JP4484612B2 - Composition, coating composition, antireflection film, polarizing plate, image display device - Google Patents

Description

  The present invention relates to a composition, a coating composition, an optical film formed from the coating composition, an antireflection film, a polarizing plate using the antireflection film, and an image display device.

  In general, the antireflection film is used in a display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD), and a contrast reduction or image due to reflection of external light. In order to prevent reflection of light, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference.

  Such an antireflection film can be generally produced by forming a low refractive index layer having an appropriate film thickness and a lower refractive index than the support on the support. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer. Further, since the antireflection film is used on the outermost surface of the display, high scratch resistance is required. In order to realize high scratch resistance in a thin film having a thickness of about 100 nm, the strength of the coating itself and the adhesion to the lower layer are required.

  To lower the refractive index of the material, there are means of (1) introducing fluorine atoms and (2) lowering the density (introducing voids). The low refractive index and high scratch resistance are both difficult problems.

  As a method for increasing the film strength to some extent, there is a method using a fluorine-containing sol-gel film as described in Patent Documents 1 and 2, but (1) a long time is required for curing, and the production load is large. (2) The saponification liquid (alkaline treatment liquid) is not resistant, and a great restriction occurs such that the support surface cannot be saponified after the formation of the antireflection film.

On the other hand, it is known that introduction of a polyfunctional acrylate such as a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) is effective in improving scratch resistance. Patent Document 3 describes means for lowering the refractive index by introducing a fluorine-containing polyfunctional (meth) acrylate, but even if DPHA is replaced with these fluorine-containing polyfunctional (meth) acrylates, The number of crosslinkable groups decreases due to the mass number, and sufficient scratch resistance cannot be obtained.
Thus, a composition capable of forming a film having a low refractive index and excellent scratch resistance, which can be applied to optical applications such as an antireflection film, has been desired.
JP 2002-265866 A JP 2002-317152 A Japanese Patent Laid-Open No. 11-60637

  An object of the present invention is to provide a composition capable of forming a cured film having a low refractive index and strong scratch resistance, and a coating composition comprising the composition, and sufficient antireflection using the coating composition. An object is to provide an antireflection film having improved scratch resistance while having properties. Furthermore, it is providing the polarizing plate and image display apparatus using such an antireflection film.

＜２＞
前記Ｌが、炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、−Ｏ−、−Ｓ−、−Ｎ（Ｒ）−、炭素数１〜１０のアルキレン基と−Ｏ−、−Ｓ−または−Ｎ（Ｒ）−を組み合わせて得られる基、炭素数６〜１０のアリーレン基と−Ｏ−、−Ｓ−または−Ｎ（Ｒ）−を組み合わせて得られる基のいずれかを表すことを特徴とする＜１＞に記載の組成物。ただし、前記Ｒは水素原子又は炭素数１〜５のアルキル基を表す。
＜３＞
含フッ素多官能モノマーが下記Ｘ−２１、Ｘ−２２、Ｘ−２７、Ｘ−２８、Ｘ−３０、またはＸ−３１であることを特徴とする＜１＞または＜２＞に記載の組成物。

＜４＞
前記含フッ素多官能モノマーが、液相フッ素化の手法を用いて製造されたことを特徴とする、＜１＞〜＜３＞のいずれかに記載の組成物。
＜５＞
＜１＞〜＜４＞のいずれかに記載の組成物からなることを特徴とするコーティング組成物。
＜６＞
透明支持体上に、＜５＞に記載のコーティング組成物から形成された硬化皮膜層を有することを特徴とする光学フィルム。
＜７＞
前記硬化皮膜層の屈折率が１．２０以上１．４６以下であることを特徴とする＜６＞に記載の光学フィルム。
＜８＞
＜６＞又は＜７＞に記載の光学フィルムの硬化皮膜層が低屈折率層であり、さらに前記硬化皮膜層以外に少なくとも一層の機能層を有することを特徴とする反射防止フィルム。
＜９＞
前記中空のシリカ微粒子の平均粒径が、低屈折率層の厚みの３０％以上１５０％以下であることを特徴とする＜８＞に記載の反射防止フィルム。
＜１０＞
＜８＞または＜９＞に記載の反射防止フィルムが、偏光板における偏光子の保護フィルムの少なくとも一方に用いられていることを特徴とする偏光板。
＜１１＞
＜８＞もしくは＜９＞に記載の反射防止フィルム、または＜１０＞に記載の偏光板が、ディスプレイの最表面に用いられていることを特徴とする画面表示装置。
なお、本発明は上記＜１＞〜＜１１＞に関するものであるが、参考のためその他の事項、例えば下記（１）〜（１７）などについても記載した。
（１）重合性基を２つ以上有する含フッ素多官能モノマーと、中空のシリカ微粒子を含有することを特徴とする組成物。
（２）前記含フッ素多官能モノマーが重合性基を３つ以上有し、かつ該含フッ素化合物のフッ素含有率が分子量の３５．０質量％以上であることを特徴とする、上記（１）に記載の組成物。
（３）前記含フッ素多官能モノマーが下記式（１）で表されることを特徴とする、上記（１）又は（２）に記載の組成物。
式（１） Ｒｆ｛−（Ｌ）ｍ−Ｙ｝ｎ
（式中、Ｒｆは少なくとも炭素原子及びフッ素原子を含み、酸素原子及び／又は水素原子を含んでもよい、鎖状又は環状の、ｎ価のフッ化炭化水素基を表し、ｎは３以上の整数を表す。Ｌは二価の連結基を表し、ｍは０又は１を表す。Ｙは重合性基を表す。）
（４）前記含フッ素多官能モノマーの重合性基を重合させたとき、すべての架橋間分子量の計算値が３００以下であることを特徴とする、上記（１）〜（３）のいずれかに記載の組成物。
（５）前記含フッ素多官能モノマーが、液相フッ素化の手法を用いて製造されたことを特徴とする、上記（１）〜（４）のいずれかに記載の組成物。
（６）前記含フッ素多官能モノマーの重合性基が、アクリロイル基、メタアクリロイル基、及び−Ｃ(Ｏ)ＯＣＨ＝ＣＨ₂から選ばれるいずれかの基あることを特徴とする、上記（１）〜（５）のいずれかに記載の組成物。
（７）前記含フッ素多官能モノマーが下記式（２）で表されることを特徴とする、上記（１）〜（６）のいずれかに記載の組成物。
式（２） Ｒｆ−｛ＣＨ₂−ＯＣ（Ｏ）ＣＨ＝ＣＨ₂｝_n
（式中、Ｒｆ、ｎは、式（１）と同じ意味を表す。）
（８）前記含フッ素多官能モノマーが下記式（３）で表されることを特徴とする、上記（１）〜（６）のいずれかに記載の組成物。
式（３） Ｒｆ−｛Ｃ（Ｏ）ＯＣＨ＝ＣＨ₂｝_n
（式中、Ｒｆ、ｎは、式（１）と同じ意味を表す。）
（９）上記（１）〜（８）のいずれかに記載の組成物からなることを特徴とするコーティング組成物。
（１０）透明支持体上に、上記（９）に記載のコーティング組成物から形成された硬化皮膜層を有することを特徴とする光学フィルム。
（１１）上記（１０）に記載の光学フィルムの硬化皮膜層が低屈折率層であり、さらに前記硬化皮膜層以外に少なくとも一層の機能層を有することを特徴とする反射防止フィルム。
（１２）前記中空のシリカ微粒子の平均粒径が、低屈折率層の厚みの３０％以上１５０％以下であることを特徴とする、上記（１１）に記載の反射防止フィルム。
（１３）前記低屈折率層が下記式（４）で表される含フッ素ポリマーの架橋生成物を含有することを特徴とする、上記（１１）又は（１２）に記載の反射防止フィルム。
式（４） As a result of intensive studies, the inventor of the present invention uses a low refractive index layer formed from a composition containing a fluorine-containing polyfunctional monomer having two or more polymerizable groups and hollow silica fine particles. It was found that the scratch resistance can be drastically improved while suppressing an increase in the rate and without being restricted by long-time thermal curing or saponification treatment.
According to the present invention, there are provided a composition having the following constitution, a coating composition comprising the composition, and an antireflection film, a polarizing plate, and an image display device formed from the coating composition. Achieved.
<1>
A composition comprising a fluorine-containing polyfunctional monomer having three or more polymerizable groups and hollow silica fine particles, wherein the fluorine-containing polyfunctional monomer has a fluorine content of 35.0 mass% or more of the molecular weight, When the polymerizable group of the fluorine polyfunctional monomer is polymerized, all the calculated molecular weights between crosslinks are 300 or less, and the refractive index of the layer formed of the composition is 1.20 or more and 1.46 or less, And this fluorine-containing polyfunctional monomer is represented by following formula (1), The composition characterized by the above-mentioned.
Formula (1): Rf {-(L) m-Y} n
(In the formula, Rf represents an n-valent group selected from the following f-1 to f-10, n represents an integer of 3 or more, L represents a divalent linking group, and m represents 0 or 1. Y represents any group selected from an acryloyl group, a methacryloyl group, and —C (O) OCH═CH _2. )

<2>
L is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -O-, -S-, -N (R)-, an alkylene group having 1 to 10 carbon atoms and -O-, A group obtained by combining —S— or —N (R) —, or a group obtained by combining —O—, —S— or —N (R) — with an arylene group having 6 to 10 carbon atoms; The composition according to <1>, wherein the composition is represented. However, said R represents a hydrogen atom or a C1-C5 alkyl group.
<3>
The composition according to <1> or <2>, wherein the fluorine-containing polyfunctional monomer is X-21, X-22, X-27, X-28, X-30, or X-31 below .

