TW201534670A - Coating liouid for forming a transparent coating film and method for making a substrate with a transparent coating film - Google Patents

Abstract

This invention provides a coating liquid for forming a transparent coating film containing fine particles of inorganic oxides and resin emulsion dispersed in a dispersion medium including at least one of water and an organic solvent. The coating liquid contains a total solid components having a concentration of 0.03~70wt%, a concentration (CP) of solid component of the fine particles of inorganic oxides of 0.0009~56wt%, and a concentration (CR) of the resin emulsion of 0.006~68wt%. The fine particles of inorganic fine particles contain solid components of alkali metal having a sum of concentration, based on the oxides (Me2O,Me=Li,Na,K), of 1000 ppm or less. When a substrate having the coating liquid coated thereon is stretched or when the coating liquid is applied to the substrate while the substrate is being stretched, a substrate with a transparent coating film having a flat surface free of spots and uneven film patterns (islands) can be obtained.

Description

Coating liquid for forming transparent film and manufacturing method of substrate with transparent film

The present invention relates to a coating liquid for forming a transparent film, and a method for producing a substrate with a transparent film using the coating liquid.

Conventionally, various transparent films have been formed on the surface of a substrate such as glass, a plastic sheet, a resin film, or a plastic lens. For example, an organic resin film or an inorganic film is formed on the surface of the substrate as a hard coat film. Further, inorganic particles such as resin particles or cerium oxide may be blended in an organic resin film or an inorganic film to improve scratch resistance.

The applicant discloses a hard coating film composed only of an organic resin, and an anti-reflection/anti-charge charge comprising porous cerium oxide particles coated with cerium oxide (or cerium oxide particles having pores therein) The film is laminated on a substrate (Japanese Laid-Open Patent Publication No. 2005-119909; Patent Document 1), but the hard coat function (scratch resistance, film strength, etc.) is still insufficient. Further, it is also known that a conductive film containing metal fine particles and conductive oxide fine particles is formed on a substrate such as a display device. Anti-charging performance and electromagnetic wave shielding performance (Japanese Laid-Open Patent Publication No. 2003-105268; Patent Document 2). At this time, tin oxide, tin oxide doped with F, Sb or P, indium oxide, indium oxide doped with Sn or F, cerium oxide, or sub-titania are disclosed as conductive oxide fine particles. Further, the present applicant has disclosed a hard coat film in which antimony pentoxide particles are formulated in order to impart antistatic properties to the hard coat film itself (JP-A-2004-50810; Patent Document 3). Further, a transparent film in which chain-like pentoxide particles are formulated is disclosed (Japanese Laid-Open Patent Publication No. 2005-139026; Patent Document 4).

Further, it is known that a coating liquid containing low refractive index fine particles containing cerium oxide particles or the like is applied to a surface of a substrate to form an antireflection film (Japanese Patent Laid-Open Publication No. Hei 7-133105); 5). In addition, in order to impart antistatic property and electromagnetic wave shielding performance to the substrate, an antireflection film is formed on the conductive film on which the conductive film containing the metal fine particles and the conductive oxide fine particles is formed. practice. As described above, even when the antireflection film or the conductive film is provided, in order to improve the scratch resistance, it is also possible to form a hard coat film between the substrate and at least one of the antireflection film and the conductive film. Japanese Patent Laid-Open Publication No. 2007-321049 (Patent Document 6), JP-A-2008-19358 (Patent Document 7), and JP-A-2010-128309 (Patent Document 8) disclose A coating liquid for forming an anti-reflection film.

In particular, when the substrate is a resin film, a transparent film is conventionally formed on a film substrate having a predetermined thickness. However, in recent years, from the viewpoints of productivity, safety, and environmental considerations, the following production methods are required. The coating liquid for forming a transparent film is also applied to the film before stretching to form The film is coated and then cured after stretching, or a coating liquid for forming a transparent film is applied while stretching the film before stretching to form a coating film, followed by hardening.

However, when a conventional coating liquid is used, spots are generated by the blending particles at the time of stretching, or film waviness is generated due to instability or unevenness of the coating liquid, and flatness is impaired, or The stretched film with a transparent film which is deteriorated in appearance and has insufficient transparency and haze is required to be improved.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-119909

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-105268

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-50810

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-139026

[Patent Document 5] Japanese Patent Laid-Open No. 7-133105

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2007-321049

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2008-19358

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2010-128309

Therefore, an object of the present invention is to provide a coating liquid for forming a transparent film and a substrate with a transparent film which can suppress formation of spots during stretching of a resin film after coating, formation of film corrugations Manufacturing method.

The inventors of the present application have found that when the coating liquid containing the inorganic oxide fine particles and the resin emulsion dispersed in at least one of water and an organic solvent is used, the resin film after coating can be suppressed from being stretched. Generation of spots and generation of film corrugations. In this case, the total solid content concentration of the coating liquid is set to 0.03 to 70% by weight, and the concentration (C _P ) of the inorganic oxide fine particles in the coating liquid is set to be in the range of 0.0009 to 56% by weight in terms of solid content. The concentration (C _R ) of the resin emulsion is set in the range of 0.006 to 68% by weight in terms of solid content. In addition, the total solid concentration of the alkali metal contained in the inorganic oxide fine particles is 1000 ppm or less in terms of oxide (Me ₂ O, Me=Li, Na, K).

According to the coating liquid of the present invention, even if the substrate is stretched after being applied to the substrate, or coated while stretching the substrate, the film does not generate spots or corrugations (island-like patterns), and is provided. The surface is a flat substrate with a transparent film.

Here, it is preferred to surface-treat the inorganic oxide fine particles with at least one of an organic cerium compound and a polymer dispersing agent. In this case, the organic cerium compound, when expressed as R _n -SiX _(4-n)/2 , is in the range of 1 to 100% by weight based on the solid content of the inorganic oxide fine particles, and regarding the polymer dispersant, The inorganic oxide fine particles are in the range of 1 to 300% by weight in terms of solid content.

Further, the inorganic oxide fine particles are at least one of monodisperse inorganic oxide fine particles (A) and at least one of chain-connected inorganic oxide fine particles (B) having a primary particle diameter of 3 to 30, and inorganic oxide fine particles. The average particle diameter (D _PA ) of (A) is in the range of 3 ≦ D _PA ≦ 100 nm, and the average primary particle diameter (D _PB ) of the inorganic oxide fine particles (B) is in the range of 3 ≦ D _PB ≦ 50 nm.

The average diameter of the resin emulsion is in the range of 10 to 500 nm, and the concentration ratio (C _P /C _R ) of the concentration (C _P ) of the inorganic oxide fine particles to the concentration (C _R ) of the resin emulsion is preferably in the range of 0.03 to 4. .

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

[coating liquid for forming a transparent film]

In the coating liquid for forming a transparent film of the present invention, the inorganic oxide fine particles and the resin emulsion are dispersed in a dispersion medium containing at least one of water and an organic solvent. At this time, the total solid content concentration of the coating liquid is in the range of 0.03 to 70% by weight, and the concentration (C _P ) of the inorganic oxide fine particles is in the range of 0.0009 to 56% by weight in terms of solid content, and the concentration of the resin emulsion (C _R ) is in the range of 0.006 to 68% by weight in terms of solid content. In this case, the inorganic oxide fine particles are obtained by using a solid content concentration of an alkali metal as a high purity of 1000 ppm or less in total of oxides (Me ₂ O). When the total amount of the alkali metals of the inorganic oxide fine particles exceeds 1000 ppm, it is not uniformly dispersed in the coating liquid, and the stability is insufficient. Therefore, the strength and scratch resistance of the transparent film are lowered, and the haze value is improved.

Further, the inorganic oxide fine particles are preferably surface-treated with at least one of an organic cerium compound and a polymer dispersing agent. In this case, the organic cerium compound is 1 to 100% by weight based on R _x -SiX _(4-n)/2 in terms of solid content with respect to the inorganic oxide fine particles. When the amount of the organic ruthenium compound is small, the affinity with the resin emulsion or the dispersion medium in the coating liquid described later is low, and the stability is insufficient, and the coating liquid cannot be uniformly dispersed. The polymer dispersant is present in the range of from 1 to 300% by weight based on the solid content of the inorganic oxide fine particles. When the amount of the polymer dispersant is less than 1% by weight, the affinity with the resin emulsion or the dispersion medium in the coating liquid for forming a transparent film described later is low, the stability is insufficient, and the coating liquid cannot be uniformly dispersed. . When the amount of the polymer dispersant exceeds 300% by weight, the dispersibility is not further improved.

In the inorganic oxide fine particles, at least one of the monodisperse inorganic oxide fine particles (A) and the chain-shaped inorganic oxide fine particles (B) having a primary particle diameter of 3 to 30 are connected in a chain form. In this case, the average particle diameter (D _PA ) of the inorganic oxide fine particles (A) is in the range of 3 ≦ D _PA ≦ 100 nm, and the average primary particle diameter (D _PB ) of the inorganic oxide fine particles (B) is set to 3 ≦D _PB ≦50nm range.

The state of the coated film varies depending on the concentration of the inorganic oxide fine particles in the coating liquid, but when the average particle diameter (D _PA ) of the inorganic oxide fine particles (A) is less than 3 nm, the inorganic The oxide fine particles (A) are irregularly aggregated and arranged in an array, so that the haze value of the transparent film is increased, or the strength, scratch resistance, scratch strength, and the like of the film are insufficient. When the average particle diameter (D _PA ) exceeds 100 nm, the transparency is insufficient, or the film thickness is insufficient due to the difference in film thickness of the transparent film. When the average primary particle diameter (D _PB ) of the chain-like inorganic oxide fine particles (B) is less than 3 nm, they are not linked in a chain shape and become aggregated particles. When the average primary particle diameter (D _PB ) exceeds 50 nm, it is difficult to obtain chain-like particles.

The elements constituting the coating liquid will be described in detail below.

Inorganic oxide particles

The inorganic oxide fine particles used in the present invention can be selected from conventionally known inorganic oxide fine particles depending on the application. The solid content concentration of the alkali metal contained in the inorganic oxide fine particles must be 1000 ppm or less in terms of the total of the oxides (Me ₂ O). Me can be exemplified by sodium (Na) or potassium (K) or lithium (Li).

When the total of the alkali metals in the inorganic oxide fine particles exceeds 1000 ppm, the amount of inclusion ions may increase, and the coating liquid may not uniformly disperse, and the stability may be insufficient, and the inorganic oxide fine particles may aggregate. Therefore, the strength or scratch resistance of the transparent film is lowered, the haze value is improved, or the properties such as conductivity and reflectance are insufficient. As a method of reducing an alkali metal, a conventionally known washing method using an ultrafiltration membrane or an ion exchange resin can be exemplified.

The inorganic oxide fine particles may be exemplified by oxidation of TiO ₂ , ZrO ₂ , SiO ₂ , Sb ₂ O ₅ , ZnO ₂ , SnO ₂ , In ₂ O ₃ , antimony-doped tin oxide (ATO), and tin doping. At least one of indium (ITO), tin-doped tin oxide (FTO), phosphorus-doped tin oxide (PTO), and aluminum-doped zinc oxide (AZO) or a composite oxide or mixture thereof. It can be suitably selected from the above-mentioned inorganic oxide fine particles in accordance with the use of the transparent film. Specifically, when a high refractive index film or the like is formed, TiO ₂ , ZrO ₂ , Sb ₂ O ₅ , ZnO ₂ , SnO ₂ , In ₂ O ₃ or the like is suitable. When a hard coat film, a low refractive index film, an easy-adhesive film, an anti blocking film, or the like is formed, SiO ₂ or the like is suitable.

In particular, a low-refractive-index film for the purpose of anti-reflection is suitable for the hollow cerium hollow particles having pores therein as disclosed in Japanese Laid-Open Patent Publication No. 2001-233611 and Japanese Patent Application Laid-Open No. 2003-192994. . This is because the refractive index of the hollow particles of cerium oxide is substantially lower from 1.10 to 1.40, which is fine particles in the colloidal region, and is excellent in dispersibility and the like. Further, cerium oxide hollow fine particles are also suitable as a heat insulating film. In addition, among the cerium oxide fine particles (sometimes referred to as cerium oxide solid particles) having no pores therein, relatively small particles (having a particle diameter of approximately 100 nm or less) can increase the hardness and the particle diameter is larger. The particles are suitable for imparting anti-blocking properties.

