JP2011184497A - Coating composition, and method for producing antireflective member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition which provides an antireflective member having both low reflectance and mar resistance and abrasion resistance by a simple method. <P>SOLUTION: The coating composition at least includes a component X, a component Y, and a particle Z. The component X has been subjected to surface treatment X with a fluorine compound having a reactive site. The component Y has been subjected to surface treatment Y with a compound B which is hydrolyzed to form a plurality of silanol groups in the molecule and a compound C which has a reactive site and is hydrolyzed to form a plurality of silanol groups in the molecule. The particle Z has been subjected to neither the surface treatment X nor Y. The coating composition can produce an antireflective member having both low reflectance and mar resistance and abrasion resistance by a simpler method. There is also provided a method for producing the antireflective member. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  In general, the antireflection member prevents 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). Therefore, it is placed on the outermost surface of the display so as to reduce the reflectivity 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. A so-called multi-coating produced on the surface of a supporting substrate such as a film is known (Patent Document 1).

  Further, since the antireflection member is disposed on the outermost surface of the display, it is required that the surface has good scratch resistance and wear resistance. Patent Documents 2 and 3 show low luminous reflectance. An antireflection film having good scratch resistance and wear resistance while maintaining it and an electronic image display device using the same have been proposed. Patent Document 2 discloses an antireflection property in which a hard coat layer and a low refractive index layer are laminated in this order on a transparent substrate film via an adhesive layer, and the visibility reflectance is 0.5% or less. A film is described. Patent Document 3 describes a coating for an antireflection film containing perfluoropolyoxyalkyl diisocyanate. Patent Document 4 discloses a curable resin composition containing a specific component as a curable resin composition containing a metal oxide subjected to a treatment for bonding an organic compound. On the other hand, as a method for forming an antireflection member having the above structure by a simpler method, Patent Document 5 describes a method for producing an antireflection film having two layers having different refractive indexes on at least one surface of a support substrate. Has been.

  Since the antireflection member targeted by the present invention is disposed on the outermost surface of the display and directly touches the eyes of the user, it is required to have good scratch resistance and wear resistance while maintaining low reflectance. It is done. In addition, since these antireflection members are composed of a plurality of layers, the coating process is complicated because it usually requires three or more coatings, and simplification is required.

  However, in Patent Document 2, modified hollow silica is used as a low refractive index layer component, and the wear resistance is about 100 times of friction, which is not sufficient for the required quality. In Patent Document 3, even if the antireflection performance is the lowest, the minimum reflectance is about 1.0%, which is significantly lower than the antireflection performance where the minimum reflectance currently required by the user is 0.5% or less. Inferior. Further, the wear resistance is about 200 times, and the wear resistance is not sufficient. Patent Document 4 has been confirmed by the present inventors, and this method does not have sufficient wear resistance, and the idea of the surface treatment method of the present invention has not been obtained. In patent document 5, with respect to the complexity of the coating process, at least one kind of inorganic particles uses inorganic particles whose surface is treated with a fluorine compound, thereby forming two layers in one coating. In addition, the use of metal chelates has improved the scratch resistance, but the present inventors have confirmed that the scratch resistance and wear resistance assumed to be scratched with a nail are insufficient. Moreover, the idea of the present invention has not been conceived. Moreover, when all of patent documents 1, 2, and 3 make anti-reflective property and abrasion resistance compatible, at least 3 times or more coating is required on a support base material, and a manufacturing process is complicated.

Japanese Patent Application Laid-Open No. 7-5542 JP 2009-3354 A JP-A-11-80312 JP 2007-238897 A JP 2009-58954 A

  Therefore, the problem to be solved by the present invention is to provide a coating composition capable of producing an antireflection member having both low reflectance, scratch resistance and wear resistance by a simpler method, and a method for producing the antireflection member. Is to provide.

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 at least the following component X, component Y, and particles Z.
Component X: Particles obtained by surface treatment with fluorine compound A (hereinafter, this surface treatment is referred to as surface treatment X)
(Fluorine compound A: R ¹ -R ⁷ -R ^f )
Component Y: Particles obtained by surface treatment with compound B and compound C (hereinafter, this surface treatment is referred to as surface treatment Y).
(Compound B: SiR ³ _n1 (OR ⁴ ) _4-n1 )
(Compound _{^{C: R 2 -R 8 -SiR 5}} n2 (OR 6) 3-n2)
Particle Z: Particle not subjected to surface treatment X and surface treatment Y.
(Where R ^f is a fluoroalkyl group, R ¹ and R ² are reactive sites, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, R ⁷ and R ^8. Represents an alkylene group having 1 to 3 carbon atoms or an ester structure derived therefrom, and n1 and n2 each represent an integer of 0 to 2 and each may have a side chain in the structure.
2) The coating composition according to 1), wherein the surface treatment X is a surface treatment of the particles with the fluorine compound A and the compound D.
(Compound _{^{D: R 9 -R 12 -SiR 10}} n3 (OR 11) 3-n3)
Wherein R ⁹ is a reactive double bond group, R ¹⁰ and R ¹¹ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, R ¹² is an alkylene group having 1 to 3 carbon atoms or an ester derived therefrom. And n3 represents an integer of 0 to 2, and each side chain may be included in the structure.)
3) The coating composition of 1) or 2) containing a metal chelate compound.
4) The coating composition according to 3), wherein the metal chelate compound is an aluminum-containing chelate compound.
5) The coating composition according to any one of 1) to 4), wherein the mass ratio of the component Y to the particles Z is 0.05 or more and 4.0 or less.
6) The coating composition according to any one of 1) to 5), wherein the surface treatment Y satisfies the following requirements.

0.1 <((W ^B + W ^C ) / (W ^B + W ^C + W ^Y )) <2.0
0.05 <W ^B / W ^C <0.95
(W ^B : Shows the mass part of Compound B when surface-treating the particles with Component Y.)
(W ^C : indicates the mass part of Compound C when surface-treating the particles with Component Y.)
(W ^Y : indicates the mass part of the raw material particles when the surface treatment of the component Y is performed.)
7) By applying the coating composition of any one of 1) to 6) once on at least one surface of the supporting substrate, a liquid film of one layer is formed to form an antireflection layer composed of two or more layers. The manufacturing method of the reflection preventing member including the process to do.

  ADVANTAGE OF THE INVENTION According to this invention, the coating composition which can manufacture the reflection preventing member which is compatible with a low reflectance, abrasion resistance, and abrasion resistance with a simpler process can be provided. Further, by using the production method of the present invention, the production process can be simplified while maintaining good antireflection performance, excellent scratch resistance, and wear resistance, and thus productivity can be improved. .

  Furthermore, according to a more preferable aspect of the present invention, it is possible to form a high refractive index hard coat layer and a low refractive index layer as two layers having different refractive indexes constituting the antireflection layer, and to achieve good reflection. The coating composition which can manufacture the favorable antireflection member which shows prevention property and outstanding abrasion resistance with a simple process can be obtained. That is, even when a film having no hard coat layer is used as a supporting substrate, antireflection properties, scratch resistance and abrasion resistance are simultaneously imparted by applying the coating composition of the present invention once. The obtained antireflection member can be obtained, and the productivity is excellent.

It is an example of the reflection preventing member which is the target object of this invention. It is a more preferable example of the antireflection member which is the target of the present invention.

As a coating composition capable of producing an antireflection member having both low reflectance, scratch resistance, and abrasion resistance in a simpler process, the present inventors have specified components and particles for different types of particles. This was achieved by including: That is, the present invention is a coating composition containing at least component X, component Y, and particle Z, wherein component X is subjected to surface treatment X with fluorine compound A, and component Y is subjected to surface treatment Y with compound B and compound C. The particle Z is characterized in that neither the surface treatment X nor Y is performed. Here, compounds B and C are represented by the following general formula, compound B is a compound in which a plurality of silanol groups are formed in the molecule by hydrolysis, compound C has a reactive site, and It is a compound in which a plurality of silanol groups are formed in the molecule by hydrolysis.
(Compound B: SiR ³ _n1 (OR ⁴ ) _4-n1 )
(Compound _{^{C: R 2 -R 8 -SiR 5}} n2 (OR 6) 3-n2)
First, the surface treatment X of the component X with the fluorine compound A results in a difference in surface energy from the other components Y and particles Z, which selectively causes the component X in the drying process of the coating film. By moving and arranging on the surface of the coating film, it becomes possible to spontaneously form a layer structure. This makes it possible to form an antireflection layer consisting of a plurality of layers by only one coating step without performing a plurality of coating steps as in the prior art, and consists of a plurality of layers in a simple process. An antireflection member can be formed.

  Secondly, the component Y has the surface treated with the compound B and the compound C, so that a plurality of silanol groups by the hydrolyzate of the compound B and a reactive site by the hydrolyzate of the compound C are formed on the surface. Two different crosslinking reaction points are introduced. Thus, after coating on the substrate surface, a drying or curing step is performed, thereby reacting between the reactive sites of the compound C formed on the raw material particle surface and the silanol group of the compound B formed on the raw material particle surface. Both of the condensation reactions proceed and the crosslink density between the components Y increases, so that the wear resistance and scratch resistance are improved.

