JP2002341107A - Electrically conductive antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrically conductive antireflection film capable of achieving a lowered cost from both constitution and process, excellent in antifouling property and mechanical strength and suitable for use as an antireflection film for a display or the like. SOLUTION: The electrically conductive antireflection film is obtained by forming an optically functional layer obtained by alternately stacking electrically conductive layers and low refractive index layers comprising an organic resin in two layers on a transparent plastic film substrate and a resin or compound having antifouling property is contained in the low refractive index layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film on a display screen of a display or the like, and more particularly to an antireflection film having conductivity and antifouling property.

[0002]

2. Description of the Related Art Many displays are used in an environment where external light or the like is incident regardless of whether indoors or outdoors. The incident light such as the external light is specularly reflected on the display surface or the like, and the reflected image is mixed with the display light, thereby deteriorating the display quality.
It makes it difficult to see the displayed image. In particular, with the recent shift to office automation, the use of computers has increased,
Longer time facing the display. Thus, it is considered that the deterioration of the display quality due to the reflection image or the like is a cause of a health disorder such as eye fatigue. Furthermore, in recent years, with the spread of outdoor life, opportunities for using various displays outdoors tend to increase more and more, and there is a demand for a display capable of further improving display quality and clearly displaying a display image. .

Further, for a CRT screen or the like, a conductive antireflection film is required for the purpose of preventing dust due to charging and shielding electromagnetic waves. In order to satisfy these requirements, for example, a light-absorbing conductive layer made of a metal oxide or the like and a low-refractive-index layer are laminated on the surface of a transparent base material by a dry coating method, and an antireflection effect is obtained over a wide range of visible light. An antireflection film having the same is known. However, there is often a need for an antifouling layer on the outermost surface for the purpose of preventing dirt and the like, and there is a problem that the number of laminated layers of the antireflection film increases. Therefore, there is a strong demand for a cost reduction of the antireflection film.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made in consideration of the above-mentioned problems. It is an object of the present invention to provide an anti-reflection film.

[0005]

In order to solve the above-mentioned problems, the invention according to claim 1 is to alternately form a light-absorbing conductive layer and a low-refractive-index layer made of an organic resin on a transparent plastic film substrate. An antireflection film having an optical function layer formed by laminating two layers, wherein an antifouling resin or compound is added to the low refractive index layer.

According to a second aspect of the present invention, there is provided the antireflection film according to the first aspect, wherein a low-refractive index comprising a light-absorbing conductive layer and an organic resin having a refractive index of 1.70 or less is provided on the transparent plastic film substrate. An optical functional layer in which two layers are alternately laminated is formed.

[0007] The invention according to claim 3 is the invention according to claim 1 or 2.
The antireflection film according to the above, wherein a hard coat layer is provided between the transparent plastic film substrate and the optical functional layer.

According to a fourth aspect of the present invention, there is provided the antireflection film according to any one of the first to third aspects, wherein the surface of the antireflection film opposite to the low refractive index layer provided on the conductive layer has silicon, An adhesion layer made of any one of silicon oxide and silicon nitride or a mixture of two or more thereof is formed.

According to a fifth aspect of the present invention, in the antireflection film according to any one of the second to fourth aspects, the light absorbing conductive layer is made of titanium nitride.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail. FIG. 1 is a sectional view showing an example of the antireflection film of the present invention. As shown in FIG. 1, the antireflection film 1 of the present invention comprises a transparent plastic film substrate 2, a hard coat layer 3, an adhesion layer 4, and an antireflection layer 5 as an optical functional layer. further,
The antireflection layer 5 includes a light-absorbing conductive layer 5a and a low-refractive-index layer 5b to which a resin or compound having antifouling properties is added.

As the transparent plastic film substrate 2 in the present invention, substrates composed of various organic polymers can be mentioned. In general, substrates used as optical members are made of polyolefins (polyethylene, polypropylene, etc.) in view of optical properties such as transparency, refractive index and dispersion, and various physical properties such as impact resistance, heat resistance and durability. ), Polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, ethylene vinyl alcohol, acrylic, cellulose (triacetyl cellulose) , Diacetylcellulose, cellophane, etc.), or copolymers of these organic polymers.

These transparent plastic film substrates 2
Any known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a coloring agent, an antioxidant, a flame retardant and the like can be used in the organic polymer constituting the above.

The transparent plastic film substrate 2 may be a single layer or a laminate of a plurality of organic polymers. The thickness is not particularly limited, but is preferably 70 to 200 μm.

The hard coat layer 3 in the present invention improves the hardness of the surface of the transparent plastic film substrate 2,
It is possible to prevent scratches caused by a load, such as a pencil, from scratching, to suppress the occurrence of cracks in the antireflection layer due to bending of the transparent plastic film substrate, and to improve the mechanical strength of the antireflection film. The hard coat layer 3 is made of a polymer mainly composed of a polyfunctional monomer having two or more (meth) acryloyloxy groups in one molecule.