In the case of preventing interference fringes, TiO ₂ forming a high refractive index film is suitable. In addition, when forming an antistatic film, Sb ₂ O ₅ , In ₂ O ₃ , antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), doped tin oxide (FTO), doping Phosphorus tin oxide (PTO), aluminum-doped zinc oxide (AZO), etc., are suitable because they have electrical conductivity.

The inorganic oxide fine particles are preferably at least one of monodisperse inorganic oxide fine particles (A) and chain-like inorganic oxide fine particles (B) having a chain-like primary particle. Here, monodisperse means that the particles are in a non-agglomerated state.

The average particle diameter (D _PA ) of the inorganic oxide fine particles (A) varies depending on the type of the transparent film, but may be 3 ≦ D _PA ≦ 100 nm, preferably 5 ≦ D _PA ≦ 80 nm, more preferably 8≦D _PA ≦80nm range.

The state of the coated film varies depending on the concentration of the inorganic oxide fine particles in the coating liquid, but when the average particle diameter (D _PA ) of the inorganic oxide fine particles (A) is less than 3 nm, the inorganic The oxide fine particles (A) are irregularly aggregated and arranged in an array, and the haze value of the transparent film may be increased, or the strength, scratch resistance, scratch strength, and the like of the film may be insufficient. Further, in the case of the cerium oxide hollow fine particles, the ratio of pores inside the cerium oxide-based hollow fine particles is small, and the refractive index may not be 1.40 or less, and the antireflection performance may be insufficient. Further, in the case of crystalline conductive particles such as ATO or ITO, the crystallinity may be insufficient and the conductivity may be insufficient. When the average particle diameter (D _PA ) exceeds 100 nm, the transparency may be insufficient. Further, the strength of the film may be insufficient due to the difference in film thickness of the transparent film. Further, a high-density unevenness may be formed on the surface of the transparent film, and the haze value may be increased, or the scratch resistance and the scratch strength may be insufficient.

Further, the average primary particle diameter (D _PB ) of the chain-like inorganic oxide fine particles (B) is 3 ≦ D _PB ≦ 50 nm, preferably 5 ≦ D _PB ≦ 30 nm, and the average number of links of the primary particles is 3 to 30, more preferably in the range of 5 to 20.

The state of the coated film varies depending on the concentration of the inorganic oxide fine particles in the coating liquid, but when the average primary particle diameter (D _PB ) of the chain-like inorganic oxide fine particles (B) is less than 3 nm In the case of agglomerated particles, the haze value of the transparent film may increase, or the strength, scratch resistance, scratch strength, and the like of the film may become insufficient. When the average primary particle diameter (D _PB ) exceeds 50 nm, it is difficult to obtain chain-like particles, and even if it is obtained, the chain-like particles become long chains, and the haze value of the transparent film may be increased, or the strength and scratch resistance of the film may be obtained. Sex, scratch strength, etc. become insufficient.

The concentration (C _P ) of the inorganic oxide fine particles in the coating liquid for forming the transparent film is from 0.0009 to 56% by weight, more preferably from 0.03 to 40% by weight, based on the solid content. When the concentration (C _P ) is too low, the adhesion to the substrate, the film strength, the surface flatness, the scratch resistance, the scratch strength, and the like may be insufficient. Further, sometimes the desired effect (electrical conductivity, antireflection performance, etc.) may not be sufficiently obtained. When the concentration (C _P ) is too high, not only the adhesion, the film strength, the scratch resistance, the scratch strength, and the like are insufficient, but the haze value of the transparent film may be increased. Further, since the elongation of the coating film during stretching cannot follow the stretching of the substrate, cracking sometimes occurs.

Further, inorganic oxide fine particles (C) may be further contained in the coating liquid. Further, the inorganic oxide fine particles (C) may be contained in place of at least one of the inorganic oxide fine particles (A) and the chain-like inorganic oxide fine particles (B).

The average particle diameter (D _PC ) of the inorganic oxide fine particles (C) is 100 < D _PC ≦ 500 nm, preferably 100 < D _PC ≦ 400 nm, more preferably 100 < D _PC ≦ 300 nm. By the addition of the inorganic oxide fine particles (C), a convex portion can be formed on the surface of the transparent film, so that sufficient anti-blocking property can be obtained.

The state of the coated film varies depending on the concentration of the inorganic oxide particles in the coating liquid, but is transparent when the average particle diameter (D _PC ) of the inorganic oxide fine particles (C) is less than 100 nm. The film after the film is made thinner, and it is sometimes impossible to form a convex portion on the surface of the transparent film. When the film is coated with a transparent film, a coating liquid for forming a transparent film is applied. And drying, and then, after hardening, when the substrate with the transparent film is taken up, the surface of the transparent film is closely adhered to the substrate in the substrate with the transparent film which is taken up later (sometimes called For blocking, it is sometimes difficult to peel off after use. When the average particle diameter (D _PC ) exceeds 500 nm, the transparency of the film is lowered, and not only the film haze is improved, but also the transmittance is lowered, and the unevenness of the surface is excessively increased, and the hardness of the film such as scratch resistance may be lowered.

The concentration (C _PC ) of the inorganic oxide fine particles (C) in the coating liquid for forming the transparent film is in the range of 0.000003 to 3% by weight, more preferably 0.000015 to 1.5% by weight, based on the solid content. When the concentration (C _PC ) is less than 0.000003% by weight, the density of the convex portion formed on the surface of the coating film obtained by using the coating liquid for forming a transparent film is too low, and sometimes sufficient anti-blocking property cannot be obtained. . When the concentration (C _PC ) exceeds 3% by weight, the density of the convex portions formed on the surface of the coating film is too high, and the transparency, scratch resistance, and antireflection performance may be insufficient.

Here, the inorganic oxide fine particles are preferably surface-treated with at least one of an organic cerium compound and a polymer dispersing agent. The organic cerium compound enhances the affinity of the inorganic oxide particles to the resin emulsion. On the other hand, the polymer dispersant can improve the affinity not only as described above, but also suppress the generation of voids between the filler and the binder caused by stretching, and is particularly suitable when the stretching ratio is high.

In the case where water is used for the surface treatment, it is preferably an organic solvent dispersion which constitutes the surface-treated inorganic oxide fine particles after being subjected to surface treatment instead of being an organic solvent. Thereby, the dispersibility of the inorganic oxide fine particles to the resin can be enhanced in the coating liquid. As the organic solvent, the same organic solvent as the coating liquid for forming a transparent film described later can be used.

The following describes the case where the inorganic oxide fine particles are surface-treated with (i) an organic cerium compound and (ii) a polymer dispersing agent.

(i) organic germanium compounds

An organic ruthenium compound represented by the following formula (1) can be used.

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: an alkoxy group having 1 to 4 carbon atoms, decyl alcohol Base, halogen, hydrogen, n: an integer from 0 to 3)

In the formula (1), when n is from 1 to 3, an organic ruthenium compound having an organic functional group reactive with a functional group of a resin emulsion to be described later is preferably used. For example, when a resin having an epoxy group, a methacryl group, an acryl group, an isocyanate group or the like is used as the resin emulsion, the organic ruthenium compound is preferably one having a glycidoxy group, a methacryloxy group, or a propyleneoxy group. An organic ruthenium compound having a functional group such as a vinyl group, an isocyanate group, a urea group or an amine group. When the inorganic oxide fine particles surface-treated with the organic cerium compound are used, a transparent film excellent in film strength, scratch resistance, scratch strength, and the like can be formed.

The surface treatment of the inorganic oxide fine particles may be carried out by a conventionally known method, for example, adding an organic cerium compound to an alcohol dispersion liquid which is quantitatively determined by the inorganic oxide fine particles, adding water, and adding an acid or a base as a hydrolysis contact as needed. The medium is used for hydrolysis. In this case, the organic cerium compound is from 1 to 100% by weight, preferably from 2 to 80% by weight, based on the solid content of R _n -SiX _(4-n)/2 , relative to the inorganic oxide fine particles. The best is in the range of 5 to 70% by weight.

When the amount of the organic ruthenium compound is small, the affinity with the resin emulsion or the dispersion medium in the coating liquid for forming a transparent film described later is low, and the stability is insufficient, and it is not uniformly dispersed in the coating liquid, and as the case may be, inorganic Oxide fine particles may aggregate, and the strength and scratch resistance of the transparent film may be lowered, the haze value may be improved, or performance such as conductivity and reflectance may be insufficient. Even if the amount of the organic cerium compound is too large, the dispersibility is not further improved. When the cerium oxide hollow fine particles are used, the refractive index is increased, and the antireflection performance may be insufficient. In the case of the conductive fine particles, the antistatic property may be insufficient.

(ii) Polymer dispersant

The dispersing agent used in the present invention is a polymer compound which can dissolve or disperse a crosslinking agent or a polymerization initiator which will be described later, and which can disperse the inorganic oxide fine particles, as long as the resin emulsion is not dissolved and the emulsion property is maintained. can.

Specifically, a generally known polymer dispersant such as polyethylene, polyacrylic acid, polycarboxylic acid, or polyurethane can be used. More specifically, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl ester, etc., and copolymers thereof may be used as the polyethylene polymer; polyacrylic acid, sodium polyacrylate, and polyacrylic acid polymer may be used. Polyacrylic acid ammonium and the like and copolymers thereof; polycarboxylic acid polymers, polycarboxylic acid sodium, polybasic ammonium carboxylate, etc., and the like; and polyamine polymers, polyamines can be used. For example, a formic acid ester or the like, a copolymer of these, or the like, or a copolymer of such a copolymer or a sulfonic acid polymer or the like can be used.

When a polymeric dispersant is used, the haze after stretching can be reduced. The amount of the polymer dispersant is from 1 to 300% by weight, more preferably from 1 to 100% by weight, based on the solid content of the inorganic oxide fine particles. When the amount of the polymer dispersant is less than 1% by weight, the affinity with the resin emulsion or dispersion medium in the coating liquid for forming a transparent film described later is low, the stability is insufficient, and the coating liquid cannot be uniformly formed. Dispersed, depending on the situation, inorganic oxide micro The particles sometimes aggregate, and the strength and scratch resistance of the transparent film are lowered, the haze value is improved, or the properties such as conductivity and reflectance are insufficient. When the amount of the polymer dispersant exceeds 300% by weight, the dispersibility is not further improved. When the hollow particles of ceria are used, the refractive index rises, and the antireflection performance sometimes becomes insufficient. When the conductive particles are used, the antistatic property is exhibited. Sometimes it will be insufficient.

Further, the polymer dispersant of the present invention has a molecular weight of from 1,000 to 100,000, more preferably from 5,000 to 50,000. When the molecular weight is less than 1,000, the polymer dispersant cannot follow the stretching, and when the stretching ratio is high, voids are generated after stretching to increase the haze. When the molecular weight exceeds 100,000, the inorganic oxide fine particles aggregate and the haze of the film rises.

(resin emulsion)

The resin emulsion is an organic resin which is stably dispersed in a dispersion state in a liquid droplet state, that is, in an emulsion state, and the resin may be any one of a thermoplastic resin or a heat (including an electron beam) hardening resin, and may be a lipophilic resin. The hydrophilic resin which is dispersed in a solvent such as water or alcohol, or a hydrophilic resin having affinity with water is dispersed in a lipophilic solvent having a low polarity. Such a resin emulsion means a non-coherent one having a resin which does not dissolve in a dispersion medium to form an emulsion. The droplet state of the emulsion is maintained at the time of film formation, and is also maintained in the present invention at the time of stretching.

In the case of a lipophilic dispersion medium, a hydrophilic resin (A) having affinity with water is used, and in the case of a hydrophilic dispersion medium, a lipophilic resin (B) having no affinity with water is used.

The hydrophilic resin (A) having affinity with water may be selected from the group consisting of an epoxy resin, a polyester resin, a polycarbonate resin, and a polyamide resin. Polyphenylene ether resin, vinyl chloride resin, fluororesin, vinyl acetate resin, polyoxynoxy resin, polyurethane resin, melamine resin, butyral resin, phenol resin, unsaturated polyester resin, or the like At least one of two or more types of copolymers and modified substances, and a lipophilic resin (B) having no affinity with water, may be selected from the group consisting of polyoxyxylene resins, polyurethane resins, and thermoplastic acrylic resins. At least one of a thermosetting acrylic resin and an ultraviolet curable acrylic resin.