  Third, by including in the coating composition particles Z that have not been surface-treated with compound B and compound C, transparency deterioration due to aggregation in the drying process of the coating film and stability of the coating composition can be ensured. . Further, by using the compound D for the surface treatment of the component X, it becomes possible to provide more silanol groups on the surface of the component X. As a result, the cross-linking density between the components X is increased, and the cross-linking reaction between the component X and the particles Z is brought about, so that the cross-linking density between the layers can be improved.

  Furthermore, by containing a metal chelate in the coating composition, the metal chelate acts as a catalyst for the silanol condensation reaction, strengthens the silanol condensation between the components X, Y and the binder raw material, and further improves the crosslinking density. Can do. At this time, by defining the mass ratio of the component Y and the particle Z and the mutual mass ratio of the compound B, the compound C, and the particle Z, which are materials used for the surface treatment of the component Y, within the scope of the present invention, the effect can be obtained. Can be increased.

  Hereinafter, embodiments of the present invention will be described in detail. The number of particles contained in the coating composition of the present invention is preferably two or more, and at least one of the two or more types preferably has a lower refractive index than the other particles.

[Coating composition]
The coating composition of the present invention needs to contain at least component X, component Y, and particle Z in the coating composition that is one liquid, whereby the coating composition of the present invention is applied to the supporting substrate once. By coating only, an antireflection member having an antireflection layer composed of two layers having different refractive indexes on a supporting substrate, such as a high refractive index layer and a low refractive index layer, can be obtained. Details of the component X, the component Y, and the particles Z will be described later.

  Here, the “component” in the present specification refers to a surface-treated particle, and a chemical bond (covalent bond, hydrogen bond, ionic bond, van der Waals bond, particle to particle) Including a compound having a hydrophobic bond or the like) or adsorbing (including physical adsorption or chemical adsorption), the mass indicates a particle and a compound. Specifically, the mass of the “component” is obtained from each component dispersion from the solid content concentration and the amount added to the coating composition, and details will be described later.

  The coating composition of the present invention may contain components X, Y, and particles Z, and preferably contains a metal chelate compound. By including the metal chelate compound, the wear resistance and scratch resistance of the antireflection layer formed by coating the coating composition on the substrate are further improved. Furthermore, the metal chelate compound is more preferably an aluminum-containing chelate compound.

  The ratio of the component Y to the particles Z in the coating composition of the present invention has a preferred range, preferably 0.05 or more and 4.0 or less, more preferably 0.08 or more and 2.0 or less. If it is smaller than this range, the scratch resistance and abrasion resistance will be reduced, and if it is larger, the stability of the coating composition, the transparency of the resulting coating film will be decreased, and the reflectance will be increased. To do.

  In addition to this, the coating composition of the present invention may contain a solvent, a binder raw material, and a curing agent, a surfactant, a dispersant, a fluorine compound having a reactive site, and the like as other components.

  In the coating composition of the present invention, the component containing particles other than the component X and the component X, specifically, the component Y and the particle Z are preferably made of different types of particles or different types of particles. Therefore, it is preferable that the coating composition of this invention contains two or more types of particle | grains. Hereinafter, particles suitable as Component X, Component Y, and Particle Z will be described.

[particle]
In the coating composition of the present invention, the coating composition contains at least component X, component Y and particles Z. Component X, component Y, and particle Z may be either organic particles or inorganic particles. Here, the organic particles refer to particles formed of an organic compound, that is, a polymer compound, and the inorganic particles refer to particles formed of an inorganic compound. This particle may have the same elemental composition from the surface to the center of the particle, or may be a particle formed by laminating a plurality of elemental compositions from the center. The number of types of particles is preferably 2 or more and 20 or less, more preferably 2 or more and 10 or less, still more preferably 2 or more and 3 or less, and most preferably 2 types.

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. . Therefore, the component Y and the particle Z may be the same type of particles or different types.

[Component X]
The component X in the coating composition will be described. As the particles suitable as a raw material for the component X, inorganic particles containing an element selected from Si, Na, K, Ca, and Mg are preferably exemplified, and more preferably silica particles (SiO ₂ ), alkali metal fluorides ( NaF, KF, etc.), and an inorganic particle containing a compound selected from the alkaline earth metal fluoride _(such as CaF 2, MgF _2), durability, refractive index, silica particles from the viewpoint of cost is particularly preferred. The silica particles refer to particles containing a composition composed of either a silicon compound or a polymerized (condensed) organic silicon compound, and, as a general example, is a general term for particles derived from a silicon compound such as SiO _2. .

  The shape of the particles suitable for the raw material of component X is not particularly limited, but a spherical shape is preferable from the viewpoint of the refractive index and optical anisotropy of the antireflection layer formed by the coating composition of the present invention. More preferably, the component X contains silica particles, and part or all of the silica particles are preferably hollow and / or porous. Here, the hollow silica particles are silica particles having cavities inside the particles, and the porous silica particles are silica particles having pores on the surface and inside of the particles.

  By using particles having hollow and / or porous properties, the density of the obtained antireflection layer is lowered, and as a result, the effect of lowering the refractive index is obtained. In addition, the hollow and / or porous particles are hereinafter referred to as hollow particles.

  The number average particle diameter of the particles to be used (in the case of surface-treated particles, the number average particle diameter before the surface treatment) is preferably 1 nm or more and 200 nm. If it exceeds 200 nm, good transparency cannot be obtained due to light scattering, which is not preferable. In addition, although there is no particular influence on the small particle size, the lower limit of the number average particle size of particles that can be obtained in a practically stable manner is about 1 to 5 nm.

  The number average particle diameter of the particles refers to the particle diameter determined with a transmission electron microscope. The sample in a state where the dispersion is evaporated and dried is observed with a transmission electron microscope, the measurement magnification is 500,000 times, the outer diameter of 100 particles existing on the screen is measured, and the average value is obtained. It was.

  Here, the outer diameter means the maximum diameter of the particle (that is, the longest diameter of the particle and indicates the longest diameter in the particle). Similarly, in the case of a particle having a cavity inside, the maximum diameter of the particle is also defined. To express.

  Next, the surface treatment X of the component X contained in the coating composition of this invention is demonstrated. The surface treatment X with the fluorine compound A on the above-mentioned particles, particularly particles such as silica, refers to a step of chemically modifying the particles and introducing the fluorine compound A into the particles, and may be performed in one step. It 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. Here, introduction means that the fluorine compound A is chemically bonded (including covalent bond, hydrogen bond, ionic bond, van der Waals bond, hydrophobic bond, etc.) or adsorbed (including physical adsorption and chemical adsorption) to the particle surface. Refers to the state of being.

This fluorine compound A is a compound represented by the following general formula (I).
R ¹ -R ⁷ -R ^f General formula (I)
Here, R ^f represents a fluoroalkyl group, R ¹ represents a reactive site, and R ⁷ represents an alkylene group having 1 to 3 carbon atoms or an ester structure derived therefrom. Each may have a side chain in the structure. The fluoroalkyl group is a substituent in which part or all of hydrogen contained in 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.

One method of surface treatment X for introducing the fluorine compound A is a fluoroalkoxy in which R ¹ is an alkoxysilyl group, a silyl ether group, or a silyl ether group in the general formula (I). At least one kind of silane compound and particles or particle dispersion and solvent, catalyst, etc. are stirred together, heated or dealcoholized in some cases, and condensed with silanol groups on the particle surface. Is the method.

The particle dispersion as used herein refers to a state in which the particles are dispersed in a solvent, sometimes called a sol, a suspension, a slurry, or a colloidal solution. A stabilizer, etc., such as an agent and a surface treatment agent, may be included. From the viewpoint of handling the particles in a finely dispersed state, the surface treatment is preferably performed in the state of a dispersion.
Specific examples of the fluorine compound A in this case include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxy. Silane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,3-trifluoropropyltriisocyanate silane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluoro Examples include octylethyltriisopropoxysilane, 2-perfluorooctylethyltrichlorosilane, and 2-perfluorooctyl isocyanate silane.
As another method of the surface treatment X, there is a method in which particles or particle dispersions are treated with the compound D and then bonded to the pre-fluorine compound A.

  This compound D refers to a compound having no fluorine in the molecule, but having at least one reactive site capable of reacting with the fluorine compound A and one site capable of reacting with inorganic particles such as hollow silica particles. The site capable of reacting with inorganic particles such as silica is preferably an alkoxysilyl group, a silyl ether group, and a silanol group 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.

In this method, specifically, silica particles (particularly hollow silica particles) are treated with the compound D represented by the following general formula (II) and the fluorine compound A represented by the above general formula (I). Preferably, silica particles (particularly hollow silica particles) are treated with the compound D represented by the following general formula (II), and then treated with the fluorine compound A represented by the aforementioned general formula (I).
R ⁹ -R ¹² -SiR ¹⁰ _n3 (OR ¹¹ ) _3-n3 general formula (II)
R ⁹ in the general formula (II) represents a reactive site, R ¹² represents an alkylene group having 1 to 3 carbon atoms and an ester structure derived therefrom, and R ¹⁰ and R ¹¹ represent hydrogen or a carbon number. 1 to 4 represents an alkyl group, n3 represents an integer of 0 to 2, and each may have a side chain in the structure.

