JP2000147209A - Antireflection film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antireflection film having high adhesion between the substrate and antireflection layer and excellent in scratch and wear resistance and surface hardness. SOLUTION: When an antireflection layer is laminated on a substrate film by way of a hard coat layer to obtain an antireflection film, the proportion of Si in the element composition of the surface of the hard coat layer is adjusted to 2-35 at.% of the total amount of Si, C and O by blending the materials in an appropriate ratio or by applying discharge treatment, and the antireflection layer is laminated on the resultant surface of the hard coat layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film which can be suitably used for flat panel displays and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, flat panel displays (liquid crystal displays, plasma displays, EL displays, etc.) and CRT displays have had a problem that external light is reflected on the surface and visual information inside is difficult to see. To prevent such a problem, anti-reflection is performed by etching the surface, but there is a drawback that not only is there variation in quality but also transmission image quality is deteriorated.

Therefore, a method has been proposed in which an antireflection film is formed by a combination of a low refractive index layer and a high refractive index layer by a method such as coating, vapor deposition, sputtering, or plasma CVD.
The material of the low-refractive-index layer and the high-refractive-index layer in the antireflection film is mainly made of a metal oxide material. .1
A single layer and a plurality of layers of a metal-containing thin film of about μm are laminated.

[0004]

However, the antireflection film has a problem that it has poor adhesion to the substrate and abrasion resistance, and has a low surface hardness due to the thick film. for that reason,
A technique of providing a layer having an acrylate-based functional group as a hard coat layer (cured coating layer) on a base material to improve the surface hardness is widely used. However, there remains a problem in adhesion between the hard coat layer made of an organic material and the metal-containing thin film made of an inorganic material, and a problem such as peeling of the surface of the metal-containing thin film remains. As a method of improving the adhesion between the metal-containing thin film and the hard coat layer, for example, a method of performing corona discharge treatment on the surface of an acrylic hard coat is known, but the effect of improving the adhesion is not sufficient. When the treatment time is extended, the surface of the base material is greatly deteriorated, and conversely, the adhesion is reduced. Also, a method of mixing amorphous silica particles with an acrylic hard coat paint to improve the adhesion to a metal-containing thin film (Japanese Patent Laid-Open No. 5-162261) and a method of improving the adhesive properties by using an organopolysiloxane are known. Although these methods have been proposed, the surface hardness is certainly improved, but the effect on the adhesion is insufficient.

The present invention solves the above-mentioned problems, has excellent surface hardness, has high adhesion between a substrate and an antireflection layer via a hard coat layer, and is used as a film suitable for antireflection applications. It is an object of the present invention to provide an antireflection film that can be used and a method for manufacturing the same.

[0006]

Means for Solving the Problems In order to achieve the above object, the present invention according to claim 1 (hereinafter referred to as "the present invention 1").
In an antireflection film in which an antireflection layer is laminated on a base film via a hardcoat layer, the hardcoat layer is a polyfunctional acrylate (A) 100
Curing a composition comprising 1 part by weight of at least one silicon-based compound (B) selected from the group consisting of silica particles, organopolysiloxane, and silicon acrylate surface-coated with an organic substance Wherein the ratio of Si in the elemental composition of the surface of the hard coat layer is 2 to 35 atomic% with respect to the total amount of Si, C and O. I will provide a. In the present invention described in claim 2 (hereinafter referred to as “the present invention 2”), in the antireflection film in which an antireflection layer is laminated on a base film via a hardcoat layer, Is at least one silicon-based compound (B) 1-70 selected from the group consisting of 100 parts by weight of a polyfunctional acrylate (A), silica particles surface-coated with an organic substance, an organopolysiloxane, and silicon acrylate. % Of urethane acrylate (C) and 5 to 100 parts by weight of a urethane acrylate (C), and the ratio of Si in the elemental composition of the surface of the hard coat layer is S
Provided is an antireflection film, which is 2 to 35 atomic% based on the total amount of i, C, and O.

Further, in the present invention described in claim 3 (hereinafter referred to as “the present invention 3”), the antireflection layer is constituted by a laminate of a SiO ₂ layer and a TiO ₂ layer. 3. An antireflection film according to 1 or 2.
Further, in the present invention described in claim 4 (hereinafter referred to as “the present invention 4”), the ratio of Si in the element composition on the surface of the hard coat layer is 2 to the total amount of Si, C, and O. ~
The antireflection film according to any one of claims 1 to 3, further comprising a hard coat layer that has been subjected to a discharge treatment so as to have a concentration of 35 atomic%. In the present invention according to claim 5 (hereinafter referred to as “the present invention 5”), a method for producing an antireflection film by laminating an antireflection layer on a base film via a hard coat layer, The ratio of Si in the elemental composition on the surface of the hard coat layer is 2 with respect to the total amount of Si, C, and O.
The surface is subjected to a discharge treatment so as to have a discharge current density of 0.1 to 35 atomic%.
The production of an antireflection film according to any one of claims 1 to 4, wherein a discharge plasma is generated by applying an electric field so as to be ² to 300 mA / cm2, and an antireflection layer is laminated. Provide a way.

According to the present invention, a pulsed electric field is applied between the pair of opposed electrodes. Provided is a method for manufacturing an antireflection film. Further, in the present invention described in claim 7 (hereinafter referred to as “the present invention 7”), the voltage rise time in applying the pulsed electric field is 100 μs or less, and the intensity of the pulse electric field is 1 to 100 kV / The method for producing an antireflection film according to claim 6, wherein the thickness is in the range of cm. The present invention described in claim 8 (hereinafter referred to as “the present invention 8”)
), The frequency of the pulsed electric field is 0.
The method for producing an antireflection film according to claim 6 or 7, wherein the pulse width is 5 to 100 kHz and one pulse duration is 1 to 1000 µs.

<Base Film> The material of the base film used in the present invention is not particularly limited. For example, polyethylene, polypropylene, polyester, regenerated cellulose, diacetyl cellulose, triacetyl cellulose, polyvinyl chloride, polyvinyl chloride Examples include vinylidene, polyvinyl alcohol, polystyrene, polyethylene terephthalate (PET), polycarbonate (PC), polyimide, and nylon. Preferably, it is a transparent resin substrate, and these are not particularly limited, and examples thereof include triacetyl cellulose, polyethylene terephthalate, and polycarbonate.

<Hard Coat Layer> Examples of the polyfunctional acrylate (A) used in the present invention include pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol penta (meth) acrylate, Dipentaerythritol penta (meth) acrylate, pentaerythritol (meth) tetraacrylate, dipentaerythritol (meth) tetraacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol glycidyl (meth) acrylate , Trimethylolpropane tri (meth) acrylate, and derivatives and modified products thereof. These may be used alone or in combination of two or more.

