JP2005336420A - Coating film having durability in sliding, liquid coating material and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating film having durability in sliding, formed on an organic substrate by coating a liquid coating material, having high refractive index and excellent durability in sliding and suitable as an optical material and the like, and to provide a liquid coating material capable of forming the coating film. <P>SOLUTION: The coating film is formed by coating a liquid coating material on an organic substrate and has 10-500 nm thickness, wherein the coating film has ≤10.0% haze value, ≥1.7 refractive index, and ≥95% remaining rate of the film component after a sliding test of 30 round trips of 6 cm width with 2.94 N/cm<SP>2</SP>loading, the liquid coating material comprises a hydrolyzate condensate of a titanium alkoxide and a particulate metal oxide having 3-300 nm particle diameter, and the ratio of the reduced mass expressed in TiO<SB>2</SB>and of the condensate hydrolyzate of the titanium alkoxide to the particulate metal oxide is 0.20-4.00. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a sliding resistant coating film, a liquid coating material, and a laminate. More specifically, the present invention is formed by coating a liquid coating material on an organic substrate, has a high refractive index and excellent sliding durability, and is a sliding resistant coating film suitable as an optical material or the like. The present invention relates to a liquid coating material obtained by forming the coating film, and a laminate including the coating film.

As a method for forming a coating film on an organic substrate, a vapor deposition method (dry method) such as a vacuum deposition method, a sputtering method, or an ion plating method, and a wet method in which a liquid coating material is applied and formed are known. It has been.
When a coating film is formed on the organic substrate by the vapor phase method, a coating film having sliding durability can be obtained (for example, see Patent Document 1). A coating film having high sliding durability has characteristics such as excellent adhesion to an organic base material and less scratching, so that it is easy to maintain transparency. However, in this vapor phase method, when the substrate to be processed becomes large, the vacuum apparatus to be used becomes very large, the apparatus becomes expensive, and the time required for evacuation is also increased, thereby increasing the productivity. Can not. Moreover, since the target, which is a coating material, is expensive and needs to be converted after being used at several tens of percent, there is a problem that the use efficiency is low, and there is a great demerit in cost.

  On the other hand, in a method of forming a coating film by a wet method, for example, a method of coating a liquid coating material containing a metal oxide such as an organic polymer compound or a hydrolyzed / condensed product of a metal alkoxide, In the case of molecular compounds, it seems that there is a limit to the sliding durability due to the characteristics of the material. On the other hand, in the case of metal oxides, heat treatment at high temperatures cannot be performed on organic substrates, so the gas phase It was difficult to obtain a coating film having satisfactory high sliding durability compared with the method.

On the other hand, in optical materials such as various display devices, solar cells, and plastic lenses, a laminated body in which layers having different refractive indexes are alternately laminated is disclosed for preventing reflection of light (for example, Patent Document 2, Patent). Reference 3 and Patent Document 4). In these laminates, a coating layer having a high refractive index is used, but these are produced by a sputtering method having a problem in cost.
On the other hand, with respect to a coating film having a high refractive index by a solution method (wet method), a titanium oxide thin film made of a hydrolyzed / condensed product of titanium alkoxide is disclosed (for example, see Patent Document 5). However, this titanium oxide thin film is not always satisfactory in terms of its sliding durability.

Japanese Patent Laid-Open No. 2001-253007 JP 2003-139907 A JP 2003-123859 A JP 2003-195003 A JP 2003-54951 A

  Under such circumstances, the present invention is formed by coating a liquid coating material on an organic substrate, has a high refractive index and excellent sliding durability, and is suitable as an optical material. An object of the present invention is to provide a slidable coating film, a liquid coating material capable of forming the coating film, and a laminate including the coating film.

  As a result of intensive studies to achieve the above object, the present inventors have a specific range of thicknesses formed by applying a liquid coating material on an organic substrate, and a haze value, It has been found that a coating film in which the refractive index and the residual ratio of the film components after the sliding test are in a certain range can meet the purpose as a sliding resistant coating film.

  Further, a liquid coating material containing a specific amount of a hydrolyzed / condensed product of titanium alkoxide and a particulate metal oxide having a certain range of particle diameters can provide the sliding-resistant coating film, and Suitable for optical materials and the like, which is a laminate comprising at least one sliding-resistant coating film, wherein the refractive index of the layer in contact with the coating film is lower than a certain value than the refractive index of the coating film It has been found that it can be used.

