JP2012185413A - Coating composition and method of manufacturing antireflection member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition that can be used to manufacture an antireflection member having an excellent antireflection performance, transparency, and antistatic performance in a simple method and to provide a method of manufacturing an antireflection member using the same.SOLUTION: A coating composition contains at least inorganic particles A, inorganic particles B, inorganic particles C and a binder material. The inorganic particles A are inorganic particles which are surface-treated with a fluorine compound A. The inorganic particles B are inorganic particles having a refractive index of 1.65 or higher. The inorganic particles C are inorganic particles having a volume resistance value of 1×10(Ω cm) or lower.

Description

  The present invention relates to a coating composition suitable for manufacturing an antireflection member and a method for manufacturing an antireflection member using the coating composition.

  The antireflection member is generally used to prevent a decrease in contrast and reflection of an image due to reflection of external light in an image display device such as a cathode ray tube display (CRT), a plasma display panel (PDP), or a liquid crystal display (LCD). In addition, it is disposed on the outermost surface of the display so as to reduce the reflectivity by using the principle of optical interference. As such an antireflection member, in order to reduce the reflectance in a wider wavelength region, a multilayer coating of a high refractive index layer made of a material having a high refractive index and a low refractive index layer made of a material having a low refractive index is used. So-called multi-coating, which is laminated on the surface of a supporting substrate such as a film, is known (Patent Document 1).

  As a method of manufacturing this antireflection member with a small number of steps, a method of manufacturing an antireflection laminate in which two or more layers are formed from a single liquid film formed by one application has been proposed. Patent Document 2 states that “An antireflection laminate including a coating film formed by one coating using a coating composition in which low refractive index fine particles and medium to high refractive index fine particles are dispersed in a binder resin. By using silica fine particles treated with a fluorine-based compound as the low refractive index fine particles, the low refractive index fine particles are unevenly distributed in the upper part to the middle part of the coating film due to the difference in specific gravity, and in the middle part to the lower part. To high-refractive index fine particles are unevenly distributed. "Patent Document 3 discloses" one liquid containing two or more types of inorganic particles having different constituent elements. " A method for producing an antireflection film comprising a plurality of layers having different reflectivities only in a step of applying, drying and curing a coating composition once, wherein at least one kind of inorganic particles is made of a fluorine compound. Method for producing an antireflection film characterized in that the surface treatment is made. "Has been proposed. Further, Patent Document 4 states that “a substrate and a method for producing a laminate having a multilayer structure thereon, on the substrate or a layer formed on the substrate, the following component (A): A liquid curable resin composition containing ~ (F) is applied to form a coating film, and two or more layers are formed by evaporating the solvent from this one coating film. Manufacturing method "has been proposed.

  Moreover, when using such an anti-reflective member on the surface of various displays, such as PDP and LCD, it is necessary to bond with a some functional film. Within the pasting step, there are steps such as unwinding the film wound up in a roll shape and peeling off the protective film. In these steps, peeling charging occurs and adhesion of dust occurs in the manufacturing process. Cheap. In order to prevent these problems, the antireflection member is required to have antistatic performance.

  As a method for imparting antistatic properties to the antireflection member, Patent Document 5 proposes an antireflection film in which the high refractive index layer has conductivity.

Japanese Patent Application Laid-Open No. 7-5542 JP 2007-272132 A JP 2008-070414 A JP 2005-297539 A JP 2002-31702 A

  In order to produce an antireflection member having antistatic performance in addition to good antireflection performance and transparency by a simple method, the present inventors have produced two layers from one liquid film formed by a single application. Although the method of patent documents 2-4 was used as a manufacturing method which forms the above layer, and it tried to combine the method of patent documents 5 and 6 as a method of giving antistatic performance to this, antireflection performance, It was impossible to achieve both transparency and antistatic performance.

  Therefore, the problem to be solved by the present invention is a coating composition capable of producing an antireflection member having antireflection performance in addition to good antireflection performance and transparency by a simple method, and using the same It is providing the manufacturing method of an antireflection member.

In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows.
1) A coating composition containing inorganic particles A, inorganic particles B, inorganic particles C, and a binder raw material.

  Inorganic particles A: Inorganic particles surface-treated with the fluorine compound A.

  Inorganic particles B: Inorganic particles having a refractive index of 1.65 or more at 25 ° C.

Inorganic particles C: Inorganic particles having a volume resistivity at 25 ° C. of 1 × 10 ¹⁰ (Ω · cm) or less.

  2) The binder material according to 1), wherein the binder material has 3 or more reactive sites per molecule, and a hydroxyl value based on JIS K 0070-1992 is 20 or more and 150 or less. Paint composition.

  3) When the mass ratio of the inorganic particles C to the inorganic particles B (“mass of the inorganic particles C” / “mass of the inorganic particles B”) is C / B, the C / B is 0.8 or more and 1 The coating composition as described in 1) or 2) above, which is 5 or less.

  4) The coating composition according to any one of 1) to 3), wherein a difference in surface charge between the inorganic particles B and the inorganic particles C is 30 μeq / g or less.

  The coating composition of the present invention can produce an antireflection member having antireflection performance in addition to good antireflection performance and transparency by a simple method. Moreover, productivity can also be improved by using the manufacturing method of this invention.

It is an example of the antireflection member obtained by the coating composition of this invention. It is another example of the antireflection member obtained by the coating composition of this invention.

  In the method for producing an antireflection member composed of two or more layers by applying the coating composition once on a supporting substrate, the present inventors have disclosed the conventional techniques of Patent Documents 2 to 4 and Patent Document 5 There are two reasons why anti-reflection performance, transparency and anti-static performance cannot be achieved with the combination of the prior arts.

  First, the first reason is the refractive index of the high refractive index layer. In the method of manufacturing an antireflection laminate in which two or more layers are formed from one liquid film formed by a single coating, the formation of the two layers is spontaneously generated during the drying process. The shape becomes an uneven shape due to the capillary force of the solvent component during drying. In addition, since the layer structure is spontaneously formed at the initial stage of the drying process and the coating film surface is coated, a concentration gradient of the solvent component is created in the coating film, so that the gradient structure of particles in the obtained coating film That is, a structure in which a binder component having a relatively low refractive index is increased on the interface side of the two layers and particles are increased on the substrate side is formed.

  As a result, this structure (the uneven structure of the interface and the inclined structure in the layer) is effective for suppressing interference unevenness, scratch resistance and abrasion resistance of the coating film, but for the manifestation of the antireflection function. In order to obtain the same antireflection performance, two layers are formed when a spontaneous layer structure is formed as compared with the case where two layers are formed by two coatings. It is necessary to make a large refractive index difference between the particles to be processed.

  As a result, if the refractive index of the particles on the low refractive index layer side is about 1.30, the particles on the high refractive index layer side have a high refractive index of 1.65 or more in order to exhibit a sufficient antireflection function. Although a refractive index material is required, these inorganic particles are either an insulator or have conductivity, but are insufficient to obtain antistatic performance.

On the other hand, the inorganic particles capable of obtaining sufficient antistatic performance described in Patent Documents 5 and 6 are substituted solid solution particles having a uniform phase as a whole, or a core in which a substituted solid solution portion is formed in a part of one particle. It is a bonded particle in which particles of different shell types and types are bonded. Such particles may replace the metal or metalloid element (for example, tetravalent tin in ATO) with an element having a different oxidation number (for example, pentavalent antimony in ATO), which constitutes the insulating inorganic particles as a host. (Referred to as doping), oxygen vacancies (for example, SnO _2-x ) are introduced into the crystal structure of the inorganic particles serving as the host (this is referred to as defect introduction), and a valence band is formed to conduct electricity. Expresses sex. Therefore, since the refractive index basically depends on the refractive index of the particles serving as the host, the maximum is as low as about 1.60. Therefore, when these materials are used for the high refractive index material, the antireflection function cannot be obtained.

  The second reason is the aggregation of particles during the drying process. In the production method of an antireflection laminate in which two or more layers are formed from one liquid film formed by a single coating, the formation of two layers occurs spontaneously during the drying process. At the time of formation, the distance between the particles is close and aggregation between the particles tends to occur simultaneously. As a result, depending on the combination of the two types of particles, the formation of the layer structure may be significantly inhibited, and the layer structure may not be formed.

  Furthermore, in contrast to the case where the film thicknesses of the first layer and the second layer are substantially equal as described in the case of Patent Documents 2 to 4, a single coating provides not only an antireflection function but also a hard coat property. In this case, since the thickness of the first layer is significantly thinner than the thickness of the second layer, the amount of particles contained in the first layer is smaller than the amount of the binder component. In this case, since the occurrence of aggregation is promoted by the depletion effect during the drying process, the formation of the spontaneous layer structure requires more limited conditions.

  Under such conditions, the materials having high refractive index and antistatic performance described in Patent Documents 5 and 6 introduce doping into host particles and introducing defects as described above. In comparison, the charge on the particle surface (referred to as the surface charge amount) is increased, and aggregation during the drying process is likely to occur. When only such particles are used for the high refractive index particles, the formation of a spontaneous total structure during the drying process is suppressed, and the antireflection function and the antistatic function cannot be obtained.

