JP5370150B2 - Antireflection film, polarizing plate, display device, and production method of antireflection film - Google Patents

Abstract

An antireflection film which comprises a transparent support and one or more layers formed thereon including an antireflection layer, characterized in that it has, as an outermost layer, a low-refractive-index layer comprising hollow silica particles and a silicone and having a refractive index of 1.20-1.49 and that the hollow silica particles are contained in an amount of 30-80 mass% based on the solid components. The antireflection film is further characterized in that when the film is examined by X-ray photoelectron spectroscopy, that average proportion of the Si-C bond peak intensity (Ros) for the depth range of from the outermost surface to a depth of 5 nm which is represented by the following equation (A) is 0.40 or higher and the average proportion of the Si-C bond peak intensity (Rot) for the range of from the outermost surface to a depth of 10-25 nm is 0.0005 to 0.10. Equation (A): (Proportion of Si-C bond peak intensity) = (Si-C bond peak intensity)/{(Si-C bond peak intensity)+(Si-O bond peak intensity)}

Description

  The present invention relates to an antireflection film, and particularly relates to an antireflection film having excellent scratch resistance, low reflectance, and excellent visibility when used in a display device.

  For an antireflection film used on the outermost surface of an image display device such as a liquid crystal, a technique has been proposed in which an antireflection layer of an optical interference system is provided to achieve a low reflectance.

  As a technique for reducing the reflectance, there is a method of reducing the refractive index of the outermost surface layer. For this purpose, a method of lowering the refractive index by using a low refractive index material for the outermost surface layer or increasing the number of voids has been proposed. However, film strength and scratch resistance are weak points.

  A technology that uses hollow silica particles that are porous or hollow inside, and further uses silicone (for example, see Patent Document 1) has been proposed as a means for reducing the refractive index due to voids while maintaining the film strength. Yes.

  However, in a low refractive index layer containing hollow silica particles in a solid content of 20% by mass or more, the antifouling property contributed by silicone is deteriorated. Therefore, additional silicone is added to increase the film strength and antifouling property. And adjusted the relationship.

  Moreover, in the case of silicone having a reactive group with high antifouling properties, in addition to the deterioration of the film strength, aggregation may easily occur.

  On the other hand, antireflection films have come to be used for many purposes, and further improvements in film strength and antifouling properties are required.

  As a method for improving film strength, a method of forming a low refractive index layer with a metal oxide film by a sol-gel method (see Patent Document 2) is known. Moreover, the technique (for example, refer patent document 3) which uses a fluororesin as a binder component and processes a hollow particle with a silane coupling agent is disclosed.

However, even when these methods are combined, the film strength and the antifouling property cannot be satisfied while reducing the refractive index.
JP 2002-79616 A JP 2000-910 A JP 2006-117924 A

  An object of the present invention is to provide an antireflection film having excellent scratch resistance and antifouling properties, low reflectance, and excellent visibility when used in a display device.

One aspect of the present invention for achieving the above object is an antireflection film having at least an antireflection layer on a transparent support, and having a refractive index of 1 containing at least hollow silica particles and silicone on the outermost surface. X-ray photoelectron spectrometer having a low refractive index layer of 20 to 1.49, the hollow silica particles being contained in a solid content of 30 to 80% by mass, and in a depth range from the outermost surface to 5 nm. The average value of Si—C bond peak intensity ratios measured and represented by the following formula (A) is 0.40 or more, and the average of the Si—C bond peak intensity ratios at a depth of 10 to 25 nm from the outermost surface The antireflection film has a value Rot of 0.0005 to 0.10.
Formula (A) (Si—C bond peak intensity ratio) = (Si—C bond peak intensity) / {(Si—C bond peak intensity) + (Si—O bond peak intensity)}

The above object of the present invention is achieved by the following configurations.
(1) A low-refractive index layer having an antireflective film having at least an antireflective layer on a transparent support, and having a refractive index of 1.20 to 1.49 containing at least hollow silica particles and silicone on the outermost surface The hollow silica particles are contained in an amount of 30 to 80% by mass in the solid content, measured by an X-ray photoelectron spectrometer in a depth range from the outermost surface to 5 nm, and represented by the following formula (A) The average value Ros of the Si—C bond peak intensity ratio is 0.40 or more, and the average value Rot of the Si—C bond peak intensity ratio at a depth of 10 to 25 nm from the outermost surface is 0.0005 to 0.10. An antireflection film characterized by being.
Formula (A) (Si—C bond peak intensity ratio) = (Si—C bond peak intensity) / {(Si—C bond peak intensity) + (Si—O bond peak intensity)}
(2) The antireflection film as described in (1) above, wherein the antireflection film has a hard coat layer on the transparent support and between the antireflection layers.
(3) The antireflective film as described in (1) or (2) above, wherein the low refractive index layer contains an organosilane condensate represented by the following general formula (1).

General formula (1) Si (X1) ₄
X1 represents an alkoxy group.
(4) In the method for producing an antireflection film as described in (3) above, which comprises a step of forming a high refractive index layer on a transparent support and a step of forming a low refractive index layer on the high refractive index layer. The low refractive index layer hydrolyzes the organosilane represented by the general formula (1) to produce a low condensate having a weight average molecular weight of 500 to 1,000, and hollow silica is mixed into the low condensate. A method for producing an antireflection film, which is formed by coating and drying a coating solution obtained through a process of further continuing hydrolysis and condensation.
(5) In the step of mixing hollow silica particles with the low condensate and further continuing hydrolysis, an organosilane represented by the general formula (2) is mixed. A method for producing an antireflection film.

General formula (2) (R) _m Si (X2) _4-m
R represents an organic group that is not hydrolyzed. X2 represents an alkoxy group. m represents an integer of 1 to 4.
(6) The method for producing an antireflection film as described in (4) or (5) above, further comprising a step of forming a hard coat layer before the step of forming the high refractive index layer.
(7) The method for producing an antireflection film as described in (6) above, wherein an irregular shape is formed on the surface of the transparent support or the hard coat layer to impart antiglare properties.
(8) After the step of forming the low refractive index layer, the step of winding the antireflection film into a roll shape and the step of performing a heat treatment at 50 to 160 ° C. in a state of being wound into a roll shape. The method for producing an antireflection film according to any one of (4) to (7), which is characterized in that
(9) A polarizing plate using the antireflection film according to any one of (1) to (3).
(10) The polarizing plate according to (9), wherein the antireflection film has antiglare properties.
(11) A display device using the antireflection film according to any one of (1) to (3).
(12) The display device according to (11), wherein the antireflection film has an antiglare property.

  According to the present invention, it is possible to provide an antireflection film having excellent scratch resistance, low reflectance, and excellent visibility when used in a display device.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  Conventionally, there has been a technique of using hollow silica particles in the low refractive index layer in order to reduce the reflectance. However, in order to further reduce the reflectance with this technique, it is necessary to increase the content of the hollow silica particles. It was.

  Usually, an antifouling agent such as silicone is used on the outermost surface of the display device in order to prevent adhesion of dirt. However, when the amount of particles such as hollow silica and colloidal silica is increased, this antifouling property deteriorates. The phenomenon that occurred.

  As a result of examining the relationship between the increase in the amount of hollow silica particles and the antifouling property, the present inventor has found that when the amount of particles is increased, the amount of the outermost silicone responsible for the antifouling property decreases, resulting in deterioration of the antifouling property. I found out. This is presumably because silicone is adsorbed on the surface of the hollow silica particles and is not oriented on the outermost surface of the low refractive index layer.

  The present invention has found that the amount of silicone on the outermost surface of the antireflective film can be increased if it is an antireflective film produced through a process in which hollow silica particles are placed in the presence of a low condensate of organosilane. It is.

  This is thought to be due to a decrease in the amount of silicone adsorbed on the surface of the hollow silica particles.