The present invention has been completed based on such findings.
That is, the present invention
(1) A coating film having a thickness of 10 to 500 nm formed by applying a liquid coating material on an organic substrate, having a haze value of 10.0% or less and a refractive index of 1.7 or more. In addition, using a cotton canvas, the remaining rate of the film component after the sliding test for 1 minute is 95% or more at a speed of 30 reciprocations / minute with a load of 2.94 N / cm ² and a width of 6 cm. Sliding resistant coating,
(2) The sliding-resistant coating film according to (1) above, comprising a hydrolyzed / condensed product of titanium alkoxide and a particulate metal oxide having a particle size of 3 to 300 nm as main components,
(3) The sliding-resistant coating film according to (2) above, wherein the mass ratio of the particulate metal oxide to the TiO ₂ converted mass of the hydrolyzed / condensed product of titanium alkoxide is 0.20 to 4.00.
(4) The sliding-resistant coating film according to (2) or (3) above, wherein the particulate metal oxide has a refractive index of 1.6 or more,
(5) The sliding-resistant coating film according to (2), (3) or (4) above, wherein the particulate metal oxide is rutile titanium oxide,
(6) The content ratio of the hydrolyzed / condensed product of titanium alkoxide and the fine particle metal oxide having a particle size of 3 to 300 nm containing the organic polymer compound continuously decreases from the coating surface to the organic substrate direction. The sliding-resistant coating film according to any one of (2) to (5) above, which has a component gradient structure
(7) The sliding resistant coating according to any one of (1) to (6) above, comprising at least one aluminum compound and / or zirconium compound selected from salts, complexes and alkoxides. film,
(8) The mass of the particulate metal oxide with respect to the TiO ₂ equivalent mass of the titanium alkoxide hydrolysis / condensate and the particulate metal oxide having a particle size of 3 to 300 nm and the hydrolysis / condensation product of the titanium alkoxide. A liquid coating material characterized by a ratio of 0.20 to 4.00,
(9) Item (8) above, which contains 2-ethoxyethanol as a main solvent, has a solid content concentration of 35% by mass or less, and has a light scattering intensity change rate of 20% or less after standing at a temperature of 10 ° C. for 168 hours. Liquid coating material as described in
(10) A layered product including at least one sliding-resistant coating film according to any one of (1) to (7) above, wherein the layer is in contact with the sliding-resistant coating film. And (11) the total light transmittance in a wavelength region of 400 to 800 nm is 80% or more, and the haze value is The laminate according to the above item (10), which is 10% or less,
Is to provide.

  According to the present invention, a liquid coating material is applied on an organic base material, and has a high refractive index and excellent sliding durability. The liquid coating material which can form a coating film, and the laminated body containing at least 1 layer or more of the said coating films can be provided.

First, the sliding resistant coating film of the present invention will be described.
The sliding-resistant coating film of the present invention is a coating film having a thickness of 10 to 500 nm formed by coating a liquid coating material on an organic substrate, and has a haze value of 10.0% or less. The refractive index is 1.7 or more, and the remaining ratio of the film component after the sliding test by a specific method is 95% or more.

In the coating film of the present invention, if the thickness is in the range of 10 to 500 nm, it has good sliding resistance and hardly causes interference fringes or cracks. A preferred thickness is selected in the range of 30 to 350 nm.
The refractive index is 1.7 or more, preferably 1.8 or more in the above thickness range. Although there is no restriction | limiting in particular about the upper limit, Usually, it is about 2.30. Further, the haze value is 10% or less, preferably 7.0% or less in the above thickness range. The total light transmittance in the wavelength range of 400 to 800 nm is preferably 80% or more, and more preferably 85% or more. In addition, the measuring method of the thickness of a coating film, a refractive index, and a haze value is explained in full detail later.

Moreover, in the said coating film, the residual rate of the film | membrane component after the sliding test by the following method is 95% or more. If the residual ratio is 95% or more, the sliding durability is excellent.
<Sliding test>
The coating film was slid for 1 minute at a speed of 30 reciprocations per minute with a cotton canvas (TOSCO Co., Ltd., Cherry Diamond Mark, No. 6) with a load of 2.94 N / cm ² and a width of 6 cm, The coating film before and after sliding was measured by fluorescent X-ray [Seiko Instruments Co., Ltd., “SEA2120”, tube current 122 μA, tube voltage 15 kV, under vacuum, strength measurement], and the difference in X-ray intensity [ = (After sliding / before sliding) × 100 (%)] is calculated and set as the remaining rate of the film component.
In the sliding resistant coating film of the present invention, it is preferable that a hydrolysis / condensation product of titanium alkoxide and a particulate metal oxide having a particle size of 3 to 300 nm are contained as main components. That is, the liquid coating material used to form the coating film contains, as main components, a hydrolysis / condensation product of the titanium alkoxide and a fine particle metal oxide having a particle size of 3 to 300 nm. preferable.

  As the titanium alkoxide, a titanium tetraalkoxide having an alkoxyl group having 1 to 4 carbon atoms is preferably used. In this titanium tetraalkoxide, the four alkoxyl groups may be the same or different, but the same one is preferably used from the viewpoint of availability. Examples of the titanium tetraalkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-sec- Examples include butoxide and titanium tetra-tert-butoxide. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The hydrolysis / condensation product of titanium alkoxide can be obtained as follows. First, preferably, the titanium tetraalkoxide is hydrolyzed and condensed to prepare a titania sol solution. This titanium tetraalkoxide hydrolysis-condensation reaction is carried out by using alcohols, preferably alcohols having an ether oxygen having 3 or more carbon atoms, as a solvent, and allowing water to act on titanium tetraalkoxide in the presence of an acidic catalyst. Done.