  In order to manufacture an antireflection member having an antistatic performance in addition to a good antireflection performance and transparency by a new simple method, the present inventors have prepared a single-layer liquid film formed by a single application. It has been found that in the production method for continuously and stably producing an antireflection member for forming two or more layers, the problem can be solved by using the following coating composition.

  The coating composition of the present invention makes it possible to develop an antireflection function while having an antistatic function by paying attention to specific inorganic particles and binder raw materials.

Specifically, the coating composition of the present invention includes inorganic particles A, inorganic particles B, inorganic particles C, and a binder raw material, and the inorganic particles A are inorganic particles and inorganic particles surface-treated with a fluorine compound A. B is an inorganic particle having a refractive index of 1.65 or more, and the inorganic particle C is an inorganic particle having a volume resistivity of 1 × 10 ¹⁰ (Ω · cm) or less.

  As long as the inorganic particles A, B, and C satisfy the above characteristics, the “particle types” described later may be the same or different, but the inorganic particles A and the inorganic particles B and C are different types. Is more preferable, and it is more preferable that all of the inorganic particles A, B, and C are of different types.

  Here, the fluorine compound A used for the surface treatment of the inorganic particles A is a compound represented by the following general formula (2). When the inorganic particles A are not surface-treated with the fluorine compound A, the spontaneous total structure may not be sufficiently formed.

  As described above, the refractive index of the inorganic particles B needs to be 1.65 or more, preferably 1.68 or more, and more preferably 1.70 or more. The refractive index described here refers to a value at a wavelength of 589.3 nm (sodium D line), which is a general way of expressing the refractive index.

  Here, when the refractive index of the inorganic particles B is less than 1.65, the antireflection performance is insufficient for the reasons described above. Although the refractive index of the inorganic particle B is high, there is no problem, but in reality, the upper limit is about 3.0.

  Although there is no problem with the high refractive index of the inorganic particles C, the upper limit is about 1.65 in the raw material that can be actually obtained in the conductive material described later.

  The refractive index of the inorganic particles described here refers to the refractive index in the particle state actually used in the coating composition, not the refractive index measured for a single crystal of each inorganic particle, and is the same as the type of particle. Even including crystallinity and shape. Therefore, the particles suggested in this specification may differ from literature values for the same material and type and the main crystalline polymorph, and even for the same type of particles, surface treatment, particle size, crystallization Varies depending on the degree. A method for measuring the refractive index of the particles will be described later.

Although the volume resistivity at 25 ° C. of the inorganic particles C is required to be ^{1 × 10 10 (Ω · cm} ) or less as described above, is preferably ^{1 × 10 9 (Ω · cm} ) or less, 1 × 10 ⁸ (Ω · cm) or less is more preferable.

When the volume resistivity at 25 ° C. of the inorganic particles C is higher than 1 × 10 ¹⁰ (Ω · cm), the antistatic performance becomes insufficient. In addition, there is no problem if the volume resistivity of the inorganic particles C is low, but if it is an oxide particle, the limit is practically about 1 × 10 ² (Ω · cm).

Although the volume resistivity of the inorganic particles B is low, there is no problem, but the material having the above-described refractive index has a limit of about 1 × 10 ¹⁰ (Ω · cm) in the raw material that can be actually obtained.

  The volume resistivity of the inorganic particles B and the inorganic particles C is obtained by measuring the volume resistivity of the inorganic particles used in the coating composition, and the detailed measurement method will be described later.

  In the coating composition of this invention, there exists a preferable range in the structure and physical property of a binder raw material. Specifically, the binder raw material has 3 or more reactive sites per molecule, and the hydroxyl value based on JIS K 0070-1992 is preferably 25 or more and 150 or less, more preferably 20 or more and 130 or less. More preferably, it is 30 or more and 130 or less.

  The binder raw material described here is a compound contained in the coating composition, and is a raw material of the binder component in the antireflection layer of the antireflection member obtained by using the coating composition. That is, the binder material that is contained in the antireflection layer when the binder raw material contained in the coating composition of the present invention is cured by heat or ionizing radiation is referred to as a binder component. Some binder materials may be present in the antireflection layer in the same state as in the coating composition (there may be unreacted and exist in the antireflection layer). The thing in a prevention layer is called a binder component.

  Here, the reactive site is the same as the description regarding the fluorine compound A in the section of the inorganic particle A described later. The number of reactive sites is determined from the formula of the binder component.

  When the number of reactive sites per molecule of the binder raw material is less than 2, the wear resistance and scratch resistance are lowered. Although there is no problem with the large number of reactive sites, the upper limit is generally about 20.

  The hydroxyl value is a quantification of the amount of hydroxyl group per molecule of the binder material. Specifically, when 1 g of a sample is acetylated, potassium hydroxide required to neutralize acetic acid bonded to the hydroxyl group. The higher the numerical value, the greater the number of hydroxyl groups in the molecule.

  When the hydroxyl value is less than 20, the dispersion stability of the inorganic particles B and C in the coating composition is reduced, and the inorganic particles B and C aggregate in the drying process to form a spontaneous layer structure. The anti-reflection function, the transmittance decreases. On the other hand, when the hydroxyl value is larger than 150, the dispersion stability of the inorganic particles A in the coating composition is lowered, the inorganic particles A are likely to aggregate in the drying process, and the antireflection function and transmittance are lowered.

  Furthermore, in the coating composition of this invention, there exists a preferable range also in the mass ratio of the said inorganic particle B and the inorganic particle C. FIG. Specifically, when the mass ratio of the inorganic particles C to the inorganic particles B (“the mass of the inorganic particles C” / “the mass of the inorganic particles B”) is C / B, the C / B is 0.00. It is preferably 8 or more and 1.5 or less. The method for evaluating the mass of the inorganic particles described here will be described later.

  When the mass ratio (C / B) of the inorganic particles C to the inorganic particles B is less than 0.8, the antistatic function is lowered, and when it is larger than 1.5, the antireflection function is lowered.

  Further, there is a preferable range in the surface state of the inorganic particles B and the inorganic particles C. Specifically, the difference in the surface charge amount between the inorganic particles B and the inorganic particles C is preferably 30 μeq / g or less, and 25 μeq / g. More preferably, it is more preferably 20 μeq / g or less.

  Here, the surface charge amount of particles refers to the surface charge amount per unit particle gram (μeq / g), and can be measured by a method such as colloid streaming potential method or electrophoresis method.

  The difference in the amount of surface charge refers to the absolute value of the difference between the surface charge of the inorganic particles B and the surface charge of the inorganic particles C, and the surface charge of either the inorganic particles B or the inorganic particles C may be large. If the difference in surface charge between the inorganic particles B and the inorganic particles C is larger than 20 μeq / g, the inorganic particles B and the inorganic particles C tend to aggregate during the drying process, and the antireflection function and transparency are deteriorated. If the difference in the amount of surface charge is small, it may be 0 without any problem. The surface charge amount can be adjusted, for example, by changing the kind of the organosilicon compound, the surface treatment amount, or the like.

Hereinafter, embodiments of the present invention will be described in detail.
[Coating composition]
It is important that the coating composition of the present invention contains at least inorganic particles A, inorganic particles B, inorganic particles C, and a binder raw material. Thereby, the antireflection member which has antireflection performance and antistatic performance can be obtained by applying the coating composition of the present invention to the support substrate only once.

  Here, “inorganic particles” include those obtained by treating the surface of inorganic particles. This surface treatment means introducing a compound onto the surface of inorganic particles by chemical bonds (including covalent bonds, hydrogen bonds, ionic bonds, van der Waals bonds, hydrophobic bonds, etc.) and adsorption (including physical adsorption and chemical adsorption). Point to.

  The coating composition of the present invention preferably contains two or more kinds of particles. At least one of the two or more types of particles preferably has a relatively low refractive index relative to the other particle, and the particles having a low refractive index are preferably inorganic particles A.

Here, the type of particle is determined by the type of element constituting the particle, and when performing some kind of surface treatment, it is determined by the type of element constituting the particle before the surface treatment. For example, titanium oxide (TiO ₂ ) is different from nitrogen-doped titanium oxide (TiO _2−x N _x ) in which part of oxygen in titanium oxide is replaced by nitrogen as an anion because the elements constituting the particles are different. It is a kind of particle. In addition, if particles (ZnO) consisting only of the same element, for example, Zn or O, even if there are a plurality of particles having different particle diameters or the composition ratio of Zn and O is different, these are The same type of particles. Even if there are a plurality of Zn particles having different oxidation numbers, as long as the elements constituting the particles are the same (in this example, all elements other than Zn are the same), these are the same kind of particles. .

The coating composition of the present invention may contain components other than the inorganic particles A, the inorganic particles B, the inorganic particles C, and the binder raw material. Examples of such components include a curing agent, a surfactant, and a dispersant. In addition, a hydrophobic compound B having a reactive site may be included.
[Inorganic particles A]
The inorganic particles A are preferably inorganic particles treated with the fluorine compound A. This inorganic particle A is suitable as a constituent component of the first layer. By having the inorganic particles A in the coating composition, when the coating composition of the present invention is applied on a supporting substrate, the inorganic particles A move to the air side and have a layer having a low refractive index (hereinafter referred to as “refractive index”). The outermost layer is referred to as a first layer, and a layer having a relatively low refractive index is referred to as a low refractive index layer).