The above polyfunctional monomers include 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (Meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (meth) acryloyloxypropinate, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2-hydroxyethyl) isocyanate di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane, poly1,2-butadienedi (meth) acrylate, 1,2- Bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecaneethylene glycol di (meth) acrylate, 10-decanediol (meth) acrylate, 3,8-bis (meth) acryloyloxymethyltricyclo [ 5.2.10] decane, hydrogenated bisphenol A di (meth) acrylate, 2,2
-Bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 1,4-bis ((meth) acryloyloxymethyl) cyclohexane, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether di (Meth) acrylate, ethoxy-modified bisphenol A di (meth) acrylate, and the like.

The above polyfunctional monomer may be used alone or in combination of two or more. Also,
If necessary, copolymerization can be carried out in combination with a monofunctional monomer. More preferably, the refractive index of the hard coat layer 3 is equal to or close to that of the transparent plastic film substrate 1. If the film thickness is 3 μm or more, sufficient strength will be obtained, but the range of 5 to 15 μm is preferable from the viewpoint of transparency, coating accuracy and handling.

The hard coat layer 3 has an average particle size of 0.0
Inorganic or organic fine particles of 1 to 3 μm can be mixed and dispersed. In addition, by making the surface shape uneven, light diffusion processing generally called antiglare can be performed. Although these fine particles are not particularly limited as long as they are transparent, low refractive index materials are preferable, and silicon oxide and magnesium fluoride are preferable in terms of stability, heat resistance and the like. These hard coat layers 3 may be applied in any manner as long as they are applied smoothly and uniformly to the transparent plastic film substrate 2.
Furthermore, after application, embossing can also be performed.

The adhesion layer 4 in the present invention is provided for the purpose of further improving the mechanical strength represented by the adhesion strength. The material for forming the adhesion layer may be any material as long as it improves the strength. For example, silicon, silicon oxide, or silicon nitride is suitable from the viewpoint of the effect. These film formation methods include PVD (Physical Vapor Depo).
method (vacuum deposition method, reactive deposition method, ion beam assist method, sputtering method, ion plating method, etc.), CVD (Chemical Vapor)
A known method such as a deposition method can be used, and among them, a sputtering method is suitable from the viewpoint of the effect.

The antireflection layer 5 of the present invention has a function by laminating a light-absorbing conductive layer 5a and a low-refractive-index layer 5b in a predetermined thickness in order. In the present invention, the light-absorbing conductive layer 5a has an ability to absorb light in a visible light region, and has a light absorption of 10% to 60%.
Of the range. When the light absorptance is 10% or less, good antireflection cannot be obtained in many cases, and when the light absorptivity is 60% or more, a problem that the screen becomes too dark occurs. The low refractive index layer 5b has a refractive index of 1.70.
These are: If the refractive index is higher than 1.70, a good antireflection effect cannot be obtained.

The material for forming the light-absorbing conductive layer 5a includes a metal or a metal compound, and a metal nitride. Among them, metal nitride is excellent in antireflection performance.
Examples of the material include titanium nitride, zirconium nitride, and hafnium nitride. Among them, titanium nitride is suitable from the viewpoint of performance and cost. This light-absorbing conductive layer 5a is made of PVD (Physical V).
apor Deposition method (vacuum deposition method, reactive deposition method, ion beam assist method, sputtering method, ion plating method, etc.), CVD (Chemi)
It is formed by a known method such as a cal vapor deposition method.

Metals or metal compounds and metal nitrides are generally widely known, especially in the case of thin films, but undesired unavoidable oxidation is likely to occur due to residual gas components during film formation and the atmosphere. For this reason, the metal or metal compound and the metal nitride in the present invention naturally include those in which slight oxidation has occurred within a common sense. For example, in the case of titanium nitride, substantially T
In many cases, the composition is iNxOy.

The material for forming the antifouling layer 5b may be any material as long as it is a low refractive index material. For example, an organosilicon compound, or a composition comprising any one of the polymers of this organosilicon compound, a fluorine-containing organosilicon compound having antifouling properties, or a composition comprising any of the polymers of this fluorine-containing organosilicon compound A resin or compound to which a substance is added is used.

Examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetra-
n-propoxysilane, tetraisopropoxysilane,
Tetrabutoxy silane, vinyl group-containing silicon compound [vinyl trimethoxy silane, vinyl triethoxy silane, etc.], amino group-containing silicon compound [N- (2-aminoethyl) -3-aminopropyl trimethoxy silane, 3-amino propyl tri Methoxysilane, 3-aminopropyltriethoxysilane, etc.), an epoxy group-containing silicon compound [3-glycidoxypropyltrimethoxysilane, 2-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.), chloro group-containing silicon compounds [3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, etc.], methacryloxy group-containing silicon compounds [3-methacryloxypropyl] Trimethoxysilane, 3
-Methacryloxypropyltriethoxysilane, etc.), acryloxy group-containing silicon compound [3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, etc.], isocyanate group-containing silicon compound [3-isocyanatopropyltrimethoxy Silane, 3
-Isocyanatopropyltriethoxysilane and the like], and these may be used alone or in combination of two or more.

Also, a fluorine-containing organic silicon having antifouling properties
As the compound, CF_Three(CH_Two)_TwoSi (OCH_Three)_Three,
CF_ThreeCF_Two(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(C
F_Two)_Two(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(CF_Two)_Three
(CH_Two)_TwoSi (OCH_Three)_Three, CF_Three(CF_Two)_Four(C
H_Two)_TwoSi (OCH_Three)_Three, CF_Three(CF_Two)_Five(CH_Two)_Two
Si (OCH_Three)_Three, CF_Three(CF_Two)₆(CH_Two)_TwoSi
(OCH_Three)_Three, CF_Three(CF_Two)₇(CH_Two)_TwoSi (OC
H_Three)_Three, CF_Three(CF_Two)₈(CH_Two)_TwoSi (OC
H_Three)_Three, CF_Three(CF_Two)₉(CH_Two)_TwoSi (OC
H_Three)_Three, CF_Three(CH_Two)_TwoSi (OC_TwoH_Five)_Three, CF_ThreeC
F_Two(CH_Two)_TwoSi (OC_TwoH_Five)_Three, CF_Three(CF_Two)
_Two(CH_Two)_TwoSi (OC_TwoH_Five)_Three, CF_Three(CF_Two)_Three(C
H_Two)_TwoSi (OC_TwoH_Five)_Three, CF_Three(CF _Two)_Four(CH_Two)_Two
Si (OC_TwoH_Five)_Three, CF_Three(CF_Two)_Five(CH_Two)_TwoSi
(OC_TwoH_Five)_Three, CF_Three(CF_Two)₆(CH_Two)_TwoSi (OC
_TwoH_Five)_Three, CF_Three(CF_Two)₇(CH_Two)_TwoSi (OC_TwoH_Five)
_Three, CF_Three(CF_Two)₈(CH_Two)_TwoSi (OC_TwoH_Five)_Three, C
F_Three(CF_Two)₉(CH_Two)_TwoSi (OC_TwoH_Five)_ThreeIs an example
Use them alone or in combination of two or more
Is also good.

A polymer using the above organosilicon compound,
The method for producing a copolymer using a polymer containing a fluorine-containing organic silicon compound having antifouling properties is not limited,
As a catalyst for producing a copolymer by hydrolysis, hydrochloric acid, oxalic acid, nitric acid, acetic acid, hydrofluoric acid, formic acid, phosphoric acid,
Examples include oxalic acid, ammonia, aluminum acetonate, dibutyltin laurate, tin octylate compounds, methanesulfonic acid, trichloromethanesulfonic acid, paratoluenesulfonic acid, trifluoroacetic acid, and the like. These may be used alone or in combination of two or more. You may.

A composition comprising any one of the above-mentioned organosilicon compounds or a polymer of this organosilicon compound is added to a fluorine-containing organosilicon compound having antifouling properties or a polymer of this fluorine-containing organosilicon compound. Is added.

The above low refractive index material is usually applied after being diluted in a volatile solvent. Although what is used as a diluting solvent is not particularly limited, alcohols such as methanol, ethanol, isopropanol, butanol, and 2-methoxyethanol are considered in consideration of the stability of the composition, wettability to a substrate, volatility, and the like, Acetone, methyl ethyl ketone, ketones such as methyl isobutyl, methyl acetate, ethyl acetate, esters such as butyl acetate, ethers such as diisopropyl ether, ethylene glycol,
Glycols such as propylene glycol and hexylene glycol, glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol and butyl carbitol, aliphatic hydrocarbons such as hexane, heptane and octane, halogenated hydrocarbons, benzene and toluene ,
Aromatic hydrocarbons such as xylene, N-methylpyrrolidone,
Dimethylformamide and the like. The solvent is 1
Not only the kinds but also a mixture of two or more kinds can be used.

The low refractive index material diluted in the above solvent is
Wet coating method (dip coating method, spin coating method, flow coating method, spray coating method, roll coating method, gravure roll coating method, air doctor coating method, plaid coating method, wire doctor coating method, knife coating method, reverse coating method ,
Coating is performed by a transfer roll coating method, a microgravure coating method, a kiss coating method, a cast coating method, a slot orifice coating method, a calendar coating method, a die coating method, or the like. After coating, the solvent in the coating film is volatilized by heating and drying, and thereafter, the coating film is cured by heating, humidification, ultraviolet irradiation, electron beam irradiation, and the like to form a low refractive index layer.