From the viewpoint of environmental load, a resin emulsion using a lipophilic resin (B) having no affinity for water and a hydrophilic dispersion medium is suitable.

Further, the resin (B) may have a functional group such as a carboxyl group, a sulfonyl group, an amine group, a phosphonium group, a hydroxyl group or the like, in order to form an emulsion, or may be used to react with each other or with a resin. Any functional group to which the surface-treated organic hydrazine compound is crosslinked, such as an epoxy group, a carbodiimide group, an isocyanate group, an acryl group, a vinyl group or the like. Among them, a polyurethane resin, a PVA resin, and an acrylic resin are preferably used because the obtained film is transparent and is a thermoplastic resin.

Specifically, the "Adeka Bontighter" series by ADEKA Co., Ltd., the "Vondic" series by the DIC Corporation, the "Hydran" series, the "Miractran" series by Nippon Polyurethane Co., Ltd., and the Bayer company can be used. "Impranil" series, "Soflanate" series by Nippon Soflan Co., Ltd., "Poiz" series by Kao Co., Ltd., "Sanplen" series by Sanyo Chemical Co., Ltd., Hodogaya Chemical "Aizelax" series manufactured by Co., Ltd., "Superflex" series manufactured by Daiichi Kogyo Co., Ltd., "Elastron" series, "Neorez" series manufactured by Zeneca Co., Ltd., etc. Ester resin emulsion.

The resin emulsion is substantially spherical and may have a diameter in the range of 10 to 500 nm, preferably 20 to 300 nm. When the diameter of the resin emulsion is less than 10 nm, it is difficult to obtain an emulsion, and even if it is obtained, shrinkage at the time of hardening is large, and cracking may occur. When the diameter of the resin emulsion is more than 500 nm, the inorganic oxide fine particles are difficult to uniformly disperse, and the in-plane reflectance causes film waviness, and the appearance sometimes deteriorates.

For measuring the diameter (diameter) of the resin emulsion, a dynamic scattering particle diameter measuring device (FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.) was used.

The concentration (C _R ) of the resin emulsion in the coating liquid for forming the transparent film is preferably from 0.006 to 68% by weight, more preferably from 0.2 to 49, in terms of solid content. When the concentration (C _R ) is less than the solid content, the resin is small, and the inorganic oxide fine particles are excessive, and the film strength, scratch resistance, scratch strength, and the like may be insufficient. Further, the elongation of the transparent film during stretching is insufficient, and cracking may occur. Further, when the concentration (C _R ) is too large, not only adhesion to the substrate, film strength, surface flatness, scratch resistance, scratch strength, and the like may be insufficient, and the inorganic oxide fine particles may be insufficient, and may not be sufficient. Conductivity, anti-reflective properties, etc. are obtained.

The ratio (C _P /C _R ) of the concentration (C _P ) of the inorganic oxide fine particles in the coating liquid to the concentration (C _R ) of the resin emulsion varies depending on the use and usage of the transparent film, but is preferably It lies in the range of 0.03 to 4. Examples of the use of the transparent film include hard coating, antistatic charging, easy adhesion, antireflection, anti-blocking property, heat insulating property, and the like, and a preferable range can be appropriately set as needed.

Specifically, in the case of a hard coat film, (C _P /C _R ) is preferably in the range of 0.1 to 4, more preferably in the range of 0.25 to 2.4. When it is in this range, a transparent hard coat film excellent in adhesion to a substrate, film strength, surface flatness, scratch resistance, scratch strength, and the like can be formed.

In the case of the antistatic film, (C _P /C _R ) is preferably in the range of 0.03 to 2.4, more preferably in the range of 0.05 to 1. When it is in this range, it is excellent in the adhesiveness with a base material, film strength, and anti-charging property (electroconductivity), and is excellent in surface flatness, abrasion resistance, scratch intensity, etc..

In the case of the adhesion layer, (C _P /C _R ) is preferably in the range of 0.03 to 1, more preferably in the range of 0.05 to 0.25. When it is in this range, an easy-adhesion layer excellent in adhesion to a substrate can be formed without impairing the function of the substrate and other functional films provided on the upper layer.

In the case of an easy-contact layer, inorganic oxide fine particles (C) may be further included. Further, a part of the particles of at least one of the inorganic oxide fine particles (A) and the chain-like inorganic oxide fine particles (B) may be substituted with the inorganic oxide fine particles (C). By using the inorganic oxide fine particles (C), an easy-adhesion layer excellent in blocking resistance can be formed.

Further, when the surface is not treated by the above organic cerium compound as the inorganic oxide fine particles, the inorganic oxide fine particles are appropriately in a state of aggregation, and interference fringes can be suppressed by scattering light. Alternatively, it is also possible to select particles as inorganic oxide particles in such a manner that the refractive index of the obtained easily-adhesive layer is close to the refractive index of the substrate, thereby suppressing Interference fringes.

In the antireflection film, (C _P /C _R ) is preferably in the range of 0.1 to 4, more preferably in the range of 0.25 to 2.4. When it is in this range, a transparent antireflection film excellent in adhesion to a substrate, film strength, and antireflection performance can be formed.

In the case of the anti-adhesive film, inorganic oxide fine particles (C) may be further included. Further, a part of the particles of at least one of the inorganic oxide fine particles (A) and the chain-like inorganic oxide fine particles (B) may be substituted with the inorganic oxide fine particles (C). By using the inorganic oxide fine particles (C), an easy-adhesive layer can be formed. In this case, when (C _P /C _R ) is in the range of 0.03 to 1, more preferably in the range of 0.05 to 0.25, an anti-adhesive film excellent in adhesion to the substrate, film strength, and the like can be formed.

In the case of the heat insulating film, (C _P /C _R ) is preferably in the range of 0.1 to 4, more preferably in the range of 0.25 to 2.4. When it is in this range, a transparent heat-insulating film excellent in adhesion to a substrate, film strength, surface flatness, scratch resistance, scratch strength, and the like can be formed.

(dispersion medium)

The dispersion medium is a solvent which can be dispersed in an emulsion state without dissolving the resin emulsion. For example, water or an organic solvent can be used. Further, the crosslinking agent or the polymerization initiator described later may be dissolved or dispersed, and the inorganic oxide fine particles may be dispersed, and are not particularly limited.

Specific examples thereof include alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, decyl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexanediol, and isopropanol; Methyl ester, ethyl acetate, acetic acid Esters such as esters; 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, etc. Ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetamidine acetate; methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, Isophorone, N,N-dimethylformamide, and the like. Among them, water or alcohol is suitable.

(crosslinking agent)

A crosslinking agent may be added to the coating liquid as needed. The crosslinking agent is used when the resin of the resin emulsion is a thermoplastic resin. The crosslinking agent is not particularly limited as long as it has a functional group reactive with a reactive group of the resin emulsion, and may be appropriately selected from conventionally known crosslinking agents depending on the resin. An epoxy compound, an amine compound, an isocyanate compound, a carbodiimide compound or the like using water as a dispersion medium is used.

The amount of the crosslinking agent to be added is not particularly limited, and is different from the type of the resin emulsion, and is 100% by weight or less based on the solid content of the resin emulsion, and the crosslinking agent is 200% by weight or less based on the solid content, more preferably 10 to 100%. The range of % by weight. When the amount of the crosslinking agent added is small, the curing of the transparent film may be insufficient depending on the type of the resin emulsion. When the amount of the crosslinking agent added is too large, the stability of the coating liquid may be insufficient, and the resulting transparent film may be cracked.

(polymerization initiator)

In the coating liquid, in the case of a curing resin, a polymerization initiator may be added as necessary. The polymerization initiator is not particularly limited as long as it can polymerize and cure the resin emulsion, and can be appropriately selected depending on the resin.

For example, an azo compound such as azonitrile or azoamine or an organic peroxide such as benzamidine peroxide or butanone peroxide may be mentioned.

The amount of the polymerization initiator to be added varies depending on the type of the resin emulsion. When added, the amount of the polymerization initiator is 100% by weight or less based on the solid content of the resin emulsion, and more preferably 200% by weight or less based on the solid content. A range of 10 to 100% by weight. When the amount of the polymerization initiator is small, the hardening of the transparent film is sometimes insufficient. When the amount of the polymerization initiator used is too large, the stability of the coating liquid may be insufficient, and the resulting transparent film may be cracked.

The total solid content concentration of the coating liquid for forming the transparent film is preferably from 0.03 to 70% by weight, more preferably from 1 to 50% by weight.

When the solid content concentration of the coating liquid is too low, it is difficult to adjust the film thickness, and waviness is likely to occur in a dry state. Further, when the base film is stretched after the application of the coating liquid, it may be difficult to obtain a desired film thickness, and cracking may occur. When the solid content concentration of the coating liquid for forming the transparent film is too high, the stability is lowered, the coatability is lowered, and the adhesion between the obtained transparent film and the substrate, film strength, scratch resistance, scratching Strength and the like sometimes become insufficient. In particular, the viscosity of the coating liquid is increased, and it is sometimes difficult to uniformly apply the coating in accordance with the stretching of the substrate, or it is sometimes difficult to uniformly stretch the coating film upon stretching after coating to produce spots or films. Corrugated (island pattern), cracked.

Next, a method of producing a substrate to which a film is attached using the above coating liquid will be described.

[Manufacturing method of substrate with transparent film]

The method for producing a substrate coated with a transparent film of the present invention comprises the steps of applying a coating liquid and the step of stretching the substrate film. Specifically, as long as (1) the coating liquid is applied to the substrate, the method of stretching the substrate with the coating film before the coating film is dried, and (2) coating the substrate while stretching the substrate The method of coating the coating liquid, the number of times of applying the coating liquid or the direction or number of stretching is not particularly limited. More specific methods are listed, and the following four types are listed.

‧1st type

In the first type, the step of biaxial stretching is carried out after the coating step.

That is, it is sequentially performed: (a) a step of applying a coating liquid onto the resin film substrate, and (b) a step of subjecting the resin film with the coating film to biaxial (longitudinal and transverse) stretching, ( c) a step of removing (drying) the dispersion medium contained in the coating film, and (d) a step of hardening.

Step (a)

The above coating liquid was applied onto a resin film substrate. Here, the substrate before stretching is used. The thickness of the substrate before stretching is usually in the range of 400 to 5000 μm. Specific examples thereof include a polyester substrate such as polyethylene terephthalate or polyethylene naphthalate, and a polyolefin substrate such as a polyethylene film, a polypropylene film or a cyclic polyolefin film, and nylon-6. Polyacrylamide film, nylon-66, etc., in addition, polyacrylic acid film, polyurethane film, polycarbonate film, polyether film, polyether film, polystyrene film, polymethyl A substrate such as a pentene film, a polyether ketone film, or an acrylonitrile film. In particular, a polyester substrate or a polyacrylic film is excellent in heat resistance and high in transparency, and can be preferably used.

Coating method for coating liquid, spray method, rotation A generally known method such as a coating method, a roll coating method, a bar coating method, a slit coating printing method, a gravure printing method, a micro gravure printing method, or the like. In the present invention, a roll coating method, a slit coating printing method, a gravure printing method, and a micro gravure printing method are recommended.

The coating amount at this time is applied so that the film thickness of the transparent film after stretching becomes a desired thickness. For example, in the case of an easy-adhesion layer and an anti-adhesive film, it is applied in such a manner that the average film thickness (T _F ) becomes 10 to 2000 nm, preferably 20 to 800 nm. In the case of the antireflection film, it is applied in such a manner that the average film thickness (T _F ) is from 80 to 400 nm, preferably from 90 to 300 nm. In the case of hard coating, it is applied in such a manner that the average film thickness (T _F ) is from 0.5 to 30 μm, preferably from 1 to 10 μm. In the case of resisting the charged film, it is applied in such a manner that the average film thickness (T _F ) is 1 to 20 μm, preferably 3 to 15 μm. In the case of the heat insulating film, the film is applied so that the average film thickness (T _F ) is from 1 to 300 μm, preferably from 5 to 100 μm.