The inorganic particles that are the constituent material of the inorganic particles A are preferably inorganic particles containing at least one element selected from the group consisting of Si, Na, K, Ca, and Mg. More preferably, inorganic particles containing at least one compound selected from the group consisting of silica particles (SiO ₂ ), alkali metal fluorides (NaF, KF, etc.) and alkaline earth metal fluorides (CaF ₂ , MgF _2, etc.) It is. Silica particles are particularly preferable from the viewpoints of durability and refractive index.

Silica particles refer to particles composed of any composition of a polymer compound (condensed) of a silicon compound or an organosilicon compound, and as a general example, is a generic term for particles derived from a silicon compound such as SiO ₂ .

  When hollow silica particles or porous silica particles are used as the inorganic particles that are the constituent material of the inorganic particles A, the hollow silica particles and the porous silica particles are easily contained in the low refractive index layer of the antireflection layer. This is preferable because the density of the low refractive index layer, which is a part, is lowered and the effect of lowering the refractive index is obtained.

  The number average particle diameter of the inorganic particles A before being treated with the fluorine compound A is preferably 1 nm or more and 200 nm or less. The number average particle size is more preferably from 20 nm to 200 nm, particularly preferably from 40 nm to 150 nm. When the number average particle diameter of the inorganic particles is smaller than 1 nm, the void density in the first layer is lowered, and the refractive index may be increased or the transparency may be lowered. When the number average particle diameter of the inorganic particles is larger than 200 nm, the thickness of the low refractive index layer is increased, and the antireflection performance may be lowered.

  As described above, the inorganic particles A mean inorganic particles treated with the fluorine compound A. Here, the fluorine compound A is a compound represented by the following general formula (2).

  The fluoroalkyl group in the general formula (2) is a substituent in which part or all of the hydrogen of the alkyl group is replaced with fluorine, and is a substituent mainly composed of a fluorine atom and a carbon atom.

  The reactive site refers to a site that reacts with other components by external energy such as heat or light. Examples of such reactive sites include alkoxysilyl groups and silanol groups in which alkoxysilyl groups are hydrolyzed from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. From the viewpoints of reactivity and handling properties, an alkoxysilyl group, a silyl ether group, a silanol group, an epoxy group, and an acryloyl (methacryloyl) group are preferable.

  The treatment with the fluorine compound A for the inorganic particles to obtain the inorganic particles A may be performed in one stage or may be performed in multiple stages. Further, the fluorine compound A may be used in a plurality of stages, or the fluorine compound A may be used only in one stage.

  Moreover, the fluorine compound A preferably used in the treatment for the inorganic particles may be a single compound or a plurality of different compounds. The treatment with the fluorine compound A refers to a step of chemically modifying the inorganic particles and introducing the fluorine compound A into the inorganic particles.

  As a method of directly introducing fluorine compound A into inorganic particles, one kind of fluoroalkoxysilane compound having both a fluorine segment and a silyl ether group (including a silanol group obtained by hydrolyzing a silyl ether group) in one molecule. There is a method of stirring the above together with the initiator. However, when the fluorine compound A is introduced directly into the inorganic particles, it may be difficult to control the reactivity, or coating spots may easily occur during coating after coating.

  Further, as another method for obtaining the inorganic particles A, there is a method in which the inorganic particles are treated with a crosslinking component and joined with the fluorine compound A (treated with the fluorine compound A). As the fluorine compound A in this case, fluoroalkyl alcohol, fluoroalkyl epoxide, fluoroalkyl halide, fluoroalkyl acrylate, fluoroalkyl methacrylate, fluoroalkyl carboxylate (including acid anhydrides and esters), and the like can be used. .

  The crosslinking component refers to a compound having no fluorine in the molecule, but having at least one site capable of reacting with the fluorine compound A and one site capable of reacting with the inorganic particles. The site capable of reacting with the inorganic particles is preferably silyl ether or a hydrolyzate of silyl ether from the viewpoint of reactivity. These compounds are generally called silane coupling agents. For example, glycidoxyalkoxysilanes, aminoalkoxysilanes, acryloylsilanes, methacryloylsilanes, vinylsilanes, mercaptosilanes, etc. may be used. it can.

A more preferable form of the inorganic particles A is particles obtained by treating inorganic particles with a compound represented by the following general formula (1) and further treating with a fluorine compound A represented by the following general formula (2).
B—R ⁴ —SiR ⁵ _n (OR ⁶ ) _3-n ... General formula (1)
^{DR 7} -R ^f2 General formula (2)
(B and D in the above general formula represent reactive sites. R ⁴ and R ⁷ represent an alkylene group having 1 to 6 carbon atoms and an ester structure derived therefrom. R ⁵ and R ⁶ represent Hydrogen or an alkyl group having 1 to 4 carbon atoms, R ^f2 represents a fluoroalkyl group, n represents an integer of 0 to 2, and each may have a side chain in the structure).

  As the reactive site of the fluorine compound A, a reactive double bond group is more preferable. This reactive double bond group is a functional group that chemically reacts with radicals generated by receiving energy such as light or heat, and specific examples include vinyl, allyl, acryloyl, and methacryloyl groups. It is done.

  Specific examples of the general formula (1) include acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyheptyltri Methoxysilane, methacryloxyethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxy Examples include silane and compounds in which the methoxy group in these compounds is substituted with other alkoxyl groups and hydroxyl groups. That.

  Specific examples of the general formula (2) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluoro Butyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- Perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadeca Fluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2 -Hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluoro Decylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5- Methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoro Heptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafur Examples include orobutyl methacrylate.

By treating the inorganic particles with the compound represented by the general formula (1) having no fluoroalkyl group R ^f2 in the molecule, the inorganic particles can be modified under simple reaction conditions. In addition, functional groups whose reactivity can be easily controlled can be introduced into the inorganic particles. As a result, the fluorine compound A of the general formula (2) having the reactive site and the fluoroalkyl group R ^f2 can be reacted with the inorganic particles via the compound represented by the general formula (1).
[Inorganic particles B, inorganic particles C]
The inorganic particles B and C will be described. The inorganic particles B and the inorganic particles C are formed by applying the coating composition of the present invention on a supporting base material, thereby forming a layer having a high refractive index (hereinafter referred to as 2 from the outermost surface side) formed at the second position from the outermost surface side. The layer at the second position is referred to as a second layer, and a layer having a relatively high refractive index is referred to as a high refractive index layer).

  The inorganic particles B and C are not particularly limited as long as they satisfy the above-mentioned properties (volume resistivity of inorganic particles, refractive index of particles), but may be mainly composed of metal, metalloid oxides, nitrides and borides. Preferably, it is added (doping) by forming a solid solution in a single particle with a metal, metalloid or typical element different from this component, oxide, nitride, boride, or core-shell particle, bonding particle, etc. Further, structural defects such as oxygen vacancies may be introduced into the crystal structure.

As described above, the inorganic particles C are required to have a volume resistivity of 1 × 10 ¹⁰ or less, but the conductive mechanism may be either ionic conductivity or electronic conductivity.

  More preferably, the inorganic particles B and C are oxide particles mainly containing at least one metal or semimetal selected from the group consisting of Zr, Ti, Al, Zn, Sb, Sn, and Ce.

Specifically, zirconium oxide (ZrO ₂ ), titanium oxide (TiO _2, Ti ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide ( At least one metal oxide or metalloid oxide selected from the group consisting of SnO ₂ ), cerium oxide (CeO ₂ ), and antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ ), or antimony oxide (Sb _2). O ₃ , Sb ₂ O ₅ ), indium oxide (In ₂ O ₃ ), phosphorus oxide (P ₂ O ₅ ), gallium oxide (Ga ₂ O ₅ ), cobalt oxide (CoO, Co ₃ O _4, Co ₂ O ₃₎ Or a solid solution with at least one metal oxide, metalloid oxide, or typical element oxide selected from the group consisting of:

Particularly preferably, the inorganic particles B are preferably zirconium oxide (ZrO ₂ ) or titanium oxide (TiO ₂ ) in terms of refractive index, and the inorganic particles C are antimony-added tin oxide (solid oxide of diantimony pentoxide 5 and tin oxide ( ATO), antimony pentoxide 5 and phosphorus-added tin oxide (PTO), which is a solid solution of phosphorus pentoxide and tin oxide, are preferred.

  The number average particle diameter of the inorganic particles B and C is preferably 1 nm or more and 150 nm or less. The number average particle diameter is more preferably 2 nm to 100 nm, particularly preferably 2 nm to 25 nm, and most preferably 2 nm to 20 nm. When the number average particle diameter of the inorganic particles B is smaller than 1 nm, the transparency may be decreased due to a decrease in the void density in the layer mainly containing other inorganic particles. If the number average particle diameter of the other inorganic particles is larger than 150 nm, the thickness of the high refractive index layer becomes too large, and it becomes difficult to obtain good antireflection performance.

  As described above, the difference in surface charge between the inorganic particles B and the inorganic particles C has a preferable range as described above. A method for adjusting the difference in surface charge includes surface treatment of particles, which is chemically modified in the same manner as the treatment with the fluorine compound A applied to the inorganic particles A, and the inorganic particles B or inorganic particles. It refers to a process for introducing a compound into C, and may be performed in one step or may be performed in multiple steps. The compound used for this treatment is preferably compound B.

  This compound B is a compound shown by the said general formula (I).