<4>
The composition according to any one of <1> to <3>, wherein the fluorine-containing polyfunctional monomer is produced using a liquid phase fluorination technique.
<5>
<1>-<4> It consists of a composition in any one of <4>, The coating composition characterized by the above-mentioned.
<6>
An optical film comprising a cured film layer formed from the coating composition according to <5> on a transparent support.
<7>
<6> The optical film according to <6>, wherein the cured film layer has a refractive index of 1.20 or more and 1.46 or less.
<8>
<6> or <7> The antireflective film characterized by the cured film layer of the optical film being a low refractive index layer and further having at least one functional layer in addition to the cured film layer.
<9>
The average particle diameter of the hollow silica fine particles is 30% or more and 150% or less of the thickness of the low refractive index layer, The antireflection film as described in <8>.
<10>
<8> or <9> The antireflection film as described in <9> is used for at least one of the protective films of the polarizer in a polarizing plate, The polarizing plate characterized by the above-mentioned.
<11>
<8> or <9> The antireflection film as described in <9>, or the polarizing plate as described in <10> is used for the outermost surface of a display, The screen display apparatus characterized by the above-mentioned.
Although the present invention relates to the above <1> to <11>, other matters such as the following (1) to (17) are also described for reference.
(1) A composition comprising a fluorine-containing polyfunctional monomer having two or more polymerizable groups and hollow silica fine particles.
(2) The above (1), wherein the fluorine-containing polyfunctional monomer has three or more polymerizable groups, and the fluorine content of the fluorine-containing compound is 35.0% by mass or more of the molecular weight. A composition according to 1.
(3) The composition according to (1) or (2) above, wherein the fluorine-containing polyfunctional monomer is represented by the following formula (1).
Formula (1) Rf {-(L) m-Y} n
(In the formula, Rf represents a chain or cyclic n-valent fluorinated hydrocarbon group containing at least a carbon atom and a fluorine atom, and may contain an oxygen atom and / or a hydrogen atom, and n is an integer of 3 or more. L represents a divalent linking group, m represents 0 or 1, Y represents a polymerizable group.
(4) When the polymerizable group of the fluorine-containing polyfunctional monomer is polymerized, the calculated values of all cross-linking molecular weights are 300 or less, and any one of (1) to (3) above The composition as described.
(5) The composition according to any one of (1) to (4) above, wherein the fluorine-containing polyfunctional monomer is produced using a liquid phase fluorination technique.
(6) The polymerizable group of the fluorine-containing polyfunctional monomer is any group selected from an acryloyl group, a methacryloyl group, and —C (O) OCH═CH _2. -Composition in any one of (5).
(7) The composition according to any one of (1) to (6) above, wherein the fluorine-containing polyfunctional monomer is represented by the following formula (2).
Equation _{(2) Rf- {CH 2 -OC} (O) CH = CH 2} n
(In the formula, Rf and n represent the same meaning as in formula (1).)
(8) The composition according to any one of (1) to (6) above, wherein the fluorine-containing polyfunctional monomer is represented by the following formula (3).
Equation (3) Rf- {C (O ) OCH = CH 2} n
(In the formula, Rf and n represent the same meaning as in formula (1).)
(9) A coating composition comprising the composition according to any one of (1) to (8) above.
(10) An optical film comprising a cured film layer formed from the coating composition according to (9) above on a transparent support.
(11) An antireflection film, wherein the cured film layer of the optical film according to (10) is a low refractive index layer, and further has at least one functional layer in addition to the cured film layer.
(12) The antireflection film as described in (11) above, wherein the hollow silica fine particles have an average particle size of 30% to 150% of the thickness of the low refractive index layer.
(13) The antireflection film as described in (11) or (12) above, wherein the low refractive index layer contains a cross-linked product of a fluoropolymer represented by the following formula (4).
Formula (4)

(Wherein L represents a linking group having 1 to 10 carbon atoms, m represents 0 or 1, X represents a hydrogen atom or a methyl group, A represents a polymerized unit of any vinyl monomer, and a single component. Or x, y, and z may represent mol% of each component, and satisfy 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Represents the value.)
(14) A polarizing plate, wherein the antireflection film according to any one of (11) to (13) is used for at least one of the two protective films of the polarizer in the polarizing plate.
(15) Of the two protective films of the polarizer, the film other than the antireflection film is an optical compensation film having an optical compensation layer comprising an optically anisotropic layer, and the optical anisotropic layer is discotic. A layer formed from a compound having a structural unit, wherein the disc surface of the discotic structural unit is inclined with respect to the transparent support surface, and the disc surface of the discotic structural unit and the transparent support surface form The polarizing plate according to (14), wherein the angle is changed in the depth method of the optical anisotropic layer.
(16) An image characterized by using the antireflection film according to any one of (11) to (13) above or the polarizing plate according to (14) or (15) above on the outermost surface of a display. Display device.
(17) The image display device according to (16), wherein the image display device is a TN, STN, VA, IPS, or OCB mode transmissive, reflective, or transflective liquid crystal display device. Image display device.

  According to the present invention, it is possible to provide a composition capable of forming a cured film having a low refractive index and a high scratch resistance, and a coating composition comprising the composition. Moreover, the antireflection film using the coating composition is excellent in scratch resistance while having sufficient antireflection performance. Furthermore, the image display device provided with the antireflection film of the present invention and the image display device provided with a polarizing plate using the antireflection film of the present invention have little reflection of external light and background reflection, and are extremely visible. Is expensive.

Hereinafter, the polarizing plate and the image display apparatus using the composition, coating composition, antireflection film, antireflection film of the present invention will be described in detail.
In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In addition, in this specification, for example, descriptions of “(meth) acryloyl”, “(meth) acrylate”, “(meth) acrylic acid” and the like are “acryloyl and / or methacryloyl”, “acrylate and / or methacrylate”, respectively. ”,“ Acrylic acid and / or methacrylic acid ”.

[Composition, coating composition]
The composition of the present invention contains a fluorine-containing polyfunctional monomer having two or more polymerizable groups and hollow silica fine particles. The composition can form a film having a low refractive index and excellent scratch resistance, that is, can be preferably used as a coating composition (coating agent) for coating.

(Fluorine-containing polyfunctional monomer)
Hereinafter, the fluorine-containing polyfunctional monomer preferably used in the present invention will be described in detail.
The fluorine-containing polyfunctional monomer used in the present invention mainly consists of a plurality of fluorine atoms and carbon atoms (however, it may partially contain oxygen atoms and / or hydrogen atoms) and does not substantially participate in polymerization. At least two having an atomic group (hereinafter also referred to as “fluorine-containing core”) and a polymerizable group such as a radical polymerizable group, an ionic polymerizable group, or a condensation polymerizable group via a linking group such as an ester bond or an ether bond. It is a compound having a polymerizable group.

The fluorine-containing polyfunctional monomer preferably has three or more polymerizable groups. The fluorine-containing polyfunctional monomer is preferably represented by the following formula (1).
Formula (1) Rf {-(L) m-Y} n
In the formula, Rf represents a chain or cyclic n-valent fluorinated hydrocarbon group containing at least a carbon atom and a fluorine atom, and may contain an oxygen atom and / or a hydrogen atom, and n is an integer of 3 or more. To express. L represents a divalent linking group, and m represents 0 or 1. Y represents a polymerizable group. In the present invention, the fluorine-containing polyfunctional monomer may be a crosslinking agent having a polymerizable group as a crosslinking group.

The compound represented by formula (1) will be described in more detail below.
Rf represents a “fluorine-containing core part”, and represents a chain or cyclic, n-valent fluorinated hydrocarbon group that contains at least carbon atoms and fluorine atoms, and may contain oxygen atoms and / or hydrogen atoms.
It is preferable that the number of hydrogen atoms / number of fluorine atoms in Rf is 1/4 or less, preferably 1/9 or less. When the number of hydrogen atoms / number of fluorine atoms in Rf is ¼ or less, the antifouling property is good, which is preferable. On the other hand, when the number of hydrogen atoms / number of fluorine atoms in Rf exceeds 1/4, the refractive index of the polymer increases, and the average reflectance when formed into a coating film increases, which is not preferable.
n represents an integer of 3 or more, and n is preferably 4 or more, and more preferably 5 or more. Rf is preferably a group having a molecular weight between crosslinks of 300 or less when all polymerizable groups are polymerized (or crosslinked), and the molecular weight between crosslinks will be described later.

  Specific examples of the “fluorine-containing core portion” represented by Rf include the following specific examples.

Y represents a polymerizable group selected from a (meth) acryloyl group, an allyl group, an alkoxysilyl group, an α-fluoroacryloyl group, an epoxy group, and —C (O) OCH═CH ₂ . Among these, from the viewpoint of polymerizability, (meth) acryloyl group, allyl group, α-fluoroacryloyl group, epoxy group, and —C (O) OCH═CH ₂ having radical or cationic polymerizability are preferable and more preferable. Are a (meth) acryloyl group, allyl group, α-fluoroacryloyl group, and —C (O) OCH═CH ₂ having radical polymerizability, and more preferably a (meth) acryloyl group or —C ( O) is a OCH = CH _2.

