JP2007177192A - Transparent film and its production process, polarizing plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent film having a hard coat layer satisfying both sufficient abrasion resistance and fragility and a transparent film having improved abrasion resistance while maintaining a sufficient antireflection property, and a process for production of such a transparent film. <P>SOLUTION: The transparent film has at least a hard coat layer on a transparent support in which the hard coat layer is produced by spreading a coating composition containing an ionizing radiation curing compound and at least one active halogen compound on the transparent support and drying, followed by curing by irradiation with an ionizing radiation. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a transparent film having excellent scratch resistance and brittleness, a transparent film having a sufficient antireflection ability and further improved scratch resistance, and a method for producing the same. Furthermore, the present invention relates to a polarizing plate and an image display device using the transparent film.

  In a display device such as a cathode ray tube display (CRT), plasma display (PDP), electroluminescence display (ELD) or liquid crystal display (LCD), a layer called a transparent hard coat layer is provided on a transparent support. In most cases, the film is attached to the display image surface. In general, the hard coat layer is a layer obtained by blending a liquid containing a monomer having a polyfunctional group with a photopolymerization initiator, coating and drying, and then curing by irradiation with ionizing radiation such as UV light. In recent years, a transparent film having an antiglare property and a transparent film having an antireflection function are often used in order to prevent reflection of a background of a display image and improve visibility.

In general, an antiglare film is a film in which irregularities are intentionally formed on the film surface (often the hard coat layer surface) in order to diffusely reflect external light, and has a reflection preventing function. In this method, a thin film having a lower refractive index is provided on the surface of the hard coat layer in order to prevent contrast reduction and image reflection due to reflection, and the reflectivity is reduced using the principle of optical interference. Transparent films having both antiglare and antireflection functions are also on the market.
Since such a transparent film is disposed on the outermost surface of the display, the user may rub the front surface of the image display with a cleaning tool or the like, and is easily damaged. Therefore, increasing the film strength of the hard coat layer and increasing the thickness of the hard coat layer are important from the viewpoint of scratch resistance.
However, the hard coat layer designed in this way is insufficiently flexible and poor in brittleness, and may be cracked when bent during the handling process of the transparent film, making it difficult to achieve both scratch resistance and brittleness. Met.

  On the other hand, active halogen compounds are known as one of photopolymerization initiators, and are disclosed in, for example, Patent Documents 1 and 2. However, these patents are patents limited to color filter applications and do not mention formation of the hard coat layer as described above.

  On the other hand, in general, the antireflection film is disposed on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference in order to prevent contrast reduction and image reflection due to reflection. For this reason, the establishment of scratches is high, and imparting excellent abrasion resistance was an important issue.

  Such an antireflection film generally has a low-refractive index layer having an appropriate thickness on the outermost surface, and optionally a high-refractive index layer, a medium-refractive index layer, and a hard coat between the support (base material). It can be produced by forming a layer or the like. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer. Further, since the antireflection film is used on the outermost surface of the display, high scratch resistance is required. In order to realize high scratch resistance in a thin film having a thickness of around 100 nm, the strength of the coating itself and the adhesion to the lower layer are required.

  In order to lower the refractive index of the material, there are means of introducing fluorine atoms and lowering the density (introducing voids), but both are in the direction that the film strength and adhesion are impaired and the scratch resistance is lowered, and low Reconciling refractive index and high scratch resistance has been a difficult task.

  Patent Documents 3 to 5 describe means for improving the scratch resistance by reducing the coefficient of friction on the coating surface by introducing a polysiloxane structure into the fluorine-containing polymer. Although this means is effective to some extent for improving scratch resistance, sufficient scratch resistance cannot be obtained only by this method for a film having an insufficient film strength and interfacial adhesion.

On the other hand, Patent Document 6 describes that the hardness is increased by curing a photocurable resin at a low oxygen concentration. However, in order to efficiently produce an antireflection film with a web, there is a limit to the concentration at which nitrogen can be replaced, and satisfactory hardness cannot be obtained.
Patent Documents 7 to 12 describe specific means for substituting nitrogen. However, in order to reduce the oxygen concentration until the thin film such as the low refractive index layer is sufficiently cured, a large amount of nitrogen is used. There is a problem that the manufacturing cost increases.
Patent Document 13 describes a method of irradiating ionizing radiation by wrapping around the surface of a hot roll. It was enough.

Further, Patent Document 14 describes novel compounds for avoiding that conventional active halogen compounds are sublimable or offensive odor. These novel compounds are combined with an alkali-soluble binder in a photoresist system. It was what was used.
Japanese Patent Laid-Open No. 7-311462 JP 9-179299 A JP-A-11-189621 Japanese Patent Laid-Open No. 11-228631 JP 2000-313709 A JP 2002-156508 A JP 11-268240 A Japanese Patent Laid-Open No. 60-90762 JP 59-112870 JP-A-4-301456 Japanese Patent Laid-Open No. 3-67697 JP 2003-300215 A Japanese Patent Publication No. 7-51641 JP-A-55-77742

An object of the present invention is to provide a transparent film having a hard coat layer having both sufficient scratch resistance and brittleness, and a transparent film having improved scratch resistance while having sufficient antireflection performance. Another object of the present invention is to provide a method for producing such a transparent film.
Another object of the present invention is to provide a polarizing plate and an image display device provided with the transparent film.

As a result of intensive studies, the present inventor has found that when an active halogen compound is used as a photopolymerization initiator for forming a hard layer such as a hard coat layer, it is difficult to be inhibited by oxygen in the curing step by ionizing radiation. In addition, it was found that a hard coat layer having a uniform polymerization density, that is, a hard coat layer having good brittleness, adhesion, and scratch resistance can be obtained.
Moreover, it discovered that an active halogen compound was suitable also for low refractive index layer formation.
The above object of the present invention is achieved by the following configuration.

〔一般式１中、Ｌは炭素数１〜１０の連結基を表し、ｍは０または１を表す。Ｘは水素原子またはメチル基を表す。Ａは任意のビニルモノマーの重合単位を表し、単一成分であっても複数の成分で構成されていてもよい。また、シリコーン部位を含んでいても良い。ｘ、ｙ、ｚはそれぞれの構成成分のモル％を表し、３０≦ｘ≦６０、５≦ｙ≦７０、０≦ｚ≦６５を満たす値を表す。但し、ｘ＋ｙ＋ｚ＝１００である。〕 1. A transparent film having at least a hard coat layer on a transparent support, wherein the hard coat layer is coated and dried with a coating composition containing an ionizing radiation curable compound and at least one active halogen compound on the transparent support. A transparent film characterized by being a layer formed by ionizing radiation irradiation.
2. 2. The transparent film as described in 1 above, wherein the ionizing radiation curable compound is a compound having two or more ethylenically unsaturated groups.
3. A transparent film, wherein the coating composition forming the hard coat layer of 1 or 2 further contains translucent particles having an average particle size of 0.5 to 10.0 μm.
4). A transparent film, wherein the coating composition for forming the hard coat layer of 2 or 3 further comprises a good solvent and a poor solvent for the ionizing radiation curable compound.
5. 5. The transparent film as described in 3 or 4 above, wherein the center line average roughness Ra of the hard coat layer surface is from 0 to 0.5 μm.
6). 6. The transparent film as described in any one of 3 to 5 above, wherein the hard coat layer has a surface haze of 0 to 40%.
7). Transparent having a low refractive index layer having a refractive index smaller than that of the hard coat layer by 0.05 or more on the side opposite to the transparent support of the hard coat layer described in any one of 1 to 6 above the film.
8). 8. The transparent film as described in 7 above, wherein the low refractive index layer is formed using a coating composition containing a fluorine-containing polymer.
9. 9. The transparent film as described in 8 above, wherein the fluoropolymer is a thermosetting and / or ionizing radiation curable fluoropolymer represented by the following general formula 1 or general formula 2.

[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. Moreover, the silicone site | part may be included. x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. However, x + y + z = 100. ]

General formula 2

In General Formula 2, R represents an alkyl group having 1 to 10 carbon atoms or an ethylenically unsaturated group (—O (C═O) C (—X) ═CH ₂ ) represented by General Formula 1.
m represents an integer of 1 ≦ m ≦ 10, and n represents an integer of 2 ≦ n ≦ 10.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. Moreover, the silicone site | part may be included.
x, y, z1, and z2 represent mol% of each repeating unit, and x and y satisfy 30 ≦ x ≦ 60 and 0 ≦ y ≦ 70, respectively. z1 and z2 satisfy 1 ≦ z1 ≦ 65 and 1 ≦ z2 ≦ 65. However, x + y + z1 + z2 = 100.
10. The transparent film as described in any one of 7 to 9 above, wherein the coating composition for forming the low refractive index layer contains a polysiloxane-containing vinyl monomer.
11. 11. The transparent film as described in 10 above, wherein the polysiloxane-containing vinyl monomer is represented by the following general formula I.

In the general formula I, R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. P represents an integer of 10 to 500. R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a monovalent organic group, and R ₆ represents a hydrogen atom or a methyl group. L represents a single bond or a divalent linking group, and n represents 0 or 1.
12 The transparent film as described in any one of 7 to 11 above, wherein the low refractive index layer contains hollow silica fine particles.
13. The low refractive index layer according to any one of the above 7 to 12 is coated with an ionizing radiation curable compound and at least one active halogen compound on a transparent support and dried, and then irradiated with ionizing radiation. A transparent film characterized in that it is a layer formed by curing.
14 14. The transparent film as described in any one of 1 to 13 above, wherein an antistatic layer is provided between the transparent support and the hard coat layer.
15. 14. The transparent film as described in 1 or 13 above, wherein the active halogen compound is a compound represented by the following general formulas (1) to (4).

In the general formula (1), X represents a halogen atom. Y is _{-CX 3, -NH 2, -NHR '} , - NR' represents a _2, -OR '. Here, R ′ represents an alkyl group or an aryl group. R is
—CX ^{3 represents} an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

  In the general formula (2), A represents a phenyl group, a naphthyl group, a substituted phenyl group or a substituted naphthyl group. Here, the substituent is a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, or a methylenedioxy group. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (3), W represents an unsubstituted or substituted phenyl group or an unsubstituted naphthyl group, and the substituent of the phenyl group is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or It is a C1-C4 alkoxy group. The number of substituents is one or two for a halogen atom, and one for the other. X represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (4), A represents an unsubstituted or substituted phenyl group or an unsubstituted naphthyl group, and the substituent of the phenyl group is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or It is a C1-C4 alkoxy group. The number of substituents is one or two for a halogen atom, and one for the other. X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an allyl group. Y represents a halogen atom, and n represents an integer of 1 to 3.
16. A transparent film having at least an antireflection layer and a hard coat layer on a transparent support, wherein the antireflection layer comprises at least one active halogen compound described in 15 above and an ionizing radiation curable compound A transparent film characterized in that it is a layer formed by curing by irradiation with ionizing radiation.
17. A method for producing a transparent film having at least a hard coat layer and / or an antireflection layer on a transparent support, wherein the support is obtained by the following step (1) and step (2) or (3). A method for producing a transparent film, comprising a step of forming at least one of the layers laminated thereon.
(1) A step of applying and drying a coating solution containing at least one active halogen compound and an ionizing radiation curable compound on a web that includes a support and that runs continuously to form a coating layer;
(2) A step of curing the coating layer by irradiating the coating layer on the web with ionizing radiation for 0.5 seconds or more in an atmosphere having an oxygen concentration of 3% by volume or less,
(3) A step of curing the coating layer by irradiation with ionizing radiation for 0.5 seconds or more in an atmosphere having an oxygen concentration of 3% or less while heating the coating layer on the web.
18. After the step (1) of forming the coating layer of 17 above, (4) a step of heating and curing the coating layer by heating the coating layer on the web is provided, and then the step (2) or the step ( 3) A method for producing a transparent film, comprising:
19. 19. In the method for producing a transparent film as described in 17 or 18, the web having a coating layer that has been continuously run and has undergone the step (1) or the step (4) is injected with an inert gas so as to have a low oxygen concentration. The web is further carried into an ionizing radiation reaction chamber having an oxygen concentration of 3% by volume or less in which an inert gas is installed continuously with the front chamber, and is applied in the ionizing radiation reaction chamber. A method for producing a transparent film, comprising performing a layer curing step.
20. 20. The method for producing a transparent film according to the above 19, wherein the inert gas injected into the ionizing radiation reaction chamber is blown out from at least the web entrance side of the ionizing radiation reaction chamber. Method.
21. In the curing step (2) or (3) of the coating layer, the ionizing radiation is irradiated a plurality of times to the coating layer on the web in an atmosphere having an oxygen concentration of 3% by volume or less, and at least two of these ionizing radiations 21. The method for producing a transparent film as described in 19 or 20 above, wherein the irradiation is performed in an ionizing radiation reaction chamber having a continuous oxygen concentration of 3% by volume or less.
22. Any one of 19 to 21 above, wherein a gap between the ionizing radiation reaction chamber and the front chamber constituting the web entrance side with the coating layer surface on the web is 0.2 to 15 mm. The manufacturing method of the transparent film of description.
23. In at least one of the surfaces constituting the web entrance side of the ionizing radiation reaction chamber and the front chamber, at least a part of the surface constituting the web entrance side is movable, and at least when passing through the joining member joining the web The method for producing a transparent film as described in any one of 19 to 22, wherein the thickness of the joining member is escaped.

24. The method for producing the transparent film has a step of applying a coating liquid from the slot of the tip lip, bringing the land of the tip lip of the slot die close to the surface of the web that is continuously supported by a backup roll, and
When the land length of the tip lip on the web traveling direction side of the slot die in the web traveling direction is 30 μm or more and 100 μm or less, and the slot die is set at the coating position, the land direction opposite to the web traveling direction is set. The above-described 17 to 23, wherein the coating is performed using a coating apparatus in which the gap between the tip lip and the web is set to be 30 μm or more and 120 μm or less larger than the gap between the tip lip and the web on the web traveling direction side. The manufacturing method of the transparent film in any one of.
25. The viscosity at the time of application | coating of the said coating liquid is 2.0 [mPa * sec] or less, and the quantity of this coating liquid apply | coated to the surface of a web is 2.0-5.0 [ml / m < ² >]. 25. The method for producing a transparent film as described in 24 above, wherein
26. 24. The method for producing a transparent film as described in 24 or 23 above, wherein the coating liquid is coated on the surface of a continuously running web at a speed of 25 [m / min] or more.
27. A transparent film, wherein the antireflection layer according to any one of 7 to 16 is produced by the production method according to any one of 17 to 26.
28. A transparent film, wherein the hard coat layer according to any one of 1 to 6 is produced by the production method according to any one of claims 17 to 26.
29. The transparent film in any one of said 1-16, 20, 21 is used for one of the two protective films in a polarizing plate, The polarizing plate characterized by the above-mentioned.
30. 30. An image display device, wherein the transparent film according to any one of claims 1 to 16, 20, and 21 or the polarizing plate according to claim 29 is used on an outermost surface of a display.

The image display device provided with the transparent film (especially antireflection film) or polarizing plate of the present invention has little reflection of external light and reflection of the background, and is not only highly visible, but also compared with the conventional one. Thus, it is more excellent in scratch resistance and brittleness.
Moreover, according to the manufacturing method of this invention, said transparent film (especially antireflection film) can be manufactured cheaply.

  Hereinafter, the present invention will be described in detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. .

[Layer structure of transparent film]
The transparent film of the present invention (in the present invention, the transparent film refers to a film having a transmittance of 90% or more) has the following constitutions (1) and (2).
(1) It has at least a hard coat layer on a transparent support (hereinafter also referred to as a substrate or a substrate film), and the hard coat layer contains an ionizing radiation curable compound and at least one active halogen compound. The coating composition containing the coating composition is applied on a transparent support and dried, and then cured by irradiation with ionizing radiation.
Further, the transparent film having the above-described structure comprises a light-transmitting particle having an average particle diameter of 0.5 to 10.0 μm, an ionizing radiation curable compound, and at least one active halogen compound in a coating composition forming a hard coat layer. In the present specification, in the present specification, in the case of the hard coat layer having irregularities formed on the surface thereof (that is, a hard coat layer into which translucent particles are introduced) among the hard coat layers, it is simply anti-glare. It is called a layer.
The example of the preferable structure of the transparent film of this invention of the said structure is shown below.
Base film / hard coat layer Base film / anti-glare layer Base film / anti-static layer / hard coat layer Base film / anti-static layer / anti-glare layer Anti-static layer / base film / hard coat layer Anti-static layer / Base film / Anti-glare layer The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO), and is provided by coating or atmospheric pressure plasma treatment or the like. Can do.
(2) Having a hard coat layer on the transparent support as necessary, and taking into account the refractive index, film thickness, number of layers, layer order, etc., so that the reflectivity decreases due to optical interference on it. It has a laminated antireflection layer (hereinafter, the transparent film having the structure is also referred to as “antireflection film”).
In addition, in the transparent film of said (1) and (2), the film which has sufficient abrasion resistance and brittleness can be obtained by using an active halogen compound for hard-coat layer formation.
In addition, in the antireflection film of (2), the antireflection layer, particularly the low refractive index layer was coated and dried on a transparent support with a coating composition containing an ionizing radiation curable compound and at least one active halogen compound. Thereafter, the layer is preferably cured by irradiation with ionizing radiation. By using an active halogen compound in the low refractive index layer, it is possible to obtain a film with improved anti-scratch properties while having sufficient antireflection performance.

[Layer structure of antireflection film]
As described above, the antireflection film of the present invention has a hard coat layer, which will be described later, on a support (hereinafter also referred to as a base material or a base film) as necessary, and optical interference thereon. The antireflection layer is laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance decreases. The simplest structure of the antireflection layer is obtained by coating only a low refractive index layer on a substrate. In order to further reduce the reflectance, the antireflection layer is preferably composed of a combination of a high refractive index layer having a higher refractive index than the substrate and a low refractive index layer having a lower refractive index than the substrate. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the base material side, and three layers having different refractive indices, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer). , A layer having a lower refractive index than a high refractive index layer) / a high refractive index layer / a low refractive index layer, and the like. Among them, in view of durability, optical characteristics, cost, productivity, and the like, those laminated in the order of medium refractive index layer / high refractive index layer / low refractive index layer on a substrate having a hard coat layer are preferable. The antireflection film of the present invention may have a functional layer such as an antiglare layer or an antistatic layer in addition to the hard coat layer described above.

The example of the preferable structure of the antireflection film of this invention is shown below.
Base film / low refractive index layer Base film / anti-glare layer / low refractive index layer Base film / hard coat layer / anti-glare layer / low refractive index layer Base film / hard coat layer / high refractive index layer / low Refractive index layer Base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer base film / antiglare layer / high refractive index layer / low refractive index layer base film / antiglare layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Base film / Antistatic layer / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Antistatic layer / Base film / Hard coat Layer / medium refractive index layer / high refractive index layer / low refractive index layer base film / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer antistatic layer / base film / Antiglare layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Antistatic layer / Base film / Antiglare layer / High refractive index layer / Low bending Antireflection film rate layer / high refractive index layer / low refractive index layer present invention, as long as the reflectance can be reduced by optical interference, it is not particularly limited to these layer structure. The high refractive index layer may be a light diffusing layer having no antiglare property. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO), and can be provided by coating or atmospheric pressure plasma treatment.

[Initiator]
The transparent film of the present invention has a layer formed by curing a coating composition containing at least one active halogen compound and an ionizing radiation curable compound by ionizing radiation irradiation.
Active halogen compounds include compounds that decompose directly by ionizing radiation and generate halogen radicals directly or compounds that generate chemical radicals by electron transfer from coexisting materials, such as carbon tetrabromide, iodonium, Examples include tribromoacetophenone, S-triazine and oxathiazole compounds. 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl acetate) amino ) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole.
In particular, in the present invention, it is particularly preferable to use at least one compound selected from the compounds represented by the following general formulas (1) to (4).
Hereinafter, the compounds represented by the general formulas (1) to (4) will be described.

In the general formula (1), X represents a halogen atom. Y is _{-CX 3, -NH 2, -NHR '} , - NR' represents a _2, -OR '. Here, R ′ represents an alkyl group or an aryl group. R represents —CX ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

Examples of the compound represented by the general formula (1) used in the present invention include compounds described in Bull. Chem. Soc. Japan. 42, 2924 (1969), such as 2-phenyl-4, 6-bis (trichloromethyl). -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-Netoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 '・ 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -s- Triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) ) -s-triazine, 2- (α, α, β-trichloroethyl) -4, 6-bis (trichloromethyl) -s-triazine and the like. Further, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4amino-6-trichloromethyl-s-triazine, etc. be able to. Further, compounds described in J. Org. Chem., 29, 1527 (1964), such as 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) ) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2-amino-4-methyl-6-tribromomethyl-s-triazine, 2-methoxy-4-methyl-6-trichloro And methyl-s-triazine.
A case where a compound in which Y is —CX ₃ in general formula (1) is particularly preferred. X is preferably a Cl, Br, or F atom.
Specific examples of the compound represented by the general formula (1) are as follows.

A represents a phenyl group, a naphthyl group, a substituted phenyl group or a substituted naphthyl group. Here, the substituent is a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, or a methylenedioxy group.
Y represents a halogen atom, and n represents an integer of 1 to 3.
Specific examples of the compound represented by the general formula (2) are as follows.

W represents an unsubstituted or substituted phenyl group or an unsubstituted naphthyl group, and the substituent of the phenyl group is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It is a group. The number of substituents is one or two for a halogen atom, and one for the other.
X represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms.
Y represents a halogen atom, and n represents an integer of 1 to 3.
Specific examples of the compound represented by the general formula (3) are as follows.