Compound B is a compound having (in the general formula _{^{(I), Si- (OR 2}} ) 4-n1 moiety) chemical bonding or adsorption site capable to the particle surface and the alkyl group moiety _{^(R 1 n1).}

  In this case, examples of the site that can be chemically bonded or adsorbed on the particle surface include an alkoxysilyl group and a silanol group obtained by hydrolyzing an alkoxysilyl group. These compounds are generally called silylating agents. One method of treating the inorganic particles B or inorganic particles C with the compound B is to stir, heat, and remove the compound B and the inorganic particles B or the particle dispersion of the inorganic particles B together with the catalyst, water, solvent and the like. There is a method in which alcohol is used and condensed with silanol groups on the particle surface. The particle dispersion here is as described above.

Specific examples of the compound B include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n- Examples include propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, and compounds containing a compound in which the methoxy group in these compounds is substituted with other alkoxyl groups and hydroxyl groups. .
[Binder raw material]
It is important that the coating composition of the present invention contains a binder raw material. The definition of the binder raw material is as described above.

  The binder raw material in the coating composition of the present invention is not particularly limited in structure, but as described above, the binder raw material has three or more reactive sites per molecule and is a hydroxyl group based on JIS K 0070-1992. The value is preferably 5 or more and 20 or less.

  Further, in the case of curing by UV, it is preferable that the oxygen concentration is as low as possible because oxygen inhibition can be prevented, and it is more preferable to cure in an anaerobic atmosphere. By reducing the oxygen concentration, the cured state of the outermost surface is improved and chemical resistance may be improved.

  Specifically, the binder raw material in such a coating composition is preferably a polyfunctional acrylate monomer, oligomer, alkoxysilane, alkoxysilane hydrolyzate, alkoxysilane oligomer or the like, and more preferably a polyfunctional acrylate monomer or oligomer.

  Examples of the polyfunctional acrylate monomer include polyfunctional acrylates having three or more (meth) acryloyloxy groups in one molecule and modified polymers thereof. Specific examples include pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) Acrylate or the like can be used.

These monomers can be used alone or in combination of two or more. Also, commercially available polyfunctional acrylic compositions include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol” series, etc.), Shin-Nakamura Chemical Co., Ltd. (Product name “NK Ester” series, etc.), DIC Corporation; (Product name “UNIDIC”, etc.), Toagosei Chemical Industry Co., Ltd. (“Aronix” series, etc.), Nippon Oil & Fats Corporation; (“Blemmer” series) Etc.), Nippon Kayaku Co., Ltd .; (trade name “KAYARAD” series, etc.), Kyoeisha Chemical Co., Ltd. (trade name “light ester” series, etc.), etc., and these products can be used. .
[solvent]
The coating composition of the present invention preferably contains a solvent. The “solvent” in the present invention refers to a substance that is a liquid at normal temperature and normal pressure that can be evaporated almost entirely in the drying step after coating. The coating composition of the present invention contains two or more kinds of solvents. The number of types of solvent is preferably 2 or more and 20 or less, more preferably 2 or more and 10 or less, and still more preferably 2 or more and 6 or less.

Here, the kind of solvent is determined by the molecular structure constituting the solvent. That is, the same elemental composition and the same type and number of functional groups have different bond relationships (structural isomers), which are not structural isomers, but what conformations are in three-dimensional space Those that do not overlap exactly even if they are removed (stereoisomers) are treated as different types of solvents. For example, 2-propanol and 1-propanol are handled as different solvents.
[Other additives]
The coating composition of the present invention preferably further contains a photopolymerization initiator, a curing agent and a catalyst.

  The photopolymerization initiator and the catalyst are used for promoting the reaction between the inorganic particles A, between the inorganic particles, between the binder raw materials, and between the inorganic particles A and the binder raw materials. As the initiator, those capable of initiating or accelerating polymerization and / or condensation and / or crosslinking reaction by anion, cation, radical reaction or the like of the coating composition are preferable.

  Various initiators, curing agents, and catalysts can be used. A plurality of initiators may be used at the same time or may be used alone. Furthermore, you may use together an acidic catalyst, a thermal-polymerization initiator, and a photoinitiator. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, and amine compounds, but are not limited thereto, but from the viewpoint of curability. Alkylphenone compounds are preferred, and specific examples include 2.2-dimethoxy-1.2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) Nyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenylketone, 2-methyl-1-phenylpropan-1-one, 1- [4- (2- Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and the like.

  The content ratio of the initiator and the curing agent is preferably 0.001 to 30 parts by mass, more preferably 0.05 parts by mass with respect to 100 parts by mass in total of the binder raw materials in the coating composition. 20 parts by mass, more preferably 0.1 to 10 parts by mass.

  The coating composition of the present invention may further contain additives such as surfactants, thickeners and leveling agents as necessary.

  Further, as a more preferable production method using the coating composition of the present invention, when a high refractive index hard coat layer is directly formed on a transparent substrate without providing a hard coat layer on a supporting substrate, the present coating composition In addition to the above additives, the product preferably contains a fluorine compound B having a fluoroalkyl group and a reactive site.

The fluoroalkyl group of the fluorine compound B is preferably a linear or branched fluoroalkyl group R ^f3 having 4 to 7 carbon atoms. The fluoroalkyl group R ^f3 preferably has 4 or more and 10 or less carbon atoms, more preferably 6 or more carbon atoms, from the viewpoint of suppressing the interparticle interaction between the fluorine-treated particles during drying of the coating composition. In addition, a straight chain is preferred because it is linear or has less steric hindrance than a branched chain and is easily adsorbed to Component A. By making the fluoroalkyl group a linear or branched fluoroalkyl group R ^f3 having 4 to 8 carbon atoms, the separability of the particles is improved and the spontaneous formation of two layers having different refractive indexes is facilitated. And antireflection properties are improved, which is preferable. The fluorine compound B may be a compound of the above general formula (II) or a polymer thereof. That is, the fluorine compound B may be the same compound as the fluorine compound A. The fluorine compound A is a compound corresponding to a raw material for obtaining fluorine-treated inorganic particles, while the fluorine compound B means a fluorine compound contained in the coating composition.
[Content of each component in the coating composition]
Although the coating composition of this invention contains the inorganic particle A, the inorganic particle B, the inorganic particle C, and the binder raw material, each mass relationship in a coating composition is demonstrated.

  The coating composition is inorganic particles (total of all components of inorganic particles including inorganic particles A, B, and C) / solvent (total of all components of solvent) = 0.05 to 0.2 (mass ratio). Is preferred. By setting it as the above range, both the dispersion stability of the inorganic particles and the spontaneous formation of the layer structure can be achieved.

  In a more preferred embodiment, the coating composition of the present invention contains inorganic particles A and inorganic particles A (including inorganic particles B and C), and inorganic particles A / non-inorganic particles A = 1/30 to 1/1 ( (Mass ratio).

  Here, the mass part of each component in the coating composition is the solid content concentration in the dispersion when each component is in the state of dispersion from the mass added to the coating composition when each component can be handled as a solid. Is obtained by the method described later and is multiplied by the mass of the dispersion added to the coating composition.

The coating composition is made of inorganic particles A / non-inorganic particles A = 1/30 to 1/1 (mass ratio), so that the anti-reflection member obtained by coating the coating composition on a substrate is low. The ratio between the thickness of the refractive index layer and the thickness of the high refractive index layer can be made constant. For this reason, since it is easy to make the thickness of a low refractive index layer and a high refractive index layer into the thickness which has an antireflection function simultaneously by one coating, it is preferable. In addition, even when trying to increase the thickness of the high refractive index layer and give a hard coat function, without impairing the antireflection function,
Since the required thickness can be obtained by one coating, the inorganic particles A / non-inorganic particles A can be made within the above range from the viewpoint of both the antireflection function and the hard coat function.

  The coating composition is more preferably inorganic particles A / non-inorganic particles A = 1/29 to 1/5 (mass ratio), more preferably 1/26 to 1/10 (mass ratio), and particularly preferably 1/23. ~ 1/15 (mass ratio).

More preferably, in 100% by mass of the coating composition of the present invention, the total of inorganic particles is 0.2% by mass to 40% by mass, the total of solvent is 40% by mass to 98% by mass, and the binder raw material is 1% by mass. The other components such as the initiator, the curing agent, the catalyst, and the fluorine compound B are 0.1% by mass or more and 20% by mass or less. More preferably, the total of the inorganic particles is 1% by mass to 35% by mass, the total of the solvent is 50% by mass to 97% by mass, the binder raw material is 2% by mass to 25% by mass, and the other components are 1% by mass. It is the aspect containing 15 mass% or less.
[Antireflection member]
The antireflection member obtained by using the coating composition of the present invention refers to a member in which a layer having an antireflection function is formed on at least one surface of various supporting substrates. Generally, when the supporting substrate is a plastic film. Called antireflection film. As described in JP-A-59-50401, the necessity and required performance are preferably 0.03 or more, more preferably two or more layers having a refractive index difference of 0.05 or more. This is an aspect constituted by laminating an antireflection layer on a supporting substrate. Moreover, it is preferable that the refractive index difference of the layer on a support base material, ie, each layer in an antireflection layer, is 5.0 or less. This refractive index difference is a value obtained by relatively comparing the refractive indexes between adjacent layers. A layer having a relatively low refractive index is called a low refractive index layer, and a layer having a relatively high refractive index is a high refractive index. Call a layer.