  The present invention is characterized in that the organosilane does not have a functional group used as a so-called silane coupling agent.

  Furthermore, it is preferable to mix with hollow silica particles when hydrolysis proceeds to some extent and a low condensate of organosilane is formed.

  Although this organosilane is expected to have an effect as a material having a low refractive index as a binder main component of the low refractive index layer, the present invention has found an action on hollow silica particles.

  In general, it is well known that the particle surface is treated with a silane coupling agent. However, in the application of the present invention, the effect of treatment with a silane coupling agent from the beginning is not sufficient. By coexisting when a low-condensation product of organosilane that cannot be expected to act as a coupling agent is formed, the effect on the particles is exhibited.

  Conventionally, the organosilane condensate and the hollow silica particles are mixed after the hydrolysis of the organosilane is completely completed.

  Hereinafter, the present invention will be described in detail.

The antireflection film of the present invention comprises, as a basic structure, a high, medium and low refractive index layer having an antireflection function, a hard coat layer thereunder, and a transparent support for supporting these layers.
<Low refractive index layer>
The refractive index of the low refractive index layer according to the present invention is lower than the refractive index of the transparent support that is the support, and is preferably in the range of 1.30 to 1.45 at 23 ° C. and a wavelength of 550 nm.

  The film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and even more preferably 30 nm to 0.2 μm.

  The low refractive index layer used in the present invention has hollow silica particles, silicone, and a binder as basic components.

  Furthermore, it is preferable to contain at least two types of silica particles including hollow silica particles, and the other one type of silica fine particles is colloidal silica, and the average particle size of the colloidal silica is 1 of the average particle size of the hollow silica particles. .1 to less than 20 times.

<Si—C bond peak intensity ratio of outermost surface>
In the present invention, the outermost surface means the outermost surface of the antireflection layer and the outermost surface of the low refractive index layer. The antireflection film of the present invention contains at least hollow silica particles and silicone on the outermost surface. Silicone has Si—C bonds and Si—O bonds in the molecule, while silica particles have Si—O bonds in the molecule. Therefore, the ratio of the Si—C bond peak intensity to the sum of the Si—C bond peak intensity and the Si—O bond peak intensity measured using an X-ray photoelectron spectrometer (hereinafter abbreviated as XPS) is the antireflection layer. It becomes an index representing the proportion of silicone present on the outermost surface.

  In the present invention, the average value Ros of the Si—C bond peak intensity ratio represented by the following formula (A) in the depth range from the outermost surface to 5 nm is 0.40 or more. The average value Rot of the Si—C bond peak intensity ratio at a depth of 10 to 25 nm from the outermost surface is 0.0005 to 0.10.

  This means that silicone is localized at a depth of 5 nm from the outermost surface, and there is only a certain amount or less at a depth of 10 to 25 nm.

The Si—C bond peak intensity ratio is obtained by adopting a sputtering ion gun that generates C60 ions in an X-ray photoelectron spectrometer (XPS), and Si—C bond energy (Si—C bond peak intensity under the following etching conditions). ) And Si—O bond energy (Si—O bond peak intensity). Etching with an Ar beam is liable to destroy the organic structure (Si—C bond) of the silicone, so that an accurate organic silicone ratio cannot be measured. Etching with C60 ions makes it difficult for the organic structure to be destroyed and enables more accurate measurement.
Formula (A) (Si—C bond peak intensity ratio) = (Si—C bond peak intensity) / {(Si—C bond peak intensity) + (Si—O bond peak intensity)}
Note that the Si—C bond peak value is 102 eV ± 0.5 eV, and the Si—O bond peak value is 103 eV ± 0.5 eV.
(Etching conditions)
Apparatus: ULVAC-PHI 06-C60
Acceleration voltage: 10 kV
Ion beam current: 15 mA
Ion incidence angle: 45 °
Etching rate: 1.5 nm / min (in SiO)
Etching area: 2.5 mm square (XPS measurement conditions)
Apparatus: Quantera SXM manufactured by ULVAC-PHI
X-ray: Al (monochrome) 25W15kV
Beam diameter: 100 μm
Ros is an average value of Si—C bond peak intensity ratios in a depth range from the outermost surface to 5 nm, that is, a molecular ratio at an etching time of 0 seconds under the above conditions. This is because XPS can obtain information up to a depth of 5 nm by measurement on the outermost surface.

  A depth of 10 nm from the outermost surface corresponds to a depth at an etching time of 400 seconds under the above conditions, and a depth of 25 nm from the outermost surface corresponds to a depth at an etching time of 1000 seconds.

<Hollow silica particles>
The hollow silica particles whose inside is porous or hollow (hereinafter also simply referred to as hollow particles) will be described.

  The hollow particle is (I) a composite particle comprising a porous particle and a coating layer provided on the surface of the porous particle, or (II) having a cavity inside, and the content is a solvent, a gas or a porous substance It is a hollow particle filled with.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation.

  The average particle size of such hollow particles is 5 to 200 nm, preferably 10 to 70 nm. The particle size of the hollow particles is preferably monodispersed with a coefficient of variation of 1 to 40%.

  The average particle diameter can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.

  When the hollow particles are composite particles, the thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is 1 to 20 nm, preferably 2 to 15 nm.

  In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and the coating liquid component can easily enter the composite particles to reduce the internal porosity. However, the effect of lowering the refractive index may not be obtained sufficiently.

  In addition, when the thickness of the coating layer exceeds 20 nm, the coating liquid component does not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of lowering the refractive index is sufficiently obtained. It may disappear.

  In the case of hollow particles, when the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even when the thickness exceeds 20 nm, the effect of lowering the refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. In addition, components other than silica may be contained. Specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like.

Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like.

Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned.

In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3.

It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, particles having a small pore volume and a low refractive index cannot be obtained.

In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a low refractive index. is there.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles.

  The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned.

  These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow particles, for example, the method for preparing complex oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is preferably employed. It is more preferable to perform heat treatment as disclosed in paragraphs [0024] to [0025] of Japanese Patent Laid-Open No. 2001-233611.

  The content of the hollow particles of the present invention in the solid content in the low refractive index layer is preferably 30 to 80% by mass. Solid content means what was left after drying and removing all the solvents used for application | coating.

  In the present invention, commercially available hollow particles can be used. Specific examples of commercially available particles include ELECOM V-8209 manufactured by Catalyst Kasei Kogyo Co., Ltd.

<Colloidal silica>
The colloidal silica preferably used in the present invention is obtained by dispersing silicon dioxide in water or an organic solvent in a colloidal form, and is spherical, acicular or beaded.

  The average particle size of the colloidal silica is 1.1 to less than 20 times the average particle size of the hollow particles, preferably 1.5 to 5.0 times. Therefore, the average particle diameter of colloidal silica is preferably in the range of 50 to 300 nm.

  The particle size of colloidal silica is preferably monodispersed with a coefficient of variation of 1 to 40%. The average particle diameter can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like.

  Specifically, a micrograph (1000 times transmission mode) of the sample containing the particles was taken, and the diameter of the particles in the photograph was measured with an image processing device LUZEX-III (manufactured by Nireco), and the average The value was calculated as the average particle size.

  You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. However, when the ratio between the average particle size of colloidal silica and the average particle size of hollow particles is obtained, the same measurement method must be used.

  Such colloidal silica used in the present invention is commercially available, and examples thereof include the Snowtex series of Nissan Chemical Industries, the Cataloid-S series of Catalytic Chemical Industry, and the Rebacil series of Bayer.

  Also, beaded colloidal silica in which primary particles of cation-modified with alumina sol or aluminum hydroxide are bonded in a bead shape by bonding the particles with divalent or higher metal ions.