A represents an unsubstituted or substituted phenyl group or an unsubstituted naphthyl group, and the substituent of the phenyl group is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It is a group. The number of substituents is one or two when it is a halogen atom, and is one in other cases.
X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an allyl group.
Y represents a halogen atom, and n represents an integer of 1 to 3.
Specific examples of the compound represented by the general formula (4) are as follows.

Although there is no restriction | limiting in particular in the usage-amount of an active halogen compound, It is preferable to use in the range of 0.1-30 mass parts with respect to 100 mass parts of ionizing radiation-curable compounds, More preferably, it is 1-20 mass parts. is there. In addition, the active halogen compounds of the general formulas (1) to (4) may be used in a plurality of types, or may be used in combination with other radical polymerization initiators or photosensitizers.
By using these active halogen compounds, preferably the compounds represented by the general formulas (1) to (4), the diffusibility is improved due to the relatively small size of the generated radical molecules, and ionizing radiation. Even if the temperature at the time of curing by irradiation is low, there is an effect that a polymer exhibiting a desired hardness can be formed.

[Coating method]
In the present invention, after coating a coating composition for forming a layer on a transparent support, it is cured by irradiation with ionizing radiation directly after the drying step, or is cured by heating after drying and further irradiation with ionizing radiation. May be.
The method for producing the transparent film of the present invention, particularly the antireflection film, is carried out by performing the step (2) or (3) after the step (1) below or by the heat curing (4) after the step (1). It has the process of forming at least one layer laminated | stacked on a support body by performing a process and performing the process of (2) or (3) after that.
(1) Applying and drying a coating solution containing at least one active halogen compound and an ionizing radiation curable compound on a web including a support that runs continuously, and forming a coating layer (2) A step of curing the coating layer by irradiating the coating layer on the web with ionizing radiation for 0.5 seconds or more in an atmosphere having an oxygen concentration of 3% by volume or less (3) while heating the coating layer on the web, A step of curing the coating layer by irradiating with ionizing radiation for 0.5 seconds or more in an atmosphere having an oxygen concentration of 3% by volume or less. (4) The coating layer on the web is heated and cured by performing a heat curing treatment Process

[Curing with ionizing radiation]
Irradiation with ionizing radiation is performed in an atmosphere having an oxygen concentration of 3% by volume or less. More preferably, it is 1 volume% or less, More preferably, it is 0.1 volume% or less. In order to reduce the oxygen concentration more than necessary, a large amount of inert gas is required, which is not preferable from the viewpoint of production cost. As a means for reducing the oxygen concentration, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another inert gas, and particularly preferably with nitrogen (nitrogen purge). It is.
In the present invention, the coating layer is cured by irradiating the coating layer on the web with ionizing radiation for 0.5 seconds or more in an atmosphere having an oxygen concentration of 3% by volume or less. The irradiation time is preferably from 0.7 seconds to 60 seconds, more preferably from 0.7 seconds to 10 seconds from the start of irradiation. If it is less than 0.5 seconds, the curing reaction cannot be completed and sufficient curing cannot be performed.
In the present specification, the “web” may be the support itself or a layer formed on the support.

In the present invention, the curing step is preferably performed in an ionizing radiation reaction chamber (hereinafter sometimes simply referred to as “reaction chamber”) controlled to a desired oxygen concentration. When supplying the inert gas to the ionizing radiation reaction chamber, the reaction chamber is designed to eliminate the transport air accompanying the web transport by slightly blowing it out to the web entrance side of the reaction chamber (which is the entrance for loading the web). Can be effectively reduced, and the substantial oxygen concentration at the extreme surface where the inhibition of curing by oxygen is large can be efficiently reduced. The direction of the inert gas flow on the web entrance side of the reaction chamber can be controlled by adjusting the balance between supply and exhaust of the reaction chamber. In addition, it is also preferable as a method for removing the carry air that the inert gas is blown directly onto the surface of the coating layer on the web immediately before the coating layer on the web is irradiated with ionizing radiation.
In particular, it is preferable that the low refractive index layer which is the outermost layer and is thin is cured by this method.

It is also preferable to provide a front chamber before the reaction chamber. The anterior chamber is preferably replaced with an inert gas and has a low oxygen concentration, preferably an oxygen concentration of 5% by volume or less and an oxygen concentration of 0.01% by volume or more. It is possible to simply pass (carry) the web before irradiation with ionizing radiation through the front chamber, and by directly blowing the inert gas onto the surface of the coating layer on the web, which is a method of removing the above-described carried air. Also good.
By providing the front chamber and excluding oxygen on the surface of the coating layer of the web in advance, it becomes possible to maintain a low oxygen concentration in the reaction chamber, and the curing can proceed more efficiently.

Further, at least one of the side surfaces constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber has a gap of 0.2 to 15 mm with the surface of the coating layer on the web in order to use the inert gas efficiently. It is preferable that the thickness is 0.2 to 10 mm, and most preferably 0.2 to 5 mm. Here, the gap refers to the length between the surface of the coating layer on the web and the upper end of the web entrance on the side surface constituting the web entrance side.
However, in order to continuously manufacture the web, it is necessary to join and connect the webs, and a method of sticking with a joining tape or the like is widely used for joining. For this reason, if the gap between the entrance of the ionizing radiation reaction chamber or the front chamber and the surface of the coating layer on the web is too narrow, there arises a problem that the joining member such as the joining tape is caught. For this reason, in order to narrow the gap, it is preferable to make at least a part of the entrance surface of the ionizing radiation reaction chamber or the front chamber movable and to widen the gap by the junction thickness when the junction enters. In order to realize this, (A) an ionization radiation reaction chamber or an entrance surface of an anterior chamber is made movable forward and backward, and when the joint passes, it moves forward and backward to widen the gap, or (B) There is a method in which the entrance surface of the ionizing radiation reaction chamber or the front chamber is movable in the vertical direction with respect to the web surface, and moves up and down to widen the gap when the joint passes.

In the following, the operation of the web entrance surface of the front chamber is taken as an example, and an example of the operation of the web entrance surface of the reaction chamber or the front chamber applicable in the present invention will be described with reference to FIGS. Then, a web having a coating layer (not shown) is simply referred to as “web”).
FIG. 1 is a schematic view of a production apparatus including an ionizing radiation reaction chamber and an anterior chamber that are preferably used in the present invention.
FIG. 2 is a side view schematically showing an example of the operation of the web entrance surface of the production apparatus equipped with an ionizing radiation reaction chamber and an anterior chamber preferably used in the present invention. Indicates. The apparatus having the configuration of FIG. 2 detects a joining member with a sensor before the joining member that joins and joins the web enters the front chamber entrance at the time of web conveyance, and the sensor and the sensor through a control unit (not shown). An air cylinder attached to at least a part of the web entrance surface of the front chamber that operates in conjunction with it allows the entrance surface to be moved back and forth in the direction of web travel, thereby escaping the thickness of the joining member It is something that can be done.

  3 and 4 are views showing the above-described embodiment (B), FIG. 3 is a view schematically showing the web entrance surface of the front chamber, and FIG. 4 is an operation of the web entrance surface of the front chamber. FIG. A gap between the web and the entrance surface is determined by making a part of the web entrance surface of the front chamber movable and contacting both ends of the web with the bearing touch roll. When the joining member passes, the bearing touch roll gets over the joining member, and the gap at the web entrance surface is kept constant. The moving means at the entrance is not limited as long as it can escape the joint.

In the present invention, when the coating layer on the web is cured, it is also preferable to perform ionizing radiation irradiation performed in an atmosphere of 3% by volume or less in the curing step in a plurality of times.
In this case, it is preferable that the ionizing radiation irradiation is performed at least twice in a reaction chamber having a continuous oxygen concentration of 3% by volume or less. By performing a plurality of times of ionizing radiation irradiation in a reaction chamber having a low oxygen concentration, the reaction time required for curing can be effectively ensured. In particular, when the production rate is increased for high productivity, multiple ionizing radiation irradiations are necessary to ensure the energy of ionizing radiation necessary for the curing reaction, and this is combined with ensuring the reaction time necessary for the curing reaction. The above aspect is effective.
“Consecutive reaction chamber” refers to an embodiment in which ionizing radiation is irradiated at least twice in a reaction chamber having an oxygen concentration of 3% by volume or at least two reaction chambers having an oxygen concentration of 3% by volume or less. There is an embodiment in which the gap is a low oxygen zone having an oxygen concentration of 3% by volume or less. In the latter case, each reaction chamber may have a different oxygen concentration as long as the oxygen concentration is 3% by volume or less.

  In this invention, it is also preferable to perform the said hardening process, heating a web so that the coating layer surface temperature may be 25 degreeC or more. It is also preferable to heat in an atmosphere having an oxygen concentration of 3% by volume or less simultaneously and / or continuously with ionizing radiation irradiation. By using the curing step in combination with heating, the curing reaction is accelerated by heat, and a film with more excellent physical strength and chemical resistance can be formed.

  The heating is preferably performed at a coating layer surface temperature of 25 ° C. or more and 170 ° C. or less. When the temperature is lower than 25 ° C., there is little curing by heating, while when it exceeds 170 ° C., problems such as deformation of the base material occur. A more preferable temperature is 25 ° C to 100 ° C. Further, the time during which the surface temperature of the coating layer is maintained at the above temperature is preferably 0.1 seconds or more and 300 seconds or less from the start of ionizing radiation irradiation, and more preferably 10 seconds or less. If the time for maintaining the temperature of the coating layer surface temperature in the above temperature range is too short, the reaction of the curable composition for forming the film cannot be promoted. There are also problems in manufacturing such as an increase in size.

  The heating method is not particularly limited, but a method of heating a roll to contact the web, a method of spraying heated nitrogen, irradiation with far infrared rays or infrared rays is preferable. A method of heating a rotating metal roll described in Japanese Patent No. 2523574 by flowing a medium such as hot water, steam or oil can also be used. As a heating means, a dielectric heating roll or the like may be used.

The ionizing radiation species in the present invention is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of curable composition forming the film. You can choose. In the present invention, irradiation with ultraviolet rays is preferred. Ultraviolet curing is preferred because the polymerization rate is fast and the equipment can be made compact, and there are abundant and low-priced compound types that can be selected.
In the case of ultraviolet rays, an ultra-high 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 case of electron beam irradiation, energy of 50 to 1000 keV emitted from various electron beam accelerators such as Cockloft Walton type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type. An electron beam having the following is used.

[Curing by heat treatment]
In the heat curing of (4), the film surface is preferably heated at 60 ° C. or higher and 170 ° C. or lower. If it is less than 60 ° C., there is little curing by heating, and if it exceeds 170 ° C., problems such as deformation of the substrate occur. Furthermore, this preferable temperature is 60 degreeC-130 degreeC. The film surface refers to the film surface temperature of the layer to be cured. The heating time may be within a range in which deformation of the substrate does not occur, preferably 2 minutes to 20 minutes, and more preferably 3 minutes to 15 minutes.

[Film-forming binder]
In the present invention, an ionizing radiation curable compound, preferably a compound having an ethylenically unsaturated group, is used as the main film-forming binder component of the curable composition for forming a film. It is preferable in terms of membrane productivity. The main film-forming binder component refers to a component that occupies 10% by mass or more and 100% by mass or less of the film-forming component excluding inorganic particles. Preferably, they are 20 mass% or more and 100 mass% or less, More preferably, they are 30 mass% or more and 95% or less.
In the present specification, the “ionizing radiation curable compound” may be any compound that is cured by irradiation with ionizing radiation.
The main film-forming binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as the main chain, and more preferably a polymer having a saturated hydrocarbon chain as the main chain. Furthermore, these polymers preferably have a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
Further, in the case of forming a film having a high refractive index, the monomer structure contains at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. It is preferable.

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

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

  Polymerization of these monomers having an ethylenically unsaturated group is carried out by irradiation with ionizing radiation or heating in the presence of other photoradical initiators or thermal radical initiators as required in addition to the active halogen compounds. Can do.

As photo radical polymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 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 benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (P.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba 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.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as ammonium sulfate, potassium persulfate and the like, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), etc. And diazoaminobenzene, p-nitrobenzenediazonium and the like.

  In the present invention, a polymer having a polyether as a main chain can also be used. A ring-opening polymer of a polyfunctional epoxy compound is preferred. The ring-opening polymerization of the polyfunctional epoxy compound can be carried out by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator, if necessary, in addition to the active halogen compound. Known photoacid generators and thermal acid generators can be used.

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

Next, the hard coat layer and the antiglare layer will be described below.
[Hard coat layer and antiglare layer]
The hard coat layer has a hard coat property for improving the scratch resistance of the film. Further, it is also preferably used for the purpose of contributing to the film the light diffusibility due to scattering of at least one of surface scattering and internal scattering. Accordingly, it is preferable to contain a translucent resin for imparting hard coat properties and translucent particles for imparting light diffusibility. Further, if necessary, the refractive index is increased, crosslinking shrinkage is prevented, Contains an inorganic filler for strengthening.

The film thickness of the hard coat layer may be in the range of 1 to 40 μm for the purpose of imparting hard coat properties, but 1 to 30 μm is particularly preferable.
When the film thickness is in the above range, the hard coat property is sufficiently imparted, and further, the curability and brittleness are not deteriorated and the workability is not lowered.

Since the hard coat layer has both excellent scratch resistance and brittleness, a coating composition containing an ionizing radiation curable compound and at least one active halogen compound for forming a translucent resin is coated on a transparent support. After drying, it is preferably cured by irradiation with ionizing radiation.
On the other hand, when imparting light diffusibility to the film, translucent particles for imparting antiglare properties, ionizing radiation curable compounds for forming a translucent resin, and at least one active halogen compound. It is preferable that the coating composition containing the coating composition is coated and dried on a transparent support and then cured by irradiation with ionizing radiation (hereinafter, the hard coat layer containing translucent particles is also referred to as an “antiglare layer”). ).
The antiglare layer according to the present invention has surface irregularities, and thereby has antiglare properties. In particular, the antiglare layer-forming coating composition has at least translucent particles having an average particle diameter of 0.5 to 10.0 μm, It is preferable to contain a good solvent and a poor solvent for one type of active halogen compound, ionizing radiation curable compound, and ionizing radiation curable compound. In this method, as the good solvent decreases at the time of coating and drying, the ionizing radiation curable compound that forms the translucent resin in the poor solvent is gelled to form irregularities on the surface. Patent No. 3515426 It is described in detail. It is important to select the size of the translucent particles, the good solvent for the ionizing radiation curable compound, and the poor solvent.
If this technique is used, the surface irregularities of the thick hard coat layer can be formed using relatively small light-transmitting particles, and a design advantageous for scratch resistance is possible.
The thickness of the hard coat layer and the antiglare layer may be in the range of 1 to 40 μm, but 1 to 30 μm is particularly preferable.
The surface shape and optical characteristics of the antiglare layer will be described later.
Hereinafter, the translucent resin, translucent particles, and other additives used for the hard coat layer and the antiglare layer will be described by taking the method for forming the antiglare layer as an example.

<Translucent fine particles>
The translucent particles used in the hard coat layer are used for the purpose of imparting antiglare property or light diffusibility, and have an average particle size of 0.5 to 15 μm, preferably 1.0 to 10.0 μm. is there. If the average particle size is less than 0.5 μm, the light scattering angle distribution spreads to a wide angle, resulting in a decrease in the character resolution of the display, and it becomes difficult to form surface irregularities, resulting in insufficient antiglare properties. Therefore, it is not preferable. On the other hand, when the thickness exceeds 15 μm, it is necessary to increase the thickness of the hard coat layer, which causes problems such as an increase in curling and an increase in material cost.
Specific examples of the translucent fine particles include, for example, poly ((meth) acrylate) particles, crosslinked poly ((meth) acrylate) particles, polystyrene particles, crosslinked polystyrene particles, crosslinked poly (acryl-styrene) particles, and melamine resin particles. Preferred examples include resin particles such as benzoguanamine resin particles. Further, silica particles, inorganic particles of agglomerated silica having a secondary particle size in the above range, or TiO ₂ particles may be used. Of these, crosslinked polystyrene particles, crosslinked poly ((meth) acrylate) particles, crosslinked poly (acryl-styrene) particles, and silica particles are preferably used, and the refractive index of each light-transmitting fine particle selected from these particles is used. In addition, by adjusting the refractive index of the translucent resin, the internal haze, surface haze, and center line average roughness of the antiglare layer according to the present invention can be achieved. Specifically, an ionizing radiation curable compound having a tri- or higher functional (meth) acrylate monomer as a main component that is preferably used in the antiglare layer according to the present invention described later (having a refractive index of 1.50 after curing). 1.53) and a translucent fine particle comprising a cross-linked poly (meth) acrylate polymer having an acrylic content of 50 to 100 weight percent is preferable. In particular, the ionizing radiation curable compound and the cross-linked poly (styrene-acryl) are both co-polymerized. A combination with translucent fine particles made of a polymer (refractive index: 1.48 to 1.54) is preferable.
The translucent particles can be either spherical or indefinite.

  Further, two or more kinds of translucent fine particles having different particle diameters may be used in combination. It is possible to impart an antiglare property with the light-transmitting fine particles having a larger particle diameter, and to reduce the roughness of the surface with the light-transmitting fine particles having a smaller particle diameter. For example, when a transparent film (particularly an antireflection film) is attached to a high-definition display of 133 ppi or more, it is required that there is no optical performance defect called glare. Glare is derived from the fact that the unevenness of the film surface (which contributes to antiglare properties) causes the pixels to be enlarged or reduced and loses brightness uniformity, but is smaller than the light-transmitting particles that impart antiglare properties. The diameter can be greatly improved by using translucent particles different from the refractive index of the binder.

  Further, the particle size distribution of the translucent particles is most preferably monodispersed, and the particle size of each particle is preferably as close as possible. For example, when a particle having a particle size of 20% or more than the average particle size is defined as a coarse particle, the proportion of the coarse particle is preferably 1% or less, more preferably 0.1% of the total number of particles. Or less, more preferably 0.01% or less. The translucent particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree thereof.

In the formed anti-glare layer, the light-transmitting fine particles are 3 to 30% by mass in the total solid content of the anti-glare layer in consideration of light diffusing effect, image resolution, haze cloudiness, glare and the like. Formulated to contain. More preferably, it is 5-20 mass%. If it is less than 3% by mass, the antiglare property is insufficient, and if it exceeds 30% by mass, problems such as image blur, surface turbidity and glare occur.
Moreover, the density of the translucent fine particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .
The particle size distribution of the translucent particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

In the present invention, the refractive index of the translucent resin and the translucent fine particles is preferably 1.45 to 1.70, more preferably 1.48 to 1.65. In order to set the refractive index within the above range, the kind and amount ratio of the light-transmitting resin and the light-transmitting fine particles may be appropriately selected. How to select can be easily known experimentally in advance.
In the present invention, the difference in refractive index between the translucent resin and the translucent fine particles (the refractive index of the translucent fine particles−the refractive index of the translucent resin) is preferably 0.001 to an absolute value. It is 0.030, More preferably, it is 0.001-0.020, More preferably, it is 0.001-0.015. If this difference exceeds 0.030, problems such as film character blur, a decrease in dark room contrast, and surface turbidity occur.
Here, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry. The refractive index of the translucent fine particles is obtained by measuring the turbidity by dispersing an equal amount of the translucent fine particles in a solvent in which the refractive index is changed by changing the mixing ratio of two kinds of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the turbidity is minimized with an Abbe refractometer.

<Translucent resin>
The translucent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to increase the refractive index of the binder polymer, the monomer structure has a high refractive index including at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. It is also possible to select a monomer having a ratio, a monomer having a fluorene skeleton in the molecule, and the like.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid [for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3- Chlorohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], ethylene oxide-modified products and caprolactone-modified products of the above esters, vinylbenzene and its derivatives [eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2- Acryloyl ethyl ester, 1,4-divinylcyclohexanone], vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.

  Specific examples of the high refractive index monomer include (meth) acrylates having a fluorene skeleton, bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, etc. Is mentioned. Two or more of these monomers may be used in combination.

Polymerization of these monomers having an ethylenically unsaturated group (ionizing radiation curable compound (translucent resin precursor)) can be performed by irradiation with ionizing radiation in the presence of a photo radical initiator or a thermal radical initiator. it can.
Therefore, the antiglare layer is composed of an ionizing radiation curable compound such as the above-mentioned ethylenically unsaturated monomer, an active halogen compound, a light-transmitting fine particle, and an inorganic fine particle, a photo radical initiator, or a thermal radical start as described later if necessary. It can be formed by preparing a coating liquid containing an agent, coating and drying the coating liquid on a transparent support, and then curing it by a polymerization reaction using ionizing radiation.
In addition to the above, a photosensitizer that may be contained in the low refractive index layer may be used.

Photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, inorganic complexes, coumarins and the like.
Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone.
Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is.
Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler's ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like.
Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like.
Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.
Examples of borate salts include ion complexes with cationic dyes.
Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Examples of coumarins include 3-ketocoumarin.
These initiators may be used alone or in combination.
“Latest UV Curing Technology”, Technical Information Association, 1991, p. Various examples are also described in 159 and are useful in the present invention.

  Commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 819, 907, 1870 (CGI-403 / Irg184 = 7/3 mixed initiator, 500) manufactured by Ciba Specialty Chemicals Co., Ltd. , 369, 1173, 2959, 4265, 4263), OXE01), etc., and Kayacure (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, manufactured by Nippon Kayaku Co., Ltd. , ITX, QTX, BTC, MCA, etc.), Esacure manufactured by Sartomer (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) and the like are preferable examples.