  FIG. 1 shows an example of an antireflection member obtained by the coating composition of the present invention. In the antireflection member 1, an antireflection layer composed of two layers having different refractive indexes is formed on the hard coat layer 5 on one surface of the support base 2. The antireflection layer is formed of three layers on a supporting substrate, which is composed of a low refractive index layer 4 and then a high refractive index layer 3 on the outermost surface side. In the case of this configuration, three coatings are usually required on the support substrate, but by using the coating composition of the present invention, two coatings (hard coat layer and antireflection layer) are applied. Can be formed.

  FIG. 2 shows an example in which a high refractive index hard coat layer 6 is provided by imparting scratch resistance to the high refractive index layer instead of the hard coat layer. The high refractive index hard coat layer also has a function of strengthening the adhesion between the support base 2 and the low refractive index layer 3. In the case of this configuration, it is usually necessary to apply the coating twice on the supporting base material, but the strength of the high refractive index hard coat layer is preferably 1 or more and H or more in pencil hardness of 1 kg load, It is more preferably 2H or more, and most preferably 3H or more. By using the coating composition of the present invention, it can be formed by a single coating.

  In addition, the antireflection layer in the antireflection member of the present invention has a clear arrangement due to the arrangement of particles between the high refractive index layer and the low refractive index layer which are two or more layers having different refractive indexes. Preferably there is an interface.

  A clear interface in the present invention refers to a state in which one layer can be distinguished from another layer. The distinguishable interface represents an interface that can be determined by observing a cross section using a transmission electron microscope (TEM), and can be determined according to a method described later.

  In order to exhibit good performance as an antireflection member, the minimum reflectance is preferably 0% or more and 1.0% or less, more preferably 0% or more and 0.8% or less, and further preferably 0% or more in spectroscopic measurement. It is 0.6% or less, and particularly preferably 0% or more and 0.5% or less.

  Moreover, in order to exhibit good properties as an antireflection member, it is further desirable that the transparency is high. If the transparency is low, it is not preferable when used as an image display device because image quality is deteriorated due to a decrease in image saturation. A haze value can be used for evaluating the transparency of the antireflection member obtained by the production method of the present invention. Haze is an index of turbidity of a transparent material defined in JIS K 7136 (2000). The smaller the haze, the higher the transparency. The haze value of the antireflection member is preferably 2.0% or less, more preferably less than 1.8%, still more preferably less than 1.5%, and the smaller the value, the better the transparency. However, it is difficult to set it to 0%, and a realistic lower limit value is considered to be about 0.01%. If the haze value exceeds 2.0%, the possibility of image deterioration is increased, which is not preferable.

  In order to exhibit good properties as an antireflection member, it is desirable that the thickness of the high refractive index layer and the low refractive index is a specific thickness, and the thickness of the low refractive index layer is preferably 50 nm or more and 200 nm or less, more preferably 70 nm. The thickness is not less than 150 nm and particularly preferably not less than 90 nm and not more than 130 nm. If the thickness of the low refractive index layer is less than 50 nm, the light interference effect cannot be obtained, the antireflection effect cannot be obtained, and the reflection of the image becomes large. Further, when the thickness exceeds 200 nm, the light interference effect cannot be obtained, and the reflection of the image becomes large, which is not preferable.

  The thickness of the high refractive index layer is preferably 50 nm or more and 200 nm or less, more preferably 70 nm or more and 150 nm or less, and particularly preferably 90 nm or more and 130 nm or less.

  Moreover, when forming a high refractive index layer without providing a hard-coat layer on a support base material, it is preferably 500 nm or more and 2000 nm or less, more preferably 600 nm or more and 2000 nm or less, and particularly preferably 600 nm or more and 1500 nm or less. desirable. By setting the thickness of the second layer (second layer) from the outermost layer on the antireflection layer side to 500 nm or more and 2000 nm or less, scratch resistance, wear resistance, curl, reflectance, and transmittance of the antireflection member This is desirable because it can improve the cracking and suppress the occurrence of cracks on the coating film surface.

The antireflection member of the present invention may further be provided with an easy adhesion layer, a moisture proof layer, an antistatic layer, a shield layer, an undercoat layer, a protective layer, and the like. The shield layer is provided to shield electromagnetic waves and infrared rays.
[Supporting substrate]
Except for the case where the antireflection member is provided directly on the CRT image display surface or the lens surface, it is important that the antireflection member has a supporting base material. Although there is no limitation in particular in a support base material, a plastic film is more preferable than a glass plate. Examples of plastic film materials include cellulose esters (eg, triacetylcellulose, diacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene-2). , 6-Naphthalene dicarboxylate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic) Polystyrene), polyolefin (eg, polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyester -Terimide, polymethyl methacrylate, polyether ketone and the like are included, among which triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are particularly preferable.

  In a preferred embodiment of the antireflection member obtained by applying the coating composition of the present invention on a substrate and the antireflection member obtained by the method of producing the antireflection member of the present invention, the scratch resistance as described above is used. Even if a plastic with insufficient properties is used for the support substrate, it is possible to impart scratch resistance in addition to antireflection properties by controlling the thickness of the high refractive index layer. It is not always necessary to provide a hard coat layer. Further, as described above, the supporting base material can be a film having various functional layers such as an adhesive layer, a shield layer, and a sliding layer.

  The surface roughness of the surface of the supporting substrate on which the coating composition is applied is preferably 40 nm or less. The surface roughness is more preferably 35 nm or less, and particularly preferably 30 nm or less. Here, when a glass plate or plastic film having a functional layer other than the antireflection layer is used as a supporting substrate and a coating composition is applied on the functional layer, the surface roughness of the surface on which the coating composition is applied Is not the surface roughness of the surface of the functional layer, but the surface roughness of the glass plate or plastic film on the side where the functional layer is laminated. In addition, when a coating composition is applied to a treated surface using a glass plate or plastic film that has been subjected to various treatments, the surface roughness of the surface on which the coating composition is applied Is the surface roughness of the treated glass plate or plastic film.

Various surface treatments can be applied to the surface of the support substrate. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.
[Method for producing inorganic particles A, B, C]
Inorganic particles A, B, and C can be produced in the form of powders from various pigment and inorganic compound manufacturers, or particle dispersions (particle dispersions, colloidal solutions, or sols) dispersed in a solvent (also called dispersion medium). It can be obtained by performing surface treatment on any inorganic particles obtained in the form of (called), if necessary, but it is better to treat inorganic particles obtained in the form of a particle dispersion. It is preferable in terms of removal of coarse particles and dispersion stability of the coating composition.

  When surface treatment is performed on the inorganic particles A and the inorganic particles B and C, various compounds including a fluorine compound A, a solvent, a reaction catalyst, a polymerization initiator, a reaction stopper, It is obtained by adding a polymerization inhibitor, an anti-agglomeration agent, a dispersing agent, etc., and reacting in a heated or cooled state while mixing and stirring. Dehydration treatment, ion exchange resin, ion exchange treatment with an ion exchange membrane, or the like may be performed.

  The solid content concentration during the surface treatment is preferably as low as possible, preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and the solid content concentration is higher than this. If it is too low, the reaction cannot proceed sufficiently. If it is too high, foreign matter may be generated due to aggregation of inorganic particles, and further gelation, aggregation, and sedimentation may occur. Moreover, after completion | finish of reaction, in order to provide stability, you may add dilution with a solvent, a reaction terminator, a polymerization inhibitor, and an aggregation inhibitor.

The treatment may be performed by combining a plurality of reaction systems. For example, a treatment by silanol condensation and a treatment by radical polymerization may be combined. In this case, either simultaneous or sequential methods may be used, but it is more preferable to carry out sequentially.
[Method for producing coating composition]
The coating composition is obtained by mixing inorganic particles A, B, C, binder raw materials, other additives (solvent, initiator, curing agent, catalyst, etc.), and hydrophobic compound B. The production method is obtained by measuring the prescribed amounts of the above components by mass or volume and mixing them by stirring. At this time, in addition, a solvent removal treatment using a reduced pressure or a reverse osmosis membrane, a dehydration treatment using a molecular sieve, an ion exchange treatment using an ion exchange resin, or the like may be performed.

  The inorganic particles A, B, and C may be added in the form of either a particle dispersion or a powder, but handling in the form of a particle dispersion is preferable in terms of preventing aggregation and foreign matter generation. When the powder is handled as a raw material, it is preferable that the powder is dispersed in a solvent (dispersion medium) by various dispersing machines such as a media type dispersing machine. As the formulation amount when added as a particle dispersion, the mass of the particles obtained from the product of the solid content concentration of the particle dispersion and the mass of the particle dispersion can be used.

