JP2002003751A - Antistatic hard-coating composition, antistatic hard coat, method for producing the same, and laminated film with the antistatic hard coat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic hard-coating composition having stable antistatic performance and excellent hard-coating performance, and highly adhesive to an inorganic thin film which is laminated on the formed hard coat and has additional functions, to provide an antistatic hard coat by using the same, to provide a method for producing the same, and to provide a laminated film with the antistatic hard coat. SOLUTION: This antistatic hard-coating composition is obtained by compounding (A) a polyfunctional acrylate in an amount of 100 pts.wt. with (B) conductive fine particles having a particle diameter 10-30 nm in an amount of 50-400 pts.wt. together with (C) at least one kind of silicon-based compound selected from a group comprising silica particles subjected to surface treatment with organic compounds, organopolysiloxsanes, and silicon acrylates in an amount of 10-80 pts.wt. The antistatic hard coat is formed by curing the antistatic hard-coating composition. Further, the laminated film with the antistatic hard coat is obtained by forming the antistatic hard coat on a base film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for an antistatic hard coat, an antistatic hard coat, a method for producing the same,
And an antistatic hard coat laminate film, more specifically, a composition for an antistatic hard coat having stable antistatic performance and having excellent surface hardness and adhesion, which is suitably used for an image display device and the like, The present invention relates to an antistatic hard coat used, a method for producing the same, and an antistatic hard coat laminate film.

[0002]

2. Description of the Related Art In recent years, the range of use of image display devices has been expanding to include in-vehicle car navigation, mobile phones, mobile computers, and the like, in addition to televisions and computer monitors. In addition to the type of CRT, LC
D, the diffusion rate of plasma displays and the like is increasing. In these screen display units, a plastic film substrate having an upper layer provided with a hard coat layer obtained by curing an acrylic material or the like by UV (ultraviolet) or heat, and a lower layer (back side) provided with an adhesive layer is provided with the above image display. Often adhered to the part. Due to the hard coat layer as such a cured film, the plastic substrate alone has a pencil hardness of B or less (JI
SK6894) can exhibit a surface hardness of 3H or more.

[0003] However, the surface of these image display sections is generally easily charged, and the resulting stains make it difficult to recognize the screen information. In addition, as the number of cases where mobile devices are used outdoors is increasing, dust is likely to adhere, and in addition, external light is reflected on the display screen,
The visibility of the screen information is often reduced.

[0004] In order to solve these problems, conventionally, an ion conductive material such as an alkali metal has been added to the inside or upper layer of the hard coat, and the coating has been applied to prevent static electricity. For example, in JP-A-5-339306, an antistatic property is obtained by using an alkali metal or ammonium salt in combination with an imidazoline surfactant.

[0005] However, in this method, if the antistatic layer is not on the uppermost layer, ionic conduction is not performed smoothly, and the antistatic function is extremely reduced. For this reason, it becomes difficult to add a layer having additional functions such as antireflection, UV cut, and heat ray cut to the upper layer of the antistatic layer. Further, in performing ion conduction, since moisture in the outside air serves as a medium, there is a problem that the surface resistance changes due to the influence of humidity and the quality becomes unstable.

As another method, a method has been proposed in which inorganic conductive particles such as ATO (tin oxide doped with antimony pentoxide) are added to a hard coat material or an organic binder (fixing agent) to exhibit antistatic performance. ing. In this method, the surface resistance can be stably set to 10 regardless of the humidity of the outside air.
^Although it can be reduced to ¹¹ Ω / □ or less, generally, there is no affinity between the organic (hard coat) material and the inorganic particles, and as a result, the particles become brittle, so that the hardness of the hard coat decreases even after UV curing or heat curing. .

On the other hand, an inorganic thin film is usually formed on a hard coat having an antistatic function by a sputtering method, a vapor deposition method, a CVD method, a coating method or the like in order to provide an additional function such as an antireflection function. However, at this time, the adhesion between the inorganic thin film and the hard coat surface, which is an organic material, is poor. Therefore, in a durability test using a high-temperature and high-humidity bath, a tape-peeling test (JIS D020) having a grid pattern is drawn.
As a result of 2), there is a problem that the inorganic thin film causes tape peeling.

As a method of improving the adhesion between the inorganic thin film and the hard coat layer provided with an antistatic function, for example, a method of corona-treating the surface of the hard coat is known. In this method, only the outermost surface is treated. Therefore, the effect of improving the adhesion is low. Further, when the treatment time is extended, the surface of the base material is greatly deteriorated, and conversely, the adhesion is reduced.

In addition, a method of mixing amorphous silica particles with an acrylic hard coat paint to improve adhesion to a metal thin film (JP-A-5-162261), and an adhesive property using an organosiloxane resin. There are known methods for improving the surface roughness, and these methods certainly improve the surface hardness, but have insufficient effects on the adhesion.

[0010]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention simultaneously has a stable antistatic property and excellent hard coat performance (pencil hardness of 3H or more). Provided is a composition for an antistatic hard coat having high adhesion to an inorganic thin film or the like having an additional function to be laminated thereon, an antistatic hard coat using the same, a method for producing the same, and further an antistatic hard coat laminate film. The purpose is to:

[0011]

Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies, and as a result, have determined that a specific conductive fine particle and a specific silicon-based compound have a specific ratio to polyfunctional acrylate. After preparing the composition prepared by blending and curing the composition, the composition was subjected to a surface treatment. The composition had a stable antistatic performance and an antistatic hard coat or an antistatic hard coat having excellent surface hardness and adhesion. The inventors have found that a coated laminate film can be obtained, and have completed the present invention.