The silicon-based compound (B) used in the present invention comprises at least one silicon-based compound selected from the group consisting of silica particles, organopolysiloxane and silicon acrylate, surface-coated with an organic substance. Examples of the silica particles surface-coated with the organic material include those shown in FIGS. Here, Co-Si indicates colloidal silica, and in FIG. 2, R ¹ and R ² each represent an alkyl group. Note that R ¹ and R ² may be different from each other or may be the same. Examples of the silica particles surface-coated with the organic material include Toshiba Silicone Co., Ltd .; product numbers “UVHC-1103” and “UVHC-
1105 "and the like.

If the particle size of the silica particles surface-coated with the organic material is too small, the viscosity of the hard coat paint becomes high, so that the coating becomes difficult. If the particle size is too large, the haze value after the coating decreases, 0.1
To 3 μm, more preferably 0.2 to 0.7 μm.
μm is preferred.

As the organosiloxane resin, those having the following structures can be used.

[0014]

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[0015]

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[0016]

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Here, m and n are integers of 0 or more, and m
≧ 0, n ≧ 0, 10 ≦ m + n ≦ 100, more preferably 15 ≦ m + n ≦ 50. When m + n <10, the hardness is low, and the hard coat performance is inferior. When m + n> 100, the coating material has a high viscosity, which causes a problem in coating.

The silicon acrylate has the general formula (C)
H_ThreeO)_ThreeSiR^ThreeO-CO-CR ^Four= CH_TwoIndicated by
And R^Three, R^FourRepresents an alkyl group
You. Note that R^ThreeAnd R^FourMay be different
However, they may be the same.

If the amount of the silicon-based compound (B) is too small, the surface hardness of the obtained hard coat layer will be low, and if it is too large, cracks will occur in the cured hard coat and the adhesion will be reduced. . Therefore, in the present invention 1, 1 to 40 parts by weight of the polyfunctional acrylate (A) is used.
It is preferably 3 parts by weight, more preferably 3 to 20 parts by weight. If the amount is less than 1 part by weight, the surface height is low and the adhesion is not improved. On the other hand, when the amount is more than 40 parts by weight, cracks occur in the hard coat after curing, and the adhesion is reduced. In the present invention 2, the polyfunctional acrylate (A) 10
0 parts by weight, preferably 1 to 70 parts by weight, more preferably 10 to 70 parts by weight based on 5 to 100 parts by weight of urethane acrylate.
６０60 parts by weight. If the amount is less than 1 part by weight, the surface height is low and the adhesion is not improved. If the amount is more than 70 parts by weight, cracks occur in the hard coat after curing,
Adhesion decreases.

In order to adjust the viscosity of the hard coat paint, a diluting solvent may be used. These are not particularly limited as long as they are non-polymerizable, and include, for example, toluene, xylene, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, isopropyl alcohol, methyl ethyl ketone and the like. These diluting solvents may be used alone or in combination of two or more.

The urethane acrylate (C) used in the present invention is produced by a known method using a polyol, a diisocyanate, and a hydroxy (meth) acrylate which are used alone or in combination of two or more.

Examples of the above polyol include spiroglycol, ethoxylated bisphenol A, ethoxylated bisphenol S, polytetramethylene oxide diol, polytetramethylene oxide triol, polypropylene oxide diol, and polypropylene oxide triol.

As the diisocyanate, for example,
Tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2, 4-
Tolylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalenediisocyanate,
3,3′-dimethyl-4,4-diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate and the like.

Examples of the hydroxy (meth) acrylate include 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane and bis [4- (3-acryloxy-2-hydroxypropoxy) Phenyl] methane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4,4-bis [4- (3 -Acryloxy-2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene,
9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] anthraquinone, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, glycidol dimethacrylate, pentaerythritol triacrylate and the like.

Examples of the urethane acrylate (C) include those manufactured by Dainichi Seika; product number "EXS-07".

If the amount of the urethane acrylate (C) is too small, the flexibility and adhesion of the obtained hard coat layer are reduced, and if it is too large, the hard coat performance after curing is reduced. Therefore, polyfunctional acrylate (A)
The urethane acrylate (C) is preferably 5 to 100 parts by weight, more preferably 7 to 40 parts by weight, based on 100 parts by weight and 1 to 70 parts by weight of the silicon compound (B). If the amount is less than 5 parts by weight, the flexibility and the adhesion are not improved. If the amount is more than 100 parts by weight, the performance of the hard coat is reduced. As a more preferable composition of the hard coat layer, a composition comprising 100 parts by weight of the polyfunctional acrylate (A), 10 to 60 parts by weight of the silicon-based compound (B), and 7 to 40 parts by weight of the urethane acrylate (C) is exemplified. .

In the present invention, to form a hard coat layer, a composition comprising a polyfunctional acrylate (A), a silicon compound (B) and a urethane acrylate (C) is applied on a transparent substrate, Dry and cure. As a method of applying the composition on a transparent substrate, a known coating method such as spray coating, gravure coating, roll coating, bar coating, or the like can be used. The coating amount is adjusted to a desired thickness in consideration of required physical properties.

The method of curing the hard coat composition coated on the transparent substrate and dried as described above is not particularly limited as long as it initiates and accelerates the polymerization reaction of acryloyl groups. Instead, it can be performed by a known method.

In the case of curing by ultraviolet irradiation, a conventionally known photopolymerization initiator can be used.
-Dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, benzoinpropyl ether, benzyldimethyl ketal, N, N, N ', N'- Examples thereof include tetramethyl-4,4'-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and other thioxantho-based compounds.

In the case of curing by heating, examples of the initiator include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate and the like. These initiators may be used alone or in combination of two or more.

In the composition for hard coating, pigments, fillers, surfactants, dispersants, plasticizers, ultraviolet absorbers, antioxidants, etc. are used as needed, as long as the performance is not impaired. You may. These may be used alone or in combination of two or more.

The thickness of the hard coat layer is 1 to 15 μm.
m is preferable, and more preferably, 2 to 8 μm. If the thickness is less than 1 μm, the hardness is lowered, and if it is more than 15 μm, cracks occur in the hard coat layer itself, and the adhesion to the antireflection layer is reduced.

In the present invention, the ratio of Si occupying in the elemental composition on the surface of the hard coat layer on the substrate is Si,
The composition is designed, coated, cured, and the like so that the total amount of C and O is 2 to 35 atomic%. The ratio of Si on the surface was analyzed by ESCA, and the amount of Si / (S
i amount + C amount + O amount).

<Surface Treatment> The hard coat layer of the present invention comprises:
In order to adjust the amount of Si elements on the surface, a surface treatment may be performed after the hard coat is applied. When performing surface treatment by electric discharge treatment, the surface of the hard coat layer is etched, and-
There is no particular limitation as long as it has an effect of exposing the SiO-bond. Corona discharge, plasma discharge, treatment with an excimer laser, and the like, and chemicals for controlling the amount of Si elements by eroding the hard coat layer surface with an organic solvent. Processing and the like. Among them, a method by corona treatment or plasma treatment is preferable. The depth of the surface treatment by the above method is not particularly limited as long as there is no damage to the base material.
The angle is preferably about 150 °, more preferably 10 ° to 80 °. If it is shallower than 5 °, -SiO
-Sufficient adhesion may not be obtained due to low bond formation. On the other hand, when the angle exceeds 150 °, the damage to the substrate is large, and the interface may be separated between the hard coat and the substrate.

