JP2005275226A - Antireflection coating, antireflection film, method of manufacturing them, polarizing plate, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection coating comprising a high refractive index film containing conductive titanium dioxide fine particles having superior conductivity and antiweatherability, and to provide an antireflection film, a polarizing plate, and an image display device. <P>SOLUTION: The antireflection film having the high refractive index film containing conductive titanium dioxide fine particles containing cobalt, the antireflection film, the polarizing plate, and the image display device are provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antireflection film, an antireflection film, a production method thereof, a polarizing plate, and an image display device.

In recent years, liquid crystal display devices (LCDs) have been increased in screen size, and liquid crystal display devices provided with antireflection films are increasing.
Antireflection films are used in various image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT) to reflect external light and In order to prevent a decrease in contrast due to reflection, it is arranged on the surface of the display. Therefore, the antireflection film is required to have high physical strength (such as scratch resistance), transparency, chemical resistance, and weather resistance (such as moisture and heat resistance). Furthermore, measures are required to prevent dust (such as dust) that reduces the visibility of the display from adhering to the surface of the antireflection film.

  As an antireflection layer (a high refractive index layer, a medium refractive index layer, a low refractive index layer, etc.) used for an antireflection film, a multilayer film obtained by laminating a transparent thin film of metal oxide has been conventionally used. The metal oxide transparent thin film has been usually formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method which is a kind of physical vapor deposition method. However, a method for forming a transparent thin film of metal oxide by vapor deposition has low productivity and is not suitable for mass production, and therefore, a method of forming by high productivity coating has been proposed.

  When the antireflection film is produced by coating, the high refractive index layer is preferably produced by finely dispersing inorganic fine particles having a high refractive index and introducing them into the film. It is known that a transparent high refractive index layer having a higher refractive index is formed by introducing more inorganic fine particles having a higher refractive index into the film while maintaining a fine dispersion state ( For example, Patent Documents 1 to 7). Moreover, it is known that it is very effective to introduce titanium dioxide fine particles having an extremely high refractive index into the high refractive index layer (for example, Patent Documents 3 to 7).

On the other hand, it is known to provide an antistatic layer on the antireflection film in order to prevent dust (such as dust) that reduces the visibility of the display from adhering to the surface of the antireflection film.
When an antireflection film is produced by coating, it is common practice to introduce conductive inorganic fine particles (for example, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO)) into the antistatic layer. (For example, Patent Documents 8 to 12). ATO, ITO, etc. have a relatively high refractive index (refractive index 1.9 to 2.1), and a relatively high refractive index can be obtained by introducing more into the film while maintaining a fine dispersion state. It is also known that a transparent high refractive index layer having a refractive index is formed (for example, Patent Documents 2 to 5).

  However, when titanium dioxide is used in the antireflection film as described above, since the titanium dioxide fine particles have a photocatalytic function, the organic compound contained in the antireflection film when used for a long time under sunlight. This causes a problem that the physical strength, optical performance, etc. are significantly deteriorated. Such a phenomenon occurs particularly remarkably when used in a high-refractive index layer having high transparency, in which fine particles of titanium dioxide are kept in a finely dispersed state, and the transparency and weather resistance of the antireflection film. It is extremely difficult to satisfy the scratch resistance.

  On the other hand, in order to produce a high refractive index layer having a higher refractive index and antistatic performance, a conductive material having a refractive index higher than that of ATO or ITO (refractive index 1.9 to 2.1). Are required.

  Incidentally, a polarizing plate is an indispensable optical material in a liquid crystal display device, and generally has a structure in which a polarizing film is protected by two protective films. The protective film used for the polarizing plate needs to have sufficient adhesion to be bonded to the polarizing film. As a method for improving the adhesion to the polarizing film, it is a common practice to saponify the protective film to hydrophilize the surface of the protective film. If an antireflection function can be imparted to these protective films, significant cost reduction and thinning of the display device can be achieved.

JP-A-8-110401 JP-A-8-179123 JP-A-11-153703 JP 2001-166104 A JP 2001-188104 A JP 2002-116323 A JP 2002-156508 A Japanese Patent Laid-Open No. 11-42729 JP-A-11-326602 JP 2002-311208 A JP 2003-39586 A JP 2003-292826 A

The present invention has been made in view of the above problems, and its first purpose is excellent in dust resistance and weather resistance, and further has high physical strength such as scratch resistance, transparency, An object is to provide an antireflection film and an antireflection film excellent in chemical properties.
Moreover, it is providing the manufacturing method which can manufacture the antireflection film and antireflection film excellent in the said various performance cheaply and in large quantities.
Furthermore, an object of the present invention is to provide a polarizing plate and an image display device that are anti-reflection treated by appropriate means and are excellent in the above-mentioned various performances.

The said subject is achieved by the antireflection film of the following structure, an antireflection film, those manufacturing methods, a polarizing plate, and an image display apparatus.
(1) An antireflection film having a high refractive index film containing conductive titanium dioxide fine particles containing cobalt.
(2) The antireflection film as described in (1) above, which has an outermost layer containing a cured product of a compound having a crosslinkable or polymerizable functional group on the high refractive index film.
(3) The antireflection film as described in (2) above, wherein the compound having a crosslinkable or polymerizable functional group has a thermosetting functional group as the crosslinkable or polymerizable functional group.
(4) The antireflection film as described in (2) above, wherein the compound having a crosslinkable or polymerizable functional group has an ionizing radiation curable functional group as the crosslinkable or polymerizable functional group.
(5) The antireflection film as described in any one of (2) to (4) above, wherein the cured product contained in the outermost layer contains an organic compound.

(6) The antireflection film as described in any one of (1) to (5) above, wherein the outermost layer contains a fluorine-containing compound.
(7) The fluorine-containing compound contained in the outermost layer contains a copolymer composed of a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in a side chain. The antireflection film according to (6).
(8) The antireflection film as described in (7) above, wherein the copolymer is represented by the following general formula 1.

In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, and m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents a polymerization unit of any vinyl monomer, and may be a single component or a plurality of components. x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65.
(9) The antireflection film as described in (7) above, wherein the copolymer is represented by the following general formula 2.

In general formula 2, X, x, and y are as defined in general formula 1. B represents a polymerization unit of any vinyl monomer, and may be a single component or a plurality of components. z1 and z2 represent mol% of each constituent component, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. n represents an integer satisfying 2 ≦ n ≦ 10.
(10) The antireflection film as described in (9) above, wherein the copolymer represented by the general formula 2 satisfies 40 ≦ x ≦ 60, 30 ≦ y ≦ 60, and z2 = 0.
(11) The antireflection film as described in any one of (1) to (10) above, wherein the outermost layer contains a polysiloxane compound represented by the following general formula (A) and / or a derivative thereof.
Formula (A)

In general formula (A), R ^{1 to} R ⁴ each independently represent a substituent having 1 to 20 carbon atoms, and when there are a plurality of each group, they may be the same or different from each other, R ¹ , R ³ and R ⁴ represent a cross-linkable or polymerizable functional group. p represents an integer satisfying 1 ≦ p ≦ 4. q represents an integer satisfying 10 ≦ q ≦ 500, r represents an integer satisfying 0 ≦ r ≦ 500, and may be a random copolymer or a block copolymer.
(12) The above (11), wherein the polysiloxane compound represented by the general formula (A) and / or a derivative thereof has an ionizing radiation curable functional group as a crosslinkable or polymerizable functional group. The antireflection film as described.
(13) Any of the above (1) to (12), wherein the outermost layer contains a compound that crosslinks or polymerizes with the fluorine-containing compound and / or the polysiloxane compound and / or a derivative thereof. An antireflective film according to any one of the above.

(14) The cured product of the outermost layer is
A fluorine-containing compound having a crosslinkable or polymerizable functional group;
A polysiloxane compound represented by the general formula (A) and / or a derivative thereof,
And / or a compound that crosslinks or polymerizes with the fluorine-containing compound having the crosslinkable or polymerizable functional group, and
The antireflection film as described in any one of (1) to (13) above, which is a cured product formed from
(15) The antireflection film as described in any one of (1) to (14) above, wherein the outermost layer contains fine particles.
(16) The antireflection film as described in (15) above, wherein at least one kind of fine particles contained in the outermost layer is hollow fine particles.
(17) The antireflection film as described in (15) or (16) above, wherein the average particle size of the fine particles contained in the outermost layer is 20 to 100% of the thickness of the outermost layer.
(18) The antireflection film as described in any one of (15) to (17) above, wherein the fine particles contained in the outermost layer are fine particles of silicon dioxide.
(19) The antireflection film as described in any one of (1) to (18) above, wherein the outermost layer is a low refractive index layer.
(20) The antireflection film as described in any one of (1) to (19) above, wherein the outermost layer is formed in an atmosphere having an oxygen concentration of 10% by volume or less.

(21) The antireflection film as described in any one of (1) to (19), wherein the outermost layer is formed in an atmosphere having an oxygen concentration of 4% by volume or less.
(22) The antireflection film as described in any one of (1) to (19), wherein the outermost layer is formed in an atmosphere having an oxygen concentration of 1% by volume or less.
(23) The gas according to any one of (20) to (22) above, wherein an atmosphere having an oxygen concentration of 10% by volume or less is obtained by removing other gases by nitrogen gas replacement (nitrogen purge). Antireflection film.
(24) The conductive titanium dioxide fine particles containing cobalt, wherein the surface of the titanium dioxide fine particles is conductive titanium dioxide fine particles containing cobalt coated with a conductive material ( The antireflection film according to any one of 1) to (23).
(25) The antireflection film as described in (24) above, wherein the conductive substance is an inorganic compound containing at least one element selected from tin, indium, antimony and zinc.
(26) The conductive material is antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide (AZO), fluorine-doped tin oxide (FTO), zinc-doped indium oxide (IZO) ), At least one inorganic compound selected from antimony oxide and indium oxide, The antireflection film as described in (25) above.
(27) The above-mentioned (24) to (26), wherein the content of the conductive substance is 0.5 to 50% by mass with respect to the total mass of the conductive titanium dioxide fine particles containing cobalt. The antireflection film according to any one of the above.
(28) The above-mentioned (24) to (26), wherein the content of the conductive substance is 0.5 to 30% by mass with respect to the total mass of the conductive titanium dioxide fine particles containing cobalt. The antireflection film according to any one of the above.
(29) The above-mentioned (24) to (26), wherein the content of the conductive substance is 1.0 to 20% by mass with respect to the total mass of the conductive titanium dioxide fine particles containing cobalt. The antireflection film according to any one of the above.

(30) The antireflection film as described in any one of (1) to (29) above, wherein the cobalt is contained in an amount of 0.05 to 30% by mass with respect to titanium.
(31) The antireflection film as described in any one of (1) to (29) above, wherein the cobalt is contained in an amount of 0.1 to 10% by mass with respect to titanium.
(32) The antireflection film as described in any one of (1) to (31) above, wherein the cobalt is present inside the particles.
(33) Any of the above (1) to (32), wherein the conductive titanium dioxide fine particles containing cobalt contain at least one element selected from aluminum, silicon, zirconium, and manganese. The antireflection film described in 1.
(34) The antireflection film as described in (33) above, which contains 0.05 to 30% by mass of at least one element selected from aluminum, silicon, zirconium and manganese with respect to titanium.
(35) The antireflection film as described in (33) above, which contains 0.1 to 20% by mass of at least one element selected from aluminum, silicon, zirconium and manganese with respect to titanium.

(36) The above (33) to (35), wherein at least one element selected from aluminum, silicon, zirconium, and manganese is present inside conductive titanium dioxide fine particles containing cobalt. The antireflection film according to any one of the above.
(37) Conductive titanium dioxide fine particles containing cobalt are conductive titanium dioxide fine particles coated with at least one compound that reduces or eliminates the photocatalytic activity. (1) The antireflection film according to any one of to (36).
(38) The antireflection according to (37), wherein the compound that decreases or eliminates the photocatalytic activity is an inorganic compound containing at least one element selected from cobalt, aluminum, zirconium, and silicon. film.
(39) The antireflection film as described in (37) above, wherein the compound that decreases or eliminates the photocatalytic activity is an inorganic compound containing aluminum and / or zirconium.

(40) Any of the above (37) to (39), wherein the compound that reduces or eliminates the photocatalytic activity is a compound represented by the following general formula (1) and / or a derivative thereof: The antireflection film described in 1.
General formula (1)
(R ¹ ) _m −Si (OR ² ) _n
(In the formula, R ¹ represents a substituted or unsubstituted alkyl group or an aryl group. R ² represents a substituted or unsubstituted alkyl group or an acyl group. M represents an integer of 0 to 3. N represents an integer of 1 to 4. The sum of m and n is 4.)
(41) The antireflection film as described in (40) above, wherein the substituent represented by R ¹ of the compound represented by the general formula (1) is any one of an acyloxy group, an acylamino group, and an epoxy group.
(42) The compound represented by the general formula (1) is 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and / or a derivative thereof. (40) The antireflection film according to
(43) The antireflection film as described in any one of (37) to (42) above, wherein the compound that reduces or eliminates the photocatalytic activity is a compound having an anionic group.
(44) The antireflection film as described in (43) above, wherein the anionic group of the compound that decreases or eliminates the photocatalytic activity is a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
(45) The antireflection film as described in (43) or (44) above, wherein the compound that reduces or eliminates the photocatalytic activity has a crosslinked or polymerizable functional group.
(46) The antireflection film as described in any one of (43) to (45) above, wherein the compound that reduces or eliminates the photocatalytic activity has a (meth) acryloyl group or an allyl group.
(47) The above (37), wherein the content of the compound that reduces or eliminates the photocatalytic activity is 0.5 to 50% by mass with respect to the total mass of the conductive titanium dioxide fine particles containing cobalt. ) To (46).

(48) The above (37), wherein the content of the compound that reduces or eliminates the photocatalytic activity is 0.5 to 30% by mass with respect to the total mass of the conductive titanium dioxide fine particles containing cobalt. ) To (46).
(49) The above (37), wherein the content of the compound that reduces or eliminates the photocatalytic activity is 1.0 to 20% by mass with respect to the total mass of the conductive titanium dioxide fine particles containing cobalt. ) To (46).

(50) The antireflection film as described in any one of (1) to (49) above, wherein the conductive titanium dioxide fine particles containing cobalt have a refractive index of 1.80 to 2.80.
(51) The antireflection film as described in any one of (1) to (49) above, wherein the refractive index of the conductive titanium dioxide fine particles containing cobalt is 1.90 to 2.60.
(52) The antireflection according to any one of (1) to (51), wherein the powder resistance of the conductive titanium dioxide fine particles containing cobalt is 1 × 10 ⁵ Ω · cm or less. film.
(53) The antireflection according to any one of (1) to (51) above, wherein the powder resistance of the conductive titanium dioxide fine particles containing cobalt is 1 × 10 ³ Ω · cm or less. film.
(54) The antireflection film as described in any one of (1) to (53) above, wherein the conductive titanium dioxide fine particles containing cobalt have an average particle diameter of 1 to 200 nm.
(55) The antireflection film as described in any one of (1) to (54) above, wherein the conductive titanium dioxide fine particles containing cobalt have a specific surface area of 1 to 400 m ² / g.

(56) The antireflection film as described in any one of (1) to (55) above, wherein the conductive titanium dioxide fine particles containing cobalt are dispersed using a dispersant.
(57) The antireflection film as described in (56) above, wherein the dispersant has an anionic group.
(58) The antireflection film as described in (57), wherein the anionic group is a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
(59) The antireflection film as described in any one of (56) to (58) above, wherein the dispersant has a crosslinked or polymerizable functional group.
(60) The antireflection film as described in (59) above, which is a dispersant having the cross-linked or polymerizable functional group in a side chain.
(61) The antireflection film as described in any one of (59) or (60) above, wherein the crosslinking or polymerizable functional group of the dispersant is a (meth) acryloyl group or an allyl group.
(62) The antireflection film as described in any one of (56) to (61) above, wherein the dispersant has a mass average molecular weight (Mw) of 1000 or more.

(63) The antireflection film as described in any one of (1) to (62) above, wherein the high refractive index film contains a cured product of a compound having a crosslinked or polymerizable functional group.
(64) The antireflection film as described in (63) above, wherein the high refractive index film contains a cured product formed from the dispersant and a compound having a crosslinkable or polymerizable functional group.
(65) The antireflection film as described in (63) or (64) above, wherein the high refractive index film contains a cured product formed by crosslinking or polymerization reaction of an ionizing radiation curable compound.
(66) The high refractive index film includes a cured product formed by crosslinking or polymerization reaction of an ionizing radiation curable compound, and the initiator in the crosslinking or polymerization reaction is a photopolymerization initiator. (63) The antireflection film according to any one of (65).
(67) The antireflection film as described in (66) above, wherein the photopolymerization initiator in the crosslinking or polymerization reaction of the high refractive index film is a photoradical polymerization initiator.
(68) The antireflection film as described in any one of (63) to (67), wherein the cured product contained in the high refractive index film contains an organic compound.
(69) The antireflection film as described in any one of (63) to (68), wherein the high refractive index film is subjected to a hard coat treatment.

(70) The antireflection film as described in any one of (63) to (69), wherein the high refractive index film is formed in an atmosphere having an oxygen concentration of 10% by volume or less.
(71) The antireflection film as described in any of (63) to (69) above, wherein the high refractive index film is formed in an atmosphere having an oxygen concentration of 4% by volume or less.
(72) The antireflection film as described in any one of (63) to (69), wherein the high refractive index film is formed in an atmosphere having an oxygen concentration of 1% by volume or less.
(73) The gas according to any one of (70) to (72) above, wherein an atmosphere having an oxygen concentration of 10% by volume or less is obtained by removing other gases by nitrogen gas replacement (nitrogen purge). Antireflection film.
(74) The antireflection film as described in any of (1) to (73) above, wherein the high refractive index film has a surface resistance of 1 × 10 ¹⁴ Ω / □ or less.

(75) The antireflection film as described in any one of (1) to (73) above, wherein the high refractive index film has a surface resistance of 1 × 10 ¹² Ω / □ or less.
(76) The antireflective film as described in any one of (1) to (75) above, wherein the high refractive index film has a refractive index of 1.55 to 2.40.
(77) The antireflective film according to any one of (1) to (75) above, wherein the high refractive index film has a refractive index of 1.70 to 2.40.
(78) The above-mentioned (1) to (77), comprising a medium refractive index film having a refractive index between the refractive index of the outermost layer and the refractive index of the high refractive index film below the high refractive index film. The antireflection film according to any one of the above.

(79) The antireflection film as described in any one of (1) to (78) above, wherein the surface resistance is 1 × 10 ¹⁴ Ω / □ or less.
(80) The antireflection film as described in any one of (1) to (79) above, wherein the surface resistance is 1 × 10 ¹² Ω / □ or less.
(81) The antireflection film as described in any one of (1) to (80) above, wherein the dynamic friction coefficient is 0.25 or less.
(82) The antireflection film as described in any one of (1) to (81) above, wherein the surface has a contact angle with water of 90 ° or more.
(83) A composition for forming a high refractive index film, which is used for forming the antireflection film according to any one of (1) to (82).
(84) The manufacturing method of the anti-reflective film in any one of said (1)-(82).
(85) An antireflection film comprising the antireflection film according to any one of (1) to (82) on a transparent support.

(86) The antireflection film as described in (85) above, which contains an organosilane compound represented by the following general formula (a) and / or a derivative thereof in any layer on the transparent support. .
Formula (a) (R ¹⁰ ) _s -Si (Z) _4-s
In general formula (a), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z represents a hydroxyl group or a hydrolyzable group. s represents an integer of 1 to 3.

(87) The antireflection film as described in (86) above, wherein the organosilane compound derivative represented by the general formula (a) is an organosilane compound derivative produced in the presence of an acid catalyst.
(88) The antireflection film as described in (86) or (87) above, wherein the group represented by R ¹⁰ has a crosslinkable or polymerizable functional group.
(89) The antireflection film as described in any one of (86) to (88) above, wherein the group represented by R ¹⁰ has any of an acyloxy group, an acylamino group, and an epoxy group.

(90) The organosilane compound represented by the general formula (a) and / or a derivative thereof is represented by the following general formula (b), and is described in any one of the above (86) to (89) Antireflection film.
General formula (b)

In general formula (b), R ¹¹ 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, an ester group, an amide group, an ether group, or a urea group. L1 represents a divalent linking chain. t represents 0 or 1; R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z represents a hydroxyl group or a hydrolyzable group.
(91) The layer containing the organosilane compound and / or derivative thereof contains a compound that crosslinks or undergoes a polymerization reaction with the organosilane compound and / or derivative thereof. (86) to (90) The antireflection film according to any one of the above.
(92) The layer containing the organosilane compound and / or derivative thereof is the outermost layer and / or the adjacent layer of the outermost layer, described in any one of (86) to (91) above Antireflection film.

(93) The antireflection film as described in any one of (85) to (92) above, which has a layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm between the transparent support and the outermost layer. .
(94) The antireflection film as described in (93) above, wherein the inorganic fine particles having an average particle diameter of 1 to 200 nm have a specific surface area of 1 to 400 m ² / g.
(95) The antireflection film as described in (93) or (94) above, wherein the inorganic fine particles having an average particle diameter of 1 to 200 nm are dispersed using a dispersant.
(96) The antireflection film as described in (95) above, wherein the dispersant has an anionic group.
(97) The antireflection film as described in (96) above, wherein the anionic group is a carboxyl group, a sulfonic acid group or a phosphoric acid group.

(98) The antireflection film as described in any one of (95) to (97) above, wherein the dispersant has a crosslinkable or polymerizable functional group.
(99) Any of the above (93) to (98), wherein the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm contains a cured product of a compound having a crosslinked or polymerizable functional group. An antireflection film according to claim 1.
(100) The above (95), wherein the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm contains a cured product formed from a dispersant and a compound having a crosslinkable or polymerizable functional group. ) To (99).
(101) The above (93) to (100), wherein the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm contains a cured product formed by crosslinking or polymerization reaction of an ionizing radiation curable compound. ). The antireflection film according to any one of

(102) The antireflection film as described in any of (93) to (101) above, wherein the cured product of the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm contains an organic compound.
(103) The refractive index of the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm is 1.45 to 2.40, as described in any of (93) to (102) above Antireflection film.
(104) The refractive index of the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm is 1.65 to 2.20, according to any one of (93) to (102) above Antireflection film.

(105) The antireflection film as described in any of (93) to (104) above, wherein the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm is subjected to a hard coat treatment.
(106) The antireflection film as described in any one of (93) to (105), wherein the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm is an optical interference layer.
(107) The antireflection film as described in any one of (85) to (106) above, which has a layer containing particles having an average particle diameter of 0.2 to 10 μm.
(108) The difference in refractive index between the refractive index of the particles having an average particle diameter of 0.2 to 10 μm and the refractive index of the matrix of the layer containing the particles is 0.02 or more. The antireflection film as described in (107).
(109) The antireflection film as described in (107) or (108) above, wherein the following S value indicating a particle size distribution of particles having an average particle size of 0.2 to 10 μm is 2.0 or less. .
S = [D (0.9) -D (0.1)] / D (0.5)
D (0.1): 10% of the integrated value of the volume-converted particle diameter,
D (0.5): 50% of the integrated value of the volume-converted particle diameter,
D (0.9): 90% of the integrated value of the volume-converted particle diameter.

(110) The antireflection film as described in (109) above, wherein the S value is 1.0 or less.
(111) The above-mentioned (107) to (110), wherein the layer containing particles having an average particle diameter of 0.2 to 10 μm contains a cured product of a compound having a crosslinked or polymerizable functional group. The antireflection film according to any one of the above.
(112) The above (107) to (107), wherein the layer containing particles having an average particle diameter of 0.2 to 10 μm contains a cured product formed by crosslinking or polymerization reaction of an ionizing radiation curable compound. The antireflection film according to any one of (111).