  There are beaded colloidal silicas such as SNOWTEX-AK series, SNOWTEX-PS series, SNOWTEX-UP series of Nissan Chemical Industries.

  The content of the colloidal silica in the low refractive index layer is preferably 30 to 60% by mass with respect to the solid content in the low refractive index layer.

  In order to obtain the effect of lowering the refractive index, it is preferably 30% by mass or more, and when it exceeds 40% by mass, the binder component is decreased and the film strength becomes insufficient.

  The content ratio of the hollow particles and the colloidal silica in the low refractive index layer is selected from the viewpoint of the reflectance reduction effect and the surface hardness, but is preferably 1: 0.1 to 10, more preferably 1: 0.8 to 5. preferable.

<silicone>
The silicone used in the present invention is an organopolysiloxane in which an organic group is bonded to a siloxane bond.

  Silicones used in the present invention can be broadly classified into straight silicone oils and modified silicone oils depending on the type of organic group bonded to silicon atoms.

  Straight silicone oil refers to those bonded with a methyl group, a phenyl group, or a hydrogen atom as a substituent. A modified silicone oil is one having a component that is secondarily derived from a straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

Silicone oil Straight silicone oil 1-1. Non-reactive silicone oil: dimethyl, methylphenyl substitution, etc. 1-2. Reactive silicone oil: methyl hydrogen substitution, etc. Modified silicone oil Modified silicone oil was born by introducing various organic groups into dimethyl silicone oil 2-1. Non-reactive silicone oil: Alkyl, alkyl / aralkyl, alkyl / polyether, polyether, higher fatty acid ester substitution, etc. Alkyl / aralkyl-modified silicone oil is a part of the methyl group of dimethyl silicone oil with a long chain alkyl group or phenyl Silicone oils substituted with alkyl groups, polyether-modified silicone oils are silicone-based polymer surfactants in which hydrophilic polyoxyalkylene is introduced into hydrophobic dimethyl silicone, and higher fatty acid-modified silicone oils are methyl methyl dimethyl silicone oil. Silicone oil and amino-modified silicone oil in which a part of the group is substituted with higher fatty acid ester is a silicone oil having a structure in which a part of methyl group of silicone oil is substituted with aminoalkyl group. The silicone oil has a structure in which a part of the methyl group of the silicone oil is replaced with an epoxy group-containing alkyl group, and the carboxyl-modified or alcohol-modified silicone oil has a part of the methyl group of the silicone oil. Silicone oil having a structure substituted with a group 2-2. Reactive silicone oil: amino, epoxy, carboxyl, alcohol substitution and the like.

  Of these silicones, reactive silicone oil is preferably added.

  The number average molecular weight of the silicone of the present invention is, for example, 500 to 50,000, preferably 1,000 to 20,000.

  Specific products include Nippon Unicar Co., Ltd. L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ. -3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56 KF995, KF351, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100 and the like.

  Further, for example, manufactured by Nippon Unicar Co., Ltd., silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ- 2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164, FZ-2166, FZ-2191 etc. are mentioned.

  Furthermore, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  In addition, as a preferable structure of these nonionic silicones in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a linear chain in which a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. It is preferably a block copolymer.

  Specific examples include silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208, and FZ-2222 manufactured by Nippon Unicar Co., Ltd. Among these silicones, those having a polyether group are preferred.

  Moreover, BYK series manufactured by BYK Japan, BYK-300 / 302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK -330, BYK-331, BYK-333, BYK-337, BYK-340, BYK-344, BYK-370, BYK-375, BYK-377, BYK-352, BYK-354, BYK-355 / 356, BYK -358N / 361N, BYK-357, BYK-390, BYK-392, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-Silclean3700, dimethyl silicone series manufactured by GE Toshiba Silicone, XC96-723, YF3800, XF3 05, YF3057, YF3807, YF3802, YF3897 can be preferably used.

  The silicone of the present invention is used in an amount of 0.5 to 40% by mass, preferably 1 to 25% by mass, based on the binder.

<binder>
It is preferable that a low refractive index layer contains 5-80 mass% binder in the whole low refractive index layer. The binder has a function of binding hollow particles, colloidal silica, and silicone to form a structure of a low refractive index layer including voids.

  The usage-amount of a binder is adjusted so that the intensity | strength of a low refractive index layer can be maintained, without filling a space | gap. The binder itself is a compound having a low refractive index, and is an organosilane represented by the following general formula (1), a hydrolyzate thereof, or a condensate thereof.

General formula (1) Si (X1) ₄
In formula, X1 is an alkoxy group, Preferably it is a C1-C4 alkoxy group. As specific compound compounds, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

  The low refractive index layer may also contain an organosilane represented by the following general formula (2) or a condensate thereof as a binder.

General formula (2) (R) _m Si (X2) _4-m
R represents an organic group that is not hydrolyzed. X2 represents an alkoxy group. m represents an integer of 1 to 4.

  Examples of the organosilane represented by the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxy Silane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidylo Xylpropyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Also, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane Γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldi Ethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminop Examples include propylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, methylvinyldimethoxysilane and methylvinyldiethoxysilane Preferably, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxy Propyl methyl dimethoxy silane, .gamma. acryloyloxypropyl diethoxysilane, .gamma.-methacryloyloxy propyl methyl dimethoxy silane and .gamma.-methacryloyloxy propyl methyl diethoxy silane is particularly preferred.

  Two or more types may be used in combination. In addition to the organosilanes shown above, other organosilanes may be used. Other organosilanes include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate t. -Butyl) and hydrolysates thereof.

  Examples of other binders for the low refractive index layer include polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, and alkyd resin.

  In the present invention, the organosilane of the general formula (2) is preferably used in the range of 1 to 50% by mass, and in the range of 5 to 40% by mass with respect to the organosilane of the general formula (1). Is particularly preferred.

<Other additives>
(Fluorosurfactant)
The low refractive index layer preferably contains a fluorinated surfactant. It is effective in reducing coating unevenness and improving the antifouling property of the film surface.

  Fluorosurfactants include perfluoroalkyl group-containing monomers, oligomers, and polymers as the core, and include derivatives such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyoxyethylene. It is done.

  Commercially available products may be used as the fluorosurfactant, for example, Surflon “S-381”, “S-382”, “SC-101”, “SC-102”, “SC-103”, “SC-104”. (All manufactured by Asahi Glass Co., Ltd.), Florard “FC-430”, “FC-431”, “FC-173” (all manufactured by Fluorochemical-Sumitomo 3M), Ftop “EF352”, “EF301”, “EF303” (both manufactured by Shin-Akita Kasei Co., Ltd.), Schwego Fureer “8035”, “8036” (both manufactured by Schwegman), “BM1000”, “BM1100” (all manufactured by BM Himmy) , MegaFuck “F-171”, “F-470” (both manufactured by Dainippon Ink & Chemicals, Inc.), and the like.

  The fluorine content of the fluorosurfactant in the present invention is 0.05 to 2% by mass, preferably 0.1 to 1% by mass. The above-mentioned fluorosurfactants can be used alone or in combination of two or more, and can be used in combination with other surfactants.

<Formation of low refractive index layer>
For formation of the low refractive index layer of the present invention, generally known methods can be used as they are, and a coating solution containing an organosilane hydrolyzate is applied and dried.

  Specifically, water or a hydrophilic organic solvent such as methanol, ethanol, or acetonitrile is dissolved in the organosilane so that water or an organometallic compound and water can be easily mixed. A decomposition catalyst is added to hydrolyze and condense the organosilane.

  When GPC measurement has progressed to a certain degree of hydrolysis, the hollow particles are mixed to obtain a low refractive index layer coating solution, and then the GPC is measured by condensation through a process of continuing hydrolysis. After the increase in molecular weight and the degree of crosslinking are observed, the low refractive index layer can be formed by applying it on a substrate and drying it.