Step (b)

The resin film with the coating film is stretched. The stretching method employs biaxial stretching. At this time, the thickness of the substrate after stretching is usually preferably in the range of 20 to 200 μm. Here, the biaxial stretching means stretching (longitudinal axis stretching) in the direction in which the substrate (roller) with the coating film is taken up, and stretching in the direction perpendicular thereto (horizontal axis stretching) ).

Step (c)

The drying method is not particularly limited as long as it is a dispersion medium capable of removing the coating liquid. For example, it may be air-dried or the resin film on which the coating film is formed may be dried under heating. The heating temperature is approximately 50 to 200 ° C, and the time is approximately It is 1 second to 1 hour.

Step (d)

The method of curing the coating film differs depending on the type of the resin emulsion used in the coating liquid, and may be heat-cured when a heat-curable resin is used, ultraviolet light is used when an ultraviolet-curable resin is used, and heating is required as necessary. A method known in the past. In the case of a thermoplastic resin, it is hardened by cooling after heating.

‧Type 2

In the second type, after the step of coating the substrate after the longitudinal axis stretching, the step of stretching on the horizontal axis is performed.

That is, it is sequentially performed: (a') a step of applying a coating liquid onto the resin film substrate stretched by the longitudinal axis, and (b') performing a horizontal axis stretching on the resin film with the coating film. And (c) a step of removing (drying) the dispersion medium contained in the coating film, and (d) a step of hardening.

Step (a')

The coating liquid for forming a transparent film described above was applied onto the resin film substrate stretched by the longitudinal axis. The thickness of the substrate after stretching on the longitudinal axis is usually in the range of 40 to 500 μm. The base material is the base material described in the first embodiment, and the coating method of the coating liquid is also the same. The coating amount at this time is preferably applied so that the average film thickness (T _F ) of the finally obtained transparent film is within the above range.

Step (b')

The resin film with the coating film was subjected to horizontal axis stretching. At this point, after stretching The thickness of the substrate is usually stretched in the range of 20 to 200 μm.

Step (c) and step (d) are the same as the first type.

‧3rd type

In the third type, the coating step and the vertical axis stretching step are simultaneously performed.

That is, (a") a step of coating the coating liquid on the resin film substrate while stretching the substrate on the vertical axis, and (b") performing the resin film with the coating film on the coating film. The step of stretching on the horizontal axis, (c) the step of removing (drying) the dispersion medium contained in the coating film, and (d) the step of hardening.

Step (a")

The coating liquid was applied onto the resin film substrate while stretching the substrate on the vertical axis.

The stretching method of the substrate is the same as the vertical stretching method of the second type. The base material is the base material described in the first embodiment, and the coating method of the coating liquid is also the same. The coating amount at this time is preferably applied so that the average film thickness (T _F ) of the finally obtained transparent film is within the above range.

Step (b")

The resin film with the coating film was subjected to horizontal axis stretching. At this time, the thickness of the substrate after stretching is usually stretched so as to be in the range of 20 to 200 μm.

Steps (c) and (d) are the same as the first and second forms.

‧4th type

In the fourth type, the coating step and the biaxial stretching step are simultaneously performed.

That is, sequentially (a"') on the substrate, the step of coating the coating solution while stretching the substrate on the biaxial (vertical axis and the horizontal axis), (c) removing (drying) The step of dispersing the medium contained in the coating film, and (d) the step of hardening.

Step (a"')

The coating liquid was applied to the resin film substrate while biaxially stretching the substrate. The stretching method employs a biaxial stretching method. In this case, the thickness of the base material after stretching is usually preferably in the range of 20 to 200 μm, and the substrate described in the first type is used as the substrate, and the coating method of the coating liquid is also carried out in the same manner. The coating amount at this time is preferably applied so that the average film thickness (T _F ) of the finally obtained transparent film is within the above range.

Steps (c) and (d) are the same as the first to third forms.

Thus, a method of producing a substrate coated with a transparent film of the present invention can be produced.

The average film thickness of the obtained transparent film varies depending on the type of the transparent film, and is preferably in the above range. For example, when the average thickness (T _F ) of the antireflection film is less than 80 nm when the substrate with the antireflection film is attached, the strength and scratch resistance of the antireflection film may be insufficient, and the expectation may not be obtained. Reflectivity. When the average film thickness (T _F ) exceeds 400 nm, the antireflection film is likely to be cracked, so that the strength of the antireflection film is insufficient, and when the film is too thick, the antireflection performance may be insufficient. When the average film thickness (T _F ) of the antireflection film is in the above range, an antireflection film having a low reflectance (bottom reflectance and visual reflectance) and excellent film strength and the like can be obtained.

In the present invention, the measurement of the average film thickness (T _F ) of the transparent film is carried out by taking a cross section of a transparent film by a transmission electron microscope (TEM: Transmitting Electron Microscope).

The content of the inorganic oxide fine particles in the transparent film is preferably from 3 to 80% by weight, more preferably from 5 to 70% by weight. When the content of the inorganic oxide fine particles in the transparent film is less than 3% by weight, the adhesion to the substrate, the film strength, the surface flatness, the scratch resistance, the scratch strength, and the like may become insufficient. When the film is reflected, the degree of reduction in the refractive index may be insufficient to make the antireflection performance insufficient. When the content of the inorganic oxide fine particles in the transparent film exceeds 80% by weight, the film strength, the scratch resistance, the scratch strength, and the like become insufficient due to the excessive number of particles, and the fog may be more likely to occur in the antireflection film. The degree is increased. Further, since the elongation of the transparent film at the time of stretching cannot follow the stretching of the substrate, cracks sometimes occur.

The content of the resin derived from the resin emulsion in the transparent film is preferably from 20 to 97% by weight, more preferably from 30 to 95% by weight. For this reason, the inventors of the present invention have considered that the resin emulsion maintains a droplet shape (emulsion state) in the coating film at least before drying, and therefore, even if the substrate is stretched during stretching, it can be stretched and coated. Movement or deformation in the film. The droplets are melted or hardened by a subsequent drying and hardening treatment, and are film-formed into one.

When the content of the resin derived from the resin emulsion in the transparent film is less than the solid content, the resin is less, not only the film strength, abrasion resistance The scratch, the scratch strength, and the like may become insufficient, and the haze value of the transparent film may be increased due to excessive particles. Further, the elongation of the transparent film during stretching cannot follow the stretching of the substrate, and cracks sometimes occur. When the content of the resin derived from the resin emulsion in the transparent film is too large, the adhesion to the substrate, the film strength, the surface flatness, the scratch resistance, the scratch strength, and the like may become insufficient due to the small number of particles, and There are few inorganic oxide fine particles, and the function of the transparent film may be insufficient.

The invention is illustrated by the following examples, but the invention is not limited thereto.

[Example 1] Modulation of coating liquid (H-1P) for forming a hard coating film

An ultrafiltration membrane was used, and the dispersion medium was replaced with ethanol, and the cerium oxide sol (manufactured by Co., Ltd.: Cataloid-SN, average particle diameter: 12 nm, SiO ₂ concentration: 20% by weight, aqueous dispersion medium) was prepared. An alcohol dispersion of cerium oxide fine particles (H-1V) having a solid concentration of 20% by weight was obtained.

4 g of a decane coupling agent (methyltrimethoxy decane) (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-13) was added to 100 g of an alcohol dispersion liquid of cerium oxide fine particles (H-1V) having a solid concentration of 20% by weight. The mixture was heat-treated at ° C to prepare an alcohol dispersion of the surface-treated cerium oxide microparticles (H-1VS) having a solid concentration of 20% by weight. The dispersion medium was replaced with water using a rotary evaporator to prepare an aqueous dispersion of the surface-treated cerium oxide microparticles (H-1VS) having a solid concentration of 40.5% by weight. At this time, the alkali concentration was 200 ppm.

Next, the polyurethane resin emulsion (First Industrial Pharmaceutical) Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 11.4 g, isopropyl alcohol 5.3 g mixed with surface treated cerium oxide particles (H-1VS) 10.0 g of the dispersion liquid was prepared to prepare a coating liquid (H-1P) for forming a hard coat film having a solid content concentration of 30.0% by weight.

Manufacture of stretch film substrate (H-1F) with hard coating

70 wt% of ethylene terephthalate, 70 wt% of ethylene glycol, 0.01 wt% of calcium acetate as a transesterification catalyst, and 0.03 wt% of antimony trioxide as a polycondensation catalyst, and the temperature was raised to 220. °C to distill off the theoretical methanol and terminate the transesterification reaction. Next, 0.04% by weight of trimethyl phosphate was added to the system. The inside of the system was decompressed, and a polycondensation reaction was carried out for 4 hours under a reduced pressure of 1 mmHg at a temperature of 290 ° C to prepare a polyester resin.

The obtained polyester resin was flaky at 295 ° C by an extruder to prepare a polyester resin film (1) for a substrate. The thickness of the polyester resin film (1) was 1,125 μm. After the polyester resin film (1) was subjected to longitudinal stretching (140 ° C, 2.5 times stretching), a coating liquid for forming a hard coating film was applied by a bar coating method (rod #60) ( H-1P), after drying at 140 ° C for 120 seconds, was subjected to horizontal axis stretching (140 ° C, 4.5 times stretching) to produce a stretched film substrate (H-1F) having a hard coat film. At this time, the thickness of the film substrate was 100 μm, and the film thickness of the hard coat film was 5 μm.

The total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), presence or absence of cracks of the obtained stretched film substrate (H-1F) with a hard coating film were measured. Flatness and scratch resistance of the film surface, the result is Shown in the table. The total light transmittance and haze were measured by a haze meter (manufactured by Suga Test Instruments Co., Ltd.).

Only the base material was similarly stretched to a thickness of 100 μm with the polyester resin film (1), and the total light transmittance was 93.14%, and the haze was 0.27%.

Pencil hardness

The pencil hardness was measured by a pencil hardness tester in accordance with JIS K 5400. That is, the pencil was placed at an angle of 45 degrees with respect to the surface of the hard coating film, and a predetermined load was applied and pulled at a constant speed to observe the presence or absence of damage.

Adhesiveness

11 parallel cuts were formed on the surface of the stretched film substrate (H-1F) with the hard coat film by the blade at intervals of 1 mm in the longitudinal direction and the transverse direction to make 100 small squares, and then the cellophane tape was then Here, the cellophane tape was peeled off, and the number of small squares in which the film was not peeled off at this time was classified into the following three stages, thereby evaluating the adhesion. The results are shown in the table.

The number of remaining small squares is more than 90: ◎

The number of remaining small squares is 85 to 89: ○

The number of remaining small squares is 84 or less: △

Membrane ripple (island pattern)

The surface was visually observed and evaluated by the following criteria.

The corrugated appearance was not confirmed on the surface: ◎

It is almost impossible to confirm the appearance of a corrugated appearance on the surface: ○

Only a few corrugated appearances were observed on the surface: △

A corrugated appearance was clearly observed on the surface: ×

Crack

The surface was observed with an electron microscope and evaluated by the following criteria.

No cracks were observed at all: ◎

Only minor cracks were observed: ○

Fine cracking was observed clearly: △

Fine cracks and large cracks were observed: ×

Film surface flatness

The flatness (Ra) of the surface was measured by an atomic force microscope (AFM: Atomic Force Microscope) manufactured by Hitachi Hi-Tech Science Co., Ltd., and evaluated by the following criteria.

Ra value is less than 10nm: ◎

Ra value is 10 nm or more and less than 20 nm: ○

Ra value is 20 nm or more and less than 50 nm: △

Ra value is above 50 nm: ×

Determination of scratch resistance

Using #0000 steel wool, the surface of the film was visually observed by sliding 50 times at a load of 500 g/cm ² and evaluated by the following criteria. The results are shown in the table.

No long damage was observed: ◎

Only a few long strips of damage were observed: ○

Many long strips of damage were observed: △

The entire surface is removed: ×

[Embodiment 2] Modulation of coating liquid (H-2P) for forming a hard coating film

Polyurethane resin emulsion (manufactured by Daiichi Kogyo Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 16.0 g, isopropyl alcohol 4.7 g mixed with the examples 1 5.9 g of an aqueous dispersion of the surface-treated cerium oxide microparticles (H-1VS) prepared in the same manner to prepare a coating liquid (H-2P) for forming a hard coating film having a solid content concentration of 30.0% by weight. .

