JP2005208290A - Soil-resistant optical thin film, stain-resistant antireflection film, polarizing plate using the same and display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stain-resistant optical thin film and a stain-resistant antireflection film which exhibit wear resistance by adhering strongly with the base and have excellent surface soil-resistant properties, and to provide a polarizing plate using the above films and a display apparatus. <P>SOLUTION: The stain-resistant optical thin film is produced by subjecting the surface of a film containing at least a silicon oxide and a silane coupling agent to hydrophilic treatment and further applying a coating layer containing a fluorine-containing silane compound on the treated surface. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antifouling optical thin film, an antifouling antireflection film, a polarizing plate using the same, and a display device.

  In order to improve the visibility of the image display device, a method of performing low reflection treatment on the surface has been proposed in order to eliminate the reflection and improve the light transmittance. Among these, in the formation of an antireflection film by a coating method, it is generally known that the adhesion to the base can be strengthened by adding a coupling agent. Further, a method of introducing a surfactant for ensuring the flatness and uniformity of the coating film is known.

  On the other hand, it is necessary for such an image display device that the surface is not easily soiled and easy to wipe. Therefore, it is known to apply an antifouling treatment to the surface of the antireflection film. However, the original performance of such an antifouling treatment depends on the surface state of the antireflection film as a base. Therefore, as disclosed in Patent Document 1, an attempt has been made to develop performance by pretreating the surface of the antireflection film.

However, such a method can be applied to the surface treatment of only inorganic compounds formed by vacuum deposition or sputtering, but the conditions include organic components such as coupling agents and surfactants. Anti-reflection for easy and effective development of anti-fouling treatment, because the surface of the anti-reflective coating must be cleaned, treated for good anti-fouling properties, and organic components in the film must be removed. There has been a need to optimize each stage of film formation, surface treatment, and antifouling layer formation.
JP 2000-308846 A

  The object of the present invention has been studied in view of the above requirements. Specifically, the antifouling optical material exhibits wear resistance and has excellent surface antifouling properties by having strong adhesion to the ground. An object is to provide a thin film, an antifouling antireflection film, a polarizing plate using the same, and a display device.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
An antifouling optical thin film comprising: a surface of a film containing at least silicon oxide and a silane coupling agent; and a coating layer containing a fluorine-containing silane compound provided thereon.

(Claim 2)
The silicon oxide is a composite particle having a porous particle and a coating layer provided on the surface of the porous particle, or a hollow particle filled with a solvent, gas, or porous substance inside. Item 2. The antifouling optical thin film according to Item 1.

(Claim 3)
The antifouling optical thin film according to claim 1 or 2, wherein the fluorine-containing silane compound is silazane or alkoxysilane.

(Claim 4)
The antifouling optical thin film according to any one of claims 1 to 3, wherein the film containing at least a silicon oxide and a silane coupling agent further contains a surfactant.

(Claim 5)
5. The antifouling optical thin film according to claim 4, wherein the surfactant is dimethylpolysiloxane or a modified product thereof.

(Claim 6)
The antifouling optical thin film according to any one of claims 1 to 5, wherein the hydrophilization treatment is a treatment selected from ultraviolet irradiation treatment, O ₃ treatment, corona discharge treatment and atmospheric pressure plasma treatment. .

(Claim 7)
An antifouling antireflection film, wherein the antifouling optical thin film according to any one of claims 1 to 6 is provided on a cellulose ester film.

(Claim 8)
A polarizing plate comprising the antifouling antireflection film according to claim 7.

(Claim 9)
A display device comprising the polarizing plate according to claim 8.

  According to the present invention, an antifouling optical thin film, antifouling antireflection film, and a polarizing plate using the same, exhibiting abrasion resistance by having strong adhesion to the substrate and having excellent surface antifouling properties, and a display using the same A device can be provided.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The antifouling optical thin film of the present invention is characterized in that at least the surface of a film containing silicon oxide and a silane coupling agent is subjected to a hydrophilic treatment, and a coating layer containing a fluorine-containing silane compound is provided thereon. To do.

  In particular, in order to form an antifouling optical thin film that exhibits abrasion resistance by having strong adhesion to the base, the base is characterized by a film containing a silicon oxide and a silane coupling agent. Furthermore, the silicon oxide constitutes a composite particle having a porous particle and a coating layer provided on the surface of the porous particle, or a fine particle which is a hollow particle filled with a solvent, gas, or porous substance inside It is a preferred embodiment that it is contained as an element, the fluorine-containing silane compound is silazane or alkoxysilane, and contains a specific surfactant.

  Hereinafter, the present invention will be described in detail for each element.

The film containing the silicon oxide and the silane coupling agent according to the present invention is preferably a low reflective optical film which is a low refractive index layer. (Hereinafter also referred to as a low refractive index layer.)
The silicon oxide is an inorganic silicon oxide or a silicon oxide having an organic group.

  The inorganic silicon oxide is preferably silicon oxide (SiOx) fine particles, and it is also preferable to use a layer formed as a microvoid between or within the fine particles. The average particle diameter of the fine particles is preferably 0.5 to 200 nm, more preferably 1 to 100 nm, still more preferably 3 to 70 nm, and most preferably in the range of 5 to 40 nm. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible.

As inorganic fine particles, SiO ₂ is particularly preferable.

Particles having microvoids in the inorganic fine particles can be formed, for example, by crosslinking silica molecules forming the particles. Crosslinking silica molecules reduces the volume and makes the particles porous. (Porous) inorganic fine particles having microvoids are prepared by a sol-gel method (described in JP-A-53-112732 and JP-B-57-9051) or a precipitation method (described in APPLIED OPTICS, 27, 3356 (1988)). Can be directly synthesized as a dispersion. Further, the powder obtained by the drying / precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available porous inorganic fine particles (for example, SiO ₂ sol) may be used.

  These inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone) are preferable.

  Microvoids between particles can be formed by stacking at least two fine particles. When spherical particles having the same particle diameter (completely monodispersed) are closely packed, microvoids between particles with a porosity of 26% by volume are formed. When spherical fine particles having the same particle diameter are simply filled with cubic particles, microvoids between fine particles having a porosity of 48% by volume are formed. In an actual low-refractive index layer, the particle size distribution of fine particles and intra-particle microvoids exist, so the porosity varies considerably from the above theoretical value. When the porosity is increased, the refractive index of the low refractive index layer is lowered. When microvoids are formed by stacking fine particles, the size of the microvoids can be adjusted to an appropriate value (does not scatter light and cause no problem with the strength of the low refractive index layer) by adjusting the particle size of the fine particles. You can adjust. Furthermore, by making the particle diameters of the fine particles uniform, it is possible to obtain an optically uniform low refractive index layer in which the size of microvoids between particles is uniform. As a result, the low refractive index layer is microscopically a microvoided porous film, but can be made optically or macroscopically uniform. The interparticle microvoids are preferably closed in the low refractive index layer by fine particles and a polymer. The closed air gap also has an advantage that light scattering on the surface of the low refractive index layer is less than that of an opening opened on the surface of the low refractive index layer.

  By forming the microvoids, the macroscopic refractive index of the low refractive index layer becomes lower than the sum of the refractive indexes of the components constituting the low refractive index layer. The refractive index of the layer is the sum of the refractive indices per volume of the layer components. The refractive index of the constituent component of the low refractive index layer such as fine particles or polymer is larger than 1, whereas the refractive index of air is 1.00. Therefore, a low refractive index layer having a very low refractive index can be obtained by forming microvoids.

  Further, the low refractive index layer according to the present invention is a composite particle having porous particles and a coating layer provided on the surface of the porous particles, or hollow particles filled with a solvent, gas, or porous substance inside. It is particularly preferable for

  The inorganic fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having a cavity inside, and the content is a solvent, gas or porous substance It is preferable that the low refractive index layer contains either (I) composite particles or (II) hollow particles, or both of them. Other particles may also be included.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with a content such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle diameter of such inorganic fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The average particle diameter of the inorganic fine particles used is appropriately selected according to the thickness of the transparent film to be formed, and is in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. It is desirable to be in These inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and silicate monomers and oligomers with a low degree of polymerization, which are coating liquid components described later, are easy. In some cases, the inside of the composite particle enters the inside and the porosity of the inside is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. The coating layer of the composite particle or the particle wall of the hollow particle may contain a component other than silica, specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO _2. and _{CeO 2, P 2 O 3,} Sb 2 O 3, MoO 3, ZnO 2, WO 3 and the like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MOX / SiO ₂ when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOX) is 0.0001 to 1.0, preferably It is desirable to be in the range of 0.001 to 0.3. It is difficult to obtain porous particles having a molar ratio MOX / SiO ₂ of less than 0.0001, and even if obtained, those having a lower refractive index are not obtained. On the other hand, if the molar ratio MOX / SiO _{2 of} the porous particles exceeds 1.0, the silica ratio decreases, so that particles having a small pore volume and a low refractive index may not be obtained.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  Incidentally, the pore volume of such porous particles can be obtained by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous material used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used in preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such inorganic fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, the inorganic compound particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium Salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. I can do it. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When the seed particle dispersion is used, the pH of the seed particle dispersion is adjusted to 10 or more, and then the aqueous solution of the compound is added to the above-described alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. In this way, when seed particles are used, it is easy to control the particle size of the porous particles to be prepared, and particles having a uniform particle size can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. Particle deposition occurs on the top. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to oxide (MOx), and the molar ratio of MOx / SiO ₂ is 0.05 to 2.0, preferably It is desirable to be within the range of 0.2 to 2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing hollow particles, the molar ratio of MOx / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded via oxygen. By removing inorganic compounds (elements other than silicon and oxygen) from such a porous particle precursor, porous particles having a more porous and large pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, a silicic acid solution obtained by removing the alkali metal salt of silica from the porous particle precursor dispersion obtained in the first step. Alternatively, it is preferable to form a silica protective film by adding a hydrolyzable organosilicon compound. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than the silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. I can do it. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

  The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organosilicon compound used for forming the silica protective film includes a general formula RnSi (OR ′) 4-n [R, R ′: hydrocarbon such as alkyl group, aryl group, vinyl group, acrylic group, etc. An alkoxysilane represented by the group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third Step: Formation of Silica Coating Layer In the third step, a hydrolyzable organosilicon compound or silicic acid solution is added to the porous particle dispersion prepared in the second step (in the case of hollow particles, a hollow particle precursor dispersion). Etc. is added to coat the surface of the particles with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

  Examples of the hydrolyzable organosilicon compound used for forming the silica coating layer include the general formula RnSi (OR ′) 4-n [R, R ′: alkyl group, aryl group, vinyl group, acrylic group as described above. Etc., and alkoxysilanes represented by n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. A silicic acid solution may be used in combination with the alkoxysilane for forming a coating layer. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.44. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. The refractive index of the low refractive index layer according to the present invention is preferably 1.30 to 1.50, and more preferably 1.35 to 1.44.