The thickness (d) of the low refractive index layer is preferably nd = λ / 4, where n is the refractive index of the low refractive index layer.

[0030]

Embodiments of the present invention will be described below in detail, but the present invention is not limited to the following embodiments. An acrylic hard coat having a thickness of 12 μm was formed as a hard coat layer 3 on a PET film (188 μm thick, refractive index n = 1.65) of the transparent plastic film substrate 2 by a microgravure method.

Next, a silicon nitride layer was formed as the adhesion layer 4. The film formation method was magnetron sputtering using a silicon target and using oxygen gas as a reaction gas. Further, it was formed with a target film thickness of 1 nm.

Next, a titanium nitride layer was formed as the light absorbing conductive layer 5a. The film formation method was magnetron sputtering using a titanium target and using nitrogen gas as a reaction gas. Further, it was formed with a target film thickness of 10 nm.

Next, 95 mol of Si (OC ₂ H ₅ ) 4 was added.
%, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
mol%, a low refractive index material using 1.0N-HCl as a catalyst was prepared, and a coating solution was applied at a film thickness of 100 nm using a microgravure method.
After drying for a minute, a low refractive index layer was formed.

The results of evaluation of the antireflection film obtained above are as follows. The average reflectance of the antireflection film is 0.2 in a wavelength range of 450 nm to 650 nm.
The transmittance was 89.2% at 550 nm. In addition, steel wool (Nippon Steel Wool Co., Ltd.,
Bonstar No. 0000), the surface of the antireflection film was rubbed 20 times with a load of 200 g / cm ² to perform a scratch resistance test. As a result, no scratch was observed and the sample had good scratch resistance. When a fingerprint was attached to the surface, it could be easily wiped off with tissue paper. Furthermore, the surface internal resistance of the antireflection film measured at a diagonal of A4 size was 1.7 kΩ.
In addition, the performance as an anti-reflection film could be maintained even after reliability tests such as humidity resistance, heat cycle, and ultraviolet irradiation. As described above, it has been found that a conductive antireflection film having excellent antireflection performance and having practically sufficient mechanical strength can be obtained.

[0035]

According to the present invention, the substrate / hard coat layer /
Excellent antifouling property and mechanical strength by forming an adhesion layer / conductive layer / low refractive index layer, giving an antifouling function to the outermost low refractive index layer, and forming it by a wet coating method. In addition, the cost of the conductive antireflection film can be reduced. The conductive antireflection film of the present invention can be suitably used as an antireflection film for a display or the like.

[Brief description of the drawings]

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Anti-reflection film 2 ... Transparent plastic film base material 3 ... Hard coat layer 4 ... Adhesion layer 5 ... Anti-reflection layer 5a ... Conductive layer 5b ... Low refractive index layer

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G09F 9/00 313 G02B 1/10 A H04N 5/72 Z (72) Inventor Tetsuya Takahashi 1-5 Taito, Taito-ku, Tokyo No. 1 Letterpress Printing Co., Ltd. (72) Inventor Haruo Uyama 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd. F-term (reference) 2K009 AA02 AA05 CC02 CC09 CC24 CC42 DD02 EE03 EE05 4F100 AA12B AA20D AB11D AD04B AD05D AK01C AK25 AK42 AT00A BA03 BA04 BA07 BA10A BA10C CC00D EH66 GB41 JD14B JG01B JK01 JK12D JL06C JN01A JN06 JN18C JN30 5C058 DA01 DA04 DA10 5G435 AA00H03 A01H11

Claims (5)

[Claims] 1. An anti-reflection film comprising an optical functional layer in which a conductive layer and a low refractive index layer made of an organic resin are alternately laminated on a transparent plastic film substrate. An antireflection film to which a resin or compound having antifouling properties is added. 2. An optical functional layer comprising a light absorbing conductive layer and a low refractive index layer made of an organic resin having a refractive index of 1.70 or less alternately laminated on a transparent plastic film substrate. The anti-reflection film according to claim 1, wherein: 3. The anti-reflection film according to claim 1, wherein a hard coat layer is provided between the transparent plastic film substrate and the optical functional layer. 4. An adhesion layer made of any one of silicon, silicon oxide, and silicon nitride, or a mixture of two or more thereof, is formed on a surface opposite to the low refractive index layer provided on the conductive layer. The anti-reflection film according to any one of claims 1 to 3, wherein 5. The anti-reflection film according to claim 2, wherein said light-absorbing conductive layer is made of titanium nitride.