That is, according to the first aspect of the present invention,
From 100 to 100 parts by weight of the polyfunctional acrylate (A), 50 to 400 parts by weight of conductive fine particles (B) having a particle size of 10 to 30 nm, and silica particles, organopolysiloxane, and silicon acrylate surface-treated with an organic substance. The present invention provides a composition for an antistatic hard coat, comprising 10 to 80 parts by weight of at least one silicon compound (C) selected from the group consisting of:

According to a second aspect of the present invention, the first aspect
In the invention, the conductive fine particles (B) are ATO and / or
Alternatively, there is provided an antistatic hard coat composition characterized by being ITO.

Further, according to the third invention of the present invention, in the first invention, the compounding amount of the conductive fine particles (B) and the silicon-based compound (C) is not more than one.
200 to 300 parts by weight and 20 to 60 parts by weight with respect to 00 parts by weight, respectively, are provided.

According to a fourth aspect of the present invention, there is provided the composition for an antistatic hard coat according to the first aspect, further comprising an optional photo-curing agent or radical initiator. Things are provided.

On the other hand, according to the fifth invention of the present invention, the first
An antistatic hard coat formed by curing the composition for antistatic hard coat according to any one of the inventions, wherein the ratio of Si in the elemental composition of the surface of the antistatic hard coat is Si. , C and O
An antistatic hard coat is provided, wherein the hard coat is 0 to 35 atomic%.

According to a sixth aspect of the present invention, there is provided an antistatic hard coat laminate film comprising the antistatic hard coat according to the fifth aspect formed on a substrate film.

Further, according to a seventh aspect of the present invention, in the sixth aspect, an adhesive layer is formed on the base film opposite to the side having the antistatic hard coat. An antistatic hardcoat laminate film is provided.

Further, according to an eighth aspect of the present invention, in the seventh aspect, the adhesive layer comprises 100 parts by weight of an acrylic polymer and 1 to 20 parts by weight of a silane compound. A hard coat laminate film is provided.

Further, according to the ninth aspect of the present invention, the sixth aspect
Alternatively, in the invention according to the seventh aspect, there is provided an antistatic hard coat laminate film, wherein a film having an additional function is formed on an outermost layer.

Further, according to a tenth aspect of the present invention,
In a ninth aspect, there is provided an antistatic hard coat laminate film, wherein the film having an additional function is an antireflection film, an IR cut filter, or a UV cut filter.

According to an eleventh aspect of the present invention, on the other hand, the antistatic hard coat composition according to any one of the first to fourth aspects is applied to a base film, dried and cured. An arbitrary surface selected from the following: a corona discharge, a plasma discharge, a physical treatment using a low-pressure mercury lamp or an excimer laser, or a chemical treatment in which the surface of the cured product is eroded with an organic solvent to control the amount of Si element. There is provided a method for producing an antistatic hard coat, which comprises performing a treatment.

According to a twelfth aspect of the present invention, in the eleventh aspect, the curing of the composition for an antistatic hard coat is performed by irradiating ultraviolet rays or heating. A manufacturing method is provided.

Further, according to a thirteenth aspect of the present invention,
In the eleventh aspect, there is provided a method for producing an antistatic hard coat, wherein the surface treatment is performed by corona discharge, plasma discharge, or a low-pressure mercury lamp.

Further, according to a fourteenth aspect of the present invention, in the thirteenth aspect, the surface treatment is performed between the pair of counter electrodes under a pressure near the atmospheric pressure and in an air and / or rare gas atmosphere. There is provided a method for producing an antistatic hard coat, wherein the method is performed by applying an electric field so that a discharge current density becomes 0.2 to 300 mA / cm ² .

Further, according to a fifteenth aspect of the present invention,
In the fourteenth aspect, a pulsed electric field is applied between the pair of opposed electrodes, and the voltage rise time is 100 μs.
Below, and the intensity of the pulse electric field is 1 to 100 kV / c
m, and the frequency of the electric field is 0.5 to 100 kHz.
A method for producing an antistatic hard coat is provided.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 1. Polyfunctional acrylate (A) The polyfunctional acrylate (A) in the present invention is not particularly limited, and examples thereof include pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol penta (meth) acrylate, Dipentaerythritol penta (meth) acrylate, pentaerythritol (meth)
Tetraacrylate, dipentaerythritol (meth)
Examples thereof include tetraacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, and derivatives and modified products thereof. The term (meth) acrylate in the present specification means that it may be acrylate or methacrylate.

Further, as the polyfunctional acrylate (A), for example, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate manufactured by Nippon Kayaku Co., Ltd .; Examples of the modified products include urethane-based polyfunctional acrylates, etc. These may be used alone or in combination of two or more.

2. Conductive Fine Particles (B) Examples of the material of the conductive fine particles (B) in the present invention include ATO (tin oxide doped with antimony pentoxide), ITO (indium oxide doped with tin dioxide), Sb ₂ O ₅ , TiO ₂ , ZnO _{2 and the} like can be mentioned. Among them, ATO and ITO are preferably used. These may be used alone or in combination of two or more. Further, the particle size of the conductive fine particles,
It needs to be controlled to 10 to 30 nm, and preferably 15 to 25 nm. When the particle size is smaller than 10 nm, the light transmittance of the antistatic hard coat is reduced, and the application of the product is limited. On the other hand, when the particle size is larger than 30 nm, the haze becomes high and causes a problem.

The amount of the conductive fine particles is preferably 50 to 400 parts by weight, more preferably 200 to 400 parts by weight, per 100 parts by weight of the polyfunctional acrylate (A).
300 parts by weight. If the compounding amount is less than 50 parts by weight, the conductive path of the particles is cut and the antistatic property is not obtained.
When the amount is more than 400 parts by weight, the light transmittance is reduced (haze is increased) and the coating becomes brittle, so that the hard coat performance is also reduced.