In the present invention, commercially available SiO ₂ fine particles can be used. Specific examples of commercially available particles include P-4 manufactured by Catalytic Chemical Industry Co., Ltd.

  As the material for the low refractive index layer according to the present invention, it is also preferable to use a silicon oxide having an organic group in addition to the inorganic silicon oxide. These are generally called sol-gel materials, but metal alcoholates, organoalkoxy metal compounds and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. Tetraalkoxysilane and its hydrolyzate are particularly preferable.

  In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  The low refractive index layer according to the present invention contains the silicon oxide and the following silane coupling agent.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Specific examples of the silane coupling agent include: Shin-Etsu Chemical Co., Ltd. KBM-303, KBM-403, KBM-402, KBM-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE- 503, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-802, KBM-803 and the like.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  A specific method of surface treatment with a coupling agent is shown below.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the above-described silicon oxide particles and the surface of the silicon oxide having an organic group easily react, and a stronger film is formed. Moreover, you may add the hydrolyzed silane coupling agent in a coating liquid previously.

  The low refractive index layer can also contain a polymer in an amount of 5-50% by weight. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treatment agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer and performing a polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to carry out a combination of two or all of the above (1) to (3), and to carry out a combination of (1) and (3) or (1) to (3) all of the combinations. Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. When the fine particles are made of SiO _{2, the} surface treatment with the silane coupling agent described above can be carried out particularly effectively.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Mention may be made of esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides), methacrylamide and acrylonitrile.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after the coating of the low refractive index layer, by a polymerization reaction (further crosslinking reaction if necessary). Even if a small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

  Further, the low refractive index layer according to the present invention may be a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”).

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (produced by Osaka Organic Chemicals) or M-2020 (produced by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). The latter can introduce a crosslinked structure after copolymerization by adding a compound that reacts with a functional group in the polymer and one or more reactive groups. No. 147739. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is cross-linked by heating by a cross-linking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, the thermosetting type In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, etc., it is an ionizing radiation curable type .

  In addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (R) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR) and the like. It is done.

  The low refractive index layer containing a cross-linked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

  Moreover, it is preferable to add a surfactant to the low refractive index layer of the present invention. Specific examples of preferable surfactants include modified silicone oil having a polydimethylsiloxane skeleton, specifically hydrophilic special modification, polyalkylene oxide modification, block copolymer with polyalkylene oxide, alkoxy modification, alcohol modification, carboxyl modification. And amino-modified silicone oil.

For example, the amount of surfactant used in the low refractive index layer is preferably ^{0.01mg / m 2 ~10mg / m 2} .

  Each layer of the low refractive index layer according to the present invention is a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). It can be formed by coating. Two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, It is described in Asakura Shoten (1973).

  Each film thickness of the low refractive index layer according to the present invention is preferably 50 to 200 nm, and more preferably 60 to 150 nm.

(Anti-fouling layer)
The coating layer containing the fluorine-containing silane compound according to the present invention is a layer that functions as an antifouling layer, and is prepared by coating a silane compound solution having a fluoroalkyl group or a fluoroalkyl ether group. In particular, the fluorine-containing silane compound is preferably silazane or alkoxysilane.

  In addition, among the silane compounds having the fluoroalkyl group or the fluoroalkyl ether group, the fluoroalkyl group in the silane compound is bonded to Si atoms at a ratio of 1 or less to one Si atom, and the remaining Is preferably a silane compound which is a hydrolyzable group or a siloxane bond group.

  The hydrolyzable group here is a group such as an alkoxy group, for example, and becomes a hydroxyl group by hydrolysis, whereby the silane compound forms a polycondensate.

  For example, the silane compound is usually reacted with water (in the presence of an acid catalyst if necessary) in the range of room temperature to 100 ° C. while distilling off by-produced alcohol. As a result, the alkoxysilane is (partially) hydrolyzed to cause a partial condensation reaction, and can be obtained as a hydrolyzate having a hydroxyl group. The degree of hydrolysis and condensation can be adjusted as appropriate depending on the amount of water to be reacted, but in the present invention, water is not actively added to the silane compound solution used for antifouling treatment, and after preparation, It is preferable to dilute and use the solid content concentration of the solution in order to cause a hydrolysis reaction mainly by moisture in the air during drying.

  Preferably, in the antifouling layer forming composition, the silane compound having a fluoroalkyl group is represented by the following general formula (A), and the concentration of the silane compound is diluted to 0.01 to 5% by mass. It is used as an antifouling treatment.

Formula (A)
_{CF 3 (CF 2) m (} CH 2) n -Si- (ORa) 3
Here, m is an integer of 1-10. n is an integer of 0-10. Ra represents the same or different alkyl group.

  In the compound represented by the general formula (A), Ra has 3 or less carbon atoms and is preferably an alkyl group consisting of only carbon and hydrogen, for example, a group such as methyl, ethyl, isopropyl and the like.

Examples of the silane compound having a fluoroalkyl group or fluoroalkyl ether group preferably used in the present invention include CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ). ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₄ H ₉ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC _{3 H 7) 3, CF 3} (CF 2) 7 (CH 2) 2 Si (OCH 3) (OC 3 H 7) 2, CF 3 (CF 2) 7 _{CH 2) 2 Si (OCH 3} ) 2 OC 3 H 7, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 (OCH 3) 2, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 ( OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₃ H ₇ ) ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , C ₇ F ₁₅ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₅ ( _{CH 2) 2 Si (CH 3} ) (OCH 3) 2, CF 3 (CF 2) 5 (CH 2) 2 Si (CH 3) (OC 3 H 7) 2, CF 3 (CF 2) 2 O (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ), C ₇ F ₁₅ CH ₂ O (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ O (CH ₂ ) ₃ Si Examples include (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCHO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , but not limited thereto.

  Examples of the fluorine-based silane compound include KP801M and X-24-9146 manufactured by Shin-Etsu Chemical Co., Ltd., GE Toshiba Silicones Co., Ltd. XC98-A5382, XC98-B2472, Daikin Industries Co., Ltd. As the compound for surface treatment, perfluoroalkylsilazane, perfluoroalkylsilane, or perfluoropolyether group-containing silane compound, particularly perfluoroalkyltrialkoxysilane, perfluoropolyethertrialkoxysilane, Examples include perfluoropolyether ditrialkoxysilane.

  When these silane compounds are used, they are diluted to 0.01 to 10% by mass, preferably 0.03 to 5% by mass, more preferably 0.05 to 2% by mass with an organic solvent not containing fluorine. It is preferable to use in.

  In the present invention, an organic solvent containing no fluorine is preferably used to prepare the silane compound solution, and the following may be mentioned.

  As a solvent of the coating composition for an antifouling layer of the present invention, propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, propylene glycol mono (C1-C4) alkyl Specific examples of the ether include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether and the like. The propylene glycol mono (C1 to C4) alkyl ether ester includes propylene glycol monoalkyl ether acetate, specifically, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. Propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, etc., alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol, t-butanol, cyclohexanol , Ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetone, esters such as ethyl acetate, methyl acetate, ethyl lactate, isopropyl acetate, amyl acetate and ethyl butyrate, hydrocarbons such as benzene, toluene and xylene, dioxane, N, N-dimethylformamide and other solvents. Alternatively, these solvents are used by being appropriately mixed. The solvent to be mixed is not particularly limited to these.

  A particularly preferred range is one or more organic solvents selected from ethanol, isopropyl alcohol, propylene glycol, and propylene glycol monomethyl ether.

  Among these solvents, those having a boiling point of less than 100 ° C. (low boiling solvent) such as methanol, ethanol and isopropyl alcohol, and boiling points of 100 ° C. or more such as propylene glycol monomethyl ether and n-butyl alcohol. (Boiling point solvent) is preferably used in combination, and in particular, those having a boiling point of 60 to 98 ° C. and those having a boiling point of 100 to 160 ° C. are preferably used in combination. The ratio of the low boiling point solvent and the high boiling point solvent when used in combination is preferably 98.0% by mass or more and the high boiling point solvent is 0.5 to 2% by mass in the composition.

  In the composition for forming an antifouling layer of the present invention, it is preferable to adjust the pH to 5.0 or less by adding an acid. Since the acid promotes hydrolysis of the silane compound and acts as a catalyst for the polycondensation reaction, the polycondensation film of the silane compound can be easily formed on the surface of the substrate, and the antifouling property can be improved. The pH is preferably in the range of 1.5 to 5.0. If the pH is 1.5 or less, the acidity of the solution is too strong, and the container or the piping may be damaged. Preferably it is the range of pH2.0-4.0.

  In the present invention, it is preferable not to positively add water to the silane compound solution used for the antifouling treatment, but to cause a hydrolysis reaction by moisture in the air after the preparation, mainly at the time of drying. Therefore, it is used when the solid content concentration of the solution is diluted. If too much water is added to the treatment liquid, the pot life is shortened accordingly.