(113) The antireflection according to any one of (107) to (112), wherein the cured product of the layer containing particles having an average particle size of 0.2 to 10 μm contains an organic compound. the film.
(114) The antireflection film as described in any one of (107) to (113), wherein the layer containing particles having an average particle diameter of 0.2 to 10 μm is subjected to a hard coat treatment.
(115) The reflection according to any one of (107) to (114), wherein the layer containing particles having an average particle diameter of 0.2 to 10 μm is a layer adjacent to the outermost layer. Prevention film.
(116) The antireflection film as described in any one of (85) to (115) above, wherein the surface on the side having the high refractive index film has depressions and projections and has antiglare properties. .
(117) The antireflection film as described in (116) above, wherein there is no recess having an area of a cut surface of 1000 μm ² or more per 1 mm ² area of the surface of the antireflection film.
(118) The antireflection film as described in (116) or (117) above, wherein the average surface roughness (Ra) per 1 mm ² area of the surface of the antireflection film is from 0.01 to 1 μm.
(119) Concave and convex on the surface having the high refractive index film are formed on the outermost layer on the layer in which the concave and convex are formed by a layer containing particles having an average particle diameter of 0.2 to 10 μm. The antireflection film according to any one of the above (116) to (118), which is formed by forming

(120) Any one of the above (85) to (119), wherein any layer on the transparent support contains a cured product formed by crosslinking or polymerization reaction of an ionizing radiation curable compound. The antireflection film as described.
(121) In a cured product formed by a crosslinking or polymerization reaction of an ionizing radiation curable compound contained in any layer on the transparent support, the initiator in the crosslinking or polymerization reaction is a photopolymerization initiator. The antireflection film as described in (120) above, wherein
(122) The antireflection film as described in (120) or (121) above, wherein any layer on the transparent support is formed in an atmosphere having an oxygen concentration of 10% by volume or less.
(123) The antireflection film as described in (120) or (121) above, wherein any layer on the transparent support is formed in an atmosphere having an oxygen concentration of 4% by volume or less.
(124) Any one of the layers on the transparent support is formed in an atmosphere having an oxygen concentration of 1% by volume or less, and the antireflection according to any one of (120) and (121) above the film.

(125) The gas according to any one of (122) to (124) above, wherein an atmosphere having an oxygen concentration of 10% by volume or less is obtained by removing other gases by nitrogen gas replacement (nitrogen purge). Antireflection film.
(126) Any layer on the transparent support is crosslinked or polymerized with the compound having the crosslinkable or polymerizable functional group simultaneously with or after the coating of the coating material containing the compound having the crosslinkable or polymerizable functional group. The antireflection film as described in any one of (85) to (125) above, which is a layer formed by reacting.
(127) A method for producing an antireflection film having a high refractive index film on a transparent support, wherein at least one layer on the transparent support is mainly composed of ketones, aromatic hydrocarbons, or esters. The antireflection film as described in any one of (85) to (126), which is formed by applying a paint containing a certain solvent.
(128) The antireflection film as described in (127) above, wherein the main component of the solvent is a ketone or an ester.
(129) The antireflection film as described in any one of (85) to (128) above, wherein the transparent support is formed from triacetylcellulose or polyester.
(130) The method for producing an antireflection film according to any one of (85) to (129).

(131) An antireflection film obtained by saponifying the antireflection film according to any one of (85) to (129).
(132) The antireflection film as described in (131) above, wherein a contact angle of water on the surface of the transparent support opposite to the side having the high refractive index film is 40 ° or less.
(133) A method for producing an antireflection film, comprising subjecting the antireflection film according to any one of (85) to (129) to a saponification treatment.

(134) A polarizing plate having a polarizing film and a protective film, wherein the antireflection film according to any one of (85) to (129), (131), and (132) is used as at least one of the protective films. A polarizing plate characterized by
(135) A polarizing plate having a polarizing film and a protective film, wherein the antireflection film according to any one of (85) to (129), (131), and (132) is protected with two polarizing films A polarizing plate having an optical compensation film having one of the films and an optically anisotropic layer on the other protective film.
(136) The optical compensation film has an optically anisotropic layer made of a compound having a discotic structural unit, the disc surface of the discotic structural unit is inclined with respect to the film surface, and the discotic structure The polarizing plate as described in (135) above, wherein the angle formed by the disk surface of the unit and the film surface changes in the depth direction of the optically anisotropic layer.

(137) An image display device comprising the antireflection film according to any one of (85) to (129), (131), and (132) disposed on an image display surface.
(138) An image display device, wherein the polarizing plate according to any one of (134) to (136) is disposed on an image display surface.
(139) Of the two polarizing plates disposed on both sides of the liquid crystal cell, the polarizing plate according to any one of the above (134) to (136) is provided as a polarizing plate on the display side, and the polarizing plate The image display device as described in (138) above, wherein the antireflection film as the protective film is a liquid crystal display device disposed on the side opposite to the liquid crystal cell with respect to the polarizing film.

(140) Any of the above (137) to (139), wherein the image display device is a TN, STN, IPS, VA or OCB mode transmissive, reflective or transflective liquid crystal display device An image display device according to claim 1.
Is to provide.

  The titanium dioxide fine particles used in the present invention are coated with a compound containing cobalt and further suppressing catalytic activity (for example, an inorganic compound (for example, a conductive material), an organometallic compound, an organic compound, a metal, etc.). Therefore, the photocatalytic activity is suppressed or disappears and has excellent weather resistance. Moreover, the titanium dioxide fine particles used in the present invention have an antistatic performance and a high refractive index. Therefore, the antireflective film and antireflective film of the present invention using the high refractive index film containing the titanium dioxide fine particles, and the polarizing plate and the image display device using the antireflective film are both dustproof and weatherproof. In addition, it has high physical strength such as scratch resistance, and is excellent in transparency and chemical resistance.

Details of the present invention will be described below. 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”. . “(Meth) acryloyl” means “acryloyl or methacryloyl, and both”. The same applies to “(meth) acrylate”, “(meth) acrylic acid” and the like.
(Conductive titanium dioxide fine particles)
The conductive titanium dioxide fine particles used in the present invention contain cobalt (Co) in order to reduce or eliminate the photocatalytic activity of titanium dioxide. Moreover, it is preferable to have a higher refractive index, and it is preferable that the content of titanium dioxide is large among the components constituting the particles. The content of titanium dioxide is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% by mass with respect to the total mass of the conductive titanium dioxide fine particles. % Or more.

The crystal structure of the conductive titanium dioxide fine particles is preferably rutile, a mixed crystal of rutile / anatase, anatase, or an amorphous structure, and particularly preferably has the most components of the rutile structure.
The conductive titanium dioxide fine particles in the present invention preferably have a refractive index of 1.80 to 2.80, more preferably 1.90 to 2.60, and 2.00 to 2.60. Is more preferable, and it is most preferable that it is 2.10-2.60.
The powder resistance of the conductive titanium dioxide fine particles is preferably as low as possible, preferably 1 × 10 ⁵ Ω · cm or less, more preferably 1 × 10 ⁴ Ω · cm or less, further preferably 1 × 10 ³ Ω · cm or less, Particularly preferably, it is 1 × 10 ² Ω · cm or less. The powder resistance can be obtained, for example, by molding a sample powder at a pressure of 100 kg / cm ² to form a green compact, and measuring the direct current resistance. For example, it is described in JP-A-6-92636.

The primary average particle diameter of the conductive titanium dioxide fine particles 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 mass average diameter is represented by the average value of the maximum diameters of the respective fine particles. For example, in the case of a spindle shape, the average value of the major axis diameters of the respective fine particles is defined as the mass particle diameter.
The particle diameter of the conductive titanium dioxide fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the conductive titanium dioxide particles is preferably 1~400m ² / g, more preferably from 10 to 200 m ² / g, and most preferably 20~150m ² / g. The specific surface area can be calculated by the BET method or the like.

  The shape of the conductive titanium dioxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape, and particularly preferably an indefinite shape or a spindle shape.

By containing cobalt (Co) in conductive titanium dioxide fine particles, the photocatalytic activity of titanium dioxide can be reduced or eliminated, and the weather resistance of the high refractive index film used in the present invention is improved. Can do. In the present specification and claims, cobalt contained in the titanium dioxide fine particles may be a simple substance or a compound thereof (for example, a monovalent to tetravalent cobalt compound). Examples of the compound include cobalt oxide ( CoO, CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.), cobalt-containing composite oxide (cobalt-titanium composite oxide (CoTiO ₃ etc.), cobalt-aluminum composite oxide etc.), cobalt hydroxide, cobalt Examples thereof include hydrated salt, cobalt chloride, cobalt sulfate, cobalt nitrate, and cobalt carbonate.

  The content of Co with respect to titanium (Ti) in the conductive titanium dioxide fine particles is preferably 0.05 to 30% by mass, more preferably 0.1 to 10% by mass, and still more preferably 0.5 to It is 7% by mass, particularly preferably 0.5 to 5% by mass, and most preferably 0.5 to 4% by mass.

Cobalt (Co) is present inside or on the surface of the conductive titanium dioxide fine particles. In terms of effectively reducing or eliminating the photocatalytic activity, it is preferably present inside the conductive titanium dioxide fine particles, and more preferably present both inside and on the surface.
There are various methods for causing Co to be present inside the conductive titanium dioxide fine particles (for example, doping). For example, ion implantation method (Surface Science, Vol.18, No.5, pp.262-268, 1998; Yasushi Aoki), JP-A-10-330236, JP-A-11-263620, JP-A-11 It can be carried out by the same method as described in JP-A-5512336, European Patent 0335773, JP-A-5-330825, and JP-A-2003-327430.

  In the process of forming conductive titanium dioxide fine particles, Co is introduced by, for example, Japanese Patent Publication No. 11-512336, European Patent No. 0335773, Japanese Patent Laid-Open No. 5-330825, Japanese Patent Laid-Open No. 10-330236. It is preferable to use the methods disclosed in Japanese Patent Laid-Open No. 2003-327430, and in particular, the methods disclosed in Japanese Patent Laid-Open Nos. 10-330236 and 2003-327430 are preferably used. The method of No. Gazette is the most preferable. Co is preferably present as an oxide.

  The conductive titanium dioxide fine particles may further contain other elements as appropriate. Examples of other elements include aluminum (Al), zirconium (Zr), silicon (Si), manganese (Mn), tin (Sn), antimony (Sb), phosphorus (P), sodium (Na), potassium ( K), lithium (Li), copper (Cu), calcium (Ca), magnesium (Mg), zinc (Zn), vanadium (Ba), iron (Fe), nickel (Ni), chromium (Cr), sulfur ( S) and the like.

In particular, by containing at least one element selected from the group of Al, Si, Zr, Mg, Zn, and Mn in addition to Co, the photocatalytic activity can be further effectively reduced or eliminated. It is preferable to contain an element selected from Al, Si, Zr and Zn in addition to Co, more preferably an element selected from Al and Zn, and most preferable. It is to contain Al.
Further, by containing at least one element selected from Al and Si, sintering of the conductive titanium dioxide fine particles can be prevented. Therefore, when Co is introduced into titanium dioxide, the growth of titanium dioxide fine particles can be suppressed even if the firing temperature is increased. In addition, it is possible to suppress color developability due to Co caused by firing at a high temperature. In particular, the inclusion of both elements of Al and Si can increase the Co content more effectively and can control the color developability of Co, which is a preferred embodiment.

  Content of each said element other than Co can be set arbitrarily, 0.05-30 mass% is preferable with respect to titanium (Ti), More preferably, it is 0.1-20 mass%, Most preferably, it is 0.00. 5 to 10% by mass. It is also preferable to use two or more of the above elements in combination. Moreover, each said element exists in the inside of the electroconductive titanium dioxide fine particle used for this invention, or also on the surface. In terms of effectively reducing or eliminating the photocatalytic activity, it is more preferably present inside the conductive titanium dioxide fine particles, and most preferably present both inside and on the surface. As a method for introducing each element other than Co, it is preferable to use a method similar to the method for introducing Co.

The conductive titanium dioxide fine particles used in the present invention contain zinc (Zn), tin (Sn), indium (In), antimony (Sb), and cerium (Ce) in order to impart conductivity. Is preferred. In particular, it is preferable to contain an inorganic compound containing zinc, an inorganic compound containing tin, an inorganic compound containing indium, an inorganic compound containing antimony, an inorganic compound containing cerium (Ce), and the like. Aluminum doped zinc oxide (AZO), tin oxide (SnO ₂ ), antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), indium oxide (In ₂ O ₃ ), zinc doped Indium oxide (IZO), indium oxide doped with tin (ITO), and antimony oxide (Sb ₂ O ₅ ) are more preferable, and AZO, ATO, SnO ₂ , In ₂ O ₃ , and ITO are most preferable.

  Content of each said element for providing electroconductivity can be set arbitrarily, 0.5-50 mass% is preferable with respect to titanium (Ti), More preferably, it is 0.5-30 mass%, Especially Preferably it is 1.0-20 mass%. It is also preferable to use two or more of the above elements in combination. Moreover, each said element for providing electroconductivity exists in the inside of the electroconductive titanium dioxide fine particle used for this invention, or also on the surface. From the viewpoint of effectively imparting conductivity, it is preferably present on the surface of the conductive titanium dioxide fine particles, and more preferably present both on the inside and on the surface. The technique for introducing each element for imparting conductivity can be carried out by the same technique as that for introducing Co.

The conductive titanium dioxide fine particles used in the present invention are preferably coated (surface-treated) with a compound (for example, an inorganic compound, an organic metal compound, an organic compound, a metal, etc.) that lowers or eliminates the photocatalytic activity. . The surface treatment may be performed with two or more kinds of compounds.
Examples of inorganic compounds used for the surface treatment include inorganic compounds containing cobalt (Co) (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.), inorganic compounds containing aluminum (Al) (Al ₂ O _3). , Al (OH) _3, etc.), zirconium (Zr) containing inorganic compounds (ZrO ₂ , Zr (OH) ₄ etc.), silicon (Si) containing inorganic compounds (SiO ₂ , Si (OH) ₄ etc.) , Inorganic compounds containing iron (Fe) (such as Fe ₂ O ₃ ), compounds containing manganese (Mn) (such as MnO ₂ ), inorganic compounds containing zinc (Zn) (such as ZnO, AZO), tin Inorganic compounds containing (Sn) (SnO ₂ , ATO, FTO, etc.), Indium (In) containing inorganic compounds (In ₂ O ₃ , IZO, ITO, etc.), Antimony (Sb) containing inorganic compounds (Sb) oxides such as b ₂ O ₅ and / or hydrous oxides.

In terms of reducing or eliminating the photocatalytic activity of the conductive titanium dioxide fine particles and further effectively imparting conductivity, an inorganic compound containing zinc (Zn), an inorganic compound containing tin (Sn), indium ( In) -containing inorganic compounds, antimony (Sb) -containing inorganic oxides (for example, the above oxides and / or hydrated oxides) are preferable, and AZO, SnO ₂ , ATO, FTO, In ₂ O ₃ , ITO and Sb ₂ O ₅ are more preferable, and AZO, ATO, In ₂ O ₃ and ITO are most preferable.
The content of the conductive substance that reduces or eliminates the photocatalytic activity is preferably 0.5 to 50% by mass, more preferably 0.5 to 30% by mass with respect to the total mass of the conductive titanium dioxide fine particles. %, More preferably 1.0 to 20% by mass, particularly preferably 1.0 to 15% by mass.

Furthermore, it contains an inorganic compound containing cobalt (Co), an inorganic compound containing aluminum (Al), and zirconium (Zr) in that the photocatalytic activity of the conductive titanium dioxide fine particles is effectively reduced or eliminated. It is preferable to use an inorganic compound, an inorganic compound containing silicon (Si) or the like (for example, an oxide and / or a hydrous oxide), and an inorganic compound containing cobalt, Al (OH) ₃ , Zr (OH More preferably, ₄ is used. In particular, it is preferable to use both an inorganic compound containing aluminum (Al) and an inorganic compound containing zirconium (Zr).

The content of the compound that reduces or eliminates the photocatalytic activity is preferably 0.5 to 50% by mass, more preferably based on the total mass of the conductive titanium dioxide fine particles used in the present invention. It is 0.5-30 mass%, More preferably, it is 1.0-20 mass%, Most preferably, it is 1.0-15 mass%.
Regarding the method of coating the surface of the conductive titanium dioxide fine particles used in the present invention with the above inorganic compound, for example, Japanese Patent Publication No. 40-12166, Japanese Patent Publication No. 47-19514, Japanese Patent Publication No. 56-41603. JP-A-56-114215, JP-A-56-114218, JP-A-56-140028, JP-A-56-156604, JP-A-57-167357, JP-A-61. JP-A-141616, JP-A-61-286221, JP-A-1-264932, JP-A-2-137726, JP-A-3-23221, JP-A-3-50120, JP-A-4-154621. JP-A-6-49387, JP-A-6-49388, JP-A-6-279618, and the like.

  Examples of the organometallic compound used for the surface treatment include a silane coupling agent, a titanate coupling agent, and / or a derivative thereof. Particularly preferred are silane coupling agents represented by the following general formula and / or derivatives thereof.

General formula (1)
(R ¹ ) _m −Si (OR ² ) _n
In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or aryl group. R ² represents a substituted or unsubstituted alkyl group or acyl group. m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4. m is preferably 0, 1, 2 and particularly preferably 1.
In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

  Although there is no restriction | limiting in particular as a substituent, Halogen (fluorine, chlorine, bromine, etc.), a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), Aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryloxy (phenoxy, etc.), alkylthio groups (methylthio) , Ethylthio etc.), arylthio group (phenylthio etc.), alkenyl group (vinyl, 1-propenyl etc.), alkoxysilyl group (trimethoxysilyl, triethoxysilyl etc.), acyloxy group (acetoxy, (meth) acryloyl etc.), alkoxy Carbonyl group (methoxycarbonyl, ethoxycarbonyl) Bonyl etc.), aryloxycarbonyl group (phenoxycarbonyl etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl etc.), acylamino group (acetylamino, benzoylamino) , Acrylicamino, methacrylamino and the like).

  Of these, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group ((meth) acryloyl). A polymerizable acylamino group (acrylamino, methacrylamino). These substituents may be further substituted.

R ² represents a substituted or unsubstituted alkyl group or acyl group. The description of the alkyl group, acyl group and substituent is the same as R ¹ . R ² is preferably an unsubstituted alkyl group or an unsubstituted acyl group, and particularly preferably an unsubstituted alkyl group.

When R ¹ or R ² there are a plurality, it may be different even multiple of R ¹ or R ² respectively the same.
Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

Among these specific examples, (1), (12), (18), (19) and the like are particularly preferable.
Examples of titanate coupling agents include metal alkoxides such as tetramethoxy titanium, tetraethoxy titanium, and tetraisopropoxy titanium, and preneact (KR-TTS, KR-46B, KR-55, KR-41B, etc .; manufactured by Ajinomoto Co., Inc.) , Both are trade names).

The amount of these organometallic compounds is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and particularly preferably 2 to 10% by mass with respect to the total mass of the conductive titanium dioxide fine particles. %.
With respect to the method of coating the surface of the conductive titanium dioxide fine particles with the organometallic compound, for example, JP-A-10-324817, JP-A-2001-26423, JP-A-2003-327430, JP-A-2003-2003 No. 335979.

  Examples of the organic compound used for the surface treatment include silicone, lecithin, fluorine compound, ultraviolet absorber, polyhydric alcohol, amino acid, fatty acid, carboxylate, and the like. In particular, fluorine compound (perfluoroalkyl phosphate ester) Etc.), polyhydric alcohol (such as alkanolamine), carboxylate, fatty acid (such as stearic acid), and other organic compounds having an anionic group (such as carboxyl group, sulfonic acid group, or phosphoric acid group) are preferable. .

Stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid and the like can be preferably used.
The organic compound used for the surface treatment preferably further has a crosslinked 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.), cationic polymerizable groups capable of addition and polymerization reactions with radical species. (Epoxy groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like can be mentioned, and groups having an ethylenically unsaturated group are preferred.
The amount of the surface treatment of these organic compounds is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, particularly preferably 2 to 2%, based on the total mass of the conductive titanium dioxide fine particles. 10% by mass.

With respect to the method of coating the surface of the conductive titanium dioxide fine particles with the above organic compound, methods such as JP-A-9-124968, JP-A-2001-106939, JP-A-2003-327430 and the like can be mentioned.
Two or more kinds of the surface treatments described above can be used in combination. It is particularly preferable to use a conductive inorganic compound and an inorganic compound containing aluminum and / or an inorganic compound containing zirconium.
The conductive titanium dioxide fine particles used in the present invention may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.

  The content of all compounds that reduce or eliminate the photocatalytic activity is preferably 0.5 to 50% by mass, more preferably 0.8%, based on the total mass of the conductive titanium dioxide fine particles used in the present invention. It is 5-30 mass%, More preferably, it is 1.0-20 mass%, Most preferably, it is 1.0-15 mass%.

(High refractive index film)
The high refractive index film (hereinafter referred to as a high refractive index layer) in the present invention is characterized by containing conductive titanium dioxide fine particles containing cobalt (Co). Hereinafter, the high refractive index layer in the present invention will be described in detail.
The refractive index of the high refractive index layer in the present invention is preferably 1.55 to 2.40, which is a so-called high refractive index layer or a medium refractive index layer. In the present specification below, This layer is collectively referred to as a high refractive index layer.

(Dispersant)
A dispersant can be used for dispersing the conductive titanium dioxide fine particles used in the high refractive index layer in the present invention.
By dispersing using a dispersant, the conductive titanium dioxide used in the present invention can be dispersed very finely, making it possible to produce a transparent high refractive index layer.
For dispersing the conductive titanium dioxide fine particles 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. 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. The number of anionic groups contained in the dispersant per molecule may be one or more.
In order to further improve the dispersibility of the conductive titanium dioxide fine particles, a plurality of anionic groups may be contained. 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.

  Commercially available dispersants include phosphanol (PE-510, PE-610, LB-400, EC-6103, RE-410, etc .; manufactured by Toho Chemical Co., Ltd., all trade names), Disperbyk (−110, − 111, -116, -140, -161, -162, -163, -164, -164, -170, -171, etc .; manufactured by Big Chemie Japan Co., Ltd., all trade names), Ajisper (PA111, etc .; Ajinomoto Finetech) It is preferable to use a product name manufactured by Co., Ltd.

  The dispersant preferably further contains a crosslinkable 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.

  The dispersant used for dispersing the conductive titanium dioxide fine particles used in the high refractive index layer in the present invention has an anionic group and a crosslinkable or polymerizable functional group, and the crosslinkable or polymerizable functional group is used as a side chain. It is particularly preferable to have a dispersant.

  The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited, but is preferably 1000 or more. . The more preferable mass average molecular weight (Mw) of the dispersant is 2000 to 1000000, more preferably 5000 to 200000, and particularly preferably 10000 to 100000.

  The dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain has the anionic group in the side chain or terminal. Examples of the method for introducing an anionic group into the side chain include an anionic group-containing monomer (for example, (meth) acrylic acid, maleic acid, partially esterified maleic acid, itaconic acid, crotonic acid, 2-carboxyethyl (meth) acrylate. , Polymer reaction such as a method of polymerizing 2-sulfoethyl (meth) acrylate, mono-2- (meth) acryloyloxyethyl ester of phosphoric acid, a method of allowing an acid anhydride to act on a polymer having a hydroxyl group, an amino group, etc. Can be synthesized by using

In the dispersant having an anionic group in the side chain, the composition of the anionic group-containing polymer units is in the range of 10 ^{−4 to} 100 mol%, preferably 1 to 50 mol%, particularly preferably, of all the polymer units. Is 5 to 20 mol%.
On the other hand, as a technique for introducing an anionic group at the terminal, a technique for carrying out a polymerization reaction in the presence of an anionic group-containing chain transfer agent (for example, thioglycolic acid), an anionic group-containing polymerization initiator (for example, Wako Pure Chemical Industries, Ltd.) It can be synthesized by a technique of performing a polymerization reaction using Industrial V-501 (trade name).
Particularly preferred dispersants are those having an anionic group in the side chain.

  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. Preferred are groups having an ethylenically unsaturated group.

  The average number of cross-linkable or polymerizable functional groups contained in the dispersant per molecule is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the crosslinking or polymerizable functional group contained in the dispersant may contain a plurality of types in one molecule.