3. Silicon Compound (C) The silicon compound (C) in the present invention comprises at least one silicon compound selected from the group consisting of silica particles surface-treated with an organic substance, organopolysiloxane, and silicon acrylate. Examples of the silica particles surface-treated with the organic material include those shown in the schematic diagrams of FIGS. Here, Co-Si indicates colloidal silica, and R ¹ and R ² in FIG. 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-treated with the organic substance include Toshiba Silicone Co .; product numbers “UVHC-1103” and “UVHC-1105”.

If the particle size of the silica particles surface-treated with the organic material is too small, the viscosity of the composition before curing becomes high, so that it is difficult to produce an antistatic hard coat,
If it is too large, the haze value of the antistatic hard coat decreases, and the transparency may decrease.
m is preferable, and more preferably, 0.2 to 0.7 μm. As the organopolysiloxane, those having the following structures can be used.

[0033]

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[0034]

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[0035]

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Here, m and n are integers of 0 or more.
≧ 0, n ≧ 0, 10 ≦ m + n ≦ 100, more preferably 15 ≦ m + n ≦ 50. When m + n <10, the hardness is low and the antistatic hard coat performance is inferior. When m + n> 100, the viscosity of the composition before curing becomes high, so that it becomes difficult to produce an antistatic hard coat.

Further, the silicon acrylate has a general formula (CH ₃ O) ₃ SiR ³ O—CO—CR ⁴ ＣＨCH ₂
Wherein R ³ and R ⁴ each represent an alkyl group. Note that R ³ and R ⁴ may be different from each other or may be the same.

The amount of the silicon compound (C) is as follows:
10 to 100 parts by weight of the polyfunctional acrylate (A)
80 parts by weight, preferably 20 to 60 parts by weight. If the amount is less than 10 parts by weight, the surface hardness of the antistatic hard coat is low and the adhesion is not improved. On the other hand, if the amount is more than 80 parts by weight, cracks occur in the cured antistatic hard coat, and the adhesion to a film having an additional function laminated on the hard coat is reduced.

4. Other Components In the composition for an antistatic hard coat of the present invention, a diluting solvent may be used in order to adjust the viscosity of the composition before curing. These are not particularly limited as long as they are non-polymerizable, and include, for example, methyl ethyl ketone, toluene, xylene, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, isopropyl alcohol, diacetone alcohol and the like. Is mentioned. These may be used alone or in combination of two or more.

In the composition for an antistatic hard coat of the present invention, an initiator, a photocuring agent and the like can be used in order to promote the curing.
There is no particular limitation as long as it initiates and accelerates the polymerization reaction of the acryloyl group present therein.

For example, in the case of curing by irradiation with ultraviolet light, a conventionally known photopolymerization initiator (photocuring agent) can be used, and a typical example is 2,2-dimethoxy-
2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone,
-Chlorobenzophenone, 4,4'-dimethoxybenzophenone, benzoin propyl ether, benzyldimethyl ketal, N, N, N ', N'-tetramethyl-
Examples thereof include 4,4'-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and other thioxantho-based compounds.

When curing by heating, conventionally known initiators (radical initiators) can be used.
Representative examples 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.

Further, the composition for an antistatic hard coat of the present invention may be added, if necessary, in a range that does not impair the performance.
Pigments, fillers, surfactants, dispersants, plasticizers, ultraviolet absorbers, antioxidants and the like may be used. These may be used alone or in combination of two or more.

5. Antistatic Hardcoat The antistatic hardcoat of the present invention is formed by curing a composition containing the above-mentioned polyfunctional acrylate (A), conductive fine particles (B) and silicon-based compound (C).
At that time, the formed hard coat may be provided on the base film.

The material of the substrate film used is not particularly limited as long as it is transparent. Examples of the material include polyethylene, polypropylene, polyester, regenerated cellulose, diacetyl cellulose, triacetyl cellulose, polyvinyl chloride, and the like. Examples include polyvinylidene chloride, polyvinyl alcohol, polystyrene, polyethylene terephthalate (PET), polycarbonate (PC), polyimide, and nylon. Preferably, triacetyl cellulose, polyethylene terephthalate, and polycarbonate having excellent transparency are used.

In the present invention, in order to form an antistatic hard coat, it is preferable to apply the above-described composition for an antistatic hard coat on a substrate film, and then dry and cure the composition.
The order of application of the hard coat composition before curing is not particularly limited, and the polyfunctional acrylate (A), the conductive fine particles (B) and the silicon-based compound (C) may be mixed and applied. Each of them may be applied in combination.

At this time, as a method for applying the above composition on the substrate film, a known coating method such as spray coating, gravure coating, roll coating, bar coating and the like can be used. The amount of application takes into account the required physical properties,
It is adjusted to have a desired thickness.

Further, as described above, on the substrate film
As a method of curing the applied and dried composition,
There is no particular limitation.
It can be done in a known manner. Cured by UV irradiation
If you want to make
Are, for example, high-pressure mercury lamps, halogen lamps, xeno
Lamp, nitrogen laser, electron beam accelerator, radioactive element
Such a source is used. The irradiation dose of the energy ray source is
The integrated exposure amount at an ultraviolet wavelength of 365 nm is 50 to 5
000mJ / cm ²Is preferred. The irradiation dose is 50mJ /
cm²If it is less than 100%, curing will be insufficient,
The wear resistance and hardness of the hard coat may decrease.
You. 5000mJ / cm²Exceeds
The antistatic hard coat is colored and the transparency is reduced.
There is.

