JP2001318206A - Reflection-reducing material and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reflection-reducing material, having high hardness and appearance with less-colored reflected light and to provide its use. SOLUTION: The reflection-reducing material is obtained by disposing one or more hard coat layers on the surface of a transparent substrate directly or by way of one or more layers and forming a low refractive index layer which becomes the outermost layer on the hard coat layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reflection-reducing material having both appearance with less coloring of reflected light and high hardness, and an electronic image display device using the same.

[0002]

2. Description of the Related Art When a low-refractive-index layer made of a substance having a lower refractive index than that of a substrate is formed on the outermost layer of a transparent substrate with a thickness (about 100 nm) of 1/4 of the wavelength of visible light, surface reflection is caused by an interference effect. It is known that the transmittance decreases and the transmittance improves.
It is applied as an anti-reflective material in a field where reduction of surface reflection in a transparent substrate portion such as an electric product, an optical product, and a building material is required.

As a method of forming the antireflection layer, a so-called dry coating method in which magnesium fluoride or the like is vapor-deposited and sputtered (JP-A-63-261646),
And a wet coating method in which the material is applied to a substrate in a liquid form such as a solution or dispersion, dried, and cured if necessary (JP-A-7-48543, JP-A-9-3140).
No. 38) is known. Of these, the dry coating method requires large equipment with a high vacuum, and has problems such as low productivity. On the other hand, the wet coating method has a small capital investment and is excellent in terms of productivity and a large area.

In the wet coating method, a single-layer antireflection material in which a low refractive index layer is directly coated on a transparent substrate, a hard coat layer, a high refractive index layer,
A three-layer antireflective material coated with a low refractive index layer is generally known. However, the single-layer anti-reflection material has a problem that surface strength such as pencil hardness and scratch resistance is not sufficient. In addition, the three-layer antireflection material has a problem that the coloring of the reflected light becomes strong.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an anti-reflection material having both appearance with less coloring of reflected light and high hardness.
And its use.

[0006]

According to the present invention, the following anti-reflective material and its use are provided. [1] An anti-reflective material comprising one or more hard coat layers provided directly or via one or more layers on the surface of a transparent substrate, and a low refractive index layer as an outermost layer provided thereon. [2] The above-mentioned [1] in which an adhesive layer is provided on the back surface of the transparent substrate.
Anti-reflective material. [3] The anti-reflective material according to [1] or [2], wherein the transparent substrate or the hard coat layer also has antiglare properties. [4] The above-mentioned [1] to [3], wherein the hard coat layer is obtained by polymerizing and curing an ultraviolet curable composition containing a polyfunctional acrylate.
The anti-reflective material according to item 1. [5] The above-mentioned [1] to [4], wherein the low refractive index layer has a refractive index in the range of 1.30 to 1.48 and is lower than the hard coat layer immediately below by 0.01 or more. Anti-reflective material. [6] The low refractive index layer obtained by polymerizing and curing an ultraviolet curable composition containing a fluorine-containing polyfunctional acrylate [1] to
The anti-reflective material according to [5]. [7] The antireflective material according to [6], wherein the fluorine-containing polyfunctional acrylate of the low refractive index layer is represented by the following formula [1].

[0007]

Embedded image

[X ¹ and X ² are the same or different groups, each representing a hydrogen atom or a methyl group, and Y ¹ represents (i)
Fluorine atoms having two or more fluoroalkylene group having 1 to 14 carbon atoms, (ii) a cycloalkylene group having 3 to 14 carbon atoms and having a fluorine atom four or ^{more, (iii) -C (Y 2} )
An HCH ₂ — group (where Y ² represents a C 1-14 fluoroalkyl group having 3 or more fluorine atoms or a C 3-14 cycloalkyl group having 4 or more fluorine atoms), (iv ) A group represented by the following formula [2]:

[0009]

Embedded image

Wherein Y ³ is a fluoroalkyl group having 1 to 14 carbon atoms having two or more fluorine atoms, X ³ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Z ¹ is a hydrogen atom, and acrylic acid residue. Or a group represented by a methacrylic acid residue. ｝, And (v) any of the groups represented by the following formula [3].

[0011]

Embedded image

(Where Y ⁴ is a fluoroalkylene group having 1 to 14 carbon atoms having two or more fluorine atoms, Z ² and Z ³ are the same or different groups, and are a hydrogen atom, an acrylic acid residue, [8] An electronic image display device using the anti-reflection material according to any one of [1] to [7].

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The material of the transparent substrate used in the present invention is not particularly limited.
Preferable examples include polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA) copolymer, triacetyl cellulose (TAC), polyolefin (PO), polyamide (PA), polyvinyl chloride (PVC), and the like. Can be. Here, “transparent” indicates a light transmittance of 30% or more, more preferably 50% or more, and further preferably 80% or more.

The shape of the transparent substrate is not particularly limited, and examples thereof include a plate-like or film-like one. Film-like ones are preferred in terms of productivity and transportability, and those having a thickness of 10 to 500 μm are more preferred in terms of transparency and workability. Further, those having antiglare properties are preferable.

In the present invention, the hard coat layer is a layer provided between the low refractive index layer and the transparent substrate for the purpose of improving the hardness. This layer can be formed as a single layer or a laminate of two or more layers as necessary. When two or more layers are stacked, these layers may be the same or different. The hardness obtained by forming these layers is preferably H or higher in pencil hardness, more preferably 2H or higher.