The solid concentration was measured by weighing about 2 g of the particle dispersion in an aluminum dish (this mass is W ₁ ) (this mass is W ₂ ) and then drying in a hot air oven at 120 ° C. for 1 hour. after cooling to room temperature in a desiccator, weighed (to the mass and W ₃₎ and can be obtained having a solid content concentration according to the following equation.
Solid content concentration = (W ₃ −W ₁ ) / (W ₂ −W ₁ ) × 100
The obtained coating composition may be subjected to an appropriate filtration treatment before coating. This appropriate filtration process is a choice of solvent, filter material that matches the polar state of the particle surface, and filter openings, shear rate that does not destroy the dispersion state of the particle dispersion, and pressure conditions that match the filter structure. More preferably, it is filtered.
[Production Method of Antireflection Member]
As a method for producing the antireflection member of the present invention, a single-layer liquid film formed by applying the coating composition of the present invention only once on at least one surface of a supporting substrate is composed of the two layers. A method of forming an antireflection layer is desirable. This manufacturing method is preferable in terms of economy because two layers can be formed in the coating process.

  Here, the one-layer liquid film formed by coating the coating composition only once on at least one surface of the supporting substrate means that one kind of liquid film is applied to the supporting substrate in one coating step. This refers to the formation of a single-layer liquid film composed of a coating composition, and simultaneous multi-layer coating in which a liquid film composed of a plurality of layers is coated once in a single coating process, or during one coating. One layer of liquid film applied multiple times, continuous sequential coating with drying process, one layer of liquid film applied multiple times at the time of one coating, then dried, wet on wet coating, etc. It means not to do.

  First, the coating composition of the present invention is coated on a supporting substrate by a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method (see US Pat. No. 2,681,294).

  Of these coating methods, the gravure coating method or the die coating method is preferable as the coating method.

  Next, the liquid film coated on the support substrate is dried. In addition to completely removing the solvent from the resulting antireflective member, the drying process also heats the liquid film from the viewpoint of promoting the movement of particles in the liquid film to spontaneously form a layer structure. Is preferably accompanied.

  Examples of the drying method include heat transfer drying (adherence to a high-temperature object), convection heat transfer (hot air), radiant heat transfer (infrared ray), and others (microwave, induction heating). Among these, in the manufacturing method of the present invention, a method using convective heat transfer or radiant heat transfer is preferable because it is necessary to make the drying speed uniform in the width direction.

  Further, the two layers on the support substrate formed after the drying step may be subjected to further curing operation (curing step) by irradiating with heat or energy rays. From the viewpoint of properties, electron beams (EB rays) and / or ultraviolet rays (UV rays) are preferable. In the case of curing with ultraviolet rays, the oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable.

  When curing is performed by heat, the drying step and the curing step may be performed simultaneously. Moreover, the antireflection member of this invention can provide the image display apparatus excellent in antireflection property by providing in the visual recognition side surface of various image display apparatuses, such as PDP. In this case, it is important to provide an antireflection member or the like with the support base material side of the antireflection member as the image display device side.

Next, although this invention is demonstrated based on an Example, this invention is not necessarily limited to these.
[Preparation of inorganic particles A]
[Inorganic particle A dispersion (a)]
Hollow silica particle isopropyl alcohol dispersion (Hollow silica manufactured by JGC Catalysts & Chemicals Co., Ltd .: solid content concentration 20% by mass, number average particle size 60 nm) and KBM-503 (Shin-Etsu Chemical Co., Ltd. γ-methacryloxypropyltrimethoxy) (Silane) 1.37 g, 10 mass% formic acid aqueous solution 0.17 g and water 0.306 g were mixed and stirred at 70 ° C. for 1 hour. Then, 1.38 g of H ₂ C═CHCOO (CH ₂ ) ₂ (CF ₂ ) ₈ F and 0.057 g of 2,2-azobisisobutyronitrile were added as fluorine compound A, and then at 90 ° C. for 60 minutes. Stir with heating. Next, after confirming the solid content concentration by the method described later, methyl isobutyl ketone was added as a diluent solvent and diluted to obtain an inorganic particle A dispersion (a) having a solid content of 3.5% by mass.

[Preparation of inorganic particle A dispersion (b)]
Similar to the inorganic particle A dispersion (a) except that the hollow silica particle isopropyl alcohol dispersion was replaced with a colloidal silica isopropyl alcohol dispersion (manufactured by Nissan Chemical Industries, Ltd .: solid concentration 30 mass%, number average particle diameter 40 nm). Thus, an inorganic particle A dispersion (b) was obtained.

[Preparation of inorganic particle A dispersion (c)]
An inorganic particle A dispersion (c) is obtained in the same manner except that the fluorine compound A is replaced with H ₂ C═CHCOO (CH ₂ ) ₆ (CF ₂ ) ₆ F with respect to the inorganic particle A dispersion (a). It was.

[Preparation of inorganic particle A dispersion (d)]
An inorganic particle A dispersion (d) was obtained in the same manner as in the inorganic particle A dispersion (a) except that the fluorine compound A was used instead of 1-6 hexanediol diacrylate.
[Preparation of inorganic particles B]
[Inorganic particle B dispersion (a)]
To 100 g of titanium oxide methanol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: “ELECOM” number average particle size 8 nm, solid content concentration 30 mass%), KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., γ-acryloxypropyltrimethoxy) Silane) (1.5 g) was added dropwise and stirred uniformly. Next, 5 g of a 20% acetic acid aqueous solution was added dropwise thereto, and after completion of the dropwise addition, the reaction was carried out at 35 ° C. for 30 minutes and at 60 ° C. for 3 hours.
Furthermore, 200 g of methyl isobutyl ketone was added as a substitution solvent, demethanol treatment was performed on a rotary evaporator, and after confirming the solid content concentration by the method described later, finally the solid content concentration was adjusted to 30% by mass with methyl isobutyl ketone. Microfiltration was performed to obtain inorganic particle B dispersion (a).

[Inorganic particle B dispersion (b)]
For inorganic particle B dispersion (a), titanium oxide methanol dispersion was replaced with zirconium oxide methanol dispersion (manufactured by Nissan Chemical Industries, Ltd .: “Nanouse OZ-30M” number average particle diameter 15 nm, solid content concentration 30 mass%) Except for the above, an inorganic particle B dispersion (b) was obtained in the same manner.

[Inorganic particle B dispersion (c)]
For inorganic particle B dispersion (a), except that titanium oxide methanol dispersion was replaced with zinc oxide isopropyl alcohol dispersion (manufactured by Hux Itec Corp .: number average particle size 20 nm, solid content concentration 30% by mass), Inorganic particle B dispersion (c) was obtained.

[Inorganic particle B dispersion (d)]
3 g of LS-2430 (Shin-Etsu Chemical Co., Ltd. tetraethoxylane) was added dropwise to 100 g of titanium oxide methanol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: “ELECOM” number average particle diameter 8 nm, solid content concentration 30% by mass). And stirred uniformly. Next, 5 g of a 20% acetic acid aqueous solution was added dropwise thereto, and after completion of the dropwise addition, the reaction was carried out at 35 ° C. for 30 minutes and at 60 ° C. for 3 hours.
Furthermore, 200 g of methyl isobutyl ketone was added as a substitution solvent, demethanol treatment was performed on a rotary evaporator, and after confirming the solid content concentration by the method described later, finally the solid content concentration was adjusted to 30% by mass with methyl isobutyl ketone. Microfiltration was performed to obtain inorganic particle B dispersion (d).

[Inorganic particle B dispersion (e)]
Except that the titanium oxide methanol dispersion was replaced with the aluminum oxide methanol dispersion (manufactured by Nissan Chemical Industries, Ltd .: number average particle size 15 nm, solid content concentration 30% by mass) with respect to the inorganic particle B dispersion (a). Inorganic particle B dispersion (e) was obtained.

[Preparation of inorganic particles C]
[Inorganic particle C dispersion (a)]
To 50 g of an antimony pentoxide-zinc oxide double oxide methanol dispersion (manufactured by Nissan Chemical Co., Ltd .: “CELNAX CX-Z610M-F2” solid content concentration 60 mass% number average particle size 20 nm), KBM-5103 (Shin-Etsu Chemical Co., Ltd.) 3 g of Kogyo Co., Ltd. (γ-acryloxypropyltrimethoxysilane) was added dropwise and stirred uniformly. Next, 2.5 g of a 20% aqueous acetic acid solution was added dropwise thereto, and after completion of the dropwise addition, the mixture was reacted at 35 ° C. for 30 minutes and at 60 ° C. for 3 hours.
Furthermore, 200 g of methyl isobutyl ketone was added as a substitution solvent, demethanol treatment was performed on a rotary evaporator, and after confirming the solid content concentration by the method described later, finally the solid content concentration was adjusted to 30% by mass with methyl isobutyl ketone. Microfiltration was performed to obtain inorganic particle C dispersion (a).

[Inorganic particle C dispersion (b)]
3. Antimony-added tin oxide ethanol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: “ELECOM” solid concentration 20 mass% 8 nm) 150 g, KBM-5103 (Shin-Etsu Chemical Co., Ltd. γ-acryloxypropyltrimethoxysilane) 5 g was added dropwise and stirred uniformly. Next, 7.5 g of a 20% aqueous acetic acid solution was added dropwise thereto, and after completion of the dropwise addition, the reaction was carried out at 35 ° C. for 30 minutes and at 60 ° C. for 3 hours. Furthermore, 200 g of methyl isobutyl ketone was added as a substitution solvent, demethanol treatment was performed on a rotary evaporator, and after confirming the solid content concentration by the method described later, finally the solid content concentration was adjusted to 30% by mass with methyl isobutyl ketone. Microfiltration was performed to obtain inorganic particle C dispersion (b).