In the antistatic hard coat of the present invention, the ratio of Si in the elemental composition of the surface of the cured product (hereinafter referred to as “cured product”) is S.
It needs to be 10 to 35 atomic% based on the total amount of i, C, and O. At that time, the ratio of Si on the surface was analyzed by ESCA, and the Si amount / (Si amount + C
Amount + O amount).

If the proportion of Si in the elemental composition on the surface of the cured product is less than 10 atomic%, the proportion of -SiO- exposed on the surface decreases, so that a film having an additional function is laminated thereon. On the other hand, if it exceeds 35 atomic%, cracks occur in the antistatic hard coat, and the adhesion with the laminated film having an additional function is reduced. Preferably it is 11 to 30 atomic%.

Here, the surface of the cured product refers to a depth of about 50 to 1500 nm from the outermost surface, preferably a depth of about 100 to 800 nm.

The thickness of the antistatic hard coat is from 1 to
It is preferably 15 μm, more preferably 2 to 8 μm. If the thickness is less than 1 μm, the hardness may decrease. If the thickness is more than 15 μm, cracks occur in the antistatic hard coat itself, and the adhesion to the film having an additional function laminated on the hard coat is reduced. May be.

6. Method for Producing Antistatic Hard Coat In the present invention, as a method for controlling the ratio of Si in the elemental composition on the surface of the cured product to the above range, the surface of the cured product is mildly etched to expose -SiO- bonds. There is no particular limitation as long as it is effective,
Chemical treatments such as corona discharge, plasma discharge, low pressure mercury lamp, physical treatment with an excimer laser, and the like, in which the surface of the cured product is eroded by an organic solvent to control the amount of Si element, and the like. Among them, a corona discharge treatment, a plasma discharge treatment, and a treatment method using a low-pressure mercury lamp have high effects and are preferable.

The depth of the surface treatment by the above method is not particularly limited as long as the cured product is not damaged.
It is preferably about 500 nm, more preferably 100 to 800 nm. If it is shallower than 50 nm,
The formation of SiO-bonds is so small that sufficient adhesion may not be obtained. On the other hand, when the thickness exceeds 1500 nm, the substrate is greatly damaged, and interface peeling may occur between the antistatic hard coat and a film having an additional function laminated on the hard coat.

In the method for producing an antistatic hard coat according to the present invention, the pressure near the atmospheric pressure is 1.33 × 10 ⁴ to 1
It refers to a pressure of 0.64 × 10 ⁴ Pa. Above all, 9.31 × 10 ⁴ to 1 which facilitates pressure adjustment and facilitates device configuration.
It is preferable to set the pressure range to 0.37 × 10 ⁴ Pa.

The surface treatment in the present invention is preferably performed in an atmosphere of air and / or a rare gas. At that time, rare gases used include helium, neon, argon,
Xenon, nitrogen and the like. An argon atmosphere is preferable because a milder surface treatment is performed than a surface treatment performed in an air atmosphere.

When the discharge current density between the opposing electrodes in the present invention is low, surface treatment missing portions are generated, and it is difficult to expect an improvement in adhesion. When the discharge current density is high, organic substances on the surface of the hard coat are decomposed and the adhesion is reduced. 0.2
It is preferably from 300 to 300 mA / cm ² , and more preferably from 5 to 200 mA / cm ² .

Here, the discharge current density between the electrodes in the present invention refers to a value obtained by dividing the value of the current flowing between the electrodes by discharge by the area of the discharge space in the direction orthogonal to the current flow direction. When a parallel plate type is used, it is equivalent to a value obtained by dividing the current value by the facing area.

When a pulsed electric field is applied 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 calculated by the above-described method. It means the value divided by the area.

In the present invention, when a pulsed electric field is applied between the electrodes, the hard coat surface can be mildly and uniformly formed in a shorter time by using a pulse waveform instead of the conventional AC wave. Processing can be performed. At this time, the pulse waveform is not particularly limited, but may be an impulse type as illustrated in FIGS. 3A and 3B, a square wave type as illustrated in FIG. ) Can be used. Although FIG. 3 illustrates an example in which the applied voltage is a repetition of positive and negative, a pulse voltage having only one of positive and negative polarities, that is, 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 gas is ionized during the generation of plasma. For this reason, the rise of the pulse voltage applied between the electrodes is preferably 100 μs or less,
More preferably, it is 10 μs or less. If it exceeds 100 μs, the discharge state easily shifts to arc discharge, and becomes unstable. Further, there is an effect of realizing a discharge state having a high electron density by such a pulse electric field having a fast rising time.

The fall time of the pulse voltage is not particularly limited, but is preferably as fast as the rise time, more preferably 100 μs or less. The upper limit of the rise / fall time is not particularly limited, but is realistically 40 μs or more in consideration of a power supply device or the like. 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.

If the intensity of the pulse electric field in the present invention is too low, the discharge becomes sparse, and it becomes difficult to perform a uniform surface treatment. On the other hand, if it is too strong, the surface of the hard coat is damaged, and it is difficult to improve the adhesion to the film having an additional function laminated on the hard coat. Therefore, 1 to 10
It is preferably 0 kV / cm, more preferably 5 to 60 kV / cm.

The pulse electric field formed between the electrodes has a pulse waveform, rise and fall times, and
The frequency may be appropriately modulated. Incidentally, the pulse electric field having a higher frequency and a shorter pulse width is more suitable for high-speed processing.

In the present invention, if the frequency of the pulse electric field applied between the opposing electrodes is too small, the discharge becomes sparse, while if it is too large, the hard coat surface is damaged and the additional function laminated on the hard coat is obtained. It is difficult to improve the adhesiveness to the film having the. Therefore, usually 0.5 to
The frequency is preferably in the range of 100 kHz, more preferably 2 to 40 kHz.