The hard coat layer may have
In addition to the improvement of hardness, one or more functions such as anti-glare, anti-Newton ring prevention, antistatic function, blocking of light in a specific wavelength range, improvement in adhesion, and color tone correction can be provided. When two or more layers are stacked, different functions may be imparted to each. A known method can be used for giving each function.

For the above-mentioned layer, an inorganic material, an organic material, or a mixture thereof can be used. As the organic material to be used, for example, a cured product such as a polyfunctional or monofunctional (meth) acrylic acid ester or a silicon compound such as tetraethoxysilane is exemplified. From the viewpoint of compatibility between productivity and hardness, it is particularly preferable to be a polymerized and cured product of an ultraviolet-curable polyfunctional acrylate monomer composition. Here, (meth) acryl means acryl and / or methacryl.

The UV-curable polyfunctional acrylate monomer composition is not particularly limited.
A mixture of at least one known UV-curable polyfunctional acrylate monomer or a known UV-curable hard coat material can be used as it is or with other components added. Examples of the ultraviolet-curable polyfunctional acrylate monomer are not particularly limited. , 1,6-hexanediol diacrylate, 1,
Preferred are polyfunctional alcohol derivatives such as 6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane, polyethylene glycol diacrylate, and polyurethane acrylate.

The hard coat layer may contain other components in addition to the above-mentioned compounds as long as the effects of the present invention are not impaired. Other components are not particularly limited, for example, inorganic or organic fillers, inorganic or organic fine particles, inorganic or organic pigments, polymers, and polymerization initiators, polymerization inhibitors, antioxidants, dispersants, Examples include additives such as a surfactant, a light stabilizer, a light absorber, and a leveling agent. An arbitrary amount of solvent can be added as long as drying is performed after film formation in the wet coating method.

The method for forming the layer is not particularly limited. When an organic material is used, a roll coat, a die coat, etc.
It can be formed by a general wet coat method. The formed layer can be subjected to a curing reaction by heating or irradiation with active energy rays such as ultraviolet rays and electron beams as necessary.

The thickness of the hard coat layer is preferably 2 to 20 μm. When the thickness is less than 2 μm, it is difficult to obtain a sufficient hardness such as a decrease in pencil hardness, and when the thickness exceeds 20 μm, problems such as a decrease in bending resistance occur. In the case of laminating two or more layers, the total thickness may be within the above range,
The thickness of one layer is not particularly limited.

The refractive index of the hard coat layer is not particularly limited. However, when the difference in refractive index from the low refractive index layer formed immediately above the hard coat layer is 0.15 or more, the hard coat layer does not function as a high refractive index layer. It is preferable to control the thickness. For example, the thickness of the layer is adjusted so as not to be [wavelength of light intended for anti-reflection / (4 × refractive index of layer)] (nm).

In the present invention, the low refractive index layer may be a conventionally known layer, and the method for forming the layer is not limited. For example,
A method such as a dry coating method and a wet coating method can be used. In view of productivity and cost, a wet coating method is particularly preferable. The wet coating method may be a known method, and examples thereof include a roll coating method, a spin coating method, and a dip coating method. A method capable of continuous formation, such as a roll coating method, is preferable from the viewpoint of productivity.

The low refractive index layer is formed on the hard coat layer, and preferably has a refractive index relatively lower than that of the hard coat layer immediately below by 0.01 or more. Refractive index difference is 0.01
If it is less than the layer or more than the layer immediately below, the anti-reflection effect tends to decrease. In addition, the refractive index is preferably 0.03 or more, more preferably 0.
An excellent anti-reflection effect can be obtained by lowering by at least 05.

The refractive index of the low refractive index layer is preferably 1.3.
0 to 1.48, more preferably 1.30 to
It is within the range of 1.45. The refractive index of the low refractive index layer is 1.
If it exceeds 48, it is difficult to obtain a sufficient anti-reflection effect by wet coating, and if it is less than 1.30, it tends to be practically difficult to form a layer.

The thickness of the low refractive index layer of the present invention depends on the type of the substrate,
Although it depends on the shape, the wavelength of the target light, and the structure of the layer, the thickness of each layer is preferably equal to or less than the wavelength of the visible light. For example, when adjusting the anti-reflection effect to human luminosity, the layer thickness is 125 / (refractive index of low refractive index layer) ≦ thickness of low refractive index layer (nm) ≦ 165 / (refraction of low refractive index layer). Rate).

As a material for the low refractive index layer, inorganic substances such as silicon oxide, lanthanum fluoride, magnesium fluoride, cerium fluoride, magnesium fluoride and the like, and fluorine-containing organic compounds can be used alone or as a mixture. Further, a non-fluorinated monomer or polymer can be used as a binder.

The fluorinated organic compound is not particularly restricted but includes, for example, monofunctional or polyfunctional fluorinated (meth) acrylic esters, fluorinated itaconic esters, fluorinated maleic esters, fluorinated silicon compounds, etc. And the like. Particularly, a fluorine-containing (meth) acrylate is preferred from the viewpoint of reactivity. By curing these fluorine-containing organic compounds, a layer having a low refractive index and a high hardness can be formed.