Examples of the polymerized unit having an ethylenically unsaturated group in the side chain in the preferred dispersant of the present invention include poly-1,2-butadiene and poly-1,2-isoprene structures or esters of (meth) acrylic acid. Alternatively, an amide polymer unit having a specific residue (the R group of —COOR or —CONHR) bound thereto can be used. Examples of the specific residue (R group) include — (CH ₂ ) _n —CR ¹ = CR ² R ³ , — (CH ₂ O) _n —CH ₂ CR ¹ = CR ² R ³ , — (CH ₂ CH ₂ O) _n -CH ₂ CR ¹ = CR ² R ³ ,-(CH ₂ ) _n -NH-CO-O-CH ₂ CR ¹ = CR ² R ³ ,-(CH ₂ ) _n -O-CO -CR ¹ = CR ² R ³ and-(CH ₂ CH ₂ O) ₂ -X (R ^{1 to} R ³ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, respectively. R ¹ and R ² or R ³ may be bonded to each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue. There are).

Specific examples of R of the ester residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ O—CH ₂ CH═CH ₂ , —CH ₂ CH ₂ OCOCH═CH ₂ , —CH ₂ CH ₂ OCOC ( CH ₃ ) = CH ₂ , -CH ₂ C (CH ₃ ) = CH ₂ , -CH ₂ CH = CH-C ₆ H ₅ , -CH ₂ CH ₂ OCOCH = CH-C ₆ H ₅ , -CH ₂ CH ₂ -NHCOO-CH ₂ CH = CH ₂ and -CH ₂ CH ₂ OX (X is a dicyclopentadienyl residue) are included. Specific examples of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (Y is a 1-cyclohexenyl residue) and —CH ₂ CH ₂ —OCO—CH═CH ₂ , —CH ₂ CH ₂ —OCO—C (CH ₃ ) ═CH ₂ is included.

  In the dispersant having an ethylenically unsaturated group, a free radical (a polymerization initiation radical or a growth radical of a polymerization process of a polymerizable compound) is added to the unsaturated bond group, and the polymer compound is directly or between molecules. Addition polymerization is carried out through the polymerization chain, and a crosslink is formed between the molecules to cure. Alternatively, atoms in the molecule (for example, hydrogen atoms on carbon atoms adjacent to the unsaturated bond group) are extracted by free radicals to form polymer radicals that are bonded together to form a bridge between the molecules. Harden.

  A method for introducing a cross-linkable or polymerizable functional group into the side chain is, for example, as described in JP-A-3-249653, etc., a crosslinkable or polymerizable functional group-containing monomer (for example, allyl (meth) acrylate, glycidyl (meth) acrylate, Copolymerization of trialkoxysilylpropyl methacrylate, etc., copolymerization of butadiene or isoprene, copolymerization of vinyl monomers having a 3-chloropropionic acid ester moiety followed by dehydrochlorination, crosslinking or polymerization by polymer reaction Can be synthesized by introduction of a functional group (for example, polymer reaction of an epoxy group-containing vinyl monomer to a carboxyl group-containing polymer).

  The cross-linked or polymerizable functional group-containing unit may constitute all polymer units other than the anionic group-containing polymer unit, preferably 5 to 50 mol% of all cross-linked or polymer units, Most preferably, it is 5-30 mol%.

  A preferable dispersant in the present invention may be a copolymer with an appropriate monomer other than a monomer having a crosslinking or polymerizable functional group or an anionic group. Although it does not specifically limit regarding a copolymerization component, It selects from various viewpoints, such as dispersion stability, compatibility with another monomer component, and the intensity | strength of a formed film. Preferable examples include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene and the like.

  The form of the preferred dispersant in the present invention is not particularly limited, but is preferably a block copolymer or a random copolymer, and particularly preferably a random copolymer from the viewpoint of cost and synthetic ease.

  Specific examples of preferable dispersants in the present invention are shown below, but are not limited thereto. In addition, a specific example is applicable in each copolymer of a block copolymer, a graft copolymer, and a random copolymer.

  The amount of the dispersant used relative to the conductive titanium dioxide fine particles is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass, and 5 to 20% by mass. Most preferred. Two or more dispersants may be used in combination.

(High refractive index layer and formation method thereof)
The conductive titanium dioxide fine particles used for the high refractive index layer are used for forming the high refractive index layer in a dispersion state. In the dispersion of the conductive titanium dioxide fine particles, the fine particles are dispersed in a dispersion medium in the presence of the dispersant.

  As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-meth Shi-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred.

  Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The conductive titanium dioxide fine particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, bead mill with pins), dyno mills, high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. Particularly preferred are sand grinder mills, dyno mills, and high speed impeller mills. 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 conductive titanium dioxide fine particles are preferably made as fine as possible in the dispersion medium, and the mass average diameter is preferably 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm.
By refining the conductive titanium dioxide fine particles to 200 nm or less, a high refractive index layer that does not impair the transparency can be formed.

  The high refractive index layer used in the present invention is preferably added to a dispersion in which conductive titanium dioxide fine particles are dispersed in a dispersion medium as described above. Radiation curable polyfunctional monomers and polyfunctional oligomers), photopolymerization initiators, etc. are added to form a coating composition for forming a high refractive index layer, and a coating composition for forming a high refractive index layer is formed on a transparent support. It is preferably formed by coating and curing by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

Further, it is preferable to cause the binder of the high refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the application of the layer.
The binder of the high refractive index layer thus prepared is, for example, the above-mentioned preferred dispersant and an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer cross-linked or polymerized, and the binder is anionic. The base is incorporated. Furthermore, the binder of the high refractive index layer has a function in which the anionic group maintains the dispersed state of the conductive titanium dioxide fine particles, and the crosslinked or polymerized structure imparts a film-forming ability to the binder, so that the conductive titanium dioxide. Improves physical strength, chemical resistance and weather resistance of high refractive index layer containing fine particles.

The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic diesters of alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, (meth) acrylic diesters of polyoxyalkylene glycols such as polypropylene glycol di (meth) acrylate, and (meth) polyhydric alcohols such as pentaerythritol di (meth) acrylate Acrylic acid diesters, 2,2-bis {4- (acryloxy-diethoxy) phenyl} propane, 2--2-bis {4- (acryloxy-polypropoxy) phenyl} propane, etc. (Meth) acrylic acid diesters of Chiren'okishido or propylene oxide adducts, and the like.

  Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

  Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate , Tripentaerythritol hexatriacrylate and the like.

Two or more polyfunctional monomers may be used in combination.
It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
Examples of the radical photopolymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.

  As a commercially available photo radical polymerization initiator, Kayacure (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc., all trade names), Irgacure (651, 184, 500, 907, 369, 1173, 2959, 4265, 4263 etc., all trade names) made by Ciba Specialty Chemicals, manufactured by Sartomer Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT are all trade names) and the like.

In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in “Latest UV Curing Technology” by Kazuhiro Takashiro (Technical Information Association, Inc., page 159, 1991).
Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907, trade names) manufactured by Ciba Specialty Chemicals.

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. Examples of commercially available photosensitizers include Kayacure (DMBI and EPA, both trade names) manufactured by Nippon Kayaku Co., Ltd.
The photopolymerization reaction is preferably performed by ultraviolet irradiation after the high refractive index layer is applied and dried.

The high refractive index layer used in the present invention can also contain a compound represented by the general formula (1) and / or a derivative compound thereof.
Among these specific examples, (1), (12), (18), (19) and the like described as the compound examples of the general formula (1) are particularly preferable.
As for content of the compound of General formula (1), 1-90 mass% of the total solid of a high refractive index layer is preferable, More preferably, it is 2-80 mass%, Most preferably, it is 5-50 mass%.

In the high refractive index layer, the binder preferably further has a silanol group. When the binder further has a silanol group, the physical strength, chemical resistance, and weather resistance of the high refractive index layer are further improved.
For the silanol group, for example, a compound represented by the general formula (1) having a crosslinked or polymerizable functional group is added to the coating composition for forming the high refractive index layer, and the coating composition is coated on the transparent support. Then, the dispersant, the polyfunctional monomer, the polyfunctional oligomer, and the compound represented by the general formula (1) can be introduced into the binder by a crosslinking reaction or a polymerization reaction.

  Particularly preferred among the compounds represented by the general formula (1) are compounds having a (meth) acryloyl group as a crosslinkable or polymerizable functional group, such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyl. Examples include trimethoxysilane.

In the high refractive index layer, the binder preferably has an amino group or a quaternary ammonium group.
For the binder of the high refractive index layer having an amino group or quaternary ammonium group, for example, a monomer having a crosslinkable or polymerizable functional group and an amino group or quaternary ammonium group is added to the coating composition for forming the above high refractive index layer. And it can form by apply | coating a coating composition on a transparent support body, carrying out a crosslinking reaction or a polymerization reaction with said dispersing agent, a polyfunctional monomer, or a polyfunctional oligomer.

  A monomer having an amino group or a quaternary ammonium group functions as a dispersion aid for conductive titanium dioxide fine particles in the coating composition. Furthermore, after coating, maintaining a good dispersibility of the conductive titanium dioxide fine particles in the high refractive index layer by cross-linking reaction or polymerization reaction with a dispersant, a polyfunctional monomer or polyfunctional oligomer, or making it a binder, A high refractive index layer excellent in physical strength, chemical resistance and weather resistance can be produced.

Preferred monomers having an amino group or a quaternary ammonium group include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, (meth) acrylic acid hydroxypropyltrimethylammonium chloride, dimethyl And allyl ammonium chloride.
It is preferable that the usage-amount with respect to the dispersing agent of the monomer which has an amino group or a quaternary ammonium group is 1-40 mass%, More preferably, it is 3-30 mass%, Most preferably, it is 3-20 mass%. If the binder is formed by crosslinking or polymerization reaction simultaneously with or after the application of the high refractive index layer, these monomers can be effectively functioned before the application of the high refractive index layer.

  The crosslinked or polymerized binder has a structure in which the main chain of the polymer is crosslinked or polymerized. Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

  The polyolefin main chain is composed of a saturated hydrocarbon. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. The polyurethane main chain has repeating units bonded by urethane bonds (—NH—CO—O—).

  The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group). The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). In the polyamine main chain, repeating units are bonded by an imino bond (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group. The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group). The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked or polymerized structure.

The anionic group is preferably bonded to the main chain as a side chain of the binder via a linking group.
The linking group that binds the anionic group and the main chain of the binder is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked or polymerized structure chemically bonds (preferably covalently bonds) two or more main chains. The crosslinked or polymerized structure preferably has three or more main chains covalently bonded. The crosslinked or polymerized structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof. .

  The binder is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked or polymerized structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96 mol%, more preferably 4 to 94 mol%, and most preferably 6 to 92 mol%. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked or polymerized structure in the copolymer is preferably 4 to 98 mol%, more preferably 6 to 96 mol%, and most preferably 8 to 94 mol%.

The repeating unit of the binder may have both an anionic group and a crosslinked or polymerized structure. The binder may contain other repeating units (repeating units having neither an anionic group nor a crosslinked or polymerized structure).
Other repeating units are preferably repeating units having a silanol group, an amino group or a quaternary ammonium group.

  In the repeating unit having a silanol group, the silanol group is directly bonded to the main chain of the binder or is bonded to the main chain via a linking group. The silanol group is preferably bonded to the main chain as a side chain via a linking group. The linking group that connects the silanol group and the main chain of the binder is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. When the binder includes a repeating unit having a silanol group, the ratio is preferably 2 to 98 mol%, more preferably 4 to 96 mol%, and most preferably 6 to 94 mol%. preferable.

  In the repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the binder or bonded to the main chain via a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6. The counter ion of the quaternary ammonium group is preferably a halide ion.

  The linking group that connects the amino group or the quaternary ammonium group to the main chain of the binder is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the binder contains a repeating unit having an amino group or a quaternary ammonium group, the proportion is preferably 0.1 to 32 mol%, more preferably 0.5 to 30 mol%. Most preferred is ˜28 mol%.

In addition, even if the silanol group, amino group, and quaternary ammonium group are contained in the repeating unit having an anionic group or the repeating unit having a crosslinked or polymerized structure, the same effect can be obtained.
The binder that has been crosslinked or polymerized is preferably formed by coating a coating composition for forming a high refractive index layer on a transparent support, and by crosslinking or polymerization reaction simultaneously with or after coating.

The conductive titanium dioxide fine particles have a function of controlling the refractive index of the high refractive index layer and a function of suppressing curing shrinkage.
In the high refractive index layer, the conductive titanium dioxide fine particles are preferably dispersed as finely as possible, and the mass average diameter is preferably 1 to 200 nm. The mass average diameter of the conductive titanium dioxide fine particles in the high refractive index layer is preferably 5 to 150 nm, more preferably 10 to 100 nm, and most preferably 10 to 80 nm.
By refining the conductive titanium dioxide fine particles to 200 nm or less, a high refractive index layer that does not impair the transparency can be formed.

The content of the conductive titanium dioxide fine particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the mass of the high refractive index layer. % By mass. Two or more kinds of conductive titanium dioxide fine particles may be used in combination in the high refractive index layer.
The high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, P, etc. Binders obtained by crosslinking or polymerization reaction such as ionizing radiation curable compounds can also be preferably used.
In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably It is 1.60 to 2.40, more preferably 1.65 to 2.40, and particularly preferably 1.70 to 2.40.

For the high refractive index layer, in addition to the above components (conductive titanium dioxide fine particles, binder, polymerization initiator, photosensitizer, etc.), resin, surfactant, antistatic agent, coupling agent, thickener , Anti-coloring agents, coloring agents (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, conductivity Metal fine particles can also be added.
Moreover, a high refractive index layer can also serve as the glare-proof layer which added the particle | grains of the average particle diameter of 0.2-10 micrometers mentioned later and provided the glare-proof function.
The film thickness of the high refractive index layer can be appropriately designed depending on the application. When using a high refractive index layer as an optical interference layer described later, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm. When the high refractive index layer also serves as the hard coat layer, the thickness is preferably 0.5 to 10 μm, more preferably 1 to 7 μm, and particularly preferably 2 to 5 μm.

In the formation of the high refractive index layer, the crosslinking reaction or polymerization reaction of the ionizing radiation curable compound is preferably carried out in an atmosphere having an oxygen concentration of 10% by volume or less.
By forming the high refractive index layer in an atmosphere having an oxygen concentration of 10% by volume or less, the physical strength, chemical resistance, and weather resistance of the high refractive index layer, and further, the high refractive index layer and the high refractive index layer are adjacent to each other. Adhesion with the layer can be improved.
Preferably, it is formed by a crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, particularly preferably an oxygen concentration of 2 Volume% or less, most preferably 1 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.
Preferred coating solvents for the high refractive index layer include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), Examples include alcohols (methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water, and the like.
Particularly preferred coating solvents are ketones, aromatic hydrocarbons or esters, and most preferred solvents are ketones. Of the ketones, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are particularly preferable.

  The coating solvent may contain other solvents. For example, aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, , Diethyl ether, dioxane, tetrahydrofuran) and ether alcohol (eg, 1-methoxy-2-propanol).

In the coating solvent, the content of the ketone solvent is preferably 10% by mass or more of the total solvent contained in the paint. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.
The strength of the high refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400.

Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.
The haze of the high refractive index layer is preferably as low as possible when it does not contain particles that impart an antiglare function. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

The lower the surface resistance of the high refractive index layer, the higher the dustproof effect. The surface resistance value of the high refractive index layer is preferably 1 × 10 ¹⁴ Ω / □ or less. More preferably, it is 1 × 10 ¹² Ω / □ or less, further preferably 1 × 10 ¹⁰ Ω / □ or less, particularly preferably 1 × 10 ⁹ Ω / □ or less, and most preferably 1 × 10 ⁸ Ω / □ or less.
The antireflection film having a high refractive index layer thus prepared has high physical strength (such as scratch resistance), transparency, chemical resistance, and weather resistance (such as moist heat resistance and light resistance). The antireflection film having a high refractive index layer having a surface resistance of 1 × 10 ¹⁴ Ω / □ or less can prevent dust (such as dust) that reduces the visibility of the display from adhering to the surface of the antireflection film.

By constructing a layer having a refractive index lower than that of the high refractive index layer on the high refractive index layer in the present invention, the antireflection film of the present invention can be produced.
Hereinafter, each layer of the antireflection film of the present invention will be described in detail.

(Outermost layer)
On the high refractive index layer, a layer having a refractive index lower than that of the high refractive index layer is constructed to produce an antireflection film. The outermost layer on the high refractive index layer is formed by a vapor phase method (vacuum deposition). Method, sputtering method, ion plating method, plasma CVD method, or the like) or a coating method, but the coating method is preferable because it can be manufactured at low cost. When producing by the apply | coating method, it is preferable that an outermost layer contains the hardened | cured material of the compound which has a bridge | crosslinking or a polymerizable functional group.
Improve the physical strength (scratch resistance, etc.), chemical resistance, and weather resistance (wet heat resistance, light resistance, etc.) of the antireflection film by containing a cured product of a compound having a crosslinkable or polymerizable functional group in the outermost layer. it can.

As the crosslinkable or polymerizable functional group, a thermosetting functional group and an ionizing radiation curable functional group are particularly preferable.
As the hardened material of the outermost layer, both inorganic compounds (such as silicon compounds described later) and organic compounds can be preferably used, but organic compounds are particularly preferable. Among them, an organic compound having an ionizing radiation-curable functional group is preferable, and examples thereof include polyfunctional monomers having a photopolymerizable functional group such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. ) A cured product containing a photopolymerizable polyfunctional monomer having an acryloyl group is preferred. Specific examples include the photopolymerizable polyfunctional monomer exemplified in the high refractive index layer.

Moreover, it is preferable that an outermost layer contains a fluorine-containing compound at the point which can improve the antifouling property of an antireflection film, and also can produce a layer with a low refractive index.
In particular, it is preferable to construct an outermost layer mainly composed of a fluorine-containing compound. The outermost layer mainly composed of a fluorine-containing compound functions as a low refractive index layer or an antifouling layer. Here, “mainly comprising a fluorine-containing compound” means that the mass ratio of the fluorine-containing compound is the largest among the constituent components of the outermost layer contained in the outermost layer, and the content ratio of the fluorine-containing compound Is preferably 50% by mass or more, and more preferably 60% by mass or more, based on the total mass of the outermost layer.

  The outermost fluorine-containing compound is preferably formed by a crosslinking or polymerization reaction of a fluorine-containing compound having a crosslinking or polymerizable functional group, and the crosslinking or polymerizable functional group is ionized with a thermosetting functional group. It is preferably a radiation curable functional group. Hereinafter, the fluorine-containing compound preferably used for the outermost layer will be described.

(Fluorine-containing compounds)
The refractive index of the fluorine-containing compound contained in the outermost layer is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47, More preferably, it is 1.38-1.45.
Examples of the fluorine-containing compound include a fluorine-containing polymer, a fluorine-containing silane compound, a fluorine-containing surfactant, and a fluorine-containing ether.
Examples of the fluorine-containing polymer include those synthesized by crosslinking or polymerization reaction of ethylenically unsaturated monomers containing fluorine atoms. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Fluorinated vinyl ethers and esters of fluorine-substituted alcohols with acrylic acid or methacrylic acid are included.

As the fluorine-containing polymer, a copolymer comprising a repeating structural unit containing a fluorine atom and a repeating structural unit not containing a fluorine atom can also be used.
The copolymer can be obtained by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom and an ethylenically unsaturated monomer not containing a fluorine atom.
Examples of ethylenically unsaturated monomers not containing fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (eg, methyl acrylate, ethyl acrylate, acrylic acid-2- Ethyl hexyl, etc.), methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene and its derivatives (eg, styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.) , Vinyl ether (eg, methyl vinyl ether), vinyl ester (eg, vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamide (eg, N-tert-butylacrylamide, N-cyclohexylacrylamide, etc.), Ruamido and acrylonitrile, and the like.

  Examples of the fluorine-containing silane compound include silane compounds containing a perfluoroalkyl group.

  Fluorine-containing surfactants are those in which part or all of the hydrocarbon hydrogen atoms constituting the hydrophobic part are replaced by fluorine atoms, and the hydrophilic part is anionic, cationic, nonionic and amphoteric. Any of these may be used.

  The fluorine-containing ether is a compound generally used as a lubricant. Examples of the fluorinated ether include perfluoropolyether.

  As the outermost fluorine-containing compound, a fluorine-containing polymer into which a crosslinked or polymerized structure is introduced is particularly preferable. The fluorine-containing polymer into which a crosslinked or polymerized structure is introduced can be obtained by crosslinking or polymerizing a fluorine-containing compound having a crosslinked or polymerizable functional group.

  The fluorine-containing compound having a crosslinkable or polymerizable functional group can be obtained by introducing a crosslinkable or polymerizable functional group as a side chain into a fluorine-containing compound having no crosslinkable or polymerizable functional group. The crosslinkable or polymerizable functional group is a functional group that reacts with light (preferably ultraviolet irradiation), electron beam (EB) irradiation or heating to cause the fluorinated polymer to have a crosslinked or polymerized structure. preferable. Examples of the crosslinkable or polymerizable functional group include groups such as (meth) acryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene. A commercially available product may be used as the fluorine-containing compound having a crosslinkable or polymerizable functional group.

  The outermost fluorine-containing compound preferably contains a copolymer composed of a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in the side chain as a main component. The component derived from the copolymer is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the outermost layer. Below, the said copolymer preferable to be used for outermost layer is demonstrated.

Fluorinated vinyl monomers include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (trade name) , Osaka Organic Chemical Industry Co., Ltd.), M-2020 (trade name, manufactured by Daikin Industries, Ltd.), etc.), or fully or partially fluorinated vinyl ethers, and the like, preferably perfluoroolefins, From the viewpoints of refractive index, solubility, transparency, availability, etc., hexafluoropropylene is particularly preferred.
The fluorine-containing vinyl monomer is preferably introduced so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass.

  The copolymer has a repeating unit having a (meth) acryloyl group. The method for introducing the (meth) acryloyl group is not particularly limited. For example, (i) after synthesizing a polymer having a nucleophilic group such as a hydroxyl group or an amino group, (meth) acrylic acid chloride, (meth) (Ii) a method of reacting acrylic acid anhydride, (meth) acrylic acid and methanesulfonic acid mixed acid anhydride, (Iii) a method of allowing a compound having both an isocyanate group such as methacryloyloxypropyl isocyanate and a (meth) acryloyl group to act on the polymer having the nucleophilic group, and (iv) after synthesizing a polymer having an epoxy group ( (V) a method of allowing meth) acrylic acid to act; (v) an epoxy group such as glycidyl methacrylate and (meth) acryloyl on a polymer having a carboxyl group Examples thereof include a method of allowing a compound having a group to act, and (vi) a method of dehydrochlorination after polymerizing a vinyl monomer having a 3-chloropropionic acid ester moiety. Among these, in the present invention, it is particularly preferable to introduce a (meth) acryloyl group by the method (i) or (ii) to a polymer containing a hydroxyl group.

  The repeating unit having a (meth) acryloyl group in the side chain preferably occupies 5 to 90% by mass, more preferably 30 to 70% by mass, and 40 to 60% by mass in the copolymer. It is particularly preferred.

  In addition to the repeating unit derived from the fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, the copolymer includes adhesion to a lower layer such as a transparent support, polymer Tg (for coating hardness). Other vinyl monomers can be suitably copolymerized from various viewpoints such as solubility in solvents, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer, more preferably 0 to 40 mol%, particularly preferably 0. ˜30 mol%.

  The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p-methoxystyrene, etc.) ), Vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate) , Vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tert-butylacrylamide, N-cyclohexylacrylamide) Etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile derivatives and the like.

  As a preferred form of a copolymer composed of a repeating unit derived from a fluorine-containing vinyl monomer used in the present invention and a repeating unit having a (meth) acryloyl group in the side chain, one represented by the following general formula 1 can be mentioned.

In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, and particularly preferably a linking group having 2 to 4 carbon atoms. It may have a structure and may have a hetero atom selected from O, N, and S.
Preferred _{examples, * - (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, ** represents a linking on the (meth) acryloyl group side) Represents a part). m represents 0 or 1;

  In general formula 1, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In general formula 1, 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, and adheres to a lower layer such as a transparent support. , Polymer Tg (contributes to film hardness), solubility in solvent, transparency, slipperiness, dustproof / antifouling properties, etc., can be selected as appropriate. You may be comprised by the vinyl 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.
The copolymer represented by the general formula 1 may be a regular copolymer such as a block copolymer or a graft polymer, or a random copolymer.

