g of resin (Dainippon Ink Co., Ltd .: Unidec V5500) and IPA / butyl cellosolve = 9 /
1 g of the mixed solution 52 g was mixed and stirred to prepare a transparent colored film forming coating solution (R3) having a solid content concentration of 30% by weight (pigment particle content in the solid content 6.7% by weight).
Production of transparent colored film-coated substrate (RF-3) In Example 1, the transparent colored film-coated substrate (RF-3) was used in the same manner except that the transparent colored film-forming coating solution (R3) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (RF-3) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Comparative Example 4] (in [Example 5] (thick Au, no oxide coating)
Preparation of coating liquid (R4) for forming transparent colored film Gold fine particle dispersion (catalyst conversion: CG-001, solid content concentration 10% by weight, water dispersion medium, average particle diameter 2 nm) and acrylic UV curable resin ( Dainippon Ink & Co., Ltd .: Unidec V5500) 26 g and IPA / butyl cellosolve = 9/1 mixed solution 54 g were mixed and stirred, and the solid content concentration was 30 wt% (the content of gold fine particles in the solid content was 13.3% wt). A transparent colored film forming coating solution (RF-4) was prepared.
Production of transparent colored film-coated substrate (RF-4) In Example 1, the transparent colored film-coated substrate (RF-) was used except that the transparent colored film-forming coating solution (RF-4) was used. 4) was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (RF-4) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Claims (8)

Consisting of a substrate and a transparent colored film formed on one or both sides of the substrate,
The transparent colored film is
Comprising a matrix component and, as a colorant, (i) pigment particles coated with silica or resin and / or (ii) metal fine particles coated with silica or resin, and the matrix component is a resin matrix,
The colorant is surface-treated with an organosilicon compound represented by the following formula (1),
The content of the colorant in the colored film is in the range of 0.1 to 50% by weight, and the content of the resin matrix is in the range of 60.5 to 93.3% by weight (however, the total amount does not exceed 100% by weight) A substrate with a transparent colored film,
_{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 or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3) 2. The substrate with a transparent colored film according to claim 1, wherein the organosilicon compound represented by the formula (1) is an organosilicon compound represented by the following formula (2).
X'-R'-Si (OR '') ₃ (2)
(In the formula , R ″ represents an unsubstituted hydrocarbon group having 1 to 4 carbon atoms. X′-R′- represents γ-glycidoxymethyl, γ-glycidoxyethyl, γ-glycidoxypropyl. , Γ- (β-glycidoxyethoxy) propyl, γ- (meth) acrylooxymethyl, γ- (meth) acrylooxyethyl, γ- (meth) acrylooxypropyl ).   The base material with a transparent colored film according to claim 1 or 2, wherein the transparent colored film further comprises a dye as a colorant. The transparent colored film is
The light transmittance (I) at least at a wavelength of 560 to 620 nm is 40 to 98%, or the light transmittance (II) at a wavelength of 450 to 500 nm is in the range of 40 to 98%. The base material with a transparent coloring film in any one of -3.   Furthermore, the other coating film of the said transparent coloring film is provided, The base material with a transparent coloring film in any one of Claims 1-4 characterized by the above-mentioned. A matrix-forming component, and (i) pigment particles coated with silica or resin and / or (ii) fine metal particles coated with silica or resin as a colorant,
The matrix forming component is a resin matrix, and the colorant is surface-treated with an organosilicon compound represented by the following formula (1),
The total concentration of the matrix-forming component and the colorant is in the range of 0.5-60% by weight as solids,
The colorant is contained in the transparent colored film in a solid content of 0.1 to 50% by weight, and the resin matrix content is in the range of 60.5 to 93.3% by weight (the total does not exceed 100% by weight). A coating liquid for forming a transparent colored film, characterized in that:
_{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 or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3) The coating solution for forming a transparent colored film according to claim 6, wherein the organosilicon compound represented by the formula (1) is an organosilicon compound represented by the following formula (2).
X'-R'-Si (OR '') ₃ (2)
(In the formula , R ″ represents an unsubstituted hydrocarbon group having 1 to 4 carbon atoms. X′-R′- represents γ-glycidoxymethyl, γ-glycidoxyethyl, γ-glycidoxypropyl. , Γ- (β-glycidoxyethoxy) propyl, γ- (meth) acrylooxymethyl, γ- (meth) acrylooxyethyl, γ- (meth) acrylooxypropyl).   The coating liquid for forming a transparent colored film according to claim 6 or 7, further comprising a dye as a colorant.