A more preferable form in the above general formula is that the reactive site represented by R ^{1 in the} general formula (I) and R ⁹ in the general formula (II) is a reactive double bond group. This reactive double bond group is a functional group that chemically reacts with radicals generated by receiving energy such as light or heat. Specific examples include vinyl, allyl, acryloyl, and methacryloyl groups. Can be mentioned.

  Specific examples of the compound D include acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyheptyltrimethoxysilane. , Methacryloxyethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxysilane and Examples include compounds in which the methoxy group in these compounds is substituted with other alkoxyl groups and hydroxyl groups.

  Specific examples of the fluorine compound A in this case include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3 -Perfluorobutyl-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-methylhexyl Ethyl acrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, Hexadecafluorononyl 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-perfluorodecylethyl 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, octafluoro Pentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate Rate, hexafluorobutyl methacrylate and the like.

By using the compound D represented by the general formula (II) having no fluoroalkyl group R ^f in the molecule, it becomes possible to modify the surface of silica particles such as hollow silica under simple reaction conditions. Instead, it is possible to introduce a functional group whose reactivity is easily controlled on the surface of the silica particle, and as a result, the fluorine compound A having a reactive double bond and a fluoroalkyl group R ^f is reacted on the surface of the silica particle. Is possible.

  Further, the surface treatment X may be performed using compounds E1 and E2 represented by the following general formulas (VI) and (VII) in addition to the fluorine compound A and the compound D.

Formula (VI)

Here, R ¹⁵ represents a reactive site, R ¹⁶ represents an alkylene group having 1 to 3 carbon atoms or an ester structure derived therefrom, m represents an integer in the range of 20 to 200, and k represents 0 or 1. Each may have a side chain in the structure.
Formula (VII)

(Here, y represents an integer from 1 to 200, and z represents an integer from 1 to 20.)
By subjecting these components X to surface treatment with fluorine compound A, compound D, and compound E1 or E2, in addition to improving the crosslink density, it becomes possible to impart slipperiness to the surface of the antireflection member, resulting in scratch resistance. And wear resistance can be further improved.
[Component Y, Particle Z]
The component Y and particles Z in the coating composition will be described. As the particles suitable for the raw material of component Y and the particles Z, different types of particles from those suitably used for the raw material of component X are preferably used. The raw material of component Y and the particles Z may be the same or different. The particles are not particularly limited, but are preferably inorganic compounds, particularly metals, metalloid oxides, nitrides, borides, and are selected from the group consisting of Zr, Ti, Al, In, Zn, Sb, Sn, and Ce. More preferably, it is an oxide particle of at least one selected metal. Further, the particles suitably used as the raw material for component Y and the particles Z are preferably particles having a higher refractive index than the particles suitably used for the raw material for component X, specifically zirconium oxide (ZrO ₂ ), Titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), and indium tin At least one inorganic compound selected from oxides (In ₂ O ₃ ), or a solid solution between these inorganic compounds, and some elements are substituted, or some elements enter between lattices, or some element lattice points Is a solid solution lacking, particularly preferably phosphorus-containing tin oxide (PTO), antimony-containing tin oxide (ATO), gallium-containing zinc oxide (GZO) ), Titanium oxide (TiO ₂ ), and zirconium oxide (ZrO ₂ ).

  The number average particle size of the raw material of component Y and the particles used for the particle Z (in the case of surface-treated particles, the number average particle size before the surface treatment) is preferably 150 nm or less. Preferably it is 50 nm or less. A practically manufacturable particle diameter has a lower limit of about 1 nm.

  In addition, the number average particle diameter here refers to the particle diameter determined by a transmission electron microscope, and the dispersion containing the particles is evaporated and dried, and the sample is observed with a transmission electron microscope. The measurement magnification was 500,000 times, and the outer diameters of 100 particles existing on the screen were measured to obtain the average value. As described above, the outer diameter represents the maximum diameter of the particles (that is, the long diameter of the particles, indicating the longest diameter in the particles).

  In addition, as a preferred method for producing an antireflection member using the coating composition of the present invention, a step of forming a single-layer liquid film by coating the coating composition once on at least one surface of a supporting substrate. In the case of using the production method including the above, since the formation of a spontaneous layer structure is facilitated, it is preferable that the number average particle diameter of the other particles is smaller than 30 nm.

  The refractive index of the raw material of component Y and the particles suitable as the particles Z is preferably 1.55 to 2.80, more preferably 1.58 to 2.50. When the refractive index of the particles is smaller than 1.55, the refractive index of the high refractive index layer formed on the resulting antireflection member is lowered, and the components Y and Z with the low refractive index layer including the component X are reduced. When the refractive index difference with the high refractive index layer containing becomes small and good antireflection performance cannot be obtained and the refractive index of the particles becomes larger than 2.80, the low refractive index layer containing component X and component Y, The refractive index difference between the high refractive index layer containing the particles Z and the refractive index difference between the high refractive index layer and the supporting base material are increased, and good antireflection performance cannot be obtained. It may cause a change in interference color, and interference fringes resulting from the change may be detected and deteriorated in appearance.

Furthermore, in the coating composition of the present invention, when the particles used as the raw material for the component X are silica particles, it is particularly preferable that the raw materials for the component Y and the particle Z are particles having a higher refractive index than the silica particles. As the particles having a higher refractive index than the silica particles, inorganic compounds having a number average particle diameter of 20 nm or less and a refractive index of 1.60 to 2.80 are preferably used. Specific examples of such inorganic compounds include antimony-containing tin oxide (ATO), phosphorus-containing tin oxide (PTO), lithium-containing zinc oxide (GZO), zirconium oxide (ZrO ₂ ), and / or titanium oxide (TiO _2). In particular, from the viewpoint of antireflection properties, titanium oxide and zirconium oxide having a high refractive index are more preferable.

  Next, the surface treatment Y of the component Y contained in the coating composition of this invention is demonstrated.

  The surface treatment Y for the raw material particles of the component Y mentioned above refers to the step of chemically modifying the raw material particles of the component Y and introducing the compound B and the compound C into the raw material particles of the component Y, and is performed in one step. It may be performed in multiple stages.

This compound B and compound C are compounds represented by the following general formulas (IV) and (V).
SiR ³ _n1 (OR ⁴ ) _4-n1 general formula (IV)
_{^{R 2 -R 8 -SiR 5 n2 (}} OR 6) 3-n2 general formula (V)
Here, R ² is a reactive site, R ³ , R ⁴ , R ⁵ and R ⁶ are alkyl groups having 1 to 4 carbon atoms, R ⁸ is an alkylene group having 1 to 3 carbon atoms or an ester structure derived therefrom. Indicates. N1 and n2 each represent an integer of 0 to 2, and each may have a side chain in the structure. The reactive site here is as described above.

  Compound B refers to a compound having at least one site that can be chemically bonded or adsorbed on the particle surface, and compound C includes at least one site that can be chemically bonded or adsorbed to the particle surface and the aforementioned reactive site. A compound that has more than one place. The sites that can be chemically bonded or adsorbed on the particle surface include silanol groups, thiol groups, amino groups, carboxyl groups, and hydroxyl groups in which alkoxysilyl groups and alkoxysilyl groups are hydrolyzed. A hydrolyzate of ether and silyl ether is preferred. These compounds are generally called silane coupling agents. For example, glycidoxyalkoxysilanes, aminoalkoxysilanes, acryloylsilanes, methacryloylsilanes, vinylsilanes, mercaptosilanes, etc. may be used. it can.

  One method of the surface treatment Y is to stir, heat, dealcoholize, etc. the compound B, the compound C and the raw material particles of the component Y, or the raw material particle dispersion of the component Y together with the catalyst, water, solvent, etc. There is a method of condensing with silanol groups on the particle surface. The particle dispersion here is as described above.

A more preferable form in the above general formula is that R ¹² is a reactive double bond group or an epoxy group. This reactive double bond group is a functional group that chemically reacts with radicals generated by receiving energy such as light or heat. Specific examples include vinyl, allyl, acryloyl, and methacryloyl groups. Can be mentioned.

  The ratio of the raw material particles of the compound B, the compound C, and the component Y, which are essential elements in the surface treatment Y, has a preferable range, which is as follows.

0.1 <((W ^B + W ^C ) / (W ^Y + W ^B + W ^C )) <2.0
0.05 <(W ^B / W ^C ) <0.95
Here, W ^B is the weight of the compound B at the time of surface treatment Y particles, W ^C is the mass of the compound C when surface treated Y particles, W ^Y is the time of surface treatment Y particles The part by mass of the particles is shown. Furthermore, the following ranges are more preferable.

0.3 <((W ^B + W ^C ) / (W ^Y + W ^B + W ^C )) <0.8
0.3 <(W ^B / W ^C ) <0.5
Here, when the particle dispersion is used as the raw material particle of the component Y, a value obtained from the solid content concentration of the particle and the added amount of the particle is used, and the method will be described later.