The monofunctional fluorine-containing (meth) acrylic acid ester includes, for example, (meth) acrylic acid-2,
2,2-trifluoroethyl, (meth) acrylic acid-
2,2,3,3,3-pentafluoropropyl, (meth) acrylic acid-2,2,3,3,4,4,4-heptafluorobutyl, (meth) acrylic acid-2,2,3,3
3,4,4,5,5,5-nonafluoropentyl, (meth) acrylic acid-2,2,3,3,4,4,5,5
6,6,6-undecafluorohexyl, (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6
7,7,7-tridecafluoroheptyl, (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6
7,7,8,8,8-pentadecafluorooctyl,
(Meth) acrylic acid-2,2,3,3,4,4,5
5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl, (meth) acrylic acid-2,2,3
3,4,4,5,5,6,6,7,7,8,8,9,
9,10,10,10-nonadecafluorodecyl, 3,3,3-trifluoropropyl (meth) acrylate,
(Meth) acrylic acid-3,3,4,4,4-pentafluorobutyl, (meth) acrylic acid-3,3,4,4,4
5,5,5-heptafluoropentyl, (meth) acrylic acid-3,3,4,4,5,5,6,6,6-nonafluorohexyl, (meth) acrylic acid-3,3,4 4,
5,5,6,6,7,7,7-undecafluoroheptyl, (meth) acrylic acid-3,3,4,4,5,5
6,6,7,7,8,8,8-tridecafluorooctyl, (meth) acrylic acid-3,3,4,4,5,5
6,6,7,7,8,8,9,9,9-pentadecafluorononyl, (meth) acrylic acid-3,3,4,4,
5,5,6,6,7,7,8,8,9,9,10,1
0,10-heptadecafluorodecyl, (meth) acrylic acid-3,3,4,4,5,5,6,6,7,7,8,
8,9,9,10,10,11,11,11-nonadecafluoroundecyl, (meth) acrylic acid-3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,11,11,12,12,12-Heneicosafluoroundecyl, (meth) acrylic acid- (1-trifluoromethyl) -2,2,2-trifluoroethyl, (meth) acrylic acid -(2-hydroxy) -4,
4,5,5,6,6,7,7,7-nonafluoroheptyl, (meth) acrylic acid- (2-hydroxy) -4,
4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl, (meth) acrylic acid- (2-hydroxy) -4,4,5,5,6 , 6,7,7,8,
8,9,9,10,10,11,11,11-nonadecafluoroundecyl, (meth) acrylic acid- (2-hydroxy) -4,4,5,5,6,6,7,7, 8,8,
9, 9, 10, 10, 11, 11, 12, 12, 13,
13,13-heneicosafluorotridecyl and the like.

The polyfunctional fluorine-containing (meth) acrylate is preferably a bifunctional to tetrafunctional fluorine-containing (meth) acrylate. Among them, examples of the bifunctional fluorine-containing (meth) acrylate include 1,2-di (meth) acryloyloxy-
4,4,4-trifluorobutane, 1,2-di (meth)
Acryloyloxy-4,4,5,5,5-pentafluoropentane, 1,2-di (meth) acryloyloxy-4,4,5,5,6,6,6-heptafluorohexane, 1,2- Di (meth) acryloyloxy-4,4,
5,5,6,6,7,7,7-nonafluoroheptane,
1,2-di (meth) acryloyloxy-4,4,5
5,6,6,7,7,8,8,8-undecafluorooctane, 1,2-di (meth) acryloyloxy-4,
4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononane, 1,2-di (meth) acryloyloxy-4,4,5,5,6 6, 7, 7, 8, 8,
9,9,10,10,10-pentadecafluorodecane, 1,2-di (meth) acryloyloxy-5,5
6,6,7,7,8,8,9,9,10,10,10-
Tridecafluorodecane, 1,2-di (meth) acryloyloxy-4,4,5,5,6,6,7,7,8,
8,9,9,10,10,11,11,11-heptadecafluoroundecane, 1,2-di (meth) acryloyloxy-4,4,5,5,6,6,7,7,8, 8,
9, 9, 10, 10, 11, 11, 12, 12, 12-
Nonadecafluorododecane, 1,2-di (meth) acryloyloxy-5,5,6,6,7,7,8,8,9,
9,10,10,11,11,11-heptadecafluorododecane, 1,2-di (meth) acryloyloxy-
4-trifluoromethyl-5,5,5-trifluoropentane, 1,2-di (meth) acryloyloxy-5-
Trifluoromethyl-6,6,6-trifluorohexane, 1,2-di (meth) acryloyloxy-3-methyl-4,4,5,5,5-pentafluoropentane,
1,2-di (meth) acryloyloxy-3-methyl-
4,4,5,5,6,6,6-hexafluorohexane, 1,4-di (meth) acryloyloxy-2,2
3,3-tetrafluorobutane, 1,5-di (meth) acryloyloxy-2,2,3,3,4,4-hexafluoropentane, 1,6-di (meth) acryloyloxy-2,2 3,3,4,4,5,5-octafluorohexane, 1,7-di (meth) acryloyloxy-
2,2,3,3,4,4,5,5,6,6-decafluoroheptane, 1,8-di (meth) acryloyloxy-
2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorooctane, 1,9-di (meth) acryloyloxy-2,2,3,3,4,4 , 5,5,6,6,
7,7,8,8-tetradecafluorononane, 1,10
Di (meth) acryloyloxy-2,2,3,3
4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane, 1,11-di (meth) acryloyloxy-2,2,3,3,4 4,5,5,6
6,7,7,8,8,9,9,10,10-octadecafluoroundecane, 1,12-di (meth) acryloyloxy-2,2,3,3,4,4,5,5 6,6
7,7,8,8,9,9,10,10,11,11-eicosafluorododecane, 2-hydroxy-4,4,4
-Trifluorobutyl-2 ', 2'-bis {(meth) acryloyloxymethyl} propionate, 2-hydroxy-4,4,5,5,5-pentafluoropentyl-
2 ', 2'-bis {(meth) acryloyloxymethyl} propionate, 2-hydroxy-4,4,5,
5,6,6,6-heptafluorohexyl-2 ', 2'
-Bis {(meth) acryloyloxymethyl} propionate, 2-hydroxy-4,4,5,5,6,6
7,7,7-nonafluoroheptyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} propionate, 2-hydroxy-4,4,5,5,6,6,7,
7,8,8,9,9,9-Tridecafluorononyl-
2 ', 2'-bis {(meth) acryloyloxymethyl} propionate, 2-hydroxy-4,4,5,
5,6,6,7,7,8,8,9,9,10,10,1
1,11,11-nonadecafluoroundecyl-2 ′,
2'-bis {(meth) acryloyloxymethyl} propionate, 2-hydroxy-4,4,5,5,6,
6,7,7,8,8,9,9,10,10,11,1
Preferred examples include 1,12,12,13,13,13-heneicosafluorotridecyl-2 ', 2'-bis {(meth) acryloyloxymethyl} propionate.