Manufacture of stretch film substrate (H-2F) with hard coating film

A stretched film substrate with a hard coat film was produced in the same manner as in Example 1 except that (H-2P) was used instead of (H-1P) as a coating liquid for forming a hard coat film ( H-2F). At this time, the thickness of the film substrate was 100 μm, and the film thickness of the hard coat film was 4.8 μm.

For the obtained stretched film substrate (H-2F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Example 3] Modulation of coating liquid (H-3P) for forming a hard coating film

Polyurethane resin emulsion (manufactured by Dai-Il Pharmaceutical Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 6.9 g, and isopropanol 6.0 g were mixed with the examples. 1 same party 13.8 g of an aqueous dispersion of the surface-treated cerium oxide microparticles (H-1VS) prepared by the preparation was prepared to prepare a coating liquid (H-3P) for forming a hard coating film at a solid concentration of 30.0% by weight.

Manufacture of stretch film substrate (H-3F) with hard coating

In Example 1, except that (H-3P) was used instead of (H-1P) as a coating liquid for forming a hard coat film, the stretching with a hard coat film was produced in the same manner as in Example 1. Film substrate (H-3F). At this time, the thickness of the film substrate was 100 μm, and the film thickness of the hard coat film was 5.4 μm.

For the obtained stretched film substrate (H-3F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), and crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Example 4] Modulation of coating liquid (H-4P) for forming a hard coating film

Polyurethane resin emulsion (manufactured by Daiichi Kogyo Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 11.4 g, pure water 10.6 g, isopropyl alcohol 8.0 g 10.0 g of an aqueous dispersion of the surface-treated cerium oxide microparticles (H-1VS) prepared in the same manner as in Example 1 was mixed to prepare a coating liquid for forming a hard coating film having a solid content concentration of 20.0% by weight. (H-4P).

Manufacture of stretch film substrate (H-4F) with hard coating

A stretching with a hard coating film was produced in the same manner as in Example 1 except that (H-4P) was used instead of (H-1P) in Example 1 as a coating liquid for forming a hard coating film. Film substrate (H-4F). At this time, the thickness of the film substrate is The film thickness of the hard coat film was 100 μm, which was 3.2 μm.

For the obtained stretched film substrate (H-4F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), and crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Example 5] Modulation of coating liquid (H-5P) for forming a hard coating film

An urethane resin emulsion (manufactured by First Industrial Pharmaceutical Co., Ltd.: Superflex 150, resin concentration: 30% by weight, particle diameter: 70 nm, dispersion medium: water), 13.5 g, and isopropyl alcohol, 3.5 g, were mixed with Example 1. 10.0 g of the aqueous dispersion of the surface-treated cerium oxide fine particles (H-1VS) prepared in the same manner was prepared to prepare a coating liquid (H-5P) for forming a hard coat film at a solid concentration of 30.0% by weight.

Manufacture of stretch film substrate (H-5F) with hard coating

A stretching with a hard coating film was produced in the same manner as in Example 1 except that (H-5P) was used instead of (H-1P) in Example 1 as a coating liquid for forming a hard coating film. Film substrate (H-5F). At this time, the thickness of the film substrate was 100 μm, and the film thickness of the hard coat film was 4.9 μm.

For the obtained stretched film substrate (H-4F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), and crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Embodiment 6] Modulation of coating liquid (H-6P) for forming a hard coating film

The urethane resin emulsion (manufactured by Dai-Il Pharmaceutical Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water), 17.1 g, isopropyl alcohol, 6.8 g, was mixed in the examples. The solid content concentration of 1 was adjusted to 60% by weight of surface-treated cerium oxide microparticles (H-6VS) (10.0 g) to prepare a coating liquid for forming a hard coating film with a solid concentration of 35.3 wt% (H- 6P).

Manufacture of stretch film substrate (H-6F) with hard coating

The coating liquid (H-6P) for forming a hard coat film was applied onto the polyester resin film (1) for a substrate prepared in the same manner as in Example 1 by a bar coating method (rod #72). Then, it was 2.5 times in the direction of the vertical axis and 4.5 times in the direction of the horizontal axis, and was stretched at 140 ° C under heating, and then dried at 140 ° C for 120 seconds to produce a hard coat film. Stretched film substrate (H-6F). At this time, the thickness of the substrate was 100 μm, and the film thickness of the hard coat film was 2 μm.

For the obtained stretched film substrate (H-6F) having a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), and crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Embodiment 7] Manufacture of stretch film substrate (H-7F) with hard coating

The substrate was prepared by stretching the polyester resin film (1) prepared in the same manner as in Example 1 while heating at 140 ° C in a manner of 2.5 times in the direction of the longitudinal axis, and by a bar coating method ( Bar #60) The coating liquid (H-1P) for forming a hard coat film prepared in the same manner as in Example 1 was applied, followed by heating at 140 ° C in a manner of 4.5 times in the horizontal axis direction. Stretching, then The film was dried at 140 ° C for 120 seconds to produce a stretched film substrate (H-7F) with a hard coat film. At this time, the thickness of the substrate was 100 μm, and the film thickness of the hard coat film was 5.1 μm.

For the obtained stretched film substrate (H-7F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Embodiment 8] Manufacture of stretched film substrate (H-8F) with hard coating

The base material for a polyester resin film (1) prepared in the same manner as in Example 1 was stretched at a temperature of 140 ° C in a manner of 2.5 times in the direction of the longitudinal axis and 4.5 times in the direction of the horizontal axis. The coating liquid (H-1P) for forming a hard coat film prepared in the same manner as in Example 1 was applied by a bar coating method (rod #16), followed by drying at 140 ° C for 120 seconds to manufacture. A stretched film substrate (H-8F) to which a hard coat film is attached is attached. At this time, the thickness of the substrate was 100 μm, and the film thickness of the hard coat film was 5 μm.

For the obtained stretched film substrate (H-8F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Embodiment 9] Modulation of coating liquid (H-9P) for forming a hard coating film

2 g of a polyacrylic acid dispersant (Aron SD-10, manufactured by Toagosei Co., Ltd.) was added to the solid content concentration of 20% by weight obtained in Example 1. 100 g of an alcohol dispersion of cerium oxide microparticles (H-1V) was heat-treated at 50 ° C, and then the dispersion medium was replaced with ethanol using an ultrafiltration membrane to prepare cerium oxide microparticles having a solid concentration of 20% by weight. Alcohol dispersion of (H-9VS). The dispersion medium was replaced with water using a rotary evaporator to prepare an aqueous dispersion of the surface-treated cerium oxide microparticles (H-9VS) having a solid concentration of 40.5% by weight. At this time, the alkali concentration was 200 ppm.

Next, a polyurethane resin emulsion (manufactured by Dai-Il Pharmaceutical Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water), 11.4 g, and isopropyl alcohol (5.3 g) were mixed on the surface. 10.0 g of an aqueous dispersion of the cerium oxide microparticles (H-9VS) after the treatment was prepared to prepare a coating liquid (H-9P) for forming a hard coating film at a solid concentration of 30.0% by weight.

Manufacture of stretch film substrate (H-9F) with hard coating

The substrate prepared in the same manner as in Example 1 was stretched with a polyester resin film (1) at a temperature of 140 ° C in a manner of 2.5 times in the direction of the longitudinal axis, followed by a bar coating method (rod) #60) The coating liquid (H-9P) for forming a hard coating film was applied, dried at 80 ° C for 120 seconds, and then hardened by irradiation with ultraviolet rays of 600 mJ/cm ² to be 4.5 times in the horizontal axis direction. In the manner of stretching at 140 ° C under heating, and then drying at 140 ° C for 120 seconds, a stretched film substrate (H-9F) with a hard coat film was produced. At this time, the thickness of the substrate was 101 μm, and the thickness of the hard coat film was 5 μm.

For the obtained stretched film substrate (H-9F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. , the flatness of the film surface and scratch resistance, the results such as Shown in the table.

[Comparative Example 1] Modulation of coating liquid (RH-1P) for forming a hard coating film

Mixed dipentaerythritol hexaacrylate (Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd.: Kayarad KS-HDDA) 5.9g, single-end methacrylic acid polyoxygenated oil (Xingfu Chemical Industry Co., Ltd.: X-22-174DX) 0.4g, propylene glycol monomethyl ether 75.5g, and photopolymerization initiator 2,4,6 - 3.5 g of trimethylbenzhydryl diphenylphosphine oxide (manufactured by BAS Japan Co., Ltd.: Lucirin TPO) to prepare a matrix-forming component solution (1) having a solid concentration of 44% by weight.

Then, 30.0 g of an alcohol dispersion liquid of cerium oxide fine particles (H-1VS) having a solid content concentration of 40% by weight, which was prepared in the same manner as in Example 1, was mixed with a solid content concentration of 44% by weight of the matrix-forming component solution (1): 30.0 g, Further, 22.6 g of isopropyl alcohol was prepared to prepare a coating liquid (RH-1P) for forming a transparent film having a solid concentration of 30% by weight.

Manufacture of stretch film substrate (RH-1F) with hard coating

The substrate prepared in the same manner as in Example 1 was stretched with a polyester resin film (1) at a temperature of 140 ° C in a manner of 2.5 times in the direction of the longitudinal axis, followed by a bar coating method (rod) #60) The coating liquid (RH-1P) for forming a hard coating film was applied, dried at 80 ° C for 120 seconds, and then hardened by irradiation with ultraviolet rays of 600 mJ/cm ² to be 4.5 times in the horizontal axis direction. In the manner of stretching at 140 ° C under heating, and then drying at 140 ° C for 120 seconds, a stretched film substrate (RH-1F) with a hard coat film was produced. At this time, the thickness of the substrate was 100 μm, and the film thickness of the hard coat film was 5 μm.

For the obtained stretched film substrate (RH-1F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Comparative Example 2] Modulation of a coating liquid (RH-2P) for forming a hard coating film

Mixed polyurethane resin emulsion (manufactured by Dai-Il Pharmaceutical Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 3.8 g, isopropanol 17.4 g, methyl isobutyl 1.8 g of ketone and 1.7 g of isopropyl glycol were prepared to prepare an emulsion diluent.

As a result of observing the emulsion diluent, it was considered to be transparent, and since the particle diameter could not be measured, it was presumed that the resin emulsion disappeared.

Then, 3.28 g of an aqueous dispersion of the surface-treated cerium oxide microparticles (H-1VS) prepared in the same manner as in Example 1 was added to prepare a coating liquid for forming a hard coating film having a solid concentration of 9.5% by weight. (RH-2P).

Manufacture of stretch film substrate (RH-2F) with hard coating

The substrate prepared in the same manner as in Example 1 was stretched at 140 ° C in a manner of 2.5 times in the direction of the longitudinal axis, and then stretched with a polyester resin film (1), followed by a bar coating method (rod) #50) Coating liquid (RH-2P) for forming a hard coat film, followed by drying at 140 ° C for 120 seconds, and then heating at 140 ° C in a manner of 4.5 times in the horizontal axis direction. The stretched film substrate (RH-2F) with a hard coat film was produced by stretching. At this time, the thickness of the substrate is 100μ m, the film thickness of the hard coat film was 5 μm.

For the obtained stretched film substrate (RH-2F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Comparative Example 3] Manufacture of stretch film substrate (RH-3F) with hard coating

The base material prepared in the same manner as in Example 1 was biaxially stretched with a polyester resin film (1) to prepare a polyester resin film substrate having a thickness of 100 μm.

Then, a coating liquid (RH-1P) for forming a transparent film having a solid content concentration of 30.0% by weight prepared in the same manner as in Comparative Example 1 was applied by a bar coating method (rod #18), and dried at 80 ° C. After 120 seconds, ultraviolet rays of 600 mJ/cm ² were irradiated and hardened to produce a stretched film substrate (RH-3F) with a hard coat film. At this time, the thickness of the substrate was 100 μm, and the film thickness of the hard coat film was 5 μm.

For the obtained stretched film substrate (RH-3F) with a hard coat film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The flatness and scratch resistance of the film surface are shown in the table.