  L represents a divalent linking group, specifically, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -O-, -S-, -N (R)-, 1 to carbon atoms. A group obtained by combining 10 alkylene group and —O—, —S— or —N (R) —, an arylene group having 6 to 10 carbon atoms and —O—, —S— or —N (R) —; The group obtained by combining is represented. R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. When L represents an alkylene group or an arylene group, the alkylene group and the arylene group represented by L are preferably substituted with a halogen atom, and preferably substituted with a fluorine atom.

More preferred as the fluorine-containing polyfunctional monomer is one represented by the formula (2) or (3) from the viewpoint of refractive index and polymerizability.
Equation _{(2) Rf- {CH 2 -OC} (O) CH = CH 2} n
Equation (3) Rf- {C (O ) OCH = CH 2} n
In the above formula, Rf and n represent the same meaning as in formula (1).

  Although the preferable specific example of a fluorine-containing monomer is given to the following, this invention is not limited by these.

  These compounds can be synthesized, for example, by the methods described in JP-A-10-182558 and JP-A-11-60637.

  The fluorine-containing polyfunctional monomer preferably has a fluorine content of 35% by mass or more, more preferably 40% by mass or more, and further preferably 45% by mass or more of the molecular weight of the fluorine compound. When the fluorine content is less than 35% by mass of the molecular weight of the fluorine compound, the refractive index of the polymer is increased, and the average reflectance when formed into a coating film is not preferable.

  The fluorine-containing polyfunctional monomers X-1 to X-32 have a fluorine content of 48.5, 16.3, 26.8, 34.2, 27.2, 24.8, 44.0, 19. 2, 26.2, 34.1, 26.3, 31.4, 35.6, 30.6, 45.9, 48.2, 54.9, 34.8, 41.4, 45.0, 37.5, 46.2, 48.6, 47.7, 49.8, 45.8, 36.6, 39.8, 44.0, 35.1, 44.9, 36.2% by mass is there.

  In addition, the fluorine-containing polyfunctional monomer is preferably a fluorine-containing polyfunctional monomer in which all the calculated values of the molecular weight between crosslinks are 300 or less when all the polymerizable groups of the fluorine-containing polyfunctional monomer are polymerized from the viewpoint of crosslinking density. . The calculated value of the molecular weight between cross-links is (a) a total of 3 or more carbon atoms substituted with 3 or more carbon atoms or silicon atoms in the polymer (or cross-linked product) in which all polymerizable groups have reacted. When a silicon atom substituted with a carbon atom or an oxygen atom is (b), (a) and (a), (b) and (b), or an atomic group sandwiched between (a) and (b) Refers to molecular weight. For example, X-22 will be described as an example of the fluorine-containing polyfunctional monomer. Assuming that all the polymerizable groups of X-22 are polymerized, it is expressed as in Formula (5).

Formula (5)

In this case, the partial structure that is the target of calculation of the molecular weight between crosslinks defined above is a portion surrounded by a broken line in formula (5), and the calculated value of the molecular weight between crosslinks is C ₂ F ₄ O = 116, respectively. 0.0 and C ₅ H ₂ F ₆ O ₃ = 224.1, both of which are 300 or less.

  The calculated value of the molecular weight between crosslinks is more preferably 250 or less, and still more preferably 200 or less. When the molecular weight between crosslinks when all the polymerizable groups of the fluorine-containing polyfunctional monomer are polymerized exceeds 300, the hardness when formed into a coating film is lowered, and further, the antifouling property and scratch resistance are deteriorated.

  As a method for producing these fluorine-containing polyfunctional monomers, a compound having an ester bond, a dialkoxy group, and / or a halogen atom is subjected to liquid phase fluorination, whereby 80 mol% or more, preferably 90 mol% or more of hydrogen atoms. A method of introducing two or more polymerizable groups, preferably three or more polymerizable groups, more preferably five or more polymerizable groups after substituting with a fluorine atom is suitable. Liquid phase fluorination is described, for example, in US Pat. No. 5,093,432.

The compound subjected to liquid phase fluorination is required to be dissolved in a fluorine-based solvent used for liquid phase fluorination or to be liquid, but there is no particular limitation other than that. From the viewpoint of such solubility and reactivity, a compound containing fluorine in advance may be used. In addition, a compound having an ester bond, a dialkoxy group, and / or a halogen atom is preferable because it can serve as a reaction point when a polymerizable group is introduced after liquid phase fluorination.
By introducing fluorine atoms by liquid phase fluorination, it is possible to extremely increase the fluorine content of the portion other than the polymerizable group to be introduced later, and to give a polymer having a very low refractive index. Monomers can be obtained.

(Polymerizable monomer that can be used in combination with fluorine-containing polyfunctional monomers)
The composition and coating composition of the present invention may contain other monomers copolymerizable with the fluorine-containing polyfunctional monomer.

  As the other monomer to be copolymerized, known and commonly used monomers can be used. Particularly, typical monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2 -Trifluoroethyl (meth) acrylate, 2,3-pentafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H , 1H, 9H-hexadecafluorononyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meta ) Acrylate, allyl alcohol Radical polymerizable monomers such as ethyl allyl ether, α-fluoroacrylic acid methyl ester, vinyl acetate, ethyl vinyl ketone, butyl vinyl ketone, tetraethoxysilane, ethyltrimethoxysilane, chlorotrimethoxysilane, aminopropyltriethoxysilane , Vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, or glycerol diglycidyl ether, glycerol triglycidyl ether, 1,1,1 -Trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, bisphenol-A-diglycidyl ether, hydroquinone diglycidyl ether, resorci And cationically polymerizable monomers such as diglycidyl ether, fluoroglycinol triglycidyl ether, triglycidyl isocyanurate, ethyl vinyl ether, and cyclohexyl vinyl ether. Among these, from the viewpoint of polymerizability, radical or cation polymerizable monomers are preferable, and radical polymerizable monomers are more preferable.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, a method of adding an acid, a method of irradiating light after adding a photoacid generator, a method of dehydrating condensation by heating, and the like. These polymerization methods and polymerization initiation methods are described in, for example, Tsuruta Junji, “Polymer Synthesis Method” revised edition (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu and Masato Kinoshita, ", Chemistry Dojin, 1972, pp. 124-154.

  Among the above polymerization methods, in order to obtain a thin film in particular, radical polymerization is performed (by light irradiation) after preparing a composition and a coating composition by diluting with a solvent, applying the composition on a substrate, drying and removing the solvent. It is preferable to do this.

  Examples of the solvent used for preparing the composition and the coating composition include ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, Examples include benzene, toluene, acetonitrile, methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like. These may be used alone or in combination of two or more.

  As the initiator for radical polymerization, any form of those generating radicals by the action of heat or those generating radicals by the action of light is possible.

As the compound that initiates radical polymerization by the action of heat, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

When a compound that initiates radical polymerization by the action of light is used, the coating is cured by irradiation with active energy rays.
Examples of such radical photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds , Disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Sensitizing dyes can also be used in combination with these photoradical polymerization initiators.

  The amount of the radical polymerization initiator added is not particularly limited as long as the radical reactive group is an amount capable of initiating a polymerization reaction, but is generally 0.1% with respect to the total solid content in the composition and the coating composition. -15 mass% is preferable, More preferably, it is 0.5-10 mass%, Most preferably, it is 2-5 mass%.

  The polymerization temperature is not particularly limited, but may be appropriately adjusted depending on the type of initiator. In addition, when a radical photopolymerization initiator is used, heating is not particularly required, but heating may be performed.

(Hollow silica fine particles)
Next, the hollow silica fine particles contained in the composition and coating composition of the present invention will be described.

The hollow silica fine particles used in the present invention have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and still more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x is calculated by the following formula (A).
Formula ^{(A) x = (4πa 3} /3) / (4πb 3/3) × 100
The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%. If the hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the low refractive index is less than 1.17. Rate particles do not hold.
The refractive index of these hollow silica particles was measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

  By containing the hollow particles in the composition and the coating composition, the refractive index of the formed cured film layer can be lowered. For example, when a low refractive index layer is formed using a coating composition containing hollow particles, the refractive index of the layer is preferably 1.20 or more and 1.46 or less, more preferably 1.25 or more and 1.41. Or less, most preferably 1.30 or more and 1.39 or less. The method for preparing hollow silica is described in, for example, JP-A Nos. 2001-233611 and 2002-79616.

Further, coating amount of the hollow silica fine particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , further preferably 10mg / m ² ~60mg / m ² is there. If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The hollow silica fine particles desirably have a low refractive index when contained in the low refractive index layer.
The average particle diameter of the hollow silica fine particles is preferably 30% or more and 150% or less, more preferably 35% or more and 80% or less, and still more preferably 40% or more and 60% or less of the thickness of the low refractive index layer. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the hollow silica fine particles is preferably 30 nm or more and 150 nm or less, more preferably 35 nm or more and 80 nm or less, and still more preferably 40 nm or more and 60 nm or less.
If the particle diameter of the hollow silica fine particles is too small, the effect of improving the scratch resistance is reduced. The hollow silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. Here, the average particle diameter of the hollow silica fine particles is measured by a Coulter counter.