From the viewpoints of refractive index and hardness, 1,2-di (meth) acryloyloxy-4,4,5,5 is particularly preferable.
5,6,6,7,7,8,8,9,9,10,10,1
1,11,11-heptadecafluorododecane, 1,1
0-di (meth) acryloyloxy-2,2,3,3
4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane, 2-hydroxy-4,4,
5,5,6,6,7,7,8,8,9,9,10,1
0,10-heptadecafluoroundecyl-2 ', 2'
-Bis {(meth) acryloyloxymethyl} propionate. These di (meth) acrylates can be used alone or as a mixture when used.

Further, as the fluorine-containing polyfunctional (meth) acrylate other than the above bifunctional, trifunctional and quaternary
Functional fluorine-containing polyfunctional (meth) acrylates are exemplified. Specific examples of the trifunctional fluorine-containing polyfunctional (meth) acrylate include, for example, 2- (meth) acryloyloxy-4,4,5,5,6,6,7,7,7
7-nonafluoroheptyl-2 ', 2'-bis {(meth) acryloyloxymethyl} propionate, 2-
(Meth) acryloyloxy-4,4,5,5,6
6,7,7,8,8,9,9,9-Undecafluorononyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} propionate, 2- (meth) acryloyloxy-4,4 5, 5, 6, 6, 7, 7, 8, 8, 9,
9,10,10,11,11,11-heptadecafluoroundecyl-2 ', 2'-bis {(meth) acryloyloxymethyl} propionate, 3-{(1-trifluoromethyl) octafluorocyclopentyl}- 2-
Acryloyloxypropyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} propionate, 3-
{(1-trifluoromethyl) decafluorocyclohexyl} -2-acryloyloxypropyl-2 ′, 2 ′
-Bis {(meth) acryloyloxymethyl} propionate, 3-{(1-trifluoromethyl) hexafluorocyclobutyl} -2-acryloyloxypropyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} propionate And 1- (meth) acryloyloxymethyl-3,3,4,4,5,5,6,6,6
-Nonafluorohexyl-2 ', 2'-bis ｛(meth)
Acryloyloxymethyl dipropionate, 1- (meth) acryloyloxymethyl-3,3,4,4,5,
5,6,6,7,7,8,8,8-Undecafluorooctyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} propionate, 1- (meth) acryloyloxymethyl-3,3 , 4,4,5,5,6,6,7,
7,8,8,9,9,10,10,10-heptadecafluorodecyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} propionate, 2-{(1-trifluoromethyl) octafluoro Cyclopentyl I-1-
(Acryloyloxymethyl) ethyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} propionate, 2-{(1-trifluoromethyl) decafluorocyclohexyl} -1- (acryloyloxymethyl) ethyl-2 ′ , 2′-bis {(meth) acryloyloxymethyl} propionate, 2-{(1-trifluoromethyl) hexafluorocyclobutyl} -1- (acryloyloxymethyl) ethyl-2 ′, 2′-bis} (meth ) Acryloyloxymethyl dipropionate and the like. From the viewpoint of the refractive index and hardness, particularly preferably 2-
(Meth) acryloyloxy-4,4,5,5,6
6,7,7,8,8,9,9,10,10,11,1
1,11-heptadecafluoroundecyl-2 ′, 2 ′
-Bis {(meth) acryloyloxymethyl} propionate.