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. Furthermore, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.
Examples of commercially available photosensitizers include Kayacure (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as ammonium sulfate, potassium persulfate and the like, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), etc. And diazoaminobenzene, p-nitrobenzenediazonium and the like.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation in the presence of an active halogen compound and, if necessary, a photoacid generator or a thermal acid generator.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, translucent fine particles, an active halogen compound, and, if necessary, a photoacid generator, a thermal acid generator, or inorganic fine particles is prepared, and the coating liquid is used as a transparent support. After coating, it can be cured by a polymerization reaction by ionizing radiation to form an antiglare layer.

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

In addition to the above light-transmitting fine particles, silicon, titanium, zirconium, aluminum, indium, zinc, tin are used for the antiglare layer in order to adjust the refractive index of the layer and reduce the haze value caused by internal scattering. And an inorganic filler comprising an oxide of at least one metal selected from antimony and having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less. Good. Since these inorganic fillers generally have a specific gravity higher than that of organic substances and can increase the density of the coating composition, they also have the effect of slowing the sedimentation rate of the light-transmitting fine particles.
In order to increase the difference in refractive index from the translucent particles, the hard coat layer using the high refractive index translucent particles uses silicon oxide to keep the refractive index of the layer low. Is preferred.
Specific examples of the inorganic filler used in the hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ . TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler used in the antiglare layer is also preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
When using these inorganic fillers, the addition amount is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass with respect to the total mass of the antiglare layer. It is.
Such an inorganic filler does not scatter because its particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.
Further, at least one of an organosilane compound, a hydrolyzate of organosilane and / or a partial condensate (sol) thereof can be used for the antiglare layer.
The amount of the sol component added to the layers other than the low refractive index layer is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, based on the total solid content of the containing layer (added layer). 05-10 mass% is still more preferable, and 0.1-5 mass% is especially preferable. In the case of the hard coat layer, the organosilane compound is preferably used because the restriction on the amount of the organosilane compound or its sol component added is not as strict as the low refractive index layer.

The bulk refractive index of the mixture of translucent resin and translucent particles is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to set the refractive index within the above range, the kind and amount ratio of the light-transmitting resin and the light-transmitting particles may be appropriately selected. How to select can be easily known experimentally in advance.
The difference in refractive index between the translucent resin and the translucent particles (the refractive index of the translucent particles−the refractive index of the translucent resin) is preferably 0.02 to 0.2, more preferably 0.05. ~ 0.15. When this difference is within the above range, the effect of internal scattering is sufficient, no glare occurs, and the film surface does not become cloudy.
The refractive index of the translucent resin is preferably 1.45 to 2.00, more preferably 1.48 to 1.70.
Here, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry.

<Surfactant for antiglare layer>
In particular, the antiglare layer of the present invention is free of fluorine-based or silicone-based surfactants or both in order to ensure surface uniformity such as coating unevenness, drying unevenness, and point defects. It is preferable to contain in the coating composition for glare layer formation. In particular, a fluorosurfactant is preferable because an effect of improving surface defects such as coating unevenness, drying unevenness, point defects and the like of the transparent film of the present invention (particularly, an antireflection film) appears at a smaller addition amount. Used.
The purpose is to increase productivity by giving high-speed coating suitability while improving the surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): Copolymers with acrylic resins and methacrylic resins containing the corresponding repeating units, and vinyl monomers copolymerizable therewith (for example, the monomer (ii) below) are useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula

General formula

In the general formula A, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, m is an integer of 1-6, and n is an integer of 2-4. To express. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) a monomer represented by the following general formula (b) copolymerizable with (i) above

General formula

In the general formula B, R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

The amount of the fluoroaliphatic group-containing monomer represented by the general formula (a) used in the fluoropolymer used in the present invention is 10 mol% or more based on each monomer of the fluoropolymer, preferably Is 15 to 70 mol%, more preferably in the range of 20 to 60 mol%.

The preferred weight average molecular weight of the fluoropolymer used in the present invention is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5% by mass, preferably in the range of 0.005 to 3% by mass, and more preferably, with respect to the coating solution. It is the range of 0.01-1 mass%. If the addition amount of the fluorine-based polymer is less than 0.001% by mass, the effect is insufficient, and if it exceeds 5% by mass, the coating film may not be sufficiently dried or the performance as a film (for example, reflectance, Adversely affects the scratch resistance).

  Examples of the specific structure of the fluoropolymer composed of the fluoroaliphatic group-containing monomer represented by the general formula (i) are shown below, but this is not restrictive. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

However, the use of such a fluoropolymer reduces the surface energy of the antiglare layer due to segregation of functional groups containing F atoms on the surface of the antiglare layer, resulting in low refraction on the antiglare layer. When the rate layer is overcoated, there arises a problem that the antireflection performance deteriorates. This is presumably because minute unevenness that cannot be visually detected in the low refractive index layer deteriorates because the wettability of the curable composition used for forming the low refractive index layer deteriorates. To solve such problems, by adjusting the structure and amount of the fluorine-based polymer, the surface energy of the antiglare layer preferably in ^{20mN · m -1 ~50mN · m -1} , more preferably it was found that it is effective to control the ^{30mN · m -1 ~40mN · m -1} . In order to realize the surface energy as described above, F / C, which is a ratio of a peak derived from a fluorine atom and a peak derived from a carbon atom, measured by X-ray photoelectron spectroscopy is 0.1 to 1.5. is required.

  Alternatively, by selecting a fluorine-based polymer that is extracted by the solvent that forms the upper layer when the upper layer is applied, it is not unevenly distributed on the lower layer surface (= interface), so that the adhesion between the upper layer and the lower layer is provided. The anti-glare layer before application of the low refractive index layer can be prevented by reducing the surface free energy, which can provide an anti-glare and anti-reflection transparent film that maintains surface uniformity even at high speed application and has high scratch resistance. The object can also be achieved by controlling the surface energy within the above range. Examples of such materials include an acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable therewith, containing a repeating unit corresponding to a fluoroaliphatic group-containing monomer represented by the following general formula C (For example, a monomer represented by the following (iv)).

(Iii) A fluoroaliphatic group-containing monomer represented by the following general formula C

General formula C

In the general formula C, R ²¹ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. X ² represents an oxygen atom, a sulfur atom or —N (R ²² ) —, more preferably an oxygen atom or —N (R ²² ) —, and still more preferably an oxygen atom. m is an integer from 1 to 6 (more preferably from 1 to 3, more preferably 1), and n is an integer from 1 to 18 (more preferably from 4 to 12, and even more preferably from 6 to 8). Represents. R ²² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.
In addition, two or more kinds of fluoroaliphatic group-containing monomers represented by the general formula C may be contained in the fluorine-based polymer as constituent components.

(Iv) a monomer represented by the following general formula D copolymerizable with the above (iii)

General formula D

In the general formula D, R ²³ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. Y ² represents an oxygen atom, a sulfur atom or —N (R ²⁵ ) —, more preferably an oxygen atom or —N (R ²⁵ ) —, and still more preferably an oxygen atom. R ²⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group.
R ²⁴ is an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkyl group containing a poly (alkyleneoxy) group, and an optionally substituted aromatic group. (For example, a phenyl group or a naphthyl group). A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms is more preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is more preferable. .

  Hereinafter, examples of specific structures of fluoropolymers containing a repeating unit corresponding to the fluoroaliphatic group-containing monomer represented by formula (c) are shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

  Further, if the surface energy is prevented from being lowered when the low refractive index layer is overcoated on the antiglare layer, the deterioration of the antireflection performance can be prevented. When applying an anti-glare layer, the surface tension of the coating solution is lowered by using a fluoropolymer to improve surface uniformity and maintain high productivity by high-speed application. After applying the anti-glare layer, corona treatment, UV treatment, heat treatment, saponification Corona treatment is particularly preferred using surface treatment techniques such as treatment and solvent treatment, but the surface energy of the antiglare layer before application of the low refractive index layer is controlled within the above range by preventing the surface free energy from decreasing. You can also achieve your goals.

  Moreover, you may add a thixotropic agent in the coating composition for forming the glare-proof layer of this invention. Examples of the thixotropic agent include silica and mica of 0.1 μm or less. In general, the content of these additives is preferably about 1 to 10 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin.

In the antiglare layer of the present invention, a solvent can be used for wet coating the coating composition directly on the transparent support. The requirements as a preferable solvent in the present invention are that various solutes such as the above-mentioned translucent resin are sufficiently dissolved, the above-mentioned translucent fine particles are not dissolved, and coating unevenness and drying unevenness are unlikely to occur in the coating to drying process. In addition, the support may not be dissolved (necessary for preventing deterioration of flatness, whitening, etc.), and conversely, the support may be swollen to a minimum extent (necessary for adhesion).
As a specific example, when triacetyl cellulose is used for the support, various ketones (methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, etc.) and various cellosolves (ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.) are used as the main solvent. Preferably used. Moreover, antiglare property can be adjusted by adding a small amount of a solvent having a hydroxyl group to the main solvent selected from the above, which is particularly preferable. Since a small amount of the solvent having a hydroxyl group can increase the antiglare property by remaining until after the main solvent in the drying step of the coating composition, the vapor pressure at a certain temperature in the range of 20 to 30 ° C. Preferably it is low relative to the main solvent. For example, a preferable example is a combination of propylene glycol (vapor pressure at 20.0 ° C .: 0.08 mmHg) as a small amount solvent having a hydroxyl group with respect to methyl isobutyl ketone (vapor pressure at 21.7 ° C .: 16.5 mmHg) as the main solvent. As mentioned. The mixing ratio of the main solvent and the small amount solvent having a hydroxyl group is preferably 99: 1 to 50:50, more preferably 95: 5 to 70:30 in terms of weight ratio. If it exceeds 50:50, the stability of the coating solution and the variation in surface quality in the drying step after coating increase, which is not preferable.

  The formation of the hard coat layer of the transparent film of the present invention can also be carried out in the same manner as the antiglare layer, except that translucent particles are added.

[Material for low refractive index layer]
Next, the low refractive index layer will be described below.
[Low refractive index layer]
The refractive index of the low refractive index layer in the antireflection film of the present invention is preferably 1.20 to 1.46, more preferably 1.25 to 1.46, and 1.30 to 1.46. It is particularly preferred that
When the refractive index is less than 1.30, the antireflection performance is improved, but the mechanical strength of the film is lowered, and when it exceeds 1.55, the antireflection performance is remarkably deteriorated.
Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.
Formula (I)
(Mλ / 4) × 0.7 <n1 × d1 <(mλ / 4) × 1.3
In the formula, m is a positive odd number, n1 is the refractive index of the low refractive index layer, and d1 is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength and is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.
Furthermore, in the antireflection film of the present invention, the low refractive index layer preferably has a refractive index smaller than the hard coat layer by 0.05 or more, more preferably 0.07 to 0.3. If the difference in refractive index between the low refractive index layer and the hard coat layer is less than 0.05, the reflectance increases and the antireflection ability is lost, which is not preferable.

Examples of the low refractive index layer include a low refractive index layer (embodiment 1) formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorinated resin before crosslinking”), and a low refractive index by a sol-gel method. A layer (embodiment 2), and a low refractive index layer (embodiment 3) having voids between or inside the particles using the particles and the binder polymer are used.
A material for forming a low refractive index layer (embodiment 1) composed of a crosslink of a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”) will be described below.
The low refractive index layer is a cured film formed, for example, by applying, drying and curing a curable composition containing a fluorine-containing polymer as a main component.

<Fluoropolymer for low refractive index layer>
The fluoropolymer has a cured film with a coefficient of dynamic friction of 0.03 to 0.20, a contact angle with water of 90 to 120 °, and a sliding angle of pure water of 70 ° or less, and heat or ionization. A polymer that is cross-linked by radiation is preferable in terms of improving productivity in the case of coating and curing a roll film while transporting the web.
Also, when the antireflection film of the present invention is mounted on an image display device, the lower the peel strength from a commercially available adhesive tape, the easier it is to peel off after sticking a seal or memo, so the peel strength is preferably 500 gf or less, 300 gf or less is more preferable, and 100 gf or less is most preferable.
The peeling force can be measured according to JIS Z0237-1980.
Further, the higher the surface hardness measured with a microhardness meter, the harder it is to scratch. Therefore, the surface hardness is preferably 0.3 GPa or more, and more preferably 0.5 GPa or more.

  The fluorine-containing polymer used in the low refractive index layer is preferably a fluorine-containing polymer containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. In addition to hydrolyzate and dehydration condensate of alkyl group-containing silane compound [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], a fluorine-containing monomer unit and a crosslinking reactive unit are constituted. Examples thereof include a fluorine-containing copolymer as a unit. In the case of a fluorinated copolymer, the main chain preferably consists of only carbon atoms. That is, it is preferable that the main chain skeleton does not have an oxygen atom or a nitrogen atom.

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

  Examples of the crosslinking reactive unit include a structural unit obtained by polymerization of a monomer having a self-crosslinking functional group in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether; carboxyl group, hydroxy group, amino group, sulfo group A structural unit obtained by polymerization of a monomer having, for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc. And a structural unit in which a crosslinkable reactive group such as a (meth) acryloyl group is introduced by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group).

  In addition to the fluorine-containing monomer unit and the cross-linking reactive unit, from the viewpoint of solubility in a solvent, film transparency, and the like, a monomer not containing a fluorine atom is appropriately copolymerized to introduce another polymerization unit. You can also. There are no particular limitations on the monomer units that can be used in combination, such as olefins [ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.], acrylic esters [methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2 -Ethylhexyl], methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers [methyl Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters [vinyl acetate, vinyl propionate, vinyl cinnamate, etc.], acrylamides [N-tertbutylacrylamide, N-silane] B hexyl acrylamide], methacrylamides, and acrylonitrile derivatives.

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

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

The low refractive index layer according to the present invention is more preferably a cured film formed from a coating solution having a fluorine-containing polymer and / or a polysiloxane-containing vinyl monomer.
In this case, the fluorine-containing polymer is preferably a copolymer having a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in the side chain as essential constituent components. After film formation, the copolymer-derived component preferably occupies 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. From the viewpoint of achieving both low refractive index and film hardness, a curing agent such as polyfunctional (meth) acrylate is also preferably used in an addition amount within a range that does not impair the compatibility.
Further, compounds described in JP-A-11-228631 are also preferably used.

The copolymer preferably used for forming the low refractive index layer in the present invention will be described below.
Examples of the fluorine-containing vinyl monomer 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.) and R-2020 (trade name, manufactured by Daikin Industries, Ltd.)), and 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. Increasing the composition ratio of these fluorinated vinyl monomers can lower the refractive index but lowers the film strength. In the present invention, 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%. This is a case of mass%.

  In the present invention, the copolymer preferably has a repeating unit having a (meth) acryloyl group in the side chain as an essential component. If the composition ratio of these (meth) acryloyl group-containing repeating units is increased, the film strength is improved, but the refractive index is also increased. Generally, the (meth) acryloyl group-containing repeating unit preferably occupies 5 to 90% by mass, more preferably 30 to 70% by mass, although it varies depending on the type of repeating unit derived from the fluorine-containing vinyl monomer. It is particularly preferred to account for ~ 60% by weight.

  In the copolymer useful for the present invention, in addition to the repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, it contributes to adhesion to the substrate and Tg of the polymer (film hardness). And other vinyl monomers can be copolymerized as appropriate from various viewpoints such as solubility in a solvent, 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 in total, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 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, methyl acrylate, ethyl acrylate, acrylic acid) -2-ethylhexyl, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethyl) Styrene, p-methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (acetic acid) Nyl, 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), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  In the present invention, a thermosetting and / or ionizing radiation curable fluorine-containing polymer described by the following general formula 1 or general formula 2 is preferably used.

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, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, or may have a heteroatom selected from O, N, and S.
Preferred examples include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * — (CH ₂ ). _{6 -O - **, - (CH} 2) 2 -O- (CH 2) 2 -O - **, * - CONH- (CH 2) 3 -O - **, * - CH 2 CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a connecting site on the polymer main chain side, and ** represents a connecting site on the (meth) acryloyl group side) And the like. 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 the 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. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

  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.

  General formula 2 is also mentioned as a fluorine-containing polymer used for this invention.

In the general formula 2, R represents an alkyl group having 1 to 10 carbon atoms or an ethylenically unsaturated group of the general formula 1 (—O (C═O) C (—X) ═CH ₂ ).
m represents an integer of 1 ≦ m ≦ 10, preferably 1 ≦ m ≦ 6, and particularly preferably 1 ≦ m ≦ 4.
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. Moreover, the silicone site | part may be included.
x, y, z1, and z2 represent mol% of each repeating unit, and x and y satisfy 30 ≦ x ≦ 60 and 0 ≦ y ≦ 70, respectively, preferably 35 ≦ x ≦ 55, 0 ≦ y ≦ 60, particularly preferably 40 ≦ x ≦ 55 and 0 ≦ y ≦ 55. z1 and z2 satisfy 1 ≦ z1 ≦ 65, 1 ≦ z2 ≦ 65, preferably 1 ≦ z1 ≦ 40, 1 ≦ z2 ≦ 10, and 1 ≦ z1 ≦ 30, 1 ≦ z2 ≦ 5. Is particularly preferred. However, x + y + z1 + z2 = 100.
Preferable specific examples of the copolymer represented by the general formula 1 or 2 include those described in [0035] to [0047] of JP-A-2004-45462, and the method described in the publication Can be synthesized.

Furthermore, the fluorine-containing polymer of the present invention preferably has a structural unit having the following polysiloxane structure in order to impart antifouling properties.
Preferred fluorine-containing polymers having a polysiloxane structure in the present invention are (a) a fluorine-containing vinyl monomer polymerized unit, (b) a hydroxyl group-containing vinyl monomer polymerized unit, and (c) a side chain represented by the following general formula 3. Examples thereof include fluorine-containing polymers each containing at least one kind of polymerized unit having a graft site containing a polysiloxane repeating unit and having a main chain composed only of carbon atoms.

Formula 3

In General Formula 3, R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. As an alkyl group, C1-C4 is preferable and a methyl group, a trifluoromethyl group, an ethyl group etc. are mentioned as an example. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. p represents an integer of 2 to 500, preferably 5 to 350, and particularly preferably 8 to 250.

  The polymer having a polysiloxane structure represented by the general formula 3 in the side chain is, for example, an epoxy group, a hydroxyl group as described in J. Appl. Polym. Sci. 2000, 78, 1955, JP-A-56-28219, etc. The reactive group (for example, an amino group, a mercapto group, a carboxyl group, a hydroxyl group, etc. with respect to an epoxy group or an acid anhydride group) is separated from a polymer having a reactive group such as a carboxyl group or an acid anhydride group. It can be synthesized by a method of introducing a polysiloxane having a terminal (for example, Silaplane series (manufactured by Chisso Corporation)) by a polymer reaction or a method of polymerizing a polysiloxane-containing silicon macromer, and both methods are preferably used. Can do. In the present invention, a method of introducing by polymerization of silicon macromer is more preferable.

  Any silicon macromer may be used as long as it has a polymerizable group capable of copolymerization with a fluorine-containing olefin, and preferably has a structure represented by any one of formulas 4 to 7.

In General Formulas 4 to 7, R ¹ , R ² and p represent the same meaning as in General Formula 3, and preferred ranges thereof are also the same. R ^{3 to} R ⁵ each independently represents a substituted or unsubstituted monovalent organic group or a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, an octyl group, etc.), a carbon number of 1 10 to 10 alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group and the like), aryl groups having 6 to 20 carbon atoms (for example, phenyl group, naphthyl group and the like) are preferable, and alkyl groups having 1 to 5 carbon atoms are particularly preferable. . R ⁶ represents a hydrogen atom or a methyl group. L ₁ represents an arbitrary linking group having 1 to 20 carbon atoms, and includes a substituted or unsubstituted linear, branched or alicyclic alkylene group, or a substituted or unsubstituted arylene group. It is an unsubstituted linear alkylene group of 1 to 20, particularly preferably an ethylene group or a propylene group. These compounds are synthesized, for example, by the method described in JP-A-6-322053.

  Any of the compounds represented by the general formulas 4 to 7 can be preferably used in the present invention. Of these, the structure represented by the general formula 4, 5 or 6 is particularly preferred from the viewpoint of copolymerization with the fluorinated olefin. Those are preferred. The polysiloxane moiety preferably occupies 0.01 to 20% by mass of the graft copolymer, more preferably 0.05 to 15% by mass, and particularly preferably 0.5 to 10%. This is the case.

  Although the preferable example of the polymer unit of the polymer graft part which contains a polysiloxane part in the side chain useful for this invention below is shown, this invention is not limited to these.

S- (36) Silaplane FM-0711 (manufactured by Chisso Corporation)
S- (37) Silaplane FM-0721 (same as above)
S- (38) Silaplane FM-0725 (same as above)

  By introducing the polysiloxane structure, the film is imparted with antifouling property and dustproof property, and the film surface is provided with slipperiness, which is advantageous for scratch resistance.

  Preferred examples of the fluorine-containing polymer useful in the present invention are shown below, but the present invention is not limited thereto.

  The copolymer used for this invention is compoundable by the method as described in Unexamined-Japanese-Patent No. 2004-45462. The copolymer used in the present invention can be synthesized by various polymerization methods other than those described above, for example, precursors such as a hydroxyl group-containing polymer by solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. Can be carried out by introducing a (meth) acryloyl group by the polymer reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating ionizing radiation, and the like. These polymerization methods and polymerization initiation methods are described in, for example, Tsuruta Junji, “Polymer Synthesis Method” revised edition, Nikkan Kogyo Shimbun, 1971 and Takatsu Otsu, Masaaki Kinoshita, “Experimental Methods for Polymer Synthesis”, Chemistry 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 (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, Benzene, toluene, acetonitrile, methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture of two or more kinds of organic solvents may be used. A mixed solvent 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, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to carry out the polymerization in the range of 50 to 100 ° C.

