JP2010111787A - Coating agent and hard coat member using the same - Google Patents

Abstract

The present invention provides a coating agent capable of forming a hard coat film having excellent scratch resistance and the like on a substrate, and a hard coat member using the coating agent.
A coating agent containing (A) a hydrolyzed / condensed product of a metal alkoxide having a functional group containing an unpaired electron-containing element other than an oxygen atom in the molecule, and (B) a zinc ion, and a substrate It is a hard coat member formed by applying the coating agent on at least one surface and drying to form a hard coat film.
[Selection figure] None

Description

  The present invention relates to a coating agent and a hard coat member using the same. More specifically, the present invention relates to a coating agent capable of forming a hard coat film having a high hardness even on a thin film on a substrate, and a hard coat member having a hard coat film formed using the coating agent on a substrate. Is.

  Conventionally, hard coat members have been used for various image display devices such as LCD (Liquid Crystal Display), touch panel, CRT (CRT), PDP (Plasma Display Panel), EL (Electroluminescence), etc., as well as anti-glare properties. It is used for purposes such as antireflection. Moreover, in LCD, it is used in order to protect a polarizer.

  This hard coat member is generally produced by, for example, applying and curing a silica particle dispersed in an acrylic binder on a film. If the particle dispersion state is poor, precipitates are generated in the coating agent. Or the uniformity when the coating film is formed. In particular, in the case of a transparent hard coat member, there is a problem that the transparency is lowered when there are many aggregates. Further, the smaller the particle size of the particles to be added, the better the transparency, but generally the smaller the particle size, the worse the dispersibility and the higher the cost. Further, as a method for dispersing particles, devices called ball mills and bead mills using zirconia balls of several mm to several tens of μm are known, but the cost for introducing these is also required.

In order to impart hard coat properties, metal (metal oxide) particles are added, while when the metal oxide particles have a function, for example, zinc oxide has an ultraviolet absorbing ability, zinc antimonate, and ITO particles have conductivity ( However, since these functional metal (metal oxide) particles are more expensive than silica particles, there is a problem that the cost is high to give them as an unnecessary function. There is.
Further, since zinc antimonate is blue-green, there is a problem that the coating film is colored.

On the other hand, as a technique for forming a hard coat film by a sol-gel method, a composition containing an alkoxysilane and a zinc compound, which is a hard coat film coated on at least one surface of a plastic substrate, is applied to the sol-gel method. There is disclosed a transparent hard coat film for plastic substrates, characterized in that it comprises a thin film obtained by hydrolysis and polycondensation by (see, for example, Patent Document 1).
Japanese Patent Laid-Open No. 7-304873

  The alkoxysilane used in the technique disclosed in Patent Document 1 is a commonly used normal alkoxysilane compound, and a functional group containing an unpaired electron-containing element other than an oxygen atom is introduced into the molecule. In addition, since zinc alkoxide is used as the zinc compound, the performance of the hard coat film obtained by forming zinc oxide by hydrolysis is not necessarily sufficient.

  Under such circumstances, an object of the present invention is to provide a coating agent capable of forming a hard coat film having a high hardness even on a thin film on a substrate, and a hard coat member using the coating agent. Is.

  As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.

A siloxane bond network is formed by hydrolyzing and condensing an alkoxysilane compound having an unpaired electron-containing functional group capable of coordinating with a metal, for example, by a sol-gel method. It is considered that the hard coat property of the coating film is imparted by forming a network by coordination bonds with ions. On the other hand, the hard coat agent reacts in a homogeneous system and no precipitate is generated. The resulting film is colorless and transparent. In addition, although zinc ion was added, since it was not zinc oxide (confirmed by X-ray diffraction (XRD)), it discovered that ultraviolet absorptivity was not expressed (confirmed by ultraviolet visible spectrophotometer UV-VIS).
The present invention has been completed based on such findings.