Si occupying the elemental composition on the surface
Is too small, the ratio of -SiO-
Is reduced, the adhesion to the anti-reflection layer formed thereon is not improved, and if too large, the hard coat substrate cracks, and the adhesion to the anti-reflection layer is reduced. To 35 atomic% based on the total amount of, C and O
And it is preferably 4 to 30%.

<Anti-reflection layer> As the anti-reflection layer of the present invention
Is TiO_TwoOn the layer and SiO_TwoUsing a laminate with layers
Is preferred. The laminate has a refractive index on the hard coat layer.
High TiO_TwoA layer (refractive index: about 1.8 to 2.2) is formed
And the TiO_TwoLow refractive index SiO on the layer _TwoLayer (refraction
Rate: about 1.4 to 1.5); a two-layer laminate formed;
On top of this, a TiO 2_TwoOn layer and SiO_Twolayer
Is preferably a four-layer laminate formed in this order. This
Such a two-layer or four-layer laminate anti-reflection layer
And can reduce the reflectance of light of a specific wavelength.
You. The thickness of the antireflection layer is such that antireflection performance is exhibited.
The thickness is not particularly limited as long as it is a transparent material,
It is preferable that the film thickness be small from the viewpoint of transmittance.

The wavelength region of visible light for which an anti-reflection effect is expected is 380 to 780 nm, and the wavelength range of particularly high visibility is 4.
Since the thickness is in the range of 50 to 650 nm, if the thickness of the antireflection layer is set within a range of ± 30% around the thickness capable of coping with the wavelength of 550 nm, the antireflection effect for visible light can be sufficiently expected.

When the antireflection layer is formed of two or more thin films, the uppermost layer (surface layer) should be near the λ / 4 film of the low refractive index material, and the high refractive index material and Preferably, the refractive indices are arranged alternately. Where 2
The film thicknesses after the first layer are set so that the reflectance at a wavelength of 450 to 650 nm becomes small, and it has a balance with the refractive index. This allows
The wavelength range of low reflection can be broadened as compared with a single-layer antireflection layer.

The method of laminating the above-mentioned antireflection layer is not particularly limited.
CVD), coating and the like. Preferably, it is formed by a normal pressure plasma CVD method.

The above TiO_TwoThe layer vaporizes the Ti raw material,
Carrier gas (Ar alone gas or O _TwoGas mixture with gas
After mixing with (a), conductivity is obtained by atmospheric pressure plasma CVD.
SiO on hard coat layer or already laminated_TwoOn the layer
It is formed by forming a film. The above SiO_TwoThe layers are
The Si raw material is vaporized and the carrier gas (Ar or N2
Single gas or a mixture thereof; these gases and O_Two
Normal pressure plasma CVD after mixing with
TiO already laminated by the method_TwoDepositing on a layer
Formed by

In the present invention, the method for producing the antireflection layer on the surface of the hard coat layer which has been subjected to the discharge treatment is a method in which the discharge current is applied between the opposing electrodes in a gas atmosphere containing a metal compound under a pressure near atmospheric pressure. Density of 0.2 to 300 mA / cm ²
A discharge plasma is generated by applying an electric field so as to form an antireflection layer.
Hereinafter, the antireflection layer formed by the normal pressure plasma CVD method will be described in detail. When the antireflection layer is formed under the following conditions, a film quality equivalent to sputtering can be obtained, and a continuous film formation equivalent to a coating method can be performed, so that productivity is very high.

In the above method for forming an anti-reflection layer, the pressure near the atmospheric pressure means a pressure of 100 to 800 Torr.
The pressure is preferably in the range of 00 to 780 Torr.

The term “discharge current density between electrodes” in the present invention refers to a value obtained by dividing a current value flowing between electrodes by discharge by an area in a direction orthogonal to a current flow direction in a discharge space. When a flat type is used, it corresponds to a value obtained by dividing the above current value by its facing area.

When a pulsed electric field is formed between the electrodes, a pulsed current flows. In this case, the maximum value of the pulse current, that is, the peak-to-peak value is divided by the above area. Value.

In the method for forming the antireflection layer of the present invention (hereinafter sometimes referred to as a thin film forming method as appropriate), a solid dielectric is provided on at least one of the opposing surfaces of the opposing electrode, and one of the electrodes is provided. The substrate is disposed between the solid dielectric placed on the opposite surface of the substrate and the other electrode, or between the solid dielectric placed on both the opposite surfaces of the counter electrode, to perform the treatment. Is preferred.

In a glow discharge under a pressure near the atmospheric pressure,
The discharge current density reflects the plasma density for the following reasons. Under a pressure near the atmospheric pressure of the gas atmosphere containing the metal compound, the discharge current density between the electrodes was set to 0.2
By setting the range to ３００300 mA / cm ² , it becomes possible to excite the metal compound with plasma and to maintain the plasma in a glow discharge state to form an antireflection layer.

Generally, the electron density in plasma, that is, the plasma density, is measured by a probe method or an electromagnetic wave method.

However, at a pressure near the atmospheric pressure, the discharge between the electrodes originally tends to shift to an arc discharge. Therefore, in the probe method in which the probe is inserted into the plasma, an arc current flows through the probe. , Accurate measurement is not possible.

Further, the electromagnetic wave method based on emission spectroscopy or laser absorption analysis is difficult to analyze because the information obtained differs depending on the type of gas.

On the other hand, in a glow discharge under a pressure close to the atmospheric pressure, the gas molecule density is higher than that in a low gas pressure discharge, so that the life after ionization and recombination is short, and the mean free path of electrons is also small. short. Therefore, there is a feature that the glow discharge space is limited to the space between the electrodes.

Therefore, the electrons in the plasma are directly converted into a current value through the electrode, and the electron density (plasma density) is considered to be a value reflecting the discharge current density. It has been found that the formation of a thin film can be controlled by the discharge current density.

FIG. 3 shows a discharge plasma generator used by the present inventors and a measurement circuit diagram used for measuring the discharge voltage and the discharge current.

In this discharge plasma generator, a pulsed power supply 3 applies kV between a pair of parallel plate type electrodes 1 and 2.
By applying a pulsed electric field of the order
A pulsed electric field was formed between the electrodes 1 and 2, and a solid dielectric 4 was provided on a surface facing one of the electrodes 2.

Then, a resistor 5 is connected in series between the one electrode 2 and the ground potential, and both ends of the resistor 5 are connected to an oscilloscope 7 via a BNC terminal 6 so that the resistor 5 is connected.
Was measured, and the discharge current was converted using the resistance value of the resistor 5.