  Furthermore, what is represented by General formula 2 is mentioned as an especially preferable form of the said copolymer.

In General Formula 2, X, x, and y have the same meanings as in General Formula 1, and the preferred ranges are 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 General formula 1 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.
As the copolymer represented by the general formula 2, those satisfying 40 ≦ x ≦ 60, 30 ≦ y ≦ 60, and z2 = 0 are particularly preferable.
The copolymer represented by the general formula 2 may be a regular copolymer such as a block copolymer or a graft polymer, or a random copolymer.

  In the copolymer represented by the general formula 1 or the general formula 2, for example, a (meth) acryloyl group is introduced into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. Can be synthesized.

  The preferred specific examples of the copolymer consisting of the repeating unit derived from the fluorine-containing vinyl monomer used in the present invention and the repeating unit having a (meth) acryloyl group in the side chain are shown below, but the present invention is not limited thereto. It is not something. In addition, a specific example is applicable in each copolymer of a block copolymer, a graft copolymer, and a random copolymer.

  The copolymer is synthesized by synthesizing a precursor such as a hydroxyl group-containing polymer by various polymerization methods such as solution polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization, ) It can be carried out by introducing an acryloyl group. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system. A method for synthesizing the copolymers represented by the general formulas 1 and 2 used in the present invention is described in detail in JP-A-2004-045462.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are described in, for example, the revised version of “Polymer Synthesis Method” by Teiji Tsuruta (published by Nikkan Kogyo Shimbun, 1971) and “Experimental Methods for Polymer Synthesis” by Takayuki Otsu and Masato Kinoshita. Doujin, 1972, pp. 124-154.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method include, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, A single organic organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture of two or more thereof may be used, or a mixed solvent with water may be used.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, and the like, and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to perform the polymerization in the range of 50 to 100 ° C.

  The reaction pressure can be selected as appropriate, but is usually 98 kPa to 9.8 MPa, particularly about 98 kPa to 2.94 MPa. The reaction time is about 5 to 30 hours.

  As the reprecipitation solvent for the obtained polymer, isopropanol, hexane, methanol and the like are preferable.

  The composition used for preparing the outermost layer in the present invention is preferably in the form of a paint, and is prepared by dissolving various additives and a radical polymerization initiator in an appropriate solvent as necessary. At this time, the concentration of the solid content is appropriately selected depending on the use, but is preferably 0.01 to 60% by mass, more preferably 0.5 to 50% by mass, and particularly preferably about 1% to 20% by mass. .

The outermost layer includes additives such as fillers (for example, inorganic fine particles and organic fine particles), slip agents (polysiloxane compounds such as dimethyl silicone), organosilane compounds and derivatives thereof, binders, surfactants and the like according to the purpose. Can be contained. In particular, it is preferable to add a filler (for example, inorganic fine particles or organic fine particles) and a slipping agent (polysiloxane compound such as dimethyl silicone).
Hereinafter, preferred fillers, slip agents and the like used for the outermost layer will be described.

(Preferred filler for outermost layer)
A filler (for example, inorganic fine particles or organic fine particles) is preferably added in view of improving the physical strength (such as scratch resistance) of the outermost layer. As the filler added to the outermost layer, inorganic fine particles are preferable, and among them, silicon dioxide (silica) having a low refractive index, fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride) and the like are preferable. Particularly preferred is silicon dioxide (silica).

  The mass average particle diameter of the primary particles of the filler is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. It is preferable that the filler is more finely dispersed in the outermost layer. The shape of the filler is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a short fiber shape, a ring shape, a needle shape, or an indefinite shape. Particularly preferred are a spherical shape and an indefinite shape. The filler may be crystalline or amorphous.

  Fillers are used in physical dispersions such as plasma discharge treatment and corona discharge treatment in order to stabilize dispersion in the dispersion or paint, or to improve the affinity and binding to the components of the outermost layer. Surface treatment, chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. A surface treatment with a coupling agent is particularly preferred. As the coupling agent, an alkoxy compound (eg, titanate coupling agent, silane coupling agent) is preferably used. In particular, silane coupling agent treatment is effective.

  For the surface treatment of the filler, it is preferable to carry out the surface treatment in advance before the preparation of the outermost layer coating. However, in the case of a surface treatment with a coupling agent, a coupling agent is added to the coating during the preparation of the coating. It is also preferable to carry out.

  The filler is preferably dispersed in advance in a medium (such as a solvent).

  It is preferable that the addition amount of a filler is 5-70 mass% with respect to the total mass of outermost layer, More preferably, it is 10-50 mass%, Most preferably, it is 20-40 mass%. If the amount is too small, the effect of improving the physical strength (such as scratch resistance) decreases, and if the amount is too large, the outermost layer may become cloudy.

  The average particle diameter of the filler is preferably 20 to 100%, more preferably 30 to 80%, particularly preferably 30 to 50% with respect to the film thickness of the outermost layer.

  When the filler added to the outermost layer is silicon dioxide fine particles, it is particularly preferable to use hollow silicon dioxide fine particles. The hollow silicon dioxide fine particles preferably have a refractive index of 1.17 to 1.45, more preferably 1.17 to 1.40, and still more preferably 1.17 to 1.37. Here, the refractive index of the hollow silicon dioxide fine particles represents the refractive index of the entire particles, and does not represent the refractive index of only the outer silicon dioxide forming the hollow silicon dioxide fine particles. The refractive index of the outermost layer can be lowered by using hollow silicon dioxide fine 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 expressed by the following formula (1).

Equation ^{(1) 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%.

  It is also preferable to use two or more fillers in combination. Further, particles having different average particle diameters can be used in combination.

(Preferable slipping agent for outermost layer)
The slipping agent is preferably added in terms of improving the physical strength (such as scratch resistance) and antifouling property of the outermost layer.
Examples of the slip agent include fluorine-containing ether compounds (perfluoropolyether and derivatives thereof), polysiloxane compounds (dimethylpolysiloxane and derivatives thereof), and the like. Polysiloxane compounds are preferred.

  Preferable examples of the polysiloxane compound include those having a substituent at the terminal and / or side chain of a compound containing a plurality of dimethylsilyloxy units as repeating units. The compound containing a dimethylsilyloxy unit as a repeating unit may contain a structural unit (substituent) other than the dimethylsilyloxy unit. The substituents may be the same or different, and a plurality of substituents are preferable.

  Examples of preferred substituents include groups containing (meth) acryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done.

  Although there is no restriction | limiting in particular in the molecular weight of a slip agent, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000. Although there is no restriction | limiting in particular in Si atom content of a siloxane compound, it is preferable that it is 5 mass% or more, it is especially preferable that it is 10-60 mass%, and it is most preferable that it is 15-50 mass%.

Particularly preferred slip agents are polysiloxane compounds having a crosslinkable or polymerizable functional group represented by the following general formula (A) and derivatives thereof (for example, crosslinks or polymers of polysiloxane compounds represented by the general formula (A), A reaction product of a polysiloxane compound represented by the general formula (A) and a compound having a crosslinkable or polymerizable functional group other than the polysiloxane compound).
Formula (A)

In general formula (A), R ^{1 to} R ⁴ each independently represent a substituent having 1 to 20 carbon atoms, and when there are a plurality of each group, they may be the same or different from each other, R ¹ , R ³ and R ⁴ represent a cross-linkable or polymerizable functional group.
p represents an integer satisfying 1 ≦ p ≦ 4. q represents an integer satisfying 10 ≦ q ≦ 500, r represents an integer satisfying 0 ≦ r ≦ 500, and the polysiloxane portion surrounded by {} is a block copolymer even if it is a random copolymer. There may be.

  The outermost layer in the present invention preferably contains a cured product containing a polysiloxane compound having a crosslinkable or polymerizable functional group represented by the general formula (A) and / or a derivative thereof and a fluorine-containing compound.

  The content of the polysiloxane compound and / or derivative thereof is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1 to 10% by mass with respect to the fluorine-containing compound. %.

  In the polysiloxane compound and / or derivative thereof, a preferable crosslinkable or polymerizable functional group can form a bond by crosslinking or polymerizing with other constituent components (fluorine-containing compound, binder, etc.) of the outermost layer. Any functional group may be used, for example, a group having an active hydrogen atom (for example, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a mercapto group, a β-ketoester group, a hydrosilyl group, a silanol group, etc.), a group capable of cationic polymerization ( Epoxy groups, oxetanyl groups, oxazolyl groups, vinyl groups, vinyloxy groups, etc.), groups having unsaturated double bonds that can be crosslinked or polymerized by radical species (such as (meth) acryloyl groups, allyl groups), hydrolyzable silyls Groups (eg alkoxysilyl groups, acyloxysilyl groups, etc.), acid anhydrides, isocyanate groups, Group (active halogen atom, a sulfonic acid ester, etc.) which may be substituted by agents.

  These crosslinkable or polymerizable functional groups are appropriately selected according to the constituent components of the outermost layer. Preferably, it is an ionizing radiation curable functional group.

  The crosslinkable or polymerizable functional group of the general formula (A) is preferably crosslinked or polymerized with the crosslinkable or polymerizable functional group of the fluorine-containing compound, and the particularly preferred functional group is a cationic ring-opening polymerization reaction. A reactive group (in particular, an epoxy group, an oxetanyl group, etc.) and a radical polymerization reactive group (in particular, a (meth) acryloyl group).

The substituent represented by R ^{2 in the} general formula (A) is a substituted or unsubstituted organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a hexyl group). Etc.), fluorinated alkyl groups (trifluoromethyl group, pentafluoroethyl group, etc.) or aryl groups having 6 to 20 carbon atoms (for example, phenyl group, naphthyl group, etc.), more preferably alkyl having 1 to 5 carbon atoms. Group, a fluorinated alkyl group or a phenyl group, particularly preferably a methyl group. These may be further substituted with these groups.
In the case where R ¹ , R ³ and R ^{4 in the} general formula (A) are not a crosslinkable or polymerizable functional group, the organic group can be taken.

  p represents an integer satisfying 1 ≦ p ≦ 4. q represents an integer satisfying 10 ≦ q ≦ 500, preferably 50 ≦ q ≦ 400, and particularly preferably 100 ≦ q ≦ 300. r represents an integer satisfying 0 ≦ r ≦ 500, preferably 0 ≦ r ≦ q, and particularly preferably 0 ≦ r ≦ 0.5q.

The polysiloxane structure of the compound represented by the general formula (A) may be a homopolymer in which the repeating unit (—OSi (R ² ) ₂ —) is composed of only a single substituent (R ² ). A random copolymer constituted by a combination of repeating units having different substituents or a block copolymer may be used.

The compound represented by the general formula (A) preferably has a mass average molecular weight of 10 ³ to 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ , and particularly preferably 10 ⁴ to 10 ⁵ . is there.

  The polysiloxane compound represented by the general formula (A) is commercially available, for example, KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22. −164C, X−22−5002, X−22−173B, X−22−174D, X−22−167B, X−22−161AS, X−22−174DX, X−22−2426, X−22−170DX , X-22-176D, X-22-1821 (manufactured by Shin-Etsu Chemical Co., Ltd., all trade names), AK-5, AK-30, AK-32 (manufactured by Toagosei Co., Ltd., all products) Name), Silaplane FM-0275, FM-0721, FM-0725, FM-7725 (manufactured by Chisso Corporation, all trade names), DMS-U22, RMS-033, RMS-083, UMS-182 (Gelest A company name, a brand name) etc. can also be used. Moreover, it can also produce by introduce | transducing a crosslinking or polymerizable functional group into the hydroxyl group, amino group, mercapto group, etc. which a commercially available polysiloxane compound contains.

  Examples of preferred polysiloxane compounds represented by formula (A) are shown below, but the present invention is not limited thereto.

  The addition amount of the polysiloxane compound represented by the general formula (A) and / or its derivative is preferably 0.05 to 30% by mass, more preferably 0.1 to 30% by mass with respect to the total solid content of the outermost layer. 20 mass%, More preferably, it is 0.5-15 mass%, Most preferably, it is 1-10 mass%.

(Outermost layer and its formation method)
The outermost layer is prepared by applying a paint in which the above-mentioned fluorine-containing compound, and further, if necessary, the above-mentioned filler, the above-mentioned polysiloxane compound and / or derivative thereof, and other binders are dissolved or dispersed in a solvent. It is preferable.
Preferred solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), alcohols (methanol, ethanol, etc.) Isopropyl alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.
Particularly preferred solvents are ketones, aromatic hydrocarbons and esters, and most preferred solvents are ketones. Of the ketones, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are particularly preferable. The solvent preferably has a ketone solvent content of 10% by mass or more of the total solvent contained in the paint. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.
Two or more kinds of solvents can be used in combination.

In the case of a fluorine-containing compound having a crosslinkable or polymerizable functional group, it is preferable that the outermost layer is produced by crosslinking or polymerizing the fluorine-containing compound simultaneously with or after the application of the outermost layer.
If the fluorine-containing compound has a functional group that crosslinks or polymerizes with a radical, it is preferable to perform a crosslinking or polymerization reaction using a radical polymerization initiator, particularly a photoradical polymerization initiator. Moreover, if it has a functional group which crosslinks or polymerizes with a cation, it is preferable to carry out a crosslinking or polymerization reaction using a cationic polymerization initiator, particularly a photocationic polymerization initiator.

  As the radical polymerization initiator, those that generate radicals by the action of heat or those that generate radicals by the action of light are preferable. Particularly preferred are radical photopolymerization initiators.

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 using a compound that initiates radical polymerization by the action of light, for example, the outermost layer can be prepared by curing by irradiation with light according to the compound used such as ultraviolet rays.
Examples of radical photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides There are 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.
In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in “Latest UV Curing Technology” by Kazuhiro Takashiro (Technical Information Association, Inc., page 159, 1991).
Commercially available radical photopolymerization initiators can also be preferably used, and examples include the initiators described in the high refractive index layer.

The photopolymerization initiator is preferably used in a range of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the photocrosslinking or polymerizable compound contained in the outermost layer. Part range.
Furthermore, a photosensitizer can be preferably used in combination with these photopolymerization initiators, and examples thereof include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Commercially available photosensitizers can also be preferably used, and examples include sensitizers described in the high refractive index layer.

The binder is preferably added in terms of improving the physical strength of the outermost layer (such as scratch resistance) and the adhesion between the outermost layer and the adjacent layer.
For example, if the fluorine-containing compound is a compound having a crosslinkable or polymerizable functional group, the binder is preferably a binder having a functional group that crosslinks or polymerizes with the fluorine containing compound.
In particular, if the fluorine-containing compound is a compound having a photocrosslinkable or photopolymerizable functional group, the binder is preferably a polyfunctional monomer having a photocrosslinkable or photopolymerizable functional group. Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include those described for the high refractive index layer. Two or more polyfunctional monomers may be used in combination.
The fluorine-containing compound in the outermost layer includes a fluorine-containing compound having a crosslinkable or polymerizable functional group, a polysiloxane compound represented by the general formula (A) and / or a derivative thereof, and / or the crosslinkable or polymerizable compound. It is preferably a cured product formed from a fluorine-containing compound having a functional group and a binder that crosslinks or polymerizes.

For the outermost layer, a fluorine-containing compound or a coating material in which the constituents of the outermost layer are dissolved or dispersed is subjected to light irradiation, electron beam irradiation, heat treatment, etc. at the same time or after application, and then a crosslinking or polymerization reaction. It is preferable to make them.
In the case of ultraviolet irradiation, ultraviolet rays emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. can be used.

  In the production of the outermost layer, particularly when the outermost layer is formed by crosslinking or polymerization reaction of an ionizing radiation curable compound, it is preferable to carry out in an atmosphere having an oxygen concentration of 10% by volume or less.

By producing the outermost layer in an atmosphere having an oxygen concentration of 10% by volume or less, the physical strength of the outermost layer (such as scratch resistance), chemical resistance, weather resistance, and further, the outermost layer and a layer adjacent to the outermost layer Can improve the adhesion.
Preferably, it is prepared by crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 4% by volume or less, more preferably an oxygen concentration of 2% by volume or less, particularly preferably an oxygen concentration. Is 1% by volume or less, most preferably 0.5% 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.

  When the outermost layer is used as the low refractive index layer, the film thickness is preferably 30 to 200 nm, more preferably 50 to 150 nm, and particularly preferably 60 to 120 nm. When using the outermost layer as an antifouling layer, the film thickness is preferably 3 to 50 nm, more preferably 5 to 35 nm, and particularly preferably 7 to 25 nm.

  In order to improve the physical strength of the antireflection film, the outermost layer preferably has a surface dynamic friction coefficient of 0.25 or less. The dynamic friction coefficient described here refers to a dynamic friction coefficient between a surface and a stainless hard sphere having a diameter of 5 mm when a load of 0.98 N is applied to a stainless hard sphere having a diameter of 5 mm and the surface is moved at a speed of 60 cm / min. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.

Further, in order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of the surface with respect to water is 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.
Further, it is desirable that the contact angle of the surface of the outermost layer with respect to water does not change before and after the saponification treatment, which will be described later, and the amount of change before and after the saponification treatment is preferably within 10 °, particularly preferably within 5 °. .

  The haze of the outermost layer is preferably as low as possible. It is preferably 3% or less, more preferably 2% or less, and particularly preferably 1% or less.

  The strength of the outermost layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

  In the outermost layer, in addition to the above-described components (fluorine compound, polymerization initiator, photosensitizer, filler, slip agent, binder, etc.), surfactant, antistatic agent, coupling agent, thickener, Add anti-coloring agents, coloring agents (pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, etc. You can also

(Low refractive index layer)
The low refractive index layer may also serve as the outermost layer, or may be positioned below the outermost layer.
When the low refractive index layer also serves as the outermost layer, what has already been described for the outermost layer can be applied. When the low refractive index layer is located in the lower layer of the outermost layer, the low refractive index layer preferably contains a silicon compound.
The refractive index of the low refractive index layer is preferably 1.20 to 1.55. More preferably, it is 1.30-1.50, More preferably, it is 1.35-1.48, Most preferably, it is 1.37-1.45.

  When the low refractive index layer is positioned below the outermost layer, the low refractive index layer can be produced by a coating method or a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.). The coating method is preferable because it can be manufactured at a low cost.

  When the low refractive index layer is prepared by coating, from the silicon compound represented by the following general formula (I) and derivatives thereof (hydrolyzate and crosslinked silicon compound formed by condensation of the hydrolyzate). It is preferable to prepare with a compound selected from the group consisting of, and particularly preferable to prepare with a crosslinked or polymerized silicon compound.

Formula (I) (X1) _a (Y1) _b Si (Z1) _4-ab

In general formula (I): X1 is an organic group having 1 to 12 carbon atoms (for example, alkyl, aryl, alkyl halide, aryl halide, alkenyl, or epoxy group, (meth) acryloxy group, mercapto group, amino group). , A cyano group and the like. Y1 is a hydrocarbon group having 1 to 3 carbon atoms. Z1 represents a halogen atom or an alkoxy group (for example, OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ etc.). a and b may be the same or different and are integers of 0 to 2;

  Although not particularly limited, specific examples of the general formula (I) include tetraalkoxysilanes such as methyl silicate and ethyl silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltrimethoxysilane. Butoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,

Vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane , Γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) amino Trialkoxy or triacyloxysilanes such as propyltrimethoxysilane, β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldimethoxysilane,

Phenylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ- Chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercapto Propylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane Such as dialkoxy or di acyloxysilane such as emissions and the like.

  In particular, when hardness is required, an ionizing radiation curable silicon compound, particularly a silicon compound having a molecular weight of 5,000 or less having a plurality of functional groups that undergo crosslinking or polymerization reaction by ionizing radiation is preferable. For example, single-end vinyl functional polysilane, double-end vinyl functional polysilane, single-end vinyl functional polysiloxane, double-end vinyl functional polysiloxane, or vinyl functional polysilane obtained by reacting these compounds, or vinyl functional polysiloxane Etc. A silicon compound containing an epoxy group or a (meth) acryloyl group is preferred. These silicon compounds can be used alone or in combination of two or more.

  These silicon compounds are preferably cured using various curing agents and catalysts. For example, Lewis acids, various acids and bases including Lewis bases, and neutral or basic salts prepared therefrom, such as organic carboxylic acids , Chromic acid, hypochlorous acid, boric acid, bromic acid, selenious acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminate, carbonic acid metal salt, especially alkali metal salt or ammonium salt, further aluminum, Zirconium, titanium alkoxides, or complex compounds of these. Particularly preferred are aluminum chelate compounds such as ethyl acetoacetate aluminum diisopropylate, aluminum trisethyl acetoacetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, aluminum trisacetylacetate and the like. is there.

In addition, it is preferable to add inorganic fine particles, for example, fine particles such as LiF, MgF ₂ , and SiO ₂ to the low refractive index layer, and SiO ₂ is particularly preferable.

The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.
The lower the haze of the low refractive index layer, the better. It is preferably 3% or less, more preferably 2% or less, and particularly preferably 1% or less.
The strength of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

(Antireflection film)
In the present invention, the antireflection film preferably has a dynamic friction coefficient of 0.25 or less on the surface having the high refractive layer in order to improve physical strength (such as scratch resistance). The dynamic friction coefficient described here is the side having the high refractive index layer when a load of 0.98 N is applied to a stainless hard sphere having a diameter of 5 mm and the surface having the high refractive index layer is moved at a speed of 60 cm / min. The coefficient of dynamic friction between the surface of the stainless steel and a stainless hard sphere having a diameter of 5 mm. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.

The antireflection film preferably has a contact angle with water of 90 ° or more on the surface having the high refractive index layer in order to improve the antifouling performance. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.
The lower the surface resistance of the outermost layer of the antireflection film, the higher the dustproof effect. The surface resistance value of the outermost layer is preferably 1 × 10 ¹⁴ Ω / □ or less. More preferably, it is 1 × 10 ¹² Ω / □ or less, further preferably 1 × 10 ¹¹ Ω / □ or less, particularly preferably 1 × 10 ⁹ Ω / □ or less, and most preferably 1 × 10 ⁸ Ω / □ or less.
The antireflection film thus produced has high physical strength (such as scratch resistance), transparency, chemical resistance, weather resistance (such as moist heat resistance and light resistance), and the surface resistance of the outermost layer. An antireflection film having a value of 1 × 10 ¹⁴ Ω / □ or less can prevent dust (such as dust) that reduces the visibility of the display from adhering to the surface of the antireflection film.
When the antireflection film does not have an antiglare function, the haze is preferably as low as possible.

When the antireflection film has an antiglare function, the haze is preferably 0.5 to 50%, more preferably 1 to 40%, and most preferably 1 to 30%.
The antireflection film of the present invention can be produced by constructing the antireflection film on a transparent support.
Hereinafter, the transparent support and each layer which the antireflection film of the present invention has will be described in detail.

(Transparent support)
The transparent support is preferably a plastic film. As the plastic film, cellulose ester (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate, poly-1, 4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, poly Methylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethacrylate And polyether ketones. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred, and triacetyl cellulose is particularly preferred when used in a liquid crystal display device.

  When the transparent support is a triacetyl cellulose film, a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent is prepared by a single layer casting method or a multi-layer co-casting method. A cellulose film is preferred.

In particular, from the viewpoint of environmental conservation, a triacetyl cellulose film prepared using a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a low temperature dissolution method or a high temperature dissolution method is preferable. .
The triacetyl cellulose film preferably used in the present invention is exemplified in the Japan Society for Invention and Innovation (public technical number 2001-1745).

The film thickness of the transparent support is not particularly limited, but the film thickness is preferably 1 to 300 μm, preferably 30 to 150 μm, particularly preferably 40 to 120 μm, and most preferably 40 to 100 μm.
The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more.
The haze of the transparent support is preferably low. It is preferably 2.0% or less, and more preferably 1.0% or less.
The refractive index of the transparent support is preferably 1.40 to 1.70.

An infrared absorber or an ultraviolet absorber may be added to the transparent support. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass.
In addition, an inert inorganic compound particle may be added to the transparent support as a slipping agent. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin.