That is, the present invention
(1) (A) a hydrolyzing / condensation product of a metal alkoxide having a functional group containing an unpaired electron-containing element other than an oxygen atom in the molecule; and (B) a zinc ion.
(2) A metal alkoxide having a functional group containing an unpaired electron-containing element other than an oxygen atom in the molecule is represented by the general formula (I)
R ¹ _(mn) M (OR ² ) _n (I)
(In the formula, at least one of R ¹ is an unpaired electron-containing functional group, and when R ¹ is plural, they may be the same or different, and R ² is an alkyl group having 1 to 6 carbon atoms, M is Si, Ti, Zr or Al, m is the valence of M, 3 or 4, n is 1 to 3 in the case of Si, Ti or Zr, and 1 or 2 in the case of Al. )
The coating agent according to item (1), which is a compound represented by:
(3) The coating agent according to (1) or (2) above, wherein the metal alkoxide is alkoxysilane,
(4) The coating agent according to any one of (1) to (3) above, wherein the functional group containing an unpaired electron-containing element other than an oxygen atom is a mercaptoalkyl group and / or an aminoalkyl group.
(5) In any one of the above items (1) to (4), the content ratio of the functional group containing an unpaired electron-containing element other than an oxygen atom with respect to zinc ions is 0.5 to 200 times on a molar basis. The coating agent described,
(6) The coating agent according to any one of (1) to (5) above, wherein the zinc ion concentration in the solid content is 0.1 to 40% by mass, and (7) at least one side of the substrate. A hard coat member, characterized in that a hard coat film is formed by applying and drying the coating agent according to any one of (1) to (6) above,
Is to provide.

  According to the present invention, there are provided a coating agent that can form a hard coat film having a high hardness even on a thin film on a substrate, and a hard coat member having a hard coat film formed using the coating agent on a substrate. be able to.

First, the coating agent of the present invention will be described.
The coating agent of the present invention comprises (A) a hydrolyzed / condensed product of a metal alkoxide having a functional group containing an unpaired electron-containing element other than an oxygen atom in the molecule, and (B) a zinc ion. To do.

  The component (A) has a function as a binder component in the hard coat film formed by the coating agent of the present invention.

  Since the metal alkoxide of the component (A) has a functional group containing an unpaired electron-containing element capable of coordinating with a metal, the metal alkoxide can be hydrolyzed and condensed by a sol-gel method. For example, when an alkoxysilane compound is used as the metal alkoxide, a hard coat property of the coating film is imparted by forming a network of siloxane bonds and forming a network by coordination bonds with zinc ions. Seem.

In the coating agent of the present invention, the metal alkoxide having a functional group containing an unpaired electron-containing element other than an oxygen atom in the molecule, which is a raw material for the hydrolysis / condensation product of the component (A), is, for example, the general formula (I )
R ¹ _(mn) M (OR ² ) _n (I)
The compound represented by these can be used.

In the general formula (I), R ¹ represents a functional group containing an unpaired electron-containing element other than an oxygen atom. The functional group containing the unpaired electron-containing element is not particularly limited as long as it is a functional group having an element other than an oxygen atom having an unpaired electron (for example, a sulfur atom, a nitrogen atom, etc.). Preferred examples include about 2 to 5 mercaptoalkyl groups and aminoalkyl groups. Specifically, 2-mercaptoethyl group, 3-mercaptopropyl group, 2-mercaptopropyl group, 4-mercaptobutyl group, 3-mercaptobutyl group, 2-mercaptobutyl group, 2-aminoethyl group, 3-aminopropyl Group, 2-aminopropyl group, 4-aminobutyl group, 3-aminobutyl group, 2-aminobutyl group and the like.

On the other hand, R ² represents an alkyl group having 1 to 6 carbon atoms, which may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like.

  M represents Si, Ti, Zr or Al, m represents the valence of M, 3 or 4, n represents 1 to 3 in the case of Si, Ti or Zr (all valence 4), Al In the case of (valence 3), it is 1 or 2.

