JP2003236970A - Antireflection layer with reinforced surface, antireflection material, and antireflection article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To simultaneously realize antireflection properties, coating film hardness and strength when an antireflection material or an antireflection article is to be made by forming a low reflective-index layer with a coating method. <P>SOLUTION: The antireflection material 1 with reinforced surface provides the solution against the problem by laminating the antireflaction layer consisting of the low reflective-index layer 3 and a hard-coat thinner layer 4 via a hard- coat layer 5 when required on a transparent base material 2. The material without the transparent base material 2 is, also, applicable to various base article. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection layer which can be applied to the surface of various articles to prevent light reflection and has a reinforced surface. The present invention also laminates an antireflection layer having a reinforced surface with a transparent substrate, and an antireflection material which can be applied to other articles or an antireflection layer having a reinforced surface is directly laminated on various substrates. It also relates to the antireflection body.

[0002]

2. Description of the Related Art Glass plates, plastic films, etc.
Utilizing these transparency, it is applied to the windows of buildings and vehicles that need to be seen through, and the surfaces of measuring instruments and display parts of various devices. In particular, on the surface of a display that displays data or video, they are often used as a surface material that normally constitutes a part of the display.

The surface material of the display is required to have high transparency in order to ensure the transparency, and to prevent the reflection of outside light such as indoor lighting or sunlight when it is outdoors. Sex is required.

Conventionally, a low refractive index layer having a lower refractive index than that of the surface to be provided with antireflection property is laminated, or a lower refractive index layer is used as the outermost surface, but a high refractive index layer is provided as a lower layer. And repeatedly stacking the low refractive index layer, or
An antireflection film is formed by sequentially laminating a high refractive index layer and a medium refractive index layer under the outermost low refractive index layer to realize antireflection property.

Methods for laminating the layers having various refractive indexes as described above are roughly classified into a vapor phase method and a liquid phase method. The vapor phase method includes a physical vapor phase method (PVD) such as a vacuum vapor deposition method and a sputtering method and a chemical vapor phase method (CVD), and it is possible to form a uniform, thin, and high quality layer. Although it is possible, the equipment used is relatively special, a vacuum system is required, the utilization efficiency of film forming raw materials is low, continuous processing and high-speed processing are difficult, and large area processing and processing of complicated shapes are performed. There is a disadvantage that it is difficult to obtain a large device suitable for. When forming the low refractive index layer, MgF ₂ (n = 1.38, n is the refractive index) and CaF are suitable materials for the vapor phase method.
₂ (n = 1.36) and so on, and it is difficult to obtain one having a lower refractive index than these.

The liquid phase method includes a plating method, an anodic oxidation method, and a sol-gel method, and the coating method is most widely used. When the coating method is used, the quality of the layer obtained is slightly inferior to the case of using the vapor phase method described above, but the equipment used is not complicated, the utilization efficiency of film forming raw materials is high, and continuous processing or high-speed processing is performed. There are advantages for

Among the film-forming materials for forming the low refractive index layer by the coating method, the resin component has a low refractive index,
A polymer containing a fluorine atom in its molecular structure may be used. However, in a polymer containing a fluorine atom in its molecular structure, when the content of the fluorine atom is increased, the refractive index decreases, but the hardness and strength of the surface of the obtained coating film also tend to decrease, and scratch resistance The sex is insufficient. Alternatively, there has been proposed a method of lowering the refractive index by allowing air having a refractive index of 1.0 in the form of voids, bubbles, or pores in the coating film to exist within a range not impairing the transparency of the film. (JP-A-58-161945, JP-A-60-2)
35745, JP-A-3-261047, JP-A-6-35.
01), the presence of air essentially reduces the mechanical strength of the coating, resulting in poor scratch resistance.

[0008]

In the present invention, the low refractive index layer is formed by the coating method as described above,
When obtaining an antireflection material or an antireflection body, it is an object to simultaneously realize antireflection properties, coating film hardness, and strength.

[0009]

According to the study of the inventor, the surface of a low refractive index layer formed by a coating method is laminated with a layer of high hardness and very thin, preferably thinner than the low refractive index layer. It was possible to obtain an antireflection layer which, while having improved hardness, does not impair the antireflection property.

A first invention is characterized in that a hard coat thin layer having a refractive index higher than that of the antireflection layer is laminated on the antireflection layer. It is about. A second aspect of the present invention relates to the surface-reinforced antireflection layer according to the first aspect, wherein the antireflection layer is a low refractive index layer. A third aspect of the present invention relates to the surface-enhanced antireflection layer as defined in the first aspect, wherein the antireflection layer is a multilayer having a low refractive index layer on the hard coat thin layer side. is there. In a fourth aspect based on the third aspect, the antireflection layer has a laminated structure of the low refractive index layer and a high refractive index layer below the low refractive index layer, and the surface is reinforced. The present invention relates to a coated antireflection layer. A fifth invention is characterized in that, in the third invention, the antireflection layer has a laminated structure in which a high refractive index layer and a medium refractive index layer are sequentially laminated on a lower layer side of the low refractive index layer. The present invention relates to an antireflection layer having a reinforced surface. A sixth invention is characterized in that, in any one of the first to fifth inventions, the low refractive index layer has a refractive index of 1.10 to 1.46 and a thickness of 30 to 150 nm. The present invention relates to an antireflection layer having a reinforced surface. In a seventh aspect based on any one of the first to sixth aspects, the hard coat thin layer has a refractive index of 1.30 to 1.
60, which is 0.14 more than the refractive index of the low refractive index layer.
~ 0.28 larger and 5-50 nm thick,
The present invention relates to an antireflection layer having a reinforced surface, which is ½ or less of the thickness of the low refractive index layer.
An eighth invention is the ionizing radiation according to any one of the first to seventh inventions, wherein the hard coat thin layer contains a thermosetting resin composition containing a thermosetting resin and / or an ionizing radiation curable resin. The present invention relates to an antireflection layer having a reinforced surface, which is composed of a cured resin composition composed of a cured product of a curable resin composition. A ninth aspect of the present invention relates to the surface-reinforced antireflection layer according to the eighth aspect, wherein the cured resin composition contains a polyfunctional acrylate. A tenth aspect of the present invention relates to the surface-reinforced antireflection layer according to the ninth aspect, wherein the cured resin composition contains a polysiloxane component. An eleventh invention relates to the surface-reinforced antireflection layer in the ninth or tenth invention, wherein the cured resin composition contains urethane acrylate.
A twelfth invention relates to the antireflection layer having a reinforced surface according to any one of the eighth to eleventh inventions, characterized in that the thin hard coat layer further contains ultrafine inorganic particles. is there. The thirteenth invention is the first
In any one of the twelfth invention, a surface-enhanced reflection characterized in that a hard coat layer is further laminated on the side opposite to the hard coat thin layer of the antireflection layer. It relates to the prevention layer. First
The invention of No. 4 relates to the antireflection layer having a strengthened surface, characterized in that, in the fourth or fifth invention, the lowermost layer constituting the antireflection layer also serves as a hard coat layer. A fifteenth invention is that a transparent base material is laminated on the opposite side of the surface-reinforced antireflection layer according to any one of the first to fourteenth inventions from the side where the hard coat thin layer is laminated. The present invention relates to an antireflection material having a reinforced surface. A sixteenth invention is characterized in that a substrate is laminated on the opposite side of the surface-enhanced antireflection layer of any one of the first to fourteenth inventions from the laminated hard coat thin layer. The present invention relates to an antireflection body having a reinforced surface.