  Examples of the alcohols having ether oxygen having 3 or more carbon atoms include solvents having an interaction with titanium tetraalkoxide, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether (2-ethoxyethanol), ethylene glycol monopropyl. Cellosolve solvents such as ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono Butyl ether etc. That. Among these, a cellosolve solvent having a strong interaction with titanium tetraalkoxide is particularly preferable. These solvents may be used singly or in combination of two or more.

  By using a solvent having such an interaction with titanium tetraalkoxide as a solvent, the titania sol solution obtained by the hydrolysis-condensation reaction of titanium tetraalkoxide can be stabilized, and the condensation reaction can proceed. However, gelation and particle formation hardly occur and stable film formation becomes possible.

The hydrolysis-condensation reaction of titanium tetraalkoxide is usually 4 to 20 times mol, preferably 5 to 12 times mol of the alcohol, and usually 0.5 to 4 times mol, preferably 1 with respect to titanium tetraalkoxide. The reaction is carried out at a temperature in the range of usually 0 to 70 ° C., preferably 20 to 50 ° C. in the presence of an acidic catalyst such as hydrochloric acid, sulfuric acid, nitric acid, etc. An acidic catalyst is 0.1-1.0 times mole normally with respect to titanium tetraalkoxide, Preferably it is used in 0.2-0.7 times mole.
In this way, a hydrolyzed / condensed product of titanium alkoxide can be obtained.

  On the other hand, the fine particle metal oxide is preferably a fine particle after reaction, and is preferably spherical. Further, the refractive index is preferably 1.6 or more, more preferably 1.9 or more, and particularly preferably 2.0 or more. For example, particulate titanium oxide (refractive index: 2.52 to 2.76), zirconium oxide (refractive index: 2.1 to 2.2), cerium oxide (refractive index: 2.2), tin oxide (refractive index) : 2.0), zinc oxide (refractive index: 1.9 to 2.1), antimony oxide (refractive index: 2.0 to 2.3), aluminum oxide (refractive index: 1.6 to 1.8) Etc. can be used. These may be used individually by 1 type and may be used in combination of 2 or more type. Of these, particulate titanium oxide is preferred. As this titanium oxide, crystalline titanium oxide of anatase type (refractive index 2.52) and / or rutile type (refractive index 2.76) is more preferable, and from the viewpoint of refractive index and surface activity, rutile type titanium oxide. Is most preferred.

  The particle size of the particulate metal oxide is preferably in the range of 3 to 300 nm. When the particle size is in the above range, the production is possible and the dispersion stability in the liquid coating material containing the particle size is good. A more preferable particle size is in the range of 5 to 100 nm.

In the present invention, the mass ratio of the particulate metal oxide to the TiO ₂ converted mass of the hydrolysis / condensation product of the titanium alkoxide is preferably in the range of 0.20 to 4.00. When the mass ratio is in the above range, the coating properties of the liquid coating material are good and the resulting coating film has a high refractive index. From the viewpoint of coating properties and refractive index, the mass ratio is preferably in the range of 0.25 to 3.00.

  The coating film and the liquid coating material forming the coating film may contain at least one aluminum compound and / or zirconium compound selected from salts, complexes and alkoxides. Specific examples of such compounds include aluminum nitrate, aluminum triacetylacetonate, and tetra-n-propoxyzirconium. These may be used individually by 1 type and may be used in combination of 2 or more type. By containing these compounds in the hydrolyzed / condensed product of titanium alkoxide, crystallization of the hydrolyzed / condensed product of titanium alkoxide can be suppressed, and the occurrence of cracks and the like in the coating film can be suppressed. . In particular, aluminum nitrate is preferred from the viewpoint of effects.

  When using this aluminum nitrate, the usage-amount is normally selected in 5-50 mol% with respect to the titanium atom of the hydrolysis * condensate of a titanium alkoxide. If the amount of aluminum nitrate used is in the above range, the effect of inhibiting the crystallization of the hydrolysis / condensation product of titanium alkoxide is exhibited, and the physical properties inherent to the titania binder are retained. The preferred amount of aluminum nitrate used is in the range of 15 to 30 mol%.

  In the sliding resistant coating film of the present invention, the content ratio of the hydrolyzed / condensed product of titanium alkoxide and the particulate metal oxide having a particle size of 3 to 300 nm contains an organic polymer compound from the coating film surface. It can have a component gradient structure that continuously decreases in the direction of the organic substrate.