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

In the above surface treatment, the cured product before the surface treatment may be heated or cooled, but it can be sufficiently treated even at room temperature.

7. Antistatic hard coat laminate film In the antistatic hard coat laminate film of the present invention, an adhesive layer may be laminated on the antistatic hard coat via a base film. As a base film,
The one described above is used.

As the adhesive layer, an optical component such as a glass or plastic plate to which a substrate film or an antistatic hard coat is attached can be firmly bonded, and does not foam even under high temperature and high humidity conditions. What is preferred is, for example, an acrylic pressure-sensitive adhesive is suitably used. Among these, a particularly preferred pressure-sensitive adhesive includes a composition comprising 100 parts by weight of an acrylic polymer and 1 to 20 parts by weight of a silane compound.

As the acrylic polymer, for example,
An acrylic copolymer containing an alkyl (meth) acrylate as a main component is exemplified. Examples of the alkyl (meth) acrylate include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl (meth) acrylate. ) Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, acetyl (meth) acrylate, Stearyl (meth) acrylate and the like can be mentioned. These may be used alone or in combination of two or more.

When the content of the above alkyl (meth) acrylate is small, the cohesive strength is increased and sufficient pressure-sensitive adhesiveness is hardly obtained, and when the content is large, the cohesive strength is reduced and it is difficult to obtain sufficient shear strength. In the above acrylic copolymer, it is preferably 50 to 98% by weight, more preferably 70 to 95% by weight.

In the acrylic copolymer, other vinyl monomers may be copolymerized if necessary. For example, (meth) acrylic acid, itaconic acid, crotonic acid,
(Anhydride) maleic acid, (anhydride) fumaric acid, carboxyl group-containing vinyl monomers such as carboxyalkyl (meth) acrylates such as carboxyethyl acrylate, 2
-Hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, modified caprolactone (meth)
Hydroxyl-containing vinyl monomers such as acrylate, polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate, (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyllaurylolactam, (meth) acryloylmorpholine, (Meth) acrylamide, dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide,
Nitrogen-containing vinyl monomers such as dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, vinyl acetate, vinyl pivalate, vinyl propionate, styrene, Examples include isobornyl (meth) acrylate, which may be copolymerized alone or in combination of two or more.

When the content of the other vinyl monomer is low, the cohesive strength is low and it is difficult to obtain a sufficient shear strength, and when the content is high, the cohesive strength is high and it is difficult to obtain sufficient pressure-sensitive adhesiveness. In the acrylic copolymer, the content is preferably 2 to 50% by weight, more preferably 5 to 3% by weight.
0% by weight.

As a method for obtaining the acrylic copolymer, solution polymerization is preferred in that the polymerization reaction can be easily controlled, and in this case, a thermal polymerization initiator is generally used. Examples of the thermal polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, isobutyryl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, P- Diacyl peroxides such as chlorobenzoyl peroxide, hydroperoxides such as diisopropylbenzene hydroperoxide and t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane;
1,3-bis- (t-butylperoxyisopropyl)
Dialkyl peroxides such as benzene and di-t-butyl peroxide; 1,1-di-t- (butylperoxy) -3,3,5-trimethylcyclohexane;
Peroxyketals such as 1-di- (t-butylperoxy) cyclohexane, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxydicarbonate, bis- (4
-T-butylcyclohexyl) In addition to organic peroxides such as percarbonates such as peroxydicarbonate,
2,2′-azobis-isobutyronitrile, 2,2′-
Azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, Azobis compounds such as 4,4'-azobis-4-cyanovaleric acid and 2,2'-azobis- (2-aminopropane) dihydrochloride are exemplified.

When polymerizing the acrylic copolymer,
A chain transfer agent may be added for the purpose of suppressing the variation of the polymerization reaction and appropriately adjusting the molecular weight of the obtained copolymer, for example, n-dodecyl mercaptan, 2-mercaptoethanol, β-mercaptopropionic acid, β Thiol compounds such as octyl mercaptopropionate, methoxybutyl β-mercaptopropionate, trimethylolpropane tris (β-thiopropionate), butyl thioglycolate, propanethiols, butanethiols, and thiophosphites; And halogen compounds such as carbon chloride.

The weight-average molecular weight of the acrylic copolymer obtained by the above polymerization method is preferably 800,000 or more, more preferably 1,000,000 or more, since low stress makes it difficult to obtain sufficient stress relaxation.

The acrylic copolymer may be cross-linked by a cross-linking agent. The cross-linking agent is capable of reacting with a polar group in the acrylic copolymer used in general solvent-type pressure-sensitive adhesives. Can be used. For example, tolylene diisocyanate (TDI), naphthylene-1,5-diisocyanate, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPD)
I) isocyanate-based cross-linking agents such as xylene diisocyanate (XDI) and modified TDI, and epoxy-based cross-linking agents such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether; , N-hexamethylene-1,6-bis (1-aziridinecarboxamide) and the like.

On the other hand, as the silane compound as another component of the adhesive, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, diphenylmethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, alkoxysilane such as isobutyltriethoxysilane, methyltrichlorosilane,
Chlorosilanes such as ethyltrichlorosilane, dimethylchlorosilane, diethyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, phenyltrichlorosilane and diphenyldichlorosilane, and methyl hydrogen silicone are exemplified.