[Embodiment 10] Modulation of a coating liquid (P-10P) for forming an easy-adhesion layer

Polyurethane resin emulsion (manufactured by Dai-Il Pharmaceutical Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 88.5 g, isopropyl alcohol 89.1 g, pure water 233.2 g 33.2 g of an aqueous dispersion of cerium oxide microparticles (H-1VS) obtained in Example 1 and a cerium oxide organosol (manufactured by Nippon Chemical Co., Ltd.: ELCOM V-8901, average particle diameter: 120 nm, SiO _{2 )} A coating liquid (P-10P) for forming an easy-adhesion layer was prepared by dissolving a solid concentration of 10.0% by weight in a concentration of 20% by weight in a dispersion medium: methanol.

Manufacture of stretched film substrate (P-10F) with easy adhesion layer

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then coated by a bar coating method (rod #4). The coating liquid (P-10P) which forms an easy-adhesion layer was dried at 140 ° C for 120 seconds, and then subjected to transverse-axis stretching (140 ° C, 4.5-fold stretching) to produce a stretched film with an easy-adhesion layer. Substrate (P-10F). At this time, the thickness of the substrate was 100 μm, and the film thickness of the easily-adherent layer was 0.1 μm.

For the obtained stretched film substrate (P-10F) with an easy-to-adhere layer, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The film surface was flat, scratch-resistant, anti-blocking, and adhesive. Further, interference fringes were observed, and the results are shown in the table. Anti-adhesion, adhesion and interference fringes were evaluated by the following methods.

(anti-adhesive)

A part of the stretched film substrate (P-10F) with an easy-adhesion layer is cut into two pieces, and the other stretched film substrate (substrate + easy-adhesion layer) with an easy-adhesion layer is superposed on one side. The stretched film substrate (substrate + easy-adhesion layer) with an easy-adhesion layer was attached, and the weight was placed so as to apply a load of 10 kg per 1 cm ² , and the evaluation was carried out for 24 hours after the following reference. The ease of peeling.

Very easy to peel off: ◎

Can be easily peeled off: ○

Slightly difficult to peel off: △

Unable to peel or difficult to peel: ×

(interference fringes)

The light of the fluorescent lamp is reflected on the surface of the transparent peritoneum in a state where the background of the stretched film substrate (P-10F) with the easy-to-adhere layer is made black, and the interference of light is observed by visual observation. The generation of rainbow lines is evaluated by the following criteria.

No rainbow pattern observed at all: ◎

Only a few rainbow lines were observed: ○

Obviously observed rainbow pattern: △

Vividly observed rainbow pattern: ×

(adequate assessment)

The hard coating (manufactured by Nippon Chemical Co., Ltd.: ELCOM HP-1004) was applied to a stretched film substrate (P-10F) with an easy-to-attach layer by a bar coating method (rod #12). After drying at 80 ° C for 1 minute, it was hardened by irradiating 600 mJ/cm ² with an ultraviolet irradiation device (manufactured by Nippon Battery Co., Ltd.: UV irradiation device CS30L21-3) equipped with a high-pressure mercury lamp (120 W/cm). Hard coating film and substrate for easy adhesion layer. At this time, the thickness of the hard coat film was 5 μm, and the total film thickness was 5.6 μm.

The adhesion of the obtained hard coat film was measured by the aforementioned method, and evaluated as adhesion.

[Comparative Example 4] Modulation of a coating liquid (RP-10P) for forming an easy-adhesion layer

Mixed polyurethane resin emulsion (manufactured by Daiichi Kogyo Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 38.0 g, isopropanol 170.4 g, methyl isobutyl 18.0 g of ketone and 17.0 g of isopropyl glycol were prepared to prepare an emulsion diluent.

As a result of observing the emulsion diluent, it was considered to be transparent, and since the particle diameter could not be measured, it was presumed that the resin emulsion disappeared.

Then, 33.2 g of an aqueous dispersion of cerium oxide fine particles (H-1VS) prepared in the same manner as in Example 1 and a cerium oxide organosol (ELCOM V-8901, manufactured by Nippon Chemical Co., Ltd., average particle diameter: 120 nm) were added. The SiO ₂ concentration was 20% by weight, and the dispersion medium: methanol was 0.6 g, and a coating liquid (RP-4P) for forming an easy-adhesion layer was prepared at a solid concentration of 7.4% by weight.

Manufacture of stretched film substrate (RP-1) with easy adhesion layer

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then coated by a bar coating method (rod #6). The coating liquid (RP-4P) which forms an easy-adhesion layer was dried at 140 ° C for 120 seconds, and then subjected to transverse-axis stretching (140 ° C, 4.5-fold stretching) to produce a stretched film with an easy-adhesion layer. Substrate (RP-4F). At this time, the thickness of the substrate was 100 μm, and the film thickness of the easily-adherent layer was 0.1 μm.

For the obtained stretched film substrate (RP-4F) with an easy-to-attach layer, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. , flatness of the film surface, scratch resistance Sex and anti-adhesive properties, the results are shown in the table. Further, a hard coat film was formed and evaluated in the same manner as in Example 9 except for the adhesiveness.

[Example 11] Modulation of a coating liquid (AS-11P) for forming an antistatic film

Sb-doped tin oxide (ATO) fine particles (manufactured by Nippon Chemical Co., Ltd.: ELCOM TL-30HK, Sb ₂ O ₅ content: 16% by weight, average particle diameter: 8 nm) 60 g of hydrogen peroxide dispersed in a concentration of 4.3% by weight 140 g of a potassium aqueous solution was pulverized by a sand mill for 3 hours while maintaining the dispersion at 30 ° C to prepare a sol.

Subsequently, the sol was subjected to de-ionization treatment with an ion exchange resin until the pH became 3.0, and then pure water was added to prepare a Sb-doped tin oxide fine particle dispersion (AS-11V) having a solid concentration of 20% by weight. The pH of this ATO microparticle dispersion was 3.3. Further, the average particle diameter was 8 nm.

Next, 100 g of ATO fine particle dispersion (AS-11V) having a concentration of 20% by weight was adjusted to 25 ° C, and a decane coupling agent (methyltrimethoxy decane) (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-13) 1.0 g was added thereto over 3 minutes. After that, stir for 30 minutes. Then, 100 g of ethanol was added thereto over 1 minute, and the temperature was raised to 50 ° C over 30 minutes to carry out a superheat treatment for 15 hours. The solid content concentration at this time was 10% by weight.

Then, the surface treated ATO fine particle aqueous dispersion (AS-11VS) having a solid concentration of 30% by weight was prepared by ultrafiltration using water as a dispersion medium and replacing it with water from an ethanol mixed solvent. At this time, the concentration of the alkali metal was 100 ppm.

Next, a polyurethane resin emulsion (manufactured by Dai-Il Pharmaceutical Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water), 38.6 g, and isopropyl alcohol (6.4 g) were mixed on the surface. 5.0 g of the treated ATO fine particle aqueous dispersion (AS-11VS) was prepared to prepare a coating liquid (AS-11P) having a solid content concentration of 30.0% by weight to form an antistatic film.

Manufacture of stretch film substrate (AS-11F) with antistatic film

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then coated by a bar coating method (rod #42). The coating liquid (AS-11P) which forms an antistatic film is dried at 140 ° C for 120 seconds, and then subjected to transverse axis stretching (140 ° C, 4.5 times stretching) to produce a stretched film with an antistatic film. Substrate (AS-11F). At this time, the thickness of the film substrate was 100 μm, and the film thickness of the antistatic film was 3 μm.

For the obtained stretched film substrate (AS-11F) with antistatic film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The flatness, scratch resistance and surface resistance of the film surface are shown in the table. The surface resistance value was measured by a surface resistance meter (manufactured by Mitsubishi Chemical Corporation: Hyrester).

[Comparative Example 5] Modulation of a coating liquid (RAS-5P) for forming an antistatic film

Mixed polyurethane resin emulsion (manufactured by Daiichi Kogyo Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 38.0 g, isopropanol 170.4 g, methyl isobutyl 18.0 g of ketone and 17.0 g of isopropyl glycol were prepared to prepare an emulsion diluent.

As a result of observing the emulsion diluent, it was considered to be transparent, and since the particle diameter could not be measured, it was presumed that the resin emulsion disappeared.

Then, 4.9 g of the surface-treated ATO fine particle aqueous dispersion (AS-11VS) having a solid content concentration of 30% by weight prepared in the same manner as in Example 10 was added to prepare a solid content concentration of 5.9% by weight to form an antistatic film. Coating solution (RAS-5P).

Manufacture of stretch film substrate (RAS-5F) with antistatic film

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then coated by a bar coating method (rod #48). The coating liquid (RAS-5P) which forms an antistatic film was dried at 140 ° C for 120 seconds, and then subjected to transverse axis stretching (140 ° C, 4.5 times stretching) to produce a stretched film with an antistatic film. Substrate (RAS-5F). At this time, the thickness of the film substrate was 100 μm, and the film thickness of the antistatic film was 3.1 μm.

For the obtained stretched film substrate (RAS-5F) with an antistatic film, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The flatness, scratch resistance and surface resistance of the film surface are shown in the table.

[Embodiment 12] Modulation of coating liquid (HI-12P) for forming a heat insulating film

Polyurethane resin emulsion (manufactured by Daiichi Kogyo Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 24.0 g mixed with hollow ceria organosol (daily touch Media Chemical Co., Ltd.: Sururia 4110, solid content concentration of 20.5%, average particle size of 60nm, dispersion medium: isopropanol) 98.0g, borrowed The solvent was removed by a rotary evaporator to prepare a coating liquid (HI-12P) for forming a heat-insulating film having a solid concentration of 50.0% by weight. At this time, the concentration of the alkali metal was 5 ppm.

Manufacture of stretched film substrate (HI-12F) with thermal insulation film

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then a coating for forming a heat-insulating film was carried out by a spray method. The liquid (HI-12P) was coated with 45 μm, dried at 140 ° C for 120 seconds, and then subjected to horizontal axis stretching (140 ° C, 4.5 times stretching) to produce a stretched film substrate (HI) with a heat insulating film. -12F). At this time, the thickness of the film substrate was 300 μm, and the thickness of the heat-insulating film was 30 μm.

The obtained stretched film substrate (HI-12F) with a heat-insulating film was measured for total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), and cracking. The presence or absence, flatness of the film surface, scratch resistance and thermal conductivity are shown in the table. The thermal conductivity was measured by the following method.

Determination of thermal conductivity

The heat transfer rate of the obtained stretched film substrate (HI-12F) with a heat-insulating film was measured using a hot wire probe type thermal conductivity measuring device (manufactured by Kyoto Electronics Co., Ltd.: QTM-500).

[Comparative Example 6] Modulation of coating liquid (RHI-6P) for forming a heat insulating film

Mixed polyurethane resin emulsion (manufactured by Daiichi Kogyo Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 38.0 g, isopropanol 50.2 g, methyl isobutyl Ketone 18.0g, different Propylene glycol 17.0 g was prepared to prepare an emulsion diluent.

As a result of observing the emulsion diluent, it was considered to be transparent, and since the particle diameter could not be measured, it was presumed that the resin emulsion disappeared.

Then, a hollow cerium oxide organosol (Sururia 4110, solid content concentration: 20.5%, average particle diameter: 60 nm, dispersion medium: isopropyl alcohol), 151.2 g, was added to prepare heat insulating properties. Film coating solution (RHI-6P).

Manufacture of stretched film substrate (RHI-6F) with thermal insulation film

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then a coating for forming a heat-insulating film was carried out by a spray method. The liquid (RHI-6P) was coated with 45 μm, dried at 140 ° C for 120 seconds, and then subjected to horizontal axis stretching (140 ° C, 1.5 times stretching) to produce a stretched film substrate (RHI) with a heat insulating film. -6F). At this time, the thickness of the film substrate was 300 μm, and the thickness of the heat-insulating film was 30 μm.

The obtained stretched film substrate (RHI-6F) with a heat-insulating film was measured for total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), and cracking. The presence or absence, flatness of the film surface, scratch resistance and thermal conductivity are shown in the table.