When (W ^B + W ^C ) / (W ^Y + W ^B + W ^C ) is smaller than the above range, the wear resistance and scratch resistance of the coating film are lowered, and (W ^B + W ^C ) / (W ^Y + W). ^{When B} + W ^C ) is larger than the above range, the stability of the coating composition with time (sedimentation, aggregation, white turbidity of solids in the coating composition) and the surface state of the coating (foreign matter, whitening, white turbidity) Gets worse. W B ^/ W ^C is the abrasion resistance of the coating film is smaller than the above range, the scratch resistance is reduced, the greater is the abrasion resistance of the coating film, in addition to the decrease in the scratch resistance, coating compositions Stability of the product over time (sedimentation, aggregation, white turbidity of solids in the coating composition) and surface condition (foreign matter, whitening, white turbidity) of the coating film deteriorate.

  Specific examples of compound B include tetramethoxysilane, tetraethoxysilane, tetra n-propoxy silane, tetraisopropoxy silane, tetra n-butoxy silane, tetraisobutoxy silane, methyl trimethoxy run, methyl triethoxy silane, ethyl tri Examples include methoxysilane, isobutyltrimethoxysilane, and compounds containing methoxy groups in these compounds substituted with other alkoxyl groups and hydroxyl groups. These may be used alone or in combination, and may be used after partial hydrolysis.

Specific examples of compound C include vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltrimethoxysilane, γ -Ureidopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutylto Limethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyheptyltrimethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltri Examples include methoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxysilane, and compounds containing a compound in which the methoxy group in these compounds is substituted with other alkoxyl groups and hydroxyl groups.
[Metal chelate]
The coating composition used in the present invention preferably further contains a metal chelate in addition to the above-described component X, component Y and particles Z. The metal chelate is a general term for compounds in which a compound having a multidentate ligand in the molecule forms a complex so that a metal ion is sandwiched between them. Since the metal chelate compound has an effect of promoting the curing of a resin containing a silanol group or an oxirane ring, the components Y, the components X, the components X and the components Y, and further the components X, the components Y and the binder raw material Used to promote the reaction between. This effect is promoted by heating. The temperature suitable for heat curing in the drying process is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 130 ° C. or higher. Setting the heating temperature to 100 ° C. or higher is preferable because curing of a resin containing silanol or the like proceeds in a very short time. The metal ion species in the metal chelate is not particularly limited as long as it is an alkali metal element, an alkaline earth metal element, a metal element, or the like.

Specific examples of the metal chelate compound include, for example, triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri -N-butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxy bis (acetylacetonato) titanium Di-n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (Acetylacetonato) titanium, di-t-but Si-bis (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono -N-butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy Mono (ethyl acetoacetate) titanium, tri-n-propoxy, mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium The -Sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (Ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n- Butoxy Tris (Ethyl Acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl) Titanium chelate compounds such as acetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium, triethoxy mono (acetylacetonato) zirconium, tri- n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium Tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonate) Zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy Bis (acetylacetonato) zirconium, monoethoxy-tris (acetylacetonato) zirconium, mono-n-propoxy-tris (acetylacetonato) zirconium, mono-i-propoxy-tris (acetylacetonate) Zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetylacetonate) Zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl aceto) Acetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (eth) Ruacetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di- sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium Mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) ) Zirconium, mono-t-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) ) Zirconium chelate compounds such as zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium, aluminum trisethylacetoacetate, aluminum alkyl acetoacetate / diisopropylate, aluminum bisethylacetoacetate / monoacetylacetonate, aluminum tris Aluminum key such as acetylacetonate, aluminum ethylacetoacetate, diisopropylate, etc. Over preparative compounds; and the like can be illustrated, preferably the chelating compound of titanium or aluminum, particularly preferable examples thereof include chelate compounds of titanium. These metal chelate compounds may be used alone or in combination of two or more. In these chelate compounds, from the viewpoint of the stability of the coating composition with time (sedimentation, aggregation, white turbidity of solids in the coating composition), the surface state of the coating (foreign matter, whitening, white turbidity), contribution to film curability, etc. Aluminum compounds are particularly preferred.
[solvent]
In addition to the above-mentioned component X, component Y, and particle Z, the coating composition of the present invention preferably further contains a solvent. A solvent here refers to the liquid which can evaporate almost most in the drying process after coating. By including a solvent in the coating composition, it becomes easy to spread the liquid film, so that the film thickness control accuracy is improved and the movement of the fluorinated particles to the air side (the outermost surface layer on the antireflection layer side) is improved. Since it becomes easy, the antireflection performance is improved.

The solvent is not particularly limited, but usually a solvent having a boiling point of 200 ° C. or less at normal pressure is preferable. Specifically, water, alcohols, ketones, ethers, esters, hydrocarbons, amides, fluorines and the like are used. These can be used alone or in combination of two or more. Specific examples include propylene glycol monomethyl ether (PGME), cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methanol, isopropyl alcohol and the like, and isopropyl alcohol, propylene glycol and the like are particularly preferable from the viewpoint of dispersion stability of the particles. . Examples of alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, benzyl alcohol, phenethyl alcohol, and the like. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ethers include dibutyl ether and propylene glycol monoethyl ether acetate. Examples of the esters include ethyl acetate, butyl acetate, ethyl lactate, methyl acetoacetate, and ethyl acetoacetate. Examples of aromatics include toluene and xylene. Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
[Binder raw material]
The coating composition of the present invention preferably contains a binder raw material. Although it does not specifically limit as a binder raw material in a coating composition, From a viewpoint of manufacturability, it is preferable that it is a binder raw material which can be hardened by heat and / or active energy rays, etc. It may be present, or two or more kinds may be mixed and used. Here, the binder raw material is a compound contained in the coating composition, and is a raw material for the binder component of the antireflection layer. That is, what the binder raw material contained in the coating composition of this invention hardened | cured with the heat | fever, ionizing radiation, etc. is called 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.

  Further, from the viewpoint of retaining the component X, component Y, particle Z, etc. in the present invention in the film, the molecule has an alkoxy group, a silanol group, a reactive double bond, and a functional group capable of ring-opening reaction. It is preferable that the monomer and oligomer which are the binder raw material. Further, in the case of curing with UV rays, oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in an anaerobic atmosphere is more preferable. 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 preferably contains a polyfunctional acrylate monomer, oligomer, alkoxysilane, alkoxysilane hydrolyzate, alkoxysilane oligomer and the like, and details will be described below. The alkoxysilane and the alkoxysilane hydrolyzate include the following general formula (VIII), the hydrolyzate of the general formula (VIII), and a condensate of the hydrolyzate (silanol condensate). The hydrolyzate of the following general formula (VIII) is obtained by adding a predetermined amount of water to the compound represented by the general formula (VIII) and reacting it while distilling off the by-product alcohol in the presence of an acid catalyst. Represents the resulting compound.

_{^{A-R 17 -SiR 18 n (}} OR 19) 3-n Formula (VIII)
(A in the general formula represents a reactive functional group, an alkyl group having 1 to 8 carbon atoms, or a fluoroalkyl group having 1 to 8 carbon atoms. R in the general formula (VIII)) ¹⁷ represents an alkylene group having 1 to 3 carbon atoms or an ester structure derived therefrom, wherein R ¹⁸ and R ¹⁹ in the above general formula (VIII) are hydrogen or have 1 to 4 carbon atoms. In the general formula (VIII), n represents an integer of 0 to 2. A, R ¹⁷ , R ¹⁸ and R ¹⁹ each have a side chain in the structure. and may be provided that, ^a, determination of ^{R 17} are deemed preferentially as ^{R 17} for example, ^{a-R 17} _{is, CH 3 (CH 2) 5} -.. ^{if, R 17} is _{(CH 2)} 3, A becomes CH ₃ (CH ₂ ) _2. )
Moreover, the hydrolyzate of general formula (VIII) and the condensate of the hydrolyzate in the present invention represent an unreacted compound that has not reacted with the surface of the inorganic particles in the coating composition. In the coating composition, the presence or absence of the hydrolyzate of general formula (VIII) and the condensate of the hydrolyzate can be confirmed by the following analysis method. The coating composition of the present invention is centrifuged with a Hitachi tabletop ultracentrifuge (manufactured by Hitachi Koki Co., Ltd .: CS150NX) (rotation speed 30000 rpm, separation time 30 minutes), and the compounds reacted with the inorganic particles and the surface of the inorganic particles. After settling, the obtained supernatant was concentrated to dryness and redissolved using DMSO-d6 (manufactured by Taiyo Nippon Sanso Corporation, dimethyl sulfoxide-d6) as a solvent, and then C ¹³ -NMR (manufactured by JEOL Ltd.). / By using a nuclear magnetic resonance apparatus JNM-GX270), it is possible to confirm the presence or absence of a hydrolyzate of the general formula (VIII) unreacted with inorganic particles. Here, the reactive functional group in the present invention represents a functional group that undergoes a chemical reaction by receiving energy such as light or heat, such as a vinyl group, an acryloyl (methacryloyl) group, an epoxy group, an amino group, and a mercapto group.