[0011]

1 is a sectional view showing a laminated structure of a typical antireflection material to which an antireflection layer of the present invention is applied. As shown in FIG. 1A, the antireflection material 1 is
For example, it has a laminated structure in which the low refractive index layer 3 and the hard coat thin layer 4 are sequentially laminated on the transparent base material 2. In this case, the low refractive index layer 3 and the hard coat thin layer 4 are , An antireflection layer having a reinforced surface. In addition, including the following, "upper" refers to the observation side,
"Down" shall mean the side opposite to the viewing side.

Alternatively, as shown in FIG. 1B, in the antireflection material 1 of the present invention, a hard coat layer 5 is laminated on a transparent substrate 2, and the surface of the hard coat layer 5 is reinforced. The antireflection layer may be laminated, that is, the low refractive index layer 3 and the hard coat thin layer 4 may be sequentially laminated.

In order to exert the antireflection property, it is necessary to laminate a layer having a refractive index lower than that of the target surface. More specifically, in the laminated structure shown in FIG. The low refractive index layer 3 having a refractive index lower than that of the base material 2 is laminated. However, when the transparent substrate 2 is used as a reference, the low refractive index layer 3 can be regarded as an antireflection layer. Therefore, including the following, as a general rule, the portion excluding the transparent substrate 2 and the uppermost hard coat thin layer 4 is excluded. Considered as an antireflection layer.

FIG. 2 shows the antireflection layer 6 in that sense.
It is a figure which shows the variation of. In either case, the transparent base material 2 in FIG.
It may be accompanied by the transparent substrate 2 and the hard coat layer 5 in (b), and the hard coat thin layer 4 is shown on the upper side of the figure.
Can be accompanied by.

The antireflection layer 6 shown in FIG. 2 (a) is composed of only the low refractive index layer L, which is the same as that shown in FIG. 1 (a).

The antireflection layer 6 shown in FIG. 2 (b) has a multilayer structure in which a high refractive index layer H and a low refractive index layer L are laminated from the bottom. Although not shown, the high refractive index layer H and the low refractive index layer L are further repeated from the lower side, and the high refractive index layer H, the low refractive index layer L, the high refractive index layer H, the low refractive index layer L,
You may repeat like .... However, the uppermost layer is always the low refractive index layer L. The lowermost high refractive index layer H may also serve as the hard coat layer 5.

The antireflection layer 6 shown in FIG. 2C may have a multi-layered structure in which a middle refractive index layer M, a high refractive index layer H, and a low refractive index layer L are stacked from the bottom. Good. Although not shown, from the bottom, the medium refractive index layer M, the high refractive index layer H, the low refractive index layer L, the medium refractive index layer M, the high refractive index layer H, the low refractive index layer L, ... May be. However, again, the uppermost layer is always the low refractive index layer L. The lowermost middle refractive index layer M may also serve as the hard coat layer 5.

Therefore, the antireflection material 1 of the present invention has the antireflection layer 6 and the hard coat, which may have a multilayer structure on the transparent substrate 2 with or without the hard coat layer 5 interposed therebetween. The thin layers 4 are laminated in this order, and the antireflection layer 6 is such that the surface on the side in contact with the hard coat thin layer 4 is always the low refractive index layer 3 (or L). Therefore, the laminated structure shown in FIG. 1A is the simplest. Hereinafter, first, the antireflection member 1 having the laminated structure shown in FIG. 1A will be described, and then the other structures will be sequentially described.

The material of the transparent substrate 2 may be a transparent resin film or a transparent resin sheet, a transparent resin plate (eg acrylic resin plate) or a transparent glass plate, but industrially,
It is preferable to use a flexible transparent resin film that can be easily processed continuously. Since the transparent substrate 2 may be colored and transparent depending on the application, the term “transparent” here includes both colorless and colored transparent.

Examples of the transparent resin film or transparent resin sheet include triacetyl cellulose (abbreviated as TAC and cellulose triacetate), diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, acrylic or methacrylic type, polyurethane type, Polyester such as polyethylene terephthalate, polycarbonate, polysulfone, polyether,
Cyclic polyolefins such as trimethylpentene, polyetherketone, (meth) acrylonitrile and polynorbornene, and thermoplastic resins such as polyimide, polyamide, polyamideimide or polysiloxane can be used. It should be noted that the term (meta) is used to mean both an item with meta and an item without meta.

The above-mentioned film or sheet made of a thermoplastic resin is flexible and easy to use, but it does not need to be bent even during handling, and when a hard material is desired, a plate of the above resin or a glass plate is used. Plate-shaped ones can also be used. The thickness of the transparent substrate 2 is preferably about 8 to 1000 μm when a flexible one is desired, but may exceed this range in the case of a sheet-shaped product or a plate-shaped product. Further, the transparent base material 2 is usually flat, but when the transparent base material 2 constitutes a surface material of various articles, it has an uneven shape or a three-dimensional shape for that purpose. May be. The transparent substrate 2 may be subjected to various treatments for the purpose of improving the adhesiveness on the side on which the antireflection layer is laminated. Further, the side other than the side on which the antireflection layer is laminated may be processed to be a surface material for various articles.