Modulation of cerium oxide hollow particles (AR-13VS) dispersion

3900 g of pure water was added to cerium oxide-alumina sol (manufactured by Nippon Kasei Chemical Co., Ltd.: USBB-120, average particle diameter: 25 nm, SiO ₂ ‧ Al ₂ O ₃ concentration: 20% by weight, solid content of Al ₂ O ₃ content: 27% by weight) 100 g, heated to 98 ° C, while maintaining this temperature, 1750 g of a sodium citrate aqueous solution having a concentration of SiO ₂ of 1.5% by weight and a concentration of 0.5% by weight as Al ₂ O ₃ were added over 6 hours. 1750 g of an aqueous sodium aluminate solution was obtained to obtain a primary particle dispersion of SiO ₂ ‧ Al ₂ O ₃ . The pH of the reaction liquid at this time was 11.8, and the solid content concentration was 0.7%. Further, the average particle diameter was 40 nm. Then, 1530 g of an aqueous solution of sodium citrate having a concentration of SiO ₂ of 1.5% by weight and 500 g of an aqueous solution of sodium aluminate having a concentration of 0.5% by weight of Al ₂ O ₃ were added over 6 hours to obtain a coated dioxide having a solid concentration of 0.8% by weight. 9,500 g of a composite oxide particle dispersion of cerium-alumina. Further, the average particle diameter was 60 nm.

Then, 1,125 g of pure water was added to 500 g of a dispersion liquid of the ceria-alumina composite oxide fine particles (1) having a solid concentration of 13% by weight, and the mixture was washed with an ultrafiltration membrane, and then concentrated into concentrated hydrochloric acid (concentration). 35.5 wt%) The pH was made 1.0 to carry out dealumination treatment. Then, while adding 10 L of a hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt was separated and washed by an ultrafiltration membrane to obtain an aqueous dispersion of cerium oxide fine particles (1) having a solid concentration of 20% by weight.

Next, 150 g of an aqueous dispersion of cerium oxide microparticles (1), and a mixture of 500 g of pure water, 1,750 g of ethanol, and 626 g of ammonia water having a concentration of 28% by weight were heated to 35 ° C, and then ethyl ruthenate (SiO ₂ concentration was added). 80% by weight of 80 g to form a ceria coating layer, and by washing with ultrafiltration membrane while adding 5 L of pure water, a cerium oxide hollow fine particle having a ceria coating layer and having a solid concentration of 20% by weight was obtained. Aqueous dispersion.

Next, ammonia water was added to the ceria hollow fine particle dispersion liquid in which the ceria coating layer was formed to adjust the pH of the dispersion to 10.5, and then aged at 150 ° C for 11 hours, and then cooled to normal temperature, using a cation exchange resin (Mitsubishi Chemical) Co., Ltd.: Diaion SK1B) 400g After performing ion exchange for 3 hours, 200 g of anion exchange resin (manufactured by Mitsubishi Chemical Corporation, Diaion SA20A) was used for ion exchange for 3 hours, and then 200 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SK1B) was used again. The ion exchange was carried out at 80 ° C for 3 hours and washed to obtain an aqueous dispersion of cerium oxide hollow fine particles (13T) having a solid concentration of 20% by weight.

Then, the ceria hollow fine particle (13T) dispersion was hydrothermally treated at 150 ° C for 11 hours, and then cooled to room temperature, and ion exchange was performed for 3 hours using 400 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SK1B). Then, 200 g of anion exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SA20A) was used for ion exchange for 3 hours, and then 200 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SK1B) was used again, and the mixture was subjected to an 80 ° C for 3 hours. The ion exchange was carried out and washed to obtain an aqueous dispersion of cerium oxide hollow fine particles (AR-13V) having a solid concentration of 20% by weight.

The dispersion medium was replaced with ethanol using an ultrafiltration membrane to prepare an alcohol dispersion of cerium oxide hollow fine particles (AR-13V) having a solid concentration of 20% by weight.

2 g of a methyl decane coupling agent (methyltrimethoxy decane) (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-13) was added to an alcohol dispersion liquid of 20% by weight of cerium oxide hollow fine particles (AR-13V) having a solid concentration of 100% by weight. The mixture was heat-treated at 50 ° C to prepare an alcohol dispersion of the surface-treated ceria hollow fine particles (AR-13VS) having a solid concentration of 20% by weight. The dispersion medium was replaced with water using a rotary evaporator to prepare a solid concentration of 20 % by weight aqueous dispersion of surface treated ceria hollow particles (AR-13VS). At this time, the concentration of the alkali metal was 5 ppm.

Modulation of coating liquid (AR-13P) for forming an anti-reflection film

Polyurethane resin emulsion (manufactured by Dai-Il Pharmaceutical Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 3.8 g, pure water 18 g, and isopropanol 1.53 g, 10.0 g of an aqueous dispersion of the surface-treated ceria hollow fine particles (AR-13VS) having a solid content concentration of 20% by weight was prepared to prepare a coating liquid for forming an antireflection film having a solid content concentration of 10.0% by weight. (AR-13P).

Manufacture of stretched film substrate (AR-1) with anti-reflection film

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then coated by a bar coating method (rod #4). The coating liquid (AR-13P) which forms the antireflection film was dried at 140 ° C for 120 seconds, and then subjected to transverse axis stretching (140 ° C, 4.5 times stretching) to produce a stretched film with an antireflection film. Substrate (AR-13F). At this time, the thickness of the film substrate was 100 μm, and the film thickness of the antireflection film was 100 nm.

The obtained stretched film substrate (AR-13F) with an antireflection film was measured for total light transmittance, haze, reflectance, refractive index of the film, adhesion, pencil hardness, speckle, film waviness (island) The pattern, the presence or absence of cracks, the flatness of the film surface, and the scratch resistance, the results are shown in the table.

[Comparative Example 7] Modulation of a coating liquid (RAR-7P) for forming an anti-reflection film

Mixed polyurethane resin emulsion (manufactured by Daiichi Kogyo Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, The dispersion medium: water) 3.8 g, isopropanol 17.4 g, methyl isobutyl ketone 1.8 g, and isopropyl alcohol 1.7 g were prepared to prepare an emulsion diluent.

As a result of observing the emulsion diluent, it was considered to be transparent, and since the particle diameter could not be measured, it was presumed that the resin emulsion disappeared.

Then, 10.0 g of an aqueous dispersion of the surface-treated ceria hollow fine particles (AR-13VS) prepared in the same manner as in Example 13 was added to prepare a coating liquid (RAR-7P) for forming an antireflection film.

Manufacture of stretched film substrate (RAR-7F) with anti-reflective film

The substrate prepared in the same manner as in Example 1 was stretched at 140 ° C in a manner of 2.5 times in the direction of the longitudinal axis, and then stretched with a polyester resin film (1), followed by a bar coating method (rod) #18) Coating a coating liquid (RAR-1P) for forming an anti-reflection film, followed by drying at 140 ° C for 120 seconds, and then heating at 140 ° C in a manner of 4.5 times in the horizontal axis direction. The stretched film substrate (RAR-1F) with an antireflection film was produced by stretching. At this time, the thickness of the substrate was 100 μm, and the film thickness of the antireflection film was 100 nm.

For the obtained stretched film substrate (RAR-1F) with an antireflection film, the total light transmittance, haze, reflectance, refractive index of the film, adhesion, pencil hardness, speckle, film waviness (island) were measured. The pattern, the presence or absence of cracks, the flatness of the film surface, and the scratch resistance, the results are shown in the table.

[Example 14] (Use of polymer dispersant of hollow ceria)

2 g of a polyacrylic acid dispersant (Aron SD-10, manufactured by Toagosei Co., Ltd.) was added to an alcohol dispersion of cerium oxide hollow fine particles (AR-13V) having a solid content concentration of 20% by weight prepared in the same manner as in Example 13. 100g, The mixture was heat-treated at 50 ° C to prepare an alcohol dispersion liquid of cerium oxide hollow fine particles (AR-2) having a solid concentration of 20% by weight. The dispersion medium was replaced with water using a rotary evaporator to prepare an aqueous dispersion of the surface-treated ceria hollow fine particles (AR-14VS) having a solid concentration of 20% by weight. At this time, the pH was 9.0. At this time, the concentration of the alkali metal was 5 ppm.

Modulation of coating liquid (AR-14P) for forming an anti-reflection film

Polyurethane resin emulsion (manufactured by Dai-Il Pharmaceutical Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 3.8 g, pure water 18 g, and isopropanol 1.53 g, 10.0 g of an aqueous dispersion of the surface-treated ceria hollow fine particles (AR-14VS) having a solid content concentration of 20% by weight was prepared to prepare a coating liquid for forming an antireflection film having a solid content concentration of 10.0% by weight. (AR-14P).

Manufacture of stretched film substrate (AR-14F) with anti-reflective film

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then coated by a bar coating method (rod #4). The coating liquid (AR-14P) which forms the antireflection film was dried at 140 ° C for 120 seconds, and then subjected to transverse axis stretching (140 ° C, 4.5 times stretching) to produce a stretched film with an antireflection film. Substrate (AR-14F). At this time, the thickness of the film substrate was 100 μm, and the film thickness of the antireflection film was 100 nm.

The obtained stretched film substrate (AR-14F) with an antireflection film was measured for total light transmittance, haze, reflectance, refractive index of the film, adhesion, pencil hardness, speckle, film waviness (island) The pattern, the presence or absence of cracks, the flatness of the film surface, and the scratch resistance, the results are shown in the table.

[Comparative Example 8] Too much polymer dispersant Modulation of a coating liquid (RAR-8P) for forming an anti-reflection film

In the same manner as in Example 14, except that 80 g of a polyacrylic acid dispersant was added, an aqueous dispersion of the surface-treated ceria hollow fine particles (RAR-8VS) was prepared, and the aqueous dispersion was added. 10.0 g, and a coating liquid (RAR-8P) for forming an antireflection film was prepared.

Manufacture of stretched film substrate (RAR-8F) with anti-reflective film

The substrate prepared in the same manner as in Example 1 was stretched at 140 ° C in a manner of 2.5 times in the direction of the longitudinal axis, and then stretched with a polyester resin film (1), followed by a bar coating method (rod) #18) Coating a coating liquid (RAR-8P) for forming an anti-reflection film, followed by drying at 140 ° C for 120 seconds, and then heating at 140 ° C in a manner of 4.5 times in the horizontal axis direction. The stretched film substrate (RAR-8F) with an antireflection film was produced by stretching. At this time, the thickness of the substrate was 100 μm, and the film thickness of the antireflection film was 100 nm.

For the obtained stretched film substrate (RAR-8F) with an antireflection film, the total light transmittance, haze, reflectance, refractive index of the film, adhesion, pencil hardness, speckle, film waviness (island) were measured. The pattern, the presence or absence of cracks, the flatness of the film surface, and the scratch resistance, the results are shown in the table.

[Comparative Example 9] Too little polymer dispersant Modulation of a coating liquid (RAR-9P) for forming an antireflection film

In Example 14, an aqueous dispersion of the surface-treated ceria hollow fine particles (RAR-9VS) was prepared in the same manner as in Example 14 except that 0.1 g of a polyacrylic acid dispersant was added, and this water dispersion was added. The coating liquid (RAR-9P) for forming an antireflection film was prepared by dissolving 10.0 g of liquid.

Manufacture of stretched film substrate (RAR-9F) with anti-reflection film

The substrate prepared in the same manner as in Example 1 was stretched at 140 ° C in a manner of 2.5 times in the direction of the longitudinal axis, and then stretched with a polyester resin film (1), followed by a bar coating method (rod) #18) Coating a coating liquid (RAR-9P) for forming an anti-reflection film, followed by drying at 140 ° C for 120 seconds, and then heating at 140 ° C in a manner of 4.5 times in the horizontal axis direction. The stretched film substrate (RAR-9F) with an antireflection film was produced by stretching. At this time, the thickness of the substrate was 100 μm, and the film thickness of the antireflection film was 100 nm.

The obtained stretched film substrate (RAR-9F) with an antireflection film was measured for total light transmittance, haze, reflectance, refractive index of the film, adhesion, pencil hardness, speckle, film waviness (island) The pattern, the presence or absence of cracks, the flatness of the film surface, and the scratch resistance, the results are shown in the table.