Specific examples of the vinyl group-containing general formula (VIII) include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriisocyanatesilane, vinyltrichlorosilane, and functional groups in these compounds substituted with alkoxyl groups and hydroxyl groups. The thing containing a compound etc. are mentioned.
Specific examples of the general formula (VIII) containing an acryloyl (methacryloyl) group include acryloxyethyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxyheptyltrimethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxypropyl. Examples include trimethoxysilane, methacryloxyheptyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxysilane, and compounds containing methoxy groups in these compounds substituted with other alkoxyl groups and hydroxyl groups. .

  Moreover, the number average molecular weight of the hydrolyzate of the general formula (VIII) is preferably 100 or more and 5000 or less, more preferably 200 or more and 4500 or less, and further preferably 300 or more and 4000 or less in terms of polystyrene.

  By setting the number average molecular weight of the hydrolyzate to 100 or more and 5000 or less, the cross-linking density of the coating film surface is increased by taking a structure in which the general formula (VIII) is cross-linked with each other. As a result, the chemical resistance, wear resistance and adhesion are greatly improved, which is preferable.

Examples of the polyfunctional acrylate monomer include polyfunctional acrylates having 3 (more preferably 4 or 5) or more (meth) acryloyloxy groups in one molecule and modified polymers thereof, and specific examples include penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate hexanemethylene diisocyanate urethane polymer, and 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. .
[Other additives]
The coating composition of the present invention preferably further contains an initiator, a curing agent and a catalyst.
The initiator and the catalyst are used to promote the reaction between the components X, the components Y, the binder materials, and the components X and Y and the binder 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 to 20 parts by mass with respect to 100 parts by mass of the binder component in the coating composition. It is a mass part, More preferably, it is 0.1 mass part-10 mass parts.

  In addition, the coating composition of the present invention may further contain additives such as a surfactant, a thickener, and a leveling agent 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 (I) or a polymer thereof.
[Content of each component in the coating composition]
The coating composition of the present invention includes at least component X, component Y, and particle Z, and in the present invention, the ratio of the respective parts by mass is component X / (component Y + particle Z) = 1/30 to 1/1. It is preferable.

  Here, the mass part of each component in the coating composition is determined based on the mass added to the coating composition when each component can be handled as a solid. When each component is in the state of dispersion, the solid part of the component in the dispersion is used. The partial concentration is obtained by the method described later, and is obtained by multiplying it by the mass of the dispersion added to the coating composition.

  By setting Component X / (Component Y + Particle Z) = 1/30 to 1/1, the thickness and high refraction of the low-refractive index layer of the antireflection member obtained by coating the coating composition on the base material The ratio of the thicknesses of the rate layers 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, when the thickness of the high refractive index layer is increased and the hard coat function is to be imparted, the antireflection function can be achieved with a single coating without impairing the antireflection function. And component X / (component Y + particles Z) can be made within the above range from the viewpoint of achieving both a hard coat function and a hard coat function.

  The content ratio (mass ratio) of component X / (component Y + particle Z) is more preferably component X / (component Y + particle Z) = 1/29 to 1/5, more preferably 1/26 to 1/10. Particularly preferred is 1/23 to 1/15.

Further preferably, in 100% by mass of the coating composition of the present invention, the total of component X, component Y and particles Z is 0.2% by mass to 40% by mass, the organic solvent is 40% by mass to 98% by mass, metal 0.005 mass% to 5 mass% of chelate compound, 1 mass% to 30 mass% of binder raw material, 0.1 mass% or more of other components such as initiator, curing agent, catalyst, and fluorine compound B 20% by mass or less,
More preferably, the total of component X, component Y, and particles Z is 1% by mass to 35% by mass, the organic solvent is 50% by mass to 97% by mass, the fluorine compound B is 2% by mass to 25% by mass, and the like. This component contains 1% by mass or more and 15% by mass or less.

As a more preferred embodiment, the component X is a fluorine-treated hollow silica particle, the raw material of the component Y, the particle Z is a metal oxide particle, and the total thereof is 2% by mass or more in 100% by mass of the coating composition of the present invention. This is an aspect in which 30% by mass or less, the organic solvent is 60% by mass or more and 95% by mass or less, the fluorine compound B is 3% by mass or more and 20% by mass or less, and the other components are 2% by mass or more and 10% by mass or less.
[Antireflection member]
The antireflection member, which is an object 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 base materials. When the base material is a plastic film, it is generally called an 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 the structure of an antireflection member that is an object of the present invention. In the antireflection member 1, an antireflection layer composed of two layers having different refractive indexes is formed on a hard coat layer 5 on one surface of a support base 2. The antireflection layer is formed of three layers on a support substrate, which is composed of a low refractive index layer 3 and then a high refractive index layer 4 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 providing a high refractive index layer with scratch resistance in addition to a function of a high refractive index 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 the following method.

  An image taken with a TEM at a magnification of 200,000 times was adjusted with software (Easy Access) so that the white balance was within the 8-bit tone curve in the brightest and darkest areas. Furthermore, the contrast was adjusted so that two types of particles could be clearly distinguished.

  At this time, when a clear boundary could be drawn at the interface between one layer and the other layer, it was considered that there was a clear interface.

  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 3.0% or less, more preferably less than 2.0%, still more preferably less than 1.6%. 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 is 3.0% or more, there is a high possibility that image degradation will occur.

  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 from the outermost layer on the antireflection layer side to 500 nm or more and 2000 nm or less, scratch resistance, wear resistance, curl and reflectance of the antireflection member, improvement of transmittance, coating film It is desirable because the occurrence of cracks on the surface can be suppressed.

  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, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, 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 light transmittance of the supporting substrate is preferably 80% or more and 100% or less, and more preferably 86% or more and 100% or less. Here, the light transmittance is a ratio of light transmitted through the sample when irradiated with light, and is an index of transparency of a transparent material that can be measured according to JIS K 7361-1 (1997). The larger the value of the light transmittance of the antireflection member, the better. The smaller value is not preferable because the haze value increases and the possibility of image deterioration increases. 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 of the support substrate is preferably 0.01% or more and 2.0% or less, and more preferably 0.05% or more and 1.0% or less.

  The refractive index of the supporting substrate is preferably 1.4 to 1.7. Here, the refractive index is a ratio of changing the angle of the traveling direction at the interface when light travels from the air to a certain substance, according to the method defined in JIS K 7142 (1996). Can be measured.

An infrared absorber or an ultraviolet absorber may be added to the support substrate. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass and more preferably 0.05 to 10% by mass with respect to 100% by mass of all the components of the support substrate. As a slip agent, particles of an inert inorganic compound may be added to the support substrate. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin. Furthermore, the support substrate may be subjected to a surface treatment.

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.
[Production Method of Component X and Component Y]
The production method of component X and component Y is a powder dispersion from various pigment and inorganic compound manufacturers, or a particle dispersion dispersed in a solvent (also referred to as a dispersion medium) (also referred to as a particle dispersion, colloidal solution, or sol). The surface treatment can be performed on any of the particles obtained in the form of particles. However, the surface treatment is performed on the particles obtained in the form of a particle dispersion. From the viewpoint of dispersion stability. When using particles obtained in a powder state, perform dispersion treatment with a media mill or the like together with a dispersion medium, a dispersant, a surface treatment agent, etc. before the surface treatment to prepare a particle dispersion. It is preferable to perform surface treatment after this.

Component X and Component Y are various compounds (including fluorine compound A, compound B, compound C, and compound D), solvent, reaction catalyst, polymerization initiator, reaction terminator, and polymerization for the particles or the particle dispersion. It is obtained by adding an inhibitor, an anti-agglomeration agent, a dispersing agent, etc., mixing, stirring, and reacting in a heated or cooled state. In addition, desolvation treatment with reduced pressure or reverse osmosis membrane, dehydration with molecular sieve Treatment, ion exchange resin, ion exchange treatment with an ion exchange membrane, or the like may be performed. The surface-treated particles are added to the particle dispersion, and in the state where the particles are dispersed, the surface treatment is performed by reacting with the reactive groups and functional groups present on the particle surface. It is preferable in terms of stability of the coating composition.
The solid concentration during the surface treatment reaction (including surface treatment X and surface treatment Y) is preferably as low as possible, preferably 1% by mass to 60% by mass, more preferably 5% by mass to 50% by mass. If the solid content concentration is too low, the reaction cannot proceed sufficiently. If it is higher than this, the generation of foreign matter due to particle aggregation, and further gelation, aggregation, and sedimentation occur. There is a case. 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.
Although the temperature of the surface treatment reaction (including surface treatment X and surface treatment Y) is different from the reaction system used for the surface treatment used, it suppresses side reactions that cause cross-linking between particles and desorbs dispersants on the particle surface. In order to suppress, it is preferable that it is as low as possible in the range which can react. For example, in the surface treatment with silanol condensation, it varies depending on the type of silane coupling agent used, but is preferably between room temperature and 90 ° C, more preferably between 30 ° C and 70 ° C. In the surface treatment with radical polymerization, the reaction temperature is completely different depending on the kind of polymerization initiator to be used. For example, when azoisobutyronitrile is used, it is preferably between 60 ° C. and 100 ° C., more preferably between 70 ° C. and 90 ° C. preferable.
The stirring conditions and the stirring device for the surface treatment reaction (including surface treatment X and surface treatment Y) are not particularly limited, but may be any device and rotation speed necessary for sufficient mixing of the entire liquid. That the local shear rate is less than 10 ⁴ S ⁻¹ and the Reynolds number in the reaction tank is 1000 or more, agglomeration due to shear fracture of the particle dispersion and agglomeration due to local residence, It is preferable for preventing sedimentation.
The surface treatment reaction (including surface treatment X and surface treatment Y) may be performed by combining a plurality of reaction systems. For example, surface treatment by silanol condensation and surface 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.
After the completion of the surface treatment reaction, an appropriate filtration treatment may be performed in order to remove side reaction products and gelled products. This appropriate filtration means selecting the solvent, the filter material according to the polar state of the particle surface, and the filter opening, and filtering under the shear rate that does not destroy the dispersion state of the particle dispersion and the pressure condition according to the filter structure. Suggest to do.