  The reaction pressure can be selected as appropriate, but usually 1 to 100 kPa, particularly about 1 to 30 kPa is desirable. 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.

  On the other hand, as the polysiloxane-containing vinyl monomer used for forming the low refractive index layer in the present invention, those represented by the following general formula I are preferable.

In the general formula I, R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. P represents an integer of 10 to 500. R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a monovalent organic group, and R ₆ represents a hydrogen atom or a methyl group. L represents a single bond or a divalent linking group, and n represents 0 or 1.

In the general formula I, R ¹ and R ² represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group. R ¹ and R ² may be the same or different. As an alkyl group, C1-C4 is preferable and a methyl group, a trifluoromethyl group, an ethyl group etc. are mentioned as an example. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. Examples of the substituent which may be substituted in R ¹ and R ² include an alkyl group having 1 to 6 carbon atoms (for example, methyl and ethyl), an aryl group having 6 to 10 carbon atoms (for example, phenyl), and 1 carbon atom. -6 alkoxy group (for example, methoxy, ethoxy), C1-C6 alkoxycarbonyl group (for example, methoxycarbonyl), cyano group, fluorine atom and chlorine atom.
p represents an integer of 10 to 500, preferably 50 to 300, and particularly preferably 100 to 250.

R ^{3 to} R ⁵ each represent a substituted or unsubstituted monovalent organic group or a hydrogen atom, preferably an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, octyl group, etc.), Represents an alkoxy group of 10 (methoxy group, ethoxy group, propyloxy group, etc.), an aryl group of 6-20 carbon atoms (phenyl group, naphthyl group, etc.), more preferably a phenyl group or an alkyl group of 1-5 carbon atoms. And particularly preferably a methyl group. R ^{3 to} R ⁵ may be the same or different. Preferable substituents which may be substituted for R ^{3 to} R ⁵ are the same as those exemplified as the substituents for R ¹ and R ² . R ⁶ represents a hydrogen atom or a methyl group. L represents a single bond or a divalent linking group, preferably having 1 to 25 carbon atoms, and is not particularly limited as long as it can link a polymerizable vinyl group, but more preferably It has a structure represented by general formula II or general formula III. n represents 0 or 1.

In the above general formula II or general formula III, L ′ represents a substituted or unsubstituted linear, branched or alicyclic alkylene group, or a substituted or unsubstituted arylene group, preferably an alkylene group having 1 to 25 carbon atoms. Or an arylene group, more preferably an unsubstituted linear alkylene group having 1 to 25 carbon atoms, and particularly preferably an ethylene group or a propylene group. As the substituent for L ′, those exemplified as the substituents for R ¹ and R ² are preferable.

  Although the preferable example of the polymerization unit which contains a polysiloxane part in the side chain useful for this invention derived from a polysiloxane containing vinyl monomer below is shown, this invention is not limited to these.

  When the fluorine-containing polymer main body contains a hydroxyl group, it is preferable to use a curing agent having two or more functional groups capable of reacting with the hydroxyl group in one molecule. The curing agent having two or more functional groups capable of reacting with a hydroxyl group in one molecule is not particularly limited. For example, polyisocyanates, partial condensates of isocyanate compounds, multimers, polyhydric alcohols, low molecular weight polyester films, etc. Adducts, blocked polyisocyanate compounds in which isocyanate groups are blocked with a blocking agent such as phenol, aminoplasts, polybasic acids or anhydrides thereof. When these curing agents are used, the content of the hydroxyl group-containing monomer unit is preferably 2% to 80%, more preferably 10% to 50%, and most preferably 25% to 50%.

  Among the curing agents that react with hydroxyl groups, in the present invention, a crosslinking reaction with a hydroxyl group-containing compound under acidic conditions from the viewpoint of compatibility between stability during storage and activity of crosslinking reaction, and strength of the formed film. Aminoplasts are preferred. Aminoplasts include an amino group capable of reacting with a hydroxyl group present in a fluorine-containing polymer, that is, a hydroxyalkylamino group or an alkoxyalkylamino group, or a carbon atom adjacent to a nitrogen atom and substituted with an alkoxy group. It is preferable that it is a compound to be. Specific examples include melamine compounds, urea compounds, benzoguanamine compounds, and the like.

  The melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, and alkoxylated methyl melamine. . In particular, methylolated melamine and alkoxylated methyl melamine obtained by reacting melamine and formaldehyde under basic conditions and derivatives thereof are preferable, and alkoxylated methyl melamine is particularly preferable in view of storage stability. There are no particular restrictions on methylolated melamine and alkoxylated methylmelamine. For example, use of various resins obtained by the method described in “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun) Is also possible.

  As the urea compound, in addition to urea, an alkoxylated methylurea which is a polymethylolated urea derivative thereof, and a compound having a glycoluril skeleton or a 2-imidazolidinone skeleton having a cyclic urea structure are also preferable. As for the amino compounds such as the urea derivatives, various resins described in the above-mentioned “Yurea / Melamine resin” can be used.

  As the compound suitably used as the crosslinking agent in the present invention, a melamine compound or a glycoluril compound is particularly preferable from the viewpoint of compatibility with the fluorine-containing copolymer, and among these, from the viewpoint of reactivity, the crosslinking agent is in the molecule. The compound preferably contains a nitrogen atom and contains two or more carbon atoms substituted with an alkoxy group adjacent to the nitrogen atom. Particularly preferred compounds are compounds having structures represented by the following H-1 and H-2, and partial condensates thereof. In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a hydroxyl group.

  As addition amount of aminoplast with respect to a fluorine-containing polymer, it is 1-50 mass parts per 100 mass parts of copolymers, Preferably it is 3-40 mass parts, More preferably, it is 5-30 mass parts. If it is 1 part by mass or more, the durability as a thin film that is a feature of the present invention can be sufficiently exhibited, and if it is 50 parts by mass or less, the low refractive index layer in the present invention when used for optical applications. This is preferable because the low refractive index, which is a characteristic of the above, can be maintained. From the viewpoint of keeping the refractive index low even when a curing agent is added, a curing agent that has a small increase in refractive index even when added is preferable, and from this viewpoint, the above compound has a skeleton represented by H-2. Compounds are more preferred.

  In the film formation of the present invention, particularly when an aminoplast type curing agent is added, it is preferable to cure the film by a crosslinking reaction between the hydroxyl group of the fluoropolymer and the curing agent while heating and / or irradiating with light. In this system, since curing is accelerated by acid, it is desirable to add an acidic substance to the curable resin composition. However, when a normal acid is added, the crosslinking reaction proceeds in the coating solution, and failure (unevenness, Cause repellency. Therefore, in order to achieve both storage stability and curing activity in a thermosetting system, it is more preferable to add a compound that generates an acid by heating as a curing catalyst.

  The curing catalyst is preferably a salt composed of an acid and an organic base. Examples of the acid include organic acids such as sulfonic acid, phosphonic acid, and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid. From the viewpoint of compatibility with the polymer, organic acids are more preferable, and sulfonic acid and phosphonic acid are more preferable. Sulphonic acid is most preferred. Preferred sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS). ), Methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), etc., and any of them can be preferably used (the abbreviations in parentheses).

  The curing catalyst varies greatly depending on the basicity and boiling point of the organic base combined with the acid. The curing catalyst preferably used in the present invention is described below from each viewpoint.

The lower the basicity of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. However, if the basicity is too low, the storage stability becomes insufficient. Therefore, it is preferable to use an organic base having an appropriate basicity. When expressed using pKa of a conjugate acid as a basic index, the pKa of the organic base used in the present invention needs to be 5.0 to 10.5, and more preferably 6.0 to 10.0. 6.5 to 10.0 is more preferable. The pKa value of an organic base is the value in an aqueous solution. Basic Manual (5th revised edition, edited by the Chemical Society of Japan, Maruzen, 20
2004) Volume II, pages II-334-340, from which organic bases having an appropriate pKa can be selected. In addition, a compound that can be presumed to have an appropriate pKa in terms of structure even if not described in this document can be preferably used. Although the compound which has suitable pKa described in this literature in the following table | surface is shown, the compound which can be preferably used for this invention is not limited to these.

  The lower the boiling point of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. Therefore, it is preferable to use an organic base having an appropriate boiling point. The boiling point of the base is preferably 120 ° C. or lower, more preferably 115 ° C. or lower, further preferably 80 ° C. or lower, and particularly preferably 70 ° C. or lower.

Examples of the organic base that can be preferably used in the present invention include, but are not limited to, the following compounds. Figures in parentheses indicate boiling points.
b-3: pyridine (115 ° C), b-14: 4-methylmorpholine (115 ° C), b-20: diallylmethylamine (111 ° C), b-19: triethylamine (88.8 ° C), b-21 : T-butylmethylamine (67-69 ° C), b-22: dimethylisopropylamine (66 ° C), b-23: diethylmethylamine (63-65 ° C), b-24: dimethylethylamine (36-38 ° C) ).
The boiling point of the organic base of the present invention is 35 ° C. or higher and 120 ° C. or lower. If the temperature is higher than this, the scratch resistance deteriorates, and if it is lower than 35 ° C., the coating solution becomes unstable. The boiling point is more preferably 35 ° C. or higher and 120 ° C. or lower, and most preferably 40 ° C. or higher and 115 ° C. or lower.

  When used as the acid catalyst of the present invention, a salt composed of the acid and the organic base may be isolated and used, or the acid and the organic base may be mixed to form a salt in the solution, and the solution may be used. . Further, only one kind of acid or organic base may be used, or a plurality of kinds may be mixed and used. When the acid and the organic base are mixed and used, it is preferable that the equivalent ratio of the acid and the organic base is 1: 0.9 to 1.5, preferably 1: 0.95 to 1.3. Is more preferable, and 1: 1.0 to 1.1 is preferable.

  The use ratio of the acid catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 100 parts by mass of the fluoropolymer in the curable resin composition. 0.2 to 3 parts by mass.

  In the present invention, in addition to the thermal acid generator described above, a compound that generates an acid upon irradiation with light, that is, a photosensitive acid generator may be further added. The photosensitive acid generator is a substance that imparts photosensitivity to the coating film of the curable resin composition and enables the coating film to be photocured by, for example, irradiation with radiation such as light. Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt; (2) β-ketoester, β-sulfonylsulfone and these Sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters and imino sulfonates; (4) sulfonimide compounds; (5) diazomethane compounds (5) Trihalomethyltriazines of the present invention; others can be mentioned and can be used as appropriate.

  The photosensitive acid generator can be used alone or in combination of two or more, and can also be used in combination with the thermal acid generator. The use ratio of the photosensitive acid generator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluoropolymer in the curable resin composition. If the ratio of the photosensitive acid generator is less than or equal to the upper limit, it is preferable because the resulting cured film has excellent strength and good transparency.

  Examples of the onium compound include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, and selenonium salts. Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of photosensitivity at the start of photopolymerization, material stability of the compound, and the like. Examples thereof include compounds described in paragraph numbers [0058] to [0059] of JP-A-2002-29162.

The use ratio of the photosensitive acid generator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the curable resin composition.
In addition, as specific compounds and methods of use, for example, the contents described in JP-A-2005-43876 can be used.

The curable composition for forming the low refractive index layer preferably contains (A) the above-mentioned fluoropolymer, (B) inorganic fine particles, and (C) an organosilane compound described later.
<Inorganic fine particles for low refractive index layer>
The inorganic fine particles that can be preferably used for the low refractive index layer in the antireflection film of the present invention will be described.
The coating amount of the inorganic fine particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.
Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include fine particles of magnesium fluoride, silica or hollow silica, and fine particles of silica or hollow silica are preferable. The average particle size of the inorganic fine particles is preferably 30% or more and 150% or less of the thickness of the low refractive index layer, more preferably 30% or more and 100% or less, still more preferably 35% or more and 80% or less, and particularly preferably 40% or more. 60% or less. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the inorganic fine particles is preferably 30 nm to 150 nm, more preferably 30 nm to 100 nm, still more preferably 35 nm to 80 nm, and particularly preferably. 40 nm or more and 60 nm or less.
If the particle size of the inorganic fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The inorganic fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to lower the refractive index of the low refractive index layer, it is preferable to use hollow silica fine particles. The hollow silica fine particles preferably have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and still more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x is calculated by the following mathematical formula (I).
(Formula ^{I) x = (4πa 3/} 3) / (4πb 3/3) × 100
The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%. If the hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Rate particles do not hold.
The refractive index of these hollow silica particles was measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).
A method for producing hollow silica is described in, for example, JP-A Nos. 2001-233611 and 2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A-2002-79616.

  When the hollow particles are used, the refractive index of the layer is preferably 1.20 or more and 1.46 or less, more preferably 1.25 or more and 1.41 or less, and most preferably 1.30 or more and 1.39 or less. It is.

In addition, at least one kind of inorganic fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle inorganic particles”) is used as the inorganic fine particles having the above particle size (“large size particles”). It is preferably used in combination with “inorganic fine particles having a diameter”.
Since the inorganic fine particles having a small particle size can exist in the gaps between the inorganic fine particles having a large particle size, they can contribute as a retaining agent for the inorganic fine particles having a large particle size.
When the low refractive index layer is 100 nm, the average particle size of the inorganic fine particles having a small size is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm, and particularly preferably 10 nm to 15 nm. Use of such inorganic fine particles is preferable in terms of raw material costs and a retaining agent effect.
As described above, the inorganic fine particles have an average particle diameter of 30 to 100% of the thickness of the low refractive index layer as described above, have a hollow structure, and have a refractive index of 1.17 to 1. What is 40 is used especially preferably.

Inorganic fine particles are treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. Of these, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
The coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is further added as an additive during preparation of the layer coating solution. It is preferable to make it contain in a layer.
The inorganic fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
Next, (C) the organosilane compound will be described.
<Organosilane compound for low refractive index layer>
The curable composition contains a hydrolyzate of an organosilane compound and / or a partial condensate thereof (hereinafter, the obtained reaction solution is also referred to as a “sol component”). In particular, it is preferable in terms of achieving both the antireflection ability and the scratch resistance.
This sol component functions as a binder for the low refractive index layer by applying the curable composition and then condensing in a drying and heating process to form a cured product. Moreover, in this invention, since it has the said fluorine-containing polymer, the binder which has a three-dimensional structure is formed by irradiation of actinic light.
The organosilane compound is preferably represented by the following general formula [A].
Formula [A]
(R ¹⁰ ) _m -Si (X) _4-m

In the 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, hexyl, decyl, hexadecyl and the like. The alkyl group is preferably an alkyl group having 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.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ), And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively.
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 (phenoxy, etc.), alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio) ), Alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl Groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino, meta Riruamino etc.), and the like. These substituents may be further substituted.

When there are a plurality of R ^{10 s} , at least one is preferably a substituted alkyl group or a substituted aryl group.
Among the organosilane compounds represented by the general formula [A], an organosilane compound having a vinyl polymerizable substituent represented by the following general formula [B] is preferable.

General formula [B]

In the general formula [B], R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ¹ ) —, and ** represents a position bonded to L.

  L 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.

n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ 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.
X has the same meaning as in the general 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.

  Two or more compounds of the general formula [A] and general formula [B] may be used in combination. Although the specific example of a compound represented by general formula [A] and general formula [B] is shown below, it is not limited.

  Of these, (M-1), (M-2), and (M-5) are particularly preferable.

The hydrolyzate and / or partial condensate of the organosilane compound is generally produced by treating the organosilane compound 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. In the present invention, it is preferable to use a metal chelate compound, an acid catalyst of inorganic acids and organic acids. Inorganic acids are preferably hydrochloric acid and sulfuric acid, and organic acids are preferably those having an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and further, acid dissociation constants in hydrochloric acid, sulfuric acid and water. Is preferably an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferably an organic acid having an acid dissociation constant of 2.5 or less in water. Specifically, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

As the metal chelate compound, (wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ³ OH alcohol and R ⁴ COCH ₂ COR ⁵ (formula represented by, R ⁴ is the number of carbon atoms 1 to 10 alkyl groups, R ⁵ 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 is selected from Zr, Ti, and Al. Any metal having a central metal as the metal can be used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ Those selected from the group of compounds represented by COCHCOR ⁵ ) _r2 are preferred and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. 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, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  In the present invention, it is preferable that a β-diketone compound and / or a β-ketoester compound is further added to the curable composition. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used in the present invention, and is used as a stability improver for the curable composition used in the present invention. It works. Here, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound 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 compounding amount of the organosilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and most preferably 1 to 10% by mass based on the total solid content of the low refractive index layer.
The organosilane compound may be added directly to the curable composition (coating liquid for antiglare layer, low refractive index layer, etc.), but the organosilane compound is treated in the presence of a catalyst in advance to prepare the organosilane compound. It is preferable to prepare a hydrolyzate and / or partial condensate of a silane compound and prepare the curable composition using the obtained reaction solution (sol solution). In the present invention, first, the organosilane compound A composition containing a hydrolyzate and / or a partial condensate and a metal chelate compound is prepared, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound thereto is added to at least an antiglare layer or a low refractive index layer. It is preferable to coat it in a single layer coating solution.

  5-100 mass% is preferable, the usage-amount of the sol component of the organosilane with respect to a fluorine-containing polymer in a low refractive index layer has more preferable 5-40 mass%, 8-35 mass% is still more preferable, 10-30 mass % Is particularly preferred. If the amount used is small, it is difficult to obtain the effect of the present invention, and if the amount used is too large, the refractive index increases or the shape / surface shape of the film deteriorates.

  In the present invention, it is preferable to add a hydrolyzate of organosilane and / or a partial condensate (sol) thereof from the viewpoint of improving the film strength. The preferable addition amount of sol is preferably 2 to 200% by mass of the inorganic oxide particles, more preferably 5 to 100% by mass, and most preferably 10 to 50% by mass.

  To the curable composition, inorganic fine particles other than the inorganic fine particles described above can be added in an addition amount that does not impair the desired effect of the present invention. Details of the inorganic fine particles will be described later.

[Other substances contained in curable composition for low refractive index layer]
The curable composition comprises the above-mentioned (A) fluorine-containing polymer, (B) inorganic fine particles and (C) organosilane compound, if necessary, various additives and a radical polymerization initiator and a cationic polymerization initiator described later. It is prepared by adding them and further dissolving them in a suitable solvent. At this time, the concentration of the solid content is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably 1% to 20% by mass. %.

  Curing agents such as polyfunctional (meth) acrylate compounds, polyfunctional epoxy compounds, polyisocyanate compounds, aminoplasts, polybasic acids or anhydrides thereof from the viewpoint of interfacial adhesion with the lower layer directly in contact with the low refractive index layer Can also be added in small amounts. When adding these, it is preferable to set it as the range of 30 mass% or less with respect to the total solid of a low refractive index layer film | membrane, It is more preferable to set it as the range of 20 mass% or less, The range of 10 mass% or less It is particularly preferable that

In the present invention, it is preferable to reduce the surface free energy on the surface of the antireflection film from the viewpoint of improving the antifouling property. Specifically, it is preferable to use a fluorine-containing compound or a silicone compound having a polysiloxane structure in the low refractive index layer.
In addition, for the purpose of imparting properties such as antifouling properties, water resistance, chemical resistance, and slipping properties, a known silicone compound or fluorine compound antifouling agent, slipping agent, and the like may be appropriately added. When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass.

Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl 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 molecular weight, 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 silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%.
Examples of preferred silicone compounds are X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), Chisso Corporation, FM-0725, FM-7725, FM-4421, FM-5521, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS- 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (named above) but not limited thereto. Moreover, the silicone type compound of Table 2 and Table 3 of Unexamined-Japanese-Patent No. 2003-112383 can also be used preferably. These polysiloxanes are preferably added in the range of 0.1 to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1 to 5% by mass.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), but alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl groups) , A perfluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C). ₄ F ₈ H, —CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , —CH ₂ C H ₂ OCF ₂ CF ₂ OCF ₂
CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.
It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, defender MCF-300 (trade name), etc., but are not limited thereto.

  For the purpose of imparting properties such as dust resistance and antistatic properties, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like can be appropriately added. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound or fluorine compound. When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferably 0.1 to 5% by mass. Examples of preferred compounds include, but are not limited to, Dainippon Ink Co., Ltd., Megafac F-150 (trade name), Toray Dow Corning Co., Ltd., SH-3748 (trade name), and the like. Do not mean.

<Solvent for low refractive index layer>
As a solvent used in the coating composition for forming the low refractive index layer according to the present invention, it is possible to dissolve or disperse each component, to easily form a uniform surface in the coating process and the drying process, and to preserve the liquid. Various solvents selected from the viewpoints of ensuring the property and having an appropriate saturated vapor pressure can be used. From the viewpoint of the drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of a solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.
Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), ethers such as tetrahydrofuran (66 ° C), ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as Luketone, 79.6 ° C, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.), propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.
Examples of the solvent having a boiling point of 100 ° C. or more include, for example, octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), and chlorobenzene (131.7 ° C.). , Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C.) 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

Polymerization of the fluorine-containing polymer and / or polysiloxane-containing vinyl monomer can be performed by irradiation with ionizing radiation or heating in the presence of the above-mentioned active halogen compound, other photoradical initiator or thermal radical initiator. .
Therefore, a coating solution containing the above fluoropolymer and / or polysiloxane-containing vinyl monomer, the above-mentioned active halogen compound, photoradical initiator or thermal radical initiator, and inorganic fine particles is prepared and supported. After coating on the body, it can be cured by a polymerization reaction with ionizing radiation or heat to form a low refractive index layer.