The low refractive index layer 3 is a resin formed by coating with a suitable transparent resin for paint and a low refractive index layer-forming coating composition containing low refractive index particles, preferably ultrafine particles. It consists of a composition. Alternatively, the low-refractive index layer 3 is formed by using a coating composition prepared with or without a low-refractive-index resin component having a low refractive index of its own, with inorganic particles or ultrafine inorganic particles. And a resin composition.

Examples of low-refractive-index inorganic particles or ultrafine inorganic particles include, for example, LiF, MgF ₂ , and 3NaF.
AlF ₃ or AlF ₃ (N = 1.
4), Na ₃ AlF ₆ (cryolite, n = 1.33), or SiO _x (1.50 ≦ x ≦ 2.00, n = 1.35)
1.48) and the like, and a coating composition is prepared using particles or ultrafine particles selected from the above, coated on the transparent substrate 2, and dried to solidify to obtain a low refractive index. The rate layer 3 can be used. Examples of low refractive index particles or ultrafine particles include fluororesin and silicone resin alone, or resin particles containing these resins. These have a refractive index of 1.30
It can be preferably used in the range of ˜1.46.

However, the transparent resin for general paints does not have a very low refractive index, and it is more preferable to use a paint composition prepared by using a fluorine-containing polymer or a fluorine-containing oligomer as a resin component. Forming the refractive index layer 4 is preferable in terms of realizing a low refractive index.

The fluorine-containing polymer or fluorine-containing oligomer is obtained by polymerizing or copolymerizing a fluorine-containing monomer having an ethylenically unsaturated bond. Examples of the fluorine-containing monomer having an ethylenically unsaturated bond include fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene ethylene, perfluorobutadiene, and perfluoro-2,2-dimethyl-1,3-dioxole. Fluoroolefins, fully or partially fluorinated alkyl, alkenyl, or aryl esters of acrylic acid or methacrylic acid (“Chemical formula 1” or “Chemical formula 2” below), and further, fully or partially fluorinated vinyl ethers, complete Alternatively, partially fluorinated vinyl esters, completely or partially fluorinated vinyl ketone and the like can be mentioned.

[0026]

[Chemical 1]

[0027]

[Chemical 2]

However, in the above formula "Chemical formula 1", R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ^f represents a fully or partially fluorinated alkyl group, alkenyl group, heterocycle, or aryl group. R ² and R ³ are each independently a hydrogen atom,
It represents an alkyl group, an alkenyl group, a hetero group, an aryl group, or a group defined by the above R ^f . R ¹ , R ² , R ³ , and R ^f may each have a substituent other than a fluorine atom. Further, arbitrary two or more groups may be bonded to R ² , R ³ and R ^f to form a ring structure.

In the above formula "Chemical formula 2", A represents a completely or partially fluorinated n-valent organic group. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ⁴ may have a substituent other than a fluorine atom. n represents an integer of 2-8. )

When a fluorine-containing polymer having a polymerizable functional group capable of polymerizing with each other and a fluorine-containing monomer and / or oligomer are combined, the fluorine-containing polymer improves the film-forming property of the coating composition for coating, Crosslink density and coating suitability are improved by the contained monomer and / or oligomer, and the balance of both components makes
It is preferable because the hardness and strength of the coating film are realized. In particular, the fluorine-containing polymer has a number average molecular weight of 20,
000 to 100,000 and a number average molecular weight of 2 as a fluorine-containing monomer and / or oligomer.
It is more preferable to use a combination of 10,000 or less because it is easy to balance various physical properties including coating suitability, film-forming property, coating film hardness, coating film strength and the like. When the refractive index of the fluoropolymer is sufficiently low, it is preferable to combine with a monomer and / or oligomer not containing fluorine because the strength of the coating film can be more easily improved. Fluorine-free monomer,
Examples of the oligomer include radically polymerizable monomers and oligomers having an ethylenically unsaturated bond, which will be mentioned later as a material for forming the hard coat thin layer 4.

In the above, as the fluorine-containing monomer or oligomer, a homopolymer or copolymer composed of one or more selected from the above-mentioned fluorine-containing monomers, or a fluorine-containing monomer as described above is used. With one or more selected types,
A copolymer with one or more fluorine-free monomers that do not contain fluorine can be used.

Fluorine-containing monomers having no polymerizable functional group can also be used. Specifically, polytetrafluoroethylene, 4-fluoroethylene-6-fluoropropylene copolymer, 4-fluoroethylene- Perfluoroalkyl vinyl ether copolymer, 4-fluoroethylene-ethylene copolymer, polyvinyl fluoride, polyvinylidene fluoride, fully or partially fluorinated alkyl, alkenyl, or aryl ester of acrylic acid or methacrylic acid (for example,
Polymers or copolymers of the above "Chemical formula 1" or "Chemical formula 2", fluoroethylene-hydrocarbon vinyl ether copolymers, or fluorine-modified epoxy, polyurethane, cellulosic, phenol, polyimide, or silicone Resin can be mentioned. In addition, amorphous transparent fluororesin (trade name of Asahi Glass Co., Ltd .;
"Cytop" etc.) can also be used. In order to improve the mechanical strength of the low refractive index layer 3, the low refractive index layer 3
It is effective to improve the adhesion between the lower layer and the lower layer, and for that purpose, any of the resin components constituting the coating composition for forming a low refractive index layer has a hydroxyl group, a carboxyl group, an amino group, an amide group, or the like. It is preferable that the polar group of is introduced.

When the low refractive index layer 3 is formed using the coating composition prepared by using the above-mentioned fluorine-containing polymer, fluorine-containing oligomer or the like as a resin component, the particles having the low refractive index described above should be used. You can From the viewpoint of ensuring more transparency, it is more preferable to contain ultrafine particles.