After completion of the surface treatment reaction (including surface treatment X and surface treatment Y), the surface-treated particles obtained in the form of a particle dispersion may be once taken out as a powder by a spray drying method or the like. Although it may be handled in the form of a particle dispersion, it is preferably handled in the form of a particle dispersion in view of ease of handling in the subsequent process (manufacturing process of coating composition) and suppression of aggregates.
[Method of obtaining particles Z]
The particles Z are available from various pigment and inorganic compound handling manufacturers in powder form or in the form of particle dispersions dispersed in a solvent (also called dispersion medium). Obtaining in the form of a particle dispersion is preferable in terms of removal of coarse particles and dispersion stability of the coating composition. When using particles obtained in a powder state, perform dispersion treatment with a media mill or the like together with a dispersion medium, a dispersant, a surface treatment agent, etc. It is better to take it.
[Method for producing coating composition]
The coating composition can be obtained by mixing component X, component Y and particles Z, preferably a binder raw material, a solvent, and other additives (initiator, curing agent, catalyst, etc.). The production method is obtained by measuring the prescribed amounts of the above components by weight 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 particle components (component X, component Y, particle Z) 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 generation of foreign matter. 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 mill. As the formulation amount when added as a particle dispersion, the weight of the particles obtained from the product of the solid content concentration of the particle dispersion and the weight 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 stirring conditions and the stirring device at the time of preparing the coating composition are not particularly limited, but may be any device and rotation speed necessary for sufficient mixing of the entire liquid, and the local shear rate in the liquid is 10 ⁴ S. It is preferable that the range is smaller than ⁻¹ and the Reynolds number is 1000 or more in order to prevent aggregation due to shear fracture of the particle dispersion, aggregation due to local residence, and poor mixing.
Component X, component Y, and particle Z at the time of coating composition preparation, in addition to the binder raw material, solvent, other additives (initiator, curing agent, catalyst) addition order and addition speed are not particularly limited, but preferably particles Addition of the mixture of the binder raw material diluted with the solvent and other additives to the dispersion in small amounts while stirring prevents aggregation due to adsorption of the binder component to the particle surface and further generation of foreign matter. It is preferable for the purpose.
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, a step of coating and drying a single layer of liquid film at the time of one coating is performed a plurality of times with a coating composition containing different kinds of particles. As a more preferable method for producing an antireflection member, an antireflection layer comprising at least two layers is formed by coating the coating composition once on at least one surface of a supporting substrate to form a single liquid film. It is desirable that the method includes a step of forming. By manufacturing by this manufacturing method, it becomes possible to form two layers by spontaneously forming a layer structure, and the interface roughness between the high refractive index layer and the low refractive index layer forming the antireflection layer. In addition, the binder component can form a uniform matrix in the antireflection layer. As a result, scratch resistance and wear resistance can be improved as described above. In addition, since two layers can be formed in one coating process, it is advantageous in terms of economy.

  The method for producing an antireflective member of the present invention includes a method in which a step of coating and drying a single layer of a liquid film at the time of one coating is performed a plurality of times with a coating composition containing different types of particles, and a support substrate. By coating the coating composition once on at least one side of the film, two layers having different refractive indexes are simultaneously formed on the support substrate by performing a step of forming a liquid film of one layer and a step of drying in this order. However, the latter method is preferable because a uniform matrix can be formed in the antireflection layer.

  Here, the step of forming a liquid film of one layer by coating the coating composition once on at least one surface of the supporting substrate is one kind in one coating step on the supporting substrate. This refers to the formation of a single-layer liquid film made of a coating composition of the above-mentioned, simultaneous multi-layer coating in which a liquid film composed of a plurality of layers is applied once in a single coating step, and single coating. Sometimes one layer of liquid film is applied multiple times, continuous sequential coating with drying process, one layer of liquid film is applied multiple times during one application, and then wet-on-wet coating It means not doing.

  First, a coating composition containing components for forming each layer is prepared as described above, and this coating composition is prepared by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, Coating is carried out on a supporting substrate by a gravure coating method or 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. The gravure coating method is excellent for coating a coating composition with a small coating amount, such as an antireflection layer, with a uniform film thickness. Among the gravure coating methods, the direct gravure method is a small gravure roll with a small gravure roll diameter. It is more preferable to use a roll from the viewpoint of securing the stability of the meniscus portion. As such a coating method, a microgravure method has been proposed.

  In addition, the die coating method requires application of bead back pressure when the coating amount is small, such as an antireflection layer, but the film thickness is controlled by the amount of liquid supplied to the coating die because of the pre-measuring method. In addition, since the coating composition does not have a staying portion and an evaporation portion in principle, the coating composition is excellent in terms of stability.

  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.

This drying process is generally divided into (A) constant rate drying period and (B) reduced rate drying period. In the former, diffusion of solvent molecules into the atmosphere on the liquid film surface is the rate-limiting rate of drying. Therefore, the drying speed is constant in this section, the drying speed is governed by the partial pressure of the solvent to be evaporated in the atmosphere, the wind speed and the temperature, and the film surface temperature is a value determined by the hot air temperature and the partial pressure of the solvent to be evaporated in the atmosphere. It becomes constant. In the latter, since the diffusion of the solvent in the liquid film is rate-limiting, the drying rate does not show a constant value in this section and continues to decrease, and is governed by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature is To rise. Here, the drying rate represents the amount of solvent evaporation per unit time and unit area, and has a dimension of g · m ⁻² · min ⁻¹ .

In the production method of the present invention, it is presumed that the formation of the spontaneous layer structure occurs during the constant rate drying period, and there is a preferred range for the drying rate in this section, 1.4 g / (m ² preferably .s) or ^less, more preferably ^{0.9 g} · m is -2 · ^{min -1} or less, preferably 0.1 g ^{/ (m} 2 .s) or more. By setting the drying rate in the constant rate drying section within this range, it is possible to prevent unevenness due to non-uniformity of the drying rate and sufficiently secure the time required to cause a spontaneous layer structure.

As long as a drying rate in the range of 0.1 g / (m ² .s) or more and 1.4 g / (m ² .s) or less can be obtained, the wind speed and temperature are not particularly limited.

  In the production method of the present invention, the layer structure is densified by the arrangement of particles during evaporation of the remaining solvent and the evaporation of the residual solvent. In this process, because of the arrangement of particles, it takes time for the arrangement along with the mobility of the particles. Therefore, there is a preferable range for the film surface temperature increase rate during the decremental drying period, and it is 5 ° C./second or less. Preferably, it is 1 ° C./second or less.

  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 production 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, in the constant rate drying period, in the width direction. In order to achieve a uniform drying rate, in the case of drying by convective heat transfer, as a method that can reduce the overall mass transfer coefficient during drying while maintaining a controllable wind speed, A method of blowing hot air in a direction that is parallel and parallel or perpendicular to the conveyance direction of the substrate is desirable.

  Furthermore, you may perform the further hardening operation (curing process) by irradiating a heat | fever or an energy ray with respect to two layers on the support base material formed after the drying process. When curing with heat in the curing step, the temperature is preferably from room temperature to 200 ° C, more preferably from 100 ° C to 200 ° C, and even more preferably from 130 ° C to 200 ° C, from the viewpoint of the activation energy of the curing reaction. It is as follows.

Moreover, when hardening with an energy ray, it is preferable that it is an electron beam (EB ray) and / or an ultraviolet-ray (UV ray) from a versatility point. 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 the oxygen concentration is high, the curing of the outermost surface is inhibited, the curing becomes insufficient, and the scratch resistance and alkali resistance may be insufficient. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. When the discharge lamp type to ultraviolet cured using a high pressure mercury lamp is, illuminance 100~3000mW / cm ² of ultraviolet, ultraviolet irradiation under the conditions preferably 200~2000mW / cm ^2, further preferably a 300~1500mW / cm ² preferably performing, integrated light quantity of ultraviolet 100~3000mJ / cm ^2, preferably 200~2000mJ / cm ^2, more preferably it is more preferable to carry out ultraviolet irradiation under the condition that the 300~1500mJ / cm ^2. Here, the ultraviolet illuminance is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

  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 Component X]
[Component X (a) dispersion]
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 40 nm) is added to fluorine compound A as (CF ₃ (CF ₂ ) ₇ (CH ₂ CH _2). ) 1.50 g of Si (OCH ₃ ) ₃ ), 0.34 g of 10% by mass aqueous formic acid solution and 0.612 g of water were mixed and stirred at 70 ° C. for 5 hours and at 90 ° C. for 30 minutes. Thereafter, isopropyl alcohol was added and diluted to obtain a component X (a) dispersion having a solid content of 3.5% by mass.