The low refractive index layer (Aspect 2) by the sol-gel method will be described.
Various sol-gel materials can also be used as the material for the low refractive index layer. As such a sol-gel material, metal alcoholates (alcohols such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  As the low refractive index layer, it is also preferable to use a layer formed by using inorganic or organic fine particles and forming microvoids between or within the fine particles. The average particle diameter of the fine particles is preferably from 0.5 to 200 mm, more preferably from 1 to 100 nm, further preferably from 3 to 70 nm, and most preferably from 5 to 40 nm. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible.

  The inorganic fine particles are preferably amorphous. The inorganic fine particles are preferably made of a metal oxide, nitride, sulfide or halide, more preferably a metal oxide or metal halide, and most preferably a metal oxide or metal fluoride. . As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb and Ni are preferred, and Mg, Ca, B and Si are more preferred. An inorganic compound containing two kinds of metals may be used. A particularly preferred inorganic compound is silicon dioxide, ie silica.

  The microvoids in the inorganic fine particles can be formed, for example, by cross-linking silica molecules forming the particles. Crosslinking silica molecules reduces the volume and makes the particles porous. (Porous) inorganic fine particles having microvoids are described in the sol-gel method (described in JP-A Nos. 53-112732 and 57-9051) or the precipitation method (APPLIED OPTICS, 27, page 3356 (1988)). ) Can be directly synthesized as a dispersion.

  Further, the powder obtained by the drying / precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available porous inorganic fine particles (for example, silicon dioxide sol) may be used. The inorganic fine particles having microvoids are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (eg, methanol, ethanol, isopropyl alcohol) and ketone (eg, methyl ethyl ketone, methyl isobutyl ketone) are preferable.

  The organic fine particles are also preferably amorphous. The organic fine particles are preferably polymer fine particles synthesized by polymerization reaction of monomers (for example, emulsion polymerization method). The organic fine particle polymer preferably contains a fluorine atom. The proportion of fluorine atoms in the polymer is preferably 35 to 80% by weight, and more preferably 45 to 75% by weight. It is also preferable to form microvoids in the organic fine particles by, for example, cross-linking the polymer forming the particles and reducing the volume. In order to crosslink the polymer forming the particles, it is preferable to use 20 mol% or more of the monomer for synthesizing the polymer as a polyfunctional monomer. The ratio of the polyfunctional monomer is more preferably 30 to 80 mol%, and most preferably 35 to 50 mol%. Examples of the monomer used for the synthesis of the organic fine particles include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene) as examples of monomers containing a fluorine atom used for synthesizing a fluorine-containing polymer. Perfluoro-2,2-dimethyl-1,3-dioxole), fluorinated alkyl esters of acrylic acid or methacrylic acid, and fluorinated vinyl ethers. A copolymer of a monomer containing a fluorine atom and a monomer not containing a fluorine atom may be used. Examples of monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic esters (eg, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate). , Methacrylates (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate), styrenes (eg, styrene, vinyl toluene, α-methyl styrene), vinyl ethers (eg, methyl vinyl ether), vinyl esters ( Examples include vinyl acetate, vinyl propionate), acrylamides (eg, N-tert-butylacrylamide, N-cyclohexylacrylamide), methacrylamides and acrylonitriles. Examples of polyfunctional monomers include dienes (eg, butadiene, pentadiene), esters of polyhydric alcohols and acrylic acid (eg, ethylene glycol diacrylate, 1,4-cyclohexane diacrylate, dipentaerythritol hexaacrylate), Esters of polyhydric alcohol and methacrylic acid (eg, ethylene glycol dimethacrylate, 1,2,4-cyclohexanetetramethacrylate, pentaerythritol tetramethacrylate), divinyl compounds (eg, divinylcyclohexane, 1,4-divinylbenzene), divinyl Examples include sulfones, bisacrylamides (eg, methylene bisacrylamide) and bismethacrylamides.

  Microvoids between particles can be formed by stacking at least two fine particles. When spherical fine particles having the same particle diameter (completely monodispersed) are closely packed, microvoids between fine particles having a porosity of 26% by volume are formed. When spherical fine particles having the same particle diameter are simply filled with cubic particles, microvoids between fine particles having a porosity of 48% by volume are formed. In an actual low-refractive index layer, the particle size distribution of fine particles and intra-particle microvoids exist, so the porosity varies considerably from the above theoretical value. When the porosity is increased, the refractive index of the low refractive index layer is lowered. By forming microvoids by stacking microparticles and adjusting the particle size of microparticles, the size of microvoids between particles can be easily adjusted to an appropriate value (does not scatter light and cause problems in the strength of the low refractive index layer). Can be adjusted. Furthermore, by making the particle diameters of the fine particles uniform, it is possible to obtain an optically uniform low refractive index layer in which the size of microvoids between particles is uniform. As a result, the low refractive index layer is microscopically a microvoided porous film, but can be made optically or macroscopically uniform. The interparticle microvoids are preferably closed in the low refractive index layer by fine particles and a polymer. The closed air gap also has an advantage that light scattering on the surface of the low refractive index layer is less than that of an opening opened on the surface of the low refractive index layer.

  By forming the microvoids, the macroscopic refractive index of the low refractive index layer becomes lower than the sum of the refractive indexes of the components constituting the low refractive index layer. The refractive index of the layer is the sum of the refractive indices per volume of the layer components. The refractive index of the constituent component of the low refractive index layer such as fine particles or polymer is larger than 1, whereas the refractive index of air is 1.00. Therefore, a low refractive index layer having a very low refractive index can be obtained by forming microvoids.

The low refractive index layer preferably contains the polymer in an amount of 5 to 50% by weight. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by weight of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treatment agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer of (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer and performing a polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to carry out a combination of two or all of the above (1) to (3), and to carry out a combination of (1) and (3) or a combination of (1) to (3). Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. When the fine particles are made of silicon dioxide, surface treatment with a silane coupling agent can be carried out particularly effectively. Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane are mentioned.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethyl Kishishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxy as those having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyl Oxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane are particularly preferred.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane couplings may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and hydrolysates thereof. The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (eg, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (eg, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by weight of fluorine atoms, more preferably 45 to 75% by weight of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Examples thereof include esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethylhexyl), methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (eg, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( Examples, methyl vinyl ether), vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (eg, N-tertbutylacrylamide, N-cyclohexylacrylamide), methacrylamide and Acrylonitrile and the like.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives Examples are 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound.

Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group.
Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. In the present invention, the cross-linking group is not limited to the above compound, and may be one showing reactivity as a result of decomposition of the functional group. Used for the polymerization reaction and crosslinking reaction of the binder polymer.

As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
An active halogen compound used in a hard coat layer or an antiglare layer is also preferably used.

  The binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after coating the low refractive index layer, by a polymerization reaction (if necessary, a crosslinking reaction). Even if a small amount of polymer (eg, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.46, and particularly preferably 1.30 to 1.46.
The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 100 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test under a 500 g load.
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.

[High (medium) refractive index layer]
In order to impart better antireflection performance to the antireflection film of the present invention, it is preferable to provide a high refractive index layer and / or a medium refractive index layer. The refractive index of the high refractive index layer in the antireflection film of the present invention is preferably 1.60 to 2.40, and more preferably 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55 to 1.80. The haze of the high refractive index layer and the medium refractive index layer is preferably 3% or less. The refractive index can be appropriately adjusted by adjusting the amount of inorganic fine particles to be added and the amount of binder used.

The high (medium) refractive index layer is made of an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony in order to increase the refractive index of the layer. Is preferably 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.
In order to increase the difference in refractive index from the mat particles contained in the high (medium) refractive index layer, the high (medium) refractive index layer using the high refractive index mat particles has a low refractive index. It is also preferred to use silicon oxide to maintain. The preferred particle size is the same as that of the inorganic filler in the hard coat layer described above.
Specific examples of the inorganic filler used in the high (medium) refractive index layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO _2. Can be mentioned. TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The addition amount of these inorganic fillers is adjusted according to the required refractive index, but in the case of a high refractive index layer, it is preferably 10 to 90% of the total mass, more preferably 20 to 80%, Especially preferably, it is 30 to 70%.
Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The high (medium) refractive index layer used in the present invention is preferably used in the dispersion liquid in which the inorganic filler is dispersed in the dispersion medium as described above, preferably the binder precursor necessary for matrix formation (the hard coat layer described above). A monomer having two or more ethylenically unsaturated groups as described above), the above-mentioned active halogen compound, etc. are added to form a coating composition for forming a high refractive index layer, and coating for forming a high refractive index layer on a support. Preferably, the composition is applied and cured by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or polyfunctional oligomer).

  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. As the radical photopolymerization initiator, the same one as the above-mentioned low refractive index layer is used.

In addition to the above components (inorganic fillers, polymerization initiators, photosensitizers, etc.), the high (medium) refractive index layer contains resins, surfactants, antistatic agents, coupling agents, thickeners, and coloring prevention. Agent, coloring agent (pigment, dye), anti-glare imparting particles, antifoaming agent, leveling agent, flame retardant, ultraviolet absorber, infrared absorber, adhesion promoter, polymerization inhibitor, antioxidant, surface modifier In addition, conductive metal fine particles can be added.
The film thickness of the high (medium) refractive index layer can be appropriately designed depending on the application. When a high (medium) refractive index layer is used as the optical interference layer, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

[Antistatic layer]
The transparent film of the present invention has an antistatic layer as necessary to prevent the occurrence of static electricity and to prevent the adhesion of dust and the effect of not being damaged by external static electricity when incorporated in a liquid crystal display or the like. It may be provided. As the performance of the antistatic layer in this case, the surface resistance after forming the transparent film is preferably 10 ¹² Ω / □ or less. However, even if it exceeds 10 ¹² Ω / □, dust adhesion can be prevented as compared with the case where no antistatic layer is provided.

  Examples of the antistatic agent contained in the antistatic resin composition include various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and first to third amino groups, and a sulfonate group. , Anionic antistatic agents having anionic groups such as sulfate ester base, phosphate ester base, phosphonate base, amphoteric antistatic agents such as amino acid and aminosulfate esters, amino alcohols, glycerols, polyethylene glycols Nonionic antistatic agents such as, various surfactant type antistatic agents such as metal chelate compounds such as organometallic compounds such as alkoxides of tin and titanium, and acetylacetonate salts thereof, and charging as described above High molecular weight antistatic agent having a high molecular weight, and tertiary amino groups and quaternary amines. Sulfonium groups, polymerizable antistatic agents such as an organic metal compound such as a coupling agent having polymerizable monomer or oligomer by ionizing radiation has a metal chelate portion, the same polymerizable functional groups by ionizing radiation may also be used.

Other antistatic agents contained in the antistatic resin composition include ultrafine particles having a particle size of 100 nm or less, such as tin oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and indium-doped zinc oxide (AZO). Antimony oxide, indium oxide, or the like can be used. In particular, it is preferable that the particle diameter is 100 nm or less, which is equal to or less than the wavelength of visible light, because the film becomes transparent after film formation and does not impair the transparency of the transparent film.

  By mixing the antistatic agent in the coating material for forming the hard coat layer and the antiglare layer, two properties of antistatic performance and hard coat property, and similarly two properties of antistatic performance and antiglare property. It becomes possible to obtain a coating film that improves the above simultaneously.

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

[Coating method]
The transparent film of the present invention, particularly the antireflection film, can be formed by the following method, but is not limited to this method.

[Formation of antireflection film]
Each layer of the antireflection film having a multilayer structure is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294) Can be formed by coating, but it is preferably coated by a die coating method, and more preferably by using a new die coater described later. Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, “Coating Engineering”, Asakura Shoten (1973), page 253.

In order to continuously produce the antireflection film of the present invention, a step of continuously feeding a roll-shaped base film, a step of applying and drying a coating liquid, a step of curing a coating film, a group having a cured layer A step of winding the material film is performed.
The base film is continuously fed from the roll-shaped base film to the clean room. In the clean room, the static electricity charged in the base film is removed by the electrostatic static neutralizer, and then it adheres to the base film. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating liquid is applied onto the base film in the coating section installed in the clean room, and the coated base film is sent to the drying room and dried.
The base film having the dried coating layer is sent from the drying chamber to the radiation curing chamber, irradiated with radiation, and the monomer contained in the coating layer is polymerized and cured. Furthermore, if necessary, the base film having a layer cured by radiation is sent to the thermosetting section and heated to complete the curing, and the base film having the cured layer is wound up and rolled. It becomes.

The above steps may be performed every time each layer is formed, or a plurality of coating units-drying chambers-radiation curing units-thermosetting chambers may be provided to form (coat) each layer continuously. However, it is preferable to continuously form each layer from the viewpoint of productivity. An example of the configuration of an apparatus for continuously applying each layer is shown in FIG. The apparatus has an appropriate number of film forming units 100, 200, 300, and 400 installed between Step 1 for continuously feeding a roll-shaped base film and Step 2 for winding the roll-shaped base film. Is. The apparatus shown in FIG. 5 is an example of a configuration in which four layers are continuously applied without winding up, but it is of course possible to change the number of film forming units in accordance with the layer configuration. The film forming unit 100 includes a process 101 for applying a coating liquid, a process 102 for drying a coating film, and a process 103 for curing the coating film.
Using an apparatus in which three film forming units are installed, a roll-shaped base film coated with the hard coat layer is continuously fed, and a medium refractive index layer, a high refractive index layer, and a low refractive index layer are provided for each. From the viewpoint of productivity, it is more preferable to wind up after sequentially coating with a film forming unit. Using the apparatus shown in FIG. 5 in which four film forming units are installed, a roll-shaped base film is continuously formed. It is more preferable from the viewpoint of significantly reducing the coating cost that the coating, the hard coat layer, the medium refractive index layer, the high refractive index layer, and the low refractive index layer are sequentially coated by each film forming unit. If necessary, the number of coating stations is reduced to two, and only two layers, the middle refractive index layer and the high refractive index layer, are formed in one step, and the results of checking the surface shape, film thickness, etc. are fed back. Thus, improving the yield is another preferable embodiment.

In the present invention, a die coating method is preferably used as a coating method from the viewpoint of a higher production rate. The die coating method is preferably used because it can achieve a high level of productivity and a surface shape without coating unevenness.
As a manufacturing method of the antireflection film of the present invention, the following coating method using such a die coating method is preferable.
That is, the manufacturing method includes a coating step of applying a coating liquid from the slot of the tip lip by bringing the land of the tip lip of the slot die close to the surface of the web that is continuously supported by the backup roll. A slot die having a land length of 30 μm or more and 100 μm or less in the web traveling direction of the tip lip on the web traveling direction side of the slot die is opposite to the web traveling direction when the slot die is set at the coating position. The gap between the tip lip and the web on the side is larger by 30 μm or more and 120 μm or less than the gap between the tip lip on the web traveling direction side and the web (hereinafter, this numerical limitation is referred to as “over bit length”). It is preferable to apply | coat using the coating device installed so that it might become.
In particular, a die coater that can be preferably used in the production method of the present invention will be described below with reference to the drawings. The die coater can be used when the wet coating amount is small (20 ml / m ² or less), and is preferable.

<Die coater configuration>
FIG. 6 is a cross-sectional view of a coater (coating apparatus) using a slot die that can suitably implement the present invention.
The coater 10 includes a backup roll 11 and a slot die 13, and a coating liquid 14 is discharged from the slot die 13 in a bead shape 14 a and applied to a web W that is supported by the backup roll 11 and continuously runs. Thus, the coating film 14b is formed on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section, and may be substantially circular or semicircular. The pocket 15 extends with its cross-sectional shape in the width direction of the slot die 13 (here, the width direction of the slot die 13 refers to the front side or the back side toward the drawing shown in FIG. 6). In the liquid storage space for the applied coating solution, the effective extension length is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper (not shown) that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W. The slot 16 has a cross-sectional shape in the width direction of the slot die 13 like the pocket 15, and the opening 16a located on the web side is generally Using a thing such as a width regulating plate (not shown), the length is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent to the web W running direction of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 18 called a land. The upstream side of the land 18 in the traveling direction of the web W with respect to the slot 16 (the traveling direction, that is, opposite to the arrow direction in the drawing) is the upstream lip land 18a, and the downstream side (the traveling direction side) is downstream. This is called side lip land 18b.
The shape of the tip lip 17 is extended on the downstream side compared to the upstream side (over bite shape), and the gap between the upstream lip land 18a and the web W is correspondingly larger than the gap between the downstream lip land 18b and the web W. Large in the above range. Further, the length of the downstream side lip land 18b is in the above-described range.
Referring to FIG. 7A, the part relating to the numerical limitation described above will be described. The land length on the traveling direction side (downstream side) of the web is a portion indicated by I _LO in FIG. The length of the overbyte is a portion indicated by LO in FIG.

Next, with reference to FIG. 7, the coating apparatus suitably used for the implementation of the method for producing an antireflection film of the present invention and a conventional coating apparatus will be described in comparison. Here, FIG. 7 shows the cross-sectional shape of the slot die 13 in comparison with the conventional one, (A) shows the slot die 13 suitable for the implementation of the present invention, and (B) shows the conventional slot die. 30 is shown.
In the conventional slot die 30, the distance between the upstream lip land 31a and the web of the downstream lip land 31b is equal. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 suitable for the implementation of the present invention, the downstream lip land length I _LO is shortened, whereby the application with a wet film thickness of 20 μm or less can be performed with high accuracy.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is preferably 30 μm to 100 μm, more preferably 30 μm to 80 μm, and most preferably 30 μm to 60 μm. If the land length I _LO of the downstream lip is 30 μm or more, the edge or land of the tip lip is hardly chipped, and it is preferable because the generation of streaks on the coating film can be suppressed. Moreover, it is easy to set the wet line position on the downstream side. Furthermore, the spread of the coating liquid on the downstream side can be suppressed, which is preferable. Spreading of the coating liquid on the downstream side due to wetting means non-uniformity of the wetting line and leads to a problem of causing a defective shape such as a streak on the coating surface. On the other hand, if the land length I _LO of the downstream lip is 100 μm or less, the bead 14a can be formed. When the coating solution forms the beads 14a, thin layer coating can be performed.

Furthermore, the downstream lip land 18b has an overbite shape closer to the web W than the upstream lip land 18a. Therefore, the degree of decompression can be reduced, and the bead formation 14a suitable for thin film coating can be achieved. The difference in the distance between the downstream lip land 18b and the web W of the upstream lip land 18a (hereinafter referred to as the overbite length LO) is preferably 30 μm to 120 μm, more preferably 30 μm to 100 μm, and most preferably 30 μm. It is 80 μm or less. When the slot die 13 has an overbite shape, the gap _GL between the tip lip 17 and the web W indicates the gap between the downstream lip land 18b and the web W.

Next, the overall coating process will be described with reference to FIG.
FIG. 8 is a perspective view showing the slot die 13 and its periphery in the coating step preferably performed in the present invention. A decompression chamber 40 is installed at a position where it does not come into contact with the slot die 13 on the side opposite to the moving direction side of the web W (that is, on the upstream side of the bead 14a) so that sufficient decompression adjustment can be performed on the bead 14a. Vacuum chamber 40, the gap between its operating efficiency has a back plate 40a and side plates 40b for holding a gap between the back plate 40a and the web W G _B, the side plate 40b and the web W G _S exists.
The relationship between the decompression chamber 40 and the web W will be described with reference to FIGS. 9 and 10 are sectional views showing the decompression chamber 40 and the web W which are close to each other.
Side plate 40b and the back plate 40a is may be of the chamber 40 body and integrally as shown in FIG. 9, for example, the back plate 40a to be appropriately changed gap G _B as shown in FIG. 10 into the chamber 40 A structure that is fastened with a screw 40c or the like may be used. In any structure, portions that are actually opened between the back plate 40a and the web W and between the side plate 40b and the web W are defined as gaps G _B and G _S , respectively. The gap G _B between the back plate 40a and the web W in the vacuum chamber 40, when the vacuum chamber 40 is placed under the web W and the slot die 13 as shown in FIG. 8, the uppermost end of the back plate 40a to the web W The gap is shown.

Is preferably installed to be larger than the gap G _L (see FIG. 7 (A)) of the end lip 17 and the web W of the slot die 13 the gap G _B between the back plate 40a and the web W, thereby backup roll Thus, the change in the degree of decompression near the bead due to the eccentricity of 11 can be suppressed. For example, when the gap G _L between the end lip 17 and the web W of the slot die 13 is 30μm or more 100μm or less, the gap G _B between the back plate 40a and the web W is preferably 100μm or 500μm or less.

<Material and accuracy>
Length in the web running direction of the traveling direction side of the end lip of the web (downstream lip land length shown in FIG. 7 (A) I _LO) is preferably in the range described above, also, the I _LO It is preferable that the fluctuation width in the slot die width direction is within 20 μm. Within this range, it is preferable that the bead does not become unstable due to slight disturbance.
As for the material of the tip lip of the slot die, it is not preferable to use a material such as stainless steel because it will sag at the stage of die processing. In the case of stainless steel or the like, it is difficult to satisfy the accuracy of the tip lip even if the downstream lip land length I _LO is in the range of 30 to 100 μm. In order to maintain high processing accuracy, it is preferable to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less. Cemented carbides include carbide crystal particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.
The downstream lip land length I _LO is important for realizing high-precision coating, and it is desirable to control the fluctuation width of the gap _{GL in} the slot die width direction. It is desirable that the backup roll 11 and the tip lip 17 achieve straightness within a range in which the fluctuation range of the gap _{GL in} the slot die width direction can be controlled. Preferably, the straightness of the tip lip 17 and the backup roll 11 is set so that the fluctuation width of the gap _{GL in} the slot die width direction is 5 μm or less.