  In the present invention, sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, boric acid, hydrofluoric acid, preferably an inorganic acid such as hydrochloric acid and nitric acid, an organic acid having a sulfo group (also referred to as a sulfonic acid group) or a carboxyl group, For example, acetic acid, polyacrylic acid, benzenesulfonic acid, p-toluenesulfonic acid, methylsulfonic acid and the like are used. The organic acid is more preferably a compound having a hydroxyl group and a carboxyl group in one molecule. For example, a hydroxydicarboxylic acid such as citric acid or tartaric acid is used. The organic acid is more preferably a water-soluble acid. For example, in addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaloacetic acid, pyruvin. Acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D-gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are preferably used. Also, benzoic acid, hydroxybenzoic acid, atorvaic acid and the like can be used as appropriate.

  The addition amount is 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the partial hydrolyzate of the silane compound. Further, the amount of water added is not limited as long as the partial hydrolyzate can theoretically be hydrolyzed by 100%, and an amount equivalent to 100% to 300%, preferably an amount equivalent to 100% to 200% is added. Good.

  By using a fluorine-containing silane compound, it is not only preferable in terms of lowering the refractive index of the antifouling layer and imparting water and oil repellency, but also has an effect of being highly scratch resistant and particularly excellent in blocking between films. .

  In the present invention, it is also preferable to use a composition obtained by further adding an alkoxysilane or an alkylalkoxysilane to a fluorine-free organic solvent solution containing the silane compound having a fluoroalkyl group.

  As examples of these alkoxysilanes and alkylalkoxysilanes, any known silane compounds may be used.

  Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), dialkyldialkoxysilane, and the like.

  These alkoxysilanes and alkylalkoxysilanes can be used in the range of 0.01 to 15% by mass in addition to the fluorine-containing silane compound when preparing the coating composition for the antifouling layer. In the same manner, by performing hydrolysis and condensation in the same manner, an integrated film is formed by polycondensation with the fluorine-containing silane compound.

  By using these alkoxysilanes and alkylalkoxysilanes in admixture with the fluorine-containing silane compound, the film strength is increased, and there are further effects in scratch resistance and prevention of blocking when stacked.

  Furthermore, it is also possible to use a composition formed by adding 0.01 to 5% by mass of a silicon isocyanate compound to a silane compound solution having a fluoroalkyl group or a fluoroalkyl ether group. The strength is further improved, and further effects can be obtained by preventing the surface from being scratched and suppressing sticking (blocking) when the films are stacked.

As the silicon isocyanate compound used in the present invention, Si (NCO) ₄ , CH ₃ Si (NCO) ₃ , (CH ₃ ) ₂ Si (NCO) ₂ , (CH ₃ ) ₃ SiNCO, CH ₂ = CHSi (NCO) ₃ , C ₂ H ₅ Si (NCO) ₃ , and the like. Si (NCO) ₄ and CH ₃ Si (NCO) ₃ are preferable, and Si (N) is preferred from the viewpoint of environmental safety, which is an object of the present invention. NCO) ₄ is more preferred.

  By mixing these silicon isocyanate compounds in the above amounts in the antifouling layer-forming composition, the crosslinking reaction with the silane compound can be performed more completely, and the effect of improving the film properties is great. These compounds do not participate in the hydrolysis, but react with a hydroxyl group (silanol group) formed by hydrolysis to complement the condensation of the silanol groups and make the film strong.

  The organic solvent that does not contain fluorine may be used as it is as the organic solvent when using these silicon isocyanate compounds. However, among the above-mentioned organic solvents, when the silicon isocyanate compound is mixed and used, ethanol, isopropyl Particularly preferred are solvents such as alcohol, propylene glycol, toluene, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and butyl acetate.

  Moreover, when mixing and using a silicon isocyanate compound, pH should just be 7.0 or less, and the range of 2.0-7.0 is good. When the pH is 7.0 or more, the reaction with the silanol group is difficult to proceed. Among them, the pH is preferably in the range of 3.0 to 6.0.

  The refractive index of the antifouling layer is preferably 1.30 to 1.50, more preferably 1.35 to 1.49. When it is 1.30 or less, the film hardness cannot be obtained, and when it is 1.50 or more, the surface reflectance increases. The antifouling layer comprising a resin formed from a hydrolyzed polycondensate of a silane compound containing a fluoroalkyl group preferably has a dynamic friction coefficient in the range of 0.03 to 0.25.

The antifouling layer coating composition thus obtained is applied on the low refractive index layer to form an antifouling layer. As a coating method, any method may be used, and a method using a normal dip coater, gravure coater, reverse roll coater, extrusion coater, etc. may be mentioned. Further, in order to improve the antifouling function of the antifouling layer, with a film, and other physical properties, it is necessary to hydrophilize the surface of the low refractive index layer in order to achieve the effects of the present invention. Yes, it is preferable to perform ultraviolet irradiation treatment, O ₃ treatment, corona discharge treatment, atmospheric pressure plasma treatment or the like.

  The corona discharge treatment is a treatment performed by applying a high voltage of 1 kV or higher between the electrodes at atmospheric pressure and discharging it, and is commercially available from Kasuga Electric Co., Ltd. and Toyo Electric Co., Ltd. It can be performed using an apparatus. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency. As one electrode (A electrode) of the corona discharge treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona discharge treatment is carried out stably and uniformly. . A commercially available one can also be used, and the material is preferably a roll made of aluminum, stainless steel, or a metal thereof, and a roll lined with ceramic, silicon, EPT rubber, hyperon rubber, or the like. It is done.

  The frequency used for the corona discharge treatment of the present invention is a frequency of 20 kHz to 100 kHz, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona discharge treatment is deteriorated, and unevenness of the corona discharge treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing a high output corona discharge treatment, but when performing a low output corona discharge treatment, it becomes difficult to perform a stable treatment. Processing unevenness occurs.

The output of the corona discharge treatment of the present invention is 1 to 5 w · min. / M ² but ² to 4 w · min. An output of / m ² is preferred.

  The distance between the A electrode and the film of the present invention is from 5 mm to 50 mm, preferably from 10 mm to 35 mm. When the gap is opened, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. If the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film comes into contact with the electrodes and scratches are generated.

Examples of the ultraviolet irradiation treatment include lamps such as metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, low pressure mercury lamps, and high pressure mercury lamps. For example, a commercially available product such as an H lamp, D lamp, or V lamp manufactured by Fusion System can be used. The metal halide lamp has a continuous spectrum as compared with a high-pressure mercury lamp (main wavelength is 365 nm), has high luminous efficiency in the range of 200 to 450 nm, and has a long wavelength range. Irradiation conditions vary depending on each lamp. For example, a low-pressure mercury lamp is used to irradiate mainly 185 nm and 254 nm ultraviolet rays with a light amount of 1 to 3,000 mJ / cm ² , and an excimer lamp is used mainly for the wavelength. Can irradiate ultraviolet rays of 172 nm with a light amount of 1 to 3,000 mJ / cm ² . Such ultraviolet rays generate active oxygen and ozone, and can decompose organic substances on the surface of the object to be coated. Also, they act directly on the surface of the object to be coated, so that hydroxyl groups and carboxyl groups are formed on the surface of the object to be coated. It is possible to generate a hydrophilic group such as a carbonyl group and improve adhesion.

Furthermore, the generation of active oxygen and ozone may be promoted by sending oxygen near the surface of the object to be coated, and the O ₃ treatment may be performed.

  The plasma discharge treatment can be performed by exposing the substrate to a high-frequency discharge atmosphere in an argon or oxygen atmosphere with a plasma discharge treatment apparatus or the like to be described later.

  All of these have the effect of facilitating chemical bonding with the antifouling layer by hydrophilizing the surface, but they can be processed in a short time and have a large surface cleaning effect, such as corona discharge treatment and atmospheric pressure plasma. The treatment is preferable, and the silane coupling agent on the surface and the atmospheric pressure plasma treatment capable of decomposing the siloxane skeleton are particularly preferable.

  The atmospheric pressure plasma treatment preferably used in the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus using nitrogen gas.

The plasma discharge processing apparatus 10 has a counter electrode composed of a first electrode 111 and a second electrode 112, and the first electrode 111 receives a first power from a first power supply 121 between the counter electrodes. A high frequency voltage V ₁ having a frequency ω ₁ is applied, and a high frequency voltage V ₂ having a _second frequency ω ₂ from the second power source 122 is applied from the second electrode 112. The first power supply 121 has a capability of applying a higher frequency voltage (V ₁ > V ₂ ) than the second power supply 122, and the first frequency ω ₁ of the first power supply 121 is the second frequency of the second power supply 122. A frequency lower than the frequency ω ₂ can be applied.

  A first filter 123 is installed between the first electrode 111 and the first power supply 121 so that the current from the first power supply 121 flows toward the first electrode 111. Is designed so that the current from the second power source 122 can easily pass through.

  In addition, a second filter 124 is installed between the second electrode 112 and the second power source 122 so that a current from the second power source 122 flows toward the second electrode 112. It is designed to make it difficult to pass the current and to easily pass the current from the first power supply 121.

  Gas G is introduced from the gas supply means into the space (discharge space) 113 between the first electrode 111 and the second electrode 112, and a high frequency voltage is applied from the first electrode 111 and the second electrode 112 to generate a discharge. Then, while the gas G is in a plasma state, it is blown out in the form of a jet to the lower side of the counter electrode (the lower side of the paper) to fill the processing space formed by the lower surface of the counter electrode and the substrate F with the gas G ° in the plasma state. A hydrophilic treatment is performed on the material F in the vicinity of the processing position 114.

  Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a sine wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  Further, as the first filter, a capacitor of several tens to several tens of thousands pF or a coil of about several μH can be used according to the frequency of the second power source. As the second filter, a coil of 10 μH or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or a capacitor.

  The plasma discharge treatment vessel 20 is preferably made of an insulating material such as a treatment vessel made of Pyrex (R) glass, but may be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be subjected to ceramic spraying to provide insulation.