Specific examples of tetrafunctional fluorine-containing polyfunctional (meth) acrylates include 1, 2, 7, and
8-tetra (meth) acryloyloxy-4,4,5
5-tetrafluorooctane, 1,2,8,9-tetra (meth) acryloyloxy-4,4,5,5,6,6
-Hexafluorononane, 1,2,9,10-tetra (meth) acryloyloxy-4,4,5,5,6
6,7,7-octafluorodecane, 1,2,10,1
1-tetra (meth) acryloyloxy-4,4,5
5,6,6,7,7,8,8-decafluoroundecane, 1,2,11,12-tetra (meth) acryloyloxy-4,4,5,5,6,6,7,7,8 , 8,
Preferred is 9,9-dodecafluorododecane. From the viewpoints of refractive index and hardness, 1,2,9,10-tetra (meth) acryloyloxy-4,4,5,5,6,6,7,7-octafluorodecane, 1,2,2 11,12-tetra (meth) acryloyloxy-4,4,5,5,6,6,7,7,8,8,
9,9-dodecafluorododecane is exemplified. In use, the above-mentioned fluorine-containing polyfunctional (meth) acrylate can be used alone or as a mixture.

Specific examples of the above-mentioned fluorine-containing silicon compound include (3,3,3-trifluoropropyl) trimethoxysilane and (3,3,4,4,4-pentafluorobutyl) trimethoxysilane , (3,3,4,4,5,
(5,5-heptafluoropentyl) trimethoxysilane, (3,3,4,4,5,5,6,6,6-nonafluorohexyl) trimethoxysilane, (3,3,4
4,5,5,6,6,7,7,7-undecafluoroheptyl) trimethoxysilane, (3,3,4,4,5,
5,6,6,7,7,8,8,8-tridecafluoro)
Trimethoxysilane, (3,3,4,4,5,5,6,
6,7,7,8,8,9,9,9-pentadecafluoro) trimethoxysilane, (3,3,4,4,5,5,
6,6,7,7,8,8,9,9,10,10,10-
Heptadecafluoro) trimethoxysilane, (3,3,
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,11,11,11-nonadecafluoro) trimethoxysilane, (3,3,4,4,5,5,6,6,6)
7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 1
Preferable examples include (2,12,12-heneicosafluoro) trimethoxysilane.

Examples of the fluorine-containing polymer include linear polymers such as homopolymers and copolymers of the above-mentioned monofunctional fluorine-containing monomers, and copolymers with fluorine-free monomers.
Examples of the polymer include a polymer containing a carbon ring or a hetero ring in the chain, a cyclic polymer, and a comb polymer.

As the non-fluorine-based monomer, conventionally known ones can be used. For example, monofunctional or polyfunctional (meth) acrylic acid esters, silicon compounds such as tetraethoxysilane and the like can be mentioned.

The low refractive index layer may contain other components in addition to the above-mentioned compounds as long as the effects of the present invention are not impaired. Other components are not particularly limited and include, for example, inorganic or organic fine particles, inorganic or organic pigments, polymers, and polymerization initiators, polymerization inhibitors, antioxidants, dispersants, surfactants, and light stability. And additives such as a light absorbing agent, a leveling agent, and the like. An arbitrary amount of solvent can be added as long as drying is performed after film formation in the wet coating method.

The low-refractive-index layer can be formed by forming a layer by wet coating, followed by a curing reaction by irradiating or heating active energy rays such as heat, ultraviolet rays, or electron beams, if necessary. The curing reaction by the active energy ray is preferably performed in an atmosphere of an inert gas such as nitrogen or argon.

Further, one or more layers can be formed on the opposite side of the transparent substrate or between the transparent substrate and the hard coat layer. For this layer, an inorganic substance, an organic substance, or a mixture thereof can be used. Its thickness is 0.005
To 20 μm, and the method for forming the layer is not particularly limited. In addition, these layers can be provided with one or more functions such as prevention of Newton rings, blocking of light in a specific wavelength range, improvement of adhesion between layers, conductivity, shielding of electromagnetic waves, and color tone correction.

The above-mentioned anti-reflection material can be used for applications requiring an anti-reflection effect and a high light transmittance. In particular, it can be used for the purpose of suppressing surface reflection of an electronic image display device. When used in these applications, an adhesive layer is provided in advance on the surface where the low refractive index layer of the anti-reflective material is not formed,
It can be used by bonding to an object. The material used for the adhesive layer is not particularly limited, and examples thereof include an acrylic pressure-sensitive adhesive, an ultraviolet curable adhesive, and a thermosetting adhesive. Further, one or more functions such as blocking of light in a specific wavelength range, improvement of contrast, and correction of color tone can be provided to the adhesive layer.

Examples of the electronic image display device include a cathode ray tube and a plasma panel display (PD).
P) and a liquid crystal display device. It can be used by directly adhering it via an adhesive layer such that the surface of the transparent material disposed on the front surface, on which the low refractive index layer of the anti-reflection material is not formed, is in contact with the transparent material.

[0042]

According to the antireflection material of the present invention, an antireflection effect having high hardness and little coloring of reflected light can be obtained. Further, in the electronic image display device of the present invention, a clear image can be obtained by anti-reflection.