When the antireflection film has a laminated structure, bright spot defects are easily noticeable when foreign matters such as dust and dust are present. The bright spot defect in the present invention is a defect that can be seen by reflection on the coating film as described above, and can be detected by an operation such as black coating on the back surface of the antireflection film after coating. The bright spot defects that can be visually observed are generally 50 μm or more. When there are many bright spot defects, the yield at the time of manufacture will fall and a large-area antireflection film cannot be manufactured.
In the antireflection film of the present invention, the number of bright spot defects is 20 or less per square meter, preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.

  In order to produce an antireflection film with few bright spot defects, it is possible to precisely control the degree of dispersion of the high refractive index ultrafine particles in the coating material for the high refractive index layer and to perform a fine filtration operation of the coating solution. At the same time, each layer forming the antireflection layer is subjected to a dusting process on the film before the coating process in the coating unit and the drying process performed in the drying chamber are performed in a clean air atmosphere and before the coating is performed. It is preferable that dust is sufficiently removed. The air cleanliness of the coating process and the drying process is desirably class 10 (353 particles / 0.5 m or more / (cubic meter) or less) based on the standard of air cleanliness in the US Federal Standard 209E. Preferably it is class 1 (35.5 particles / (cubic meter) or less) having a particle size of 0.5 μm or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

As a dust removal method used in the dust removal step as a pre-process for coating, a method of pressing a nonwoven fabric, a blade or the like against the film surface described in JP-A-59-150571, or JP-A-10-309553 Highly clean air is blown at a high speed to peel off the deposit from the film surface, and suction is performed by a suction port close to the surface. Ultrasonic-vibrated compressed air described in JP-A-7-333613 is sprayed to deposit. And a dry dust removal method such as a method of peeling and suctioning (manufactured by Shinkosha, New Ultra Cleaner, etc.).
In addition, a method of introducing a film into a cleaning tank and peeling off the adhered material by an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in Japanese Patent Application Laid-Open No. 2001-38306, a wet dust removing method such as a method in which a web is continuously rubbed with a roll wetted with a liquid and then a liquid is sprayed onto the rubbed surface for cleaning. be able to. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of dust removal effect.

  In addition, it is particularly preferable to remove static electricity on the base film before performing such a dust removal step in terms of increasing dust removal efficiency and suppressing dust adhesion. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the base film before and after dust removal and application is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

<Dispersion medium for coating>
The dispersion medium for coating is not particularly limited. You may use individually or in mixture of 2 or more types. Preferred dispersion media include aromatic hydrocarbons such as toluene, xylene and styrene, chlorinated aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene, methane derivatives such as monochloromethane, ethane derivatives such as monochloroethane, and the like. Chlorinated aliphatic hydrocarbons, alcohols such as methanol, isopropyl alcohol and isobutyl alcohol, esters such as methyl acetate and ethyl acetate, ethers such as ethyl ether and 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include ketones such as cyclohexanone, glycol ethers such as ethylene glycol monomethyl ether, alicyclic hydrocarbons such as cyclohexane, aliphatic hydrocarbons such as normal hexane, and mixtures of aliphatic or aromatic hydrocarbons. Among these solvents, a dispersion medium for coating prepared by alone or mixing two or more ketones is particularly preferable.

<Adjustment of coating solution>
First, a coating solution containing components for forming each layer is prepared. In that case, the raise of the moisture content in a coating liquid can be suppressed by suppressing the volatilization amount of a solvent to the minimum. The water content in the coating solution is preferably 5% by mass or less, and more preferably 2% by mass or less. The suppression of the volatilization amount of the solvent is achieved by improving the sealing property at the time of stirring after putting each material into the tank, minimizing the air contact area of the coating liquid at the time of liquid transfer operation, and the like. Moreover, you may provide the means to reduce the moisture content in a coating liquid during application | coating, or before and behind that.

<Filtration>
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 10 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 5 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filtration member of the wet dispersion of an inorganic compound mentioned above is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

  In particular, in the coating solution for forming the antiglare layer, almost all foreign matters (pointing to 90% or more) corresponding to the dry film thickness (about 50 nm to 120 nm) of the low refractive index layer directly formed thereon can be removed. It is preferable to perform filtration. Since the light-transmitting fine particles for imparting antiglare properties are equal to or greater than the film thickness of the low refractive index layer, the filtration should be performed on the intermediate liquid to which all materials other than the light-transmitting fine particles are added. Is preferred. In addition, when a filter capable of removing foreign substances having a small particle diameter as described above is not available, almost all foreign substances corresponding to the wet film thickness (about 1 to 10 μm) of the layer directly formed thereon are removed. It is preferable to perform filtration. By such means, the point defects of the layer formed directly thereon can be reduced.

<Physical properties of coating solution>
In the coating method by the die coating method, the upper limit speed at which coating can be performed is greatly affected by the liquid properties, so it is necessary to control the liquid properties, particularly the viscosity and the surface tension at the moment of coating.
The viscosity is preferably 2.0 [mPa · sec] or less, more preferably 1.5 [mPa · sec] or less, and most preferably 1.0 [mPa · sec] or less. Since there are some coating solutions whose viscosity changes depending on the shear rate, the above value indicates the viscosity at the shear rate at the moment of coating. When a thixotropic agent is added to the coating solution and the coating solution is subjected to high shear, the viscosity is low, and when the coating solution is hardly sheared, if the viscosity is high, unevenness during drying is less likely to occur.
Moreover, although it is not a liquid physical property, the quantity of the coating liquid apply | coated to a web also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the web is preferably 2.0 to 5.0 [ml / m ² ]. Increasing the amount of application liquid applied to the web is preferable because the upper limit of the application rate can be increased. However, excessively increasing the amount of application liquid applied to the web increases the load on drying, so the liquid formulation / process It is preferable to determine the optimum amount of coating solution to be applied to the web depending on the conditions.
The surface tension is preferably in the range of 15 to 36 [mN / m]. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating can be performed decreases, so the range of 17 [mN / m] to 32 [mN / m] is more preferred, and 19 [mN / m] to 26 [ mN / m] is more preferable.

<Wet application amount>
When forming the antiglare layer, it is preferable to apply the coating liquid in a range of 6 to 30 μm as a wet coating thickness directly or via another layer on the base film, from the viewpoint of preventing drying unevenness. Furthermore, the range of 3-20 micrometers is more preferable. Moreover, when forming a low refractive index layer, it is preferable to apply | coat a coating composition in the range of 1-10 micrometers as wet coating film thickness directly on an anti-glare layer or via another layer, More preferably, it is applied in the range of 5 μm.

<Application speed>
The manufacturing method using the above-described die coating method has a high film thickness stability at the time of high-speed application and is a pre-measuring method, so that it is easy to ensure a stable film thickness even at the time of high-speed application. As described above, when the wet coating amount is small (20 ml / m ² or less), the coating method can be applied at high speed with good film thickness stability to a low coating amount coating solution. In the method for producing an antireflection film of the present invention, a coating method using such a die coating method is preferable. In the dip coating method, vibration of the coating liquid in the liquid receiving tank is unavoidable, so stepped unevenness is likely to occur. In addition, since these coating methods are post-measuring methods, it is difficult to secure a stable film thickness. It is preferable to use it. From the standpoint of productivity, it is preferable to apply at a rate of 25 m / min or more using the above-described die coating method.

[Dry]
The antiglare layer and the low refractive index layer are applied directly on the base film or via other layers, and then conveyed by a web to a heated zone to dry the solvent. In this case, the temperature of the drying zone is preferably 25 ° C. to 140 ° C., the first half of the drying zone is relatively low temperature, and the second half is preferably relatively high temperature. However, it is preferably below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize. For example, some of the commercially available photo radical generators used in combination with ultraviolet curable resins volatilize around several tens of percent within a few minutes in warm air at 120 ° C. Some acrylate monomers and the like undergo volatilization in warm air at 100 ° C. In such a case, it is preferable that it is below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize as described above.

Moreover, the drying wind after apply | coating the coating composition of each layer on a base film has the wind speed of the coating-film surface 0.1-2 m / sec while the solid content concentration of the said coating composition is 1-50 mass%. It is preferable to be in the second range in order to prevent uneven drying.
Moreover, after apply | coating the coating composition of each layer on a base film, the temperature difference of the conveyance roll and base film which contacts the surface opposite to the application surface of a base film in a drying zone is 0 degreeC-20. Within the range of ° C., drying unevenness due to heat transfer unevenness on the transport roll can be prevented, which is preferable.

[Curing]
After the solvent drying zone, the coating is cured by passing through a zone where each coating is cured by ionizing radiation on the web. For example, if the coating film is UV curable, it is to cure each layer by irradiating an irradiation amount of ultraviolet rays of 10mJ / cm ² ~1000mJ / cm ² by an ultraviolet lamp preferred. At that time, the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation. Further, when it is necessary to purge nitrogen gas or the like to reduce the oxygen concentration in order to promote surface hardening, the oxygen concentration is preferably 0.01 vol% to 5 vol%, and the distribution in the width direction is 2 in terms of oxygen concentration. Volume% or less is preferable.
In this specification, ionizing radiation is used in a commonly used meaning, and refers to radiation that causes excitation and ionization when passing through a substance, that is, particle radiation and electromagnetic waves that are also simply called radiation. Specifically, α rays, β rays, γ rays, high energy particles, neutrons, electron beams, light rays (ultraviolet rays and visible rays), and the like. Particularly preferred ionizing radiations for the present invention are ultraviolet rays and visible rays.

  Further, when the curing rate (100-residual functional group content) of the antiglare layer becomes a certain value of less than 100%, the low refractive index layer of the present invention is provided on the antiglare layer to reduce the amount by ionizing radiation and / or heat. When the refractive index layer is cured, if the curing rate of the lower antiglare layer is higher than before the low refractive index layer is provided, the adhesion between the antiglare layer and the low refractive index layer is improved, which is preferable.

[Characteristics of transparent film]
The characteristic values of the transparent film of the present invention are as follows.
<Surface shape>
As the surface irregularity shape, the center line average roughness Ra is preferably 0 to 0.5 μm, most preferably 0.01 to 0.4 μm, and the 10-point average roughness Rz is 10 times or less of Ra, and the average mountain valley distance Sm is 1 to 100 μm, the standard deviation of the height of the convex part from the deepest part of the unevenness is 0.5 μm or less, the standard deviation of the average mountain valley distance Sm with respect to the center line is 20 μm or less, and the surface has an inclination angle of 0 to 5 degrees. It is preferable to design it to be 10% or more because sufficient anti-glare properties and a visually uniform mat feeling can be achieved. If Ra is less than 0.08, sufficient antiglare property cannot be obtained, and if it exceeds 0.30, problems such as glare and whitening of the surface when external light is reflected occur.
The center line average roughness Ra, the 10-point average roughness Rz, and the average mountain valley distance Sm can be measured with a commercially available surface roughness meter.
<Optical characteristics>
Further, the minimum reflectance of the reflected light in the CIE 1976 L ^* a ^* b ^* color space under the C light source is in the range of a ^* value −2 to 2, b ^* value −3 to 3, 380 nm to 780 nm. A ratio between the value and the maximum value of 0.5 to 0.99 is preferable because the color of the reflected light becomes neutral. Moreover, when the b ^* value of the transmitted light under the C light source is set to 0 to 3, the yellow color of white display when applied to a display device is reduced, which is preferable.

In addition, the transparent film of the present invention preferably has a haze due to internal scattering (hereinafter referred to as internal haze) of 5% to 20%, more preferably 5% to 15%. preferable. If the internal haze is less than 5%, combinations of materials that can be used are limited, and it is difficult to match antiglare and other characteristic values, and the cost is high. When the internal scattering exceeds 20%, the dark room contrast is greatly deteriorated.
Further, haze caused by surface scattering (hereinafter referred to as surface haze) is preferably 0% to 40%, more preferably 0% to 20%, and a transmission image at a comb width of 0.5 mm. A sharpness of 5% to 30% is preferable because sufficient antiglare properties and improvement in image blur and dark room contrast reduction are compatible. If the surface haze is less than 4%, the antiglare property is insufficient. Further, it is preferable that the specular reflectance is 2.5% or less and the transmittance is 90% or more because reflection of external light can be suppressed and visibility is improved.
The haze value (cloudiness value) is HR-1 manufactured by Murakami Color Research Laboratory according to JIS-K-7105.
It can be measured using 00.

The transparent film of the present invention produced as described above is used as a surface film of various known display materials with a known pressure-sensitive adhesive, or used for a liquid crystal display device by making a polarizing plate using this. be able to. In this case, it arrange | positions on the outermost surface of a display by providing an adhesive layer on one side. When the transparent film of the present invention is used for a polarizing plate, it is preferably used for at least one of two protective films sandwiching the polarizing film in the polarizing plate from both sides.
Since the film of the present invention also serves as a protective film, the manufacturing cost of the polarizing plate can be reduced. In particular, by using the antireflection film of the present invention as the outermost layer of the image display device, reflection of external light and the like are prevented, and a polarizing plate having excellent scratch resistance, brittleness, antifouling properties and the like is obtained. be able to.

  When creating a polarizing plate using the transparent film of the present invention as one of the surface protective films of two polarizing films, the surface opposite to the side having the functional layer of the transparent support in each film, That is, it is preferable to improve the adhesion on the adhesion surface by hydrophilizing the surface to be bonded to the polarizing film.

[Saponification]
When using the transparent film of this invention for a liquid crystal display device, it arrange | positions on the outermost surface of a display by providing an adhesive layer on one side. Moreover, you may use in combination with the transparent film and polarizing plate of this invention. When the transparent substrate is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is preferable in terms of cost to use the antireflection film of the present invention as it is for the protective film.

[Saponification]
(1) Method of immersing in alkali solution This is a method in which a transparent film is immersed in an alkali solution under appropriate conditions to saponify all surfaces that are reactive with alkali on the entire surface of the film. Since it is not necessary, it is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / L, particularly preferably 1 to 2 mol / L. The liquid temperature of a preferable alkali liquid is 30-75 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set according to the material and configuration of the transparent film and the target contact angle.
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 opposite to the surface having the antiglare layer or antireflection layer 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 adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle to water on the surface of the transparent support opposite to the side having the antiglare layer or the low refractive index layer, the better from the viewpoint of adhesiveness to the polarizing film. At the same time, since it is damaged by alkali from the surface having the antiglare layer and the low refractive index layer to the inside, it is important to set the necessary minimum reaction conditions. When the contact angle to water of the transparent support on the opposite surface is used as an index of damage to each layer due to alkali, particularly when the transparent support is triacetylcellulose, preferably 10 to 50 degrees, more preferably Is 30 to 50 degrees, more preferably 40 to 50 degrees. If it is 50 degrees or more, there is a problem in the adhesion to the polarizing film, which is not preferable. On the other hand, if the angle is less than 10 degrees, the damage received by the antireflection film is too large, so that the physical strength is impaired, which is not preferable.

(2) Method of applying alkaline solution As a means of avoiding damage to each film in the above immersion method, the alkaline solution is applied only to the surface opposite to the surface having the antiglare layer or antireflection film under appropriate conditions. An alkaline solution coating method of heating, washing with water and drying is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (1) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, and peeling due to alkali solution, so it is not desirable to use the immersion method. Is possible.

  In both the saponification methods (1) and (2), it can be carried out after forming each layer by unwinding from a roll-shaped support, and therefore, it is carried out by a series of operations in addition to the above-mentioned various film production steps. May be. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

(3) Method of saponifying by protecting the antiglare layer and antireflection layer with a laminate film As in the case of (2), when the antiglare layer and / or the low refractive index layer has insufficient resistance to an alkaline solution. Then, after forming the final layer, the laminate film is bonded to the surface on which the final layer is formed and then immersed in an alkaline solution to hydrophilize only the side of the triacetyl cellulose opposite to the surface on which the final layer has been formed. After being laminated, the laminate film can be peeled off. Even in this method, only the surface opposite to the surface on which the final layer of the triacetyl cellulose film is formed is subjected to the hydrophilization treatment necessary for the polarizing plate protective film without damaging the antiglare layer and the low refractive index layer. Can do. Compared with the method (2), there is an advantage that a laminate film is generated as waste, but a device for applying a special alkaline solution is unnecessary.

(4) Method of immersing in alkaline solution after forming up to antiglare layer Up to antiglare layer is resistant to alkaline solution, but when low refractive index layer is insufficiently resistant to alkaline solution, after forming up to antiglare layer It is also possible to soak both surfaces in an alkali solution to hydrophilize both surfaces, and then form a low refractive index layer on the antiglare layer. Although the manufacturing process becomes complicated, there is an advantage that the interlayer adhesion between the antiglare layer and the low refractive index layer is improved particularly when the low refractive index layer has a hydrophilic group such as a fluorine-containing sol-gel film.

(5) Method of forming an antiglare layer or an antireflection layer on a previously saponified triacetyl cellulose film Saponification is performed by immersing a triacetyl cellulose film in an alkaline solution in advance, either directly or on the other side. You may form an anti-glare layer and a low-refractive-index layer through a layer. In the case of saponification by dipping in an alkaline solution, interlayer adhesion between the antiglare layer or other layers and the triacetyl cellulose surface hydrophilized by saponification may deteriorate. In such a case, after saponification, only the surface on which the antiglare layer or other layer is formed is treated with corona discharge, glow discharge, etc. to remove the hydrophilic surface, and then the antiglare layer or other layer. Can be dealt with by forming Further, when the antiglare layer or other layer has a hydrophilic group, the interlayer adhesion may be good.

[Polarizer]
The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. The transparent film of the present invention is preferably used for at least one of two protective films (protective film for polarizing plate) sandwiching the polarizing film from both sides. As described above, the polarizing plate protective film has a water contact angle of 10 degrees to the surface of the transparent support opposite to the side having the antiglare layer or antireflection layer, that is, the surface to be bonded to the polarizing film. A range of 50 degrees is preferred.
The manufacturing cost of a polarizing plate can be reduced because the transparent film of the present invention also serves as a protective film. In particular, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance and antifouling properties can be obtained.

[Optical compensation layer]
The optical compensation film is a film having an optical compensation layer having optical anisotropy on a transparent support. As the transparent support, those used in the aforementioned transparent film and the like can be used.
By providing the polarizing plate with an optical compensation layer (retardation layer), the viewing angle characteristics of the liquid crystal display screen can be improved.
As the optical compensation layer, a known layer can be used. However, in terms of widening the viewing angle, the optical compensation layer has a layer having optical anisotropy made of a compound having a discotic structural unit, and is transparent to the discotic compound. An optical compensation layer characterized in that the angle formed with the support varies with the distance from the transparent support.
The angle preferably increases as the distance from the transparent support surface side of the optically anisotropic layer made of the discotic compound increases.
When the optical compensation film is used as a polarizing plate protective film, the surface of the optical compensation film on the side to be bonded to the polarizing film is preferably subjected to saponification treatment, and is preferably performed according to the saponification treatment.

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

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

<Liquid crystal display device>
The transparent film of the present invention 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). Since the film of the present invention has a transparent support, the transparent support is bonded to the image display surface of the image display device.

When the transparent film of the present invention is used as one side of a surface protective film of a polarizing film, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device in a mode such as a compensated bend cell (OCB). In particular, it can be preferably used for VA, IPS, OCB, etc., for applications such as large liquid crystal televisions, and can also be preferably used for TN, STN, etc., if it is used for display devices with small and medium definition. For applications such as large liquid crystal televisions, it is particularly preferable for a display screen having a diagonal of 20 inches or more and a definition of XGA or less (1024 × 768 or less in a display device having an aspect ratio of 3: 4). Can be used.
The transparent film of the present invention preferably has substantially no internal haze. In that case, the transparent film has a glare of 20 inches and a definition exceeding XGA (1024 × 768 in a display device having an aspect ratio of 3: 4). Is over the permissible level, which is not preferable when emphasizing glare. Further, since the degree of glare occurs due to the relationship between the size of the pixels and the surface unevenness of the transparent film surface, the definition becomes UXGA (with an aspect ratio of 3: 4 when the size of the display device is 30 inches. If the display device is 1600 × 1200) or less and 40 inches, the definition can be preferably up to QXGA (2048 × 1536 in a display device having an aspect ratio of 3: 4) or less.

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

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. These are disclosed in the specifications of Japanese Patent Nos. 4583825 and 5410422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

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

  In particular, for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having an effect of widening a viewing angle is used as a protective film having two polarizing films on both sides. Of these, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate by using it on the surface opposite to the antireflection film of the present invention.

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

[Example 1]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention should not be construed as being limited thereto.
(Preparation of coating solution for hard coat layer)
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
750.0 parts by weight of trimethylolpropane triacrylate (Biscoat # 295 (manufactured by Osaka Organic Chemical Co., Ltd.)), 270.0 parts by weight of polyglycidyl methacrylate having a mass average molecular weight of 15000, 730.0 parts by weight of methyl ethyl ketone, 500.0 cyclohexanone Mass parts and 50.0 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) were added and stirred. A polyglycidyl methacrylate was prepared by dissolving glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) in methyl ethyl ketone (MEK) and adding dropwise a thermal polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.). Reaction for 2 hours at 80 ° C. It was added dropwise to hexane, and the precipitate obtained was dried under reduced pressure.

(Preparation of titanium dioxide fine particle dispersion)
As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Sangyo Co., Ltd., TiO ₂ : Co ₃ O ₄ : containing cobalt and subjected to surface treatment using aluminum hydroxide and zirconium hydroxide: Al ₂ O ₃ : ZrO ₂ = 90.5: 3.0: 4.0: 0.5 weight ratio) was used.
The following dispersant (41.1 parts by mass) and cyclohexanone (701.8 parts by mass) were added to 257.1 parts by mass of the particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a weight average diameter of 70 nm.