  Such an organic-inorganic composite gradient material can be manufactured by the method shown below. The organic-inorganic composite gradient material obtained by this manufacturing method includes a composite in which a titanium oxide thin film and an organic polymer compound are chemically bonded, and the content of the titanium component and the particulate metal oxide is the surface of the material. To have a component gradient structure that continuously decreases in the thickness direction. In the present invention, such a composite gradient material is (A) an organic polymer having a metal-containing group (sometimes referred to as a hydrolyzable metal-containing group) that can be bonded to titanium oxide by hydrolysis in the molecule. A titania sol obtained by hydrolyzing and condensing a compound, and (B) a titanium alkoxide having 1 to 4 carbon atoms of the alkoxyl group in the same manner as in the above-described method for producing a sliding-resistant coating film; It forms using the coating liquid containing a metal oxide.

  The organic polymer compound having a hydrolyzable metal-containing group as the component (A) includes, for example, (a) an ethylenically unsaturated monomer having a hydrolyzable metal-containing group, and (b) an ethylenic material not containing a metal. It can be obtained by copolymerizing unsaturated monomers.

  The ethylenically unsaturated monomer having a hydrolyzable metal-containing group as the component (A) (a) is represented by the general formula (I)

（式中、Ｒ¹は水素原子またはメチル基、Ａはアルキレン基、好ましくは炭素数１〜４のアルキレン基、Ｒ²は加水分解性基または非加水分解性基であるが、その中の少なくとも１つは加水分解により、（Ｂ）成分と化学結合しうる加水分解性基であることが必要であり、また、Ｒ²が複数の場合には、各Ｒ²はたがいに同一であってもよいし、異なっていてもよく、Ｍ¹はケイ素、チタン、ジルコニウム、インジウム、スズ、アルミニウムなどの金属原子、ｋは金属原子Ｍ¹の価数である。）
で表される基を挙げることができる。

Wherein R ¹ is a hydrogen atom or a methyl group, A is an alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, and R ² is a hydrolyzable group or a non-hydrolyzable group, the first is hydrolysis, (B) must be a component chemically bonded may hydrolyzable group, and when R ² is plural, each R ² is also a mutually identical And may be different, M ¹ is a metal atom such as silicon, titanium, zirconium, indium, tin, and aluminum, and k is a valence of metal atom M ^1. )
The group represented by these can be mentioned.

In the general formula (I), examples of the hydrolyzable group that can chemically bond to the component (B) by hydrolysis of R ² include halogen atoms such as alkoxyl groups, isocyanate groups, and chlorine atoms, oxyhalogen groups, An acetylacetonate group, a hydroxyl group, etc. are mentioned, On the other hand, as a non-hydrolyzable group which does not chemically bond with (B) component, a lower alkyl group etc. are mentioned preferably, for example.

Examples of the metal-containing group represented by -M ¹ R ² _k-1 in the general formula (I) include a trimethoxysilyl group, a triethoxysilyl group, a tri-n-propoxysilyl group, a triisopropoxysilyl group, Tri-n-butoxysilyl group, triisobutoxysilyl group, tri-sec-butoxysilyl group, tri-tert-butoxysilyl group, trichlorosilyl group, dimethylmethoxysilyl group, methyldimethoxysilyl group, dimethylchlorosilyl group, methyl Dichlorosilyl group, triisocyanatosilyl group, methyldiisocyanatosilyl group, trimethoxytitanium group, triethoxytitanium group, tri-n-propoxytitanium group, triisopropoxytitanium group, tri-n-butoxytitanium group, Triisobutoxy titanium group, tri-sec-butoxy titani Group, tri-tert-butoxytitanium group, trichlorotitanium group, trimethoxyzirconium group, triethoxyzirconium group, tri-n-propoxyzirconium group, triisopropoxyzirconium group, tri-n-butoxyzirconium group, Triisobutoxyzirconium group, tri-sec-butoxyzirconium group, tri-tert-butoxyzirconium group, trichlorozirconium group, and further dimethoxyaluminum group, diethoxyaluminum group, di-n-propoxyaluminum group, diisopropoxy group Examples thereof include an aluminum group, di-n-butoxyaluminum group, diisobutoxyaluminum group, di-sec-butoxyaluminum group, di-tert-butoxyaluminum group, and trichloroaluminum group. One type of the ethylenically unsaturated monomer of component (a) may be used, or two or more types may be used in combination.

  On the other hand, examples of the ethylenically unsaturated monomer not containing a metal as the component (b) include, for example, the general formula (II)

（式中、Ｒ³は水素原子またはメチル基、Ｘは一価の有機基である。）
で表されるエチレン性不飽和単量体、好ましくは一般式（II−ａ）

(In the formula, R ³ is a hydrogen atom or a methyl group, and X is a monovalent organic group.)
An ethylenically unsaturated monomer represented by formula (II-a), preferably

（式中、Ｒ³は前記と同じであり、Ｒ⁴は炭化水素基を示す。）
で表されるエチレン性不飽和単量体、あるいは上記一般式（II−ａ）で表されるエチレン性不飽和単量体と、必要に応じて添加される密着性向上剤としての一般式（II−ｂ）

(In the formula, R ³ is the same as described above, and R ⁴ represents a hydrocarbon group.)
Or an ethylenically unsaturated monomer represented by the above general formula (II-a), and a general formula ( II-b)