As the adhesive layer in the present invention, a substrate film and a glass or plastic plate to which an antistatic hard coat is attached are adhered,
℃), high humidity (60 ℃ × 95%), it is suitable to have excellent removability even after standing. In order to realize this, it is preferable to mix 1 to 20 parts by weight of the silane compound with 100 parts by weight of the acrylic polymer. When the amount of the silane compound is too small, the removability is poor, and when the amount is too large, the adhesion is low and the film is easily peeled off. More preferably, 3-1 to 100 parts by weight of the acrylic polymer.
0 parts by weight.

A tackifier resin may be added to the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of the present invention, if necessary, as long as optical properties such as transparency are not impaired.

As the tackifying resin, for example, C5
And C9 petroleum resins, rosin resins, rosin ester resins, terpene resins, terpene phenol resins, cumarone-indene resins, disproportionated rosin ester resins, polymerized rosin resins, polymerized rosin ester resins, xylene resins, styrene resins and the like Examples thereof include hydrogenated products, which may be used alone or in combination of two or more. Since the tackifying resin becomes an uncrosslinked component in the pressure-sensitive adhesive, the cohesive strength decreases when the amount of addition increases, and it becomes difficult to obtain sufficient heat resistance and moisture resistance. Therefore, the amount of addition is 100 parts by weight of the acrylic polymer. 30 parts by weight or less with respect to

When the thickness of the pressure-sensitive adhesive layer is reduced, the adhesion to the glass or plastic plate on which the antistatic hard coat is mounted may decrease. Easily occur,
On the other hand, when the thickness increases, the residual solvent in the pressure-sensitive adhesive increases, and foaming tends to occur under high-temperature conditions, which is not desirable. Therefore, it is preferably 5 to 35 μm, more preferably 10 to 35 μm.
30 μm.

Further, in the antistatic hard coat laminated film of the present invention, the antistatic hard coat includes:
A film having an additional function may be laminated on the outermost layer. The film having an additional function to be laminated is not particularly limited, and examples thereof include applications such as an antireflection film, an IR cut filter, and a UV cut filter.

Further, although the type of film used and the compound used are different depending on the above-mentioned respective uses, the compounds usually used include, for example, TiO ₂ , SiO ₂ ,
Metal compounds such as ZrO ₂ and MgF ₂ , and Au and A
Metals such as g, Cu, Pt and the like.

The thickness of the film having the additional function is not particularly limited, and varies depending on the application and purpose. In the case of a film used as an optical material, it is usually preferably from 5 to 300 nm.

At this time, the method of laminating the film having the additional function is not particularly limited, and examples thereof include sputtering, vapor deposition, CVD, and coating.

Further, in the antistatic hard coat laminated film of the present invention, the antistatic hard coat and the outermost layer of the antistatic hard coat in which a film having an additional function is laminated on the outermost layer may have an antifouling layer as appropriate. May be formed, especially those having excellent water repellency and oil repellency as those excellent in wiping properties against oil stains from the human body such as fingerprint stains, and those having a contact angle of 80 degrees or more as the water repellency, and ,
As the oil repellency, those having a contact angle of 50 degrees or more are suitable. Examples of those having such performance include a fluorine-based silane coupling agent and a long-chain alkyl-based silane coupling agent.

[0088]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples. In addition, each physical property of the antistatic hard coat film in an Example and a comparative example was measured by the following evaluation method.

(1) Surface Si Element Amount The ratio of the Si element amount of the antistatic hard coat layer after the surface treatment was analyzed by ESCA, and the ratio of Si amount / (Si amount + C
Amount + O amount) (%). (2) Pencil hardness The pencil hardness of the antistatic hard coat film is determined by JIS-K
The evaluation was made according to 6894, and a sample in which no trace of a pencil lead remained three or more times in five measurements was regarded as good. (Table 2 shows the results of the test using 3H, in which no trace remains for 5 times.
It was described as 5/5. (3) Scratch resistance After rubbing the above antistatic hard coat film 30 times under pressure of 200 g / cm ² of steel wool (# 0000), も の is given for no scratch, and x is given for scratch. Noted. (4) Tape peeling test a) Peelability after endurance: 100 at 60 ° C. and 95% RH
0 hours later b) UV peelability; UV irradiation (fade meter) 30
After 0 hours, the antistatic hard coat film is subjected to the durability test of a) and b) above, and a 1 mm × 1 mm grid is cut on the surface of the antistatic hard coat film with a cutter knife after the test.
A block was prepared, and a tape peeling test was performed according to JIS D0202. After the peeling test, the number remaining without peeling was shown. (In the tape peeling test, the case where the antireflection layer was not peeled off and the adhesion was good was expressed as 100/100.) (5) Measurement of surface resistance value Antistatic hard coat film (10 cm × 10 cm)
Surface is measured with a two-point surface resistance meter (HI-Resist).
ance Tester Model TR-3 manufactured by Toyo Electronics Co., Ltd.), and the average value was shown.
(In Table 1, for example, 3.0 × 10 ⁷ Ω / □ is 3.0E +
07. (6) Measurement of peel strength of adhesive layer after heat resistance test A heat resistance test was performed at 80 ° C for 1000 hours with the antistatic hard coat film with the adhesive layer attached to a glass plate, and then at 23 ° C and relative humidity. The sample was allowed to stand at 50% for 24 hours to form a test piece having a width of 25 mm, and the peel strength was measured at a speed of 300 mm / min in a 90 ° direction using a tensile tester. A sample having good removability without the adhesive layer remaining on the glass plate was indicated by a circle.