Here, the ultrafine particles are smaller than those generally called fine particles having a particle diameter of several μm to several 100 μm. The specific particle size of the ultrafine particles used in the present invention is different from the optical performance required depending on the application, so it is difficult to say unconditionally, but the primary particle size is preferably in the range of 1 nm to 500 nm. Even if a primary particle size of less than 1 nm is used, the hardness and strength of the coating film are not improved. The primary particle size is 50
If it exceeds 0 nm, the transparency of the coating film is impaired, and it may not be used at all depending on the application. The ultrafine particles may be spherical, needle-like, or any other shape as long as they can be uniformly dispersed in the resin and the hardness and strength of the coating film can be secured.

The low refractive index layer 3 has a refractive index of
The thickness is preferably 1.10 to 1.46, and the thickness is preferably 30 to 150 nm.

The hard coat thin layer 4 is laminated on the surface of the antireflection layer 6 to improve the hardness and strength of the surface of the antireflection layer. The hard coat thin layer 4 mainly comprises a resin component, or more preferably comprises a resin component and inorganic ultrafine particles. The resin component for forming the hard coat thin layer 4 may be a thermoplastic resin depending on the degree of demand, but is a thermosetting resin or an ionizing radiation curable resin in the sense of ensuring hardness and strength. Is more preferable. Where "hard coat thin layer"
Is a pencil hardness test obtained by coating a coating composition and having a surface hardness of JIS K5400,
It indicates a hardness of at least H or more and a very thin thickness, for example, a few nm to a few tens nm.

As the thermosetting resin, phenol resin,
A urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, an aminoalkyd resin, a melamine-urea co-condensation resin, a silicon resin, a polysiloxane resin and the like can be used. These resins are used by adding a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc., if necessary.

The ionizing radiation-curable resin may be any one of photopolymerization and thermal polymerization in terms of reaction energy, and radical polymerization, cationic polymerization, or anion in terms of active species. It may belong to any of the polymerizations. When it contains an ethylenically unsaturated bond, photoradical polymerization and thermal radical polymerization are possible, and when it contains an epoxy group, thermosetting and photocationic polymerization are possible. In particular, when it contains an ethylenically unsaturated bond, it is polymerized directly by irradiation with visible light, ionizing radiation (ultraviolet rays or electron beams), other invisible light, or indirectly by the action of an initiator. Therefore, as in the case of photo-curing, handling from application to curing becomes easy, which is particularly preferable.

As those containing an ethylenically unsaturated bond, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polyolefin, polystyrene, polyamide, polyimide, polyvinyl chloride,
An example of the reaction-curable polymer is an unreactive polymer having no polymerizable functional group, such as polyvinyl alcohol, polyvinyl butyral, or polycarbonate, into which an ethylenically unsaturated bond is introduced.

Further, those containing an ethylenically unsaturated bond include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate and carboxy. Monofunctional (meth) acrylates such as polycaprolactone (meth) acrylate, acrylic acid, methacrylic acid, or acrylamide, ethylene glycol diacrylate, or diacrylates such as pentaerythritol diacrylate monostearate, trimethylolpropane triacrylate, or penta. Radical polymerizable compounds such as triacrylates such as erythritol triacrylate and polyfunctional acrylates such as pentaerythritol tetraacrylate. Mer, or it can be exemplified oligomers these polymerizable monomers are polymerized. In particular, it is more preferable to use a polyfunctional acrylate in order to improve the crosslink density. Further, a polymer having a (meth) acryloyl group introduced therein and a polymer such as a silicone resin can also be preferably used as long as the physical properties of the hard coat thin layer 4 are not deteriorated.

When the above radical-polymerizable oligomer or monomer having an ethylenically unsaturated bond is used, a photo-radical polymerization initiator is added, if necessary. As the photo-radical polymerization initiator, acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, lower oxides, 2,3
-Dialkyldione compounds, disulfide compounds,
A thiuram compound, a fluoroamine compound, or the like can be used, and 3 to 8 (mass ratio) is preferably added to the above radically polymerizable oligomer and monomer 100.

Specific examples of the radical photopolymerization initiator include:
1-Hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals Co., Ltd., trade name; available as Irgacure 184), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane- 1-one (Ciba Specialty Chemicals Co., Ltd., trade name; available as Irgacure 907), benzyl dimethyl ketone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1
-One, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)
2-Hydroxy-2-methylpropan-1-one, benzophenone and the like can be exemplified, and one kind or a combination of two or more kinds can be used.

The ionizing radiation curable resin composition and the thermosetting resin composition may be used in combination with a polysiloxane component, more specifically, several types of organic reactive silicon compounds such as the following. . When an organic reactive silicon compound is used in combination, the hardness and strength of the coating film are maintained, the slipperiness of the coating film surface increases, scratch resistance is improved, and the release property is imparted to the surface. There is an advantage that the property is improved.
In any of the ionizing radiation curable resin composition and the thermosetting resin composition, a hydroxyl group as a resin component,
It is possible to further improve the hardness and strength of the coating film by using a product introduced with a polar group such as a carboxyl group, an amino group, or an amide group because it forms a covalent bond with the organic reactive silicon compound. Therefore, it is more preferable.

One of the organosilicon compounds has the general formula R _m Si
(OR ') _n , where R and R'have 1 carbon
Each of the subscript m of R and the subscript n of OR ′ represents an alkyl group of 10 to 10 and is an integer satisfying the relationship of m + n = 4.

Specifically, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane. , Tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-
Butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, dimethylethoxysilane,
Dimethylmethoxysilane, dimethylpropoxysilane,
Examples thereof include dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane and hexyltrimethoxysilane.

The organosilicon compound 2 which can be used in combination with the ionizing radiation curable resin composition and the thermosetting resin composition is a silane coupling agent.

Specifically, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Methacryloxypropyl methoxysilane, N-β-
(N-Vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, aminosilane, methylmethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Examples thereof include chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, methyltrichlorosilane and dimethyldichlorosilane.

The organosilicon compound 3, which can be used in combination with the ionizing radiation curable resin composition and the thermosetting resin composition, is an ionizing radiation curable silicon compound. Specific examples thereof include a plurality of functional groups that react and crosslink upon irradiation with ionizing radiation, for example, an organosilicon compound having a molecular weight of 5,000 or less and having a polymerizable double bond group, and more specifically, one end thereof. Examples thereof include vinyl-functional polysilanes, vinyl-functional polysilanes at both ends, vinyl-functional polysiloxanes at both ends, vinyl-functional polysiloxanes at both ends, or vinyl-functional polysilanes obtained by reacting these compounds, or vinyl-functional polysiloxanes. More specifically, they are the following compounds.