[Component X (b) dispersion]
In the same manner as in Component X (a), except that 1.50 g of (CF ₃ (CF ₂ ) ₅ (CH ₂ CH ₂ ) Si (OCH ₃ ) ₃ ) is used as the fluorine compound A, Component X (b ) A dispersion was obtained.

[Component X (c) dispersion]
Hollow silica particles Isopropyl alcohol dispersion (Hollow silica manufactured by JGC Catalysts & Chemicals Co., Ltd .: solid content concentration 20 mass%, number average particle diameter 60 nm) 15 g, as compound D (CH ₂ = C (CH ₃ ) COOC ₃ H ₆ Si (OCH ₃ ) ₃ ) 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. Next, 1.38 g of H ₂ C═CHCOOCH ₂ (CF ₂ ) ₈ F and 0.057 g of 2,2-azobisisobutyronitrile were added as the fluorine compound A, followed by heating and stirring at 90 ° C. for 60 minutes. Thereafter, isopropyl alcohol was added and diluted to obtain a component X (c) dispersion having a solid content of 3.5% by mass.

[From Component X (d) Dispersion to Component X (g) Dispersion]
Component X (g) dispersion was obtained from Component X (d) dispersion in the same manner as Component X (c) except that the fluorine compound A and compound D shown in Table 1 were used.

[Component X (h) dispersion]
A component X (h) dispersion was obtained in the same manner except that the fluorine compound A was not used for the component X (c).

[Preparation of Component Y]
[Component Y (a) dispersion]
As raw material particle dispersion, 167 g (W ^Y = 50.1 g) of titanium dioxide isopropyl alcohol dispersion (ELCOM JGC Catalysts & Chemicals Co., Ltd .: solid content concentration: 30% by mass) is used as compound B (CH ₃ Si (OCH ₃ )) ₃ ) 25 g (W ^B = 25.0 g) and CH ₂ = CHCOOC ₃ H ₆ Si (OCH ₃ ) ₃ 25 g (W ^C = 25.0 g) as Compound C were added dropwise and stirred uniformly.

  Next, 12.5 g of a 20% aqueous acetic acid solution and 12.9 g of ion-exchanged water were 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. Finally, isopropyl alcohol was added for dilution to obtain a component Y (a) dispersion having a solid content concentration of 30.0% by mass.

[From component Y (b) dispersion to component Y (n) dispersion]
The component Y (b) to component Y (f) dispersion was prepared in the same manner except that the compound B or the compound shown in Table 1 was used as the compound C for the component Y (a).

  Adjustment of component Y (g) to component Y (n) dispersion was obtained in the same manner except that the amounts of compound B and compound C added to component Y (a) were changed to the amounts shown in Table 1.

[Component Y (o) dispersion]
A component Y (o) dispersion was obtained in the same manner except that the compound B was not added to the component Y (a) (W ^B = 0 g).

[Component Y (p) dispersion]
A component Y (p) dispersion was obtained in the same manner except that the compound C was not added to the component Y (a) (W ^C = 0 g).

[Particle Z]
[Particle Z (a) dispersion]
As the particle Z (a) dispersion, a titanium dioxide isopropyl alcohol dispersion (ELCOM JGC Catalysts & Chemicals Co., Ltd .: solid content concentration of 30% by mass) was used.

[Particle Z (b) dispersion]
As the particle Z (b) dispersion, a zirconium dioxide methyl ethyl ketone dispersion (nanouse OZ-30K, manufactured by Nissan Chemical Industries, Ltd., solid content concentration: 30% by mass) was used.

[Metal chelate]
[Metal chelate M (a)]
Aluminum trisacetylacetonate was used as the metal chelate M (a).
[Metal chelate M (b)]
Zirconium tetraethylacetylacetonate was used as the metal chelate M (b).
[Metal chelate M (c)]
Titanium tetraethylacetylacetonate was used as the metal chelate M (c).

[Coating composition]
[Preparation of coating compositions 1-40]
[Coating composition 1] The following materials were mixed to obtain a coating composition 1.
Component X (a) Dispersion 50 parts by weight Component Y (a) Dispersion 2.7 parts by weight Particle Z (a) Dispersion 24.3 parts by weight Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd .: solid content 100% by weight) 6.7 parts by mass 2-propanol 15.9 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.4 parts by mass R1820 (manufactured by Daikin Chemicals: solid content 100% by mass) 10. 0 parts by mass.

[Coating composition 2 to coating composition 13, and coating composition 34 to coating composition 36]
The coating composition 2 to the coating composition 13 and the coating composition 34 to the coating composition 36 are the same except that the components X, Y, and particles Z shown in Table 1 are used for the coating composition 1. Was obtained in the same manner.

[Coating composition 14]
The following materials were mixed and the coating composition 14 was obtained.
Component X (c) Dispersion 50 parts by weight Component Y (a) Dispersion 2.7 parts by weight Particle Z (a) Dispersion 24.3 parts by weight Metal chelate M (a) 0.02 parts by weight Kayarad DPHA (Nipponization) Yakuhin Co., Ltd .: solid content 100 mass%) 6.7 mass parts 2-propanol 15.9 mass parts 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.4 mass parts R1820 (Daikin) (Product made: 100 mass% solid content) 10.0 mass parts.

[Coating composition 15, coating composition 16]
The coating composition 15 and the coating composition 16 were obtained in the same manner except that the metal chelate M shown in Table 1 was used for the coating composition 14.

[Coating composition 17]
The following materials were mixed to obtain a coating composition 17.
Component X (c) Dispersion 50 parts by mass Component Y (a) Dispersion 0.81 parts by weight Particle Z (a) Dispersion 26.2 parts by weight Metal chelate M (a) 0.02 parts by weight Kayarad DPHA (Nipponization) Yakuhin Co., Ltd .: solid content 100 mass%) 6.7 mass parts 2-propanol 15.9 mass parts 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.4 mass parts R1820 (Daikin) (Product made: 100 mass% solid content) 10.0 mass parts.

[Coating composition 18, coating composition 19, and coating composition 20]
Coating composition 18, coating composition 19, and coating composition 20 were obtained in the same manner except that the amount of component Y and particles Z added to coating composition 17 was changed to parts by mass shown in Table 2.

[Coating composition 21, coating composition 28]
The coating composition 21 to the coating composition 28 were obtained in the same manner except that the component Y (a) dispersion was replaced with the component Y dispersion shown in Table 1 with respect to the coating composition 14.

[Coating composition 29]
The following materials were mixed to obtain a coating composition 29.
Component X (a) Dispersion 50 parts by mass Component Y (a) Dispersion 0.56 parts by mass Particle Z (a) Dispersion 5.04 parts by mass Kayrad DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass) 0.42 parts by mass 2-propanol 43.8 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.20 parts by mass.

[Coating composition 30]
The following materials were mixed to obtain a coating composition 30.
Component X (c) Dispersion 50 parts by weight Component Y (a) Dispersion 0.56 parts by weight Particle Z (a) Dispersion 5.04 parts by weight Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd .: solid content 100% by weight) 0.42 parts by mass 2-propanol 43.8 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.20 parts by mass.

[Coating composition 31]
The following materials were mixed and the coating composition 31 was obtained.
Component X (c) Dispersion 50 parts by weight Component Y (a) Dispersion 0.56 parts by weight Particle Z (a) Dispersion 5.04 parts by weight Metal chelate M (a) 0.02 parts by weight Kayarad DPHA (Nipponization) Yakuhin Co., Ltd .: 100 mass% solid content) 0.42 mass parts 2-propanol 43.8 mass parts 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.20 mass parts.

[Coating composition 32]
The following materials were mixed to obtain a coating composition 32.
Component X (h) Dispersion 50 parts by weight Particle Z (a) Dispersion 27 parts by weight Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd .: solid content 100% by weight) 6.7 parts by weight 2-propanol 15.9 parts by weight 2 0.4 parts by weight of hydroxy-2-methyl-1-phenyl-propan-1-one.

[Coating composition 33]
The following materials were mixed to obtain a coating composition 33.
Component X (a) Dispersion 50 parts by weight Particle Z (a) Dispersion 27 parts by weight Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd .: solid content 100% by weight) 6.7 parts by weight 2-propanol 15.9 parts by weight 2 0.4 parts by weight of hydroxy-2-methyl-1-phenyl-propan-1-one.

[Coating composition 37]
A coating composition 37 was obtained in the same manner as in the coating composition 29 except that the component Y (a) dispersion was changed to a Y (o) dispersion.

[Coating composition 38]
The following materials were mixed to obtain a coating composition 38.
Component X (a) Dispersion 50 parts by mass Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd .: solid content 100% by mass) 0.21 parts by mass 2-propanol 49.6 parts by mass 2-hydroxy-2-methyl-1-phenyl -Propan-1-one 0.20 mass part.