  Moreover, in order to suppress the influence on the base material at the time of the discharge plasma treatment to a minimum, the temperature of the base material at the time of the discharge plasma treatment may be adjusted to a temperature from room temperature (15 ° C. to 25 ° C.) to less than 200 ° C. More preferably, the temperature is adjusted to room temperature to 110 ° C. However, these conditions are not limited to this range because the upper limit of the temperature is determined depending on the physical properties of the substrate, particularly the glass transition temperature. In order to adjust to the above temperature range, the electrode and the substrate are subjected to discharge plasma treatment while being cooled by a cooling means as necessary.

  In the embodiment of the present invention, the plasma treatment is performed at or near atmospheric pressure, but the plasma treatment may be performed under vacuum or high pressure. In addition, although the atmospheric pressure vicinity represents the pressure of 20 kPa-110 kPa, in order to acquire the effect as described in this invention preferably, 93 kPa-104 kPa are preferable.

  The gas used is basically an inert gas.

  Examples of the inert gas include Group 18 elements of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, nitrogen gas, and the like. Helium, argon, and nitrogen gas are preferably used.

  In addition, inclusion of 0.01 to 5% by volume of a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, and nitrogen in the inert gas promotes the hydrophilization reaction. preferable.

  FIG. 2 is a conceptual diagram of an atmospheric pressure plasma discharge treatment apparatus having a partition wall preferably used in the present invention.

  As shown in FIG. 2, an atmospheric pressure plasma discharge treatment apparatus 1 constituted by the roll electrode 10 for holding a film substrate to be treated and a thin film forming unit (rod electrode) 20 having a cleaning film unit, and discharge A partition wall 310 is provided to control the flow of air inside and outside so as to surround the rod electrode. The film to be treated and the roll electrode are in close contact with each other, and the film and the partition are separated to such an extent that the film surface is not rubbed. At this time, in order to prevent the outside air from entering the partition wall, it is preferable that the partition wall and the film be as close as possible. Moreover, in order to improve the adhesiveness of a film and a roll electrode, it is preferable to provide the nip roll 16 which pinches | interposes a film with a roll electrode in the part which a film contacts with a roll electrode. At this time, the nip roll is installed so as to also block the outside air, and it is desirable that a gap be formed between the nip roll and the partition wall so as not to rub the roll surface, and the gap should be as narrow as possible.

  A purge inert gas supply port 301 is also provided. By providing this supply port, a large amount of gas can be sent into the partition wall, and not only the gas inside the partition wall can be quickly purged, but also the gas composition inside the partition wall can be kept constant while keeping the gas composition inside the partition wall constant. The gas composition around the discharge space can also be adjusted. Any number of the inert gas supply ports may be provided at any portion inside the partition wall.

  The exhaust port 302 may be provided in any part inside the partition wall, but as shown in FIG. 2, it is preferable to provide the exhaust port 302 above and below the apparatus in order to appropriately exhaust gases having different specific gravities.

  That is, it is preferable that there are at least two or more gas outlets in the discharge space and its peripheral part, that is, at the upper part and the lower part of the partition wall. This is to prevent the upper exhaust port from being filled with a relatively light gas concentration such as hydrogen, so that the lower exhaust port does not accumulate oxygen or argon gas. In this way, it is possible to prevent the discharge conditions of the upper discharge area and the lower discharge area from being different. In addition, the pipe that leads to the outside of the exhaust port has a mechanism that discharges the outside gas after changing the residue of the raw material gas into non-combustible gas, etc., and passes it into water to make it a gas rich in water before discharging it to the outside You may have a mechanism. By separating and exhausting in this way, hydrogen and combustible gas can be separated and exhausted, so that combustible gas can be safely released after being combusted. By having such a mechanism, it is possible to prevent dangers such as fire.

  Although supply and exhaust of inert gas are not shown, flow control is performed by a control device and a pump.

  Next, a hydrogen concentration sensor 62 and an oxygen concentration sensor 63 are provided inside the partition wall, and the concentration of hydrogen, oxygen, etc. is monitored by the mixing of outside air inside the partition wall or the accumulation of gas inside the partition wall. A signal from this sensor is sent to the control device to control the increase in the concentration of specific gases such as hydrogen and oxygen by interlocking with the above inert gas supply device and exhaust device, and the discharge space and its surroundings are inactive. Allows filling with gas. Any sensor may be a commercially available sensor. Specifically, the oxygen gas concentration sensor may be a combination of Riken Keiki OS-B11 and oxygen gas indicator Riken Keiki OX-571A. For the measurement of the hydrogen gas concentration, as a hydrogen gas concentration sensor, a combustion gas detector (HW-6211 manufactured by Riken Keiki Co., Ltd.) and a combustion gas indicator (GP-571A manufactured by Riken Keiki Co., Ltd.) are used in combination, and 100% LEL is used. A calibration curve is prepared with a hydrogen gas concentration of 4% by mass and 33% LEL as a hydrogen gas concentration of 1.33%, and the hydrogen gas concentration is converted from the measured value.

  It is preferable to control the oxygen gas concentration to 5% by mass or less in order to prevent particle failure.

  The hydrogen gas concentration is preferably 0.2% by mass or less, and the oxygen gas concentration is preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less. In particular, it is most preferably 0% by mass at the start of plasma discharge.

  The hydrogen gas concentration sensor and oxygen gas concentration sensor can also be used as these gas concentration monitors. By interlocking with the lock of the partition opening mechanism, oxygen deficiency and dangerous gas suction can be prevented. It also helps to ensure the safety of workers.

  It is also preferable to provide a pressure gauge 64 inside the partition wall. It is generally known that the plasma state changes depending on the pressure. However, by providing a pressure gauge and linking the monitored pressure value to the control device, the flow rate of the inert gas supply device and the exhaust device is appropriately controlled. I can do it. This mechanism also serves as a safety device that prevents abnormal release of inert gas from the gaps in the partition walls. Therefore, this pressure gauge does not necessarily have to exist in the vicinity of the discharge part, and only needs to be inside the partition wall.

  Furthermore, it is also preferable to provide a thermometer 65 inside the partition wall and link the monitored temperature to the control device. By monitoring abnormal heat generation in the discharge space, it is possible to monitor whether the plasma processing temperature is set appropriately, and in the case of abnormal heat generation, control the supply and stop of thin film forming gas, auxiliary gas and inert gas Because it has a mechanism that can be used, it can prevent ignition and explosion, and it can also be a safety device. The position of this thermometer is preferably closer to the discharge processing section.

(High refractive index layer and medium refractive index)
In the present invention, in order to reduce the reflectance, it is preferable to provide a high refractive index layer between the transparent support or the transparent support provided with the hard coat layer and the low refractive index layer. In addition, it is more preferable to provide a middle refractive index layer between the transparent support and the high refractive index layer in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm. The haze of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.

  The refractive index formed by applying and drying a coating solution containing an organic titanium compound monomer, oligomer or hydrolyzate thereof represented by the following general formula (1) among the high refractive index layers used in the present invention. A layer having a rate of 1.55 to 2.5 is preferred.

General formula (1)
Ti (OR ¹ ) ₄
In the formula, R ¹ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O-i- _{C 3 H 7) 4, Ti} (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7) 4 2-10 mer, Ti (O-i-C 3 H 7) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These may be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ to 10-mer and Ti (On-C ₄ H ₉ ) ₄ to 10-mer are particularly preferable.

  Among the coating solutions for the high refractive index layer used in the present invention, it is preferable to add the organic titanium compound to a solution in which water and an organic solvent described later are sequentially added. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

Moreover, it is preferable that the quantity of water is the range of 0.25-3 mol with respect to 1 mol of organic titanium compounds. When the amount is less than 0.25 mol, hydrolysis and polymerization are not sufficiently progressed and the film strength is lowered. If it exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse TiO ₂ particles and white turbidity. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount. If the water content is 10% by mass or more with respect to the total amount of the coating solution, it is not preferable because the stability of the coating solution with time deteriorates and white turbidity occurs.

  The organic solvent used in the present invention is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable. The amount of these organic solvents used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.

  The monomer, oligomer or hydrolyzate of the organic titanium compound used in the present invention preferably occupies 50.0% by mass to 98.0% by mass in the solid content contained in the coating solution. The solid content ratio is more preferably 50% by mass to 90% by mass, and further preferably 55% by mass to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and middle refractive index layer used in the present invention contain metal oxide particles as fine particles, and further contain a binder polymer.

  When the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness and uniform film of the particles It is possible to obtain a strong coating film having both flexibility.

The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The weight average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent is most preferable.

  Two or more types of coupling agents may be used in combination, and other silane coupling agents may be used in addition to the silane coupling agent. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surfaces of the organic titanium compound and the metal oxide particles described above are easy to react and a stronger film is formed. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for this hydrolysis can also be used for the hydrolysis / polymerization of the organic titanium compound.

  In the present invention, the treatment may be performed by combining two or more kinds of surface treatments. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the middle refractive index layer.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume, more preferably 10 to 60% by volume, and still more preferably 20 to 55% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The high refractive index layer and medium refractive index layer used in the present invention preferably use a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as polyolefin), and crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide, and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Further, it is further preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono). Of these, sulfonic acid groups and phosphoric acid groups are preferred. Here, the anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated. The linking group that binds the anionic group and the polymer chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked polymer which is a preferable binder polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. In this case, the ratio of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. preferable. The repeating unit may have two or more anionic groups.

  The crosslinked polymer having an anionic group may contain other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure). Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. The benzene ring has a function of increasing the refractive index of the high refractive index layer. The amino group, the quaternary ammonium group, and the benzene ring can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.