[0049]

[Chemical 3]

In the ionizing radiation curable resin composition and the thermosetting resin composition, an organometallic compound represented by the general formula A _n MB _xn may be used in combination with the above-mentioned organic reactive silicon compound. Good. In this general formula, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, M represents a metal atom, and B represents an atomic group covalently or ionically bonded to the metal atom M. . Also, B
X in the subscript x-n of is the valence of the metal atom M, and n which is also the subscript of A represents an integer of 2 or more and x or less. Examples of the hydrolyzable functional group A include an alkoxy group, a halogen such as chlorine atom, an ester group, or an amide group.

In the present invention, among the metal compounds represented by the above general formula, it is preferable to use an alkoxide having two or more alkoxy groups directly bonded to a metal atom, or a chelate thereof, because it is easy to handle and materials. From the viewpoint of cost, titanium alkoxide, zirconium alkoxide, or aluminum alkoxide,
Alternatively, it is more preferable to use a corresponding chelate thereof.

The titanium alkoxide has the general formula Ti
It is represented by (OR) ₄ , and R is an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms.
Specifically, tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-iso.
-Propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, or tetra-te
Examples thereof include rt-butoxy titanium.

Zirconium alkoxide has the general formula Zr
It is represented by (OR) ₄ , and R is an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms.
Specifically, tetramethoxy zirconium, tetraethoxy zirconium, tetra-n-propoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, or tetra-tert-butoxy zirconium. Can be mentioned.

Aluminum alkoxide has the general formula Al
It is represented by (OR) ₃ and R is an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms.
Specifically, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, or the like is used. Can be mentioned.

Preferred chelating agents for forming the corresponding chelate of the above-mentioned titanium alkoxide, zirconium alkoxide, or aluminum alkoxide are alkanolamines such as diethanolamine or triethanolamine, ethylene glycol, diethylene glycol, or dipropylene. Glycols such as glycol, acetylacetone, ethyl acetoacetate and the like, which have a molecular weight of 10,000 or less, can be exemplified, and per mol of metal atom of a free metal compound for coordinating these chelating agents. It is preferably used in a proportion of 0.1 mol to 2 mol. When the ratio of the chelating agent is less than 0.1 mol, the stabilizing effect is insufficient, and when the ratio of the chelating agent exceeds 2 mol, the chelating agent which is not consumed for the formation of the chelate remains and the ionizing radiation cures. Since it exists as an impurity of an organic substance when it is blended in the functional resin composition, the strength and transparency of the obtained coating film are likely to decrease. By using these chelating agents, it is possible to form a chelated product which is stable against the inclusion of water and has an excellent reinforcing effect on the coating film.

A urethane acrylate, particularly polyurethane acrylate, may be used in combination with the ionizing radiation curable resin composition. Generally speaking, acrylates, especially polyfunctional acrylates, give coating films with excellent hardness, but on the other hand, the impact resistance of the coating film becomes low and it becomes brittle. However, by adding polyurethane acrylate, impact resistance is improved. Is improved and the coating film becomes flexible.

The hard coat thin layer 4 may contain the above-mentioned resin component as a main component, but it is more preferable that the hard coat thin layer 4 further contains inorganic fine particles or inorganic ultrafine particles. Which has a high refractive index (refractive index n = 1.9 to 2.3), zirconia (n = 1.6 to 2.0), zinc oxide (n = 1.6).
.About.2.0), alumina (n = 1.5 to 1.7), tin oxide (n = 1.7 to 2.0), indium-doped tin oxide (= ITO, n = 1.6 to 1.9). ), Antimony-doped tin oxide (= ATO, n = 1.6 to 1.9), aluminum-doped zinc oxide (= AZO, n = 1.7 to 2.0).
Etc. can be used as long as they are within the range of the refractive index required for the hard coat thin layer 4. Further, when these inorganic fine particles having a high refractive index or inorganic ultrafine particles show conductivity, the hard coat thin layer 4 can be used as a conductive layer, and by extension, the surface layer of the antireflection layer, and further the antireflection. This is preferable because it can impart conductivity to the material and, as a result, impart antistatic performance.

The hard coat thin layer 4 is prepared by adding a solvent, an ultraviolet blocking agent, an ultraviolet absorbing agent, a surface preparation agent (leveling agent), or other additives, if necessary, in addition to the above-mentioned components. It can be formed by coating with a coating composition. As a coating method, a roll coating method, a gravure coating method, a slide coating method, a spray coating method, a dip coating method, a screen printing method, or the like can be used.

The hard coat thin layer 4 preferably has a refractive index of 1.30 to 1.60 and a thickness of 5 to 50 nm. If the thickness is less than 5 nm, the surface hardness and strength cannot be sufficiently obtained, and if the thickness exceeds 50 nm, the antireflection property is deteriorated. The hard coat thin layer 4 and the lower low-refractive index layer 3 not only define the thickness and refractive index of each layer, but also the thickness of the hard coat thin layer 4 has a low refractive index. It is preferable that the thickness is 1/2 or less of the thickness of the layer 3, and the refractive index of the hard coat thin layer 4 is 0.14 to 0.
28 is preferable.

In the present invention, the hard coat thin layer 4 having a refractive index higher than that of the low refractive index layer 3 is further laminated on the outermost low refractive index layer 3 which originally realizes low reflectivity. At first glance, it seems that antireflection properties are impaired. However, in practice, the low refractive index layer 3 and the hard coat thin layer 4 are
When the light reflectance is measured by laminating a laminated object on a reflective object, the wavelength is less than 450 nm, and the reflectance is particularly high in the ultraviolet region as compared with the case without the hard coat thin layer 4. However, in the visible range, there is virtually no increase in reflectance, and the appearance is not dazzling. Generally, it is only the reflection of visible light that people feel glare at reflected light.
Especially, since the reflectance at a wavelength of 550 nm, which has high eye sensitivity, becomes a problem, even if the reflectance increases in the ultraviolet region,
This is because it does not lead to the glare seen by people.
In addition, as an object to be subjected to such antireflection, particularly in a display-related matter, it is necessary to shut out ultraviolet light in order to extend the life of the display, and other objects also do not transmit ultraviolet light. Since it is not preferable, it can be said that the increase of reflectance in the ultraviolet region is rather preferable.