  A surface treatment may be performed on the transparent support. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and corona discharge treatment are particularly preferred.

(Hard coat layer)
The antireflection film of the present invention can be provided with a hard coat layer in order to impart physical strength. In particular, it is preferably provided between the transparent support and the outermost layer.
The hard coat layer is preferably formed by a crosslinking or polymerization reaction of an ionizing radiation curable compound. For example, it can be formed by coating a coating containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and crosslinking or polymerizing the polyfunctional monomer or polyfunctional oligomer.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include those exemplified for the high refractive index layer, and it is preferable to perform polymerization using a photopolymerization initiator and a photosensitizer. The photopolymerization reaction is preferably performed by ultraviolet irradiation after the hard coat layer is applied and dried.
The hard coat layer is preferably constructed by applying a paint for forming a hard coat layer on the surface of the transparent support.

As the coating solvent, ketones, esters, and aromatic hydrocarbons exemplified in the high refractive index layer are preferable. In particular, by using a ketone solvent, for example, the adhesion between the surface of a transparent support (particularly, triacetyl cellulose support) and the hard coat layer is further improved.
Particularly preferred coating solvents are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
The coating solvent may contain a solvent other than the ketone solvent exemplified for the high refractive index layer.

  The coating solvent preferably has a ketone solvent content of 10% by mass or more of the total solvent contained in the coating composition. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

When the hard coat layer is prepared by crosslinking or polymerization reaction of an ionizing radiation curable compound, the crosslinking or polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 4% by volume or less. By producing in an atmosphere having an oxygen concentration of 4% by volume or less, a hard coat layer excellent in physical strength (such as scratch resistance) and chemical resistance can be produced.
Preferably, it is prepared by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 3% by volume or less, more preferably an oxygen concentration of 2% by volume or less, particularly preferably an oxygen concentration of 1 Volume% or less, most preferably 0.5 volume% or less.
As a method of reducing the oxygen concentration to 4% 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.

The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 1 to 10 μm, more preferably 2 to 7 μm, and particularly preferably 3 to 5 μm.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

Resin, dispersant, surfactant, antistatic agent, silane coupling agent, thickener, anti-coloring agent, coloring agent (pigment, dye), antifoaming agent, leveling agent, flame retardant, UV Absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, and the like can also be added. In addition, for the purpose of increasing the hardness of the hard coat layer, suppressing curing shrinkage, and controlling the refractive index, inorganic fine particles having an average primary particle diameter of 1 to 200 nm described later can be added.
Furthermore, particles having an average particle size of 0.2 to 10 μm, which will be described later, may be contained for the purpose of imparting an antiglare function and a viewing angle expansion function of a liquid crystal display device.

(Unevenness on the surface of the antireflection film)
The antireflection film used in the present invention can impart antiglare properties by forming irregularities on the surface having the outermost layer.
The antiglare property correlates with the average surface roughness (Ra) of the surface. As for the surface irregularities, 1 mm ² is randomly extracted from an area of 100 cm ² , and the average surface roughness (Ra) is 0.01 to 1 μm or less per 1 mm ² area of the extracted surface. It is preferable that it is -0.4 micrometer, More preferably, it is 0.03-0.3 micrometer, More preferably, it is 0.05-0.25 micrometer, Most preferably, it is 0.07-0.2 micrometer. The average surface roughness (Ra) is described in Jiro Nara, Techno Compact Series (6) “Measurement / Evaluation Method of Surface Roughness” (General Technology Center, Inc.).
Moreover, it is preferable that there is no recess having a cut surface area of 1000 μm ² or more per 1 mm ² area of the surface. If there is a recess with a cross-sectional area of 1000 μm ² or more, when an antireflection film is placed on the surface of an image display device with a small pixel size, one of the three primary colors (red, green, and blue) existing in the pixel is emphasized. May cause a visible failure (glare failure) and may significantly deteriorate the image quality. In particular, it is preferable that there is no recess having a cross-sectional area of 800 μm ² or more.
Such concave and convex shapes on the surface of the antireflection film used in the present invention can be evaluated by an atomic force microscope (AFM).

A well-known method is used as a method of forming surface irregularities. In the present invention, a method of forming by pressing a plate having a concavo-convex shape with high pressure on the surface of the film (for example, embossing), or by incorporating particles in any layer on the antireflection film described later A method of forming an unevenness on the surface of the antireflection film by using an antiglare layer is preferable. In particular, particles having an average particle size of 0.2 to 10 μm, which will be described later, are contained in any layer, irregularities are formed on the surface of the layer, and irregularities are formed on the outermost layer surface by forming the outermost layer on the layer. The method of forming is preferable.
In the method of forming irregularities on the surface by embossing, a known method can be applied, but it is particularly preferable to form irregularities by the method described in Japanese Patent Application Laid-Open No. 2000-329905.

(Layer containing particles having an average particle size of 0.2 to 10 μm)
In the antireflection film of the present invention, it is preferable to construct a layer (for example, an antiglare layer or a light diffusion layer) containing particles having an average particle diameter of 0.2 to 10 μm between the transparent support and the outermost layer. The average particle diameter here is the mass average diameter of secondary particles (or primary particles when the particles are not aggregated).
Particles having an average particle size of 0.2 to 10 μm are used for the purpose of imparting an antiglare function and a viewing angle expansion function of a liquid crystal display device to the antireflection film of the present invention.
Examples of the particles include inorganic particles and organic particles.

  Specific examples of the inorganic particles include particles such as silicon dioxide, titanium dioxide, zirconium oxide, aluminum oxide, tin oxide, ITO, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin and calcium sulfate. Silicon dioxide and aluminum oxide are preferred.

  The organic particles are preferably resin particles. Specific examples of the resin particles include particles made from silicon resin, melamine resin, benzoguanamine resin, polymethyl methacrylate resin, polystyrene resin, and polyvinylidene fluoride resin. Preferred are particles made from melamine resin, benzoguanamine resin, polymethyl methacrylate resin, polystyrene resin, and particularly preferred are particles made from polymethyl methacrylate resin, benzoguanamine resin, polystyrene resin.

A layer for providing an antiglare function by forming irregularities on the surface of the antireflection film on the side having the outermost layer (antiglare layer), and refracting particles and matrix to provide a function for expanding the viewing angle of a liquid crystal display device. The particles used for the layer (light diffusing layer) for providing a difference in rate and diffusing light are preferably resin particles and silicon dioxide particles.
The average particle diameter of the particles is preferably 0.5 to 7.0 μm, more preferably 1.0 to 5.0 μm, and particularly preferably 1.5 to 4.0 μm.
The refractive index of the particles is preferably 1.35 to 1.80, more preferably 1.40 to 1.75, and still more preferably 1.45 to 1.75.
The narrower the particle size distribution, the better. The S value indicating the particle size distribution of the particles is represented by the following formula, preferably 2.0 or less, more preferably 1.0 or less, and particularly preferably 0.7 or less.

    S = [D (0.9) -D (0.1)] / D (0.5)

D (0.1): 10% of the integrated value of the volume-converted particle diameter,
D (0.5): 50% of the integrated value of the volume-converted particle diameter,
D (0.9): 90% of the integrated value of the volume-converted particle diameter.

The refractive index of the particles is not particularly limited, but in the case of an antiglare layer, it is almost the same as the refractive index of the layer matrix (the refractive index of the layer excluding particles having an average particle size of 0.2 to 10 μm) ( Preferably, the difference in refractive index is within 0.005) or 0.02 or more.
By making the refractive index of the particles and the refractive index of the matrix of the layers substantially the same, the contrast when the antireflection film is mounted on the image display surface is improved. On the other hand, by adding a difference in refractive index between the refractive index of the particles and the refractive index of the matrix of the layer, the visibility when the antireflection film is mounted on the liquid crystal display surface (glare failure, viewing angle of the liquid crystal display device) Characteristics, etc.) are improved.
When the refractive index difference is given between the refractive index of the particles and the refractive index of the matrix of the layer, the difference is preferably 0.03 to 0.5, more preferably 0.03 to 0.4, Especially preferably, it is 0.05-0.3.

  In the case of a light diffusion layer, the refractive index of the particles is preferably different from the refractive index of the layer matrix by 0.02 or more.

  The layer containing particles having an average particle size of 0.2 to 10 μm may be constructed between the transparent support and the outermost layer, and the layer is the hard coat layer, the high refractive index layer, the outermost layer, It may be a low refractive index layer or a medium refractive index layer described later. A hard coat layer, a high refractive index layer, and a hard coat layer are most preferable. The layer containing particles having an average particle size of 0.2 to 10 μm is preferably a layer adjacent to the outermost layer.

  Particles having an average particle size of 0.2 to 10 μm may be used in combination of a plurality of particles having different average particle sizes. It is also preferable to use a combination of a plurality of particles of different materials.

  The layer containing particles having an average particle size of 0.2 to 10 μm preferably contains an organic compound binder. Further, similarly to the high refractive index layer and the hard coat layer, the binder is preferably a cured product of a compound having a crosslinkable or polymerizable functional group, and is formed by a crosslinking or polymerization reaction of an ionizing radiation curable compound. It is preferable.

The haze of the layer containing particles having an average particle diameter of 0.2 to 10 μm is preferably 3 to 80%, more preferably 5 to 60%, particularly preferably 7 to 50%, and most preferably 10 to 10. 40%.
The strength of the layer containing particles having an average particle diameter of 0.2 to 10 μm is preferably H or more, more preferably 2H or more, and more preferably 3H or more in a pencil hardness test according to JIS K5400. Most preferred. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

(Inorganic fine particles having an average particle diameter of 1 to 200 nm)
In the antireflection film of the present invention, it is preferable to construct a layer containing inorganic fine particles having an average primary particle diameter of 1 to 200 nm between the transparent support and the outermost layer. The average particle diameter here is a mass average diameter. The layer which does not impair transparency can be produced by setting the average particle size of the primary particles to 1 to 200 nm.
Inorganic fine particles having an average primary particle size of 1 to 200 nm are used for the purpose of increasing the hardness of the layer, suppressing curing shrinkage, and controlling the refractive index.
Inorganic fine particles include aluminum oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, titanium dioxide, zirconium oxide in addition to the inorganic fine particles (conductive fine particles, fillers, etc.) exemplified in the high refractive index layer and outermost layer. Zinc oxide, zinc sulfide, aluminum doped zinc oxide (AZO), tin oxide (SnO ₂ ), antimony doped tin oxide (ATO), fluorine doped tin oxide (FTO), indium oxide (In ₂ O ₃ ), fine particles such as zinc-doped indium oxide (IZO), tin-doped indium oxide (ITO), and antimony oxide (Sb ₂ O ₅ ). Silicon dioxide, titanium dioxide, zirconium oxide, aluminum oxide, tin oxide, ATO, ITO, and zinc oxide are preferable.
Inorganic fine particles having an average particle diameter of 1 to 200 nm may be used in combination of a plurality of particles having different average particle diameters. It is also preferable to use a combination of a plurality of particles of different materials.

The average particle size of the primary particles of the inorganic fine particles is preferably 5 to 200 nm, more preferably 10 to 150 nm, still more preferably 20 to 100 nm, and particularly preferably 20 to 50 nm.
In the layer, the inorganic fine particles are preferably dispersed as finely as possible, and are preferably dispersed using a dispersant. The particle size of the inorganic fine particles in the layer is preferably 5 to 300 nm, more preferably 10 to 200 nm, still more preferably 20 to 150 nm, and particularly preferably 20 to 80 nm in terms of average particle diameter. In particular, when used for an optical interference layer, the thickness is preferably 200 nm or less.
Regarding the dispersant and the dispersion method, the matters described in the above-described high refractive index layer can be applied.

The content of the inorganic fine particles in the layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the total mass of the layer.
In the case of producing a layer having a high refractive index (for example, a high refractive index layer, a medium refractive index layer, etc.), inorganic fine particles having a high refractive index (for example, titanium dioxide, Zirconium oxide, aluminum oxide, tin oxide, ATO, ITO, zinc oxide, etc.) are preferably finely dispersed and contained in the layer.

  As the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm, the hard coat layer, the antiglare layer, the light diffusion layer, and an optical interference layer (a high refractive index layer, a medium refractive index layer, etc.) described later are preferable. is there. The layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm is preferably a layer adjacent to the outermost layer.

  The layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm preferably contains an organic compound binder. Further, similarly to the high refractive index layer and the hard coat layer, the binder is preferably a cured product of a compound having a crosslinkable or polymerizable functional group, and is formed by a crosslinking or polymerization reaction of an ionizing radiation curable compound. It is preferable.

The refractive index of the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm is preferably 1.45 to 2.40, more preferably 1.65 to 2.20, and particularly preferably 1.65. 2.00.
The haze of the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm is preferably 5% or less, more preferably 3% or less, particularly preferably 2% or less, and most preferably 1% or less.
The strength of the layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400. preferable. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

(Other layers of antireflection film)
In order to produce an antireflection film having better antireflection performance, an optical interference layer having a higher refractive index than the low refractive index layer (for example, the high refractive index in the present invention) is provided between the hard coat layer and the low refractive index layer. It is preferable to provide a refractive index layer and / or a medium refractive index layer).
The high-refractive index layer and the medium-refractive index layer are formed by finely coating particles other than the inorganic fine particles described in the description of the high-refractive index layer in the present invention (for example, inorganic fine particles having an average particle diameter of 1 to 200 nm) in the film. It can also be produced by dispersing. Regarding the dispersant and the dispersion method, the matters described in the high refractive index layer can be applied.

  In addition, the high refractive index layer and the medium refractive index layer include an ionizing radiation curable compound containing an aromatic ring and / or a halogenated element other than fluorine (for example, Br, I, Cl, etc.), S, N, P Binders obtained by crosslinking or polymerization reaction such as ionizing radiation curable compounds containing atoms such as can also be preferably used. The refractive index of the high refractive index layer and the medium refractive index layer can be appropriately controlled. When fine particles having a high refractive index are contained, the refractive index can be adjusted by controlling the fine particle content in the film. It is. The film thickness of the high refractive index layer and the medium refractive index layer can also be adjusted as appropriate. Here, it means that the refractive index of the high refractive index layer is higher than that of the middle refractive index layer.

  The preferable refractive index and film thickness of the high refractive index layer and the middle refractive index layer will be described in the configuration of the antireflection film described later. The refractive index of the high refractive index layer is preferably 1.65 to 2.40, more preferably 1.70 to 2.20, still more preferably 1.75 to 2.10, and particularly preferably 1.80 to 2.10. It is. The refractive index of the middle refractive index layer is preferably 1.55 to 1.80, more preferably 1.60 to 1.80, still more preferably 1.60 to 1.75, and particularly preferably 1.60 to 1.70. It is.

  The high refractive index layer and the medium refractive index layer preferably contain an organic compound binder. Further, similarly to the high refractive index layer and the hard coat layer, the binder is preferably a cured product of a compound having a crosslinkable or polymerizable functional group, and is formed by a crosslinking or polymerization reaction of an ionizing radiation curable compound. It is preferable.

The haze of the high refractive index layer and the middle refractive index layer is preferably 5% or less, more preferably 3% or less, particularly preferably 2% or less, and most preferably 1% or less.
The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in the pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

  The antireflection film may be provided with layers other than those described above. For example, an adhesive layer or a shield layer may be provided. The shield layer is provided to shield electromagnetic waves and infrared rays.

(Organosilane compound)
In the present invention, an organosilane compound that can be particularly preferably used for each layer of the antireflection film will be described.
It is preferable to add an organosilane compound and / or a derivative thereof to any layer on the transparent support from the viewpoint of improving the physical strength of the film (such as scratch resistance) and the adhesion between the film and the layer adjacent to the film. .

  As the organosilane compound and / or a derivative thereof, a compound represented by the following general formula (a) and / or a derivative thereof can be used. Preferred are organosilane compounds containing a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group (( (Meth) acryloyl, etc.) and a polymerizable acylamino group (acrylamino, methacrylamino, etc.).

Formula (a) (R ¹⁰ ) _s -Si (Z) _4-s

In general formula (a), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
Z represents a hydroxyl group or a hydrolyzable group. For example, an alkoxy group (an alkoxy group having 1 to 5 carbon atoms is preferable. Examples thereof include a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I and the like), and R12COO (R12 is a hydrogen atom or a carbon number of 1). preferably an alkyl group having 5. for example CH ₃ COO, include groups C ₂ H ₅ COO and the like are represented by like are), preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group.
s represents an integer of 1 to 3. 1 or 2 is preferable, and 1 is particularly preferable.
When R ¹⁰ or Z there is a plurality, the plurality of R ¹⁰ or Z may be different.

The substituent contained in R ¹⁰ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy groups (phenoxy) Etc.), alkylthio groups (such as methylthio and ethylthio), arylthio groups (such as phenylthio), alkenyl groups (such as vinyl and 1-propenyl), alkoxysilyl groups (such as trimethoxysilyl and triethoxysilyl), acyloxy groups (acetoxy, acryloyl) Oxy, methacryloyloxy, etc.), alkoxycal Nyl group (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino Groups (acetylamino, benzoylamino, acrylamino, methacrylamino and the like) and the like, and these substituents may be further substituted with these substituents.

  Of these, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group. In particular, a crosslinked or polymerizable functional group is preferable, and an epoxy group, a polymerizable acyloxy group ((meth) acryloyl), and a polymerizable acylamino group (acrylamino, methacrylamino) are preferable. These substituents may be further substituted with the above-described substituents.

When there are a plurality of R ^{10 s} , at least one of them is preferably a substituted alkyl group or a substituted aryl group. Among the organosilane compounds represented by the general formula (a) and derivatives thereof, organosilane compounds having a vinyl polymerizable substituent represented by the following general formula (b) and / or derivatives thereof are preferable.
General formula (b)

In the general formula (b), R ¹¹ 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. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond, * -COO-**, * -CONH-**, * -O-**, or * -NH-CO-NH-**, and represents a single bond, * -COO-**, * -CONH-** is preferred, single bond, * -COO-** is more preferred, and * -COO-** is particularly preferred. Here, * represents a position bonded to ═C (R ¹¹ ) —, and ** represents a position bonded to L 1.

  L1 represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferable, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferable. Examples of the substituent include a halogen, 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.

t represents 0 or 1; t is preferably 0.
R ¹⁰ has the same meaning as in formula (a), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
Z has the same meaning as in formula (a), 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 hydroxyl group or a carbon number of 1 -3 alkoxy groups are more preferred, and methoxy groups are particularly preferred. When a plurality of Zs are present, the plurality of Zs may be the same or different.

Two or more kinds of the compounds of the general formula (a), the general formula (b), and their derivatives may be used in combination.
Although the specific example of the organosilane compound represented by general formula (a) and general formula (b) below is shown, this invention is not limited to these.

Of these, (M-1), (M-2), and (M-5) are particularly preferable.
In the present invention, the derivative of the organosilane compound represented by the general formula (a) and the general formula (b) is a hydrolyzate of the organosilane compound represented by the general formula (a) or the general formula (b), It means a partial condensate. Hereinafter, preferred derivatives (hydrolyzate and / or partial condensate) of the organosilane compound used in the present invention will be described.
The hydrolysis reaction and / or condensation reaction of the organosilane compound is generally 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, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. 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 Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

The organosilane hydrolysis / condensation reaction can be carried out in the absence of a solvent or in a solvent, but an organic solvent is preferably used in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers, Ketones and esters are preferred.
The solvent preferably dissolves the organosilane and the catalyst. In addition, it is preferable to use an organic solvent as a paint or a part of the paint, and it is preferable that the solvent does not impair the solubility or dispersibility when mixed with other materials.

Among these, as alcohols, a monohydric alcohol or a dihydric alcohol can be mentioned, for example, As a monohydric alcohol, a C1-C8 saturated aliphatic alcohol is preferable.
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, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of the solid content in the reaction is not particularly limited, but is usually in the range of 1% to 90%, preferably in the range of 20% to 70%.

0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the hydrolyzable group of the organosilane compound, in the presence or absence of the above solvent, and in the presence of a catalyst. And by stirring at 25 to 100 ° C.
In the present invention, (wherein, R ¹³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ¹³ OH alcohol of the general formula R ¹⁴ COCH ₂ COR ¹⁵ (wherein represented by, R ¹⁴ is the number of carbon atoms 1 to 10 alkyl groups, R ¹⁵ represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms) and selected from Zr, Ti and Al. It is preferable to perform the hydrolysis by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a metal as a central metal.

The metal chelate compound includes an alcohol represented by a general formula R ¹³ OH (wherein R ¹³ represents an alkyl group having 1 to 10 carbon atoms) and a general formula R ¹⁴ COCH ₂ COR ¹⁵ (wherein R ¹⁴ is carbon. C 1 -C 10 alkyl group, R ¹⁵ is a compound represented by the an alkyl group or an alkoxy group having 1 to 10 carbon atoms having 1 to 10 carbon atoms) as a ligand, Zr, Ti, an Al Any metal having a selected metal as a central metal can be suitably used without particular limitation. Two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ¹³ ) _p1 (R ¹⁴ COCHCOR ¹⁵ ) _p2 , Ti (OR ¹³ ) _q1 (R ¹⁴ COCHCOR ¹⁵ ) _q2 , and Al (OR ¹³ ) _r1 (R ¹⁴ Those selected from the group of compounds represented by COCHCOR ¹⁵ ) _r2 are preferred and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.

R ¹³ and R ¹⁴ 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, phenyl group and the like. R15 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 an n-butoxy group. , Sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

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, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, preferred are tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy bis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum. . 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 used in a proportion of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass with respect to the organosilane compound. If it is less than 0.01% by mass, the condensation reaction of the organosilane compound is slow, and the durability of the coating film may be reduced. On the other hand, if it exceeds 50% by mass, the hydrolyzate and / or partial condensate of the organosilane compound And the storage stability of the composition containing the metal chelate compound may decrease, which is not preferable.

  A β-diketone compound and / or a β-ketoester compound is added to the composition containing the organosilane compound and / or derivative thereof (hydrolyzate, partial condensate) and a metal chelate compound added as necessary. It is preferable to do.

In the present invention, a β-diketone compound and / or a β-keto ester compound represented by the general formula R ¹⁴ COCH ₂ COR ¹⁵ is preferably used, and acts as a stability improver for the composition. That is, by coordinating to metal atoms in the metal chelate compounds (zirconium, titanium and / or aluminum compounds), organosilane compound derivatives (hydrolysates, partial condensates, etc.) by these metal chelate compounds It is considered that the action of accelerating the condensation reaction is suppressed and the action of improving the storage stability of the resulting composition is achieved.
R ¹⁴ and R ¹⁵ constitute a β- diketone compound and / or β- ketoester compound are the same as R ¹⁴ and R ¹⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. 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 may be inferior, which is not preferable.

  The amount of the organosilane compound and / or derivative thereof added is appropriately adjusted depending on the layer to be added. The addition amount is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, further preferably 3 to 25% by mass, and particularly preferably 5 to 20% by mass with respect to the total solid content of the layer. It is.

Organosilane compounds and / or derivatives thereof are preferred because crosslinking or polymerization reaction with other components of the layer containing them can greatly improve the physical strength (scratch resistance, etc.) of the film. . For this reason, it is preferable that the organosilane compound has a functional group that crosslinks or polymerizes, or a compound having a functional group that crosslinks or polymerizes with the organosilane compound is used in the inorganic fine particles or the binder.
For example, an organosilane compound having an ionizing radiation-curable crosslinking or polymerizable functional group and / or a derivative thereof is further crosslinked with another compound having an ionizing radiation-curable crosslinking or polymerizable functional group in the film. Or a polymerization reaction produces | generates hardened | cured material.

  Preferred layers for adding the organosilane compound are a hard coat layer, an antiglare layer, a light diffusion layer, a high refractive index layer, a low refractive index layer, and an outermost layer, and more preferably a high refractive index layer and an antiglare layer. A layer, a light diffusion layer, a low refractive index layer, and an outermost layer, and particularly preferably the outermost layer and / or an adjacent layer of the outermost layer.