Further, at least one kind of hollow silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle hollow silica fine particles”) is used as the hollow silica fine particles having the above-mentioned particle size (“ It is preferably used in combination with a large size particle size hollow silica fine particle ”.
Since the hollow silica fine particles having a small particle size can exist in the gaps between the hollow silica fine particles having a large particle size, they can contribute as a retaining agent for the hollow silica fine particles having a large particle size.
When the low refractive index layer is 100 nm, the average particle size of the hollow silica fine particles having a small size is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm, and particularly preferably 10 nm to 15 nm. Use of such hollow silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

(Surface treatment of hollow silica fine particles)
The hollow silica fine particles contained in the composition and coating composition of the present invention are preferably modified with a compound having a fluorine-containing alkyl group or a fluorine-containing aromatic group. It is more preferable that a compound having a fluorine-containing alkyl group or a fluorine-containing aromatic group interacts with the inorganic oxide fine particles, and a chemical surface treatment is performed with a fluorine-based surfactant or a coupling agent. More preferably, the surface treatment with a fluorine-based coupling agent is most preferable. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Especially, the process by a silane coupling agent is effective, and the fluorine-containing silane coupling agent represented by Formula (6) is especially effective. In the surface treatment with the silane coupling agent, it is preferable that a partial condensate of the component derived from the silane coupling agent and the hollow silica fine particles is formed.

(Fluorine-containing silane coupling agent)
A preferred fluorine-containing silane coupling agent in the present invention is represented by the following formula (6).
Equation _{(6) (R 1 f-} L 1) n -Si (R 11) n-4
In the above formula, R ₁ f represents a linear, branched, or cyclic fluorine-containing alkyl group having 1 to 20 carbon atoms or a fluorine-containing aromatic group having 6 to 14 carbon atoms. R ₁ f is preferably a linear, branched or cyclic fluoroalkyl group having 3 to 10 carbon atoms, and more preferably a linear fluoroalkyl group having 4 to 8 carbon atoms. L ₁ represents a divalent linking group having 10 or less carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group that may have a linking group (for example, ether, ester, amide) inside. The alkylene group may have a substituent, and preferable substituents in that case include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. R ¹¹ represents a hydroxyl group or a hydrolyzable group, preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom. n represents an integer of 1 to 3.

Among the fluorine-containing silane coupling agents represented by the formula (6), the fluorine-containing silane coupling agent represented by the following formula (7) is particularly preferable.
Equation _{(7) C n F 2n +} 1 - (CH 2) m -Si (R 12) 3
In the above formula, n represents an integer of 1 to 10, and m represents an integer of 1 to 5. R ¹² represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom. n is preferably 4 to 8, m is preferably 1 to 3, and R ¹² is preferably a methoxy group, an ethoxy group or a chlorine atom.

  Although the specific example of the fluorine-containing silane coupling agent represented by Formula (6) or (7) below is shown, it is not limited to this.

  These compounds can be synthesized, for example, by the method described in JP-A-11-189599.

The fluorine-containing silane coupling agent represented by the above formula (6) or (7) is preferably used in an amount of 1% by mass to 100% by mass, more preferably 2% by mass to 80% by mass with respect to the hollow silica fine particles. More preferably, it is 5 mass%-50 mass%.
Two or more kinds of fluorine-containing silane coupling agents may be used in combination, and the total addition amount is preferably 1% to 100% by mass, more preferably 20% to 80% by mass with respect to the hollow silica fine particles. It is mass%, More preferably, it is 5 mass%-50 mass%.

(Crosslinkable silane coupling agent)
In the present invention, the hollow silica fine particles are composed of at least one fluorine-containing silane coupling agent represented by the above formula (6) or (7) and a crosslinkable silane coupling agent represented by the following formula (8). It is preferably modified with at least one kind. Below, the crosslinkable silane coupling agent represented by Formula (8) is demonstrated in detail.
Formula (8)

In the above formula, R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Y represents a single bond, —COO—, —CON (R ¹⁰¹ ) — or —O—, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L represents a divalent linking group. n represents 0 or 1. R ¹⁰ represents a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and X represents a hydroxyl group or a hydrolyzable group. Examples of the substituent for R ¹⁰ include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group.

In the formula (8), R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. R ¹ is preferably a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom, more preferably a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom or a chlorine atom, And methyl groups are particularly preferred.
Y represents a single bond, —COO—, —CONH— or —O—. -COO- and -CONH- are preferably bonded to a carbon atom having a carbon-carbon double bond at the left-hand bond. Y is preferably a single bond, —COO— or —CONH—, more preferably a single bond or —COO—, and particularly preferably —COO—.

  L represents a divalent linking group, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted group having a linking group (eg, ether, ester, amide) therein. A substituted alkylene group or a substituted or unsubstituted arylene group having a linking group therein, among which a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon group having 6 to 20 carbon atoms, An arylene group, an alkylene group having 3 to 10 carbon atoms having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group, an alkylene group having an ether or ester bond therein is more preferred, and an unsubstituted alkylene group An alkylene group having an ether or ester bond inside is particularly preferred. Examples of the substituent include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ is preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X represents a hydroxyl group or a hydrolyzable group, preferably a halogen atom, a hydroxyl group, or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms; A C 1-3 alkoxy group is more preferable, and a methoxy group is particularly preferable.

  Two or more compounds represented by the formula (8) may be used in combination. Specific examples of the compound represented by formula (8) are shown below, but the present invention is not limited thereto.

Among these specific examples, (M-1), (M-2), (M-3) and the like are particularly preferable.
In the present invention, the amount of the crosslinkable silane coupling agent represented by the formula (8) is not particularly limited, but is preferably 1% by mass to 300% by mass, more preferably 3% by mass with respect to the hollow silica fine particles. It is -100 mass%, Most preferably, it is 5 mass%-50 mass%. It is preferably 1 to 300 mol%, more preferably 5 to 300 mol%, and most preferably 10 to 200 mol% per hydroxyl group on the surface of the hollow silica fine particles. When the amount of the organosilane compound used is in the above range, a sufficient stabilizing effect of the dispersion can be obtained, and the film strength is also great when forming a coating film.

  In the present invention, the ratio when the fluorine-containing silane coupling agent represented by the formula (6) or (7) and the crosslinkable silane coupling agent represented by the formula (8) are used in combination is 99: 1 to 1:99 is preferable, 75:25 to 5:95 is more preferable, and 50:50 to 25:75 is most preferable.

  Moreover, when using multiple types of silane coupling agents in the present invention, all of the silane coupling agents may be added at the same time, or after one or more types are added and the reaction proceeds, the remaining You may add 1 type or multiple types. It is also preferable to prepare a partial condensate using only a silane coupling agent in advance and then add it to the hollow silica fine particles.

  In the present invention, it is preferable to improve the dispersibility of the hollow silica fine particles by allowing the silane coupling agent to act on the surface of the hollow silica fine particles. Specifically, components derived from the silane coupling agent are bonded to the surface of the hollow silica fine particles by hydrolysis / condensation reaction of the silane coupling agent. In the hydrolysis / condensation reaction of the silane coupling agent, 0.3 to 2.0 mol, preferably 0.5 to 1.0 mol, of water is added to 1 mol of the hydrolyzable group (X). It is carried out by stirring at 15 to 100 ° C. in the presence of an acid catalyst or a metal chelate compound that can be used for the above.

(Solvent for improving dispersibility)
The dispersibility improving treatment by the hydrolyzate and / or condensation reaction product of the silane coupling agent can be performed in the absence of a solvent or in a solvent. When a solvent is used, the concentration of the hydrolyzate of the silane coupling agent and / or the partial condensate thereof can be appropriately determined. As the solvent, an organic solvent is preferably used in order to uniformly mix the components. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable.
The solvent is preferably a solvent that dissolves the hydrolyzate and / or condensation reaction product of the silane coupling agent and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating liquid or a part of the coating liquid, and those that do not impair solubility or dispersibility when mixed with other materials such as a fluorine-containing polymer are preferable.

  Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of aromatic hydrocarbons include benzene, toluene and xylene, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of esters such as diisobutylketone and the like include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. Although the density | concentration of the silane coupling agent with respect to the solvent in this process is not specifically limited, Usually, it is the range of 0.1 mass%-70 mass%, Preferably it is the range of 1 mass%-50 mass%.
In the present invention, it is preferable to disperse the hollow silica fine particles with an alcohol solvent and then perform a dispersibility improvement treatment, and subsequently replace the dispersion solvent with an aromatic hydrocarbon solvent or a ketone solvent. Substitution with a ketone solvent is preferable from the viewpoint of improving the affinity with the binder used at the time of coating and the stability of the dispersion itself.

(Catalyst for improving dispersibility)
The dispersibility improving treatment using the hydrolyzate and / or condensation reaction product of the silane coupling agent is preferably performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Organic bases such as pyridine; metal chelate compounds mainly composed of zirconium, titanium, and aluminum; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium, and the like. From the viewpoint of stability, acid catalysts (inorganic acids, organic acids) and / or metal chelate compounds are preferably used in the present invention. Among inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant in water (pKa value (25 ° C.)) of 4.5 or less, and an acid dissociation constant in hydrochloric acid, sulfuric acid, or water of 3.0 or less. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Of these, oxalic acid, phthalic acid and malonic acid are more preferred, and oxalic acid is particularly preferred.