（式中、Ｒ⁵は水素原子またはメチル基、Ｒ⁶はエポキシ基、ハロゲン原子若しくはエーテル結合を有する炭化水素基を示す。）
で表されるエチレン性不飽和単量体との混合物を挙げることができる。

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an epoxy group, a halogen atom or a hydrocarbon group having an ether bond.)
And a mixture with an ethylenically unsaturated monomer represented by the formula:

In the ethylenically unsaturated monomer represented by the general formula (II-a), the hydrocarbon group represented by R ⁴ includes a linear or branched alkyl group having 1 to 10 carbon atoms, carbon number Preferable examples include 3 to 10 cycloalkyl groups, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups, pentyl groups, hexyl groups, octyl groups, and decyl groups. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cyclooctyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group having 7 to 10 carbon atoms, such as a group, a naphthyl group, and a methylnaphthyl group, include a benzyl group, a methylbenzyl group, a phenethylyl group, and a naphthylmethyl group.

  Examples of the ethylenically unsaturated monomer represented by the general formula (II-a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate. These may be used alone or in combination of two or more.

In the ethylenically unsaturated monomer represented by the general formula (II-b), the epoxy group represented by R ⁶ , the halogen atom or the hydrocarbon group having an ether bond may be a straight chain having 1 to 10 carbon atoms. Preferred examples include a straight or branched alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. The halogen atom for the substituent is preferably a chlorine atom or a bromine atom. Specific examples of the hydrocarbon group include the same groups as those exemplified in the description of R ⁴ in the general formula (II-a).

  Examples of the ethylenically unsaturated monomer represented by the general formula (II-b) include glycidyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate, and 2- (3,4-epoxycyclohexyl). ) Ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-bromoethyl (meth) acrylate and the like can be preferably exemplified.

  In addition to these, the ethylenically unsaturated monomer represented by the general formula (II) includes styrene, α-methylstyrene, α-acetoxystyrene, m-, o- or p-bromostyrene, m -, O- or p-chlorostyrene, m-, o- or p-vinylphenol, 1- or 2-vinylnaphthalene and the like, and stabilizers for polymerizable polymers having an ethylenically unsaturated group, for example, ethylenic Antioxidants, ultraviolet absorbers and light stabilizers having an unsaturated group can also be used. These may be used alone or in combination of two or more.

  When the ethylenically unsaturated monomer represented by the general formula (II-a) and the ethylenically unsaturated monomer represented by the general formula (II-b) are used in combination, the former ethylenic monomer It is preferable to use the latter ethylenically unsaturated monomer in a proportion of 1 to 100 mol% with respect to the unsaturated monomer.

  In the presence of a radical polymerization initiator, an ethylenically unsaturated monomer having a hydrolyzable metal-containing group as the component (a) and an ethylenically unsaturated monomer having no metal as the component (b) By copolymerization, an organic polymer compound having a hydrolyzable metal-containing group as component (A) is obtained.

  In the present invention, a solution obtained by dissolving the organic polymer compound having a hydrolyzable metal-containing group as component (A) thus obtained in a suitable polar solvent such as alcohol, ketone, ether, A liquid coating material having a viscosity suitable for coating is prepared by mixing a titania sol solution as the component (B) and a fine metal oxide. At this time, if necessary, water and / or an acidic catalyst can be added to the coating material. In addition, there is no restriction | limiting in particular about the addition time of a particulate metal oxide.

  Next, a dip coating method or a spin coating is performed on the organic substrate so that the liquid coating material thus obtained has a dry coating thickness of 10 to 500 nm, preferably 30 to 350 nm. Coating is performed by a known means such as a method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method, and the solvent is evaporated to form a coating film.

  Examples of the organic substrate include acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene and ABS resins, olefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and 6-nylon. Examples include substrates made of polyamide resins such as 1,6,6-nylon, polyvinyl chloride resins, polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins, polyimide resins, and cellulose resins such as cellulose acetate. be able to.

  These organic base materials can be subjected to surface treatment by an oxidation method, an unevenness method, or the like, if desired, in order to further improve the adhesion to the gradient material according to the present invention. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of substrate.

  In addition, the organic base material in this invention has an organic coating film on the surface of the base material which consists of materials other than organic type materials, for example, metal-type material, glass, ceramics-type material, and other various inorganic type or metal type materials Also included.

  In the organic-inorganic composite gradient material thus obtained, the surface layer is substantially composed of a titanium oxide thin film and a particulate metal oxide, and the content of the metal component is successively decreased in the direction of the substrate. It is almost 0% in the vicinity of the base material. That is, the organic-inorganic composite gradient material is generally composed of a film-like material formed on a substrate, and the surface of the film-like material that is substantially in contact with the substrate is an organic polymer compound component. The other open system surface is a titanium oxide component and a particulate metal oxide.