(Anti-reflection film formation method, etc.)
In the present invention, each layer constituting the antireflection film is preferably prepared by a coating method. When formed by coating, each layer is formed by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure coating or extrusion coating (US Pat. No. 2,681, 294 specification). Two or more layers may be applied simultaneously. For the simultaneous application method, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, “Coating Engineering ", page 253, Asakura Shoten (1973). Wire bar coating, gravure coating, and micro gravure coating are preferred. In particular, the micro gravure coating method is preferable.
The micro gravure coating method is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and having a gravure pattern engraved on the entire circumference, below the support and in the transport direction of the support. In addition, the coating method is characterized in that the coating is reversely rotated, the excess coating solution is scraped off from the surface of the gravure roll by a doctor blade, and a fixed amount of coating solution is transferred to the support.

In the micro gravure coating method, the number of gravure patterns engraved on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch. The depth of the gravure pattern is preferably 1 to 600 μm, more preferably 5 to 200 μm. The rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm. It is preferable that the conveyance speed of a support body is 0.5-100 m / min, More preferably, it is 1-50 m / min.
In addition to the fine particles, polymerization initiator, and photosensitizer described above, each layer of the antireflection film includes a resin, a dispersant, a surfactant, an antistatic agent, a silane coupling agent, a thickener, and an anti-coloring agent. Agents, colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, and the like can also be added.

(Antireflection film)
In the antireflection film of the present invention, in order to improve physical strength (such as scratch resistance), the dynamic friction coefficient of the surface having the outermost layer is preferably 0.25 or less. The dynamic friction coefficient described here is the same as the surface and diameter on the side having the outermost layer when a load of 0.98 N is applied to a stainless hard sphere having a diameter of 5 mm and the surface on the side having the outermost layer is moved at a speed of 60 cm / min. The coefficient of dynamic friction between 5 mm stainless hard spheres. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.
The antireflection film preferably has a water contact angle of 90 ° or more on the surface having the high refractive index layer in order to improve the antifouling performance. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.
Furthermore, in the present invention, as described above, the antireflection film has a surface resistance value of 1 × 10 ¹⁴ on the surface having the outermost layer in order to prevent dust (dust etc.) from adhering to the surface of the outermost layer. It is preferable that it is below Ω / □.

When the antireflection film does not have an antiglare function, the haze is preferably as low as possible.
When the antireflection film has an antiglare function, the haze is preferably 0.5 to 50%, more preferably 1 to 40%, and most preferably 1 to 30%.

(Structure of antireflection film)
A preferred embodiment of the antireflection film of the present invention will be described with reference to the drawings. In the description of each drawing, the same elements are denoted by the same reference numerals.
FIG. 1 is a cross-sectional view schematically showing a layer structure of an antireflection film having excellent antireflection performance.
The embodiment shown in FIG. 1A has a layer structure in the order of a transparent support 1, a hard coat layer 2, a high refractive index layer 3, and a low refractive index layer (outermost layer) 4. The transparent support 1, the high refractive index layer 3, and the low refractive index layer 4 have a refractive index that satisfies the following relationship.
Refractive index of high refractive index layer> Refractive index of transparent support> Refractive index of low refractive index layer

  In the layer structure as shown in FIG. 1 (a), as described in JP-A-59-50401, the high refractive index layer is represented by the following formula (1), and the low refractive index layer is represented by the following formula (2). Satisfying each is preferable in that an antireflection film having further excellent antireflection performance can be produced.

Formula (1) (mλ / 4) × 0.7 <n1d1 <(mλ / 4) × 1.3
In formula (1), m is a positive integer (generally 1, 2 or 3), n1 is the refractive index of the high refractive index layer, and d1 is the layer thickness (nm) of the high refractive index layer. . λ is the wavelength of visible light, and is a value in the range of 380 to 680 (nm).

Formula (2) (nλ / 4) × 0.7 <n2d2 <(nλ / 4) × 1.3
In Equation (2), n is a positive odd number (generally 1), n2 is the refractive index of the low refractive index layer, and d2 is the layer thickness (nm) of the low refractive index layer. λ is the wavelength of visible light, and is a value in the range of 380 to 680 (nm).
In addition, satisfy | filling the said Numerical formula (1) and Numerical formula (2) means m (positive integer, generally 1, 2, or 3) which satisfy | fills Numerical formula (1) in the range of each said wavelength, and Numerical formula (2) ) Satisfying (a positive odd number, generally 1). The same applies to equations (3) to (8) below.

The mode shown in FIG. 1B has a layer structure in the order of a transparent support 1, a hard coat layer 2, a medium refractive index layer 5, a high refractive index layer 3, and a low refractive index layer (outermost layer) 4. The transparent support 1, the medium refractive index layer 5, the high refractive index layer 3, and the low refractive index layer 4 have refractive indexes that satisfy the following relationship.
Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer In the layer structure as shown in FIG. As described in the above, it is more excellent that the medium refractive index layer satisfies the following formula (3), the high refractive index layer satisfies the following formula (4), and the low refractive index layer satisfies the following formula (5). It is preferable at the point which can produce the antireflection film which has prevention performance.

Formula (3) (hλ / 4) × 0.7 <n3d3 <(hλ / 4) × 1.3
In Formula (3), h is a positive integer (generally 1, 2 or 3), n3 is the refractive index of the medium refractive index layer, and d3 is the layer thickness (nm) of the medium refractive index layer. . λ is the wavelength of visible light, and is a value in the range of 380 to 680 (nm).

Formula (4) (iλ / 4) × 0.7 <n4d4 <(iλ / 4) × 1.3
In formula (4), i is a positive integer (generally 1, 2 or 3), n4 is the refractive index of the high refractive index layer, and d4 is the layer thickness (nm) of the high refractive index layer. . λ is the wavelength of visible light, and is a value in the range of 380 to 680 (nm).

Formula (5) (jλ / 4) × 0.7 <n5d5 <(jλ / 4) × 1.3
In Equation (5), j is a positive odd number (generally 1), n5 is the refractive index of the low refractive index layer, and d5 is the layer thickness (nm) of the low refractive index layer. λ is the wavelength of visible light, and is a value in the range of 380 to 680 (nm).

In the layer configuration as shown in FIG. 1B, the middle refractive index layer satisfies the following formula (6), the high refractive index layer satisfies the following formula (7), and the low refractive index layer satisfies the following formula (8). Is particularly preferred.
Here, λ is 500 nm, h is 1, i is 2, and j is 1.
Formula (6) (hλ / 4) × 0.80 <n3d3 <(hλ / 4) × 1.00
Formula (7) (iλ / 4) × 0.75 <n4d4 <(iλ / 4) × 0.95
Formula (8) (jλ / 4) × 0.95 <n5d5 <(jλ / 4) × 1.05

The high refractive index, medium refractive index, and low refractive index described here refer to the relative refractive index between layers. Moreover, in FIG. 1 (a)-(b), the high refractive index layer is used as a light interference layer, and the antireflection film which has the very outstanding antireflection performance can be produced.
It is also preferable to prepare an antireflection film having an antiglare function by incorporating particles having an average particle diameter of 0.2 to 10 μm into the hard coat layer, the medium refractive index layer, and the high refractive index layer.

The embodiment shown in FIG. 2A has a layer structure in the order of the transparent support 1, the antiglare layer (high refractive index layer) 6, and the low refractive index layer (outermost layer) 4. The particles 7 included in the antiglare layer are particles having an average particle diameter of 0.2 to 10 μm.
In the embodiment shown in FIG. 2A, the transparent support 1 and the low refractive index layer 4 have a refractive index that satisfies the following relationship.
Refractive index of transparent support> refractive index of low refractive index layer

  The embodiment shown in FIG. 2B has a layer structure in the order of the transparent support 1, the hard coat layer 2, the antiglare layer (high refractive index layer) 6, and the low refractive index layer (outermost layer) 4. The particles 7 included in the antiglare layer 6 are particles having an average particle diameter of 0.2 to 10 μm.

2A to 2B, the transparent support 1, the antiglare layer (high refractive index layer) 6, and the low refractive index layer 4 have a refractive index that satisfies the following relationship.
Refractive index of antiglare layer> Refractive index of transparent support> Refractive index of low refractive index layer

2 (a) to 2 (b) is preferable in that an antireflection film excellent in that the low refractive index layer 4 satisfies the following mathematical formula (9) can be produced.
Formula (9) (kλ / 4) × 0.7 <n6d6 <(kλ / 4) × 1.3
In Equation (9), k is a positive odd number (generally 1), n6 is the refractive index of the low refractive index layer, and d6 is the layer thickness (nm) of the low refractive index layer. Further, λ is the wavelength of visible light, and is a value in the range of 380 to 680 (nm).
In addition, satisfy | filling said Numerical formula (9) means that k (positive odd number, generally 1) which satisfy | fills Numerical formula (9) exists in the said wavelength range.
2 (a) to 2 (b) are preferably used when hard coat properties are imparted to the high refractive index layer, and an antireflection film having extremely excellent physical strength (such as scratch resistance) is used. Can be made.

(Protective film for polarizing plate)
The antireflection film of the present invention can be used as a protective film for a polarizing film (protective film for polarizing plate). In this case, it is preferable that the contact angle with respect to water of the surface of the transparent support opposite to the side having the high refractive index layer, that is, the surface bonded to the polarizing film, is 40 ° or less. More preferably, it is 30 ° or less, and particularly preferably 25 ° or less. Setting the contact angle to 40 ° or less is effective in improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. This contact angle can be adjusted by the following saponification treatment conditions.

  As the transparent support of the antireflection film used as the protective film for polarizing plate, it is particularly preferable to use a triacetyl cellulose film.

The following two methods are mentioned as a method of producing the protective film for polarizing plates in this invention.
(1) A method of coating each of the above layers (eg, hard coat layer, low refractive index layer, high refractive index layer, outermost layer, etc.) on one surface of a saponified transparent support.
(2) After coating each of the above layers (eg, hard coat layer, high refractive index layer, low refractive index layer, outermost layer, etc.) on one surface of the transparent support, the side to be bonded to the polarizing film is saponified Technique to do.

In the method (1), when only one surface of the transparent support is saponified, each layer is coated on the side not saponified. When both surfaces of the transparent support are saponified, the surface of the saponified transparent support on the side where each layer is applied is surface-treated by a technique such as corona discharge treatment, glow discharge treatment, flame treatment, etc. It is preferable to coat each layer.
In the method (2), it is preferable to immerse the entire antireflection film in a saponification solution. In this case, the antireflection film can also be saponified on the surface of the transparent support to be bonded to the polarizing film by protecting the surface having each layer with a protective film and immersing it in a saponification solution.
Furthermore, a saponification treatment solution can be applied to the surface of the transparent support on the side to be bonded to the polarizing film of the antireflection film, and the side to be bonded to the polarizing film can be saponified.
The saponification treatment is carried out after antireflection performance is imparted on the protective film, whereby the cost can be further reduced, and the method (2) is particularly preferable in that the protective film for polarizing plate can be produced at a low cost.

Protective films for polarizing plates have optical performance (antireflection performance, antiglare performance, light diffusion function, etc.), physical performance (such as scratch resistance), chemical resistance, antifouling performance (contamination resistance, etc.), weather resistance ( It is preferable that the performance described in the antireflection film of the present invention is satisfied in terms of moisture and heat resistance and light resistance) and dustproof performance.
Therefore, the surface resistance value on the surface having the high refractive index layer is preferably 1 × 10 ¹⁴ Ω / □ or less. More preferably, it is 1 × 10 ¹² Ω / □ or less, further preferably 1 × 10 ¹¹ Ω / □ or less, particularly preferably 1 × 10 ⁹ Ω / □ or less, and most preferably 1 × 10 ⁸ Ω / □ or less.
The dynamic friction coefficient of the surface having the high refractive index layer is preferably 0.25 or less. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.
Further, the contact angle with respect to water on the surface having the high refractive index layer is preferably 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.

(Saponification treatment)
The saponification treatment is preferably carried out by a known method, for example, by immersing a transparent support or an antireflection film in an alkali solution for an appropriate time.
The alkaline liquid is preferably a potassium hydroxide aqueous solution and / or a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 N, particularly preferably 1 to 2 N. The liquid temperature of a preferable alkali liquid is 30-70 degreeC, Most preferably, it is 40-60 degreeC.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface of the transparent support is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.
The hydrophilized surface is effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component.
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 25 ° or less.

(Polarizer)
The polarizing plate of this invention has the antireflection film of this invention in at least one of the protective film (protective film for polarizing plates) of a polarizing film. As described above, the polarizing plate protective film has a water contact angle of 40 ° or less on the surface of the transparent support opposite to the side having the high refractive index layer, that is, the surface to be bonded to the polarizing film. It is preferable.

By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having an antireflection function can be produced, and the cost can be greatly reduced and the display device can be thinned.
The polarizing plate using the antireflection film of the present invention as one of the two protective films and the optical compensation film having optical anisotropy described later as the other is further provided with a contrast in a bright room of a liquid crystal display device. This is preferable because the viewing angle in the vertical and horizontal directions can be greatly widened.

(Optical compensation film)
The optical compensation film (retardation film) can improve viewing angle characteristics of a liquid crystal display screen.
As the optical compensation film, a known film can be used, but in terms of widening the viewing angle, an optically anisotropic layer made of a compound having a discotic structural unit described in JP-A-2001-100042 is disclosed. An optical compensation film characterized in that the angle formed by the discotic compound and the film surface changes in the depth direction of the optically anisotropic layer is preferable. That is, the orientation state of the compound having a discotic structural unit is preferably, for example, a hybrid orientation, a bent orientation, a twist orientation, a homogeneous orientation, a homeotropic orientation, or the like, and particularly preferably a hybrid orientation. The angle is preferably increased as the distance from the support surface side of the optical compensation film increases in the optically anisotropic layer.
When the optical compensation film is used as a protective film for the polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.

  Also, an embodiment in which the optically anisotropic layer further contains a cellulose ester, an embodiment in which an alignment layer is formed between the optically anisotropic layer and the transparent support of the optical compensation film, and the optically anisotropic layer An embodiment in which the transparent support of the optical compensation film has an optically negative uniaxial property and an optical axis in the normal direction of the surface of the transparent support, and an embodiment satisfying the following conditions are also preferable.

    20 ≦ {(nx + ny) / 2−nz} × d ≦ 400

  In the equation, nx is a refractive index in the slow axis direction in the plane (maximum refractive index in the plane), ny is a refractive index in the direction perpendicular to the slow axis in the plane, and nz is a refractive index in the direction perpendicular to the plane. Rate. D is the thickness (nm) of the optically anisotropic layer.

(Image display device)
The antireflection film can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). The antireflection film adheres the transparent support side of the antireflection film to the image display surface of the image display device.
3 and 4 are schematic cross-sectional views schematically showing various modes applied to the image display device of the antireflection film of the present invention.

  FIG. 3A is a preferred embodiment in which the antireflection film is applied to an image display device, particularly PDP, ELD, CRT. This antireflection film can adhere the transparent support 1 to the image display surface of the image display device via the pressure-sensitive adhesive layer 8.

FIGS. 3B, 4C and 4D are preferred embodiments in which the antireflection film is applied to the LCD.
In FIG. 3 (b), the transparent support 1 of the antireflection film is bonded to the protective film 9 of the polarizing film 11 via the pressure-sensitive adhesive layer 8. The protective film 10 side of the other polarizing film can be bonded to the liquid crystal display surface of the liquid crystal display device via the pressure-sensitive adhesive layer 8.

In FIG.4 (c), the transparent support 1 of the antireflection film (protective film for polarizing plates) is adhere | attached on the polarizing film 11 via the adhesive layer 8, and the other protective film 10 side of the polarizing film 11 is shown. Can be bonded to the liquid crystal display surface of the liquid crystal display device via the pressure-sensitive adhesive layer 8.
4D, in the antireflection film (protective film for polarizing plate) of the present invention, the transparent support 1 is directly bonded to the polarizing film 11, and the other protective film 10 side of the polarizing film 11 is adhesive. It can be adhered to the liquid crystal display surface of the liquid crystal display device via the layer 8. You may add additives, such as particle | grains and dye, to the adhesive layer 8. FIG.

The antireflection film and polarizing plate used in the present invention are twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB). It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of the mode.
In particular, for a TN mode or IPS mode liquid crystal display device, as described in JP-A-2001-100043, a polarizing plate having the above optical compensation film and antireflection film as a protective film is used. Thus, viewing angle characteristics and antireflection characteristics can be greatly improved.
Further, when used in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selection layer, for example, D-BEF (trade name) manufactured by Sumitomo 3M Co., Ltd.), a transmissive or transflective liquid crystal is used. In the display device, a display device with higher visibility can be obtained.
Further, by combining with a λ / 4 plate, it can be used to reduce the reflected light from the surface and inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention should not be construed as being limited thereto.

[Example 1-1]
(Preparation of coating solution for hard coat layer)
45 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd., trade name), 25.7 parts by mass of methyl ethyl ketone, 27.5 parts by mass of cyclohexanone, photopolymerization initiator (Irgacure 907, Ciba Specialty Chemicals Co., Ltd., trade name) 1.8 parts by mass was added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a hard coat layer.

(Preparation of conductive titanium dioxide fine particles)
The titanium dioxide fine particles containing cobalt (Co) were prepared with reference to a known method (Example of Japanese Patent Laid-Open No. 2003-327430), and further, a known method (Example of Japanese Patent Laid-Open No. Hei 6-279618) was prepared. ), The surface of the titanium dioxide fine particles was coated with antimony-doped tin oxide (ATO) to produce conductive titanium dioxide fine particles (specific surface area 40 m ² / g). In the conductive titanium dioxide fine particles, Co was present inside the titanium dioxide fine particles, and the mass ratio of Ti / Co was 96.2 / 3.8. The conductive titanium dioxide fine particles contain a very small amount of Al (mass ratio Ti / Al = 100/1) in the production process of the titanium dioxide fine particles.
The mass ratio of ATO to the mass of titanium dioxide fine particles containing cobalt (Co) was 90/10. The powder resistance of the conductive titanium dioxide fine particles was 50 Ω · cm.

The surface of the conductive titanium dioxide fine particles is further referred to a known method (Example of JP-A-6-49388), an aluminum compound (a mixture of aluminum hydroxide and aluminum oxide), and zirconium Conductive titanium dioxide fine particles (specific surface area 43 m ² / g) coated with a compound (mixture of zirconium hydroxide and zirconium oxide) were prepared. The mass ratio of Ti / Al / Zr was 95.5 / 3.8 / 0.7. The powder resistance of the conductive titanium dioxide fine particles was 100 Ω · cm.
The powder resistance (Ω · cm) is obtained by molding the sample powder at a pressure of 100 kg / cm ² into a cylindrical green compact (diameter 18 mm, thickness 3 mm), and measuring its DC resistance. It was calculated by the following formula.
Powder resistance (Ω · cm) = Measured value (Ω) × [2.54 (cm ² ) /0.3 (cm)]

(Preparation of conductive titanium dioxide fine particle dispersion (A))
The following dispersant (4.11 parts by mass) and cyclohexanone (70.18 parts by mass) were added to 25.71 parts by mass of the particles, followed by stirring with a disper.
The conductive titanium dioxide fine particles in the liquid were dispersed using a media disperser (using zirconia beads having a diameter of 0.1 mm). It was 70 nm as a result of evaluating the mass mean particle diameter of the electroconductive titanium dioxide microparticles | fine-particles in a dispersion liquid by the light-scattering method. In this way, a conductive titanium dioxide fine particle dispersion (A) was produced.
(Dispersant 1)

(Preparation of titanium dioxide fine particle dispersion (B))
Titanium dioxide fine particles (MPT-129C, specific surface area 40 m ² / g, trade name, manufactured by Ishihara Sangyo Co., Ltd.) containing cobalt (Co) and coated with an aluminum compound and a zirconium compound on the surface of the titanium dioxide fine particles are described above. Dispersed in the same manner as the conductive titanium dioxide fine particles, a titanium dioxide fine particle dispersion (B) (mass average particle size 70 nm) was produced. The powder resistance of MPT-129C was higher than 1 × 10 ⁵ Ω · cm.

(Preparation of coating solution for medium refractive index layer)
To 6.60 parts by mass of the above-mentioned titanium dioxide fine particle dispersion (B), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd., trade name) 4.53 parts by mass, Photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 0.24 parts by mass, photosensitizer (Kaya Cure DETX, Nippon Kayaku Co., Ltd., trade name) 0.08 mass Part, 18.64 parts by mass of methyl ethyl ketone, and 69.91 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a medium refractive index layer.

(Preparation of coating solution for high refractive index layer)
To 34.64 parts by mass of the above conductive titanium dioxide fine particle dispersion (A), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd., trade name) 1.67 Parts by mass, photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals, Inc., trade name) 0.22 parts by mass, photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd., trade name) 0 0.08 parts by mass, 35.13 parts by mass of methyl ethyl ketone, and 28.26 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.

(Preparation of coating solution for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228A, solid content concentration 6%, manufactured by JSR Corporation, trade name) 75.0 parts by mass, methyl ethyl ketone 22.0 parts by mass, cyclohexanone 3.0 parts by mass Was added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.

(Preparation of antireflection film)
A coating liquid for hard coat layer is applied on a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd., trade name) having a film thickness of 80 μm and a width of 1340 mm using a microgravure coating method and a transport speed of 20 m / min. It was applied with. After drying at 100 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with nitrogen purge (oxygen concentration of 1.0% or less), irradiation is 300 mW / cm ² . The coating layer was cured by irradiating an amount of 250 mJ / cm ² of ultraviolet rays to prepare a hard coat layer having a thickness of 3.5 μm.
On the hard coat layer, a medium refractive index layer coating solution was applied by a microgravure coating method under a transport speed of 10 m / min. After drying 60 seconds at 100 ° C., with a nitrogen purge (hereinafter oxygen concentration of 0.5%), using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co.), illuminance 400 mW / cm ^2, irradiation The coating layer was cured by irradiating ultraviolet rays in an amount of 400 mJ / cm ² to produce a medium refractive index layer (refractive index 1.63, film thickness 67 nm).

On the medium refractive index layer, a coating solution for a high refractive index layer was applied by a micro gravure coating method under the condition of a conveyance speed of 10 m / min. After drying 60 seconds at 100 ° C., with a nitrogen purge (hereinafter oxygen concentration of 0.5%), using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co.), illuminance 400 mW / cm ^2, irradiation The coating layer was cured by irradiating with an amount of 600 mJ / cm ² of ultraviolet rays to produce a high refractive index layer (refractive index 1.89, film thickness 107 nm).

On the high refractive index layer, the coating solution for the low refractive index layer was applied by a micro gravure coating method under the condition of a conveyance speed of 10 m / min.
After drying at 120 ° C. for 150 seconds and further drying at 140 ° C. for 10 minutes, a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) is used while purging with nitrogen (oxygen concentration 0.1% or less). Then, the coating layer was cured by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² , thereby producing a low refractive index layer (outermost layer) (refractive index 1.42, film thickness 87 nm). In this way, an antireflection film was produced.

[Example 1-2]
(Preparation of coating solution for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228A, solid content concentration 6%, product name, manufactured by JSR Corporation) 52.5 parts by mass, MEK dispersion of silica fine particles (MEK-ST, average particle size) Diameter 30 nm, solid content concentration 30%, Nissan Chemical Industries, Ltd., trade name) 4.5 parts by mass, methyl ethyl ketone 40.0 parts by mass, cyclohexanone 3.0 parts by mass were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in the same manner as in Example 1-1 except that the above-described coating solution for a low refractive index layer was used.

[Example 1-3]
(Preparation of organosilane compound A solution)
A reactor equipped with a stirrer and a reflux condenser, 120 parts by mass of methyl ethyl ketone, 100 parts by mass of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd., trade name), diisopropoxyaluminum ethylacetate After adding 3 parts by mass of acetate and mixing, 30 parts by mass of ion-exchanged water was added and reacted at 60 ° C. for 4 hours. The solution was cooled to room temperature to obtain a solution of organosilane compound A (solid content concentration 29%). 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 3-acryloxypropyltrimethoxysilane hardly remained.
(Preparation of coating solution for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228A, solid content concentration 6%, product name, manufactured by JSR Corporation) 52.5 parts by mass, MEK dispersion of silica fine particles (MEK-ST, average particle size) Diameter 30 nm, solid concentration 30%, manufactured by Nissan Chemical Industries, Ltd., trade name) 4.5 parts by mass, 1.5 parts by mass of the above organosilane compound A solution, 38.5 parts by mass of methyl ethyl ketone, 3.0 parts by mass of cyclohexanone Parts were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in the same manner as in Example 1-1 except that the above-described coating solution for a low refractive index layer was used.