  When the hydrolyzable group of the silane coupling agent is an alkoxy group and the acid catalyst is an organic acid, the amount of water added can be reduced because the carboxyl group or sulfo group of the organic acid supplies protons. The amount of water added relative to 1 mol of the alkoxide group of silane is 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, and particularly preferably 0 to 0.5 mol. When alcohol is used as the solvent, it is also preferred that substantially no water is added.

The amount of the acid catalyst used is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group when the acid catalyst is an inorganic acid, and the acid catalyst is an organic acid. However, when water is added, the optimal amount of use is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group. When substantially no water is added, it is 1 to 500 mol%, preferably 10 to 200 mol%, more preferably 20 to 200 mol%, still more preferably 50 to 50 mol% with respect to the hydrolyzable group. 150 mol%, particularly preferably 50 to 120 mol%.
The treatment is carried out by stirring at 15 to 100 ° C., but is preferably controlled by the reactivity of the silane coupling agent.

(Metal chelate compound)
The metal chelate compound is an alcohol represented by a general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms) and / or a general formula R ⁴ COCH ₂ COR ⁵ (where R 3 ⁴ is an alkyl group having 1 to 10 carbon atoms, and R ⁵ is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.) As long as a metal selected from Ti or Al is used as a central metal, it can be suitably used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the following general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 ,
Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 and Al (OR ³ ) _r1 (R ⁴ COCHCOR ⁵ ) _r2
Those selected from the group of compounds represented by formula (1) are preferred, and serve to promote the condensation reaction of the silane coupling agent.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. In addition, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be tetradentate or hexadentate.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropoxy Cetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetate) And aluminum chelate compounds such as acetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  The metal chelate compound is preferably 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, more preferably 0.1 to 50% by mass, based on the organosilane, from the viewpoint of the speed of the condensation reaction and the film strength when it is used as a coating film. More preferably, it is used at a ratio of 0.5 to 10% by mass.

(Dispersion stabilizing additive)
The composition or coating composition used in the present invention includes a β-diketone compound and / or a β-ketoester compound represented by R ⁴ COCH ₂ COR ⁵ in addition to the silane coupling agent and the acid catalyst or chelate compound. These preferably act as a dispersion improver for use in the present invention or as a stability improver for the composition and the coating composition. That is, by coordinating to the metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the action of promoting the condensation reaction of organosilane and metal chelate component by these metal chelate compounds is suppressed, It is considered that the resulting composition and coating composition have an effect of improving the storage stability. R ⁴ and R ⁵ in the compounds represented by R ⁴ COCH ₂ COR ⁵ are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

Specific examples of the β-diketone compound and / or β-ketoester compound represented by R ⁴ COCH ₂ COR ⁵ include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl. , Acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4- Examples include octane-dione, 2,4-nonane-dione, and 5-methyl-hexane-dione. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If it is less than 2 mol, the storage stability of the resulting composition and coating composition may be poor, which is not preferred.

(Hollow silica fine particle dispersion method)
In order to prepare the empty silica fine particles by dispersing them from a powder in a solvent, a dispersant can be used. In the present invention, it is preferable to use a dispersant having an anionic group.
As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo), a phosphoric acid group (phosphono), a sulfonamide group, or a salt thereof is effective, and in particular, a carboxyl group, a sulfonic acid group, A phosphoric acid group or a salt thereof is preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. A plurality of anionic groups may be contained for the purpose of further improving dispersibility. The average number is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.
The dispersant may further contain a crosslinking or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.
In the present invention, a disperser can be used to grind the hollow silica fine particles. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The content of the fluorine-containing polyfunctional monomer in the composition and coating composition of the present invention is preferably 1% to 90%, more preferably 10% to 50%. Further, the content of the hollow silica fine particles in the composition and the coating composition is preferably 10% or more, more preferably 20% or more, and still more preferably 30 or more.

[Optical film]
The optical film of the present invention has a hard coat layer, which will be described later, on a transparent support, if necessary, and has a refractive index, a film thickness, the number of layers, and a layer so that the reflectance decreases due to optical interference. In consideration of the order, at least one functional layer is laminated.
The optical film of the present invention preferably has a cured film layer formed from a coating composition comprising a fluorine-containing monomer having two or more polymerizable groups and hollow silica fine particles on a transparent support. More preferably, the optical film is preferably an antireflection film having a low refractive index layer and at least one other functional layer on a transparent support, and the low refractive index layer is the coating composition of the present invention. It is preferable that it is formed from.
The antireflection film (also referred to as a low reflection laminate) has a simplest configuration in which only a low refractive index layer is coated on a transparent support. In order to further reduce the reflectance, the antireflection layer on the transparent support is combined with a high refractive index layer having a higher refractive index than the transparent support and a low refractive index layer having a lower refractive index than the transparent support. It is preferable to configure. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the transparent support side, or three layers having different refractive indices, and a medium refractive index layer (with a refractive index higher than that of the transparent support or hard coat layer). Higher refractive index layer and lower refractive index layer) / high refractive index layer / low refractive index layer are laminated in this order, and more antireflection layers are also laminated. . Especially, it is preferable to apply | coat in order of a middle refractive index layer / high refractive index layer / low refractive index layer on the transparent support body which has a hard-coat layer from durability, an optical characteristic, cost, productivity, etc.

Examples of preferred layer configurations of the low reflection laminate of the present invention are shown below.
(A) Transparent support / low refractive index layer,
(B) Transparent support / antiglare layer / low refractive index layer,
(C) Transparent support / hard coat layer / antiglare layer / low refractive index layer,
(D) Transparent support / hard coat layer / high refractive index layer / low refractive index layer,
(E) Transparent support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
(F) Transparent support / antiglare layer / high refractive index layer / low refractive index layer,
(G) Transparent support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
(H) Transparent support / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
(I) antistatic layer / transparent support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
(J) Transparent support / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
(K) antistatic layer / transparent support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
(L) Antistatic layer / transparent support / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer.
As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. The high refractive index layer may be a light diffusing layer having no antiglare property. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO), and can be provided by coating or atmospheric pressure plasma treatment.

[Antireflection film]
Hereinafter, the antireflection film of the present invention will be described in detail.
The cross-sectional view schematically shown in FIG. 1 is an example of the antireflection film of the present invention. (A) is an antireflection film having the layer configuration of (c) above, and (B) is an antireflection film having the layer configuration of (e) above.

(Low refractive index layer)
The low refractive index layer of the antireflection film of the present invention is preferably formed from a coating composition comprising the fluorine-containing polyfunctional monomer and hollow silica fine particles. The coating composition preferably contains a fluorine-containing polymer as a low refractive index binder. As the fluoropolymer, a fluoropolymer that is crosslinked by heat or ionizing radiation having a dynamic friction coefficient of 0.03 to 0.15 and a contact angle with water of 90 to 120 ° is preferable.

  Examples of the fluorine-containing polymer used in the low refractive index layer include hydrolysis and dehydration condensate of perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). And a fluorine-containing copolymer having a fluorine-containing monomer unit and a structural unit for imparting crosslinking reactivity as structural components.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole. Etc.), partially (meth) acrylic acid or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) or M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.

  As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in advance in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino groups , Obtained by polymerization of a monomer having a sulfo group or the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) And a structural unit obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into these structural units by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group) And the like.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate etc.), acrylamides (N-tert-butylacrylamide, N- Black hexyl acrylamide), methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymer units of the polymer.

The thing of the said Formula (4) is mentioned as a preferable form of the copolymer used for this invention.
Formula (4)

In the formula (4), L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, May have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred examples include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * — (CH ₂ ). _{6 -O - **, * - (} CH 2) 2 -O- (CH 2) 2 -O - **, * -CONH- (CH 2) 3 -O - **, * -CH 2 CH (OH ) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a linking site on the polymer main chain side, and ** represents a linking on the (meth) acryloyl group side) Represents a part). m represents 0 or 1;

  In formula (4), X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In the formula (4), A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Adhesiveness to a transparent support, The polymer Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, etc., can be selected as appropriate, depending on the purpose. You may be comprised by the monomer.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10.

  Formula (9) is mentioned as a particularly preferable form of the copolymer used in the present invention.

Formula (9)

In the formula (9), X, x and y have the same meaning as in the formula (4), and the preferred range is also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said Formula (4) is applicable.
z1 and z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5.

  The copolymer represented by formula (4) or formula (9) can be synthesized, for example, by introducing a (meth) acryloyl group into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component. . These copolymers can be synthesized by the method described in JP-A-2004-45462.

  Although the preferable example of the copolymer useful by this invention is shown below, this invention is not limited to these.

  The synthesis of the copolymer used in the present invention is described in detail in JP-A No. 2004-45462.

(Other materials added to the low refractive index layer)
In the present invention, it is preferable to reduce the surface free energy on the surface of the antireflection film from the viewpoint of improving the antifouling property. Specifically, it is preferable to use a fluorine-containing compound or a compound having a polysiloxane structure for the low refractive index layer. Examples of the additive having a polysiloxane structure include reactive group-containing polysiloxanes (for example, KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, AK-32 (above trade name) Toray Gosei Co., Ltd.), Silaplane FM0725, Silaplane FM0721 (trade name, manufactured by Chisso Corporation, etc.) are also preferably added. Further, silicone compounds described in Tables 2 and 3 of JP-A-2003-112383 can also be preferably used. These polysiloxanes are preferably added in the range of 0.1 to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1 to 5% by mass.