  In the crosslinked polymer containing a repeating unit having an amino group or a quaternary ammonium group as a constituent unit, the amino group or quaternary ammonium group may be directly bonded to the polymer chain, or may be a side chain via a linking group. May be bonded to the polymer chain, but the latter is more preferred. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably carbon number. 1 to 6 alkyl groups. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer chain is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Is preferred. When the crosslinked polymer includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, more preferably 0.08 to 30% by mass, Most preferably, it is 0.1-28 mass%.

  The cross-linked polymer is prepared by blending a monomer for generating a cross-linked polymer to prepare a coating solution for forming a high refractive index layer and a medium refractive index layer, and is generated by a polymerization reaction simultaneously with or after coating of the coating solution. Is preferred. Each layer is formed with the production of the crosslinked polymer. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The monomer having an anionic group is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to the inorganic fine particles. The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid in the coating solution. The monomer having an amino group or a quaternary ammonium group is preferably used in an amount of 3 to 33% by mass based on the monomer having an anionic group. These monomers can be made to function effectively before application of the coating liquid by a method of forming a crosslinked polymer by a polymerization reaction simultaneously with or after application of the coating liquid.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable, and examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator mentioned later used in order to form the binder polymer of a hard-coat layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers. The coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application | coating, and may additionally process the thermosetting reaction of the formed polymer.

  For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. . Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

  In addition to the above-mentioned components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the low-reflective laminate or coating solution thereof includes a polymerization inhibitor, a leveling agent, a thickener, and coloring. An inhibitor, an ultraviolet absorber, a silane coupling agent, an antistatic agent or an adhesion promoter may be added.

(Transparent substrate film)
Next, the transparent substrate film that can be used in the present invention will be described.

  The transparent substrate film used in the present invention is easy to manufacture, has good adhesion to the actinic radiation curable resin layer, is optically isotropic, and is optically transparent. Etc. are mentioned as preferable requirements.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, a cellulose-ester type film, a polyester-type film, a polycarbonate-type film, a polyarylate-type film, a polysulfone (a polyether sulfone is also included) type film, a polyethylene terephthalate, polyethylene Polyester film such as naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, Polycarbonate film, cycloolefin polymer film (Arton (manufactured by JSR), Onex, Zeonea (above, ZEON Corporation), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate film, acrylic film, glass plate, etc. Can be mentioned. Among them, cellulose triacetate film, polycarbonate film, and polysulfone (including polyethersulfone) are preferable, and in the present invention, cellulose ester film (for example, Konica Minoltack product names KC8UX2MW, KC4UX2MW, KC8UY, KC4UY, KC5UN, KC12UR (Konica) Minolta Opto Co., Ltd.)) is preferably used from the viewpoints of production, cost, transparency, isotropy, adhesion and the like. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

The optical properties of the substrate film thickness direction retardation R _t is 0Nm～300nm, retardation R ₀ in the plane direction those 0nm~1000nm is preferably used.

  In the present invention, it is preferable to use a cellulose ester film as the substrate film. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used.

  In particular, when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, X and Y are active ray curable resin layers on a base film having a mixed fatty acid ester of cellulose in the following range And a low reflection laminate provided with an antireflection layer is preferably used.

2.3 ≦ X + Y ≦ 3.0
0.1 ≦ Y ≦ 1.2
In particular, 2.5 ≦ X + Y ≦ 2.85
It is preferable that 0.3 ≦ Y ≦ 1.2.

  When cellulose ester is used as the base film used in the present invention, the cellulose used as the raw material for the cellulose ester is not particularly limited. I can do it. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic solvent such as acetic acid or an organic solvent such as methylene chloride, and It can be obtained by reacting with a cellulose raw material using a protic catalyst.

When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804. In addition, the cellulose ester used in the present invention is obtained by mixing and reacting the amount of the acylating agent in accordance with the degree of substitution. In the cellulose ester, these acylating agents react with hydroxyl groups of cellulose molecules. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

  The cellulose ester used in the present invention is a mixed fatty acid ester of cellulose in which a propionate group or a butyrate group is bonded in addition to an acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, or cellulose acetate propionate butyrate. Is particularly preferably used. The butyryl group forming butyrate may be linear or branched.

  Cellulose acetate propionate containing a propionate group as a substituent has excellent water resistance and is useful as a film for liquid crystal image display devices.

  The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably 70,000 to 250,000 because the mechanical strength when molded is strong and an appropriate dope viscosity is preferable, and more preferably 80,000 to 150,000.

  These cellulose esters are pressurized by applying a cellulose ester solution (dope) generally called a solution casting film forming method onto, for example, an endless metal belt for infinite transport or a support for casting of a rotating metal drum. It is preferable to manufacture the dope from a die by casting (casting).

  The organic solvent used for the preparation of these dopes is preferably capable of dissolving the cellulose ester and having an appropriate boiling point, for example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetoacetate, acetone, tetrahydrofuran 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2 -Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3 , 3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone, etc. It is possible, organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, acetone, methyl acetoacetate, and the like are preferable organic solvents (i.e., good solvent), and as.

  Moreover, as shown in the following film forming process, it is used from the viewpoint of preventing foaming in the web when the solvent is dried from the web (dope film) formed on the casting support in the solvent evaporation process. The boiling point of the organic solvent is preferably 30 to 80 ° C. For example, the good solvent described above has a boiling point of methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56.32 ° C), acetone (boiling point 56.56 ° C). 3 ° C.), ethyl acetate (boiling point 76.82 ° C.) and the like.

  Among the good solvents described above, methylene chloride or methyl acetate, which is excellent in solubility, is preferably used.

  It is preferable to contain 0.1 mass%-40 mass% of C1-C4 alcohol other than the said organic solvent. It is particularly preferable that the alcohol is contained at 5 to 30% by mass. After casting the dope described above onto a casting support, the solvent starts to evaporate and the alcohol ratio increases and the web (dope film) gels, making the web strong and peeling from the casting support. It is also used as a gelling solvent for facilitating the dissolution, and when these ratios are small, it also has a role of promoting the dissolution of the cellulose ester of the non-chlorine organic solvent.

  Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like.

  Of these solvents, ethanol is preferred because it has good dope stability, relatively low boiling point, good drying properties, and no toxicity. It is preferable to use a solvent containing 5% by mass to 30% by mass of ethanol with respect to 70% by mass to 95% by mass of methylene chloride. Methyl acetate can be used in place of methylene chloride. At this time, the dope may be prepared by a cooling dissolution method.

  The cellulose ester film used in the present invention is preferably at least stretched in the width direction, and is 1.01 times to the width direction when the residual solvent amount is 3% by mass to 40% by mass in the solution casting process. The film is preferably stretched 1.5 times. More preferably, biaxial stretching is performed in the width direction and the longitudinal direction, and when the residual solvent is 3% by mass to 40% by mass, the width direction and the longitudinal direction are 1.01 times to 1.5 times, respectively. It is desirable to be stretched. By doing in this way, the light diffusable film excellent in planarity and light diffusibility can be obtained.

  The residual solvent amount is represented by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass of the web (cellulose ester film containing the solvent) at an arbitrary point in time, and N is the mass when the web of M is dried at 110 ° C. for 3 hours.

  Furthermore, by carrying out biaxial stretching and performing the knurling described above, it is possible to remarkably improve the deterioration of the winding shape during storage of the long optical film in the form of a roll.

  In the present invention, the biaxially stretched cellulose ester film is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

The cellulose ester film support used in the present invention preferably has a thickness of 10 μm to 100 μm, more preferably 40 μm to 80 μm, and moisture permeability conforms to JIS Z 0208 (25 ° C., 90% RH). The measured value is preferably 200 g / m ² · 24 hours or less, more preferably 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less. is there. In particular, it is preferable that the film thickness is 10 μm to 80 μm and the moisture permeability is within the above range.

  In the present invention, it is preferable to use a long film, and specifically, a film having a length of about 100 m to 5000 m is shown, which is usually provided in a roll shape. Moreover, it is preferable that the width | variety of a base film is 1.3-4 m.

  When a cellulose ester film is used for the low reflection laminate of the present invention, it is preferable to contain the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer or the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy For trimellitic acid plasticizers such as ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include trimethylolpropane tribenzoate, butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid and a glycol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used. As the glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The amount of these plasticizers used is preferably 1% by mass to 20% by mass and particularly preferably 3% by mass to 13% by mass with respect to the cellulose ester in terms of film performance, processability and the like.

  For the long film for the low reflection laminate of the present invention, an ultraviolet absorber is preferably used.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of the ultraviolet absorber preferably used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these.

  Specific examples of the benzotriazole-based ultraviolet absorbers include the following ultraviolet absorbers, but the present invention is not limited thereto.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- 4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
Moreover, although the following specific example is shown as a benzophenone series ultraviolet absorber, this invention is not limited to these.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber that are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal are preferable, and unnecessary coloring is less. A benzotriazole-based ultraviolet absorber is particularly preferably used.

  Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a long film, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorbers described in the general formula (1) or general formula (2) described in JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039 ( Alternatively, an ultraviolet absorbing polymer) is also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

  Moreover, in order to provide slipperiness to the cellulose-ester film used for this invention, the microparticles | fine-particles similar to what is described with the coating layer containing the below-mentioned actinic radiation curable resin can be used.

  The primary average particle diameter of the fine particles added to the cellulose ester film used in the present invention is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm. These fine particles preferably form secondary particles having a particle diameter of 0.1 to 5 μm and are contained in the cellulose ester film, and the preferable average particle diameter is 0.1 to 2 μm, more preferably 0.2 to 0.6 μm. Thereby, the unevenness | corrugation about 0.1-1.0 micrometer high can be formed in the film surface, and, thereby, appropriate slipperiness can be given to the film surface.

  The primary average particle diameter of the fine particles used in the present invention is measured by observing particles with a transmission electron microscope (magnification 500,000 to 2,000,000 times), observing 100 particles, and using the average value, the primary value is measured. The average particle size was taken.

  The apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter. A larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention. Are particularly preferably used.