  In the present invention, the organosilane represented by the general formula (1) such as tetraethoxysilane is hydrolyzed and subsequently condensed to produce a low-condensate having a predetermined molecular weight. It has the process of mixing and continuing a hydrolysis and condensation further, It is characterized by the above-mentioned.

  A predetermined molecular weight means that the weight average molecular weight of styrene conversion by GPC measured on the following conditions is 500-1000. In the process of continuing further hydrolysis and condensation, the weight average molecular weight is adjusted to be more than 1000 and 10,000 or less.

<GPC measurement conditions>
In the weight average molecular weight measurement method by GPC, the sample is diluted with THF so that the sample solid content concentration becomes 0.8% by mass, and the measurement is performed at a column temperature of 25 ° C. under the following conditions.
Column: Tosoh Corporation TSKgelG5000HXL-TSKgelG2000HXL
Eluent: THF
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Detection: RI Model 504 (manufactured by GL Sciences)
Sample concentration: 0.8%
Standard sample / calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples are used.

  When the hollow particles are mixed into the coating solution immediately after the start of hydrolysis, or when the organosiloxane is reactive as represented by the general formula (2), the silicone on the surface of the hollow particles as in the present invention There is almost no action that suppresses adsorption.

On the other hand, the organosilane represented by the general formula (2) is mixed with a low condensate such that the weight average molecular weight of the organosilane represented by the general formula (1) is 500 to 1000, so that Contributes to film strength.
<Layer structure of antireflection film>
In the antireflection film of the present invention, the antireflective layer having the antireflective function is required to have the low refractive index layer of the present invention, but in addition, an antireflective function is provided by providing a medium refractive index layer and a high refractive index layer Can be improved.

  As the medium refractive index layer and the high refractive index layer, known layers can be used, respectively. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the transparent support side, and three layers having different refractive indexes, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer). , A layer having a lower refractive index than the high refractive index layer) / a high refractive index layer / a low refractive index layer, and the like.

  Among them, from the viewpoint of durability, optical properties, productivity, etc., a medium refractive index layer / a high refractive index layer / a low refractive index layer laminated in this order on a substrate having a hard coat layer, a medium refractive index layer / What laminated | stacked the low-refractive-index layer is preferable.

As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO, etc.), and can be provided by coating or atmospheric pressure plasma treatment.
<Hard coat layer>
In the antireflection film of the present invention, a hard coat layer is preferably provided between the transparent support and an antireflection layer such as a high refractive index layer or a low refractive index layer. The hard coat layer is preferably an active energy ray curable resin layer.

  The active energy ray-curable resin layer refers to a layer mainly composed of a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used. It is formed.

  Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

  As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.

  The UV curable acrylic urethane resin generally includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

  For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Chemical Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photopolymerization initiator added thereto, and reacted to form an oligomer. Those described in US Pat. No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Specific examples of photopolymerization initiators for these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.

  The photopolymerization initiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The photopolymerization initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the composition.

  Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond.

  In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Examples of commercially available ultraviolet curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120 RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.); NK hardware B-420, B-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be appropriately selected and used.

  Specific examples of the compound include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like. .

  The cured resin layer thus obtained may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index, and to impart antiglare properties to the produced antireflection film.

  Examples of inorganic fine particles used in the hard coat layer include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, and calcined kaolin. And calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin powder. Polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added to the ultraviolet curable resin composition. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical) and polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical).

  The average particle size of these fine particle powders is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0 μm, and particularly preferably 0.1 to 4.0 μm. Moreover, it is preferable to contain 2 or more types of microparticles | fine-particles from which a particle size differs. The proportion of the ultraviolet curable resin composition and the fine particles is desirably blended so as to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.

  These hard coat layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method. After application, it is heat-dried and UV-cured.

  As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 150 mJ / cm ² , and particularly preferably 20 to 100 mJ / cm ² .

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m.

  The method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  The hard coat layer coating solution may contain a solvent, or may be appropriately contained and diluted as necessary. Examples of the organic solvent contained in the coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), It can be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or a mixture thereof can be used.

  Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

(Anti-glare)
The antireflection film of the present invention is preferably antiglare. The anti-glare property reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and the reflected image is reflected when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. It's something you don't mind. By providing appropriate unevenness on the surface, such a property can be provided.

  As a method for forming such irregularities, processing to a transparent support, processing to a hard coat layer, processing to an antireflection film after applying an antireflection layer, etc. can be selected. In the present invention, since the projections of the concavo-convex shape may break through the antireflection layer or deform the antireflection layer to impair the antireflection effect, in the present invention, processing to a transparent support, processing to a hard coat layer Is preferred.

  Examples of the concavo-convex shape referred to in the present invention include structures selected from right cones, oblique cones, pyramids, oblique pyramids, wedge shapes, convex polygons, hemispheres, and the like, and structures having these partial shapes.

  Note that the hemispherical shape does not necessarily have a true spherical shape, and may be an ellipsoidal shape or a more deformed convex curved shape.

  Moreover, the prism shape, the lenticular lens shape, and the Fresnel lens shape in which the ridge line of the concavo-convex shape extends linearly can also be mentioned. The slope from the ridge line to the valley line may be flat, curved, or a combination of both.

  The hard coat layer is preferably an antiglare hard coat layer having an arithmetic average roughness (Ra) defined by JIS B 0601: 2001 of 60 to 700 nm, preferably 80 to 400 nm. When Ra is less than 60 nm, the antiglare effect is weak, and when it exceeds 700 nm, an impression that is too coarse is visually observed.

  The arithmetic average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO).

Examples of a method for forming a concavo-convex shape on the surface of the hard coat layer and the transparent support described later include the following methods.
(1) A method in which a negative shape having a desired shape is formed on a roll or master, and the shape is given by embossing.
(2) A method in which a negative mold having a desired shape is formed on a roll or a master, a thermosetting resin is filled into the negative mold, and the film is peeled off from the negative mold after heat curing.
(3) A negative shape of a desired shape is formed on a roll or a master, and after applying ultraviolet rays or electron beam curable resin and filling the concave portions, ultraviolet rays are applied while the transparent support is coated on the intaglio via a resin liquid. Alternatively, a method in which the cured resin and the transparent support to which it is adhered are peeled from the negative mold by irradiation with an electron beam.
(4) A solvent casting method in which a negative shape having a desired shape is formed on a casting belt and the desired shape is imparted during casting.
(5) A method in which a resin that is cured by light or heating is relief-printed on a transparent substrate and is cured by light or heating to form irregularities.
(6) A method in which a resin that is cured by light or heating is printed on the surface of the transparent support by an ink jet method, and the surface of the transparent support is made uneven by curing by light or heating.
(7) A method of cutting the surface with a machine tool or the like.
(8) A method in which particles of various shapes such as spheres and polygons are pressed and integrated so as to be partially buried in the surface of the transparent support to make the surface of the transparent support uneven.
(9) A method in which particles of various shapes such as spheres and polygons dispersed in a small amount of binder are applied to the surface of the transparent support to make the surface of the transparent support uneven.
(10) A method in which a binder is applied to the surface of the transparent support, and particles of various shapes such as spheres and polygons are dispersed thereon to make the surface of the transparent support uneven.

  In the present invention, as the antiglare fine particles, for example, fluorine-containing acrylic resin fine particles are preferable in addition to the inorganic fine particles or the organic fine particles.

  The fluorine-containing acrylic resin fine particles are fine particles formed from, for example, a fluorine-containing acrylic acid ester or methacrylic acid ester monomer or polymer.

  Specific examples of the fluorine-containing acrylic ester or methacrylic ester include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H- Dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2-perfluorodecylethyl (Meth) acrylate, 3-par Fluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ) Ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3-perfluoro-3-methylbutyl- 2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate 1H-1- ( (Rifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctylethyl acrylate, 2- (perfluorobutyl) ethyl -Α-fluoroacrylate.