  To confirm such a tilted structure, for example, the surface of the tilted film is sputtered and the film is shaved, and the content of carbon atoms and metal atoms on the film surface is measured over time by X-ray photoelectron spectroscopy. Can be done.

  Although there is no restriction | limiting in particular as content of the metal component in this composite gradient film, Usually in 5-98 mass% in conversion of a metal oxide, Preferably it is 20-98 mass%, Most preferably, it is the range of 50-90 mass%. is there. The degree of polymerization and the molecular weight of the organic polymer compound are not particularly limited as long as they can be formed into a film, and may be appropriately selected according to the type of polymer compound and the desired physical properties of the gradient film material.

The present invention also includes a titanium alkoxide hydrolyzed / condensed product and a particulate metal oxide having a particle size of 3 to 300 nm, preferably 5 to 100 nm, and a TiO ₂ equivalent mass of the titanium alkoxide hydrolyzed / condensed product. There is also provided a liquid coating material characterized in that the mass ratio of the particulate metal oxide to is 0.20 to 4.00, preferably 0.25 to 3.00. This liquid coating material can be used for forming the above-mentioned sliding resistant coating film of the present invention. This liquid coating material contains 2-ethoxyethanol (ethyl cellosolve) as a main solvent, has a solid content concentration of 35% by mass or less, and has a light scattering intensity change rate of 20% after standing at a temperature of 10 ° C. for 168 hours. The following is preferable. The light scattering intensity of the liquid coating material after standing for 168 hours is usually 3000 to 100,000 cps, preferably 5000 to 50,000 cps. Here, the light scattering intensity Is is expressed by (Equation 1) (Is = light scattering intensity, Io = incident light intensity, n = refractive index of solvent, Mw = weight average molecular weight of solute, c = concentration of solute, (Dn / dc) = refractive index increment per solute concentration increase, λo = incident light wavelength, r = distance from sample to detector, N _A = Avogadro number) molecular size corresponding to Mw, that is, proportional to condensation degree The observed value is observed.

この光散乱強度（縮合度）は、水や触媒の使用量、溶媒の種類、加水分解温度や時間などによって調節することができる。該光散乱強度が前記範囲にあれば成膜性が良好で、成膜時のクラックの発生が抑制される。また、１０℃で１６８時間（１週間）放置後の光散乱強度変化率が２０％以下であれば、当該液状コーティング材料の経時安定性が良好であり、実用的に有利である。

This light scattering intensity (condensation degree) can be adjusted by the amount of water and catalyst used, the type of solvent, the hydrolysis temperature, time, and the like. When the light scattering intensity is in the above range, the film forming property is good and the generation of cracks during film formation is suppressed. Further, if the rate of change in light scattering intensity after standing at 10 ° C. for 168 hours (one week) is 20% or less, the liquid coating material has good temporal stability and is practically advantageous.

  The present invention further comprises a laminate comprising at least one of the above-mentioned sliding resistant coating film of the present invention, wherein the refractive index of the layer in contact with the sliding resistant coating film is the refractive index of the coating film. Also provided is a laminate characterized by being 0.05 or more lower than the above.

Examples of the organic substrate in the laminate include the resins exemplified above as the organic substrate. These organic base materials may be a laminate of two or more kinds, and various paints such as acrylic paints and silicone paints may be coated on the surface.
The sliding resistant coating film and laminate of the present invention are, for example, an optical material such as an antireflection film provided on the surface layer of a display device such as LCD or PDP, an ultraviolet reflective material for window glass, and further vacuum deposition or It can be used for a base film such as sputtering.

  For example, in the case of using the laminate as an optical material such as an antireflection film, the refractive index of the layer in contact with the above-mentioned sliding resistant coating film is set to be less than the refractive index of the sliding resistant coating film. It should be 05 or more, preferably 0.1 or more. Examples of the laminate having a refractive index difference of 0.1 or more include polyethylene terephthalate base material / sliding resistant coating film of the present invention / silica film, and polyethylene terephthalate base material / sliding resistance of the present invention. Examples thereof include coating film / silica film / sliding resistant coating film / silica film of the present invention.