[0043]

The present invention will be described below in more detail with reference to examples.
In addition, the refractive index of the cured product was measured as follows. 1. Measurement method of refractive index of cured product (1) Using a bar coater on a 2 mm thick acrylic plate (trade name “Deragrass A”, manufactured by Asahi Kasei Kogyo Co., Ltd.) It was applied to a thickness of about 3 μm. (2) After drying the solvent, an ultraviolet irradiation device (Iwasaki Electric Co., Ltd.)
Using a 120-W high-pressure mercury lamp under a nitrogen atmosphere and irradiating with 400 mJ of ultraviolet light. (3) After curing, the refractive index was measured using an Abbe refractometer (manufactured by Elma Corporation).

Production Example 1: Coating solution for hard coat layer (HC-
Preparation of 1) A commercially available ultraviolet-curable hard coat material (trade name "Desolite Z7521", manufactured by JSR Corporation) was used as it was as a coating liquid. The refractive index of the cured product was 1.49.

Production Example 2: Coating solution for hard coat layer (HC-
Preparation of 2) 70 parts by weight of dipentaerythritol hexaacrylate, 30 parts by weight of 1,6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane, a photopolymerization initiator (trade name “IRGACURE184”, manufactured by Ciba Geigy) 4 parts by weight and 100 parts by weight of isopropanol were mixed to prepare a hard coat layer coating liquid (HC-2). The refractive index of the cured product was 1.51.

Production Example 3: Coating solution for hard coat layer (HC-
Preparation of 3) 70 parts by weight of dipentaerythritol hexaacrylate, 20 parts by weight of tetramethylolmethane triacrylate, 10 parts by weight of 1,6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane, and an average particle diameter of 0. 200 parts by weight of indium tin oxide fine particles of 07 μm, a photopolymerization initiator (trade name “IRGACURE90”)
7 ", manufactured by Ciba-Geigy Co., Ltd.) and 4 parts by weight of isopropanol were mixed, and a coating solution for a hard coat layer (HC-
3) was prepared. The refractive index of the cured product was 1.59.

Production Example 4: Coating solution for antiglare hard coat layer (A
Preparation of G-1) A coating liquid for a hard coat layer (AG-1) was prepared in the same manner as in Production Example 1 except that 20 parts by weight of acrylic resin particles (trade name: "Art Pearl", manufactured by Negami Industry Co., Ltd.) were added. ) Was prepared.
The refractive index of the cured product was 1.51.

Production Example 5: Preparation of coating liquid (L-1) for low refractive index layer 1,2-di (meth) acryloyloxy-4,4,5
5,6,6,7,7,8,8,9,9,10,10,1
90 parts by weight of 1,11,11-heptadecafluorododecane, n-butyl acrylate and acrylic acid-3,3,4,4
4,5,5,6,6,7,7,8,8,9,9,10,
10 parts by weight of a 1: 1 copolymer of 10,10-heptadecafluorodecyl, 900 parts by weight of benzotrifluoride,
Photopolymerization initiator (trade name “KAYACURE BMS”,
5 parts by weight of Nippon Kayaku Co., Ltd.) were mixed to prepare a low refractive index layer coating solution (L-1). The cured product after solvent drying had a refractive index of 1.39.

Production Example 6 Preparation of Coating Liquid (L-2) for Low Refractive Index Layer 1,10-Diacryloyloxy-2,2,3,3
4,4,5,5,6,6,7,7,8,8,9,9-octadecafluorodecane 70 parts by weight, tetramethylolmethanetetraacrylate 20 parts by weight, butyl alcohol 900 parts by weight, photopolymerization started Agent (trade name "KAYACU"
RE BMS "(manufactured by Nippon Kayaku Co., Ltd.) in an amount of 5 parts by weight to prepare a low refractive index layer coating solution (L-2). The cured product after solvent drying had a refractive index of 1.42.

Production Example 7: Preparation of coating liquid (L-3) for low refractive index layer 1,2,9,10-tetraacryloyloxy-4,
4,5,5,6,6,7,7-octafluorodecane 5
0 parts by weight, 30% dispersion of silica fine particles (trade name “XBA
−ST ”, manufactured by Nissan Chemical Co., Ltd.) 120 parts by weight, 2 ′,
2'-bis (acryloyloxymethyl) propionic acid (2-hydroxy) -4,4,5,5,6,6,7,
7, 8, 8, 9, 9, 10, 10, 11, 11, 11-
Nonadecafluoroundecyl 10 parts by weight, butyl alcohol 900 parts by weight, photopolymerization initiator (trade name "KAYAC"
URE BMS "(manufactured by Nippon Kayaku Co., Ltd.) was mixed to prepare a low refractive index layer coating solution (L-3). The cured product after solvent drying had a refractive index of 1.47.

Production Example 8: Preparation of coating liquid (L-4) for low refractive index layer 1,2,9,10-tetraacryloyloxy-4,
4,5,5,6,6,7,7-octafluorodecane 3
0 parts by weight, 30% dispersion of silica fine particles (trade name “XBA
-ST ", Nissan Chemical Co., Ltd.) 120 parts by weight, butyl alcohol 900 parts by weight, a photopolymerization initiator (trade name" KAY
ACURE BMS "(manufactured by Nippon Kayaku Co., Ltd.) in an amount of 5 parts by weight to prepare a low refractive index layer coating solution (L-4). The cured product after solvent drying had a refractive index of 1.49.