As described above, the antireflection material 1 of the present invention.
Is between the transparent substrate 2 and the low refractive index layer 3, in other words,
The hard coat layer 5 may be interposed between the transparent substrate 2 and the antireflection layer 6. When the antireflection layer 6 has the simplest configuration, the antireflection material 1 is a transparent substrate 2 on which a hard coat layer 5, a low refractive index layer 3, and a hard coat thin layer 4 are sequentially laminated. .

The hard coat layer 5 is originally for improving the hardness of the surface of the antireflection layer 6 provided on the transparent substrate. When the low refractive index layer 4 is formed by the liquid phase method as in the present invention, the influence of the properties of the hard coat layer 5 on the antireflection layer is smaller than that in the case of the vapor phase method.

The hard coat layer 5 can be formed by using the same material as that of the hard coat thin layer 4 described above except that the hard coat layer 5 is provided with a relatively large thickness. Hard coat layer 5
As an example, the thickness is 0.5 μm or more, and preferably 20 μm or less.

The hard coat layer 5 is composed of a resin component having a relatively high refractive index, as compared with a low refractive index layer which is often composed of a resin component of a low refractive index layer, and Even if the inorganic ultrafine particles are used, the refractive index is less likely to decrease. Therefore, from the viewpoint of the refractive index, it often becomes a high refractive index layer in relation to the low refractive index layer. Needless to say, a layer having a higher refractive index can be obtained by incorporating particles having a high refractive index, preferably ultrafine particles. Therefore, by adjusting the refractive index and / or the compounding amount of the inorganic fine particles when forming the hard coat layer 5, two kinds of hard coat layers having different refractive indexes can be formed, so that the refractive index on the lower layer side can be formed. Is relatively low and the refractive index of the upper layer is relatively high, thereby forming two layers of a medium refractive index layer (which can also be seen as a hard coat layer) and a high refractive index layer from the lower layer side. You can also do it.

As described above, the antireflection layer 6 of the present invention is formed on the transparent base material 2 as an antireflection material. As a more common example, a transparent base film is used as a base material to form an antireflection film. be able to. Such an antireflection material can be applied to a window of a building, a window portion provided in a box or a case, and used as a window material. Also, by arranging it on the front surface of various displays or by using a transparent base material on the entire surface of the display as a base material, it is possible to prevent the reflection of external light such as illumination light or sunlight when visually recognizing the display. The visibility of the display content of can be improved.

By the way, the antireflection layer 6 (which may be accompanied by a hard coat layer, and the same hereinafter) is not formed only on the transparent substrate 2, but is applied to a substrate that is not necessarily transparent, or rather an opaque substrate. You can also do it. Of course, an antireflection material in which the antireflection layer 6 is applied to a transparent base material may be applied on such an opaque base material, but the opaque base material itself is used as a base material, and the base material is originally It is also possible to use an antireflection body in which the reflection of the surface that is normally held is prevented. In other words, the present invention can also be used as an antireflection body in which various articles are used as a base and an antireflection layer is applied, and the base has an uneven shape or a three-dimensional shape as in the case of a transparent base material. May be.

The antireflection layer 6 is usually formed on the transparent base material or the base material which is not necessarily transparent as described above, because the layer formation target is required. As a constitution of the transfer sheet in which the hard coat thin layer 4, the antireflection layer 6, and, if necessary, the hard coat layer 5 and the adhesive layer are sequentially laminated on the peelable surface of It can be applied to a transparent substrate or a substrate that is not necessarily transparent.

[0068]

Example A polyethylene terephthalate resin (= PET) film having a thickness of 188 μm and having a surface subjected to an easy-adhesion treatment was prepared, and a low refractive index layer was formed on the side of the easy-adhesion treatment.
And a hard coat thin layer sequentially laminated, and a hard coat layer, a low refractive index layer, and a hard coat thin layer sequentially laminated. As a hard coat layer,
The UV-curable polyfunctional acrylate compound and the thermosetting silicone-based compound are used. The low refractive index layer has two refractive indices n of 1.43 and 1.41. As the hard coat thin layer, four kinds having a refractive index n of 1.46, 1.43, 1.50 and 1.60 were prepared as follows, and reflected by various combinations of these layers. A protective film was created.

(Formation of Hard Coat Layer (1)) A composition (1) for forming a hard coat layer having the following composition is prepared, bar-coated and dried to remove the solvent, and then an ultraviolet irradiation device (fusion) is used. UV Systems Japan Co., Ltd.
Manufactured by a light source; H bulb), and irradiated and cured under the condition of an irradiation dose of 300 mJ to form a transparent hard coat layer (1) having a film thickness of 4 μm. The number of parts and the blending ratio are based on the mass, including the following. (Composition (1) for forming hard coat layer) -Pentaerythritol tetraacrylate 20.0 parts-Photopolymerization initiator 1.0 part (Ciba Specialty Chemicals Co., Ltd., trade name; Irgacure 184) -Methylisobutyl 80 parts of ketone

(Formation of Hard Coat Layer (2)) A silicone-based thermosetting transparent coating composition (manufactured by Japan AR Co., Ltd., trade name: Crystal Coat TH) is bar-coated and dried to remove the solvent. And then 100 ℃
The mixture was heated at the temperature of 2 hours for curing to form a transparent hard coat layer (2) having a film thickness of 4 μm.

(Formation of Low Refractive Index Layer (1)) Tetraethoxysilane, ethyl alcohol, deionized water, and hydrochloric acid were mixed in this order at a compounding ratio of 1/80/3 / 0.2, and the mixture was mixed at room temperature for 4 hours. Bar coating using the one that has been hydrolyzed as it is, drying to remove the solvent,
The coating was heated at a temperature of 120 ° C. for 1 hour for curing to obtain a low refractive index layer (1) composed of a cured coating film having a refractive index of 1.43.

(Formation of Low Refractive Index Layer (2)) Fluorine-based UV-curable coating composition (manufactured by JSR Corporation, trade name: OPSTAR JM5010) is bar-coated, dried to remove the solvent, and then UV-rayed. Using an irradiation device (Fusion UV Systems Japan KK, light source; H bulb),
Irradiation dose: 300 mJ was irradiated and cured to obtain a low refractive index layer (2) having a refractive index of 1.41.