  Among the fluorine-containing acrylic resin fine particles, fine particles composed of 2- (perfluorobutyl) ethyl-α-fluoroacrylate, fluorine-containing polymethyl methacrylate fine particles, fluorine-containing methacrylic acid in the presence of a crosslinking agent, a vinyl monomer Fine particles copolymerized with fluorinated polymethyl methacrylate are more preferred.

  The vinyl monomer copolymerizable with fluorine-containing (meth) acrylic acid is not particularly limited as long as it has a vinyl group. Specifically, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, and methyl acrylate. , Alkyl acrylates such as ethyl acrylate, and styrenes such as styrene and α-methylstyrene. These may be used alone or in combination.

  The crosslinking agent used in the polymerization reaction is not particularly limited, but those having two or more unsaturated groups are preferably used. For example, bifunctional dimethacrylates such as ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate are used. And trimethylolpropane trimethacrylate, divinylbenzene and the like.

  In the present invention, the polymerization reaction for producing the fluorine-containing polymethyl methacrylate fine particles may be either random copolymerization or block copolymerization.

  Specifically, for example, the method described in JP-A No. 2000-169658 can be mentioned, and examples of commercially available products include commercially available products such as Nippon Paint: FS-701 and Negami Kogyo: MF-0043. Can be mentioned.

  Note that these fluorine-containing acrylic resin fine particles may be used alone or in combination of two or more. Moreover, the state of these fluorine-containing acrylic resin fine particles may be added in any state such as powder or emulsion.

  The average particle diameter of the fluorine-containing acrylic resin fine particle powder is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0 μm, and particularly preferably 0.1 to 4.0 μm.

  Moreover, it is preferable to contain 2 or more types of microparticles | fine-particles from which a particle size differs.

The proportion of the ultraviolet curable resin composition and the fine particles is desirably blended so as to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.
<Back coat layer>
In the antireflection film of the present invention, it is preferable to provide a backcoat layer on the surface opposite to the side on which the hardcoat layer is provided on the transparent support. The back coat layer is provided in order to correct curl caused by providing an active energy ray-curable resin layer or other layers.

  That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. The back coat layer is preferably applied also as an anti-blocking layer. In this case, it is preferable that fine particles are added to the back coat layer coating composition in order to provide an anti-blocking function.

  A well-known backcoat layer according to the present invention can be used.

  The order in which the backcoat layer is applied may be before or after the hardcoat layer is applied, but when the backcoat layer also serves as an anti-blocking layer, it is preferably applied first. Alternatively, the backcoat layer can be applied in two or more steps.

The surfactant BYK series manufactured by Big Chemie Japan Co., Ltd. and the dimethyl silicone series manufactured by GE Toshiba Silicone Co., Ltd. described in the low refractive index layer can be preferably used for an antireflection layer other than the low refractive index layer.
<Transparent support>
Next, the transparent support that can be used in the present invention will be described.

  The transparent support used in the present invention is easy to manufacture, has good adhesion to the actinic radiation curable resin layer, is optically isotropic, is optically transparent, etc. Is mentioned as a preferable requirement.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, a cellulose-ester type film, a polyester-type film, a polycarbonate-type film, a polyarylate-type film, a polysulfone (a polyether sulfone is also included) type film, a polyethylene terephthalate, polyethylene Polyester film such as naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Syndiotactic polystyrene film, polycarbonate film, cycloolefin Polymer film (Arton (manufactured by JSR), ZEONEX, ZEONOR (manufactured by ZEON CORPORATION)), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, poly A methyl methacrylate film, an acrylic film, a glass plate, etc. can be mentioned.

  Among them, cellulose triacetate film, polycarbonate film, and polysulfone (including polyethersulfone) are preferable. In the present invention, cellulose ester film (for example, Konica Minolta Tack, product names KC8UX2MW, KC4UX2MW, KC8UY, KC4UNY, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4, and KC8UCR-5 (manufactured by Konica Minolta Opto Co., Ltd.) are preferably used from the viewpoints of production, cost, transparency, isotropic properties, adhesiveness, and the like.

  These films may be films produced by melt casting film formation or films produced by solution casting film formation.

<Cellulose ester>
In the present invention, it is preferable to use a cellulose ester film as the transparent support. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used.

  In particular, when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, X and Y are active ray curable resin layers on a transparent support having a mixed fatty acid ester of cellulose in the following range And a low reflection laminate provided with an antireflection layer is preferably used.

2.3 ≦ X + Y ≦ 3.0
0.1 ≦ Y ≦ 1.2
It is preferable that

  When cellulose ester is used as the transparent support used in the present invention, the cellulose used as the raw material for the cellulose ester is not particularly limited, but examples include cotton linters, wood pulp (derived from coniferous trees, derived from hardwoods), kenaf and the like. it can.

  Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively.

  The measuring method of the substitution degree of an acyl group can be measured according to the rule of ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably 70000 to 250,000, since it has high mechanical strength when molded and an appropriate dope viscosity, and more preferably 80000 to 150,000.

  These cellulose ester films are prepared by applying a cellulose ester solution (dope) generally called a solution casting film forming method onto, for example, an endless metal belt for infinite transfer or a support for casting of a rotating metal drum. It is preferable to manufacture the dope from a pressure die by casting (casting).

  The film formation is preferably stretched after casting, and is more preferably stretched 1.2 times or more from the viewpoint of improving mechanical properties.

  The film width is preferably 1 m or more from the viewpoint of productivity, more preferably 1.5 m or more, and still more preferably 1.8 m or more.

<Plasticizer>
When a cellulose ester film is used for the antireflection film of the present invention, it is preferable to contain the following plasticizer.

  Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, an aromatic polyester plasticizer, a sugar ester plasticizer, and the like can be preferably used.

  The amount of these plasticizers used is preferably from 1 to 20% by mass, particularly preferably from 3 to 13% by mass, based on the cellulose ester, in terms of film performance, processability and the like.

<Ultraviolet absorber>
For the long film for the low reflection laminate of the present invention, an ultraviolet absorber is preferably used.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of the ultraviolet absorber preferably used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these.

  As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber that are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal are preferable, and unnecessary coloring is less. A benzotriazole-based ultraviolet absorber is particularly preferably used.

  Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a long film, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorber described in the general formula (1) or general formula (2) described in JP-A-6-148430 and the general formulas (2), (6), and (7) described in Japanese Patent Application No. 2000-156039 (Or UV-absorbing polymer) is also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

<Fine particles>
Moreover, in order to provide slipperiness to the cellulose-ester film used for this invention, microparticles | fine-particles can be used.

  As fine particles, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Mention may be made of magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.

  The average primary particle size of the fine particles is preferably 5 to 50 nm, and more preferably 7 to 20 nm. These are preferably contained mainly as secondary aggregates having a particle size of 0.05 to 0.3 μm.

  The content of these fine particles in the cellulose ester film is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass. In the case of a cellulose ester film having a multilayer structure by the co-casting method, it is preferable to contain fine particles of this addition amount on the surface.

  Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.). it can.

  Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

  Examples of the polymer include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  In the cellulose ester film used in the present invention, the dynamic friction coefficient on the back side of the active energy ray-curable resin layer is preferably 1.0 or less.

<Method for producing cellulose ester film>
Next, the manufacturing method of a cellulose-ester film is demonstrated. Any known solution casting method, melt casting method, and film stretching method can be preferably employed for the cellulose ester film according to the present invention.

<Alkali treatment method>
In the production of the antireflection film of the present invention, it is preferable to perform an alkali treatment before laminating the antireflection layer.