[Inorganic particle C dispersion (c)]
For the inorganic particle C dispersion (a), an oxygen-deficient tin oxide ethanol dispersion (manufactured by CIK Nanotech Co., Ltd .: solid content concentration 30 mass% 10 nm instead of the dianhydride pentoxide-zinc oxide double oxide methanol dispersion) ) An inorganic particle C dispersion (c) was obtained in the same manner except that it was replaced with 100 g.

[Inorganic particle C dispersion (d)]
To 50 g of an antimony pentoxide-zinc oxide double oxide methanol dispersion (manufactured by Nissan Chemical Co., Ltd .: “CELNAX CX-Z610M-F2” solid content concentration 60 mass% number average particle size 20 nm), KBM-5103 (Shin-Etsu Chemical Co., Ltd.) 0.9 g of γ-acryloxypropyltrimethoxysilane (manufactured by Kogyo Co., Ltd.) was added dropwise and stirred uniformly. Next, 2.5 g of a 20% aqueous acetic acid solution was added dropwise thereto, and after completion of the dropwise addition, the mixture was reacted at 35 ° C. for 30 minutes and at 60 ° C. for 3 hours.

  Furthermore, 200 g of methyl isobutyl ketone was added as a substitution solvent, demethanol treatment was performed on a rotary evaporator, and after confirming the solid content concentration by the method described later, finally the solid content concentration was adjusted to 30% by mass with methyl isobutyl ketone. Microfiltration was performed to obtain inorganic particle C dispersion (d).

[Inorganic particle C dispersion (e)]
To 50 g of an antimony pentoxide-zinc oxide double oxide methanol dispersion (manufactured by Nissan Chemical Co., Ltd .: “CELNAX CX-Z610M-F2” solid content concentration 60 mass% number average particle size 20 nm), KBM-5103 (Shin-Etsu Chemical Co., Ltd.) 30 g of γ-acryloxypropyltrimethoxysilane (manufactured by Kogyo Co., Ltd.) was added dropwise and stirred uniformly. Next, 5 g of a 20% aqueous acetic acid solution and 2 g of ion-exchanged water were added dropwise thereto, and after completion of the addition, the reaction was carried out at 35 ° C. for 30 minutes and at 60 ° C. for 3 hours.

  Furthermore, 200 g of methyl isobutyl ketone was added as a substitution solvent, demethanol treatment was performed on a rotary evaporator, and after confirming the solid content concentration by the method described later, finally the solid content concentration was adjusted to 30% by mass with methyl isobutyl ketone. Microfiltration was performed to obtain inorganic particle C dispersion (e).

[Inorganic particle C dispersion (f)]
It produced by the method similar to the inorganic particle B dispersion (e).

[Coating composition]
[Preparation of coating compositions 1 to 23]
[Coating composition 1]
The following materials were mixed to obtain a coating composition 1.
Inorganic particle A dispersion (a) 43 parts by mass Inorganic particle B dispersion (a) 14 parts by mass Inorganic particle C dispersion (a) 14 parts by mass Binder raw material (a) Dipentaerythritol hexaacrylate (NK ester A-9570 New (Nakamura Chemical Co., Ltd .: solid content 100% by mass)
5.8 parts by mass solvent (methyl isobutyl ketone) 4.2 parts by mass solvent (diisobutyl ketone) 10.0 parts by mass photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
8.7 parts by mass [Coating compositions 2-3, 6, 15-16, 21-23]
Coating composition 1 was similarly prepared except that inorganic particle A dispersion (a), inorganic particle B dispersion (a), and inorganic particle C dispersion (a) were replaced as shown in Table 1. Products 2-3, 6, 13, 15-17, 20-23 were obtained.

[Coating composition 4]
The following materials were mixed and the coating composition 4 was obtained.
Inorganic particle A dispersion (a) 43 parts by mass Inorganic particle B dispersion (b) 14.3 parts by mass Inorganic particle C dispersion (a) 13.6 parts by mass Binder raw material (a) Dipentaerythritol hexaacrylate (NK ester) A-9570 Shin-Nakamura Chemical Co., Ltd .: solid content 100% by mass)
5.8 parts by mass solvent (methyl isobutyl ketone) 4.2 parts by mass solvent (diisobutyl ketone) 10.0 parts by mass photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
Part [Coating composition 5]
The following materials were mixed and the coating composition 5 was obtained.
Inorganic particle A dispersion (a) 43 parts by mass Inorganic particle B dispersion (c) 15.3 parts by mass Inorganic particle C dispersion (a) 12.6 parts by mass Binder raw material (a) Dipentaerythritol hexaacrylate (NK ester) A-9570 Shin-Nakamura Chemical Co., Ltd .: solid content 100% by mass)
5.8 parts by mass solvent (methyl isobutyl ketone) 4.2 parts by mass solvent (diisobutyl ketone) 10.0 parts by mass photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
Parts by mass [Coating composition 7]
The following materials were mixed to obtain a coating composition 7.
Inorganic particle A dispersion (a) 43 parts by weight Inorganic particle B dispersion (a) 11.3 parts by weight Inorganic particle C dispersion (c) 16.7 parts by weight Binder raw material (a) Dipentaerythritol hexaacrylate (NK ester) A-9570 Shin-Nakamura Chemical Co., Ltd .: solid content 100% by mass)
5.8 parts by mass solvent (methyl isobutyl ketone) 4.2 parts by mass solvent (diisobutyl ketone) 10.0 parts by mass photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
Part by mass [Coating composition 8]
The following materials were mixed to obtain a coating composition 8.
Inorganic particle A dispersion (a) 43 parts by mass Inorganic particle B dispersion (a) 11 parts by mass Inorganic particle C dispersion (c) 17 parts by mass Binder raw material (a) Dipentaerythritol hexaacrylate (NK ester A-9570 New (Nakamura Chemical Co., Ltd .: solid content 100% by mass)
5.8 parts by mass solvent (methyl isobutyl ketone) 4.2 parts by mass solvent (diisobutyl ketone) 10.0 parts by mass photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
Part by mass [Coating composition 9]
In the same manner as in the coating composition 1, except that the binder raw material (a) was replaced with (b) bisphenol AEO-modified diacrylate (Miramer M240 manufactured by MIWON Commercial Co. Ltd .: solid content: 100% by mass). 9 was obtained.

[Coating composition 10]
A coating composition 10 was prepared in the same manner except that the binder raw material (a) was replaced with (c) ditrimethylolpropane tetraacrylate (Miramer M410 manufactured by MIWON Commercial Co. Ltd .: solid content: 100% by mass) with respect to the coating composition 1. Got.

[Coating composition 11]
In the same manner as in the coating composition 1, except that the binder raw material (a) was replaced with (d) dipentaerythritol hexaacrylate (DPHA solid content 100% by mass, manufactured by Nippon Kayaku Co., Ltd.), Obtained.

[Coating composition 12]
The coating composition 12 was obtained in the same manner except that the binder raw material (a) was replaced with (e) pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., PET30 solid content: 100% by mass) with respect to the coating composition 1. It was.

[Coating composition 13]
A coating composition 13 was obtained in the same manner except that the binder raw material (a) was replaced with (f) pentaerythritol triacrylate (Daicel Cytec Co., Ltd., PETRA solid content 100% by mass) with respect to the coating composition 1.

[Coating composition 14]
The following materials were mixed and the coating composition 14 was obtained.
Inorganic particle A dispersion (a) 43 parts by mass Inorganic particle B dispersion (a) 15.6 parts by mass Inorganic particle C dispersion (a) 12.3 parts by mass Binder raw material (a) Dipentaerythritol hexaacrylate (NK ester) A-9570 Shin-Nakamura Chemical Co., Ltd .: solid content 100% by mass)
5.8 parts by mass solvent (methyl isobutyl ketone) 4.2 parts by mass solvent (diisobutyl ketone) 10.0 parts by mass photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
Parts by mass [Coating composition 17]
The following materials were mixed to obtain a coating composition 17.
Inorganic particle B dispersion (a) 14.0 parts by weight Inorganic particle C dispersion (a) 14.0 parts by weight Binder raw material (a) Dipentaerythritol hexaacrylate (NK ester A-9570, manufactured by Shin-Nakamura Chemical Co., Ltd .: solid 100% by mass)
5.8 parts by mass solvent (methyl isobutyl ketone) 47.2 parts by mass solvent (diisobutyl ketone) 10.0 parts by mass photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
Part by mass [Coating composition 18]
The following materials were mixed to obtain a coating composition 18.
Inorganic particle A dispersion (a) 43 parts by mass Inorganic particle C dispersion (a) 14.0 parts by mass Binder raw material (a) Dipentaerythritol hexaacrylate (NK ester A-9570 Shin-Nakamura Chemical Co., Ltd .: solid content 100 mass%)
5.8 parts by mass solvent (methyl isobutyl ketone) 18.2 parts by mass solvent (diisobutyl ketone) 10.0 parts by mass photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
Part by mass [Coating composition 19]
The following materials were mixed to obtain a coating composition 18.
Inorganic particle A dispersion (a) 43 parts by mass Inorganic particle B dispersion (a) 14.0 parts by mass Binder raw material (a) Dipentaerythritol hexaacrylate (NK ester A-9570 Shin-Nakamura Chemical Co., Ltd .: solid content 100 mass%)
5.8 parts by mass solvent (methyl isobutyl ketone) 18.2 parts by mass solvent (diisobutyl ketone) 10.0 parts by mass photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
Part by mass [Coating composition 20]
The following materials were mixed and the coating composition 20 was obtained.
Inorganic particle A dispersion (a) 43 parts by mass Inorganic particle B dispersion (a) 14 parts by mass Inorganic particle C dispersion (a) 14 parts by mass solvent (methyl isobutyl ketone) 10.0 parts by mass solvent (diisobutyl ketone) 10 0.0 part by mass of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one)
0.3 parts by mass of hydrophobic compound B (R1820 (manufactured by Daikin Corporation: solid content: 100% by mass)
Mass part [Preparation of antireflection member]
“Lumirror” U46 (manufactured by Toray Industries, Inc.) in which an easy-adhesive coating material was coated on a PET resin film was used as a supporting substrate.