The discharge voltage was measured by attenuating the potential of the electrode 1 to 1/1000 by the high voltage probe 8 and measuring the potential difference from the ground potential with the BNC terminal 9 to the oscilloscope 7.

In this measuring circuit, the discharge current caused by the pulsed electric field repeats energization / interruption at high speed.
The oscilloscope 7 used for the measurement was a high-frequency oscilloscope capable of measuring on the order of nanoseconds corresponding to the rising speed of the pulse, specifically, an oscilloscope DS-9122 manufactured by Iwasaki Communication Co., Ltd.

The high voltage probe 8 used for attenuating the discharge voltage was a high voltage probe SK-301HV manufactured by Iwasaki Tsushin.

FIG. 4 shows an example of the measurement result. In FIG. 4, waveform 1 is a discharge voltage, and waveform 2 is a waveform representing a discharge current. The discharge current density due to the formation of the pulse electric field is a value obtained by dividing the peak-to-peak current conversion value of the waveform 2 by the area of the electrode facing surface.

In the thin film forming method of the present invention, the discharge current density between the electrodes is 0.2 to 30 in a gas atmosphere containing a metal compound and under a pressure near the atmospheric pressure.
In order to relatively easily realize the range of 0 mA / cm ² , a method of applying a pulsed electric field between the counter electrodes can be mentioned.

At a pressure close to the atmospheric pressure, the discharge current density is 0.1
Only a low range of mA / cm ² or less is achieved, and it is difficult to maintain a plasma of a metal compound such that a metal element-containing thin film is formed. In fact, under pressure near atmospheric pressure,
It is known that a gas other than a specific gas such as helium or ketone does not stably maintain a glow discharge state, and instantaneously shifts to an arc discharge.

Accordingly, in the present invention, by applying a pulsed voltage between the electrodes, the discharge between the electrodes is stopped before the transition from the glow discharge to the arc discharge.
By forming such a periodic pulsed electric field between the electrodes, a microscopically pulsed glow discharge is repeatedly generated, and as a result, the glow discharge state is continued.

As described above, under a pressure close to the atmospheric pressure and in an atmosphere containing a metal compound, by applying a pulsed electric field between the electrodes, the discharge current density can be increased in a stable glow discharge state. 0.2-300 mA / cm ²
Is generated over a long period of time, which leads to formation of an antireflection layer.

In the present invention, the metal compound used for the anti-reflection layer is not particularly limited.
From the viewpoint of enhancing the ability to form a thin film, dimethylsilane; Si (CH ₃ ) ₂ H ₂ , tetramethylsilane; Si
(CH ₃ ) ₄ , tetradimethylaminotitanium; Ti [N
Organometallic compounds such as (CH ₃ ) ₂ ] ₄ and monosilane;
SiH ₄ , disilane; metal hydrogen compounds such as Si ₂ H ₆ , dichloride silane; SiH ₂ Cl ₂ , trichloride silane; S
iHCl ₃ , titanium chloride; metal halides such as TiCl ₄ , tetramethoxysilane; Si (OC
H ₃ ) ₄ , tetraethoxysilane; Si (OC ₂ H ₅ )
_4, tetraethoxy _{titanium; Ti (OC 2 H 5)} 4, tetraisopropoxytitanium; Ti (OC ₃ H ₇₎ or the like is preferably used a metal alkoxide such as _4. In consideration of safety, among these, metal hydrides and metal alkoxides are preferable because there is no danger of ignition or explosion at room temperature and in the air. Is more preferred.

In order to introduce the metal compound into the discharge space, the metal compound may be in a gas, liquid or solid state at normal temperature and normal pressure. In the case of a gas, it can be introduced into the discharge space as it is, but in the case of a liquid or solid, it is used after being vaporized by means such as heating or decompression.

When the metal compound is vaporized by heating, a metal alkoxide, such as tetraethoxysilane or tetraisopropoxytitanium, which is liquid at normal temperature and has a boiling point of 200 ° C. or less is suitable for the thin film forming method of the present invention. The metal alkoxide may be used after being diluted with a solvent. As the solvent, an organic solvent such as methanol, ethanol, or n-hexane, or a mixed solvent thereof may be used. The above diluting solvent is used for glow discharge.
Since it is decomposed into molecules and atoms, the effect on the formed thin film is negligible.

As described above, it is preferable to use a metal alkoxide as the metal compound of the present invention.

As described above, the “gas atmosphere containing a metal compound” means that the metal compound is contained as one component in the gas atmosphere for plasma discharge regardless of the concentration. May be occupied by the metal compound alone.

However, from the viewpoint of economy and safety, it is preferable that the above-mentioned metal compound is diluted not with a single atmosphere but with a diluent gas as exemplified below.

Examples of the diluent gas include helium, neon, argon, xenon, nitrogen and the like, and at least one mixture thereof is used.

Further, in order to obtain a high-density plasma, it is effective to decompose a gas in the presence of a compound having many electrons (compound having a large molecular weight), which can be applied to the above-mentioned diluent gas.

Accordingly, the dilution gas used in the present invention preferably has a molecular weight of 10 or more. When a gas such as helium having a molecular weight of less than 10 is used as a diluent, even if glow discharge continues, only a discharge state with a low electron density can be achieved, and a thin film is not formed, or
The formation rate is too slow, resulting in uneconomic results.

Therefore, the composition of the atmosphere gas for performing the plasma discharge is preferably a mixed gas composed of 0.0001 to 10% by volume of the metal compound and 99.9999 to 90% by volume of argon and / or nitrogen. 0.00 for metal compounds
When the content is less than 01% by volume, high-density plasma is hardly obtained, and the efficiency of forming a thin film is deteriorated.
This is because a remarkable improvement in thin film formation speed does not appear, but it is economically disadvantageous.

In the above-mentioned thin film forming method, the material of the electrode used to generate the discharge plasma is copper,
Examples thereof include simple metals such as aluminum, alloys such as stainless steel and brass, and intermetallic compounds.

Further, in order to avoid the occurrence of arc discharge due to electric field concentration, it is preferable that the electrodes have a structure in which the distance between the electrodes is substantially constant. Examples thereof include an opposed flat plate type, a spherical opposed flat plate type, a hyperboloid opposed flat plate type, and a coaxial cylindrical type structure.

In the present invention, it is preferable to provide a solid dielectric on one or both of the opposing surfaces of the electrodes. In addition, if there is a portion where the electrodes directly face each other without being covered by the fixed dielectric, an arc discharge is likely to occur therefrom, so that the solid dielectric is in close contact with the electrode on which the solid dielectric is placed and is in contact with Is completely covered.

The solid dielectric may be in the form of a sheet or a film, but preferably has a thickness of about 0.5 to 5 mm. If the thickness is too large, a high voltage is required to generate discharge plasma. If it is too thin, dielectric breakdown occurs when voltage is applied, and arc discharge occurs.