SiO ₂ fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more are, for example, a mixture of vaporized silicon tetrachloride and hydrogen burned in air at 1000 to 1200 ° C. Can be obtained. For example, it is marketed by the brand name of Aerosil 200V and Aerosil R972V (above, Nippon Aerosil Co., Ltd. product), and can use them.

The apparent specific gravity described above is calculated by the following formula by measuring a weight of SiO ₂ fine particles in a graduated cylinder and measuring the weight at that time.

Apparent specific gravity (g / liter) = SiO ₂ mass (g) / SiO ₂ volume (liter)
Examples of the method for preparing the fine particle dispersion used in the present invention include the following three types.

<< Preparation Method A >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.

<< Preparation Method B >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a small amount of cellulose triacetate is added to the solvent and dissolved by stirring. The fine particle dispersion is added to this and stirred. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

<< Preparation Method C >>
Add a small amount of cellulose triacetate to the solvent and dissolve with stirring. Fine particles are added to this and dispersed by a disperser. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

Preparation method A is excellent in the dispersibility of SiO ₂ fine particles, and preparation method C is excellent in that the SiO ₂ fine particles are difficult to re-aggregate. Among them, the preparation method B described above is a dispersion of SiO ₂ particles, a preferred preparation method SiO ₂ particles have excellent reagglomeration hardly like, both.

《Distribution method》
The concentration of SiO ₂ when the SiO ₂ fine particles are mixed with a solvent and dispersed is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and most preferably 15 to 20% by mass. A higher dispersion concentration is preferable because liquid turbidity with respect to the added amount tends to be low, and haze and aggregates are improved.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

The addition amount of SiO ₂ fine particles to the cellulose ester relative to 100 parts by weight of cellulose ester, SiO ₂ fine particles is preferably 5.0 parts by 0.01 parts by weight, 0.05 parts by weight to 1.0 parts by weight is more Preferably, 0.1 mass part-0.5 mass part is the most preferable. The larger the added amount, the better the dynamic friction coefficient, and the smaller the added amount, the less aggregates.

As the disperser, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersion of SiO ₂ fine particles, a medialess disperser is preferred because of low haze. Examples of the media disperser include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure disperser is preferable. The high pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube. When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 9.807 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 19.613 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable.

  Examples of the high-pressure dispersing apparatus include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersing apparatuses such as homogenizer manufactured by Izumi Food Machinery. And UHN-01 manufactured by Sanwa Machinery Co., Ltd.

  In addition, casting a dope containing fine particles so as to be in direct contact with the casting support is preferable because a film having high slip properties and low haze can be obtained.

  Moreover, after peeling and drying after casting and winding up into a roll, the optical thin film layer according to the present invention is provided. Until processing or shipment, packaging is usually performed in order to protect the product from dirt, static electricity, and the like. The packaging material is not particularly limited as long as the above purpose can be achieved, but a material that does not hinder volatilization of the residual solvent from the film is preferable. Specific examples include polyethylene, polyester, polypropylene, nylon, polystyrene, paper, various non-woven fabrics, and the like. Those in which the fibers are mesh cloth are more preferably used.

  The cellulose ester film used in the present invention may have a multilayer structure by a co-casting method using a plurality of dopes.

  Co-casting is a sequential multilayer casting method in which two or three layers are configured through different dies, and a simultaneous multilayer casting method in which two or three slits are combined in a die having two or three slits. Any of the multilayer casting methods combining sequential multilayer casting and simultaneous multilayer casting may be used.

  In addition, the cellulose ester used in the present invention is preferably used as a support having a small amount of bright spot foreign matter when formed into a film. In the present invention, the bright spot foreign material is a structure in which two polarizing plates are arranged orthogonally (crossed Nicols), a cellulose ester film is arranged between them, and light from a light source is applied from one side to the other side. When the cellulose ester film is observed, the light from the light source appears to leak.

  At this time, the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used. The occurrence of bright spot foreign matter is considered to be one of the causes of unacetylated cellulose contained in the cellulose ester. As countermeasures, the use of cellulose ester with a small amount of unacetylated cellulose, It can be removed and reduced by filtering the dissolved dope solution. Further, the thinner the film thickness, the smaller the number of bright spot foreign matter per unit area, and the lower the content of cellulose ester contained in the film, the fewer bright spot foreign matter.

The bright spot foreign matter having a bright spot diameter of 0.01 mm or more is preferably 200 pieces / cm ² or less, more preferably 100 pieces / cm ² or less, 50 pieces / cm ² or less, 30 pieces / cm. ² or less, preferably 10 pieces / cm ² or less, but it is particularly preferred that a 0.

The number of bright spots of 0.005 mm to 0.01 mm is preferably 200 / cm ² or less, more preferably 100 / cm ² or less, 50 / cm ² or less, 30 / cm ² or less. The number is preferably 10 / cm ² or less, but particularly preferred is the case where the bright spot is zero. A thing with few also about a bright spot of 0.005 mm or less is preferable.

  When removing bright spot foreign matter by filtration, it is preferable to filter the composition in which a plasticizer is added and mixed, rather than filtering a cellulose ester dissolved alone, because the bright spot foreign matter removal efficiency is high. As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, and fluororesins such as tetrafluoroethylene resin are preferably used, but ceramics, metals and the like are also preferably used. The absolute filtration accuracy is preferably 50 μm or less, more preferably 30 μm or less, and 10 μm or less, and particularly preferably 5 μm or less.

  These can also be used in combination as appropriate. The filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.

  Next, a coating layer useful for the low reflection laminate of the present invention will be described.

  The antireflection layer or other thin film of the present invention may be directly formed on the film-like or sheet-like substrate, but may be formed thereon via another layer.

  In the present invention, examples of the coating layer applied to the surface of the substrate on which the antireflection layer is formed include a clear hard coat layer, an antiglare layer, and an adhesive layer. In particular, in the case of a low reflection laminate, the clear hard coat layer is preferably provided as “other layer” in order to increase the surface hardness of the low reflection laminate. Further, as described above, a conductive layer and an overcoat layer are provided on the side on which the antireflection layer or other thin film is formed and the side opposite to the substrate.

  Here, the clear hard coat layer used for the low reflection laminate will be described as a coating layer as an “other layer” useful in the present invention.

  The clear hard coat layer is preferably a layer containing an ultraviolet curable compound (resin) that is cured by ultraviolet rays, and a low reflection laminate excellent in scratch resistance can be obtained.

  The ultraviolet curable resin layer of the clear hard coat layer is preferably a resin layer formed by polymerizing a component containing an ethylenically unsaturated monomer. Here, the ultraviolet curable resin layer refers to a layer mainly composed of a resin which is cured through a crosslinking reaction or the like by irradiation with an active ray such as an electron beam in addition to ultraviolet rays. Typical examples of the ultraviolet curable resin include an ultraviolet curable resin and an electron beam curable resin. However, a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.

  In general, UV-curable acrylic urethane-based resins are obtained by further reacting 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate, methacrylate) with a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, see JP-A-59-151110).

  The UV curable polyester acrylate resin can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer (see, for example, JP-A-59-151112). .

  Specific examples of the ultraviolet curable epoxy acrylate resin include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoinitiator added thereto (for example, JP-A-1- No. 105738). As this photoreaction initiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.

  Specific examples of ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate. Etc. can be mentioned.

  These resins are usually used together with known photosensitizers. Moreover, the said photoinitiator can also be used as a photosensitizer. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. Further, when using an epoxy acrylate photoreactant, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying can be added in an amount of usually 1 to 10% by mass of the composition, and 2.5 to 6 It is preferable that it is mass%.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  For example, as an ultraviolet curable resin, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo Co., Ltd.) Or KOHEI HARD A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), or Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP- 10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, large Manufactured by Seika Kogyo Co., Ltd.), or KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB Corporation), or RC-5015, RC-5016, RC-5020, RC-5031, RC- 5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.) or Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), or RCC-15C (Grace Japan Co., Ltd.) (Manufactured by company), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available ones can be used.

  The ultraviolet curable resin layer can be applied by a known method.

  As a solvent for coating the ultraviolet curable resin layer, for example, it can be appropriately selected from hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or a mixture thereof can be used. . Preferably, propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether is prepared, and propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass. The solvent contained above is used.

As the light source for forming the cured film layer by photocuring reaction of the ultraviolet curable resin, any light source that generates ultraviolet rays can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. It can be used by using a sensitizer having an absorption maximum in the near ultraviolet region to the visible light region.

  The UV curable resin composition is applied and dried, and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 from the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.

  It is preferable to add inorganic or organic fine particles to the cured film layer thus obtained in order to prevent blocking and to improve scratch resistance. Examples of inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, and the like, and examples of organic fine particles include polymethacrylic acid. Methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder Polyamide-based resin powder, polyimide-based resin powder, polyfluorinated ethylene-based resin powder, and the like can be mentioned and added to the ultraviolet curable resin composition. The average particle diameter of these fine particle powders is preferably 0.005 μm to 1 μm, and particularly preferably 0.01 to 0.1 μm.

  The proportion of the ultraviolet curable resin composition and the fine particle powder is desirably blended so as to be 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

  The layer formed by curing the ultraviolet curable resin thus formed is a clear hard coat layer having a center line average roughness Ra of 1 to 50 nm as defined in JIS B 0601. An antiglare layer of about 1 μm may be used.

  As a method for applying the clear hard coat layer or the antiglare layer to the substrate, a known method such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater or an air doctor coater can be used. The liquid film thickness (also referred to as wet film thickness) at the time of application is about 1 to 100 μm, preferably 0.1 to 30 μm, and more preferably 0.5 to 15 μm.