(Formation of Hard Coat Thin Layer (1)) A polysilazane-based thermosetting coating composition (manufactured by Clariant Japan KK, trade name; polysilazane L110) was bar-coated and dried to remove the solvent. After 120
It is heated at a temperature of ℃ for 1 hour to cure, and the refractive index is 1.46.
A thin hard coat layer (1) was obtained.

(Formation of Hard Coat Thin Layer (2)) Bar coating was performed using a polysiloxane-based UV curable coating composition (GE Toshiba Silicone Co., Ltd., trade name: UVHC8558), and the solvent was removed by drying. UV irradiation device (Fusion UV Systems Japan Co., Ltd.)
Manufactured by a light source; H bulb) and irradiated under the condition of an irradiation dose of 300 mJ and cured to obtain a low refractive index layer (2) having a refractive index of 1.43.

(Formation of Hard Coat Thin Layer (3)) Polyfunctional acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA (dipentaerythritol hexaacrylate)) / urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., product Name; UV
-1700B) = 1/2, and using the ultraviolet-curable coating composition mixed in a mixing ratio of 1, the hard coat thin layer having a refractive index of 1.50 was formed in the same manner as the formation of the above hard coat thin layer (2). 3) was obtained.

(Formation of hard coat thin layer (4)) Polyfunctional acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA (dipentaerythritol hexaacrylate) / urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name) UV-
1700B) / titania ultrafine particle dispersion liquid (Taika Co., Ltd.)
Manufactured by the trade name; TKS-251) = 1/2/1, and using a UV-curable coating composition mixed in a mixing ratio of 1, the refractive index is 1 as in the formation of the hard coat thin layer (2). .6
A low refractive index layer (4) of 0 was obtained.

The film thicknesses of the low refractive index layer and the hard coat thin layer, when measured using a spectrophotometer (manufactured by Shimadzu Corporation), have a minimum reflectance value near a wavelength of 550 nm. Was set.

(Adhesiveness of Low Refractive Index Layer and Hard Coat Thin Layer) Adhesiveness of the low refractive index layer and hard coat thin layer was evaluated. The low-refractive index layers (1) and (2) described above were laminated on the easy-adhesion treated surface of the easy-adhesion PET film, and the hard coat layer (1) was laminated on the easy-adhesion treated surface of the easy-adhesion PET film. What was laminated on top (the base material is the hard coat layer (1)), and what was laminated on top of the hard coat layer (2) was laminated on the surface of the easy adhesion PET film which was treated for easy adhesion (the base material was the hard coat layer ( 2)) is prepared,
The results of evaluation of adhesion by a cross-cut peeling test using cellophane tape are shown in "Table 1" below. In Table 1, ◎
Indicates no peeling, ○ indicates slight peeling, and Δ indicates slightly noticeable peeling.

[0079]

[Table 1]

Further, the low-refractive index layer (1) or (2) laminated on the easy-adhesion treated surface of the easy-adhesion PET film, and the hard coat thin layers (1) to (1) to The results obtained by preparing a laminate of (4) and evaluating the adhesion by a cross-cut peeling test using cellophane tape are shown in "Table 2" below. In the table, "HC thin layer"
Indicates a hard coat thin layer, and the meanings of ⊚, ◯, and Δ are the same as those in “Table 1”.

[0081]

[Table 2]

An antireflection film was prepared by combining the respective conditions A to C. That is, A (base material); a PET film without a hard coat layer (PET in the table), a laminate of hard coat layers (1) (HC layer (1) in the table), and hard coat layer (2) (HC layer (2) in the table), B (low refractive index layer, low n in the table)
Layer); low refractive index layer (1), or (2), C (hard coat thin layer, HC thin layer in the table); hard coat thin layer (1), (2), (3), or (4) Under each condition. By combining these conditions, a PET film, a low refractive index layer, and a hard coat thin layer are laminated, and a PET film, a hard coat layer, a low refractive index layer, and a hard coat thin layer are laminated, An evaluation was performed.

The two evaluation items are reflectance and film strength. The reflectance is a spectrophotometer (made by Shimadzu Corporation)
Wavelength at 550 nm, which is measured by using, and the reflectance is preferably 1.2% or less, although it depends on the application. In addition, when the haze was changed by rubbing 20 times with a constant load using # 0000 of steel wool and measuring with a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: NDH2000) The weight (unit: g) of the weight value of was used as the film strength. The film strength is preferably 200 g or more for applications where it is easily touched by human hands and the like, but even if it is less than 200, it can be used for applications in which it is infrequently touched by human hands and the like. The following "Table 3" to "Table 5" relate to Examples, and "Table 6" relates to Comparative Examples. In the table, the numbers in parentheses at the bottom of each column for low n layer and HC thin layer are
The film thickness (unit: nm) of each layer.