The material of the solid dielectric may be plastic such as polytetrafluoroethylene or polyethylene terephthalate, glass, metal oxides such as silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide, and double oxides such as barium titanate. Is mentioned.

However, the solid dielectric has a relative dielectric constant of 2
It is preferable that the above conditions (under a 25 ° C. environment, the same applies hereinafter).
Examples of such a dielectric include polytetrafluoroethylene, glass, and a metal oxide film.

When the discharge current density is 0.2 to 300 mA /
In order to stably generate discharge plasma of cm ^2, it is advantageous to use a fixed dielectric having a relative dielectric constant of 10 or more.

Although the upper limit of the relative permittivity is not particularly limited, it is known that the actual material is about 18,500. As a solid dielectric having a relative dielectric constant of 10 or more,
5 to 50% by weight of titanium oxide, 50 of aluminum oxide
It is preferable to use a metal oxide film mixed at ~ 95 wt% or a metal oxide film containing zirconium oxide and having a thickness of 10-1000 [mu] m.

The distance between the pair of electrodes in the present invention is determined in consideration of the thickness of the solid dielectric, the magnitude of the applied voltage, the purpose of using plasma, and the like, and is preferably 1 to 50 mm. If it is less than 1 mm, it is insufficient to provide a space for disposing the base material when plasma generated during the process is used for surface treatment or the like, and if it exceeds 50 mm, it becomes difficult to generate uniform discharge plasma. .

In the present invention, when a pulse voltage is applied between the electrodes, the pulse waveform is not particularly limited, but may be an impulse type as illustrated in FIGS. ) And a modulation type as illustrated in (D) can be used. This figure 5
Illustrates an example in which the applied voltage is a repetition of positive and negative, but a positive or negative pulse voltage of only one polarity,
A so-called one-sided pulse voltage may be applied.

In the present invention, as for the pulse voltage applied between the electrodes, the shorter the rise time and the fall time of the pulse, the more efficiently the ionization of the gas at the time of plasma generation.

In particular, the rise of the pulse voltage applied between the electrodes is preferably 100 μs or less. 10
When the time exceeds 0 μs, the discharge state easily shifts to arc discharge, and becomes unstable. Further, there is an effect that a pulsed electric field having such a fast rise time realizes a discharge state having a high electron density.

The fall time of the pulse voltage is not particularly defined, but is preferably as fast as the rise time, more preferably 100 μs or less.

The lower limit of the rise / fall time is not particularly limited.
The above is realistic.

Here, the rise time refers to the time during which the direction of the voltage change is continuously positive, and the fall time refers to the time during which the direction of the voltage change is continuously negative. I do.

The pulse electric field formed between the electrodes may have its pulse waveform, rise and fall times, and frequency appropriately modulated.

The higher the frequency and the shorter the pulse width of the pulse electric field, the more suitable for the high-speed continuous thin film formation.

In the present invention, the frequency of the pulse electric field applied between the electrodes is preferably in the range of 0.5 kHz to 100 kHz. If it is less than 0.5 kHz, the thin film forming speed is too slow to be realistic, and if it exceeds 100 kHz, arc discharge is likely to occur. The frequency of the pulsed electric field is more preferably 1 kHz.

Further, the pulse duration in the pulse electric field is preferably 1 μs to 1000 μs, more preferably 3 μs to 200 μs. If it is less than 1 μs, the discharge becomes unstable, and if it exceeds 1000 μs, it is easy to shift to arc discharge.

Here, the pulse duration refers to the continuous duration of one pulse waveform in a pulse electric field where ON / OFF is repeated as illustrated in FIG.
In the waveform of (a), the pulse duration = pulse duty time, whereas in the waveform of FIG. 4 (b), it refers to the time during which the ON state is continued, including a plurality of pulses.

Further, in the present invention, the intensity of the pulse electric field is appropriately selected depending on the purpose of use of the discharge plasma, and is preferably 1 to 100 kV / cm.

If the pressure is less than 1 kV / cm, the rate of forming a thin film is reduced. If the pressure exceeds 100 kV, an arc discharge is undesirably generated.

FIG. 7 is a block diagram showing an example of the configuration of a power supply circuit for forming a pulse electric field satisfying the above conditions, and FIG. 8 is an equivalent circuit diagram showing the principle of the operation. Indicated by 8, SW1 to SW4 are semiconductor elements that function as switches in the switching inverter circuit in FIG.
By using a semiconductor device having a turn-on time and a turn-off time of 0 ns or less, the electric field strength is 1 to 100
It is possible to realize a high-voltage and high-speed pulse electric field with kV / cm and pulse rise and fall times of both 40 ns to 100 μs.

Next, the principle of operation will be briefly described with reference to FIG. + E is a positive DC voltage supply unit, and -E is a negative DC voltage supply unit. SW1 to SW4 are switching elements made of the high-speed semiconductor elements described above. D
Numerals 1 to 4 denote diodes, and I1 to I4 indicate the directions in which electric charges move.

First, when SW1 is turned on, the electric charge is I1
Then, one side (positive load) of a pair of electrodes placed at both ends of the discharge space is charged.

Next, after SW1 is turned off, SW2
Is turned on instantaneously, the electric charge charged to the load of positive polarity moves in the direction of I3 through SW2 and D4.

Next, after SW2 is turned off, SW3
Is turned on instantaneously, the charge moves in the direction of I2 and charges the other electrode (negative load).

Further, after SW3 is turned off, SW4
Is turned on instantaneously, the electric charge charged to the negative load moves in the direction of I4 through SW4 and D2.

By repeating the above operation, an output pulse having the waveform shown in FIG. 9 can be obtained. [Table 1]
The operation table is shown in FIG. The numerical values shown in Table 1 correspond to the numerical values given to the waveforms in FIG.

[0102]

[Table 1]

The advantage of the above circuit is that even if the load has a high impedance,
2 and D4 or SW4 and D2 to discharge reliably, and high-speed turn-on switching elements SW1 and SW3 to perform high-speed charging. 6, it is possible to apply a pulsed electric field having an extremely short rise time and fall time to a load, that is, between a pair of electrodes.

The pulse electric field used in the thin film forming method of the present invention does not prevent superposition of a DC electric field.

The method of forming a thin film in the present invention utilizes the plasma generated between the counter electrodes by the above-described method of generating a discharge plasma unique to the present invention, and is used between the counter electrodes or one of the electrodes. When a solid dielectric is provided on the facing surface, between the solid dielectric and the other electrode, or when a solid dielectric is provided on the facing surface of both electrodes, between the solid dielectrics, Place the substrate to be treated.

In the method of the present invention, the substrate on which a thin film is to be formed may be heated or cooled, but can be sufficiently processed even at room temperature.

In the antireflection film of the present invention, an antifouling layer can be further formed on the surface of the antireflection layer. As the antifouling layer, a fluorine-based silane coupling agent,
The antireflection layer is formed by coating and drying with a coating device such as a spin coater, a dipping device, and a microgravure coater. It should be noted that continuous processing cannot be performed with a spin coater or dipping apparatus, and batch processing is performed.