(Polarizer)
The antifouling antireflection film according to the present invention is extremely excellent as a polarizing plate protective film. The polarizing plate can be produced by a general method. Similarly, in the present invention, a completely saponified polyvinyl alcohol aqueous solution is formed on both sides of a polarizing film prepared by immersing and stretching the protective film for a polarizing plate obtained by subjecting the antifouling antireflection film of the present invention to an alkali saponification treatment in an iodine solution. Use to stick together. After making the low reflection laminate of the present invention, one side of the cellulose ester film may be saponified.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the cellulose ester film having a multilayer structure according to the present invention is bonded to form a polarizing plate. It is preferably bonded with a water-based adhesive mainly composed of completely saponified polyvinyl alcohol or the like, but the low reflection laminate according to the present invention has low moisture permeability and excellent durability.

  The image display device using the polarizing plate of the present invention is excellent in durability and can display with high contrast over a long period of time.

(Image display device)
By incorporating the antifouling antireflection film of the present invention or a polarizing plate using the same into an image display device, various image display devices can be produced. Examples of the image display device include a liquid crystal image display device (reflective type, transflective type, transmissive type), an organic electroluminescence element, a plasma display, and the like. For example, in the forced deterioration treatment under high-temperature and high-humidity conditions, the antifouling antireflection film of the present invention or a polarizing plate using the same for an image display device is not easily soiled and has excellent visibility. No problems caused by the antifouling antireflection film were observed.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the embodiments of the present invention are not limited to these examples.

  The following hard coat layer was applied using a cellulose ester film KC8UX2MW (Konica Minolta Opto Co., Ltd., refractive index 1.49, acetyl group substitution degree 2.88) having a film thickness of 80 μm as a substrate.

<Hard coat layer>
A coating solution for hard coat layer having the following composition was prepared as a coating solution, applied onto the cellulose ester film using a microgravure coater so that the film thickness after curing was 3 μm, and the solvent was evaporated and dried. A hard coat film was prepared by curing with 0.2 J / cm ² ultraviolet irradiation using a mercury lamp.

<Coating liquid for hard coat layer>
Dipentaerythritol hexaacrylate 70 parts by weight Trimethylolpropane triacrylate 30 parts by weight Photoinitiator 4 parts by weight (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
Ethyl acetate 150 parts by mass Propylene glycol monomethyl ether 150 parts by mass Silicon compound 0.4 parts by mass (BYK-307 (by Big Chemie Japan))
Zirconium oxide fine particles (average particle diameter: 10 nm) were added so that the refractive index of the film formed on the composition was 1.60. Zirconium oxide was previously dispersed using a part of the solvent added to the coating solution.

《Coating back coat layer》
The following coating composition for a backcoat layer was prepared by filtering with a filter having a particle capture efficiency of 3 μm of 99% or more and 0.5 μm or less and a particle capture efficiency of 10% or less. This back coat layer coating composition was applied to the surface opposite to the surface on which the hard coat layer was applied, with an extrusion coater so that the wet film thickness was 15 μm, and dried at 90 ° C. for 30 seconds.

<Coating liquid for back coat layer>
Diacetyl cellulose (acetyl group substitution degree 2.4) 0.5 parts by mass Acetone 70 parts by mass Methanol 20 parts by mass Propylene glycol monomethyl ether 10 parts by mass Ultrafine silica AEROSIL 200V (manufactured by Nippon Aerosil Co., Ltd.)
0.002 parts by mass (The silica fine particles were added dispersed in methanol to be added.)
Further, an antireflection layer was formed on the hard coat layer of the hard coat film by the following method to obtain an antireflection film.

<< Preparation of antireflection layer (low refractive index layer) >>
(Low refractive index layer 1)
(Preparation of low refractive index layer 1 composition)
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 382 parts by mass Isopropyl alcohol 384 parts by mass To this mixed solvent, 226 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass was slowly added and mixed. After mixing and stirring
2 parts by mass of a 10% propylene glycol monomethyl ether solution of a linear dimethyl silicone-EO block copolymer (FZ-2207: manufactured by Nippon Unicar Co., Ltd.) was slowly added and mixed to obtain a composition having a low refractive index layer 1.

  Next, the low refractive index layer 1 composition was applied on the hard coat film by a microgravure method at a film thickness of 0.1 μm, dried at 120 ° C. for 1 minute, and irradiated with ultraviolet rays to give a low refractive index of 1.42. The refractive index layer 1 was formed.

(Low refractive index layer 2)
(Preparation of low refractive index layer 2 composition)
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 406 parts by mass Isopropyl alcohol 408 parts by mass To this mixed solvent, 140 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass was slowly added and mixed. After mixing and stirring
Silicon dioxide fine particle dispersion (solid content: 20% by mass) (P-4, produced by Catalyst Kasei Kogyo)
37 parts by mass A 10% propylene glycol monomethyl ether solution of a linear dimethyl silicone-EO block copolymer (FZ-2207: manufactured by Nihon Unicar) was slowly added and mixed to obtain a low refractive index layer 2 composition.

  Next, the low refractive index layer 2 composition is applied on the hard coat film by a microgravure method so as to have a film thickness of 0.1 μm, dried at 120 ° C. for 1 minute, and irradiated with ultraviolet rays to reduce the refractive index to 1.38. A refractive index layer 2 was formed.

(Low refractive index layer 3)
(Preparation of low refractive index layer 3 composition)
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 406 parts by mass Isopropyl alcohol 408 parts by mass To this mixed solvent, 140 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring
Silicon dioxide fine particle dispersion (solid content: 20% by mass) (P-4 manufactured by Catalytic Chemical Industry Co., Ltd.)
37 parts by mass was slowly added and mixed to obtain a low refractive index layer 3 composition.

  Next, the low refractive index layer 3 composition is applied on the hard coat film by a microgravure method at a film thickness of 0.1 μm, dried at 120 ° C. for 1 minute, and irradiated with ultraviolet rays to reduce the refractive index to 1.38. A refractive index layer 3 was formed.

(Low refractive index layer 4)
(Preparation of low refractive index layer 4 composition)
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 406 parts by mass Isopropyl alcohol 408 parts by mass To this mixed solvent, 140 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass was slowly added and mixed. After mixing and stirring
Silicon dioxide fine particle dispersion (solid content: 20% by mass) (P-4 manufactured by Catalytic Chemical Industry Co., Ltd.)
37 parts by mass was slowly added and mixed to obtain a low refractive index layer 4 composition.

  Next, the low refractive index layer 4 composition was applied to the hard coat film by a micro gravure method at a film thickness of 0.1 μm, dried at 120 ° C. for 1 minute, and irradiated with ultraviolet rays to reduce the refractive index of 1.38. A refractive index layer 4 was formed.

<< Hydrophilic treatment >>
The surface of the prepared antireflection film was subjected to the following hydrophilization treatment as shown in Table 1.

(Hydrophilic treatment 1: Plasma discharge treatment 1)
Hydrophilic treatment by plasma discharge was performed using the atmospheric pressure plasma discharge treatment apparatus of FIG.

<Discharge conditions>
First electrode side: 100 kHz 10 W / cm ² · h
Second electrode side: 13.56 MHz 5 W / cm ² · h
<Gas composition>
Nitrogen: 296 L / min
Oxygen: 4L / min
Gas temperature: 90 ° C
<processing time>
Treatment time: 3 seconds (Hydrophilic treatment 2: Plasma discharge treatment 2)
Hydrophilic treatment by plasma discharge was performed using the atmospheric pressure plasma discharge treatment apparatus of FIG.

<Discharge conditions>
Roll electrode side: 100 kHz 7 W / cm ² · h.
Fixed electrode (square tube electrode) side: 13.56 MHz 3.3 W / cm ² · h
<Discharge atmosphere>
The gas concentration inside the partition walls was measured by an oxygen gas concentration sensor, and after supplying an inert gas (nitrogen gas) from the inert gas supply port so that the oxygen gas became 5% by mass, discharge was started.

  Further, the gas concentration was monitored with the above sensor during the formation of the thin film, and the supply of inert gas was continued so that the concentration became constant.

  At the same time, the pressure inside the partition was monitored with a pressure gauge, and the inert gas was supplied and the gas inside the partition was exhausted from the exhaust port so that the pressure was constant.

  The temperature of the discharge part was monitored with a thermometer, and discharge was performed while confirming that no abnormal heat generation occurred.

<Gas composition>
Nitrogen: 297 L / min
Oxygen: 3L / min
Gas temperature: 90 ° C
<processing time>
Treatment time: 2 seconds (Hydrophilic treatment 3: Corona discharge treatment)
A corona discharge treatment of 25 W / m ³ · min was performed for 2 seconds.

(Hydrophilic treatment 4: UV ozone treatment)
2.5 W / cm ³ / min. With a low-pressure mercury lamp. It discharged on the conditions of and processed for 30 seconds.

<Anti-fouling layer coating>
The following composition was applied to the hydrophilic antireflection film processed surface so as to have a wet film thickness of 10 μm and dried at 80 ° C. for 5 minutes to prepare antifouling antireflection films 1 to 11 shown in Table 1. .

(Anti-fouling layer coating composition 1)
An antifouling layer coating composition 1 was prepared by diluting KP-801M manufactured by Shin-Etsu Chemical Co., Ltd. 30-fold with m-xylene hexaflouride.

(Anti-fouling layer coating composition 2)
98 parts by mass of isopropyl alcohol, 1.83 parts by mass of propylene glycol monomethyl ether and 0.03 parts by mass of nitric acid (1.38) were mixed uniformly. In this solution, 0.05 parts by mass of heptadecafluorodecyltriisopropoxysilane [CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OC ₃ H ₇ ) ₃ ] and 0.05 parts by mass of dimethyldimethoxysilane were added. Were mixed uniformly to prepare an antifouling layer coating composition 2.

  The antifouling antireflection film 9 was previously coated with the following medium refractive index layer and high refractive index layer between the hard coat layer and the low refractive index layer.

《Coating of medium refractive index layer》
On the hard coat layer, the following medium refractive index layer composition was coated with a die coater and dried for 1 minute at 80 ° C. and 0.1 m / second. After drying, using a high-pressure mercury lamp (80 W), it was cured by irradiation with ultraviolet rays of 130 mJ / cm ² to form an intermediate refractive index layer.