Example 1 <Preparation of Antistatic Hard Coat> A surface-treated colloidal silica paint (UVHC-1105, manufactured by GE Toshiba Silicone Co., Ltd.) was used for 100 parts by weight of a polyfunctional acrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.). ATO (average particle diameter 20 nm: 15 to 25 nm) 30 by weight and conductive fine particles 30
The mixed solution containing 0 parts by weight was diluted with methyl ethyl ketone such that the content of the mixed solution became 55% to prepare a composition. Next, the above composition was coated on one side of a transparent PET film (PET, OFW-188, manufactured by Teijin Limited) as a substrate film by a microgravure coater, dried by heating, and then subjected to an ultraviolet lamp at 300 mJ / cm ^2. To produce an antistatic hard coat having a thickness of 5 μm.

<Surface Treatment> The surface of the antistatic hard coat was subjected to a pulse electric field strength of 15 kV / cm and a frequency of 6 kHz.
z, pulse rise time 5 μs, discharge current density 4.5
Corona discharge treatment was performed using a wire electrode at mA / cm ² . The surface of the antistatic hard coat layer subjected to the corona discharge treatment was subjected to surface analysis by ESCA, and the Si amount / (Si amount +
C content + O content) was 9 atomic% before corona discharge treatment, and 15 atomic% after corona discharge treatment.

<Formation of Inorganic Thin Film Layer> An SiO ₂ film having a thickness of 350 nm was formed on the surface-treated antistatic hard coat by sputtering. Hereinafter, this is referred to as an antistatic hard coat film. The physical properties of the obtained antistatic hard coat film were evaluated by the above methods, and the evaluation results are shown in Table 1.

Example 2 An antistatic hard coat film was obtained in the same manner as in Example 1, except that 250 parts by weight of ITO was used instead of ATO as the conductive fine particles. The physical properties of the obtained antistatic hard coat film were evaluated by the above methods, and the evaluation results are shown in Table 1.

Example 3 As a surface treatment method, an electric power of 20 was used instead of the corona treatment.
The same operation as in Example 1 was performed, except that the surface treatment was performed for 30 seconds using a low-pressure mercury lamp (a lamp that generates a strong spectral light beam at 184.9 nm and 253.7 nm) of W, a voltage of 56 V, and a current of 0.375 A. Was performed to obtain an antistatic hard coat film. The physical properties of the obtained antistatic hard coat film were evaluated by the above methods, and the evaluation results are shown in Table 1.

Example 4 <Preparation of Adhesive Layer> In a 5-neck separable flask equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, 48.8 of 2-ethylhexyl acrylate.
Parts by weight, n-butyl acrylate 46 parts by weight, acrylic acid 5 parts by weight, 2-hydroxyethyl methacrylate 0.
2 parts by weight, 0.03 part by weight of n-dodecyl mercaptan,
And 100 parts by weight of ethyl acetate, and uniformly mixed by stirring.
Dissolved oxygen in the system was removed by purging for minutes.
Next, an initiator solution obtained by dissolving 0.03 parts by weight of benzoyl peroxide in 3 parts by weight of ethyl acetate was dropped by a dropping funnel while maintaining the temperature at 70 ° C., and then reacted under a nitrogen atmosphere for 15 hours. An acrylic copolymer having a weight average molecular weight of 900,000 by GPC was obtained. After the reaction, the mixture was diluted with ethyl acetate to obtain a solution of an acrylic copolymer having a solid content of 40% by weight.

Further, the solid content of the acrylic copolymer is 100%.
1.0 part by weight of a trimethylolpropane-modified TDI (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L", solid content: 45% by weight) was added as a crosslinking agent, and methyl silicone was further added as a silicone compound. Silicone (Shin-Etsu Silicone, product name "KF-99")
Was added to obtain a pressure-sensitive adhesive.

The above pressure-sensitive adhesive was applied to the PET film side of the antistatic hard coat film obtained in Example 1, and
By drying in an oven at 00 ° C. for 5 minutes, an antistatic hard coat film with an adhesive layer having a thickness of 25 μm was obtained. The antistatic hard coat film with the adhesive layer was allowed to stand for one week, cut into a size of 100 mm x 100 mm, and bonded together with a laminator so that air bubbles did not enter the laminated surface of the glass plate. The physical properties of the obtained antistatic hard coat film with an adhesive layer were evaluated by the above methods, and the evaluation results are shown in Table 1.

Example 5 An antistatic hard coat film with an adhesive layer was prepared in the same manner as in Example 4, except that the methyl hydrogen silicone used in the adhesive of Example 4 was changed to 10 parts by weight. did. The physical properties of the obtained antistatic hard coat film with an adhesive layer were evaluated by the above methods, and the evaluation results are shown in Table 1.

Example 6 An antistatic hard coat film with an adhesive layer was prepared in the same manner as in Example 4, except that the methyl hydrogen silicone used in the adhesive of Example 4 was changed to 15 parts by weight. did. The physical properties of the obtained antistatic hard coat film with an adhesive layer were evaluated by the above methods, and the evaluation results are shown in Table 1.

Comparative Example 1 An antistatic hard coat film was obtained in the same manner as in Example 1 except that the surface treatment was not performed. The physical properties of the obtained antistatic hard coat film were evaluated by the above methods, and the evaluation results are shown in Table 1.

Comparative Example 2 Except that 40 parts by weight of conductive fine particles (ATO) were used,
The same operation as in Example 1 was performed to obtain an antistatic hard coat film. The physical properties of the obtained antistatic hard coat film were evaluated by the above methods, and the evaluation results are shown in Table 1.

Comparative Example 3 An antistatic hard coat film was obtained in the same manner as in Example 1, except that 120 parts by weight of a surface-treated colloidal silica-containing paint (UVHC-1105, manufactured by GE Toshiba Silicone Co., Ltd.) was used. . The Si ratio after surface treatment by corona discharge was 45 atomic%. The physical properties of the obtained antistatic hard coat film were evaluated by the above methods, and the evaluation results are shown in Table 1.