  The alkali treatment method is not particularly limited as long as it is a method in which a film coated with a hard coat layer is immersed in an alkaline aqueous solution.

  As the aqueous alkali solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used, and an aqueous sodium hydroxide solution is particularly preferable.

  The alkali concentration of the aqueous alkali solution, for example, sodium hydroxide concentration is preferably 0.1 to 25% by mass, and more preferably 0.5 to 15% by mass.

  The alkali treatment temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C.

  The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The film after the alkali treatment is preferably neutralized with acidic water and then thoroughly washed with water.

<Atmospheric pressure plasma method>
In the present invention, a discharge is formed by applying a high-frequency voltage having a frequency of 50 kHz to 150 MHz between opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof, and the excitation gas formed by the discharge is transferred to a transparent support. Or after making it contact the surface of the film which has a hard-coat layer on a transparent support body, it is preferable to form an antireflection layer by application | coating.

  The frequency is preferably 50 kHz to 27 MHz.

  The opposed electrodes are composed of a first electrode and a second electrode, and the frequency of the high-frequency voltage applied to either one of the electrodes is preferably 50 kHz to 150 MHz. Moreover, it is preferable that the frequency of the high frequency voltage applied to the first electrode is 1 to 200 kHz, and the frequency of the high frequency voltage applied to the second electrode is 800 kHz to 150 MHz.

  Hereinafter, the plasma discharge treatment performed under atmospheric pressure or a pressure in the vicinity thereof is also simply referred to as an atmospheric pressure plasma method.

That is, the present invention provides a transparent electrode or a film having a hard coat layer on the transparent substrate between a counter electrode composed of a first electrode and a second electrode under atmospheric pressure or a pressure near the first electrode. A high frequency voltage having a voltage component of the first frequency ω ₁ is applied to the second electrode, and a high frequency voltage having a voltage component of the second frequency ω ₂ is applied to the second electrode to form a discharge. After bringing the surface of the transparent support into contact with the excitation gas, an antireflection layer is formed thereon.

As the atmospheric pressure plasma method applicable to the present invention, JP-A-11-133205, JP-A-2000-185362, JP-A-11-61406, JP-A-2000-147209, 2000-121804 are disclosed. The technology disclosed in the above can be referred to.
<Method for producing antireflection film>
Lamination of the antireflection layer of the present invention can be produced by a known method, for example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure on a transparent support. It can be formed by coating using a coating method, a micro gravure coating method or an extrusion coating method.

  At the time of coating, it is preferable that the transparent support is unwound in a roll shape with a width of 1.4 to 4 m, and is wound up in a roll shape after performing the above-described coating, drying and curing treatment. .

  Furthermore, the antireflection film of the present invention is preferably produced by a production method in which an antireflection layer or the like is laminated on a transparent support and then heat-treated at 50 to 160 ° C. while being wound up in a roll shape.

  The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C., it preferably ranges from 3 days to less than 30 days, and if it is 160 ° C., it ranges from 10 minutes to 1 day. preferable. Usually, it is preferably set at a relatively low temperature so that the heat treatment effect at the outside of the winding, the center of the winding, and the core is not biased, and is preferably performed at around 50 to 60 ° C. for about 7 days.

  In order to stably perform the heat treatment, it is preferably performed in a place where the temperature and humidity can be adjusted, and is preferably performed in a heat treatment chamber such as a clean room without dust.

  The winding core for winding the antireflection film into a roll is not particularly limited as long as it is a cylindrical core, but is preferably a hollow plastic core, and the plastic material is a heat resistant plastic that can withstand heat treatment temperatures. For example, resins such as phenol resin, xylene resin, melamine resin, polyester resin, and epoxy resin can be used. A thermosetting resin reinforced with a filler such as glass fiber is preferred.

  The number of windings on these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness is preferably 5 cm or more.

  Thus, when performing the heat treatment in a state of winding a long antireflection film, it is preferable to rotate the roll, and the rotation is preferably at a speed of 1 rotation or less per minute, and may be continuous. It may be intermittent rotation. Moreover, it is preferable to perform rewinding of the roll once or more during the heating period.

  In order to rotate the long antireflection film wound around the core during the heat treatment, it is preferable to provide a dedicated turntable in the heat treatment chamber.

  In the case of intermittent rotation, it is preferable that the stop time is within 10 hours, the stop position is preferably made uniform in the circumferential direction, and the stop time is within 10 minutes. More preferred. Most preferred is continuous rotation.

  As for the rotation speed in continuous rotation, the time required for one rotation is preferably 10 hours or less, and if it is early, it becomes a burden on the apparatus, so the range of 15 minutes to 2 hours is substantially preferable.

In the case of a dedicated carriage having a rotation function, it is preferable that the optical film roll can be rotated during movement and storage. In this case, rotation is effective as a countermeasure against black bands that occur when the storage period is long. Function.
<Polarizing plate>
A polarizing plate using the antireflection film of the present invention will be described.

  The polarizing plate can be produced by a general known method. The back surface side of the antireflective film of the present invention is subjected to alkali saponification treatment, and a completely saponified polyvinyl alcohol aqueous solution is used on at least one surface of a polarizer produced by immersing and stretching the treated antireflective film in an iodine solution. It is preferable to bond them together.

  The antireflection film may be used on the other surface, or another polarizing plate protective film may be used. With respect to the antireflection film of the present invention, the polarizing plate protective film used on the other surface has a retardation Ro in the in-plane direction of 590 nm, 20 to 70 nm, and a retardation Rt in the film thickness direction of 100 to 400 nm. An optical compensation film having a phase difference (a phase difference film) is preferable.

  These can be prepared, for example, by the methods described in JP-A No. 2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal.

  For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. By using in combination with the antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  As a polarizing plate protective film used on the back side, as a commercially available cellulose ester film, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5 (manufactured by Konica Minolta Opto Co., Ltd.) Etc.) are preferably used.

  A polarizer, which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass. A typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol. There are ones in which iodine is dyed on a system film and ones in which a dichroic dye is dyed, but it is not limited to this.

  For the polarizer, a polyvinyl alcohol aqueous solution is formed into a film and dyed by uniaxial stretching or dyed or uniaxially stretched and then preferably subjected to a durability treatment with a boron compound. A polarizer having a thickness of 5 to 30 μm, preferably 8 to 15 μm, is preferably used.

On the surface of the polarizer, one surface of the antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.
<Image display device>
By incorporating the antireflection film surface of the polarizing plate using the antireflection film of the present invention into the viewing surface side of the image display device, various image display devices with excellent visibility can be produced.

  The antireflection film of the present invention is a reflection type, transmission type, transflective type LCD or LCD of various drive systems such as TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. Preferably used.

  In addition, the antireflection film of the present invention has significantly less color unevenness in the reflected light of the antireflection layer, and has a low reflectance and excellent flatness, and is a plasma display, field emission display, organic EL display, inorganic EL display, electronic It is also preferably used for various display devices such as paper.

  In particular, an image display device having a large screen of 30 or more screens has an effect that there is little color unevenness and wavy unevenness, and eyes are not tired even during long-time viewing.

Example 1
In the following manner, a hard coat layer and an antireflection layer were provided on a cellulose ester film as a substrate.
(Coating composition 1 for hard coat)
Pentaerythritol triacrylate 30 parts by mass Pentaerythritol tetraacrylate 45 parts by mass Urethane acrylate (U-4HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, Ciba Specialty Chemicals ( 5 parts by mass 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals) 3 parts by mass polyoxyethylene oleyl Ether (Emulgen 404, manufactured by Kao Corporation)
0.5 parts by mass Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Acetone 45 parts by mass Polymethyl methacrylate fine particles (average particle size 4 μm) 20 parts by mass <Formation of hard coat film H-1>
The substrate is die-coated with the coating composition 1 for hard coat, dried at 80 ° C., and then irradiated with 0.30 J / cm ² of ultraviolet light with a high-pressure mercury lamp so that the film thickness after curing becomes 12 μm. Coat layer 1 was applied.