<Medium refractive index layer composition>
Solid content 15% titanium oxide fine particle dispersion (RTSPNB15WT% -G0, manufactured by CI Kasei Kogyo Co., Ltd.) 270 parts by mass Tetra (n) butoxytitanium 5 parts by mass Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 40 parts by mass Irgacure 184 (manufactured by Ciba-Geigy) 10 parts by weight Linear dimethyl silicone-EO block copolymer (FZ-2207 manufactured by Nippon Unicar) 1 part by weight Propylene glycol monomethyl ether 1470 parts by weight Isopropyl alcohol 2720 parts by weight Methyl ethyl ketone 490 parts by weight Middle refractive index layer Film thickness: 86nm
Refractive index of medium refractive index layer: 1.64
<Coating of high refractive index layer>
Next, the following high refractive index layer composition was applied on the middle refractive index layer with a die coater and dried for 1 minute at 80 ° C. and 0.1 m / second. After drying, ultraviolet rays were irradiated at 130 mJ / cm ² using a high pressure mercury lamp (80 W), and heat treatment was performed at 100 ° C. for 1 minute to form a high refractive index layer.

<High refractive index layer composition>
Solid content 15% titanium oxide fine particle dispersion (RTSPNB15WT% -G0, manufactured by CI Chemical Industry Co., Ltd.) 530 parts by mass Tetra (n) butoxytitanium 50 parts by mass γ-methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.)
10 parts by weight Linear dimethylsilicone-EO block copolymer (FZ-2207 manufactured by Nippon Unicar) 1 part by weight Propylene glycol monomethyl ether 1470 parts by weight Isopropyl alcohol 2490 parts by weight Methyl ethyl ketone 490 parts by weight High refractive index layer film thickness: 80 nm
Refractive index of the high refractive index layer: 1.85
<Production of polarizing plate>
A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.

  Subsequently, according to the following processes 1-5, the polarizing film, the said glare-proof antireflection film, and the cellulose ester film on the back side were bonded together, and the polarizing plate was produced. As the polarizing plate protective film on the back side, a cellulose ester film R (Ro = 43 nm, Rt = 132 nm) having a retardation produced by the following method was used as a polarizing plate.

  Step 1: Soaked in a 1 mol / L sodium hydroxide solution at 50 ° C. for 60 seconds, then washed with water and dried to obtain a saponified cellulose ester film bonded to the polarizer.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Lightly wipe off the excess adhesive adhering to the polarizing film in Step 2, place it on the cellulose ester film treated in Step 1, and then stack and arrange so that the antireflection layer is on the outside did.

Step 4: The antiglare antireflection film, the polarizing film, and the cellulose ester film sample laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm ² and a conveyance speed of about 2 m / min.

  Process 5: The sample which bonded together the polarizing film produced in the process 4, the cellulose-ester film, and the glare-proof antireflection film in the 80 degreeC dryer was dried for 2 minutes, and the polarizing plate was produced. Polarizing plates 1 to 11 were produced using the antiglare antireflection films 1 to 11, respectively.

<Preparation of cellulose ester film R>
(Preparation of dope solution E)
Cellulose ester (cellulose acetate propionate acetyl group substitution degree 1.9, propionyl group substitution degree 0.8) 100 parts by mass (Mn = 70000, Mw = 220,000, Mw / Mn = 3.14)
Triphenyl phosphate 8 parts by weight Ethylphthalyl ethyl glycolate 2 parts by weight Methylene chloride 300 parts by weight Ethanol 60 parts by weight The above is put into a sealed container, heated and stirred, and completely dissolved. Azumi Filter Paper Co., Ltd. Azumi filter paper No. No. 24 was filtered to prepare a dope solution E.
(Silicon dioxide dispersion E)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 10 parts by mass Ethanol 75 parts by mass The above was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 75 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution E.
(Preparation of inline additive solution E)
Methylene chloride 100 parts by weight Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 4 parts by weight Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 4 parts by weight Tinuvin 326 (manufactured by Ciba Specialty Chemicals) 2 parts by weight The solution was put into a container, heated, and completely dissolved and filtered while stirring.

  To this, 20 parts by mass of silicon dioxide dispersion diluent E was added with stirring, and further stirred for 30 minutes, and then cellulose ester (cellulose acetate propionate acetyl group substitution degree 1.9, propionyl group substitution degree 0.8). 5 parts by mass was added with stirring, and the mixture was further stirred for 60 minutes, and then filtered through a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to prepare an in-line additive solution E.

  Add 4 parts by mass of the filtered inline additive E to 100 parts by mass of the filtered dope solution E, mix thoroughly with an inline mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and then belt cast Using the apparatus, it was cast uniformly on a stainless steel band support at a temperature of 35 ° C. and a width of 1800 mm. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and then peeled off from the stainless steel band support. The web of the peeled cellulose ester film was evaporated at 55 ° C., slit to 1650 mm width, and then stretched 1.3 times at 130 ° C. in the TD direction (direction perpendicular to the film transport direction) with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 18%. Thereafter, drying is completed while transporting the drying zone at 120 ° C. and 110 ° C. with a number of rolls, slitting to a width of 1400 mm, a knurling process with a width of 15 mm and an average height of 10 μm is applied to both ends of the film, winding, cellulose ester Film R was obtained. The amount of residual solvent was 0.1%, the average film thickness was 80 μm, and the number of turns was 4000 m. This cellulose ester film had Ro = 43 nm and Rt = 132 nm, had a slow axis in the width direction, and the deviation angle of the slow axis with respect to the width direction was within ± 0.6 degrees.

<Production of liquid crystal display device>
A liquid crystal panel was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The polarizing plates on both sides of the 15-inch display VL-150SD manufactured by Fujitsu were previously peeled off, and the produced polarizing plates 1 to 11 were pasted on the glass surfaces of the liquid crystal cells, respectively.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the optical compensation film (retardation film) is on the liquid crystal cell side and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices 1 to 11 were respectively produced. The polarizing plate used was cut out from the end of a long anti-glare antireflection film whose performance tends to vary.

  The following evaluation was performed about the produced antifouling antireflection film and the liquid crystal display device.

<Evaluation>
(Pure water contact angle)
With respect to the antifouling antireflection films 1 to 11, the contact angle of pure water was set to a droplet diameter of 1. Measurement was performed at 5 mm.

(Magic wiping off)
After writing with black oily magic (Mckey extra fine manufactured by ZEBRA) on the sample surface of the antifouling antireflection film 1 to 11, it was wiped off using Bencot (Asahi Kasei Co., Ltd. BEMCOT M-3). This was repeated several times at the same location, and repeated antifouling properties were evaluated according to the following criteria.

5: Written letters lose their outlines and can be wiped lightly 4: Ink can be repelled and lightly wiped 3: Not repelled but wiped away 2: Not repelled and difficult to wipe 1: Not wiped (Abrasion resistance)
OA Tresy (manufactured by Toray Industries, Inc.) was placed on the sample surfaces of the antifouling antireflection films 1 to 11, and rubbed 100 times with a load of 1000 g. (The sample contact portion was a 20 mmφ circular flat surface so that the entire surface of the sample could be contacted without wrinkles.)
The surface of the sample after rubbing was written with black oily magic (Mckey extra fine manufactured by ZEBRA), and then wiped until clean using a non-woven fabric (CV6850P manufactured by Japan Vilene).

  The result of wiping was evaluated on the following scale.

○: The written character loses its outline and can be wiped lightly △: It does not bounce and is difficult to wipe ×: Cannot be wiped off (Visibility evaluation)
About the liquid crystal display devices 1-11, the fluorescent lamp reflection, the color irregularity of the reflected light, and the clearness of the image were comprehensively evaluated by visual observation, and were evaluated as 5 from the good one in five stages.

  The constitution of the antifouling antireflection film and the evaluation results of the antifouling antireflection film and the liquid crystal display are shown in Table 1 below.

  It turns out that the antifouling anti-reflective films 1-9 of this invention have the outstanding antifouling property from the result of a pure water contact angle, magic wiping off property, and abrasion resistance.

  Moreover, from the evaluation results of visibility, the liquid crystal display devices 1 to 9 of the present invention were excellent in the anti-reflection effect, and the color unevenness of the reflected light was extremely small, and the image clarity was excellent.

  On the other hand, the comparative liquid crystal display devices 10 and 11 were inferior in antifouling property, and the color unevenness of reflected light was recognized, and the overall visibility was inferior.

It is the schematic which showed an example of the atmospheric pressure plasma discharge processing apparatus of the system using nitrogen gas. It is a conceptual diagram of an atmospheric pressure plasma discharge treatment apparatus having a partition wall used in the present invention.

Claims (9)

An antifouling optical thin film comprising a surface of a film containing at least silicon oxide and a silane coupling agent and a coating layer containing a fluorine-containing silane compound provided thereon. The silicon oxide is a composite particle having a porous particle and a coating layer provided on the surface of the porous particle, or a hollow particle filled with a solvent, gas, or porous substance inside. Item 2. The antifouling optical thin film according to Item 1. 3. The antifouling optical thin film according to claim 1, wherein the fluorine-containing silane compound is silazane or alkoxysilane. The antifouling optical thin film according to any one of claims 1 to 3, wherein the film containing at least a silicon oxide and a silane coupling agent further contains a surfactant. 5. The antifouling optical thin film according to claim 4, wherein the surfactant is dimethylpolysiloxane or a modified product thereof. The antifouling optical thin film according to any one of claims 1 to 5, wherein the hydrophilization treatment is a treatment selected from ultraviolet irradiation treatment, O ₃ treatment, corona discharge treatment and atmospheric pressure plasma treatment. . An antifouling antireflection film, wherein the antifouling optical thin film according to any one of claims 1 to 6 is provided on a cellulose ester film. A polarizing plate comprising the antifouling antireflection film according to claim 7. A display device comprising the polarizing plate according to claim 8.

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