[Coating composition 39]
The following materials were mixed to obtain a coating composition 39.
Component Y (a) dispersion 0.56 parts by weight Particle Z (a) dispersion 5.04 parts by weight Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd .: solid content 100% by weight) 0.21 parts by weight 2-propanol 94. 0 parts by mass 2-hydroxy-2-methyl-1-phenyl-propan-1-one 0.20 parts by mass.

[Coating composition 40]
The following materials were mixed and the coating composition 40 was obtained.
Pentaerythritol triacrylate (PETA) 30.0 parts by mass Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals) 1.5 parts by mass Methyl isobutyl ketone 73.5 parts by mass.

[Preparation of antireflection member 1]
As a supporting substrate, “Lumirror” U46 (manufactured by Toray Industries, Inc.) in which an easy-adhesive paint was applied on a PET resin film was used. After coating the coating composition 40 (hard coat coating composition) on the surface of the supporting substrate on which the easy-adhesion coating is applied using a bar coater (# 16), the first step shown below. And then the second stage of drying.
First stage Hot air temperature 70 ℃
Hot air speed 2m / s
Wind direction Parallel to the coating surface Drying time 1.5 minutes Second stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 2 minutes
After drying, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² under an oxygen concentration of 0.1% by volume. And cured. Next, the coating composition 29-31, 37 is applied using a bar coater (# 10) on the surface on which the hard coat coating composition is applied, dried and cured, and then the first step shown below. And then the second stage of drying.
First stage Hot air temperature 25 ℃
Hot air wind speed 0.5m / s
Wind direction Parallel to coated surface Drying time 2 minutes 2nd stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 2 minutes
After drying, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² under an oxygen concentration of 0.1% by volume. Then, the antireflection members of Examples 29 to 31 and Comparative Example 6 were prepared.

[Preparation of antireflection member 2]
“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. On the surface of the supporting substrate on which the easy-adhesion coating is applied, the coating compositions 1-28 and 32-36 are applied using a bar coater (# 10), and then dried in the first stage shown below. Followed by a second stage of drying.
First stage Hot air temperature 25 ℃
Hot air wind speed 0.5m / s
Wind direction Parallel to coated surface Drying time 2 minutes 2nd stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 2 minutes
In addition, the measured value by a dynamic / static pressure tube was used for the wind velocity of hot air. After drying, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² under an oxygen concentration of 0.1% by volume. Then, the antireflection members of Examples 1 to 28 and Comparative Examples 1 to 5 were prepared.

[Preparation of antireflection member 3]
The coating composition 40 (hard coat coating composition) is dried and cured in the same manner as in the preparation of the antireflection member 1, and then, on the surface on which the hard coat coating composition is applied, dried and cured, After coating the coating composition 39 using a bar coater (# 6), the first stage drying shown below was performed, followed by the second stage drying.
First stage Hot air temperature 25 ℃
Hot air wind speed 0.5m / s
Wind direction Parallel to coated surface Drying time 2 minutes 2nd stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 2 minutes
After drying, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² under an oxygen concentration of 0.1% by volume. And cured. Furthermore, on the surface on which the coating composition 39 is coated, dried and cured, the coating composition 38 is applied using a bar coater (# 4), and then the first stage drying shown below is performed. The second stage of drying was then performed.
First stage Hot air temperature 25 ℃
Hot air wind speed 0.5m / s
Wind direction Parallel to coated surface Drying time 2 minutes 2nd stage Hot air temperature 130 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 2 minutes
After drying, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² under an oxygen concentration of 0.1% by volume. And cured to prepare an antireflection member of Comparative Example 7.

[Calculation of Component Y Dispersion, Solid Concentration of Particle Z Dispersion, and Component Y to Particle Z Mass Ratio]
Component Y dispersion, solid content concentration of the particles Z dispersions, each dispersion, after weighing about 2g on an aluminum dish (this mass and W ¹⁾ (for the mass and W ^2), 120 ° C. 1 hour drying in a hot air oven of, after cooling to room temperature in a desiccator, and weighed (this weight and W ^3), were determined solids concentration according to the following equation.
Solid content concentration = (W ³ −W ¹ ) / (W ² −W ¹ ) × 100
Component Y to particle Z mass ratio is:
Component Y part by mass = Component Y dispersion solid content concentration (%) x Component Y dispersion addition amount (part by mass)
Particle Z parts by mass = Particle Z dispersion solid content concentration (%) x Particle Z dispersion addition amount (parts by mass)
Component Y and particle Z mass = component Y part by mass / particle Z part by mass.

[Evaluation of antireflection member]
The following performance evaluation was performed on the manufactured antireflection member, and the obtained results are shown in Table 3. 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.

[Evaluation of interface state]
By observing the cross section using a transmission electron microscope (TEM), the presence or absence of an interface formed between the high refractive index layer and the low refractive index layer in the antireflection layer was determined. The presence / absence of the interface was determined according to the following method. An image taken at a magnification of 200,000 times with a TEM for an ultra-thin slice of the antireflection layer, with software (image processing software EasyAccess) so that the white balance falls within the 8-bit tone curve of the brightest and darkest parts Adjusted. Furthermore, the contrast was adjusted so that two types of particles could be clearly distinguished. At this time, when a clear boundary could be drawn between one layer and another layer, it was considered that there was a clear interface.
When a clear boundary can be drawn
“X” when a clear boundary cannot be drawn.

[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, and three or more points were accepted.
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 less than 2.0% was regarded as acceptable.

[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 less than 0.8% was accepted. The reflectivity showed a value when the local minimum value (minimum reflectivity) was reached near the wavelength of 550 nm.

Tables 1 and 2 summarize the composition of the coating composition, 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. Example 17 in which the mass ratio of the component Y and the particles Z is smaller than the preferred range of the present invention. In the surface treatment of the component Y, the value of (W ^B + W ^C ) / (W ^B + W ^C + W ^Y ) is a preferred range of the present invention. less than example 21, in W ^{B /} W ^C value is less example 28 than the preferred range of the present invention the surface treatment of the component Y, both wear resistance and abrasion resistance was slightly inferior However, it was an acceptable range. Example 20 in which the mass ratio of the component Y and the particles Z is larger than the preferred range of the present invention, and Example 24 in which the value of (W ^B + W ^C ) / (W ^B + W ^C + W ^Y ) is larger than the preferred range of the present invention. The transparency was slightly inferior, but it was in an acceptable range. In W ^{B /} W ^C value is preferably larger in Example 25 than the range of the present invention the surface treatment of the components Y, but the abrasion resistance and wear resistance, none of the transparency was slightly inferior, It was an acceptable range.

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.

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

Claims (7)

A coating composition comprising at least the following component X, component Y, and particles Z.
Component X: Particles obtained by surface treatment with fluorine compound A (hereinafter, this surface treatment is referred to as surface treatment X).
Fluorine compound A: R ¹ -R ⁷ -R ^f
Component Y: Particles obtained by surface treatment with compound B and compound C (hereinafter, this surface treatment is referred to as surface treatment Y).
Compound B: SiR ³ _n1 (OR ⁴ ) _4-n1
Compound _{^{C: R 2 -R 8 -SiR 5}} n2 (OR 6) 3-n2
Particle Z: Particle not subjected to surface treatment X and surface treatment Y.
Here, R ^f is a fluoroalkyl group, R ¹ and R ² are reactive sites, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, R ⁷ and R ⁸ are An alkylene group having 1 to 3 carbon atoms or an ester structure derived therefrom is shown. N1 and n2 each represent an integer of 0 to 2, and each may have a side chain in the structure. The coating composition according to claim 1, wherein the surface treatment X is a surface treatment of particles with the fluorine compound A and the compound D.
Compound D: R < ⁹ > -R < ¹² > -SiR < ¹⁰ _{> n3} (OR < ¹¹ >) _3-n3
Here, R ⁹ is a reactive double bond group, R ¹⁰ and R ¹¹ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, R ¹² is an alkylene group having 1 to 3 carbon atoms or an ester structure derived therefrom. Indicates. N3 represents an integer of 0 to 2, and each side chain may have a side chain in the structure. The coating composition according to claim 1 or 2, comprising a metal chelate compound. The coating composition according to claim 3, wherein the metal chelate compound is an aluminum-containing chelate compound. The coating composition according to any one of claims 1 to 4, wherein a mass ratio of the component Y and the particles Z is 0.05 or more and 4.0 or less. The coating composition according to any one of claims 1 to 5, wherein the surface treatment Y satisfies the following requirements.
0.1 <((W ^B + W ^C ) / (W ^B + W ^C + W ^Y )) <2.0
0.05 <W ^B / W ^C <0.95
Here, W ^B is the mass of compound B when surface treatment of the particles with component Y, W ^C is parts by weight of compound C when surface treatment of the particles with component Y, W ^Y surface of particles in component Y The mass part of the raw material particle at the time of processing is shown. By applying the coating composition according to any one of claims 1 to 6 once on at least one surface of a supporting substrate, a single-layer liquid film is formed to form an antireflection layer composed of two or more layers. The manufacturing method of the reflection preventing member characterized by including the process to do.

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