Dispersant

(Preparation of coating solution for medium refractive index layer)
In 99.1 parts by mass of the above titanium dioxide dispersion, 68.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.6 parts by mass, manufactured by Ciba Specialty Chemicals Co., Ltd., 1.2 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 279.6 parts by mass of methyl ethyl ketone, and 1049.0 of cyclohexanone. A part by mass was added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore size 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 469.8 parts by mass of the above titanium dioxide dispersion, 40.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.3 parts by mass, manufactured by Ciba Specialty Chemicals Co., Ltd., 1.1 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 526.2 parts by mass of methyl ethyl ketone, and cyclohexanone 459. 6 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 high refractive index layer.

(Preparation of coating solution for low refractive index layer)
The copolymer P-3 described in the present invention is dissolved in methyl isobutyl ketone so as to have a concentration of 7% by mass, and a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 3% with respect to the solid content and 5% by mass of the photo radical generator Irgacure 907 (trade name) with respect to the solid content (10% by mass only for sample No. 112). Prepared.

(Preparation of antireflection film 101)
A hard coat layer coating solution was applied onto a triacetyl cellulose film (TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ² , the coating layer was cured by irradiating with an irradiation amount of 300 mJ / cm ² to form a hard coat layer having a thickness of 8 μm.
A medium refractive index layer coating solution, a high refractive index layer coating solution, and a low refractive index layer coating solution on a hard coat layer at a speed of 5 to 100 m / min using a gravure coater having three coating stations. It was applied continuously.

The medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was a 180 W / cm air-cooled metal halide lamp (eye graphics The irradiance was 200 mW / cm ² and the irradiation amount was 200 mJ / cm ² .
The medium refractive index layer after curing had a refractive index of 1.630 and a film thickness of 67 nm.

The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 vol. ), And the irradiation dose was 600 mW / cm ² and the irradiation dose was 400 mJ / cm ² .
The cured high refractive index layer had a refractive index of 1.905 and a film thickness of 107 nm.

Drying conditions of the low refractive index layer 90 ° C., and 30 seconds, 1.40 m in the reaction chamber of the nitrogen purge (0.2 m ³ as the ultraviolet curing conditions the oxygen concentration falls below the ambient 0.1% by volume ³ / Using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the irradiation amount was 200 mW / cm ² and the irradiation amount was 200 mJ / cm ² .
The low refractive index layer after curing had a refractive index of 1.440 and a film thickness of 85 nm. Thus, the antireflection film 101 was produced.
Samples 102 to 117 were prepared by changing the initiator type and curing conditions of the low refractive index layer to the conditions shown in Table 2. The amount of initiator was replaced by this weight. Nitrogen gas was blown by providing a front chamber immediately before the UV irradiation chamber (reaction chamber), and setting the position of the nozzle so that the inert gas directly hit the film surface. In addition, the irradiation chamber and the front chamber were adjusted so that an inert gas was blown out from the web entrance of the front chamber. The gap between the web entrance and the coating layer surface of the web was 4 mm.
The UV irradiation amount when the coating speed was changed was set so that the irradiation amount became constant by changing the illuminance.

  In addition, the said exemplary compound 6 grade | etc., Has already been described in this specification. In particular, Example Compound 6 is described below again.

The following items were evaluated for the obtained film. The results are shown in Table 3.
[Specular reflectance]
A spectroscopic hardness meter V-550 (manufactured by JASCO Corporation) is equipped with an adapter ARV-474, and the specular reflectance at an incident angle of -5 degrees is measured at an incident angle of 5 degrees in a wavelength range of 380 to 780 nm. The average reflectance at 650 nm was calculated and the antireflection property was evaluated.
[Pencil hardness]
The pencil hardness evaluation described in JIS K 5400 was performed. After conditioning the antireflection film at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, it was evaluated using the H-5H test pencil specified in JIS S 6006 at a load of 500 g as follows. The highest hardness that results in OK was taken as the evaluation value.
In evaluation of n = 5, no scratch to one scratch: OK
In evaluation of n = 5, 3 or more scratches: NG

[Steel wool scuff resistance]
The condition of scratches was observed when a load of 1.96 N / cm ² was applied to steel steel of # 0000 and reciprocated 30 times, and the following five stages were evaluated.
◎: Scratch not found ○: Slightly invisible scratch △: Clearly visible scratch ×: Clearly visible scratch XX: Delamination of film occurred thing

  It can be seen that by using an active halogen compound and further curing under the curing conditions according to the present invention, the antireflection film has a sufficient antireflection performance and is excellent in scratch resistance. By blowing nitrogen, the scratch resistance is excellent even if the oxygen concentration in the reaction chamber is the same.

[Example 2]
In the production methods of the samples 103, 107, and 112 of Example 1, samples 118 to 126 differing only in that the web temperature at the time of ultraviolet irradiation was raised were produced, and the same evaluation was performed.
The temperature of the coated surface of the web was adjusted by changing the temperature of the metal plate in contact with the web back surface.

  In the present invention, further superior scratch resistance was obtained by raising the temperature during UV irradiation to 60 ° C. or higher. In Sample 112, heating was not required by setting the amount of the polymerization initiator used to 10% by weight, and excellent scratch resistance was obtained even at a low temperature of 40 ° C.

[Example 3]
In the sample 107 produced in Example 1, samples 127 to 130 in Table 5 were produced by changing the number of divisions of ultraviolet irradiation and the presence or absence of nitrogen substitution between ultraviolet irradiations. Evaluation similar to Example 1 was performed with respect to these samples.
In the ultraviolet irradiation division, the illuminance was adjusted so that the total irradiation amount was constant. The results are shown in Table 6.
It was found that, by dividing the ultraviolet irradiation and setting the oxygen concentration between oxygen irradiations to 3% by volume or less even when the illuminance is applied once, the abrasion resistance is not deteriorated and high-speed production suitability is obtained.

[Example 4]
In the sample 112 production method, the gap between the front chamber entrance and the web surface of the web and the flow of nitrogen gas on the entrance side are changed, and the amount of nitrogen gas for purging is set so that the oxygen concentration in the ultraviolet irradiation chamber is constant at 0.08%. Samples 131 to 134 were prepared and evaluated in the same manner as in Example 1.
It can be seen that a low oxygen concentration can be maintained with a small amount of nitrogen gas by narrowing the gap and adjusting the exhaust gas so that the nitrogen gas at the inlet side of the web is slightly blown out.

[Example 5]
As a result of performing the same evaluation by changing the fluoropolymer used in the low refractive index layer in Examples 1 to 4 to P-1 and P-2 described in the text (replacement with equal mass), the same as in Examples 1 to 4 The effect of was obtained.

[Example 6]
(Preparation of coating solution for hard coat layer)
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
────────────────────────────────
Coating composition for hard coat layer ────────────────────────────────
Desolite Z7404 100 parts by mass (Zirconia fine particle-containing hard coat composition liquid: solid content concentration 60 wt%,
Zirconia fine particle content 70 wt% vs. solid content, average particle diameter of about 20 nm,
(Solvent composition MIBK: MEK = 9: 1, manufactured by JSR Corporation)
DPHA (UV curable resin: Nippon Kayaku Co., Ltd.) 31 parts by weight KBM-5103 (Silane coupling agent: Shin-Etsu Chemical Co., Ltd.)
10 parts by mass KE-P150 (1.5 μm silica particles: manufactured by Nippon Shokubai Co., Ltd.)
8.9 parts by mass MXS-300 (3 μm crosslinked PMMA particles: manufactured by Soken Chemical Co., Ltd.)
3.4 parts by weight Methyl ethyl ketone (MEK) 29 parts by weight Methyl isobutyl ketone (MIBK) 13 parts by weight --------------- ───

(Preparation of coating solution for low refractive index layer)
A coating solution for a low refractive index layer was prepared in the same manner as in Example 1.

(Preparation of antireflection film 601)
A triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form as a transparent substrate, and the above hard coat layer coating liquid has a gravure pattern with 135 lines / inch and a depth of 60 μm. Using a micro gravure roll with a diameter of 50 mm and a doctor blade, it was applied at a transfer speed of 10 m / min, dried at 60 ° C. for 150 seconds, and further under a nitrogen purge, a 160 W / cm air-cooled metal halide lamp (eye graphics ( Co., Ltd.) was used to cure the coating layer by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² , forming a hard coat layer, and winding it. After curing, the gravure roll rotation speed was adjusted so that the thickness of the hard coat layer was 3.6 μm.

The transparent base material coated with the hard coat layer was unwound again, and the coating liquid for the low refractive index layer was coated with a microgravure roll having a diameter of 200 lines / inch and a gravure pattern with a depth of 30 μm and a diameter of 50 mm. Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of 0.1% by volume after applying for 30 seconds at 90 ° C. and applying at a conveyance speed of 10 m / min. It was used to irradiate ultraviolet rays having an illuminance of 600 mW / cm ² and an irradiation amount of 400 mJ / cm ² to form a low refractive index layer and wind it up. After curing, the rotation speed of the gravure roll was adjusted so that the thickness of the low refractive index layer was 100 nm.

  Samples 601 to 617 were produced by changing the curing conditions of the low refractive index layer as shown in Table 8.

These samples were evaluated in the same manner as in Example 1. The results are shown in Table 9.
It can be seen that by the curing method according to the present invention, excellent scratch resistance can be obtained while maintaining antireflection performance.

[Example 7]
The low refractive index layers of Examples 1 to 6 were changed to the following low refractive index layers A and B, respectively, and evaluation was performed, and similar effects of the present invention were confirmed.
By using the hollow silica particles, it was possible to produce a low-reflectance antireflection film with further excellent scratch resistance.

(Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, After 3 parts of Hope Pharmaceutical Co., Ltd. were added and mixed, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of hollow silica fine particle dispersion)
Hollow silica fine particle sol (particle size about 40-50 nm, shell thickness 6-8 nm, refractive index 1.31, solid content concentration 20%, main solvent isopropyl alcohol, particle size according to Preparation Example 4 of JP-A-2002-79616 500 parts, acryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-5103) 30 parts, and diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) ) After 1.5 parts were added and mixed, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 parts of acetylacetone, and obtained the hollow silica dispersion liquid. The resulting hollow silica dispersion had a solid content concentration of 18% by mass and a refractive index after solvent drying of 1.31.

(Preparation of coating solution A for low refractive index layer)
DPHA 3.3g
Hollow silica fine particle dispersion 40.0g
RMS-033 0.7g
Illustrative Compound 21 0.2g
Sol liquid a 6.2g
Methyl ethyl ketone 290.6g
Cyclohexanone 9.0g

(Preparation of coating solution B for low refractive index layer)
DPHA 1.4g
Copolymer P-3 5.6 g
Hollow silica fine particle dispersion 20.0g
RMS-033 0.7g
Illustrative Compound 21 0.2g
Sol liquid a 6.2g
Methyl ethyl ketone 306.9g
Cyclohexanone 9.0g

The compounds used are shown below.
KBM-5103: Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.).
DPHA: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
RMS-033: Reactive silicone (manufactured by Gelest Co., Ltd.)

[Example 8]
The low refractive index layers of Examples 1 to 7 were changed to the following low refractive index layers C and D, respectively, and evaluation was performed, and similar effects of the present invention were confirmed. The same effect was also obtained with the low-refractive index layer obtained by replacing Opstar JN7228A of the low-refractive index layer C with JTA113 (manufactured by JSR Co., Ltd.) having a higher degree of cross-linking with equal weight.
(Preparation of sol solution a)
A reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM5103 (trade name); manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, After 3 parts of Hope Pharmaceutical Co., Ltd. were added and mixed, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The weight average molecular weight is 1800,
Among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of coating solution C for low refractive index layer) Thermosetting + ionizing radiation curing system Thermal crosslinkable fluorine-containing polymer JN-7228 (6% -methyl ethyl ketone (MEK))
50.9g
MEK-ST-L (30.0% / MEK) 5.4g
Sol liquid a (29% / MEK) 2.5g
Initiator: Exemplified compound 21 (2.0% / MEK) 2.8 g
Methyl ethyl ketone 38.4g
2.8 g of cyclohexanone
A coating solution for a low refractive index layer was prepared by the above mixture addition.

(Preparation of coating solution D for low refractive index layer) For thermosetting + ionizing radiation curing system Copolymer P-43 according to the present invention (30% / MEK)
20.1g
MEK-ST-L (30.0% / MEK) 5.4g
Sol liquid a (29% / MEK) 2.5g
Cymel 303 (10.0% / MEK) 5.3g
Catalyst 4050 (1.0% / MEK) 5.1g
Initiator: Exemplified compound 21 (2.0% / MEK) 2.8 g
Methyl ethyl ketone 54.6g
2.8 g of cyclohexanone
A coating solution for a low refractive index layer was prepared by the above mixture addition.

JN-7228: Thermally crosslinkable fluorine-containing polymer (refractive index 1.42, solid content concentration 6%, manufactured by JSR Corporation)
JTA-113: Thermally crosslinkable fluorine-containing polymer (refractive index 1.44, solid content concentration 6%, manufactured by JSR Corporation)
MEK-ST-L: Silica sol (silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.)
“Cymel 303”: methylolated melamine, manufactured by Nippon Cytec Industries, Ltd. “Catalyst 4050”: trimethylammonium salt of p-toluenesulfonic acid, manufactured by Nippon Cytec Industries, Ltd.

Using the microgravure roll with a diameter of 50 mm having a gravure pattern of 200 lines / inch and a depth of 30 μm and a doctor blade, the coating liquids C and D for the low refractive index layer were applied under the condition of a conveyance speed of 10 m / min. After drying at 120 ° C. for 150 seconds and further heat-curing at 110 ° C. for 10 minutes, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, an illuminance of 200 mW / cm ² , An ultraviolet ray with an irradiation amount of 450 mJ / cm ² was irradiated to form a low refractive index layer and wound up. After curing, the rotation speed of the gravure roll was adjusted so that the thickness of the low refractive index layer was 100 nm.

[Example 9]
(Preparation of protective film for polarizing plate)
A saponification solution in which a 1.5 mol / L sodium hydroxide aqueous solution was kept at 50 ° C. was prepared.
Further, a 0.005 mol / L dilute sulfuric acid aqueous solution was prepared.
In the antireflection film according to the present invention produced in Examples 1 to 8, the surface of the transparent substrate opposite to the side having the low refractive index layer was saponified using the saponification solution.
The aqueous sodium hydroxide solution on the surface of the saponified transparent substrate is thoroughly washed with water, then washed with the above 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 substrate on the side opposite to the side having the low refractive index layer of the antireflection film was evaluated, it was 40 degrees or less. Thus, the protective film for polarizing plates 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.

(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmission type, reflection type, or transflective type in which the polarizing plate of the present invention thus prepared is mounted so that the antireflection film is the outermost surface of the display. The liquid crystal display device was excellent in antireflection performance and extremely excellent in visibility. In particular, the effect is remarkable in the VA mode.

[Example 10]
(Preparation of polarizing plate)
In an optical compensation film having an optical compensation layer (wide view film SA 12B, manufactured by Fuji Photo Film Co., Ltd.), the surface opposite to the side having the optical compensation layer was saponified under the same conditions as in Example 9.
Using the polyvinyl alcohol adhesive as the adhesive for the polarizing film produced in Example 9, the antireflection film according to the present invention produced in Examples 1 to 7 (protecting for polarizing plate) on one surface of the polarizing film The saponified triacetyl cellulose surfaces of the film) were bonded together. 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 transmission type, reflection type, or transflective type in which the polarizing plate of the present invention thus prepared is mounted so that the antireflection film is the outermost surface of the display. The liquid crystal display device has better contrast in the bright room than the liquid crystal display device equipped with a polarizing plate that does not use an optical compensation film, has a very wide viewing angle in the vertical and horizontal directions, and has excellent antireflection performance and extremely high visibility. The display and display quality were excellent.
In particular, the effect is remarkable in the VA mode.

[Example 11]
In the method for producing the antireflection film of Example 1, the coating solution formulation of the low refractive index layer was changed to LL-61 below, and coating was performed at a coating speed of 25 m / min using the following die coater. Then, after drying at 90 ° C. for 30 seconds, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.1% by volume or less, An ultraviolet ray having an illuminance of 600 mW / cm ² and an irradiation amount of 400 mJ / cm ² was irradiated to form a low refractive index layer (refractive index 1.45, film thickness 83 nm). In this way, an antireflection film (11-1) was produced.
Furthermore, the antireflective films (11-2) to (11-5) were produced by changing the low refractive index layer coating solution to the following LL-62 to 65.

(Die coater configuration)
The slot die 13 has an upstream lip land length I _UP of 0.5 mm, a downstream lip land length I _LO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and a length of the slot 16 of 50 mm. I used one. The gap between the upstream lip land 18a and the web 12 is made 50 μm longer than the gap between the downstream lip land 18b and the web 12 (hereinafter referred to as an overbite length of 50 μm), and the gap between the downstream lip land 18b and the web 12 _GL was set to 50 μm. Further, the gap G _B between the gap G _S, and the back plate 40a and the web 12 between the side plate 40b and the web 12 of the decompression chamber 40 were both 200 [mu] m.

(Preparation of coating solution for low refractive index layer (LL-61))
152.4 parts by mass of a solution obtained by dissolving the following fluorine-containing copolymer in methyl ethyl ketone so as to have a concentration of 23.7% by mass, a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 0.1 part by weight, 1.8 parts by weight of an active halogen compound (Exemplary Compound 6), 815.9 parts by weight of methyl ethyl ketone, and 28.8 parts by weight of cyclohexanone were added and stirred. The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-61). The viscosity of the coating solution was 0.61 [mPa · sec], the surface tension was 24 [mN / m], and the amount of the coating solution applied to the transparent support was 2.8 [ml / m ² ]. .
The viscosity of the coating solution was measured using a small vibration year meter {A & D Co., Ltd., “CJV5000”} in an environment of a temperature of 25 ± 0.5 ° C. Further, the surface tension was measured using a surface tension meter {Kyowa Interface Science Co., Ltd., “KYOWA CBVP SURFACE TENSIOMETER A3”} in an environment at a temperature of 25 ° C.

Fluorine-containing copolymer

(Preparation of coating solution for low refractive index layer (LL-62))
426.6 parts by mass of a solution obtained by dissolving the above fluorinated copolymer in methyl ethyl ketone to a concentration of 23.7% by mass, terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 0.0 parts by mass, 5.1 parts by mass of an active halogen compound (Exemplary Compound 6), 538.6 parts by mass of methyl ethyl ketone, and 26.7 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-62). The viscosity of the coating solution was 1.0 [mPa · sec], the surface tension was 24 [mN / m], and the amount of the coating solution applied to the transparent support was 1.5 [ml / m ² ]. .

(Preparation of coating solution for low refractive index layer (LL-63))
213.3 parts by mass of a solution obtained by dissolving the above fluorinated copolymer in methyl ethyl ketone so as to have a concentration of 23.7% by mass, a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 0.5 parts by mass, 2.5 parts by mass of an active halogen compound (Exemplary Compound 6), 754.3 parts by mass of methyl ethyl ketone, and 28.4 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-63). The viscosity of the coating solution was 0.76 [mPa · sec], the surface tension was 24 [mN / m], and the amount of the coating solution applied to the transparent support was 2.0 [ml / m ² ]. .

(Preparation of coating solution for low refractive index layer (LL-64))
85.3 parts by mass of a solution obtained by dissolving the above fluorinated copolymer in methyl ethyl ketone so as to have a concentration of 23.7% by mass, a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 0 .6 parts by mass, 1.0 part by mass of an active halogen compound (Exemplary Compound 6), 883.7 parts by mass of methyl ethyl ketone, and 29.3 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-64). The viscosity of the coating solution was 0.49 [mPa · sec], the surface tension was 24 [mN / m], and the amount of the coating solution applied to the transparent support was 5.0 [ml / m ² ]. .

(Preparation of coating solution for low refractive index layer (LL-65))
71.1 parts by mass of a solution obtained by dissolving the above fluorinated copolymer in methyl ethyl ketone to a concentration of 23.7% by mass, terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 0 0.5 parts by mass, 0.8 parts by mass of an active halogen compound (Exemplary Compound 6), 898.1 parts by mass of methyl ethyl ketone, and 29.5 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-65). The viscosity of the coating solution was 0.46 [mPa · sec], the surface tension was 24 [mN / m], and the amount of the coating solution applied to the transparent support was 6.0 [ml / m ² ]. .
The surface condition when the coating solution for the low refractive index layer was changed to LL-61 to LL-65 was evaluated. The results are shown in Table 10. When the amount of the coating solution applied to the transparent support is 2 ml / m ² or more, it is possible to apply the coating solution, but at 1.5 ml / m ² , the entire surface cannot be applied uniformly and an antireflection film is created. I couldn't. In addition, when the amount of the coating solution to be applied to the transparent support is 6 ml / m ² , the coating is possible, but since the amount of the coating solution is large, drying is not in time, and vertical streaky unevenness caused by the wind. Occurred on the entire surface.

[Evaluation of antireflection film]
The surface state of the obtained antireflection film was evaluated. Further, the average reflectance was measured in the same manner as in Example 1.
(Surface shape)
The back surface of the film 1 m ² after coating all the layers was black-coated with magic ink, and the uniformity of the density of the coated surface was visually evaluated.
○: Contrast difference is inconspicuous ×: Contrast difference is conspicuous The obtained antireflection films (11-1), (11-3) and (11-4) are displayed in the same procedure as in Examples 9 and 10. As a result, the color unevenness was less than that of the display devices of Examples 9 and 10 produced by a gravure coater, and the quality was high.