Furthermore, on the surface opposite to the surface on which the coating composition 1 for hard coat was coated, the following back coating layer coating composition was die-coated so as to have a wet film thickness of 14 μm, and a back coating layer was provided. A hard coat film (HC film) H-1 in which a hard coat layer and a back coat layer were provided on a cellulose ester film was produced.
(Coating composition for back coat layer)
Acetone 30 parts by mass Ethyl acetate 45 parts by mass Isopropyl alcohol 10 parts by mass Diacetyl cellulose 0.6 parts by mass Ultrafine silica 2% acetone dispersion 0.2 parts by mass (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)
<Preparation of antiglare hard coat film H-2>
In preparing H-1, the hard coat coating composition 1 was changed to the following antiglare hard coat coating composition 2.
(Coating composition 2 for antiglare hard coat)
Acetone 35 parts by mass Ethyl acetate 35 parts by mass Cyclohexanone 15 parts by mass Toluene 15 parts by mass Pentaerythritol triacrylate 30 parts by mass Pentaerythritol tetraacrylate 45 parts by mass Urethane acrylate 25 parts by mass (trade name U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd.)
8 parts by mass of 1-hydroxycyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
2-Methyl-1- [4- (methylthio) phenyl] -2-monophorinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals) 8 parts by mass Fluorine-containing polymethyl methacrylate fine particles (manufactured by Negami Kogyo) ), Average particle size 3.5 μm
2 parts by mass <Preparation of antiglare hard coat film H-3>
In production of H-2, the fluorine-containing polymethyl methacrylate fine particles were changed to 5 parts by mass.
<Preparation of antiglare hard coat film H-4>
In production of H-3, the fluorine-containing polymethyl methacrylate fine particles were changed to 10 parts by mass.
<Preparation of antiglare hard coat film H-5>
In production of H-2, the fluorine-containing polymethyl methacrylate fine particles were changed to 15 parts by mass.
(Preparation of intermediate film M-1)
<Atmospheric pressure plasma treatment>
Using the atmospheric pressure plasma processing apparatus shown in FIG. 7 of Japanese Patent Application No. 2005-351829, the following atmospheric pressure plasma treatment was performed on the surface of H-1 produced above.

The electrode gap is 0.5 mm, the discharge gas shown below is supplied to the discharge space, and a high frequency power source manufactured by Shinko Electric Co., Ltd. is used, the frequency is 13.5 MHz, the applied voltage Vp = 9.5 kV, and the output density is 1.5 W / Surface treatment was performed by forming a discharge as cm ² .

(Discharge gas)
Nitrogen gas 80.0% by volume
Oxygen gas 20.0% by volume
The surface of H-1 subjected to the above atmospheric pressure plasma treatment is die-coated with the following high refractive index layer coating solution 1, dried at 50 ° C., and then irradiated with ultraviolet light of 120 mJ / cm ² with a high-pressure mercury lamp and after curing. A high refractive index layer was provided so that the film thickness of the film was 130 nm, and an intermediate film M-1 having even a high refractive index layer was obtained. The refractive index of the high refractive index layer was 1.56.

(High refractive index layer coating solution 1)
Zinc antimonate sol (CX-Z610M-F2, manufactured by Nissan Chemical Industries, Ltd.)
50 parts by mass Dioxane glycol diacrylate (NK ester A-DOG, manufactured by Shin-Nakamura Chemical Co., Ltd.) 12 parts by mass 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) 2 parts by mass 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by mass 10% propylene glycol of polyoxyalkylenedimethylpolysiloxane copolymer (FZ-2207, manufactured by Toray Dow Corning Co., Ltd.) Monomethyl ether liquid
2 parts by mass Propylene glycol monomethyl ether 360 parts by mass Isopropyl alcohol 360 parts by mass Methyl ethyl ketone 200 parts by mass (Preparation of intermediate films M-2 to M-5)
In production of M-1, the hard coat film was changed to H-2 to H-5, and intermediate films M-2 to M-5 were produced.
(Production of M-6)
In preparation of M-1, the zinc antimonate sol used for the preparation of the particle dispersion A of the high refractive index layer coating solution 1 was changed to a phosphorus-doped tin oxide (SnO ₂ (P ₂ O ₅ ) x) sol, and an intermediate Film M-6 was produced.
《Preparation of antireflection film by coating low refractive index layer》
(Preparation of antireflection film 101)
On the produced intermediate film M-1, the following low refractive index layer coating solution 1 is die-coated, dried at 50 ° C., irradiated with 120 mJ / cm ² of ultraviolet light with a high pressure mercury lamp, and further subjected to heat treatment at 120 ° C. Then, a low refractive index layer was provided so that the film thickness was 92 nm, and an antireflection film 101 (Comparative 1) was produced.

  The organosilane represented by the general formula (2) is γ-methacryloxypropyltrimethoxysilane, and the reactive silicone is α-butyl-ω- [3- (2,2-bis (hydroxymethyl) butoxy). Propyl] polydimethylsiloxane.

(Low refractive index layer coating solution 1)
Propylene glycol monomethyl ether 437 parts by weight Isopropyl alcohol 437 parts by weight Acetic acid 3.00 parts by weight Hydrolyzate A (converted to 8.6% solids) 75.0 parts by weight γ-methacryloxypropyltrimethoxysilane (KBM503, Shin-Etsu Chemical Co., Ltd.) 1.25 parts by mass α-butyl-ω- [3- (2,2-bis (hydroxymethyl) butoxy) propyl] polydimethylsiloxane (FM-DA21 manufactured by Chisso Corporation) 1.05 parts by mass ELCOM V -8209
(Isopropyl alcohol-dispersed hollow silica fine particles manufactured by Catalytic Chemical Industry Co., Ltd., solid content 20%) 30.0 parts by mass Diluted isopropyl alcohol (solid) of aluminum ethyl acetoacetate diisopropylate (ALCH manufactured by Kawaken Fine Chemical Co., Ltd.) Min. 10%) 2.25 parts by mass FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Toray Dow Corning) 2.40 parts by mass <Preparation of hydrolyzate A>
A hydrolyzate A was prepared by adding ethanol and an acetic acid aqueous solution to 147 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) to give 500 g and stirring at room temperature (25 ° C.) for 25 hours. The weight average molecular weight Mw of the silane condensate was 2000, and all of the silane was not hydrolyzed and remained.
(Preparation of antireflection film 102)
In the production of the antireflection film 101, the low refractive index layer coating solution 1 was changed to the following low refractive index layer coating solution 2, and others were produced in the same manner.

(Low refractive index layer coating solution 2)
Propylene glycol monomethyl ether 437 parts by mass Isopropyl alcohol 347 parts by mass Acetic acid 3.00 parts by mass Hydrolyzate B (converted to 8.6% solids) 165 parts by mass γ-methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) ) 1.25 parts by mass α-butyl-ω- [3- (2,2-bis (hydroxymethyl) butoxy) propyl] polydimethylsiloxane (FM-DA21 manufactured by Chisso Corporation) 1.05 parts by mass Aluminum ethyl acetoacetate -Diisopropyl alcohol (ALCH manufactured by Kawaken Fine Chemical Co., Ltd.) in isopropyl alcohol (solid content 10%) 2.25 parts by mass FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Toray Dow Corning Co.) 2.40 Mass part <Hydrolyzate B Preparation>
Ethanol and an acetic acid aqueous solution were added to 147 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) to give 500 g, and the mixture was stirred at room temperature (25 ° C.) for 15 hours to prepare a hydrolyzate. The weight average molecular weight Mw of the condensate of silane was 800.