  As described above, the fluorine-containing polyfunctional monomer, the hollow silica fine particles and other additives are used as a composition and a coating composition, and each cured film layer of the optical film can be formed from this coating composition. In particular, it is suitable for forming a low refractive index layer of an antireflection film.

The low refractive index layer is irradiated with ionizing radiation simultaneously with application or after application / drying of a coating composition in which a fluorine-containing polyfunctional monomer, hollow silica fine particles, and other optional components contained therein are dissolved or dispersed. It is preferably formed by curing by a crosslinking reaction or a polymerization reaction by light irradiation, electron beam irradiation) or heating.
In particular, when the low refractive index layer is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound, the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. . By forming in an atmosphere having an oxygen concentration of 10% by volume or less, an outermost layer having excellent physical strength and chemical resistance can be obtained.
The oxygen concentration is preferably 6% by volume or less, more preferably 4% by volume or less, particularly preferably 2% by volume or less, and most preferably 1% by volume or less.

  As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

(Film-forming binder)
In the antireflection film of the present invention, it is possible to use a compound having an ethylenically unsaturated group as the main film-forming binder component of the film-forming composition for forming each layer, the film strength, the stability of the coating liquid, and the production of the coating film. It is preferable in terms of properties. The main film-forming binder refers to one that accounts for 10% by mass or more of the film-forming components excluding inorganic particles. Preferably, they are 20 mass% or more and 100 mass% or less, More preferably, they are 30 mass% or more and 95% or less.
The film-forming binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, more preferably a polymer having a saturated hydrocarbon chain as a main chain, and having a crosslinked structure. Is preferred. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to form a layer having a higher refractive index, the monomer structure must contain at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. preferable.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra ( (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polymer Acrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, , Methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination. In the present specification, “(meth) acrylate” represents “acrylate or methacrylate”.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

  Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

Photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds And fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (P.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Geigy Japan.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

  In the present invention, a polymer having a polyether as a main chain can also be used. A ring-opening polymer of a polyfunctional epoxy compound is preferred. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

(Material for hard coat layer)
The antireflection film of the present invention is preferably provided with a hard coat layer. The hard coat layer can be formed from the above-mentioned film-forming binder, matte particles for imparting antiglare properties, and an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength.

In the hard coat layer, for the purpose of imparting antiglare properties, mat particles having an average particle size of 0.1 to 5.0 μm, preferably 1.5 to 3.5 μm, such as inorganic compound particles or larger than filler particles. Resin particles can be contained. If the refractive index difference between the matte particles and the binder is too large, the film becomes cloudy, and if it is too small, a sufficient light diffusing effect cannot be obtained, so 0.02 to 0.20 is preferable, and 0.04 to Particularly preferred is 0.10. If the addition amount of the mat particles to the binder is too large, the film becomes cloudy if it is too large, and if it is too small, a sufficient light diffusion effect cannot be obtained. A percentage is particularly preferred.
As specific examples of the mat particles, inorganic particles such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
The shape of the mat particles can be either a true sphere or an indefinite shape.

  Two or more different kinds of mat particles may be used in combination. When two or more kinds of mat particles are used, the difference in refractive index is preferably 0.02 or more and 0.10 or less in order to effectively exert the refractive index control by mixing the two, and 0.03 or more. Is particularly preferably 0.07 or less. Further, it is possible to impart an antiglare property with mat particles having a larger particle size and to impart another optical characteristic with mat particles having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare. Glare originates from the fact that the pixels are enlarged or reduced due to unevenness existing on the film surface (contributing to anti-glare properties) and lose uniformity of brightness, but with a particle size smaller than that of mat particles that provide anti-glare properties. It can be greatly improved by using mat particles having a different refractive index from the binder.

  Furthermore, the particle size distribution of the mat particles is most preferably monodisperse, and the particle sizes of the particles are preferably closer to each other. For example, when particles having a particle size of 20% or more than the average particle size are defined as coarse particles, the proportion of coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1%. Or less, more preferably 0.01% or less. Matt particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a matting agent having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

The mat particles are contained in the hard coat layer so that the amount of the mat particles in the formed hard coat layer is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .
The particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

The hard coat layer has at least one selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, in addition to the above mat particles, in order to increase the refractive index of the layer and to reduce cure shrinkage. It is preferable to contain an inorganic filler which is made of one kind of metal oxide and has an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.
In order to increase the difference in refractive index from the mat particles, it is also preferable to use a silicon oxide in order to keep the refractive index of the hard coat layer using the high refractive index mat particles low. The preferred particle size is the same as that of the aforementioned inorganic filler.
Specific examples of the inorganic filler used in the hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ . TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. From the viewpoint of refractive index, titanium dioxide fine particles are most preferable. In the case of using a monomer and an initiator, a hard coat layer having excellent scratch resistance and adhesion can be formed by curing the monomer by ionizing radiation or heat polymerization after coating. The average particle diameter of the inorganic fine particles in the film is 20 to 120 nm in view of haze, dispersion stability, adhesion to the upper layer due to moderate irregularities on the surface, and suppression of photoactivity when using titanium dioxide. It is preferable that there is, more preferably 30 to 100 nm, and further preferably 40 to 90 nm.

As the titanium dioxide fine particles, inorganic fine particles mainly containing titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium are particularly preferable. The main component means a component having the largest content (mass%) among the components constituting the particles.
The inorganic fine particles mainly composed of titanium dioxide in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. 80 is most preferred.
The mass average diameter of primary particles of inorganic fine particles mainly composed of titanium dioxide is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm.

The particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic fine particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.
The crystal structure of the inorganic fine particles containing titanium dioxide as the main component is preferably a rutile, rutile / anatase mixed crystal, anatase or amorphous structure, particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

By containing at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium) in the inorganic fine particles mainly composed of titanium dioxide, the photocatalytic activity of titanium dioxide can be suppressed, The weather resistance of the hard coat layer can be improved.
A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 70%.
Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  In the present invention, the bulk refractive index of the mixture of the binder and the inorganic filler in the hard coat layer is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

The antireflection film of the present invention thus formed has a haze value of 3 to 70%, preferably 4 to 60%, and an average reflectance of 450 nm to 650 nm is preferably 3.0% or less, preferably Is 2.5% or less.
When the antireflection film of the present invention has a haze value and an average reflectance in the above range, good antiglare properties and antireflection properties can be obtained without causing deterioration of the transmitted image.

[Transparent support]
As the transparent support, it is preferable to use a plastic film. As the polymer forming the plastic film, cellulose acylate (eg, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, typically TAC-TD80U, TD80UF, etc. manufactured by Fuji Photo Film Co., Ltd.) , Polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by ZEON CORPORATION) , Etc. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. In addition, the cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and the process for producing the same are disclosed in the JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001; The cellulose acylate described herein can also be preferably used in the present invention.

[Coating film forming method]
The optical film of the present invention, particularly the antireflection film, can be formed by the following method, but is not limited to this method.
First, a coating solution containing components for forming each layer is prepared. The coating solution is applied on a transparent support by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (see US Pat. No. 2,681,294). Heat and dry. Of these coating methods, coating by gravure coating is preferable because a coating solution with a small coating amount such as each layer of the antireflection film can be applied with high film thickness uniformity. Among the gravure coating methods, the micro gravure method is more preferable because of high film thickness uniformity.
In addition, a coating solution with a small coating amount can be applied with high film thickness uniformity even by using a die coating method. Further, since the die coating method is a pre-measuring method, film thickness control is relatively easy, and the solvent in the coating part Is preferred because of less transpiration. Two or more layers may be applied simultaneously. The method of simultaneous application is described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

It is a production cost that at least two of the plurality of layers of the antireflection film of the present invention are formed by the steps of feeding the support film once, forming each optical thin film, and winding the film. From the viewpoint of the above, when the antireflection layer has a three-layer structure, it is more preferable to form the three layers in one step. In such a manufacturing method, a plurality of coating stations and drying / curing zone sets, preferably the same number or more as the number of optical thin films, are cascaded between feeding and winding of the support film of the coating machine. This is achieved by providing.
FIG. 2 shows an example of the device configuration. During one step from roll film delivery (101) to winding (112), the first coating station (102), the first drying zone (103), the first UV irradiator (104), the second Coating station (105), second drying zone (106), second UV irradiator (107), third coating station (108), third drying zone (109), third UV irradiator (110) is an example including a post-heating zone (111). For example, a medium refractive index layer, a high refractive index layer, a low refractive index layer, a hard coat layer, a high refractive index layer, Functional layers up to three layers can be formed in one step, such as three layers, a hard coat layer, an antiglare layer, and a low refractive index layer. If necessary, the number of coating stations is reduced to two, and only two layers, the middle refractive index layer and the high refractive index layer, are formed in one step, and the results of checking the surface shape, film thickness, etc. are fed back. To improve the yield, to produce an antiglare antireflection film consisting of two layers, an antiglare layer and a low refractive index layer, at low cost, or as a device configuration increased to four, a hard coat layer, Another preferred embodiment is a manufacturing method in which the refractive index layer, the high refractive index layer, and the low refractive index layer are formed in one step to significantly reduce the coating cost. In addition, it is desirable from the viewpoint of cost and installation location that the layer is formed only with the UV curable resin and the post-heating zone is omitted.