  In the present invention, it is preferable that M is Si. Examples of the metal alkoxide represented by the general formula (I) include 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and 2-mercapto. Ethyltri-n-propoxysilane, 2-mercaptoethyltriisopropoxysilane, 2-mercaptoethyltri-n-butoxysilane, 2-mercaptoethyltriisobutoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Ethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltriisopropoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltriisobutoxysilane, 2-aminoethyl Limethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethyltri-n-propoxysilane, 2-aminoethyltriisopropoxysilane, 2-aminoethyltri-n-butoxysilane, 2-aminoethyltriisobutoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltri-n-propoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropyltri-n-butoxysilane, 3 -Aminopropyltriisobutoxysilane etc. can be mentioned. One of these may be used alone, or two or more may be used in combination.

  In the present invention, together with the alkoxysilane compound having a functional group containing an unpaired electron-containing element other than the oxygen atom, to improve the hardness of the formed coating film, other metal alkoxide compounds and their An oligomer can be used in combination. Other metal alkoxide compounds (II) include alkoxide compounds such as silicon, titanium and zirconia. For example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane. Tetraalkoxysilanes such as tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, and the corresponding tetraalkoxytitanium and tetraalkoxyzirconium, trimethoxyaluminum, triethoxyaluminum, tri- n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, triisobutoxyaluminum, tri-sec-butoxyaluminum, tri Such as tert- butoxy aluminum. Moreover, as an oligomer of a metal alkoxide compound, for example, “methyl silicate 51”, “ethyl silicate 40” (both are trade names manufactured by Colcoat), “MS-51”, “MS-56” which are commercially available alkoxysilane oligomers. (Both are trade names manufactured by Mitsubishi Chemical Corporation).

  In addition, when it is desired to change the properties of the coating film in accordance with various uses such as flexibility and refractive index adjustment, a metal alkoxide compound having a non-hydrolyzable group may be combined as necessary.

  In the present invention, when using another metal alkoxide compound (II) together with the metal alkoxide compound (I) having a functional group containing an unpaired electron-containing element other than the oxygen atom, the use ratio thereof is as follows: The ratio of the metal elements contained in each is usually about 0.10 to 15.00 in molar ratio ((I) mole / (II) mole). If this use ratio is in the above-mentioned range, it has a good interaction with zinc ions as the component (B) described later, and the hardness of the coating film can be improved. A preferred use ratio is 0.20 to 12.00, more preferably 0.25 to 5.00, and further preferably 0.25 to 2 in terms of molar ratio ((I) mole / (II) mole). .50.

  By hydrolyzing and condensing these metal alkoxides, the component (A) in the coating agent of the present invention is formed. The hydrolysis / condensation method will be described in detail in the description of the coating agent production method described later.

  In the coating agent of the present invention, it is necessary that zinc contained as the component (B) is contained in an ionic form from the viewpoint of the formability of a network formed by coordination bond with an unpaired electron-containing functional group. As the zinc ion source, it is preferable to use inorganic acid zinc such as zinc chloride, zinc sulfate and zinc nitrate, organic acid zinc such as zinc acetate, and the like.

  In the coating agent of the present invention, the content ratio of the unpaired electron-containing functional group to the zinc ion is such that the unpaired electron-containing functional group has a good interaction with the zinc ion and has desired physical properties. From the viewpoint of forming a film, it is preferably about 0.5 to 200 times, more preferably 0.8 to 100 times, and particularly preferably 1 to 50 times on a molar basis.

  Moreover, 0.1-40 mass% is preferable as Zn, and, as for the zinc ion density | concentration in solid content, from viewpoints, such as the balance of the hardness of the coating film formed, and another physical property, 5-20 mass% is more preferable.