At this point, 588 g of ELCOM V-8209 (catalyst chemical industry isopropyl alcohol-dispersed hollow silica particles, solid content 20%) was mixed and stirred for another 2 hours. Finally, the solvent was distilled off to adjust the concentration. A hydrolyzate B was prepared by adjusting.
(Preparation of antireflection film 103)
In the production of the antireflection film 102, hollow silica particles were mixed when the silane weight average molecular weight Mw of the hydrolyzate B reached 500, and the others were produced in the same manner.
(Preparation of antireflection film 104)
In the production of the antireflection film 102, hollow silica particles were mixed into the system when the silane weight average molecular weight Mw of the hydrolyzate B reached 1000, and the others were produced in the same manner.
(Preparation of antireflection film 105)
In the production of the antireflection film 102, hollow silica particles were mixed into the system when the silane weight average molecular weight Mw of the hydrolyzate B reached 450, and the others were produced in the same manner.
(Preparation of antireflection film 106)
In the production of the antireflection film 102, hollow silica particles were mixed into the system when the silane weight average molecular weight Mw of the hydrolyzate B reached 1100, and the others were produced in the same manner.
(Preparation of antireflection film 107)
In the production of the antireflection film 102, α-butyl-ω- [3- (2,2-bis (hydroxymethyl) butoxy) propyl] polydimethylsiloxane ( FM-DA21 manufactured by Chisso Corp.) 1.05 parts by mass was also mixed, and the others were produced in the same manner.
(Preparation of antireflection film 108)
In the production of the antireflection film 102, α-butyl-ω- [3- (2,2-bis (hydroxymethyl) butoxy) propyl] polydimethylsiloxane ( FM-DA21 manufactured by Chisso Corporation) and γ-methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at the same time.
(Preparation of antireflection film 109)
In the production of the antireflection film 102, simultaneously with mixing the hollow silica particles of the hydrolyzate B, γ-methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed at the same time. Produced.
(Preparation of antireflection film 110)
The antireflection film 102 was prepared in the same manner except that the amount of the hydrolyzate B added to the low refractive index layer coating solution 2 was 1.5 times.
(Preparation of antireflection film 111)
The antireflection film 101 was prepared in the same manner except that the amount of the hydrolyzate A added to the low refractive index layer coating solution 1 was halved.
(Preparation of antireflection film 112)
Hollow silica particles described in JP 2006-117924 A [0164] were prepared, and the others were produced in the same manner as the anti-reflection film 101.

The results of evaluating the above antireflection film are shown in Table 1.
<Evaluation method>
<Reflectance>
Using a spectrocolorimeter CM-2500d manufactured by Konica Minolta Co., Ltd., measurement was performed at a measurement diameter of 8 mm and an observation field of view of 2 ° to obtain SCI (integral reflection). The clear film is preferably 0.7% or less, and the antiglare film is preferably 1.0% or less.
<Anti-fouling property>
The antifouling property was judged from the contact angle of pure water. The larger the contact angle, the better the antifouling property. The contact angle of pure water was measured at a droplet diameter of 1.5 mm using a contact angle meter CA-X type manufactured by Kyowa Interface Chemical Co., Ltd. in an environment of 23 ° C. and 55% RH.
《Abrasion resistance》
A sample was subjected to a load of 500 g / cm ^{2 on} # 0000 steel wool (SW) in an environment of 23 ° C. and 55% RH, and the number of scratches per 1 cm width was measured after 10 reciprocations. In addition, the number of scratches is measured at a place where the number of scratches is the largest among the portions where the load is applied.

A: Number of scratches is 0 B: Number of scratches is 1 to less than 5 C: Number of scratches is 5 or more and less than 10 D: Number of scratches is 10 or more << pencil hardness >>
In accordance with JIS K 5600, a pencil of a known hardness was scratched with a load of 1 kg with a pencil hardness tester (HA-301, Clemens-type scratch hardness tester, Tester Sangyo Co., Ltd.) and visually scratched. Evaluate the occurrence of If the scratch has occurred 5 times after scratching, it will be accepted. (Example: When a scratch is entered twice or more with a 5H pencil, 4H is designated as 4H when a scratch is entered once or less with a 4H pencil.)

Example 2
The anti-glare property was evaluated by changing the high refractive index layer and the hard coat layer as follows.
(Preparation of antireflection film 200)
In the production of the antireflection film 102, M-1 was changed to M-6, and the others were produced in the same manner.
(Preparation of antireflection film 201)
In the production of the antireflection film 102, H-1 was changed to H-2, and the others were produced in the same manner.
(Preparation of antireflection film 202)
In the production of the antireflection film 102, H-1 was changed to H-3, and the others were produced in the same manner.
(Preparation of antireflection film 203)
In the production of the antireflection film 102, H-1 was changed to H-4, and the others were produced in the same manner.
(Preparation of antireflection film 204)
In the production of the antireflection film 102, H-1 was changed to H-5, and others were produced in the same manner.

  The evaluation results are shown in Table 2.

<Evaluation method>
<Reflection>
A sample was affixed to the black image, and the reflection was visually evaluated in a room with a fluorescent lamp in accordance with the following criteria.

A: The outline of the fluorescent lamp is blurred and I don't care about the reflection at all. B: The outline of the fluorescent lamp is slightly noticeable but I don't care much. C: The outline of the fluorescent lamp is recognized, but it is an acceptable level. Clear outline and worried about reflection
Using a Suga Test Instruments Co., Ltd. product, image clarity measuring device ICM-IDP, the transmission image clarity at a comb width of 0.25 mm was measured. Transmission image clarity is a parameter that correlates with sharpness. The transmission image clarity is preferably 20% or more (comb width 0.25 mm).

  According to the present invention, it is possible to provide an antireflection film having excellent scratch resistance, low reflectance, and excellent visibility when used in a display device.

Claims (4)

The outermost surface has a low refractive index layer having a refractive index of 1.20 to 1.49 containing hollow silica particles and silicone, and the hollow silica particles are contained in an amount of 30 to 80% by mass in the solid content. The average value Ros of the Si—C bond peak intensity ratio measured by an X-ray photoelectron spectrometer in the depth range from 1 to 5 nm and represented by the following formula (A) is 0.40 or more, and the outermost surface The average value Rot of the Si—C bond peak intensity ratio at a depth of 10 to 25 nm from 0.0005 to 0.10,
Forming a high refractive index layer on the transparent support, and forming the low refractive index layer on the high refractive index layer,
The low refractive index layer hydrolyzes an organosilane represented by the following general formula (1) to produce a low condensate having a weight average molecular weight of 500 to 1000, and hollow silica is mixed into the low condensate. Formed by applying and drying a coating solution obtained through a process of continuing hydrolysis and condensation.
In the step of continuing the hydrolysis, an organosilane represented by the general formula (2) is mixed.
Formula (A) (Si—C bond peak intensity ratio) = (Si—C bond peak intensity) / {(
Si—C bond peak intensity) + (Si—O bond peak intensity)}
General formula (1) Si (X1) ₄
X1 represents an alkoxy group.
Formula (2) (R) _m Si (X2) _4-m
R represents an organic group that is not hydrolyzed in the process of continuing hydrolysis. X2 represents an alkoxy group. m represents an integer of 1 to 4.   The method for producing an antireflection film according to claim 1, further comprising a step of forming a hard coat layer before the step of forming the high refractive index layer.   The method for producing an antireflection film according to claim 2, wherein an antiglare property is imparted by forming an uneven shape on the surface of the transparent support or the hard coat layer.   After the step of forming the low refractive index layer, the method includes a step of winding the antireflection film into a roll shape, and a step of performing a heat treatment at 50 to 160 ° C. while being wound into a roll shape. The manufacturing method of the antireflection film of any one of Claims 1-3.