[Polarizer]
The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.

As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the moving direction of the film at the exit of the process of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. It can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

  The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.

(Saponification treatment)
When the antireflection film of the present invention is used in a liquid crystal display device, it is disposed on the outermost surface of the display by providing an adhesive layer on one side. When the transparent support is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is preferable in terms of cost to use the antireflection film of the present invention as it is for the protective film.

When the antireflection film of the present invention is disposed on the outermost surface of a display by providing an adhesive layer on one side, or is used as it is as a protective film for a polarizing plate, it is a transparent support for sufficient adhesion. It is preferable to carry out a saponification treatment after an outermost layer mainly composed of a fluoropolymer is formed thereon. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by dipping in a dilute acid so that the alkaline component does not remain in the film.
By saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.
The hydrophilized surface is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so that it is difficult for dust to enter between the polarizing film and the antireflection film when it is adhered to the polarizing film, thus preventing point defects due to dust. It is valid.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

Specific means for the alkali saponification treatment can be selected from the following two means (1) and (2). (1) is superior in that it can be processed in the same process as a general-purpose triacetylcellulose film, but since the surface of the antireflection film is saponified, the surface is alkali-hydrolyzed and the film deteriorates. The point that it becomes dirty when the liquid remains can be a problem. In that case, although it becomes a special process, (2) is excellent.
(1) After the antireflection layer is formed on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after the formation of the antireflection layer on the transparent support, an alkaline solution is applied to the surface of the antireflection film opposite to the surface having the low refractive index layer, followed by heating, washing with water and / or medium. By summing, only the back surface of the film is saponified.

[Image display device]
The antireflection film of the present invention, when used as one side of the surface protective film of the polarizing film, is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device in a mode such as a curry compensate bend cell (OCB).

The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Collection) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for viewing angle expansion ), (3) Liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japanese Liquid Crystal Society) (1998)) and (4) SURVAIVAL mode liquid crystal cells (announced at LCD International 98).
For a VA mode liquid crystal cell, a polarizing plate prepared by combining a triacetyl cellulose film stretched biaxially with the antireflection film of the present invention is preferably used. As for the method for producing a biaxially stretched triacetyl cellulose film, for example, the methods described in JP-A Nos. 2001-249223 and 2003-170492 are preferably used.

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. It is disclosed in the specifications of Japanese Patent Nos. 45882525 and 5410422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is also referred to as an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

  In an ECB mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and is most frequently used as a color TFT liquid crystal display device, and is described in many documents. For example, it is described in “EL, PDP, LCD display” published by Toray Research Center (2001).

  In particular, for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having an effect of widening a viewing angle is used as a protective film having two polarizing films on both sides. Among them, by using it on the surface opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate, which is particularly preferable. The optical compensation film is an optical functional film having an optical compensation layer including an optical anisotropic layer, and the optical anisotropic layer is preferably formed from a compound having a discotic structural unit. Further, it is preferable that the disc surface of the discotic structural unit is inclined with respect to the transparent support surface, and the angle formed by the disc surface and the transparent support surface is changed in the depth method of the optical anisotropic layer.

[Other uses of composition and coating composition]
The composition and coating composition of the present invention are preferably used for an antireflection film, but can also be used as a coating agent for case covers, optical lenses, spectacle lenses, window shields, light covers and helmet shields.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

[Example 1]
(Synthesis of fluorine-containing polyfunctional monomer (X-21))

  Trichlorofluoromethane (1.2 L) was placed in a 2 L Teflon reaction vessel and kept at 20 ° C. A NaF pellet packed bed and a cooler maintained at −40 ° C. were installed in series at the outlet of the reaction vessel so that the liquid condensed by the cooler could be returned to the reaction vessel through the return line. After nitrogen gas was blown for 1 hour at a rate of 30 ml / min, fluorine gas diluted to 20% with nitrogen gas (hereinafter simply referred to as fluorine gas) was blown for 45 minutes at a rate of 60 ml / min. While blowing fluorine gas at the same rate, a solution of cyclohexane-1,3,5-tricarboxylic acid heptafluorobutyl ester (20 g) in trichlorofluoromethane (300 ml) was added at a rate of 0.28 ml / min. Further, a solution of benzene (1 g) in trichlorofluoromethane (20 ml) was added at a rate of 0.15 ml / min while blowing fluorine gas at the same rate. After blowing fluorine gas at a rate of 30 ml / min for 30 minutes, nitrogen gas was blown at the same rate for 1 hour, and insoluble matters were filtered off. (The solution was concentrated in a small amount and analyzed by NMR. As a result, it was found that about 95% of H was fluorinated.)

  While slowly flowing nitrogen into the obtained solution, 19.5 g of ethanol was added dropwise and further stirred. 7.8 g of perfluorocyclohexane-1,3,5-tricarboxylic acid ethyl ester was obtained by removing the solvent of the obtained solution and purifying with a silica gel column.

  The obtained perfluorocyclohexane-1,3,5-tricarboxylic acid ethyl ester (7.8 g) was dissolved in 100 mL of vinyl acetate, and then palladium chloride (0.01 g), lithium bromide (0.027 g), sodium acetate (0.38 g) was added and reacted at 70 ° C. for 7 hours. By removing the solvent and purifying with a silica gel column, 4.5 g of perfluorocyclohexane-1,3,5-tricarboxylic acid vinyl ester (X-21) was obtained.

(Synthesis of fluorine-containing polyfunctional monomer (X-22))
By the same operation as that performed in the synthesis of the fluorine-containing polyfunctional monomer (X-21), a perfluoro compound having a structure represented by the formula (10) was obtained. The obtained solution of perfluoro compound was reduced with lithium aluminum hydride by a conventional method to obtain a compound having a structure represented by formula (11). By reacting the obtained polyhydric alcohol compound with acrylic acid chloride by a conventional method, it has a structure represented by the formula (1), fluorine content: 46.2 mass%, calculated value of molecular weight between crosslinks The larger value of the fluorinated polyfunctional monomer (X-22) was 224.1.

(Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (trade name: Kerope EP) -12, manufactured by Hope Pharmaceutical Co., Ltd.) and mixing, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, followed by cooling to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of coating solution for antiglare hard coat layer)
PET-30 50.0g
Irgacure 184 2.0g
SX-350 (30%) 1.7 g
Cross-linked acrylic-styrene particles (30%) 13.3 g
FP-132 0.75g
KBM-5103 10.0g
Toluene 38.5g
The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution.

(Preparation of hollow silica dispersion)
Hollow silica fine particle sol (Isopropyl alcohol silica sol, CS60-IPA manufactured by Catalyst Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica particle refractive index 1.31) in 500 parts, acryloyloxypropyl After adding and mixing 30 parts of trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) and 1.5 parts of diisopropoxyaluminum ethyl acetate (trade name: Kellop EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) Nine parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 parts of acetylacetone, and obtained the hollow silica dispersion liquid. The resulting hollow silica dispersion had a solid content concentration of 18% by mass and a refractive index after solvent drying of 1.31.

(Preparation of coating solution A for low refractive index layer)
X-4 3.3g
Hollow silica dispersion 40.0g
RMS-033 0.7g
Irgacure 907 0.2g
Sol liquid a 6.2g
MEK 290.6g
Cyclohexanone 9.0g

(Preparation of coating liquid B for low refractive index layer)
X-21 1.4g
P-3 5.6g
Hollow silica dispersion 20.0g
RMS-033 0.7g
Irgacure 907 0.2g
Sol liquid a 6.2g
MEK 306.9g
Cyclohexanone 9.0g

(Preparation of coating solution C for low refractive index layer)
X-22 1.4g
P-3 5.6g
Hollow silica dispersion 20.0g
RMS-033 0.7g
Irgacure 907 0.2g
Sol liquid a 6.2g
MEK 306.9g
Cyclohexanone 9.0g

(Preparation of coating solution D for low refractive index layer)
JTA113 13.0g
MEK-ST-L 1.3g
Sol liquid a 0.6g
MEK 5.0g
Cyclohexanone 0.6g

(Preparation of coating liquid E for low refractive index layer)
JN7228A 13.0g
MEK-ST-L 1.3g
Sol liquid a 0.6g
MEK 5.0g
Cyclohexanone 0.6g

(Preparation of coating solution F for low refractive index layer)
The coating solution of Example 1-1 of JP-A-11-60637 was used.
The solution was stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.

The compounds used are shown below.
X-4, X-21, X-22:
Fluorine-containing polyfunctional monomer PET-30 according to the present invention:
A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Nippon Kayaku Co., Ltd.)
Irgacure 184:
Polymerization initiator (Ciba Specialty Chemicals Co., Ltd.)
SX-350:
Cross-linked polystyrene particles with an average particle size of 3.5 μm (refractive index 1.61, Soken Chemical Co., Ltd.)
Manufactured, 30% toluene dispersion. Use after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser)
Cross-linked acrylic-styrene particles:
Average particle size 3.5 μm (refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion)
FP-132: Fluorine surface modifier

KBM-5103: Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.).
JN7228A:
Polysiloxane and hydroxyl group-containing thermally crosslinkable fluorine-containing polymer (refractive index 1.42,
6% solid content, manufactured by JSR Corporation)
JTA113:
Polysiloxane and hydroxyl group-containing thermally crosslinkable fluorine-containing polymer (refractive index 1.44,
Solid content concentration 6%, manufactured by JSR Corporation)
P-3: Perfluoroolefin copolymer P-3 represented by formula (4)
MEK-ST-L:
Silica sol (silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.)
X22-164C:
Reactive silicone (manufactured by Shin-Etsu Chemical Co., Ltd.)
RMS-033:
Reactive silicone (manufactured by Gelest Co., Ltd.)
Irgacure 907:
Photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd.)