[Example 12]
Antireflection films (12-1) to (12-5) were produced in the same manner as the antireflection film (11-1) except that the downstream lip land length I _L0 was 10 μm, 30 μm, 70 μm, 100 μm, and 120 μm. . The results are shown in Table 11. When the length of the downstream lip land is in the range of 30 μm to 100 μm, an antireflection film that does not cause surface failure is obtained. In the antireflection film (12-1), streaky unevenness occurs in the longitudinal direction of the base, and the antireflection film (12-5) cannot form the bead 14a at the same speed as the antireflection film (12-1). Application was impossible. Application was possible by reducing the application speed to half, but streaky irregularities occurred in the longitudinal direction of the base. When a display device was produced using the same procedures as in Examples 9 and 10 for the antireflection films (12-2) to (12-4), the reflection of the background was very small, and the color of the reflected light was significantly reduced. Furthermore, a display device with very high display quality in which uniformity within the display surface was ensured was obtained. On the other hand, when an antireflection film obtained from the antireflection films (12-1) and (12-5) is produced in the same procedure as in Examples 9 and 10, uneven coloring is visually recognized in the display device. It's not high-quality.

[Example 13]
Except that the overcoat length LO of the die coater was set to 0 μm, 30 μm, 70 μm, 120 μm, and 150 μm, coating was performed in the same manner as (11-1), and antireflection films (13-1) to (13-5) were applied. Created. The results are shown in Table 12. When the overbite length is in the range of 30 μm to 120 μm, an antireflection film that does not cause surface defects can be obtained. Application was possible with the antireflection film (13-1), but stepped unevenness was recognized in the base width direction when the surface shape was seen. Further, in the antireflection film (13-5), the bead 14a could not be formed at the same speed as (13-1), and the coating was impossible. Application was possible by reducing the application speed to half, but streaky irregularities occurred in the longitudinal direction of the base. In the antireflection films (13-2) to (13-4), when a display device was prepared in the same procedure as in Examples 9 and 10, the background reflection was very small, and the color of the reflected light was significantly reduced. Furthermore, a display device with very high display quality in which uniformity within the display surface was ensured was obtained. On the other hand, when a display device is prepared with the antireflection films (13-1) and (13-5) in the same procedure as in Examples 9 and 10, uneven coloring is visually recognized in the display device, which cannot be said to be high quality. .

[Example 14]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention should not be construed as being limited thereto.
(Preparation of coating solution for hard coat layer (antiglare layer))
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
25.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) was diluted with 31.3 g of methyl isobutyl ketone. Further, 1.3 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) was added and mixed and stirred. Subsequently, 0.04 g of a fluorine-based surface modifier (FP-149) described in this specification and 5.2 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) are added to the air disperser. For 120 minutes.
Finally, 30% of crosslinked poly (acryl-styrene) particles having an average particle diameter of 3.5 μm (copolymerization composition ratio = 50/50, refractive index 1.536) dispersed in this solution for 20 minutes at 10,000 rpm with a Polytron disperser. After adding 21.0 g of methyl isobutyl ketone dispersion and 15 g of isobutyl alcohol, the mixture was stirred with an air disper for 10 minutes.
In this example, the crosslinked poly (acryl-styrene) particles correspond to the translucent particles in the present invention.
Methyl isobutyl ketone is a good solvent and isobutyl alcohol is a poor solvent for the translucent resin DPHA.

(Preparation of transparent film 1001)
A hard coat layer coating solution was applied on a triacetyl cellulose film (TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. The amount of wet coating solution was 17.5 mL / m ² . After drying at 100 ° C., an illuminance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 0.1 vol% or less. ^{2. The} hard coat layer was formed by curing the coating layer by irradiating ultraviolet rays with an irradiation amount of 300 mJ / cm ² .

(Preparation of transparent films 1002 to 1008)
A transparent film in which the translucent particle size and the type of the initiator were changed with respect to the sample 1001 was produced. The amount of initiator added was the same as 1001 in terms of mole.

In addition, the said exemplary compound 6 grade | etc., Has already been described in this specification. In particular, Example Compound 6 is described below again.
(Exemplary Compound 6)

The following items were evaluated for the obtained film. The results are shown in Table 14.
[Measure haze]
The total haze (H), internal haze (Hi), and surface haze (Hs) of the obtained film were measured by the following measurements.
[1] The total haze value (H) of the film obtained according to JIS-K7136 is measured.
[2] Add a few drops of silicone oil to the front and back of the obtained film, sandwich the film between two glass plates with a thickness of 1 mm, measure the haze value, and simply add silicone oil between the same two glass plates A value obtained by subtracting the haze value measured by inserting only the haze value was calculated as the internal haze Hi.
[3] A value obtained by subtracting the internal haze (Hi) measured in [2] from the total haze (H) measured in [1] above was calculated as the surface haze (Hs).

[Center line average roughness]
The centerline average roughness Ra of the film obtained according to JIS-B0601 was measured.

The total haze H of the transparent film 1001 coated and dried with the hard coat layer was 17.5%, the internal haze Hi was 10.0%, the surface haze Hs was 7.5%, and Ra was 0.20 μm.
The thickness of the hard coat layer was 6.5 μm as measured with a film thickness meter.

[Adhesion test]
Using a cutter on the surface of the hard coat, scratches were made at intervals of 1 mm × 1 mm, and cello tape (registered trademark No. 405; manufactured by Nichiban Co., Ltd.) was applied to 100 cells, and the cello tape was peeled off after 30 seconds. . The cells after peeling were observed, and the number of cells where peeling of the film and chipping of the edges were observed was counted.
[Brittleness test]
A transparent film sample is cut to 35 mm x 140 mm, humidity is adjusted for 2 hours under the conditions of a temperature of 25 ° C and a relative humidity of 60%, and then the critical diameter at which cracks start to occur when rolled into a cylinder is measured. Evaluated.
○: No cracking occurs even with a curvature of 40 mm in diameter.
(Triangle | delta): Although a crack does not arise in a diameter 60mm curvature, generation | occurrence | production of a crack is recognized by a diameter 40mm curvature.
X: A crack occurs at a curvature of 60 mm in diameter.
[Evaluation of scratch resistance]
A load of 1.96 N / cm ² was applied to the steel wool, and the state of scratches was observed when the transparent film sample surface was reciprocated 30 times.
○: Scratches are not visible at all, or scars that are hardly visible are attached.
Δ: Scratches clearly visible.
X: There are scratches that can be clearly seen, and peeling of the film is also seen.

It can be seen that the transparent films 1004 to 1008 of the present invention have the same or good level of scratch resistance compared to Comparative Examples 1001 to 1003 using conventional photopolymerization initiators, but are particularly excellent in brittleness.
When the portion cracked in the brittleness tested sample of Comparative Example 1001 was observed with an optical microscope, the cracks were concentrated in the portion with a small amount of translucent fine particles (corresponding to the valley of the unevenness). From this, it was estimated that in the surface uneven transparent film, when the film was stretched, the stress was concentrated on the surface of the portion where the translucent particles were few, and cracks were generated.
When an active halogen compound is used as a photopolymerization initiator, it is not easily affected by oxygen inhibition in the polymerization reaction on the film surface, so the outermost surface has sufficient crosslink density, and cracking occurs even if stress concentration occurs. It is thought that it does not.
The adhesiveness of Samples 1001 to 1008 was not a problem because there were no peeling points.

[Example 15]
Samples 2001 to 2008 in which a low refractive index layer was provided on the hard coat layers of Samples 1001 to 1008 of Example 14 were produced.
However, the ultraviolet irradiation amount after coating the hard coat layer was performed by weakening to 90 mJ / cm ² .
(Adjustment of coating solution for low refractive index layer)
(Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, After 3 parts of Hope Pharmaceutical Co., Ltd. were added and mixed, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of hollow silica fine particle dispersion)
Hollow silica fine particle sol (particle size about 40-50 nm, shell thickness 6-8 nm, refractive index 1.31, solid content concentration 20%, main solvent isopropyl alcohol, particle size according to Preparation Example 4 of JP-A-2002-79616 500 parts, acryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-5103) 30 parts, and diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) ) After 1.5 parts were added and mixed, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 parts of acetylacetone, and obtained the hollow silica dispersion liquid. The resulting hollow silica dispersion had a solid content concentration of 18% by mass and a refractive index after solvent drying of 1.31.

(Preparation of coating solution for low refractive index layer)
DPHA 3.3g
Hollow silica fine particle dispersion 40.0g
RMS-033 0.7g
0.2 g of photopolymerization initiator described in the following table
Sol liquid a 6.2g
Methyl ethyl ketone 290.6g
Cyclohexanone 9.0g

The compounds used are shown below.
KBM-5103: Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.).
DPHA: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
RMS-033: Reactive silicone (manufactured by Gelest Co., Ltd.)
(Application of low refractive index layer)
On the hard coat layer, a low refractive index layer coating solution was applied using a gravure coater. The wet coating amount is 5.0 ml / m ² , dried at 120 ° C. for 150 seconds, further dried at 140 ° C. for 8 minutes, and then air-cooled metal halide of 240 W / cm in an atmosphere with an oxygen concentration of 0.1% by nitrogen purge. Using a lamp (manufactured by Eye Graphics Co., Ltd.), an ultraviolet ray having an irradiation amount of 300 mJ / cm ² was irradiated to form a low refractive index layer having a thickness of 100 nm and wound up.

[Measurement of average reflectance]
After the back surface of the film is sandpapered, it is treated with black ink and the back surface is removed, and the front side is 380 to 780 nm wavelength using a spectrophotometer (manufactured by JASCO Corporation). In the region, the specular spectral reflectance at an incident angle of 5 ° was measured, and the arithmetic average value of the specular reflectance at 450 to 650 nm was defined as the average reflectance.
All of the samples 2001 to 2008 had an average reflectance of 1.7%.
[Adhesion test]
Using a cutter on the surface of the film, scratches were made at intervals of 1 mm × 1 mm, cellotape (registered trademark No. 405; manufactured by Nichiban Co., Ltd.) was applied to 100 squares, and the cellotape was peeled off after 30 seconds. The cells after peeling were observed, and the number of cells where peeling of the film and chipping of the edges were observed was counted.

Since the interface between the low refractive index layer and the hard coat layer is relatively weak, it is easily peeled off in the adhesion test and easily damaged in the scratch resistance test. Therefore, all of Comparative Examples 2001, 2002, and 2003 are at unacceptable levels of adhesion and scratch resistance.
However, since the product of the present invention has strong bonding at the interface between the low refractive index layer and the hard coat layer, there is no failure in the adhesion and scratch resistance between the low refractive index layer / hard coat layer.

[Example 16]
(Preparation of protective film for polarizing plate)
A saponification solution in which a 1.5 mol / L sodium hydroxide aqueous solution was kept at 50 ° C. was prepared. Further, a 0.005 mol / L dilute sulfuric acid aqueous solution was prepared.
In the antireflection film according to the present invention produced in Example 15, the surface of the transparent substrate opposite to the side having the low refractive index layer of the present invention was saponified using the saponification solution.
The aqueous sodium hydroxide solution on the surface of the saponified transparent substrate is thoroughly washed with water, then washed with the above 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 substrate on the side opposite to the side having the low refractive index layer of the antireflection film was evaluated, it was 40 degrees or less. Thus, the protective film for polarizing plates 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.

(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmission type, reflection type, or transflective type in which the polarizing plate of the present invention thus prepared is mounted so that the antireflection film is the outermost surface of the display. The liquid crystal display device was excellent in antireflection performance and extremely excellent in visibility. In particular, the effect is remarkable in the VA mode.

[Example 17]
(Preparation of polarizing plate)
In the optical compensation film having an optical compensation layer (wide view film SA 12B, manufactured by Fuji Photo Film Co., Ltd.), the surface opposite to the side having the optical compensation layer was saponified under the same conditions as in Example 16.
An antireflection film (protective film for polarizing plate) according to the present invention prepared in Example 15 was formed on one surface of the polarizing film using a polyvinyl alcohol-based adhesive as an adhesive for the polarizing film prepared in Example 16. The saponified triacetyl cellulose surfaces were bonded to each other. 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 transmission type, reflection type, or transflective type in which the polarizing plate of the present invention thus prepared is mounted so that the antireflection film is the outermost surface of the display. The liquid crystal display device has better contrast in the bright room than the liquid crystal display device equipped with a polarizing plate that does not use an optical compensation film, has a very wide viewing angle in the vertical and horizontal directions, and has excellent antireflection performance and extremely high visibility. The display and display quality were excellent.
In particular, the effect is remarkable in the VA mode.

[Example 18]
Acrylic-styrene particles having an average particle diameter of 6 μm (copolymerization composition ratio = 50/50, refractive index of 1.536) as the light-transmitting particles of the comparative sample 1001 of Example 14 so as to have the same solid content addition amount. A replacement coating solution was prepared.
Furthermore, a plurality of coating solutions with different polymerization initiator types were prepared, and the coating amount was changed so that the film thickness was 15 μm, and the hard coat layer was formed on a triacetyl cellulose film (TD80UF, manufactured by Fuji Photo Film Co., Ltd.). It apply | coated using the gravure coater.
After drying at 110 ° C., an irradiance of 300 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 0.1 volume% or less. ^2. The ultraviolet ray with an irradiation amount of 225 mJ / cm ² was irradiated to cure the coating layer to form a hard coat layer.
These samples were designated as 3001 to 3005, and the produced transparent film was evaluated in the same manner as in Example 14. The results are listed in the table below.
In the table, the amount of addition is represented by the addition amount of Irgacure 184 as 100.

Comparative Example 3001 and the present invention 3002 to 3005 had almost the same antiglare property in sensory evaluation.
In Comparative Example 3001, since the film thickness was 15 μm, there was no problem with the scratch resistance, but because the film thickness was large, adhesion and brittleness were not allowed.
On the other hand, Samples 3002 to 3005 of the present invention had good scratch resistance, and showed better performance than Comparative Example 501 in adhesion and brittleness.

It is the schematic diagram which showed the manufacturing apparatus which comprised the ionizing radiation irradiation reaction chamber and the front chamber suitably used in this invention. It is the side view which showed typically an example of the operation | movement of the web entrance surface of the manufacturing apparatus provided with the ionizing radiation irradiation reaction chamber and the front chamber suitably used in this invention. It is the figure which showed typically an example of the web entrance surface of the front chamber of the manufacturing apparatus provided with the ionizing radiation irradiation reaction chamber and the front chamber suitably used in this invention. It is the side view which showed typically the operation | movement of the web entrance surface of the front chamber of FIG. It is a figure which shows an example of the apparatus which performs coating and hardening of the antireflection layer of the antireflection film of this invention. It is a schematic sectional drawing which shows one Embodiment of the die-coater preferably used in this invention. (A) It is an enlarged view of the die coater of FIG. (B) It is a schematic sectional drawing which shows the conventional slot die. It is a perspective view which shows the slot die of the application | coating process implemented preferably in this invention, and its periphery. It is sectional drawing which shows typically the relationship between the pressure reduction chamber of FIG. 8, and a web. It is sectional drawing which shows typically the relationship between the pressure reduction chamber of FIG. 8, and a web.

Explanation of symbols

A Feeding roll B Winding roll 100, 200, 300, 400 Film forming unit 101, 201, 301, 401 Coating liquid coating process 102, 202, 302, 402 Coating film drying process 103, 203, 303, 403 Coating film curing process DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Light scattering layer 4 Low refractive index layer 5 Translucent particle W Web 10 Coater 11 Backup roll 13 Slot die 14 Coating liquid 14a Bead shape 14b Coating film 15 Pocket 16 Slot 16a Slot opening 17 Tip lip 18 Land (flat part)
18a upstream lip land 18b downstream lip land I _UP land length I _UP upstream lip land 18a land length _LO downstream lip land 18b land length LO over bit length _GL gap between the tip lip 17 and web W 30 slot die 31a Upstream lip land 31b Downstream lip land 32 Pocket 33 Slot 40 Decompression chamber 40a Back plate 40b Side plate 40c Screw GB _B Gap between the back plate 40a and the web W G _S Gap between the side plate 40b and the web W

Claims (23)

  A transparent film having at least a hard coat layer on a transparent support, wherein the hard coat layer is coated and dried with a coating composition containing an ionizing radiation curable compound and at least one active halogen compound on the transparent support. A transparent film characterized by being a layer that is cured by irradiation with ionizing radiation.   The transparent film according to claim 1, wherein the ionizing radiation curable compound is a compound having two or more ethylenically unsaturated groups.   The transparent film characterized by the coating composition which forms the hard-coat layer of Claim 1 or 2 further containing the translucent particle | grains with an average particle diameter of 0.5-10.0 micrometers.   The transparent film characterized by the coating composition which forms the hard-coat layer of Claim 2 or 3 further including the good solvent and poor solvent with respect to an ionizing-radiation-curable compound.   The transparent film according to claim 3 or 4, wherein the center line average roughness Ra of the hard coat layer surface is 0 to 0.5 µm.   The surface film haze of the said hard-coat layer is 0 to 40%, The transparent film in any one of Claims 3-5 characterized by the above-mentioned.   It has the low refractive index layer whose refractive index is 0.05 or less smaller than a hard-coat layer on the opposite side to the transparent support body of the hard-coat layer as described in any one of Claims 1-6. Transparent film.   The transparent film according to claim 7, wherein the low refractive index layer is formed using a coating composition containing a fluorine-containing polymer. The transparent film according to claim 8, wherein the fluoropolymer is a fluoropolymer 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. Moreover, the silicone site | part may be included. x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. However, x + y + z = 100. ]   The transparent film according to claim 8 or 9, wherein the coating composition for forming the low refractive index layer contains a polysiloxane-containing vinyl monomer. The transparent film according to claim 10, wherein the polysiloxane-containing vinyl monomer is represented by the following general formula I:

In the general formula I, R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. P represents an integer of 10 to 500. R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a monovalent organic group, and R ₆ represents a hydrogen atom or a methyl group. L represents a single bond or a divalent linking group, and n represents 0 or 1.   The transparent film according to claim 7, wherein the low refractive index layer contains hollow silica fine particles.   After the low refractive index layer according to any one of claims 7 to 12 is coated and dried on a transparent support with a coating composition containing an ionizing radiation curable compound and at least one active halogen compound, ionizing radiation. A transparent film characterized by being a layer cured by irradiation.   The transparent film according to claim 1, further comprising an antistatic layer between the transparent support and the hard coat layer. The transparent film according to claim 1 or 13, wherein the active halogen compound is a compound represented by the following general formulas (1) to (4).

In the general formula (1), X represents a halogen atom. Y is _{-CX 3, -NH 2, -NHR '} , - NR' represents a _2, -OR '. Here, R ′ represents an alkyl group or an aryl group. R is
—CX ^{3 represents} an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

In the general formula (2), A represents a phenyl group, a naphthyl group, a substituted phenyl group or a substituted naphthyl group. Here, the substituent is a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, or a methylenedioxy group. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (3), W represents an unsubstituted or substituted phenyl group or an unsubstituted naphthyl group, and the substituent of the phenyl group is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or It is a C1-C4 alkoxy group. The number of substituents is one or two for a halogen atom, and one for the other. X represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (4), A represents an unsubstituted or substituted phenyl group or an unsubstituted naphthyl group, and the substituent of the phenyl group is a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or It is a C1-C4 alkoxy group. The number of substituents is one or two for a halogen atom, and one for the other. X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an allyl group. Y represents a halogen atom, and n represents an integer of 1 to 3.   A transparent film having at least an antireflection layer and a hard coat layer on a transparent support, wherein the antireflection layer comprises at least one active halogen compound according to claim 15 and an ionizing radiation curable compound. A transparent film, which is a layer formed by curing an object by irradiation with ionizing radiation. A method for producing a transparent film having at least a hard coat layer and / or an antireflection layer on a transparent support, wherein the support is obtained by the following step (1) and step (2) or (3). A method for producing a transparent film, comprising a step of forming at least one of the layers laminated thereon.
(1) A step of applying and drying a coating solution containing at least one active halogen compound and an ionizing radiation curable compound on a web that includes a support and that runs continuously to form a coating layer;
(2) A step of curing the coating layer by irradiating the coating layer on the web with ionizing radiation for 0.5 seconds or more in an atmosphere having an oxygen concentration of 3% by volume or less,
(3) A step of curing the coating layer by irradiation with ionizing radiation for 0.5 seconds or more in an atmosphere having an oxygen concentration of 3% or less while heating the coating layer on the web.   After the step (1) of forming the coating layer according to claim 17, there is provided (4) a step of heating and curing the coating layer by heating the coating layer on the web, and subsequently the step (2) or the step. (3) is provided, The manufacturing method of the transparent film characterized by the above-mentioned.   The method for producing a transparent film according to claim 17 or 18, wherein an inert gas is injected into the web having a coating layer that has been continuously run and has undergone the step (1) or the step (4) to reduce the oxygen concentration. And the web is further carried into an ionizing radiation reaction chamber having an oxygen concentration of 3% by volume or less into which an inert gas, which is installed continuously with the front chamber, is injected, The manufacturing method of the transparent film characterized by performing the hardening process of an application layer.   A transparent film, wherein the antireflection layer according to any one of claims 7 to 16 is produced by the production method according to any one of claims 17 to 19.   A transparent film, wherein the hard coat layer according to any one of claims 1 to 6 is produced by the production method according to any one of claims 17 to 19.   The polarizing film in which the transparent film in any one of Claims 1-16, 20, 21 is used for one of the two protective films in a polarizing plate.   The image display apparatus characterized by using the transparent film in any one of Claims 1-16, 20, 21 or the polarizing plate of Claim 22 for the outermost surface of a display.

Images