  The laminate preferably has a total light transmittance of 80% or more in a wavelength range of 400 to 800 nm, more preferably 85% or more, and a haze value of 10% or less, more preferably 3.0% or less. It is. The method for measuring the total light transmittance and haze value will be described in detail later.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the various characteristics in each example were calculated | required according to the point shown below.
(1) Measurement of Light Scattering Intensity of Coating Liquid Using “ELS-8000” manufactured by Otsuka Electronics Co., Ltd., measurement was performed 50 times using a glass cell, and the average value was obtained. At this time, the size of the pinhole was measured with the sample side having a diameter of 0.2 mm and the detection side having a diameter of 0.1 mm.
(2) Refractive index of coating film Using a "Thin Film Measuring Device F20" manufactured by Filmetics, the reflection wavelength was calculated by fitting a reflection spectrum at a measurement wavelength of 420 to 1000 nm. The refractive index was calculated on the assumption that the refractive index of the coating film was uniform throughout the layer.
(3) Sliding property of coating film Each cotton coating is made of cotton canvas (TOSCO Co., Ltd., cherry diamond mark, No. 6) with a load of 2.94 N / cm ² and a width of 6 cm at a speed of 30 reciprocations per minute. The film was slid for 1 minute, and the coating film before and after sliding was fluorescent X-ray [Seiko Instruments Co., Ltd., “SEA2120”, tube current 122 μA, tube voltage 15 kV, under vacuum, strength measurement] The sliding durability was evaluated by calculating the X-ray intensity difference [= (after sliding / before sliding) × 100 (%)] (residual ratio of film).
(4) Thickness of coating film Using a "Thin Film Measuring Device F20" manufactured by Filmmetrics, the reflection wavelength was calculated by fitting a reflection spectrum at a measurement wavelength of 420 to 1000 nm. The refractive index was calculated on the assumption that the refractive index of the coating film was uniform throughout the layer.
(5) Haze value of coating film and laminate In accordance with JIS K7361, using a haze meter “NDH2000” manufactured by Nippon Denshoku Co., Ltd., each of the three points of the coating film and the laminate was measured, and the average value was calculated. Asked.
(6) Total light transmittance of laminated body Based on JIS K7361-1, three points of the laminated body were measured using the haze meter "NDH2000" by Nippon Denshoku Co., Ltd., and the average value was calculated | required.
(7) Gradient property of component gradient film Using an XPS apparatus “PHI-5600” [manufactured by ULVAC-PHI, Inc.], argon sputtering (4 kV) is applied at intervals of 3 minutes to scrape the film, and carbon atoms and metals on the film surface The atomic content was measured by X-ray photoelectron spectroscopy to examine the gradient.

Example 1
(1) Preparation of liquid coating material After heating the mixed solution of 168.8 g of methyl methacrylate, 21.5 g of γ-methacryloxypropyltrimethoxysilane, and 328.5 g of methyl isobutyl ketone to 60 ° C., 2,2-azobisiso A solution prepared by dissolving 1.0 g of butyronitrile in 80.0 g of methyl isobutyl ketone was added with stirring and reacted at 60 ° C. for 30 hours. Thereafter, 10 g of the copolymer solution was diluted with 21.7 g of methyl isobutyl ketone to obtain a copolymer solution (a). The weight average molecular weight in terms of polymethyl methacrylate as measured by gel permeation chromatography was about 100,000.
On the other hand, a mixed solution of 1.7 g of 60 mass% nitric acid, 0.6 g of water and 7.8 g of ethyl cellosolve was slowly added dropwise to a solution obtained by dissolving 10.1 g of titanium tetraisopropoxide in 19.9 g of ethyl cellosolve. Thereafter, the mixture was stirred at 30 ° C. for 4 hours to obtain a reaction solution (b).
Next, 0.4 g of copolymer (a) was dissolved in 36.3 g of methyl isobutyl ketone to obtain an organic component solution. The reaction solution (b) (3.5 g) was diluted with ethyl cellosolve (32.4 g), mixed with the organic component solution, and further colloidal titania [rutile-type crystalline titaniisopropanol (IPA) dispersion, average particle size 20 nm, nonvolatile content 5.8 % By weight] was slowly added dropwise with sequential stirring to prepare a liquid coating material (c). The mass ratio of the particulate metal oxide to the TiO ₂ converted mass of the hydrolysis / condensation product of titanium alkoxide is 1.73.
(2) Coating film formation The liquid coating material (c) was applied to a polyethylene terephthalate (PET) film having a thickness of 188 μm with a Mayer bar having a wire diameter of 0.125 mmφ, the solvent was volatilized, and the film was evaporated in an oven at 60 ° C. Heated for hours to form a coating film. The thickness of the coating film (d) at this time was 50 nm.
(3) Evaluation results As a result of evaluating the refractive index, sliding durability, haze value, and gradient of the inorganic component of the coating film (d), 1.93,> 99%, 0.67%, and good gradient, respectively. there were. The results are shown in Table 1, and the XPS measurement results are shown in FIG.

Example 2
In the same manner as in Example 1, a copolymer (a) and a reaction solution (b) were prepared. Next, 0.5 g of copolymer (a) was dissolved in 22.5 g of methyl isobutyl ketone to obtain an organic component solution. 4.4 g of the reaction solution (b) was diluted with 21.1 g of ethyl cellosolve, mixed with the organic component solution, and further colloidal titania [IPA dispersion of rutile crystal titania, average particle size of 20 nm, nonvolatile content of 5.8% by weight. The liquid coating material (c) was prepared by slowly dropping 1.5 g while sequentially stirring. The mass ratio of the particulate metal oxide to the TiO ₂ converted mass of the hydrolysis / condensation product of titanium alkoxide is 0.28. Thereafter, a coating film was formed in the same manner as in Example 1. The results are shown in Table 1.

Example 3
In Example 1, a coating film was formed in the same manner as in Example 1 except that the copolymer (a) was not added. The results are shown in Table 1.