[Comparative Example 1-A]
(Preparation of antireflection film)
In place of the conductive titanium dioxide fine particles used in Example 1-1, titanium dioxide fine particles not containing cobalt (Co) (TTO-55N, manufactured by Ishihara Sangyo Co., Ltd., trade name) were used. Otherwise, an antireflection film was produced in exactly the same manner as in Example 1-3. The powder resistance of the particles was higher than 1 × 10 ⁵ Ω · cm.

[Comparative Example 1-B]
(Preparation of antireflection film)
Instead of the conductive titanium dioxide fine particles used in Example 1-1, the surface was coated with antimony-doped tin oxide (ATO), which is an intermediate product of the conductive titanium dioxide fine particles prepared in Example 1-1. Titanium dioxide fine particles containing cobalt (Co) before being used were used. Otherwise, an antireflection film was produced in exactly the same manner as in Example 1-3. The powder resistance of the particles was higher than 1 × 10 ⁵ Ω · cm.

[Example 1-4]
(Preparation of antireflection film)
In Example 1-3, an antireflection film was produced in exactly the same manner as in Example 1-3 except that the low refractive index layer was produced under the atmospheric condition (oxygen concentration of about 21%).

[Example 1-5]
(Preparation of antireflection film)
An antireflection film was produced in the same manner as in Example 1-3 except that a low refractive index layer was produced under a nitrogen purge (oxygen concentration of 1.5%) condition.

[Example 1-6]
(Preparation of antireflection film)
In Example 1-3, an antireflection film was produced in exactly the same manner as in Example 1-3 except that the high refractive index layer was produced under the atmospheric condition (oxygen concentration of about 21%).

[Example 1-7]
(Preparation of coating solution for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.44 (JTA113, solid content concentration 6%, manufactured by JSR Corporation, trade name) 52.5 parts by mass, MEK dispersion of silica fine particles (MEK-ST, average particle size) Diameter 30 nm, solid content concentration 30%, manufactured by Nissan Chemical Industries, Ltd., trade name) 4.5 parts by mass, organosilane compound A solution 1.5 parts by mass prepared in Example 1-3, methyl ethyl ketone 38.5 parts by mass And 3.0 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in the same manner as in Example 1-3 except that the above-described coating solution for a low refractive index layer was used.

[Example 1-8]
(Preparation of coating solution for high refractive index layer)
In 34.64 parts by mass of the conductive titanium dioxide fine particle dispersion (A) used in Example 1-1, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd., Product name) 0.84 parts by mass, 2.88 parts by mass of organosilane compound A solution prepared in Example 1-3, photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals, Inc., product name) 0 .22 parts by mass, 0.08 parts by mass of photosensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd., trade name), 33.08 parts by mass of methyl ethyl ketone, and 28.26 parts by mass of cyclohexanone were added and stirred. did. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in the same manner as in Example 1-3 except that the above-described coating solution for a high refractive index layer was used.

[Example 1-9]
(Preparation of coating solution for low refractive index layer)
A MEK dispersion of hollow silica fine particles (refractive index of 1.4) with 52.5 parts by mass of a heat-crosslinkable fluoropolymer having a refractive index of 1.44 (JTA113, solid content concentration 6%, manufactured by JSR Corporation, trade name). 31, average particle diameter 60 nm, solid content concentration 20%) 6.75 parts by mass, methyl ethyl ketone 37.75 parts by mass, cyclohexanone 3.0 parts by mass were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in the same manner as in Example 1-3 except that the above-described coating solution for a low refractive index layer was used.

[Example 1-10]
(Synthesis of perfluoroolefin copolymer)

A stainless steel autoclave equipped with a stirrer was charged with 40 parts by mass of ethyl acetate, 14.7 parts by mass of hydroxyethyl vinyl ether, and 0.55 parts by mass of dilauroyl peroxide, and the system was deaerated and replaced with nitrogen gas. Further, 25 parts by mass of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 529.2 kPa. The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 313.6 kPa, the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out.
The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 parts by mass of the polymer product was obtained.

Next, 20 parts by mass of the polymer product was dissolved in 100 parts by mass of N, N-dimethylacetamide, and 11.4 parts by mass of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution and washed with water. The organic layer was extracted and concentrated, and the obtained polymer was reprecipitated with hexane to obtain 19 parts by mass of the perfluoroolefin copolymer. The obtained perfluoroolefin copolymer had a refractive index of 1.421.
The perfluoroolefin copolymer was dissolved in methyl ethyl ketone to obtain a solution having a solid concentration of 30%.

(Preparation of coating solution for low refractive index layer)
A polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) is added to 15.0 parts by mass of the above-mentioned perfluoroolefin copolymer solution (solid content concentration: 30%). 15 parts by mass, 0.23 parts by mass of a photopolymerization initiator (Irgacure 907, Ciba Specialty Chemicals Co., Ltd., trade name), 81.82 parts by mass of methyl ethyl ketone, and 2.8 parts by mass of cyclohexanone were added. Stir. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.

(Preparation of antireflection film)
On the high refractive index layer produced in Example 1-1, the above-mentioned coating liquid for low refractive index layer was applied by a micro gravure coating method under the condition of a conveyance speed of 15 m / min.
After drying at 120 ° C. for 150 seconds, using a 240 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.1% or less), the illuminance is 400 mW / cm ² , the irradiation amount The coating layer was cured by irradiating with 900 mJ / cm ² of ultraviolet rays to produce a low refractive index layer (outermost layer) having a thickness of 87 nm. In this way, an antireflection film having a length of 1000 m was produced.

[Comparative Example 1-C]
(Preparation of antireflection film)
An antireflection film was produced in the same manner as in Example 1-10 except that the high refractive index layer produced in Comparative Example 1-A was used.

[Comparative Example 1-D]
(Preparation of antireflection film)
An antireflection film was produced in the same manner as in Example 1-10 except that the high refractive index layer produced in Comparative Example 1-B was used.

[Example 1-11]
(Preparation of antireflection film)
In Example 1-10, an antireflection film was produced in exactly the same manner as in Example 1-10, except that a high refractive index layer was produced under the conditions of atmospheric atmosphere (oxygen concentration of about 21%).

[Example 1-12]
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that a high refractive index layer was produced under a nitrogen purge (oxygen concentration of 1.5%) condition.

[Example 1-13]
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that a high refractive index layer was produced under a nitrogen purge (oxygen concentration: 6%) condition.

[Example 1-14]
(Preparation of coating solution for low refractive index layer)
In 10.5 parts by mass of the perfluoroolefin copolymer solution (solid content concentration 30%) prepared in Example 1-10, a silica fine particle MEK dispersion (MEK-ST, average particle size 30 nm, solid content concentration 30). %, Manufactured by Nissan Chemical Industries, Ltd., trade name) 4.5 parts by mass, polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 0.15 parts by mass, 0.23 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name), 81.82 parts by mass of methyl ethyl ketone, and 2.8 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that the low refractive index layer coating solution was used.

[Example 1-15]
(Preparation of coating solution for low refractive index layer)
In 10.5 parts by mass of the perfluoroolefin copolymer solution (solid content concentration 30%) prepared in Example 1-10, a silica fine particle MEK dispersion (MEK-ST, average particle size 30 nm, solid content concentration 30) was added. %, Manufactured by Nissan Chemical Industries, Ltd., trade name) 4.5 parts by mass, polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 0.15 parts by mass, Photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 0.23 parts by mass, 1.5 parts by mass of the organosilane compound A solution prepared in Example 1-3, and methyl ethyl ketone 80 .32 parts by mass and 2.8 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that the low refractive index layer coating solution was used.

[Example 1-16]
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-15, except that the high refractive index layer produced in Example 1-8 was used.

[Example 1-17]
(Preparation of coating solution for low refractive index layer)
In 10.5 parts by mass of the perfluoroolefin copolymer solution (solid concentration 30%) prepared in Example 1-10, hollow silica fine particle MEK dispersion (refractive index 1.31, average particle size 60 nm, Solid content concentration 20%) 6.75 parts by mass, polysiloxane compound having acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 0.15 parts by mass, photopolymerization initiator (Irgacure 907) Ciba Specialty Chemicals Co., Ltd., trade name) 0.23 parts by mass, organosilane compound A solution 1.5 parts by mass produced in Example 1-3, methyl ethyl ketone 78.07 parts by mass, cyclohexanone 2 .8 parts by mass was added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that the low refractive index layer coating solution was used.

[Example 1-18]
(Preparation of coating solution for low refractive index layer)
To 13.5 parts by mass of the perfluoroolefin copolymer solution (solid content concentration 30%) prepared in Example 1-10, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku ( Co., Ltd., trade name) 0.45 parts by mass, polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 0.15 parts by mass, photopolymerization initiator (Irgacure 907, Ciba Specialty Chemicals Co., Ltd., trade name) 0.23 parts by mass, 82.87 parts by mass of methyl ethyl ketone, and 2.8 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that the low refractive index layer coating solution was used.

[Example 1-19]
(Preparation of coating solution for low refractive index layer)
To 5.25 parts by mass of the perfluoroolefin copolymer solution (solid content concentration 30%) prepared in Example 1-10, a hollow silica fine particle MEK dispersion (refractive index 1.31, average particle size 60 nm, (Solid content concentration 20%) 6.75 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd., trade name) 1.575 parts by mass, poly having acryloyl group Siloxane compound (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 0.15 parts by mass, photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 0.23 Parts by mass, 1.5 parts by mass of the organosilane compound A solution prepared in Example 1-3, 81.745 parts by mass of methyl ethyl ketone, Hexanone 2.8 parts by weight was added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that the low refractive index layer coating solution was used.

[Example 1-20]
(Preparation of coating solution for low refractive index layer)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd., trade name) 4.5 parts by mass, polysiloxane compound having acryloyl group (X-22-164C, Shin-Etsu Chemical Co., Ltd.) (Trade name) 0.15 parts by mass, photopolymerization initiator (Irgacure 907, Ciba Specialty Chemicals Co., Ltd., trade name) 0.23 parts by mass, and methyl ethyl ketone 92.32 parts by mass, 2.8 parts by mass of cyclohexanone was added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that the low refractive index layer coating solution was used.

[Example 1-21]
(Preparation of coating solution for low refractive index layer)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd., trade name) 2.25 parts by mass, MEK dispersion of hollow silica fine particles (refractive index 1.31, average particle size) (Diameter 60 nm, solid content concentration 20%) 11.25 parts by mass, polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 0.15 parts by mass, photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 0.23 parts by mass, 83.32 parts by mass of methyl ethyl ketone, and 2.8 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that the low refractive index layer coating solution was used.

[Example 1-22]
(Preparation of coating solution for low refractive index layer)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd., trade name) 2.25 parts by mass, MEK dispersion of hollow silica fine particles (refractive index 1.31, average particle size) (Diameter 60 nm, solid content concentration 20%) 11.25 parts by mass, polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 0.15 parts by mass, photopolymerization initiator (Irgacure 907, Ciba Specialty Chemicals Co., Ltd., trade name) 0.23 parts by mass, 1.5 parts by mass of the organosilane compound A solution prepared in Example 1-3, and 81.82 parts by mass of methyl ethyl ketone Then, 2.8 parts by mass of cyclohexanone was added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that the low refractive index layer coating solution was used.

[Example 1-23]
(Preparation of coating solution for low refractive index layer)
15.5 parts by mass of the organosilane compound A solution prepared in Example 1-3, polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 0.15 parts by mass, 0.23 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name), 81.32 parts by mass of methyl ethyl ketone, and 2.8 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of antireflection film)
An antireflection film was produced in exactly the same manner as in Example 1-10, except that the low refractive index layer coating solution was used.

[Example 1-24]
(Preparation of coating solution for low refractive index layer)
To a mixed solvent of isopropyl alcohol / methyl ethyl ketone = 1/1 (mass ratio), 1 mol of tetramethoxysilane and 2 mol of 0.1 mol / L hydrochloric acid were added. A hydrolysis reaction was performed by stirring at room temperature for 2 hours to prepare a tetramethoxysilane hydrolyzate solution.
Isopropyl alcohol / methyl ethyl ketone = 1/1 (mass ratio), tetramethoxysilane hydrolyzate 9.0 parts by mass, pentaerythritol triacrylate 1.0 part by mass, polymerization initiator (Irgacure 907, Ciba Specialty Chemicals ( Co., Ltd., product name) 0.5 parts by mass, and the solid content concentration was added to 4.5% by mass and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the low refractive index layer.
(Preparation of coating solution for antifouling layer)
A commercially available fluorine-containing compound-containing coating (DSX, solid content concentration 0.1%, trade name, manufactured by Daikin Industries, Ltd.) was used.

(Preparation of antireflection film)
On the high refractive index layer produced in Example 1-8, the above-mentioned coating liquid for low refractive index layer was applied by the microgravure coating method under the condition of a conveyance speed of 15 m / min.
After drying at 120 ° C. for 150 seconds and further heating at 140 ° C. for 10 minutes, a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) is used while purging with nitrogen (oxygen concentration 0.1% or less) Then, an ultraviolet ray having an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² is irradiated, and further, the coating layer is cured by heating at 120 ° C. for 24 hours to form a low refractive index layer (refractive index 1.47, film thickness 83 nm). ) Was produced.
On the low refractive index layer, the antifouling layer coating solution was applied by a microgravure coating method so that the coating amount of the fluorine-containing compound was 4 mg / m ^{2 under} the condition of a conveyance speed of 15 m / min. An antifouling layer (outermost layer) was produced by heating at 120 ° C. for 1 hour. In this way, an antireflection film was produced.
[Comparative Example 1-E]
(Preparation of antireflection film)
In the high refractive index layer of Example 1-8, titanium dioxide fine particles not containing cobalt (Co) (TTO-55N, manufactured by Ishihara Sangyo Co., Ltd., trade name) were used instead of the conductive titanium dioxide fine particles. A high refractive index layer was produced.
A low refractive index layer (refractive index: 1.47, film thickness: 85 nm) was produced on the high refractive index layer in the same manner as in Example 1-24. In this way, an antireflection film was produced.

[Example 1-25]
(Preparation of coating solution for antifouling layer)
A commercially available fluorine-containing compound-containing coating (DSX, solid content concentration 0.1%, trade name, manufactured by Daikin Industries, Ltd.) was used.
(Preparation of antireflection film)
On the high refractive index layer prepared in Example 1-8, a low refractive index layer (refractive index: 1.47, film thickness: 83 nm) made of SiO ₂ was formed using a known sputtering method.
The antifouling layer coating solution was applied on the low refractive index layer by a microgravure coating method so that the coating amount of the fluorine-containing compound was 4 mg / m ^{2 under} the condition of a conveyance speed of 15 m / min. An antifouling layer (outermost layer) was produced by heating at 120 ° C. for 1 hour. In this way, an antireflection film was produced.

(Evaluation of antireflection film)
In the produced antireflection film (Examples 1-1 to 1-25, Comparative Examples 1-A to 1-E), a spectrophotometer (V-550, ARV-474, trade name, manufactured by JASCO Corporation) Was used to measure the spectral reflectance at an incident angle of 5 ° in the wavelength region of 380 to 780 nm, and the average reflectance in the wavelength range of 450 to 650 nm was determined. The average reflectance of all the antireflection films was 1. The average reflectance of the glass plate was about 4%, and the average reflectance of the triacetyl cellulose film (TD80U) was about 4%.
About the antireflection film produced above (Examples 1-1 to 1-25, Comparative Examples 1-A to 1-E), the following items were evaluated. The results are shown in Table 1.

(1) Evaluation of weather resistance Using a weather resistance tester (Super Xenon SX-75, trade name, manufactured by Suga Test Instruments Co., Ltd.), a weather resistance test was performed in an atmosphere at a temperature of 63 ° C. and a relative humidity of 50%. went.
The antireflection film after exposure was conditioned for 2 hours under conditions of a temperature of 25 ° C. and a relative humidity of 60%.

On the surface of the antireflective film on the side having the high refractive index layer, 11 squares and 11 horizontal cuts are made in a grid pattern with a cutter knife to make a total of 100 square squares. The adhesion test using a polyester adhesive tape (NO. 31B, trade name) was repeated twice at the same place. The presence or absence of peeling of the coating film was visually observed and evaluated in the following four stages.
A: No peeling was observed at 100 mm. ○: No peeling was observed at 100 mm within 2 mm. Δ: 10-100 mm was observed at 100 mm. Thing that has been peeled off at 100 mm exceeds 10 mm

(2) Evaluation of surface resistance In the antireflection film, the side having the low refractive index layer after coating the surface of the high refractive index layer before coating the low refractive index layer and the low refractive index layer (outermost layer) The surface resistance was measured using a super insulation resistance / microammeter TR8601 (trade name, manufactured by Advantest Co., Ltd.) at 25 ° C. and a relative humidity of 60%.

(3) Evaluation of dust resistance An antireflection film was attached to the monitor, and dust (cloth waste from clothes) was sprinkled on the monitor surface. The dust was wiped off with a cleaning cloth, the dust removal property was examined, and the following four grades were evaluated.
◎: Dust completely removed ○: Dust remains very slightly △: Dust remains slightly ×: Dust remains considerably

(4) Evaluation of dynamic friction coefficient The dynamic friction coefficient was evaluated as an index of the slipperiness of the surface of the antireflection film having the low refractive index layer (outermost layer). The dynamic friction coefficient was adjusted for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60% with a dynamic friction measuring machine (HEIDON-14, trade name, manufactured by Shinto Kagaku Co., Ltd.). Used, measured at a load of 0.98 N and a speed of 60 cm / min.

(5) Evaluation of scratch resistance On the surface of the antireflection film having the low refractive index layer (outermost layer), a rubbing test using steel wool was performed using a rubbing tester.
Steel wool (made by Nippon Steel Wool Co., Ltd., grade No. 0000) was used as the scraping material, moving distance (one way) 13 cm, rubbing speed 13 cm / sec, load 1.96 N / cm ² , tip contact area: 1 cm × The test was performed under the conditions of 1 cm and the number of times of rubbing 2 times. The scratches on the surface were visually observed and evaluated according to the following four levels.
A: Even if you look carefully, no scratches are visible.
○: If you look carefully, you can see slightly weak scratches.
Δ: Weak scratches are visible.
×: A conspicuous scratch can be seen at a glance.

(6) Evaluation of contact angle The antireflection film was conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. The contact angle of water on the surface of the antireflection film having the low refractive index layer (outermost layer) was evaluated.

(7) Evaluation of antifouling property A fingerprint mark is attached to the surface of the antireflective film having the low refractive index layer (outermost layer), and the state when it is wiped off with a cleaning cloth is observed. Evaluation was made in the following four stages.
◎: Fingerprint traces were wiped completely by light wiping ○: Fingerprint traces were wiped completely when wiped strongly △: Fingerprint traces were wiped away, but some remained unwieldy ×: Fingerprint traces Most of them remain without being wiped off.

(8) Evaluation of chemical resistance An oil-based magic (ZEBRA Mackie (trade name), red) was attached to the surface of the antireflection film having the low refractive index layer (outermost layer), and then wiped off with a cleaning cloth. The state of time was observed and evaluated according to the following four levels.
◎: Magic can be wiped completely by lightly wiping ○: Magic can be wiped completely by wiping strongly Most of what remained without being wiped off

As is clear from the results in Table 1, all of Comparative Examples 1-A to 1-E using titanium dioxide fine particles having no electrical conductivity had large surface resistance and poor dust resistance. Among them, Comparative Examples 1-A, 1-C, and 1-E not containing cobalt had very poor weather resistance.
On the other hand, all of Examples 1-1 to 1-25 using an antireflection film having a high refractive index film containing conductive titanium dioxide fine particles containing cobalt according to the present invention are weatherproof and dustproof. Excellent scratch resistance, antifouling properties, and chemical resistance.
Furthermore, the same result was obtained even when the triacetylcellulose film of the transparent support was changed to a polyethylene terephthalate film.

[Example 2]
The following conductive titanium dioxide fine particles (a) to (i) were produced and evaluated in the same manner as in Examples 1-1 to 1-25. As a result, the same results were obtained. It was.

(Conductive titanium dioxide fine particles (a))
The titanium dioxide fine particles containing cobalt (Co) were prepared with reference to a known method (Example of Japanese Patent Laid-Open No. 2003-327430), and further, a known method (Example of Japanese Patent Laid-Open No. Hei 6-279618) was prepared. ), The surface of the titanium dioxide fine particles was coated with antimony-doped tin oxide (ATO) to produce conductive titanium dioxide fine particles (a) (specific surface area 40 m ² / g).
In the conductive titanium dioxide fine particles (a), Co was present inside the titanium dioxide fine particles, and the mass ratio of Ti / Co was 96.2 / 3.8. The conductive titanium dioxide fine particles (a) contain a very small amount of Al (mass ratio Ti / Al = 100/1) in the production process of the titanium dioxide fine particles.
The mass ratio of ATO to the mass of titanium dioxide fine particles containing cobalt (Co) was 90/10. The powder resistance of the conductive titanium dioxide fine particles (a) was 50 Ω · cm. The powder resistance (Ω · cm) was evaluated in the same manner as in Example 1-1.

(Conductive titanium dioxide fine particles (b))
The titanium dioxide fine particles containing cobalt (Co) were prepared with reference to a known method (Example of Japanese Patent Laid-Open No. 2003-327430), and further, a known method (Example of Japanese Patent Laid-Open No. Hei 6-279618) was prepared. ), The surface of the titanium dioxide fine particles was coated with tin-doped indium oxide (ITO) to produce conductive titanium dioxide fine particles (b) (specific surface area 42 m ² / g). In the conductive titanium dioxide fine particles (b), Co was present inside the titanium dioxide fine particles, and the mass ratio of Ti / Co was 95.1 / 4.9. The conductive titanium dioxide fine particles (b) contain a very small amount of Al (mass ratio of Ti / Al = 100/1) in the production process of the titanium dioxide fine particles.
The mass ratio of ITO to the mass of titanium dioxide fine particles containing cobalt (Co) was 90/10. The powder resistance of the conductive titanium dioxide fine particles (b) was 5 Ω · cm. The powder resistance was evaluated in the same manner as in Example 1-1.

(Conductive titanium dioxide fine particles (c))
The titanium dioxide fine particles containing cobalt (Co) were prepared with reference to a known method (Example of Japanese Patent Laid-Open No. 2003-327430), and further, a known method (Example of Japanese Patent Laid-Open No. Hei 6-279618) was prepared. ), The surface of the titanium dioxide fine particles was coated with aluminum-doped zinc oxide (AZO) to produce conductive titanium dioxide fine particles (c) (specific surface area 41 m ² / g). In the conductive titanium dioxide fine particles (c), Co was present inside the titanium dioxide fine particles, and the mass ratio of Ti / Co was 96.5 / 3.5. In addition, the conductive titanium dioxide fine particles (c) contain a small amount of Al (Ti / Al = 100/1 in mass ratio) in the particles in the production process of the titanium dioxide fine particles.

  The mass ratio of AZO to the mass of titanium dioxide fine particles containing cobalt (Co) was 90/10. The powder resistance of the conductive titanium dioxide fine particles (c) was 600 Ω · cm. The powder resistance was evaluated in the same manner as in Example 1-1.

(Conductive titanium dioxide fine particles (d))
The surface of the conductive titanium dioxide fine particles (a) is further covered with an aluminum compound (mixture of aluminum hydroxide and aluminum oxide) with reference to a known method (Example of JP-A-6-49388). Conductive titanium dioxide fine particles (d) (specific surface area 42 m ² / g) were prepared. The mass ratio of Ti / Al was 95.5 / 4.5. The powder resistance of the conductive titanium dioxide fine particles (d) was 90 Ω · cm.

(Conductive titanium dioxide fine particles (e))
The surface of the conductive titanium dioxide fine particles (a) is further treated with a silicon compound (a mixture of silicon dioxide and its hydroxide) with reference to a known method (Example of JP-A-6-49388). The coated conductive titanium dioxide fine particles (e) (specific surface area 45 m ² / g) were prepared. The mass ratio of Ti / Si was 96.0 / 4.0. The powder resistance of the conductive titanium dioxide fine particles (e) was 120 Ω · cm.