Examples of commercially available fluorine-based silane coupling agents include, for example, a coating agent “KP-8” manufactured by Shin-Etsu Chemical Co., Ltd.
01M "[CF3 (CF2) n C2H4Si (NH2) 3] and Toshiba Silicon Corporation [100% solution of CF3 (CF2) 7C2H4Si (OCH3) 3]. The coating agent “KP-801M” is a solvent TFB
[Ingredient: 1,3-bis (trifluoromethyl) benzene,
Central Glass Co., Ltd.].

The antifouling layer can be formed, for example, by applying a diluting antifouling agent with a solvent using a spin coater, a dipping device, a microgravure coater or the like. When the above spin coater and dipping apparatus are used, continuous processing cannot be performed and batch processing is performed.

In the antireflection film of the present invention, a pressure-sensitive adhesive layer may be provided on the other surface of the base material (the side on which the antireflection layer is not laminated). As the pressure-sensitive adhesive, those capable of firmly bonding an optical component such as a base material or a polarizing plate, and which do not foam even under high temperature and high humidity conditions are preferable.
Acrylic adhesives are preferably used.

As the acrylic pressure-sensitive adhesive, for example,
Acrylic (meth) acrylate as a main component, 100 parts by weight of an acrylic polymer having a weight average molecular weight (Mw) of 500,000 or less and Mw / Mn (number average molecular weight) of 4 or less, dimethyl silicone oil or part of a side chain 0.01 to 5 parts by weight of a defoaming agent composed of a modified silicone oil in which is substituted by another organic group, 0.01 to 5 parts by weight of a re-stripping agent composed of a methyl hydrogen silicone oil, and 0.001 to 1 part by weight of a crosslinking agent Those comprising 5 parts by weight are preferred. As a commercially available acrylic pressure-sensitive adhesive, for example, "SK Dyne 2902" manufactured by Soken Chemical Co., Ltd. can be used.

The pressure-sensitive adhesive layer may be formed, for example, by directly applying the acrylic pressure-sensitive adhesive to a base material. After the pressure-sensitive adhesive layer is provided on release paper in advance, the base material is applied to the base material by a laminator or the like. They may be formed by lamination.

(Function) In the present invention 1, the base film is
In the antireflection film in which the antireflection layer is laminated via the hardcoat layer, the hardcoat layer is obtained by curing a composition comprising the polyfunctional acrylate (A) and the silicon compound (B). Thus, a hard coat layer having excellent surface hardness can be formed.
The ratio of Si in the elemental composition on the surface of the hard coat layer is 2 to 2 with respect to the total amount of Si, C, and O.
Since the content is 35 atomic%, the intermolecular force generally increases at the interface between the antireflection layer made of a metal oxide film and the SiO _{2 in} the hard coat layer, and the adhesion and surface hardness between the hard coat layer and the antireflection layer are exhibited. can do. In the present invention 2,
In addition to the above composition, a composition comprising a urethane acrylate (C) is cured, whereby the flexibility of the film can be easily adjusted, the generation of cracks on the surface can be suppressed, and the reflection of the hard coat layer can be prevented. The adhesion to the prevention layer and the surface hardness can be further exhibited. The present invention 3
In anti-reflection layer is constituted by a stack of the SiO ₂ layer and a TiO ₂ layer, on the hard coat layer, high refractive index TiO ₂ layer is formed further, a low refractive index SiO ₂
By stacking the layers, the reflectance of light can be lowered, and an antireflection layer having good adhesion to the hard coat layer can be formed. In the present invention 4, the ratio of Si in the element composition on the surface of the hard coat layer is S
It has a hard coat layer that has been subjected to a discharge treatment so as to be 2 to 35 atomic% with respect to the total amount of i, C, and O. By performing the discharge treatment on the hard coat layer as described above, the Si element is exposed on the surface of the hard coat, so that the bond due to the intermolecular force with the Si and Ti elements used for the antireflection layer formed thereafter becomes stronger. Therefore, adhesion and surface hardness are dramatically improved. Further, in the method for producing an antireflection film of the present invention, in the method of laminating an antireflection layer on a base film via a hardcoat layer, after performing the discharge treatment on the hardcoat layer, the normal pressure plasma C
An anti-reflection layer is laminated using a VD method. Therefore, according to the present invention, since the Si on the hard coat surface and the Si and Ti elements usually contained in the anti-reflection layer are bonded by a covalent bond such as -SiO-, the hard coat layer and the anti-reflection layer are different from the conventional product. Further, a strongly adhered antireflection film can be obtained.
Further, the formation of the antireflection layer, which has been conventionally performed under a low pressure, can be performed in a short time at around the atmospheric pressure.

[0114]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

(Example 1) <Coating of hard coat layer>
Noh acrylate (EXF37 manufactured by Dainichi Seika) 100
Parts and colloidal silica (Toshiba Silicone Co., UVH
C-1105) A mixed solution of 10 parts by weight with toluene
The mixture was diluted and adjusted so that the content of the mixed solution became 40%.
Next, transparent triacetate (hereinafter abbreviated as TAC)
Film (TAC, KC-80UV, 8 manufactured by Konica Corporation)
0 μm) on one side with a microgravure coater.
Then, after applying the above hard coating agent and drying by heating,
00mmJ / cm ^TwoIrradiate with UV lamp at 5μ thickness
m of hard coat layers were formed. <Surface treatment> The surface of the hard coat film was 0.6
The corona discharge treatment was performed four times at kW and 3 m / min. the above
Corona discharge treated hard coat layer surface by ESCA
Surface analysis was performed to determine Si content / (Si content + C content + O content).
However, although it is 10 atomic% before corona discharge treatment,
After the corona discharge treatment, the content was 17 atomic%.

<Formation of Antireflection Layer> (1) Processing Apparatus The discharge plasma processing apparatus used was composed of a stainless steel container 82 having a capacity of 10 liters, as shown in FIG. Power supply 81-2, upper power supply 84, lower power supply 85, solid dielectric 86 (also mounted on the upper electrode, but not shown in FIG. 10), base material 8
7. Gas introduction pipe 88, dilution gas introduction pipe, gas exhaust port 81
0, and an exhaust port 811. (2) Formation of TiO ₂ layer and SiO ₂ layer In the above processing apparatus, the lower electrode 85 has a diameter of 140 mm.
The surface is made of zirconium dioxide having a relative dielectric constant of 16 (hereinafter, referred to as zirconium dioxide).
The hard coat film was disposed as a substrate 87 coated with a dielectric 86 (described as ZrO ₂ ) and treated thereon.

The upper electrode 84 has a diameter of 80 mm and a diameter of 1 mm.
mm holes were provided at 5 mm intervals, and the surface was covered with a ZrO ₂ dielectric 86 having a relative dielectric constant of 16, and was disposed 2 mm above the hard coat film surface.