Example 4
In Example 2, a coating film was formed in the same manner as in Example 2 except that 0.4 g of colloidal alumina [aqueous dispersion, average particle size 20 nm, solid component concentration 20 wt%] was dropped instead of colloidal titania. did. The results are shown in Table 1. The mass ratio of the particulate metal oxide to the TiO ₂ converted mass of the hydrolyzed / condensed product of titanium alkoxide is 0.26.

Example 5
To 18.0 g of the reaction solution (b), 1.5 g of 25 mol% aluminum nitrate nonahydrate with respect to the titanium atom of the hydrolysis / condensation product of titanium alkoxide was added, and then 10.5 g of ethyl cellosolve was added to the reaction solution. (B '). In Example 1, a coating film was formed in the same manner as in Example 1 except that 3.5 g of the reaction solution (b ′) was used instead of the reaction solution (b). The results are shown in Table 1. The mass ratio of the particulate metal oxide to the TiO ₂ converted mass of the hydrolyzed / condensed product of titanium alkoxide is 2.88.

Comparative Example 1
In Example 2, the same method as in Example 1 except that the copolymer (a) and colloidal rutile-type titania were not added and the liquid coating material was applied with a Mayer bar having a wire diameter of 0.150 mmφ. A coating film was formed. The results are shown in Table 1.

Comparative Example 2
In Example 2, a coating film was formed in the same manner as in Example 1 except that no colloidal rutile type titania was added and the liquid coating material was coated with a Mayer bar having a wire diameter of 0.150 mmφ. The results are shown in Table 1.

表１から分かるように、本発明の塗膜（実施例１〜５）は、屈折率が高く、かつ摺動耐久性に優れている。

As can be seen from Table 1, the coating films of the present invention (Examples 1 to 5) have a high refractive index and excellent sliding durability.

Example 6
The coating film obtained in Example 1 was subjected to an RF output of 400 W, 0.4 Pa, an Ar flow rate of 9 cm ³ / min (standard state) with a multi-element ion sputtering apparatus [“MH92-5036” manufactured by Nippon Vacuum Technology Co., Ltd.] Then, sputtering of SiO ₂ was performed. When the total light transmittance of the obtained laminate was measured, it was 91% and the haze value was 0.6%.

  The sliding resistant coating film of the present invention is formed by coating a liquid coating material on an organic substrate, has a high refractive index and excellent sliding durability, and is suitably used as an optical material.

4 is a graph showing the relationship between the sputtering time and the carbon atom content and titanium atom content in the organic-inorganic composite gradient film formed in Example 1. FIG.

Claims (11)

A coating film having a thickness of 10 to 500 nm formed by applying a liquid coating material on an organic substrate, having a haze value of 10.0% or less and a refractive index of 1.7 or more, and A sliding resistance characterized by using a cotton canvas and having a load of 2.94 N / cm ² , a width of 6 cm, and a rate of 30 reciprocations / min. Dynamic coating.   The sliding resistant coating film according to claim 1, comprising a hydrolysis / condensation product of titanium alkoxide and a fine particle metal oxide having a particle size of 3 to 300 nm as main components. The sliding resistant coating film according to claim 2, wherein the mass ratio of the particulate metal oxide to the TiO ₂ converted mass of the hydrolyzed / condensed product of titanium alkoxide is 0.20 to 4.00.   The sliding-resistant coating film according to claim 2 or 3, wherein the particulate metal oxide has a refractive index of 1.6 or more.   The sliding-resistant coating film according to claim 2, 3 or 4, wherein the particulate metal oxide is rutile-type titanium oxide.   Component gradient that contains organic polymer compound and the content of titanium alkoxide hydrolyzed / condensed and fine metal oxide with a particle size of 3 to 300 nm continuously decreases from the coating surface toward the organic substrate. The sliding resistant coating film according to any one of claims 2 to 5, which has a structure.   The sliding resistant coating film according to any one of claims 1 to 6, comprising at least one aluminum compound and / or zirconium compound selected from salts, complexes and alkoxides. The titanium alkoxide hydrolyzed / condensed product and the particulate metal oxide having a particle size of 3 to 300 nm, and the mass ratio of the particulate metal oxide to the TiO ₂ converted mass of the titanium alkoxide hydrolyzed / condensed product was 0. A liquid coating material, characterized in that it is 20 to 4.00.   9. The liquid coating according to claim 8, which contains 2-ethoxyethanol as a main solvent, has a solid content concentration of 35% by mass or less, and a light scattering intensity change rate after standing for 168 hours at a temperature of 10 ° C. is 20% or less. material.   A laminate comprising at least one sliding resistant coating film according to any one of claims 1 to 7, wherein a refractive index of a layer in contact with the sliding resistant coating film A laminate characterized by being 0.05 or more lower than the refractive index. The laminate according to claim 10, wherein the total light transmittance in a wavelength region of 400 to 800 nm is 80% or more and the haze value is 10% or less.

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