(Conductive titanium dioxide fine particles (f))
The surface of the conductive titanium dioxide fine particles (a) is referred to a known method (Example of JP-A-2001-26423), and a silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) Surface treatment with a product name) produced conductive fine titanium dioxide particles (f). The silane coupling agent was used in an amount of 5% by mass based on the conductive titanium dioxide fine particles (a). The powder resistance of the conductive titanium dioxide fine particles (f) was 60 Ω · cm.

(Conductive titanium dioxide fine particles (g))
The surface of the conductive titanium dioxide fine particles (a) is surface-treated with stearic acid with reference to a known method (Examples of JP-A-2001-106939) to form conductive titanium dioxide fine particles (g). Was made. Stearic acid was used in an amount of 5% by mass based on the conductive titanium dioxide fine particles (a). The powder resistance of the conductive titanium dioxide fine particles (g) was 100 Ω · cm.

(Conductive titanium dioxide fine particles (h))
Except for adjusting the mass ratio of Ti / Co to 92.0 / 8.0, the conductive titanium dioxide fine particles (h) (specific surface area 41 m ² / g) were the same as the conductive titanium dioxide fine particles (a). ) Was produced. The powder resistance of the conductive titanium dioxide fine particles (h) was 45 Ω · cm.

(Conductive titanium dioxide fine particles (i))
The surface of the conductive titanium dioxide fine particles (h) was further treated in the same manner as in Example 1-1, and an aluminum compound (a mixture of aluminum hydroxide and aluminum oxide) and a zirconium compound (zirconium hydroxide and zirconium oxide). Conductive titanium dioxide fine particles (i) (specific surface area 42 m ² / g) coated with a mixture were prepared. The powder resistance of the conductive titanium dioxide fine particles (i) was 110 Ω · cm.

[Example 3]
In Examples 1-1 to 1-25 and Example 2, the following dispersant was used as the conductive titanium dioxide fine particles and / or the titanium dioxide dispersant, and the other examples were used in the same manner to prevent reflection. As a result of producing and evaluating films, the same results as in Examples 1-1 to 1-25 and Example 2 were obtained.
In addition, the antireflection film that did not use the dispersant in the dispersion of the conductive titanium dioxide fine particles had a slightly cloudy antireflection film and a slightly higher reflectance than the antireflection film using the dispersant.

(Dispersant 2)

(Dispersant 3)
_{CH 2 = CHCOO- (CH 2 CH} 2 COO) -H: CH 2 = CHCOO- (CH 2 CH 2 COO) 2 -H: CH 2 = CHCOOCH 2 CH 2 N (CH 3) 2
= 9: 6: 1 (mass ratio)

(Dispersant 4)

(Dispersant 5)

(Dispersant 6)

(Dispersant 7)
Ajisper PA111 (Ajinomoto Fine Techno Co., Ltd., trade name)

[Example 4-1]
(Preparation of coating solution for hard coat layer)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd., trade name) 55.0 parts by mass, a polymerization initiator (Irgacure 907, Ciba Specialty Chemicals Co., Ltd.) , Trade name) 2.0 parts by weight, organosilane compound (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 5.0 parts by weight, methyl isobutyl ketone 30.0 parts by weight, methyl ethyl ketone 8.0 parts by weight Was added and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.53.

Furthermore, 7.4 parts by mass of a methyl isobutyl ketone dispersion (solid content concentration 30%) of crosslinked polystyrene particles (refractive index 1.61) having an average particle diameter of 3 μm dispersed in this solution at 10,000 rpm with a polytron disperser, and polytron 15.0 parts by mass of a methyl isobutyl ketone dispersion (solid content concentration 30%) of crosslinked polystyrene particles having an average particle diameter of 1.5 μm (refractive index 1.61) dispersed at 10,000 rpm with a disperser was added and stirred.
The S value of crosslinked polystyrene particles having an average particle diameter of 3 μm was 0.5, and the S value of crosslinked polystyrene particles having an average particle diameter of 1.5 μm was 1.5.
A hard coat layer coating solution was prepared by filtering through a polypropylene filter having a pore size of 30 μm.

(Preparation of antireflection film)
A coating liquid for hard coat layer is applied on a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd., trade name) having a film thickness of 80 μm and a width of 1340 mm using a microgravure coating method and a transport speed of 20 m / min. It was applied with. After drying at 100 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration: 1.0%), the illumination intensity is 300 mW / cm ² The coating layer was cured by irradiating with 100 mJ / cm ² of ultraviolet rays to prepare a hard coat layer having a thickness of 4 μm.
On the hard coat layer, a medium refractive index layer, a high refractive index layer, a low refractive index layer, and an antifouling layer were produced in the same manner as in Examples 1-1 to 1-25, Example 2 and Example 3. did. In this way, an antireflection film was produced.

[Example 4-2]
(Preparation of coating solution for hard coat layer)
Transparent high refractive index hard coat material containing fine zirconium oxide particles (Desolite Z7404 (trade name), manufactured by JSR Corporation; solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (based on solid content), oxidation Average particle diameter of zirconium fine particles: about 20 nm, solvent composition: MIBK / MEK = 9/1) 60.0 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) Manufactured, trade name) 17.9 parts by mass, organosilane compound (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 5.89 parts by mass, methyl isobutyl ketone 12.6 parts by mass, methyl ethyl ketone 3.61 parts by mass Part was added and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.
Further, 7.4 parts by mass of a methyl isobutyl ketone dispersion (solid content concentration 30%) of crosslinked PMMA particles (refractive index 1.49) having an average particle size of 3.0 μm dispersed in this solution at 10,000 rpm with a polytron disperser, polytron 18.9 parts by mass of a methyl ethyl ketone dispersion (solid content concentration 30%) of silica particles (refractive index 1.46) having an average particle diameter of 1.5 μm dispersed at 10,000 rpm with a disperser was added and stirred.
A hard coat layer coating solution was prepared by filtering through a polypropylene filter having a pore size of 30 μm.
The S value of crosslinked PMMA particles having an average particle diameter of 3 μm was 0.6, and the S value of silica particles having an average particle diameter of 1.5 μm was 1.2.

(Preparation of antireflection film)
A coating liquid for hard coat layer is applied on a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd., trade name) having a film thickness of 80 μm and a width of 1340 mm using a microgravure coating method and a transport speed of 20 m / min. It was applied with. After drying at 100 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration: 1.0%), the illumination intensity is 300 mW / cm ² The coating layer was cured by irradiating with 100 mJ / cm ² of ultraviolet rays to prepare a hard coat layer having a thickness of 4 μm.
On the hard coat layer, a medium refractive index layer, a high refractive index layer, a low refractive index layer, and an antifouling layer were produced in the same manner as in Examples 1-1 to 1-25, Example 2 and Example 3. did. In this way, an antireflection film was produced.

(Evaluation of antireflection film)
The antireflection films produced in Examples 4-1 and 4-2 were evaluated in the same manner as in Example 1-1. As a result, the results were completely the same as in Examples 1-1 to 1-25, Example 2, and Example 3. Similar results were obtained.

[Example 5-1]
(Preparation of antireflection film)
In the antireflection films produced in Examples 1-1 to 1-25, Example 2, Example 3, and Examples 4-1 to 4-2, the method described in JP 2000-329905 A was used. Then, embossing was carried out to produce an antireflection film having antiglare properties.
The average surface roughness (Ra) on the side having the low refractive index layer (outermost layer) was evaluated using an atomic force microscope (AFM) and found to be 0.10.

[Example 5-2]
(Preparation of coating solution for hard coat layer)
50.0 parts by mass of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PET-30, manufactured by Nippon Kayaku Co., Ltd., trade name), a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) , Trade name) 2.0 parts by mass, organosilane compound (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 10.0 parts by mass and toluene 38.0 parts by mass were added and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.53.
Furthermore, 1.7 parts by mass of a toluene dispersion (solid concentration 30%) of crosslinked polystyrene particles (refractive index 1.61) having an average particle size of 3.5 μm dispersed at 10,000 rpm in a polytron disperser, and polytron 13.3 parts by mass of a toluene dispersion (solid content concentration 30%) of crosslinked acrylic-styrene particles (refractive index 1.55) having an average particle size of 3.5 μm dispersed at 10,000 rpm in a disperser was added and stirred.

The S value of crosslinked polystyrene particles having an average particle size of 3.5 μm is 0.4, and the S value of crosslinked acrylic-styrene particles having an average particle size of 3.5 μm (refractive index of 1.55) is 0.5. Met.
The solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for an antiglare hard coat layer.

(Preparation of antireflection film)
An anti-glare hard coat layer coating solution is applied on a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd., trade name) having a thickness of 80 μm and a width of 1340 mm by a microgravure coating method, and a conveyance speed of 20 m / min It apply | coated on the conditions of. After drying at 100 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.5%), irradiation intensity 300 mW / cm ² The coating layer was cured by irradiating with 100 mJ / cm ² of ultraviolet rays to prepare a hard coat layer having a thickness of 4 μm and antiglare property.
On the hard coat layer, a medium refractive index layer, a high refractive index layer, a low refractive index layer, and an antifouling layer were produced in the same manner as in Examples 1-1 to 1-25, Example 2 and Example 3. did. In this way, an antireflection film was produced.
When the average surface roughness (Ra) on the side having the low refractive index layer (outermost layer) was evaluated using an atomic force microscope (AFM), it was 0.14.

(Evaluation of antireflection film)
About the antireflection film produced in Example 5-1 and 5-2, as a result of evaluating similarly to Example 1-1, Example 1-1 to 1-25, Example 2, Example 3, and implementation The same results as in Examples 4-1 to 4-2 were obtained. Furthermore, it was excellent in the effect of preventing reflection of external light (antiglare property).

[Example 6]
(Evaluation of image display device)
The antireflective films of the present invention produced in Examples 1-1 to 1-25, Example 2, Example 3, Examples 4-1 to 4-2, and Examples 5-1 to 5-2 are displayed as images. Device (TN, STN, IPS, VA, or OCB mode, transmissive, reflective, or transflective liquid crystal display, plasma display panel (PDP), electroluminescence display (ELD), cathode tube display (CRT)). The image display device using the antireflection film of the present invention was excellent in dust resistance and antireflection performance, and was extremely good in visibility. Moreover, it was excellent in weather resistance, scratch resistance, transparency, and chemical resistance.
In addition, the antireflection films prepared in Examples 4-1 to 4-2 were particularly affected by the light scattering effect of the transmitted light due to the particles of 0.2 μm or more contained in the hard coat layer. The viewing angle was wide and the visibility was excellent.

In addition, the antireflection films produced in Examples 5-1 to 5-2 were improved in the external light reflection prevention property (antiglare property) and excellent in visibility. Furthermore, the antireflection film produced in Example 5-2 has no recess with a cut surface area of 1000 μm ² or more per 1 mm ² surface area, and has a pixel size of 100 ppi (100 pixels / inch). There was no occurrence of glare failure in the image display device (1 inch square having 100 pixels).

[Example 7]
(Preparation of protective film for polarizing plate)
A saponification solution in which a 1.5 N sodium hydroxide aqueous solution was kept at 50 ° C. was prepared. Further, a 0.01N dilute sulfuric acid aqueous solution was prepared.
In the antireflection films prepared in Examples 1-1 to 1-25, Example 2, Example 3, Examples 4-1 to 4-2, and Examples 5-1 to 5-2, the high refraction in the present invention The surface of the transparent support opposite to the side having the rate layer was saponified using the saponification solution.
The aqueous sodium hydroxide solution on the surface of the saponified transparent support is thoroughly washed with water, then washed with the above-mentioned diluted sulfuric acid aqueous solution, and further, the diluted sulfuric acid aqueous solution is thoroughly washed with water and sufficiently dried at 100 ° C. It was.
When the contact angle of the surface of the saponified transparent support on the side opposite to the side having the high refractive index layer of the antireflection film was evaluated, it was 40 degrees or less. In this way, an antireflection film (protective film for polarizing plate) was produced.

(Preparation of polarizing plate)
A polyvinyl alcohol film having a thickness of 75 μm (manufactured by Kuraray Co., Ltd.) was immersed in an aqueous solution consisting of 1000 parts by mass of water, 7 parts by mass of iodine, and 105 parts by mass of potassium iodide to adsorb iodine. Subsequently, this film was uniaxially stretched 4.4 times in the longitudinal direction in a 4% by mass boric acid aqueous solution, and then dried in a tension state to produce a polarizing film.

A saponified triacetyl cellulose surface of the antireflection film of the present invention (protective film for polarizing plate) was bonded to one surface of the polarizing film using a polyvinyl alcohol-based adhesive as an adhesive. Further, a triacetyl cellulose film saponified in the same manner as described above was bonded to the other surface of the polarizing film using the same polyvinyl alcohol-based adhesive.
Furthermore, the protective film for polarizing plates which adjusted the contact angle with respect to the water of the surface on the side bonded with a polarizing film to 41-45 degrees was shortened similarly, and the saponification time was similarly produced. Although the adhesiveness was slightly inferior to that in the case where the contact angle with water on the surface of the saponified transparent support was 40 degrees or less, there was no problem in practicality.

(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmission type, reflection type, or semi-transmission type liquid crystal display device equipped with the polarizing plate of the present invention thus manufactured is dustproof and antireflection. Excellent performance and very good visibility. Moreover, it was excellent in weather resistance, scratch resistance, transparency, and chemical resistance.
In addition, the polarizing plate having the antireflection film prepared in Examples 4-1 to 4-2 has a light scattering effect of transmitted light due to particles of 0.2 μm or more contained in the hard coat layer, and particularly, up, down, left, and right. The viewing angle was wide and the visibility was excellent.
Moreover, the polarizing plate which has the antireflection film produced in Examples 5-1 to 5-2 was improved in the external light reflection prevention property (antiglare property) and excellent in visibility. Furthermore, the polarizing plate having the antireflection film produced in Example 5-2 does not have a recess having a cut surface area of 1000 μm ² or more per 1 mm ² area of the surface, and has a pixel size of 100 ppi ( There was no occurrence of glare failure in the liquid crystal display device (100 pixels / inch: 100 pixels in 1 inch square).
In addition, the same result was obtained also in the polarizing plate produced like the above using the various well-known polarizing film.

[Example 8]
(Preparation of polarizing plate)
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 of the discotic structural unit and the transparent support surface changes with the distance from the transparent support. In the optical compensation film having an optical compensation layer (wide view film SA-12B, manufactured by Fuji Photo Film Co., Ltd., trade name), the surface opposite to the side having the optical compensation layer is subjected to the same conditions as in Example 7. Saponification treatment was performed.
The polarizing film produced in Example 7 was saponified with the antireflection film (protective film for polarizing plate) produced in Example 7 on one surface of the polarizing film using a polyvinyl alcohol-based adhesive as an adhesive. The triacetyl cellulose surface was bonded. Further, the triacetyl cellulose surface of the saponified optical compensation film was bonded to the other surface of the polarizing film using the same polyvinyl alcohol adhesive.

(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmissive, reflective, or transflective liquid crystal display device equipped with the polarizing plate of the present invention thus fabricated does not use an optical compensation film. Excellent contrast in a bright room than a liquid crystal display equipped with a polarizing plate, very wide viewing angles in the top, bottom, left and right, and dust, antireflection, weather resistance, scratch resistance, transparency and antifouling properties It was excellent.
In particular, the polarizing plate having the antireflection film prepared in Examples 4-1 to 4-2 has a particularly low visual field due to the light scattering effect of transmitted light by the particles of 0.2 μm or more contained in the hard coat layer. The corners spread remarkably and the yellowness in the left-right direction was improved.

Moreover, the polarizing plate which has the antireflection film produced in Examples 5-1 to 5-2 was improved in the external light reflection prevention property (antiglare property) and excellent in visibility. Furthermore, the polarizing plate having the antireflection film produced in Example 5-2 has no glare failure in the liquid crystal display device with a pixel size of 100 ppi (100 pixels / inch: 100 pixels in an inch square). It was.
In addition, the same result was obtained also in the polarizing plate produced like the above using the various well-known polarizing film.

[Example 9]
(Evaluation of image display device)
The antireflection films produced in Examples 1-1 to 1-25, Example 2, Example 3, Examples 4-1 to 4-2, and Examples 5-1 to 5-2 were used as organic EL display devices. When mounted, it was excellent in dust resistance and antireflection performance, and was extremely good in visibility. Moreover, it was excellent in weather resistance, scratch resistance, transparency, and chemical resistance.

Further, an antireflection film (protective film for polarizing plate) prepared in Example 7 on one surface of the polarizing film and a polarizing plate having a λ / 4 plate on the other surface were prepared in the same manner as in Example 7. When the above polarizing plate was mounted on an organic EL display device, reflection of light from the glass surface on which the polarizing plate was attached was also cut, and a display device with extremely high visibility was obtained.
Moreover, the polarizing plate which has the antireflection film produced in Examples 5-1 to 5-2 was improved in the external light reflection prevention property (antiglare property) and excellent in visibility. Furthermore, the polarizing plate having the antireflection film prepared in Example 5-2 has a glare failure in the organic EL display device having a pixel size of 100 ppi (100 pixels / inch: 100 pixels in an inch square). There was no.

  In addition, the same result was obtained also in the polarizing plate produced like the above using the various well-known polarizing film.

FIG. 1 is a schematic cross-sectional view schematically showing a layer structure of an antireflection film excellent in antireflection performance. FIG. 2 is a schematic cross-sectional view schematically showing a layer structure of an antireflection film having antiglare performance. 3A and 3B are schematic cross-sectional views schematically showing a preferred embodiment in which the antireflection film is applied to an image display device and a liquid crystal display device, respectively. 4 (c) and 4 (d) are schematic cross-sectional views schematically showing a preferred embodiment in which the antireflection film is applied to a liquid crystal display device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent support 2 Hard-coat layer 3 High refractive index layer 4 Low refractive index layer (outermost layer)
DESCRIPTION OF SYMBOLS 5 Medium refractive index layer 6 Anti-glare layer 7 Particle | grains with an average particle diameter of 0.2-10 micrometers 8 Adhesive layer 9 Protective film of polarizing film 10 Protective film of polarizing film 11 Polarizing film

Claims (40)

  An antireflection film having a high refractive index film containing conductive titanium dioxide fine particles containing cobalt.   The antireflection film according to claim 1, further comprising an outermost layer containing a cured product of a compound having a crosslinked or polymerizable functional group on the high refractive index film.   The antireflection film according to claim 2, wherein the compound having a crosslinkable or polymerizable functional group has a thermosetting functional group as the crosslinkable or polymerizable functional group.   The antireflection film according to claim 2, wherein the compound having a crosslinkable or polymerizable functional group has an ionizing radiation curable functional group as the crosslinkable or polymerizable functional group.   The antireflection film according to any one of claims 1 to 4, wherein the cured product contained in the outermost layer contains an organic compound.   The antireflection film according to claim 1, wherein the outermost layer contains a fluorine-containing compound.   The fluorine-containing compound contained in the outermost layer contains a copolymer composed of a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in a side chain. The antireflection film as described. The antireflection film according to claim 7, wherein the copolymer is represented by the following general formula 1.

(In General Formula 1, 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 It may be composed of a single component or a plurality of components, x, y, and z represent the mol% of each component, and 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. (Represents the value to satisfy.) The antireflection film according to claim 1, wherein the outermost layer contains a polysiloxane compound represented by the following general formula (A) and / or a derivative thereof.
Formula (A)

In general formula (A), R ^{1 to} R ⁴ each independently represent a substituent having 1 to 20 carbon atoms, and when there are a plurality of each group, they may be the same or different from each other, R ¹ , R ³ and R ⁴ represent a cross-linkable or polymerizable functional group. p represents an integer satisfying 1 ≦ p ≦ 4. q represents an integer satisfying 10 ≦ q ≦ 500, r represents an integer satisfying 0 ≦ r ≦ 500, and may be a random copolymer or a block copolymer.   The antireflection film according to claim 1, wherein the outermost layer contains fine particles.   The antireflection film according to claim 10, wherein at least one kind of fine particles contained in the outermost layer is hollow fine particles.   12. The conductive titanium dioxide fine particles containing cobalt are conductive titanium dioxide fine particles containing cobalt in which the surface of the titanium dioxide fine particles is coated with a conductive material. The antireflection film according to any one of the above.   The conductive titanium dioxide fine particles containing cobalt are conductive titanium dioxide fine particles containing cobalt coated with at least one kind of compound that reduces or eliminates the photocatalytic activity. The antireflection film according to any one of 1 to 12.   The antireflection film according to claim 13, wherein the compound that reduces or eliminates the photocatalytic activity is an inorganic compound containing at least one element selected from cobalt, aluminum, zirconium, and silicon. The antireflection film according to claim 1, wherein a powder resistance of the conductive titanium dioxide fine particles containing cobalt is 1 × 10 ⁵ Ω · cm or less.   The antireflection film according to claim 1, wherein the conductive titanium dioxide fine particles containing cobalt are dispersed using a dispersant.   The antireflection film according to claim 16, wherein the dispersant has an anionic group.   18. The antireflection film according to claim 16, wherein the dispersant has a crosslinkable or polymerizable functional group.   The antireflective film according to claim 1, wherein a refractive index of the high refractive index film is 1.55 to 2.40. The antireflection film according to claim 1, wherein the high refractive index film has a surface resistance of 1 × 10 ¹⁴ Ω / □ or less.   21. The intermediate refractive index film having a refractive index between the refractive index of the outermost layer and the refractive index of the high refractive index film is provided under the high refractive index film. Antireflection film. The antireflection film according to claim 1, wherein the surface resistance is 1 × 10 ¹⁴ Ω / □ or less. The antireflection film according to claim 1, wherein the surface resistance is 1 × 10 ¹² Ω / □ or less.   24. The antireflection film according to claim 1, wherein the surface has a dynamic friction coefficient of 0.25 or less.   The antireflection film according to any one of claims 1 to 24, wherein a contact angle of water on the surface is 90 ° or more.   The manufacturing method of the anti-reflective film in any one of Claims 1-25.   An antireflection film comprising the antireflection film according to any one of claims 1 to 25 on a transparent support. 28. The antireflection film according to claim 27, wherein any layer on the transparent support contains an organosilane compound represented by the following general formula (a) and / or a derivative thereof.
Formula (a) (R ¹⁰ ) _s -Si (Z) _4-s
In general formula (a), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z represents a hydroxyl group or a hydrolyzable group. s represents an integer of 1 to 3.   29. The antireflection film according to claim 27 or 28, further comprising a layer containing inorganic fine particles having an average particle diameter of 1 to 200 nm between the transparent support and the outermost layer.   30. The antireflection film according to claim 27, comprising a layer containing particles having an average particle diameter of 0.2 to 10 [mu] m.   31. The antireflection film according to claim 27, wherein concaves and convexes are formed on the surface having the high refractive index film and have antiglare properties.   The manufacturing method of the antireflection film in any one of Claims 27-31.   An antireflection film obtained by saponifying the antireflection film according to any one of claims 27 to 31.   32. A method for producing an antireflection film, comprising saponifying the antireflection film according to any one of claims 27 to 31.   A polarizing plate having a polarizing film and a protective film, wherein the antireflection film according to claim 27 is used as at least one of the protective films.   It is a polarizing plate which has a polarizing film and a protective film, Comprising: It has the antireflection film in any one of Claims 27-31 and 33 in one of the two protective films of a polarizing film, and the other protective film A polarizing plate comprising an optical compensation film having an optically anisotropic layer.   The optical compensation film has an optically anisotropic layer made of a compound having a discotic structural unit, the disc surface of the discotic structural unit is inclined with respect to the film surface, and the disc surface of the discotic structural unit 37. The polarizing plate according to claim 36, wherein an angle formed by the film surface changes in the depth direction of the optically anisotropic layer.   34. An image display device, wherein the antireflection film according to claim 27 is disposed on an image display surface.   38. An image display device, wherein the polarizing plate according to claim 35 is disposed on an image display surface.   40. The image display device according to claim 38 or 39, wherein the image display device is a TN, STN, IPS, VA, or OCB mode transmissive, reflective, or transflective liquid crystal display device.

Images