  An organic solvent is usually used for the coating agent of the present invention. As the organic solvent, alcohols are preferable, and alcohols having an etheric oxygen having 3 or more carbon atoms are more preferable from the viewpoint of controlling the hydrolysis-condensation reaction and stabilizing the condensate. Examples of alcohols having ether oxygen having 3 or more carbon atoms include cellosolv solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Examples thereof include ethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether. Among these, cellosolve solvents are particularly preferable. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The solid content concentration in the coating agent of the present invention is not particularly limited as long as it is a concentration suitable for application, but is usually about 0.5 to 30% by mass, preferably 1 to 20% by mass, and more preferably. Is 1.25 to 15% by weight.

  Next, although there is no restriction | limiting in particular about the method of manufacturing the coating agent of this invention, For example, the method shown below is employable.

  First, a solution is prepared by dissolving, in the organic solvent, a metal alkoxide having a functional group containing an unpaired electron-containing element other than an oxygen atom, and other metal alkoxide compounds and oligomers used as desired. Next, while stirring this solution, an aqueous solution containing water, a catalyst and a compound of a zinc ion source is added to this solution to hydrolyze and condense the metal alkoxide.

  As the catalyst, for example, an acid such as hydrochloric acid, sulfuric acid, nitric acid, or a cation exchange resin as a solid acid is used, which is usually hydrolyzed at a temperature of 0 to 100 ° C., preferably 20 to 60 ° C. If used, remove it. If the temperature is too low, the hydrolysis does not proceed. If the temperature is too high, the hydrolysis / polymerization reaction proceeds too quickly, making control difficult.

Various additives can be added to the coating agent of the present invention depending on the purpose. For example, in order to adjust the refractive index of a thin film after coating, such as an ionic liquid that serves as an antistatic agent and various surfactants for the purpose of antistatic, several to several tens of TiO ₂ and SiO ₂ having different refractive indexes. Examples thereof include nanometer-sized fine particles and fine particles of several hundred nm to several μm for the purpose of easy slipping.
In this way, the coating agent of the present invention can be obtained.

Next, the hard coat member of the present invention will be described.
The hard coat member of the present invention is characterized in that a hard coat film is formed by applying and drying the above-described coating agent of the present invention on at least one surface of a substrate.

  The base material used for the hard coat member of the present invention is not particularly limited as long as it is transparent, but it can be appropriately selected and used from known plastic films as the base material of conventional hard coat members. it can. Examples of such plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, diacetyl cellulose films, triacetyl cellulose films, acetyl cellulose butyrate films, and polyvinyl chloride. Film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, Polyimide film, fluororesin film, poly Amide film, acrylic resin film, norbornene resin film, a cycloolefin resin film or the like.

  These substrate films may be transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected depending on the application. For example, when used for protecting a liquid crystal display, a colorless and transparent film is suitable.

  The thickness of these substrate films is not particularly limited and is appropriately selected depending on the situation, but is usually in the range of 15 to 300 μm, preferably 20 to 200 μm. Moreover, this base film can be surface-treated by an oxidation method, an unevenness method, or the like on one side or both sides as desired for the purpose of improving adhesion to a layer provided on the surface. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Law. These surface treatment methods are appropriately selected depending on the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  In the hard coat member of the present invention, the coating agent of the present invention described above is applied to at least one surface of the substrate film by a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, Using a die coating method, a gravure coating method, or the like, coating can be performed to form a coating film, followed by drying and processing to form a hard coating film.

The thickness of the hard coat film is usually about 0.2 to 10 μm, preferably 0.25 to 5 μm. As for the performance of the hard coat film itself in the hard coat member, it is preferable not to impair the optical properties of the base film as much as possible, and the value obtained by subtracting the haze value of the base film from the haze value of the film forming the hard coat member (ΔHz) is preferably 3% or less, and more preferably 2% or less. The pencil hardness is usually H or higher. Further, when a component that absorbs ultraviolet light is not added, the transmittance of the ultraviolet light having a wavelength of 360 nm in the hard coat member is usually 50% or more, preferably 70% or more.
The method for measuring each physical property will be described later.