After exhausting the gas from the gas outlet 811 using an oil rotary pump (not shown in FIG. 10) until the pressure in the container reaches 0.1 Torr, argon (Ar) gas is introduced through the dilution gas introduction pipe 89. , Container pressure 760T
orr.

Thereafter, a mixed gas of vaporized tetraisopropoxytitanium and argon is introduced from a (reaction) gas introduction pipe 88 connected to the upper electrode 84, and a gas pressure ratio (volume ratio) in the vessel after the introduction of the mixed gas is introduced. ) Is tetraisopropoxytitanium: argon = 0.0075: 99.99
925 was adjusted.

After introducing the mixed gas for one minute, a pulse electric field having a peak value of 4 kV and a frequency of 6 kHz is applied between the upper electrode 84 and the lower electrode 85, and the titanium dioxide is discharged to the discharge plasma generating space 83 for 3 seconds. (TiO ₂ ) thin film 1
80 ° was formed on the hard coat surface.

Subsequently, a mixed gas of vaporized tetraethoxysilane, argon, and oxygen is introduced from a (reaction) gas introduction pipe 88 connected to the upper electrode 84, and a gas pressure ratio in the vessel after the introduction of the mixed gas ( (Volume ratio) is tetraethoxysilane: argon: oxygen = 0.0006: 83.9
It was adjusted to be 994: 16.

After introducing the above mixed gas for one minute, a pulse electric field having a peak value of 16 kV and a frequency of 8 kHz is applied between the upper electrode 84 and the lower electrode 85, and discharge is performed for 3 seconds in the discharge plasma generation space 83 to produce silicon dioxide. (SiO ₂ ) thin film 2
60 ° was laminated on the TiO ₂ thin film surface.

Further, in the same manner as described above, a TiO ₂ thin film 1410 # (discharge time: 20 seconds) is laminated,
_Two thin films of 880 ° (discharge time: 10 seconds) were laminated to obtain a four-layer antireflection film.

<Evaluation Method> (1) Surface Si Element Amount The ratio of the Si element amount of the hard coat layer after the surface treatment is ES.
Analyzed by CA, Si amount / (Si amount + C amount + O amount)
Was calculated. (2) Pencil hardness The pencil hardness of the anti-reflection film was determined according to JIS-K6894.
It evaluated according to. (3) Scratch resistance The anti-reflection film is made of steel wool (# 0000)
After rubbing under a pressure of 200 g / cm ² for 30 times, ○ was given if there was no damage, and X was given if there was damage. (4) Tape peeling test The above antireflection film was tested under the conditions of 60 ° C. and 95% RH.
1mm × on the film surface after 00 hours with a cutter knife
Create 100 blocks of 1 mm vertical stitches and apply JIS D
A tape peeling test was performed in accordance with No. 0202. After the peeling test, the number remaining without peeling was shown. (As a result of the tape peeling test, the case where the anti-reflection layer was
0/100) The above evaluation results are shown in Table 2.

[0125]

[Table 2]

Example 2 <Coating of Hard Coat Layer> As a hard coat agent, 100 parts by weight of a polyfunctional acrylate (EXF37, manufactured by Dainichi Seika Co., Ltd.) and colloidal silica (manufactured by Toshiba Silicone Co., Ltd., UVH
C-1105) was mixed with 5 parts by weight of a solution prepared by diluting with toluene so that the content of the mixed solution became 40%.
Next, the above hard coat agent was applied to one side of a transparent PET film (PET manufactured by Unitika Ltd., Emblet OA-188, 188 μm thick) by a microgravure coater, dried by heating, and then dried at 300 mmJ / cm ² . Irradiation with an ultraviolet lamp produced a hard coat layer having a thickness of 5 μm. <Surface Treatment> The surface of the hard coat film was subjected to a discharge treatment using the plasma treatment apparatus used in Example 1. Ar gas was used in the apparatus instead of the processing gas, and the discharge time was 1.5 seconds. The Si ratio on the surface of the hard coat layer subjected to the plasma discharge treatment was 5 atomic% before the discharge treatment, and was 19 atomic% after the discharge treatment. <Formation of anti-reflection layer> The same processing apparatus as in Example 1 was used. (Formation of TiO ₂ layer and SiO ₂ layer) In the above-described processing apparatus, the lower electrode 85 has a diameter of 140 mm and the surface has a relative dielectric constant of 16 and is made of zirconium dioxide (hereinafter referred to as ZrO ₂ ).
A hard coat film was disposed as a base material 87 covered with a dielectric 86 and treated thereon.

The upper electrode 84 has a diameter of 80 mm and a diameter of 1 mm.
mm holes were provided at 5 mm intervals, and the surface was coated with a ZrO2 dielectric 86 having a relative dielectric constant of 16, and was disposed 2 mm above the hard coat film surface.

After exhausting the gas from the gas outlet 811 with an oil rotary pump (not shown in FIG. 10) until the pressure in the container becomes 0.1 Torr, argon (Ar) gas is introduced through the dilution gas introduction pipe 89. , Container pressure 760T
orr.

Thereafter, a mixed gas of vaporized tetraisopropoxytitanium and argon is introduced from a (reaction) gas introduction pipe 88 connected to the upper electrode 84, and a gas pressure ratio (volume ratio) in the vessel after the introduction of the mixed gas is introduced. ) Is tetraisopropoxytitanium: argon = 0.0075: 99.99
925 was adjusted.

After introducing the mixed gas for one minute, a pulse electric field having a peak value of 4 kV and a frequency of 6 kHz is applied between the upper electrode 84 and the lower electrode 85, and the titanium dioxide is discharged to the discharge plasma generating space 83 for 3 seconds. (TiO ₂ ) thin film 1
80 ° was formed on the hard coat surface.

Subsequently, a mixed gas of vaporized tetraethoxysilane, argon, and oxygen is introduced from a (reaction) gas introduction pipe 88 connected to the upper electrode 84, and a gas pressure ratio in the vessel after the introduction of the mixed gas ( (Volume ratio) is tetraethoxysilane: argon: oxygen = 0.0006: 83.9
It was adjusted to be 994: 16.

After introducing the above mixed gas for one minute, a pulse electric field having a peak value of 16 kV and a frequency of 8 kHz is applied between the upper electrode 84 and the lower electrode 85, and discharge is performed for 3 seconds in the discharge plasma generation space 83 to produce silicon dioxide. (SiO ₂ ) thin film 2
60 ° was laminated on the TiO ₂ thin film surface. Table 2 shows the evaluation results.

Example 3 An antireflection film was obtained in the same manner as in Example 1, except that the surface treatment was not performed on the hard coat layer. Table 2 shows the evaluation results.