[Example 15] Modulation of titanium dioxide microparticles (T-15VS) dispersion

3 g of a methyl decane coupling agent (methyltrimethoxy decane) (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-13) was added to a titanium dioxide organosol (manufactured by Nippon Touch Chemical Co., Ltd.: Optolake 1130Z (S-25‧A8, Solid content concentration: 30%, average particle diameter 20 nm, dispersion medium: methanol) 100 g, heat treatment at 50 ° C, and then the dispersion medium was replaced with ethanol using an ultrafiltration membrane to prepare a surface having a solid concentration of 20% by weight. An alcohol dispersion of the treated titanium dioxide fine particles. After the dispersion medium is replaced with water by a rotary evaporator, the alkali ion treatment is performed by ion exchange resin until the pH becomes 3.0, and then pure water is added to prepare a solid concentration of 20 parts by weight. % aqueous dispersion of titanium dioxide fine particles (T-15VS) after surface treatment. At this time, the concentration of the alkali metal was 50 ppm.

Modulation of a coating liquid (T-15P) for forming an easy-adhesion layer

Surface-treated titanium dioxide fine particles (T-15VS) 33.2 g, polyurethane resin emulsion (manufactured by Dai-Il Pharmaceutical Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: 88.5 g of water and 10.1 g of isopropyl alcohol were mixed with cerium oxide organosol (manufactured by Nippon Chemical Co., Ltd.: ELCOM V-8901, average particle diameter: 120 nm, SiO ₂ concentration: 20% by weight, dispersion medium: methanol) 1.4 g, a coating liquid (T-15P) for forming an easy-adhesion layer was prepared at a solid concentration of 10% by weight.

Manufacture of stretched film substrate (T-15F) with easy adhesion layer

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then coated by a bar coating method (rod #6). The coating liquid (T-15P) which forms an easy-adhesion layer was dried at 140 ° C for 120 seconds, and then subjected to transverse-axis stretching (140 ° C, 4.5-fold stretching) to produce a stretched film with an easy-to-attach layer. Substrate (T-15F). At this time, the thickness of the substrate was 100 μm, and the film thickness of the easy-adhesion layer was 0.6 μm.

For the obtained stretched film substrate (T-15F) with an easy-to-adhere layer, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The film surface was flat, scratch-resistant, anti-blocking, and adhesive. Further, interference fringes were observed, and the results are shown in the table.

[Comparative Example 10] Modulation of a coating liquid (RT-10P) for forming an easy-adhesion layer

Mixed polyurethane resin emulsion (manufactured by Daiichi Kogyo Co., Ltd.: Superflex 210, resin concentration: 35 wt%, emulsion diameter: 50 nm, dispersion medium: water) 38.0 g, isopropanol 170.4 g, methyl isobutyl Ketone 18.0g, 19.4 g of isopropyl glycol was prepared to prepare an emulsion diluent.

As a result of observing the emulsion diluent, it was considered to be transparent, and since the particle diameter could not be measured, it was presumed that the resin emulsion disappeared.

Next, a cerium oxide organosol (ELCOM V-8901, an average particle diameter of 120 nm, a SiO ₂ concentration of 20% by weight, a dispersion medium: methanol) 0.6 g, and a surface-treated titanium oxide fine particle were added. (T-15VS) 14.3 g, and a coating liquid (RT-10P) for forming an easy-adhesion layer was prepared at a solid concentration of 7.4% by weight.

Manufacture of stretch film substrate (RT-10F) with easy adhesion layer

The base material prepared in the same manner as in Example 1 was subjected to longitudinal axis stretching (140 ° C, 2.5-fold stretching) with a polyester resin film (1), and then coated by a bar coating method (rod #40). The coating liquid (RT-10P) which forms an easy-adhesion layer was dried at 140 ° C for 120 seconds, and then subjected to transverse-axis stretching (140 ° C, 4.5-fold stretching) to produce a stretched film with an easy-adhesion layer. Substrate (RT-10F). At this time, the thickness of the substrate was 100 μm, and the film thickness of the easy-adhesion layer was 0.6 μm.

For the obtained stretched film substrate (RT-10F) with an easy-to-attach layer, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The film surface was flat, scratch-resistant, anti-blocking, and adhesive. Further, interference fringes were observed, and the results are shown in the table.

[Comparative Example 11] Modulation of titanium dioxide microparticles (RT-11VS) dispersion

In Example 15, the surface-treated titanium oxide fine particles were prepared in the same manner as in Example 15 except that the ion exchange resin was not added. (RT-11VS) aqueous dispersion. At this time, the concentration of the alkali metal was 1,500 ppm.

Modulation of a coating liquid (RT-11P) for forming an easy-adhesion layer Modulation of a coating liquid (RT-11P) for forming an easy-adhesion layer

10.0 g of an aqueous dispersion of the surface-treated titanium oxide fine particles (RT-11VS) was added to prepare a coating liquid (RT-11P) for forming an easy-adhesion layer.

Manufacture of stretch film substrate (RT-11F) with easy adhesion layer

The substrate prepared in the same manner as in Example 1 was stretched at 140 ° C in a manner of 2.5 times in the direction of the longitudinal axis, and then stretched with a polyester resin film (1), followed by a bar coating method (rod) #18) Coating a coating liquid (RT-11P) for forming an easy-adhesion layer, followed by drying at 140 ° C for 120 seconds, and then heating at 140 ° C in a manner of 4.5 times in the horizontal axis direction. Stretching was carried out to produce a stretched film substrate (RT-11F) with an easy-to-attach layer. At this time, the thickness of the substrate was 100 μm, and the film thickness of the easily-adherent layer was 100 nm.

For the obtained stretched film substrate (RT-11F) with an easy-to-attach layer, the total light transmittance, haze, adhesion, pencil hardness, speckle, film waviness (island pattern), crack presence or absence were measured. The film surface was flat, scratch-resistant, anti-blocking, and adhesive. Further, interference fringes were observed, and the results are shown in the table.

In the above examples and comparative examples, the organic ruthenium compound represented by the formula (1) is methyltrimethoxy decane, but other examples thereof include tetramethoxy decane, tetraethoxy decane, and tetrapropoxy hydride. Decane, tetrabutoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, methyltriethoxydecane, isobutyltrimethoxydecane, butyltrimethoxydecane, butyltriethoxydecane, isobutyl Triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, decyl III Ethoxy decane, hexyl trimethoxy decane, octyl trimethoxy decane, decyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (β methoxyethoxy) decane, 3, 3 , 3-trifluoropropyltrimethoxydecane, β-(3,4-ethoxycyclohexyl)ethyltrimethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, diphenyldiene Methoxydecane, diphenyldiethoxyoxane, γ-glycidoxypropyltrimethoxy decane, γ-glycidoxypropylmethyldiethoxy decane, γ (β-glycidoxy) Ethoxy)propyltrimethoxyoxane, γ-(meth)acryloxymethyltrimethoxysilane, γ-(meth)acryloxymethyltriethoxysilane, γ-(meth)acryloxy Ethyltrimethoxyoxane, γ-(meth)acryloxyethyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethyl Oxane, γ-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxydecane, perfluorooctylethyltriethoxydecane, perfluorooctylethyltriisopropoxide, Trifluoropropyltrimethoxysilane, N-β (aminoethyl) Γ-aminopropylmethyldimethoxydecane, N-β (aminoethyl) γ-aminopropyltrimethoxy decane, N-phenyl-γ-aminopropyltrimethoxy decane, γ-mercaptopropyltrimethyl Oxane, trimethyl decyl alcohol, methyl trichloro decane, γ-isocyanatopropyl triethoxy decane, γ-ureidopropyl triethoxy decane, and the like.

Claims (12)

A coating liquid for forming a transparent film, which is a coating liquid in which inorganic oxide fine particles and a resin emulsion are dispersed in a dispersion medium containing at least one of water and an organic solvent, wherein the total solid concentration of the coating liquid The concentration (C _P ) of the inorganic oxide fine particles is in the range of 0.0009 to 56% by weight in terms of solid content, and the concentration (C _R ) of the aforementioned resin emulsion is 0.006 to 68% by weight in terms of solid content, from 0.03 to 70% by weight. In the range of the solid content of the alkali metal contained in the inorganic oxide fine particles, the total amount of the oxide (Me ₂ O, Me = Li, Na, K) is 1000 ppm or less. The coating liquid for forming a transparent film according to the first aspect of the invention, wherein the inorganic oxide fine particles are surface-treated with at least one of an organic cerium compound and a polymer dispersing agent, the organic cerium compound, The inorganic oxide fine particles are present in the range of 1 to 100% by weight based on the solid content in terms of R _n -SiX _(4-n)/2 , and the polymer dispersant is relative to the inorganic oxide fine particles. It is present in the range of 1 to 300% by weight in terms of solid content. The coating liquid for forming a transparent film according to the first or second aspect of the invention, wherein the inorganic oxide fine particles are monodisperse inorganic oxide fine particles (A) and have a primary particle diameter in a chain shape. At least one of 3 to 30 chain-shaped inorganic oxide fine particles (B), the average particle diameter (D _PA ) of the inorganic oxide fine particles (A) is in the range of 3 ≦ D _PA ≦ 100 nm, and the inorganic oxide fine particles The average primary particle diameter (D _PB ) of ( _B ) lies in the range of 3 ≦ D _PB ≦ 50 nm. The coating liquid for forming a transparent film according to the third aspect of the invention, wherein the inorganic oxide fine particles (C) having an average particle diameter (D _PC ) of 100 < D _PC ≦ 500 nm, the inorganic substance The concentration (C _PC ) of the oxide fine particles (C) is in the range of 0.000003 to 5% by weight in terms of solid content. The coating liquid for forming a transparent film according to any one of claims 1 to 4, wherein the inorganic oxide fine particles are selected from the group consisting of TiO ₂ , ZrO ₂ , SiO ₂ , and Sb ₂ O _{5 .} , ZnO ₂ , SnO ₂ , In ₂ O ₃ , antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), F-doped tin oxide (FTO), phosphorus-doped tin oxide (PTO) And at least one of aluminum-doped zinc oxide (AZO) or a composite oxide or mixture thereof. The coating liquid for forming a transparent film according to any one of claims 1 to 5, wherein the resin of the resin emulsion is selected from the group consisting of an epoxy resin, a polyester resin, and a polycarbonate resin. Polyamide resin, polyphenylene ether resin, vinyl chloride resin, fluororesin, vinyl acetate resin, polyoxynoxy resin, polyurethane resin, melamine resin, butyral resin, phenol resin, unsaturated polyester resin At least one of an acrylic resin or a copolymer or a modified body of two or more kinds of these resins. The coating liquid for forming a transparent film according to any one of claims 1 to 6, wherein the resin emulsion has an average diameter in the range of 10 to 500 nm. The coating liquid for forming a transparent film according to any one of claims 1 to 7, wherein the concentration (C _P ) of the inorganic oxide fine particles and the concentration (C _R ) of the resin emulsion are The ratio (C _P /C _R ) lies in the range of 0.03 to 4. A method for producing a substrate with a transparent film, characterized in that the following steps (a) to (d) are sequentially performed; (a) as described in any one of claims 1 to 8 a step of applying a coating liquid for forming a transparent film to a substrate, (b) a step of stretching the substrate with the coating film by biaxial (vertical axis and horizontal axis), and (c) removing a step of (drying) the dispersion medium contained in the coating film, and (d) a step of hardening the coating film. A method for manufacturing a substrate with a transparent film, characterized in that the following steps (a') to (d) are sequentially performed; (a') will be any one of items 1 to 8 of the patent application scope. The step of coating the coating liquid for forming a transparent coating on the substrate after the longitudinal stretching, and (b') the step of stretching the substrate with the coating film on the horizontal axis, ( c) a step of removing (drying) the dispersion medium contained in the coating film, and (d) a step of hardening the coating film. A method for producing a substrate with a transparent film, characterized in that the following steps (a") to (d), (a") are carried out while stretching the substrate on the vertical axis, as in the scope of the patent application 1 The step of applying a coating liquid for forming a transparent film to the substrate according to any one of the items 8 to (b"), and performing a horizontal axis stretching step on the substrate with the coating film, ( c) a step of removing (drying) the dispersion medium contained in the coating film, and (d) a step of hardening the coating film. A method for producing a substrate coated with a transparent film, characterized in that: the following steps (a"') to (d), (a"') are performed on two sides (vertical axis and horizontal axis) a step of applying a coating liquid for forming a transparent film as described in any one of claims 1 to 8 to a substrate, and (c) removing (drying) the aforementioned coating film. a step of dispersing the medium, and (d) a step of hardening the coating film.