Production Example 9: Preparation of coating liquid (H-1) for high refractive index layer 70 parts by weight of zinc oxide fine particles having an average particle diameter of 0.05 μm, 30 parts by weight of tetramethylol methane triacrylate, a photopolymerization initiator (commercially available) 5 parts by weight of "KAYACURE BMS" (manufactured by Nippon Kayaku Co., Ltd.) were mixed to prepare a coating liquid for a high refractive index layer (H-1). The cured product after solvent drying had a refractive index of 1.65.

Examples 1-1 to 1-14 PET film having a thickness of 188 μm (trade name “A410”)
0 ", manufactured by Toyobo Co., Ltd.).
Examples 1-4 to 6 are HC-2, Examples 1-7 to 9 are HC
-3 and Examples 1-10 to 12 were each coated with AG-1 using a bar coater to a dry film thickness of about 4 μm. After drying, it was cured by irradiating it with 400 mJ of ultraviolet light using a 120 W high-pressure mercury lamp using an ultraviolet irradiation device (manufactured by Iwasaki Electric Co., Ltd.) to produce a hard-coated PET film. On top of that, the coating liquid for a low refractive index layer prepared in Production Examples 5 to 7 was coated with a dip coater (manufactured by Sugiyama Genki Kagaku Kiki Co., Ltd.) in Examples 1-1, 4, 7, and 10 to L-1.
Examples 1-2, 5, 8, and 11 show L-2, and Examples 1-3, 6, 9, and 12 show L-3, and light of a dry film thickness of λ / 4, respectively. After adjusting the thickness of the layer so as to have a wavelength of about 550 nm and applying the same, it was similarly cured with 400 mJ of ultraviolet light in a nitrogen atmosphere to produce a reflection reducing material. Further, in Example 1-13, a PET film (abbreviated HCPET; trade name “OHF”, manufactured by Teijin Limited) previously hard-coated was used. In Example 1-14, PET previously hard-coated with an anti-glare hard coating was used. Film (abbreviation AGPET; trade name “KB film N05”)
S "(manufactured by Kimoto Co., Ltd.), and a low-reflection material was similarly produced using the low refractive index layer coating solution L-1. The spectral reflectance, pencil hardness, and appearance of the obtained anti-reflection material were evaluated as follows. The results are shown in Tables 1 and 2, respectively.

2. Spectral reflectance; the surface of the anti-reflective material was roughened with sandpaper and painted with black paint to obtain a spectrophotometer ("U-best 50", manufactured by JASCO Corporation)
5 °, −5 ° regular reflectance was measured, and the minimum reflectance was read from the spectrum. When the interference of the hard coat was observed in the spectrum, the center value of the upper end and the lower end was read. 3. Pencil hardness: Pencil hardness was measured using a pencil hardness tester manufactured by Yasuda Seiki Co., Ltd. according to JIS K5400-1990 8.4.2. 4. Appearance: Coloring of the reflected light was evaluated by visual observation, and it was shown that ○: almost no coloring, Δ: coloring was felt, and ×: strong coloring.

Examples 2-1 to 2-14 Reduction was carried out in the same manner as in Example 1 except that an 80 μm thick TAC film (trade name “SH80”, manufactured by Fuji Photo Film Co., Ltd.) was used for the transparent substrate. A reflector was produced. Also,
In Example 2-13, a TAC film (abbreviated as HCTAC; manufactured by Konica Corporation) previously hard-coated was used.
In Example 2-14, using a TAC film (abbreviation: AGTAC; trade name “Soft Look AG”, manufactured by Hamakawa Paper Co., Ltd.) previously subjected to an antiglare hard coat treatment, a low refractive index layer coating solution was used. A low reflection material was produced in the same manner as in Example 1 using L-1. In the same manner as in Example 1, the spectral reflectance, pencil hardness, and appearance of the anti-reflection material were evaluated. The results are shown in Tables 3 and 4, respectively.

Examples 3-1 to 3-10 A hard coat-treated TAC film was prepared in the same manner as in Example 2, and a second hard coat layer 2 was formed thereon as shown in Table 3. A low refractive index layer was formed thereon in the same manner as in Example 1. Further, in Example 3-9, a TAC film (abbreviated as HCT
AC; manufactured by Konica Corporation), and in Example 3-10, a TAC film (abbreviation: AGTAC; trade name “Soft Look AG”, manufactured by Hamakawa Paper Co., Ltd.) previously treated with an anti-glare hard coat was used. Similarly, a reflection reducing material was produced. In the same manner as in Example 1, the spectral reflectance, pencil hardness, and appearance of the anti-reflection material were evaluated. The results are shown in Tables 5 and 6, respectively.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

[Table 5]

[0062]

[Table 6]

From the above results, in Examples 1 to 3,
The manufactured anti-reflective material has an anti-reflection function, a high surface hardness, and an appearance with little coloring of reflected light. In particular, when HC-3 having a high refractive index is used, coloring of the reflected light is slightly confirmed, but the anti-reflection effect is high. The anti-reflection effect is also high when AG-1 having an antiglare effect and L-1 having a low refractive index are used.

Comparative Examples 1 to 3 Example 1 was repeated except that the low refractive index layer was not formed.
In the same manner as 2-1 and 2-10, a hard coat-treated transparent substrate was produced. In the same manner as in Example 1, the spectral reflectance, pencil hardness, and appearance of the hard-coated transparent substrate were evaluated. Table 7 shows the results. Comparative Examples 1 to 3 did not have a low refractive index layer, and thus did not have the anti-reflection effect.