Example 4 <Coating of Hard Coat Layer> As a hard coat agent, 100 parts by weight of a polyfunctional acrylate (EXF37, manufactured by Dainichi Seika Co., Ltd.), colloidal silica (TAC, manufactured by Toshiba Silicone Co., Ltd.)
A mixed solution of 35 parts by weight of (UVHC-1105) and 10 parts by weight of urethane acrylate (EXS-07, manufactured by Dainichi Seika Co., Ltd.) was diluted and adjusted with toluene so that the content of the mixed solution became 40%. Next, a transparent PET film (PET manufactured by Unitika, Inc., OA-188, 188 μm)
m thickness) on one side with a microgravure coater
After applying the above hard coat agent and drying by heating, 300
Irradiation with an ultraviolet lamp at mmJ / cm ² was performed to form a hard coat layer having a thickness of 5 μm. Table 2 shows the evaluation results. <Formation of anti-reflection layer> The hard coat layer was not subjected to surface treatment, and four anti-reflection layers were formed in the same manner as in Example 1 to obtain an anti-reflection film.

Comparative Example 1 An antireflection film was obtained in the same manner as in Example 1, except that the colloidal silica was changed to 80 parts by weight of the hard coat agent. Table 2 shows the evaluation results.

Comparative Example 2 An anti-reflection film was obtained in the same manner as in Example 1, except that the silicon acrylate containing silica particles was not added and the surface treatment was not performed. Table 2 shows the evaluation results.

According to the first aspect of the present invention, since it has the above-mentioned structure, the adhesion between the hard coat layer and the antireflection layer and the surface hardness can be exhibited. Further, in the present invention 2, since the composition comprising urethane acrylate is cured in addition to the constitution of the present invention 1, the flexibility of the film can be easily adjusted, the generation of cracks on the surface is suppressed, and The adhesion between the coat layer and the antireflection layer and the surface hardness can be further exhibited. Also, in the present invention 3, the anti-reflection layer is made of SiO.
Because it is composed of a laminate of _two layers and TiO ₂ layer,
An antireflection layer having good adhesion to the hard coat layer can be formed. Further, in the present invention 4, the discharge treatment was performed such that the ratio of Si in the elemental composition on the surface of the hard coat layer was 2 to 35 atomic% with respect to the total amount of Si, C, and O. Due to the presence of the hard coat layer, the adhesion to the antireflection layer and the surface hardness are further dramatically improved. In the method for producing an antireflection film of the present invention, the discharge treatment is performed on the hard coat layer, and the antireflection layer is laminated using the normal pressure plasma CVD method. An antireflection film in which the antireflection layer is further firmly adhered is obtained. Further, the formation of the antireflection layer, which has been conventionally performed under a low pressure, can be performed in a short time at around the atmospheric pressure.

[0137]

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of silica particles surface-coated with an organic substance.

FIG. 2 is an explanatory diagram showing another example of silica particles surface-coated with an organic substance.

FIG. 3 is an explanatory diagram showing an example of a discharge plasma generator used in the present invention and a measurement circuit diagram used for measuring a discharge voltage and a discharge current thereof.

FIG. 4 is a discharge voltage (waveform 1) obtained by the apparatus of FIG.
7 is a graph showing measurement results of a discharge current and a discharge current (waveform 2).

FIG. 5 is an explanatory diagram showing an example of a waveform of a pulse voltage applied between a pair of electrodes in the present invention.

FIG. 6 is an explanatory diagram of a pulse electric field duration in the present invention.

FIG. 7 is a block diagram illustrating a configuration example of a power supply circuit suitable for use in a device to which the present invention is applied.

8 is an explanatory diagram of the operation principle of the circuit of FIG. 7 shown in an equivalent circuit diagram.

FIG. 9 is an explanatory diagram of a pulse voltage waveform that can be obtained by the operation principle shown in FIG. 8;

FIG. 10 is a schematic diagram showing a configuration of a discharge plasma generator used in each embodiment of the present invention.

[Explanation of symbols] [Explanation of symbols]

 Co-Si colloidal silica 1, 2 electrode 3 pulse power supply 4 solid dielectric 5 resistor 6, 9 BNC terminal 7 oscilloscope 8 high voltage probe 81-1 DC power supply 81-2 AC power supply (high voltage pulse power supply) 82 stainless steel container 83 discharge Plasma generation space 84 Upper electrode 85 Lower electrode 86 Solid dielectric 87 Base material 88 Gas introduction pipe 89 Dilution gas introduction pipe 810 Gas exhaust port 811 Exhaust port

Claims (8)

[Claims] 1. An antireflection film in which an antireflection layer is laminated on a base film via a hardcoat layer, wherein the hardcoat layer is a polyfunctional acrylate (A) 10
A composition comprising 0 parts by weight and 1 to 40 parts by weight of at least one silicon-based compound (B) selected from the group consisting of silica particles, organopolysiloxane, and silicon acrylate surface-coated with an organic substance. Anti-reflection, wherein the ratio of Si in the elemental composition on the surface of the hard coat layer is 2 to 35 atomic% with respect to the total amount of Si, C and O. the film. 2. An antireflection film in which an antireflection layer is laminated on a base film via a hardcoat layer, wherein the hardcoat layer is a polyfunctional acrylate (A) 10
0 parts by weight, 1 to 70 parts by weight of at least one silicon compound (B) selected from the group consisting of silica particles, organopolysiloxane, and silicon acrylate surface-coated with an organic substance, and urethane acrylate (C A) a composition comprising 5 to 100 parts by weight, wherein the ratio of Si in the elemental composition on the surface of the hard coat layer is 2 to 2 with respect to the total amount of Si, C, and O; An antireflection film characterized by being 35 atomic%. 3. An anti-reflection layer comprising a SiO ₂ layer and a TiO ₂ layer.
The antireflection film according to claim 1, wherein the antireflection film is formed of a layered body. 4. A hard coat which has been subjected to a discharge treatment so that the ratio of Si in the elemental composition on the surface of the hard coat layer is 2 to 35 at% with respect to the total amount of Si, C and O. The antireflection film according to claim 1, further comprising a layer. 5. A method for producing an antireflection film by laminating an antireflection layer on a base film via a hardcoat layer, wherein the ratio of Si in the elemental composition of the surface of the hardcoat layer is , Si, C, and O in a gas atmosphere containing a metal compound under a pressure near the atmospheric pressure under a pressure near atmospheric pressure. And the discharge current density between the opposite electrodes is 0.2 to 300 mA /
By applying an electric field so cm ^2, and a discharge plasma is generated, method of manufacturing the anti-reflection film of claim 1 any one claim, characterized by laminating an antireflection layer. 6. The method according to claim 5, wherein a pulsed electric field is applied between the pair of opposed electrodes. 7. The method according to claim 6, wherein the voltage rise time in applying the pulsed electric field is 100 μs or less, and the intensity of the pulse electric field is in a range of 1 to 100 kV / cm. Manufacturing method of antireflection film. 8. The method of claim 1, wherein the frequency of the pulsed electric field is 0.5.
The method for producing an antireflection film according to claim 6, wherein the pulse width is 5 to 100 kHz and one pulse duration is 1 to 1000 μs.