  The hard coat member of the present invention is suitably used as a surface protective member in various image display devices such as LCDs, touch panels, CRTs, PDPs and ELs.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

  In addition, evaluation of the performance of the hard coat film and hard coat member obtained in each example, and X-ray diffraction of the solidified coating agent are performed according to the following methods.

<Hard coat film / member>
(1) Pencil hardness Based on JIS K5400, it measures using the model name "C221A" by Yoshimitsu Seiki Co., Ltd.
(2) Haze value (ΔHz: measured value−Hz value of substrate)
Using a haze meter [manufactured by Nippon Denshoku Industries Co., Ltd., model name “NDH2000”], a haze value (ΔHz) is measured according to JIS K 7361.
(3) Transmittance of ultraviolet light having a wavelength of 360 nm The transmittance of ultraviolet light having a wavelength of 360 nm is measured using an ultraviolet / visible spectrophotometer [manufactured by JASCO Corporation, model name “V-670”].

<Coating agent>
(4) X-ray diffraction of solid matter The coating agent was dried and solidified, and the obtained powder was subjected to X-ray diffraction using an X-ray diffractometer [manufactured by Seiko Instruments Inc., model name “SEA-2120”].

Example 1
Ethyl cellosolve (EC) (602.6 g) was added to a mixture of mercaptopropyltrimethoxysilane (104.2 g) and MS-51 (34.6 g). While stirring, a mixture of 0.1 mol / L nitric acid (10.3 g), water (73.6 g), ZnCl ₂ (24.1 g) and EC (150.6 g) was added. The resulting solution was stirred at 30 ° C. for 24 hours to obtain a colorless and transparent coating agent.

  The coating agent was applied to the PET surface of a polyethylene terephthalate (PET) film [trade name “KB-G01” manufactured by Kimoto Co., Ltd.] having a thickness of 188 μm, which was hard-coated on one side, by the bar coating method (No. 10). Then, a hard coat film having a thickness of 2 μm was formed by drying at 120 ° C. for 1.5 minutes, thereby producing a hard coat member. The evaluation results of various characteristics are shown in Table 1.

Example 2
Mercaptopropyltrimethoxysilane (48.0 g), titanium tetraisopropoxide (TTIP) (146.0 g), and a mixture of MS-51 (40.0 g) with ethylene glycol-t-butyl ether (ETB) (549. 0 g) was added. While stirring, a mixture of concentrated nitric acid (49.0 g), water (14.0 g), ZnCl ₂ (16.0 g) and ETB (137.0 g) was added. The resulting solution was stirred at 30 ° C. for 4 hours to obtain a colorless and transparent coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member. The evaluation results of various characteristics are shown in Table 1.

Example 3
Ethyl cellosolve (EC) (608.3 g) was added to a mixture of mercaptopropyltrimethoxysilane (84.6 g) and MS-51 (28.1 g). While stirring, a mixture of 0.1 mol / L nitric acid (8.4 g), water (59.8 g), ZnCl ₂ (58.7 g), EC (152.1 g) was added. The resulting solution was stirred at 30 ° C. for 24 hours to obtain a colorless and transparent coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member. The evaluation results of various characteristics are shown in Table 1.

Example 4
Ethyl cellosolve (EC) (598.8 g) was added to a mixture of mercaptopropyltrimethoxysilane (116.9 g) and MS-51 (38.9 g). While stirring, a mixture of 0.1 mol / L nitric acid (11.6 g), water (82.5 g), ZnCl ₂ (1.6 g) and EC (149.7 g) was added. The resulting solution was stirred at 30 ° C. for 24 hours to obtain a colorless and transparent coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member. The evaluation results of various characteristics are shown in Table 1.