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

According to the invention of claim 1, since the hard coat thin layer having a higher refractive index than that is laminated on the antireflection layer, there is substantially no deterioration in the antireflection property. It is possible to provide a surface-reinforced antireflection layer having high surface hardness and strength. According to the invention of claim 2, in addition to the effect of the invention of claim 1, it is possible to provide a surface-reinforced antireflection layer having a simple laminated structure of a low refractive index layer and a hard coat layer. . According to the invention of claim 3, in addition to the effect of the invention of claim 1, it is possible to provide an antireflection layer having a reinforced surface, in which the antireflection layer has a multilayer structure. According to the invention of claim 4, in addition to the effect of the invention of claim 3, the antireflection layer having a strengthened surface, wherein the antireflection layer has a laminated structure of a plurality of layers of a high refractive index layer and a low refractive index layer. Can be provided. According to the invention of claim 5, in addition to the effect of the invention of claim 3,
It is possible to provide an antireflection layer having a reinforced surface, in which the antireflection layer has a laminated structure of multiple layers of a medium refractive index layer, a high refractive index layer, and a low refractive index layer. According to the invention of claim 6, in addition to the effect of the invention of any one of claims 1 to 5,
Since the refractive index and the thickness of the hard coat thin layer are defined, it is possible to provide a surface-reinforced antireflection layer having higher antireflection properties. According to the invention of claim 7,
In addition to the effect of the invention of any one of claims 1 to 6, the refractive index and thickness of the low refractive index layer are defined, so that an antireflection layer having enhanced surface antireflection property is provided. be able to. According to the invention of claim 8, claim 1
In addition to the effect of any of the inventions of claim 7, since the hard coat thin layer is made of a cured resin composition, it is possible to provide a surface-reinforced antireflection layer having a higher surface hardness and strength. . According to the invention of claim 9, in addition to the effect of the invention of claim 8, since the cured resin composition contains a polyfunctional acrylate, the crosslink density is high, and the surface hardness and strength are further enhanced. A surface-reinforced antireflection layer can be provided. According to the invention of claim 10, in addition to the effect of the invention of claim 9, since the cured resin composition contains a polysiloxane, scratch resistance and antifouling property are improved, and the surface-reinforced antireflection. Layers can be provided. According to the invention of claim 11, in addition to the effect of the invention of claim 9 or claim 10, since the cured resin composition contains urethane acrylate, the impact resistance and flexibility of the hard coat thin layer can be balanced. Also, an antireflection layer having a reinforced surface can be provided. According to the invention of claim 12, in addition to the effect of any one of claims 8 to 11, the hard coat thin layer further contains inorganic ultrafine particles, whereby the hardness and the surface strength are further improved, and the surface is strengthened. An antireflection layer can be provided. According to the invention of claim 13, in addition to the effect of the invention of any one of claims 1 to 12, the hard coat layer is laminated on the opposite side of the hard coat thin layer of the antireflection layer. It is possible to provide a surface-reinforced antireflection layer having enhanced hardness and strength on the layer side. According to the invention of claim 14, in addition to the effect of the invention of claim 4 or claim 5, since the hard coat layer also serves as the lowermost layer of the multi-layered antireflection layer, the hard coat layer is provided as the lower layer. Nevertheless, it is possible to provide a surface-reinforced antireflection layer having a more simplified laminated structure. According to the invention of claim 15, claim 1 to claim 1
4. A surface-reinforced antireflection material having the effect of any one of the inventions is laminated on a transparent base material, thereby providing a surface-reinforced antireflection material that is entirely transparent and has transparency. Can be provided. According to the invention of claim 16, the surface-reinforced antireflection layer having the effect of any one of claims 1 to 14 is laminated on the substrate to prevent reflection on the surface of the substrate. Further, it is possible to provide an antireflection body having a reinforced surface.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an antireflection material of the present invention.

FIG. 2 is a layer cross-sectional view showing a reflective layer of the present invention.

[Explanation of symbols]

1 Antireflection material 2 transparent substrate 3 or L low refractive index layer 4 Hard coat thin layer 5 Hard coat layer M Middle refractive index layer H high refractive index layer

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2K009 AA04 AA05 AA06 AA15 BB14                       BB24 BB25 BB28 CC03 CC06                       CC09 CC24 CC26 CC42 CC45                       DD02                 4F100 AA00B AG00 AJ06 AK01B                       AK25B AK25J AK41 AK51B                       AK51J AK79B AL01B AR00A                       AR00C AR00D AR00E BA02                       BA03 BA04 BA05 BA07 BA10B                       CC00B CC00E DE01B GB07                       GB31 GB41 JB13B JB14B                       JM02B JM02E JN01E JN06A                       JN18A JN18B JN18C JN18D                       YY00A YY00B YY00C YY00D

Claims (16)

[Claims] 1. A surface-reinforced antireflection layer comprising a hardcoat thin layer having a refractive index higher than that of the antireflection layer laminated on the antireflection layer. 2. The surface-reinforced antireflection layer according to claim 1, wherein the antireflection layer comprises a low refractive index layer. 3. The surface-reinforced antireflection layer according to claim 1, wherein the antireflection layer is a multilayer having a low refractive index layer on the hard coat thin layer side. 4. The surface of claim 3, wherein the antireflection layer has a laminated structure of the low refractive index layer and a high refractive index layer below the low refractive index layer. Antireflection layer. 5. The surface according to claim 3, wherein the antireflection layer has a laminated structure in which a high refractive index layer and a medium refractive index layer are sequentially laminated under the low refractive index layer. Anti-reflective layer reinforced with. 6. The low refractive index layer has a refractive index of 1.10 to 10.
The surface-reinforced antireflection layer according to claim 1, wherein the antireflection layer has a thickness of 1.46 and a thickness of 30 to 150 nm. 7. The hard coat thin layer has a refractive index of 1.
30 to 1.60, which is larger than the refractive index of the low refractive index layer by 0.14 to 0.28 and has a thickness of 5 to 50 nm.
The antireflection layer having a reinforced surface according to any one of claims 1 to 6, wherein the thickness is 1/2 or less of the thickness of the low refractive index layer. 8. A cured resin, wherein the hard coat thin layer comprises a cured product of a thermosetting resin composition containing a thermosetting resin and / or an ionizing radiation curable resin composition containing an ionizing radiation curable resin. The surface-reinforced antireflection layer according to any one of claims 1 to 7, which is composed of a composition. 9. The surface-reinforced antireflection layer according to claim 8, wherein the cured resin composition contains a polyfunctional acrylate. 10. The surface-reinforced antireflection layer according to claim 9, wherein the cured resin composition contains a polysiloxane component. 11. The surface-reinforced antireflection layer according to claim 9, wherein the cured resin composition contains urethane acrylate. 12. The surface-reinforced antireflection layer according to claim 8, wherein the thin hard coat layer further contains inorganic ultrafine particles. 13. The surface according to claim 1, wherein a hard coat layer is further laminated on the side of the antireflection layer opposite to the side where the hard coat thin layer is laminated. Anti-reflective layer reinforced with. 14. The surface-reinforced antireflection layer according to claim 4, wherein the lowermost layer constituting the antireflection layer also serves as a hard coat layer. 15. A transparent base material is laminated on the opposite side of the surface-enhanced antireflection layer according to claim 1 from which the hard coat thin layer is laminated. Anti-reflective material with a reinforced surface. 16. A substrate is laminated on the opposite side of the surface-enhanced antireflection layer according to claim 1 from which the hard coat thin layer is laminated. Anti-reflective body with reinforced surface.