[Example 2]
(1) Coating of antistatic layer A 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) was unwound in a roll form, and Pertron C-4456 manufactured by Nippon Pernox Co., Ltd. -S7 ((45% solid content) ATO-dispersed hard coat agent, trade name) was applied, dried at 60 ° C. for 150 seconds, and further air-cooled metal halide lamp (I Graphics Co., Ltd.) under nitrogen purge. The antistatic layer having a thickness of 1 μm was formed by irradiating ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² .
(2) Coating of anti-glare hard coat layer The above-mentioned anti-static layer is coated on the anti-static layer, and the non-glare layer is 80 μm thick triacetyl cellulose film (TAC-TD80U, Fuji Photo). Film (manufactured by Co., Ltd.) is unwound in the form of a roll, and directly using the above microcoat gravure roll having a diameter of 40 μm and a gravure pattern with a diameter of 40 μm and a doctor blade, and a hard coat layer coating solution. The coating was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 30 m / min, dried at 60 ° C. for 150 seconds, and further using a 160 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) under a nitrogen purge. Te, illuminance 400 mW / cm ^2, and an irradiation dose of 250 mJ / cm ² to cure the coating layer, form a layer having a thickness of 6μm Then, it was wound up.

(3) Coating of low refractive index layer The triacetyl cellulose film coated with the antistatic layer and the hard coat layer or the hard coat layer is unwound again, and the coating solution for the low refractive index layer has a line number of 180 / Using a gravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern with an inch and a depth of 40 μm, it was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 15 m / min, dried at 120 ° C. for 150 seconds, and further 140 Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm under a nitrogen purge, irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² , A low refractive index layer having a thickness of 100 nm was formed and wound up.

(Preparation of antireflection film sample)
As shown in Table 1, an antireflection film sample was prepared by the above method.

(Saponification treatment of antireflection film)
After film formation, the sample was subjected to the following treatment.
A 1.5 mol / l sodium hydroxide aqueous solution was prepared and kept at 55 ° C. A 0.01 mol / l dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.

(Evaluation of antireflection film)
The following items were evaluated for the film samples obtained after the saponification treatment.
(1) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. The average reflectance of 450-650 nm was used for the result.
(2) Pencil hardness evaluation Pencil hardness evaluation described in JIS K 5400 was performed as an index of scratch resistance. The antireflection film was conditioned at 25 ° C. and 60% RH for 2 hours, and then subjected to a load of 1 kg using a 3H test pencil specified in JIS S 6006, and evaluated as follows.
○: No scratches are observed in the evaluation of n = 5 Δ: One or two scratches in the evaluation of n = 5 ×: Three or more scratches in the evaluation of n = 5

(3) Steel wool scratch resistance evaluation A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Geledo No. 0000) was wound around the rubbing tip (1 cm × 1 cm) of a tester in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
A: Even when viewed very carefully, no scratches are visible.
○: Slightly weak scratches are visible when viewed very carefully.
○ △: Weak scratches are visible.
Δ: Moderate scratches are visible.
Δ × ˜ ×: There is a scratch that can be seen at first glance.

(4) Evaluation of adhesion The surface of the antireflective film having the low refractive index layer is cut with a cutter knife into a grid pattern with 11 vertical and 11 horizontal cuts, and a total of 100 square grids are carved. A polyester adhesive tape (NO.31B) manufactured by Denko Co., Ltd. was pressure-bonded, and the adhesion test was repeated three times at the same place. The presence or absence of peeling was visually observed, and the following four-stage evaluation was performed.
◎: No peeling was observed in 100 squares ○: No peeling was found in 100 squares within 2 squares △: peeling was observed in 100 squares 3 to 10 mm x: Thickness exceeding 100 mm was observed in 100 cells

From the results shown in Tables 1 and 2, the following is clear.
The antireflection film formed from the coating composition of the present invention has a low average reflectance and excellent scratch resistance, satisfies the properties such as pencil hardness and adhesion in a well-balanced manner, and is a total antireflection film. Performance has improved.

[Example 3]
Next, the inventive sample (saponified) film of Example 2 was bonded to a polarizing plate to produce a polarizing plate with an antiglare and antireflection function. Using this polarizing plate, a liquid crystal display device in which an antireflection layer was disposed on the outermost layer was produced. As a result, there was little reflection of external light, a favorable contrast was obtained, and the reflected image was not noticeable and had excellent visibility. It was.

[Example 4]
An 80 μm-thick triacetylcellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.), which was immersed in an aqueous 1.5 mol / l, 55 ° C. NaOH solution for 2 minutes, then neutralized and washed, and Examples A polarizing plate was prepared by adhering and protecting both sides of a polarizing film prepared by adsorbing iodine to polyvinyl alcohol on the backside saponified triacetylcellulose film of Sample 2 of the present invention. The thus-prepared polarizing plate is a liquid crystal display device of a notebook PC equipped with a transmission type TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the antireflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF made of D-BEF (having between the backlight and the liquid crystal cell) was replaced, a display device with extremely high display quality was obtained with very little background reflection.

[Example 5]
A viewing angle widening film as a protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmission type TN liquid crystal cell to which the sample of the present invention of Example 2 is attached, and on the liquid crystal cell side of the polarizing plate on the backlight side (Wide-view film SA 12B, manufactured by Fuji Photo Film Co., Ltd.), a liquid crystal with excellent contrast in a bright room, very wide viewing angles in the vertical and horizontal directions, extremely excellent visibility, and high display quality. A display device was obtained.

[Example 6]
When the sample of the present invention of Example 2 was bonded to the glass plate on the surface of the organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained.

[Example 7]
Using the sample of the present invention of Example 2, a polarizing plate with a single-sided antireflection film was prepared, and a λ / 4 plate was laminated on the opposite side of the polarizing plate having the antireflection film, with the antireflection film side being the outermost side. When attached to the glass plate on the surface of the organic EL display device so as to be on the surface, the surface reflection and the reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.

It is a schematic diagram which shows an example of a structure of the antireflection film of this invention. It is a schematic diagram which shows an example of a structure of the apparatus for manufacturing the antireflection film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Hard coat layer 4 Anti-glare hard coat layer 5 Low refractive index layer 6 Matte particle 7 Medium refractive index layer 8 High refractive index layer 101 Roll film delivery 102 First coating station 103 First One drying zone 104 First UV irradiator 105 Second coating station 106 Second drying zone 107 Second UV irradiator 108 Third coating station 109 Third drying zone 110 Third UV irradiator 111 Post-drying zone 112 Roll film winding

Claims (11)

A composition comprising a fluorine-containing polyfunctional monomer having three or more polymerizable groups and hollow silica fine particles, wherein the fluorine-containing polyfunctional monomer has a fluorine content of 35.0% by mass or more of the molecular weight, When the polymerizable group of the fluorine polyfunctional monomer is polymerized, all the calculated molecular weights between crosslinks are 300 or less, and the refractive index of the layer formed of the composition is 1.20 or more and 1.46 or less, And this fluorine-containing polyfunctional monomer is represented by following formula (1), The composition characterized by the above-mentioned.
Formula (1): Rf {-(L) m-Y} n
(In the formula, Rf represents an n-valent group selected from the following f-1 to f-10, n represents an integer of 3 or more, L represents a divalent linking group, and m represents 0 or 1. Y represents any group selected from an acryloyl group, a methacryloyl group, and —C (O) OCH═CH _2. )

  L is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -O-, -S-, -N (R)-, an alkylene group having 1 to 10 carbon atoms and -O-, A group obtained by combining —S— or —N (R) —, or a group obtained by combining —O—, —S— or —N (R) — with an arylene group having 6 to 10 carbon atoms; The composition of claim 1, wherein However, said R represents a hydrogen atom or a C1-C5 alkyl group. The composition according to claim 1 or 2 , wherein the fluorine-containing polyfunctional monomer is the following X-21, X-22, X-27, X-28, X-30, or X-31 .

The composition according to any one of claims 1 to 3 , wherein the fluorine-containing polyfunctional monomer is produced using a liquid phase fluorination technique. Claim 1 coating composition characterized by comprising a composition according to any one of 4. An optical film comprising a cured film layer formed from the coating composition according to claim 5 on a transparent support. The optical film according to claim 6, wherein the cured film layer has a refractive index of 1.20 or more and 1.46 or less. The antireflection film according to claim 6 , wherein the cured film layer of the optical film is a low refractive index layer, and further has at least one functional layer in addition to the cured film layer. The antireflection film according to claim 8 , wherein the hollow silica fine particles have an average particle size of 30% to 150% of the thickness of the low refractive index layer. A polarizing plate, wherein the antireflection film according to claim 8 or 9 is used for at least one of a protective film for a polarizer in the polarizing plate. The screen display apparatus characterized by using the antireflection film of Claim 8 or 9 , or the polarizing plate of Claim 10 for the outermost surface of a display.

Images