Example 5
Ethyl cellosolve (EC) (598.7 g) was added to a mixture of mercaptopropyltrimethoxysilane (117.3 g) and MS-51 (39.0 g). While stirring, a mixture of 0.1 mol / L nitric acid (11.6 g), water (82.9 g), ZnCl ₂ (0.8 g), EC (149.7 g) was added. The resulting solution was stirred at 30 ° C. for 24 hours to obtain a colorless and transparent coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member. The evaluation results of various characteristics are shown in Table 1.

Example 6
Ethyl cellosolve (EC) (621.0 g) was added to a mixture of phenylaminopropyltrimethoxysilane (100.2 g) and MS-51 (35.8 g). While stirring, a mixture of 0.1 mol / L nitric acid (8.7 g), water (61.2 g), ZnCl ₂ (17.8 g), EC (155.2 g) was added. The resulting solution was stirred at 30 ° C. for 24 hours to obtain a colorless and transparent coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member. The evaluation results of various characteristics are shown in Table 1.

Example 7
Ethyl cellosolve (EC) (500.0 g) was added to 500.0 g of the coating agent obtained in Example 1 to obtain a colorless and transparent coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member having a thickness of 1 μm. The evaluation results of various characteristics are shown in Table 1.

Example 8
Ethyl cellosolve (EC) (875.0 g) was added to 125.0 g of the coating agent obtained in Example 1 to obtain a colorless and transparent coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member having a thickness of 0.25 μm. The evaluation results of various characteristics are shown in Table 1.

Example 9
After adding ethyl cellosolve (EC) (875.0 g) to 81.0 g of the coating agent obtained in Example 1, a 10 wt% titanium oxide slurry (primary particle diameter by electron microscope of 20 nm, dispersion medium) was stirred. : Isopropyl alcohol) 44.0 g was added to obtain a white coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member having a thickness of 0.25 μm. The evaluation results of various characteristics are shown in Table 1.

Example 10
After adding ethyl cellosolve (EC) (875.0 g) to 50.0 g of the coating agent obtained in Example 1, 10 wt% silica slurry (primary particle diameter by electron microscope of 15 nm, dispersion medium: 75.0 g of isopropyl alcohol) was added to obtain a light white coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member having a thickness of 0.25 μm. The evaluation results of various characteristics are shown in Table 1.

Example 11
After adding ethyl cellosolve (EC) (875.0 g) to 50.0 g of the coating agent obtained in Example 1, 10 wt% magnesium fluoride slurry (with a primary particle diameter of 20 nm by an electron microscope, dispersed) with stirring. 75.0 g of medium: isopropyl alcohol) was added to obtain a light white coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member having a thickness of 0.25 μm. The evaluation results of various characteristics are shown in Table 1.

Comparative Example 1
The same procedure as in Example 1 was performed except that zinc chloride was not added. Ethyl cellosolve (EC) (598.5 g) was added to a mixture of mercaptopropyltrimethoxysilane (117.8 g) and MS-51 (39.2 g). While stirring, a mixture of 0.1 mol / L nitric acid (11.7 g), water (83.2 g) and EC (149.6 g) was added. The resulting solution was stirred at 30 ° C. for 24 hours to obtain a colorless and transparent coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member. The evaluation results of various characteristics are shown in Table 1.

Comparative Example 2
Ethyl cellosolve (EC) (595.3 g) was added to a mixture of mercaptopropyltrimethoxysilane (109.4 g) and MS-51 (36.4 g). While stirring, a mixture of 0.1 mol / L nitric acid (10.8 g), water (77.3 g), VCl ₃ (21.9 g) and EC (148.8 g) was added. The resulting solution was stirred at 30 ° C. for 24 hours to obtain a dark green transparent coating agent.
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member. The evaluation results of various characteristics are shown in Table 1.

Comparative Example 3
EC (100.0 g) was added to the coating liquid (850.0 g) obtained in Comparative Example 1, and a 30% by mass zinc oxide slurry (50.0 g) was added with stirring to obtain a white coating agent. .
Thereafter, the same operation as in Example 1 was performed to produce a hard coat member. The evaluation results of various characteristics are shown in Table 1.