Comparative Example 4 Among the surface treatment conditions, the intensity of the pulse electric field was set to 0.5 kV / c.
The operation was performed in the same manner as in Example 1 except that m was changed to m to obtain an antistatic hard coat film. The physical properties of the obtained antistatic hard coat film were evaluated by the above methods, and the evaluation results are shown in Table 1.

[0104]

[Table 1]

[0105]

Since the present invention has the above-described structure, an antistatic hard coat having excellent antistatic properties and excellent surface hardness is formed. Furthermore, the ratio of Si in the elemental composition of the surface of the antistatic hard coat is Si,
The surface treatment is performed so as to be 10 to 35 atomic% based on the total amount of C and O, so that the adhesion and the surface hardness between the antistatic hard coat and the film having an additional function are dramatically improved. can do. Moreover, by using ATO and / or ITO as the conductive fine particles, extremely stable antistatic performance can be exhibited. Further, by providing the adhesive layer via the base film, an optical component such as glass to which the antistatic hard coat is attached can be firmly bonded.

In the method for producing an anti-reflection film for a display according to the present invention, the anti-reflection film for a display in which an antistatic hard coat and an inorganic thin film are more firmly adhered to each other is obtained because a discharge treatment is performed under the above-mentioned processing conditions. Thus, the discharge treatment conventionally performed at a low pressure can be performed in a short period of time near the atmospheric pressure.

[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 waveform of a pulse voltage applied between a pair of electrodes in the present invention.

[Explanation of symbols]

 Co-Si colloidal silica

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 7/12 C09D 7/12 183/04 183/04 C09J 7/02 C09J 7/02 Z 133/00 133 / 00 F-term (reference) 4D075 AC25 BB49Z CA02 CA13 CA22 DA23 DB13 DB31 DC24 EA07 EB42 EC37 4F100 AA20 AA20A AA28A AA29A AA33A AH06A AH06C AK25A AK25C AK42 EJ42 AL05A AR00C AT00B BA02 BA03 BA02 BA03 BA02 BA03 BA04 EJ862 GB41 JD09D JD10D JG01A JG03A JK12A JL13C JM02D JN06D 4J004 AA02 AA10 AA11 AB01 CC02 CC03 EA04 FA01 4J038 DL032 FA111 FA151 FA212 HA216 HA446 KA03 KA06 KA15 NA20 PA17 PB03 PC03 J0303

Claims (15)

[Claims] 1. A conductive fine particle (B) having a particle size of 10 to 30 nm with respect to 100 parts by weight of a polyfunctional acrylate (A).
50 to 400 parts by weight, and 10 to 80 parts by weight of at least one silicon compound (C) selected from the group consisting of silica particles, organopolysiloxane, and silicon acrylate surface-treated with an organic substance. A composition for an antistatic hard coat. 2. The composition for an antistatic hard coat according to claim 1, wherein the conductive fine particles (B) are ATO and / or ITO. 3. The compounding amount of the conductive fine particles (B) and the silicon compound (C) is 100.
200 to 300 parts by weight and 20 parts by weight
The composition for an antistatic hard coat according to claim 1, wherein the amount is from 60 to 60 parts by weight. 4. The composition for an antistatic hard coat according to claim 1, further comprising an optional photocuring agent or radical initiator. 5. An antistatic hard coat formed by curing the antistatic hard coat composition according to any one of claims 1 to 4, wherein the antistatic hard coat has an elemental composition on the surface of the antistatic hard coat. Wherein the ratio of Si to the total amount of Si, C, and O is 10 to 35 atomic%. 6. An antistatic hard coat laminate film comprising the antistatic hard coat according to claim 5 formed on a base film. 7. The antistatic hard coat laminate film according to claim 6, wherein an adhesive layer is formed on the substrate film opposite to the side having the antistatic hard coat. 8. The antistatic hard coat laminate film according to claim 7, wherein the adhesive layer comprises 100 parts by weight of an acrylic polymer and 1 to 20 parts by weight of a silane compound. 9. The antistatic hard coat laminate film according to claim 6, wherein a film having an additional function is formed as an outermost layer. 10. A film having an additional function is an antireflection film,
The antistatic hard coat laminate film according to claim 9, which is an IR cut filter or a UV cut filter. 11. An antistatic hard coat formed by applying the composition for an antistatic hard coat according to any one of claims 1 to 4 to a base film, and drying and curing the composition. Antistatic characterized by performing any surface treatment selected from plasma discharge, physical treatment with a low-pressure mercury lamp or excimer laser, or chemical treatment to control the amount of Si element by eroding the surface of the cured product with an organic solvent Hard coat manufacturing method. 12. The method for producing an antistatic hard coat according to claim 11, wherein the curing of the composition for an antistatic hard coat is performed by irradiation with ultraviolet light or heating. 13. The method for producing an antistatic hard coat according to claim 11, wherein the surface treatment is performed by corona discharge, plasma discharge or a low-pressure mercury lamp. 14. A surface treatment is carried out by applying an electric field between a pair of opposed electrodes so that a discharge current density becomes 0.2 to 300 mA / cm ² under a pressure near the atmospheric pressure and in an air and / or rare gas atmosphere. 14. The method for producing an antistatic hard coat according to claim 13, wherein the method is applied. 15. A pulsed electric field is applied between a pair of opposed electrodes, the voltage rise time is 100 μs or less, the intensity of the pulse electric field is in the range of 1 to 100 kV / cm, and the frequency of the electric field is The method for producing an antistatic hard coat according to claim 14, wherein the frequency is 0.5 to 100 kHz.