  The coating compositions 1 to 23 were coated using a continuous coating apparatus having a gravure coater under the condition of a conveyance speed of 10 m / min.

First drying blast temperature and humidity: Temperature: 45 ° C, Relative humidity: 10%
Wind speed: coated side: 5 m / s, anti-coated side: 5 m / s
Wind direction: Coated surface side: parallel to base material, anti-coated surface side: vertical residence time with respect to base material: 1 minute Second drying air temperature and humidity: Temperature: 100 ° C., relative humidity: 1%
Wind speed: coated side: 5 m / s, anti-coated side: 5 m / s
Wind direction: coated surface side: vertical to substrate, anti-coated surface side: vertical residence time to substrate: 1 minute Curing process Irradiation output 600 W / cm ² Integrated light quantity 120 mJ / cm ²
Oxygen concentration 0.1% by volume
In addition, the measured value by a hot-wire anemometer (Nippon Kanomax Co., Ltd. Anemomaster anemometer / air flow meter MODEL6034) was used for the wind speed and temperature / humidity. By the above method, the antireflection member of Examples 1-16 and Comparative Examples 1-7 was created.
[Method for evaluating coating composition]
[Refractive index of inorganic particles A, B, and C]
The inorganic particle A dispersions (a) to (d), the inorganic particle B dispersions (a) to (e), and the inorganic particle C dispersions (a) to (f) are taken in an evaporator, and the dispersion medium is evaporated. Let This is dried at 120 ° C. and pulverized to produce powders of inorganic particles A, B, and C. A standard refracting liquid having a known refractive index is dropped onto a glass drop of a few drops, and the above powder is mixed therewith. Perform the above operations with various standard refraction liquids, observe the mixed liquid under the transmitted light of a low-pressure sodium lamp (sodium D line), and standard refraction when the mixed liquid (pasty) becomes transparent. The liquid was measured as the refractive index of inorganic particles.

[Volume resistivity of inorganic particles B and C]
For the volume resistivity of the inorganic particles B and C, powders of the inorganic particles A, B and C were prepared by the same method as the refractive index measurement method for the inorganic particles A, B and C described above. Using a body resistivity measurement system (MCP-PD51 type), the measurement was performed under a condition in which a load of 20 kN was applied to 2.5 g of inorganic particles.

[Hydroxyl value of binder material]
Based on the hydroxyl value measurement method of JIS K0070 (1992), the hydroxyl value of the binder material was measured by a neutralization titration method.

[Surface charge amount of inorganic particles B and C]
The surface charge amount of the inorganic particles B and C is measured using a surface potential titration device (Mutek PCD-04 manufactured by BTG Corporation), and the inorganic particle B dispersions (a) to (e) and the inorganic particle C dispersion (a) to (F) is diluted with isopropyl alcohol to prepare a dispersion having a concentration of 1% by weight as inorganic particles B or inorganic particles C, poured into a measuring container, and a polymer having a charge opposite to the particle charge is used. It was measured by titration. At this time, 0.001N polyallyldimethylammonium chloride was used as a polymer standard solution.

[Evaluation of antireflection member]
About the produced antireflection member, the following performance evaluation was implemented and the obtained result is shown in Table 2. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, and the average value was used.

[Abrasion resistance]
Describe the approximate number of scratches that can be seen when steel wool (# 0000) with a load of 250 g / cm ² is placed vertically on the anti-reflective member and make 10 reciprocations of the length of 1 cm. The score was passed.
5 points: 0 4 points: 1 or more Less than 5 3 points: 5 or more Less than 10 2 points: 10 or more Less than 20 1 point: 20 or more.

[Abrasion resistance]
At the tip of the Eraser abrasion tester manufactured by Honko Seisakusho (tip area 1 cm ² ), Shiranell (manufactured by Kowa Co., Ltd.) is attached, and a 500 g load is applied to the antireflection member 5 cm, 5000 reciprocations, and 1000 g. A load was applied and the antireflection member was rubbed back and forth 5 cm and 200 times, and the following classification was performed.
5 points: No scratch 4 points: 1 to 10 scratches 3 points: 11 to 20 scratches 2 points: 21 or more scratches 1 point: The antireflection layer of the test part was peeled entirely.

[transparency]
Transparency was determined by measuring the haze value. The measurement is based on JIS K 7136 (2000), using a Nippon Denshoku Industries Co., Ltd. haze meter so that light is transmitted from the side opposite to the support base of the antireflection member sample (antireflection layer side). The measurement was performed by placing it on the apparatus, and a haze value of 2.0% or less was regarded as acceptable. In addition, it was assumed that “whitening” did not occur for those that passed this evaluation.

[Antireflection performance]
The antireflection performance was evaluated using a spectrophotometer UV-3100 manufactured by Shimadzu Corporation in the wavelength range of 400 nm to 800 nm, the minimum reflectance (bottom reflectance) was measured, and 1.0% or less was accepted. The reflectivity showed a value when the local minimum value (minimum reflectivity) was reached near the wavelength of 550 nm.

[Antistatic performance]
As for the antistatic performance, the surface resistivity of the antireflective member on the low refractive index layer side was measured according to JIS K 6911 (1995), and a surface resistivity of 1 × 10 ¹¹ was accepted.

  Tables 1 and 2 summarize the compositions of the coating compositions, and Table 3 summarizes the configurations of Examples and Comparative Examples and the evaluation results of the obtained antireflection members. Regarding evaluation items that did not pass even one item, it was judged that the problem was not achieved.

  As shown in Table 3, the examples of the present invention passed all of the scratch resistance, abrasion resistance and transparency, and antireflection performance, and achieved the problems to be solved by the present invention.

  The antireflection member of Example 8 in which the mass ratio of the inorganic particles C to the inorganic particles B exceeded the preferable range of the present invention was slightly inferior in antireflection performance, but was in an acceptable range.

  The antireflective member of Example 9 in which the number of functional groups and the hydroxyl value of the binder raw material are smaller than the preferred range of the present invention was slightly inferior in scratch resistance, abrasion resistance, transparency, and antireflection performance. It was in the range possible.

  The antireflection member of Example 10 having a hydroxyl value smaller than the preferred range of the present invention was slightly inferior in transparency and antireflection performance, but was in an acceptable range.

The antireflection member of Example 13 having a hydroxyl value larger than the preferred range of the present invention was slightly inferior in scratch resistance, abrasion resistance, transparency, and antireflection performance, but was in an acceptable range. The antireflective member of Example 14 in which the mass ratio of C to the inorganic particles B was lower than the preferred range of the present invention was slightly inferior in antistatic performance, but was in an acceptable range.
The antireflection member of Example 15 in which the difference in the surface charge amount was larger than the preferable range of the present invention was slightly inferior in transparency and antireflection performance, but was in an acceptable range.

DESCRIPTION OF SYMBOLS 1 Antireflection member 2 Support base material 3 Antireflection layer 4 Low refractive index layer 5 High refractive index layer 6 High refractive index hard coat layer

The coating composition of the present invention, the method for producing an antireflection member using the same, and the antireflection member include, for example, a plastic optical component, a touch panel, a film-type liquid crystal element, a plastic container, a floor material as a building interior material, and a wall material. Protective coating materials to prevent scratches (scratches) and contamination of artificial marble, etc .; Antireflection films for film-type liquid crystal elements, touch panels, plastic optical components, etc .; Adhesives and sealing materials for various substrates; It can be suitably used as a binder material or the like.

Claims (4)

A coating composition comprising inorganic particles A, inorganic particles B, inorganic particles C, and a binder raw material.
Inorganic particles A: inorganic particles surface-treated with the fluorine compound A.
Inorganic particles B: inorganic particles having a refractive index of 1.65 or more.
Inorganic particles C: inorganic particles having a volume resistivity of 1 × 10 ¹⁰ (Ω · cm) or less.   The paint composition according to claim 1, wherein the binder raw material has 3 or more reactive sites per molecule, and has a hydroxyl value of 20 or more and 150 or less based on JIS K0070 (1992). object.   When the mass ratio of the inorganic particles C to the inorganic particles B (“the mass of the inorganic particles C” / “the mass of the inorganic particles B”) is C / B, the C / B is 0.8 or more and 1.5. The coating composition according to claim 1 or 2, wherein:   The coating composition according to any one of claims 1 to 3, wherein a difference in surface charge amount between the inorganic particles B and the inorganic particles C is 30 µeq / g or less.

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