Comparative Examples 4 and 5 Antireflective materials were produced in the same manner as in Examples 1-1 and 2-1 except that a low refractive index layer was formed without forming a hard coat layer. In the same manner as in Example 1, the spectral reflectance, pencil hardness, and appearance of the anti-reflection material were evaluated. Table 7 shows the results
Shown in Since there is no hard coat layer in Comparative Examples 4 and 5, the pencil hardness is very low as compared with the examples.

Comparative Example 6 Coating liquid H for high refractive index layer between hard coat layer and low refractive index layer
Except that the high refractive index layer was formed using -1, a low reflection material was produced in the same manner as in Example 1-1 in Table 1. The obtained material was evaluated for spectral reflectance, pencil hardness, and appearance of the anti-reflection material in the same manner as in Example 1. Table 7 shows the results
Shown in In Comparative Example 6, three layers of the antireflection material were used, and the coloring of the reflected light was very strong.

Comparative Example 7 An anti-reflective material was produced in the same manner as in Example 1-1, except that the low refractive index layer coating liquid L-4 was used. With respect to the obtained anti-reflection material, the spectral reflectance, pencil hardness and appearance of the anti-reflection material were evaluated in the same manner as in Example 1. Table 7 shows the results. In Comparative Example 7, since there is no difference in refractive index between the low refractive index layer and the hard coat layer, no anti-reflection effect is exhibited.

[0068]

[Table 7]

Example 4 An acrylic pressure-sensitive adhesive sheet (trade name “NON-CARRIER”, manufactured by Lintec Co., Ltd.) was attached to the back surface of the anti-reflective material prepared in Example 1-1 by a hand roller, and was applied to the surface of a CRT television. Laminated uniformly. It was confirmed that when the anti-reflection material of the present invention was used, the reflection of the background light was suppressed with little change in the color of the reflected light on the surface where the bonding was not performed, and a clear image was obtained. From the above results, it can be seen that the anti-reflection material of the present invention has excellent anti-reflection performance.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09K 3/00 G02B 1/04 G02B 1/04 C08L 101: 00 1/10 G02B 1/10 A // C08L 101: 00 ZF term (reference) 2K009 AA04 AA15 BB24 CC03 CC24 CC26 DD02 DD05 4F006 AA02 AA12 AA17 AA22 AA35 AA36 AA38 AB24 AB73 AB74 BA00 BA02 DA04 4J011 QA03 QA04 QA13 QA21 QA23 QA24 BAP ALBA BAP ALB ALBA BB12P BB13P BB17P BB18P CA01 DA48 DA62 JA01

Claims (8)

[Claims] 1. A hard coat layer comprising one or more hard coat layers directly or via one or more layers on the surface of a transparent substrate, and a low refractive index layer as an outermost layer provided thereon. Anti-reflective material. 2. The anti-reflective material according to claim 1, wherein an adhesive layer is provided on the back surface of the transparent substrate. 3. The anti-reflective material according to claim 1, wherein the transparent substrate or the hard coat layer also has an antiglare property. 4. The anti-reflective material according to claim 1, wherein the hard coat layer is formed by polymerizing and curing an ultraviolet curable composition containing a polyfunctional acrylate. 5. The low refractive index layer has a refractive index of 1.30 to 1.48.
And is 0.0% lower than the refractive index of the hard coat layer immediately below.
The anti-reflection material according to any one of claims 1 to 4, wherein the anti-reflection material is at least one lower. 6. The method according to claim 1, wherein the low refractive index layer is formed by polymerizing and curing an ultraviolet curable composition containing a fluorine-containing polyfunctional acrylate.
The anti-reflective material according to claim 5. 7. The anti-reflective material according to claim 6, wherein the fluorine-containing polyfunctional acrylate of the low refractive index layer is represented by the following formula [1]. Embedded image [X ¹ and X ² are the same or different groups and represent a hydrogen atom or a methyl group, and Y ¹ is (i) a fluoroalkylene group having 1 or more carbon atoms and having 2 or more fluorine atoms, and (ii) 3 to 14 carbon atoms having 4 or more fluorine atoms
(Iii) —C (Y ² ) HCH ₂ —
Group (however, Y ² is a group having 1 or more carbon atoms having 3 or more fluorine atoms)
4 to 14 fluoroalkyl groups or 4 fluorine atoms
And a cycloalkyl group having 3 to 14 carbon atoms. (Iv) a group represented by the following formula [2]: ｛Here, Y ³ has 1 or more carbon atoms having two or more fluorine atoms.
14, a fluoroalkyl group, X ³ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Z ¹ is a group represented by a hydrogen atom, an acrylic acid residue, or a methacrylic acid residue. ｝, And (v) any of the groups represented by the following general formula [3]. Embedded image (Where Y ⁴ has 1 to 2 carbon atoms having two or more fluorine atoms)
14 fluoroalkylene groups, Z ² and Z ^3, are the same or different groups and are groups represented by a hydrogen atom, an acrylic acid residue or a methacrylic acid residue. )] 8. An electronic image display device using the anti-reflection material according to claim 1.