［注］
*１）亜鉛イオンに対する酸素原子以外の不対電子含有官能基の含有割合
*２）コーティング剤固形分中の亜鉛イオン濃度
*３）ΔＨｚ：ハードコート膜自体のヘイズ値（測定値-基材のＨｚ値）
*４）透過率：ハードコート部材の波長３６０ｎｍ紫外光の透過率
*５）ＸＲＤ：コーティング剤固化物のＸ線回折

[note]
* 1) Content ratio of functional groups containing unpaired electrons other than oxygen atoms to zinc ions
* 2) Zinc ion concentration in the solid content of the coating agent
* 3) ΔHz: Haze value of hard coat film itself (measured value−Hz value of substrate)
* 4) Transmittance: Transmittance of the hard coat member at 360 nm wavelength ultraviolet light
* 5) XRD: X-ray diffraction of solidified coating agent

Example 12
The coating agent obtained in Examples 1, 9, 10, and 11 was applied to a silicon wafer by a spin coating method (1000 rpm, 0.5 minutes) and dried at 120 ° C. for 1.5 minutes to form a hard coat film. .
The refractive index of the obtained sample was measured using a thin film measuring apparatus [manufactured by Filmmetrics, model name “F-20”]. The results are shown in Table 2.

Example 13
The coating agent obtained in Example 9 was applied to a 125 μm-thick polyethylene terephthalate (PET) film [trade name “Lumirror T-60” manufactured by Toray Industries, Inc.] by the bar coating method (No. 10), and at 120 ° C. By drying for 1.5 minutes, a hard coat film having a thickness of 0.25 μm was formed, and a hard coat member was produced.
In the sample to which the coating agent obtained in Example 9 was applied, almost no interference was observed.

  The result of having measured the reflection spectrum in 400 nm-1000 nm of the sample obtained using the thin film measuring apparatus [The product name company make, model name "F-20"] in FIG. 1 is shown.

  The coating agent of the present invention can form a hard coat film having excellent hardness and the like on a substrate. The hard coat member of the present invention having the hard coat film is suitably used as a surface protective member in LCDs, touch panels, CRTs, PDPs, ELs and the like.

It is a measurement result chart of the reflection spectrum in Example 13.

Claims (7)

  A coating agent comprising (A) a hydrolyzed / condensed product of a metal alkoxide having a functional group containing an unpaired electron-containing element other than an oxygen atom in the molecule, and (B) a zinc ion. A metal alkoxide having a functional group containing an unpaired electron-containing element other than an oxygen atom in the molecule is represented by the general formula (I):
R ¹ _(mn) M (OR ² ) _n (I)
(In the formula, at least one of R ¹ is an unpaired electron-containing functional group, and when R ¹ is plural, they may be the same or different, and R ² is an alkyl group having 1 to 6 carbon atoms, M is Si, Ti, Zr or Al, m is the valence of M, 3 or 4, n is 1 to 3 in the case of Si, Ti or Zr, and 1 or 2 in the case of Al. )
The coating agent of Claim 1 which is a compound represented by these.   The coating agent according to claim 1 or 2, wherein the metal alkoxide is an alkoxysilane.   The coating agent according to any one of claims 1 to 3, wherein the functional group containing an unpaired electron-containing element other than an oxygen atom is a mercaptoalkyl group and / or an aminoalkyl group.   The coating agent according to any one of claims 1 to 4, wherein a content ratio of a functional group containing an unpaired electron-containing element other than an oxygen atom with respect to zinc ions is 0.5 to 200 times on a molar basis.   The coating agent according to any one of claims 1 to 5, wherein a zinc ion concentration in the solid content is 0.1 to 40% by mass.   A hard coat member, wherein a hard coat film is formed by applying and drying the coating agent according to any one of claims 1 to 6 on at least one side of a substrate.

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