JP2007025040A - Antiglare film, method for producing antiglare film, antiglare antireflection film, polarizing plate and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare film which has a desired fine concave-convex structure formed effectively and stably with good productivity, and which can effectively prevent reflection of outside light and reduction of contrast without causing decrease in the sharpness of a high-definition image due to reduction in pixel size, and a method for producing the antiglare film, and to further provide an antiglare antireflection film, a polarizing plate and a display device using the antiglare film. <P>SOLUTION: The method for producing the antiglare film includes: forming a patterned first hard coat layer comprising a water- and oil-repellent coat portion and non-coat portions on a base film; and convexly or concavely forming a second hard coat layer on the non-coat portions of the first hard coat layer by applying a hard coat material by an arbitrary applying method on the base film on which the first hard coat layer has been formed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antiglare film, a method for producing an antiglare film, an antiglare antireflection film, a polarizing plate and a display device, and more particularly, the display device has little reflection of external light and suppresses a decrease in contrast. The present invention relates to an antiglare film, a method for producing an antiglare film, an antiglare antireflection film, a polarizing plate and a display device using them.

  In recent years, development of thin and light notebook computers has been progressing. Along with this, the demand for thinner and higher performance protective films for polarizing plates used in display devices such as liquid crystal display devices is also increasing. Also, a computer provided with an anti-glare layer for improving visibility, and also provided with an anti-glare layer that prevents reflections and scatters the reflected light with a rough surface to obtain display performance with less glare. A liquid crystal image display device (also referred to as a liquid crystal display) such as a word processor or the like has been widely used.

  Various types and performance improvements have been made to the antireflection layer and antiglare layer depending on the application, and various front plates with these functions are attached to the polarizer of a liquid crystal display, etc., to improve visibility on the display. Therefore, a method of providing an antireflection function or an antiglare function is used.

  The antiglare layer reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and reflection of the reflected image is noticeable when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. It is to prevent it from becoming.

  By providing an appropriate fine concavo-convex structure on the outermost surface of the front plate of the image display device, the above properties can be provided. For example, there are various methods such as a method using fine particles (for example, refer to Patent Document 1) and a method for embossing the surface (for example, refer to Patent Document 2).

  However, in the method using fine particles, since the fine concavo-convex structure is formed only by containing the fine particles in the binder layer, it is necessary to disperse the fine particles appropriately. It was difficult to form stably, and it had a great obstacle to obtaining a sufficient antiglare effect as an antiglare film. Moreover, the method of forming a fine concavo-convex structure by embossing is inferior in productivity, and it is extremely difficult to form a fine concavo-convex structure stably.

In recent years, display devices with higher visibility have been demanded as color display and higher definition of image display devices have been developed. For example, the outermost surface of a liquid crystal display device is insufficient with these conventional anti-glare films, and with a clear hard coat anti-reflection film, there is a problem of reflection of fluorescent light, and reflection due to light interference on the anti-glare film. Many techniques relating to an antiglare antireflection film coated with a prevention layer (low refractive index layer) have been proposed (see, for example, Patent Documents 3 to 8). However, these methods have not yet achieved a sufficient antiglare property and antireflection property in obtaining a display device with higher visibility.
JP 59-58036 A JP-A-6-234175 JP 2001-281410 A Japanese Patent Laid-Open No. 2004-4404 JP 2004-125985 A JP 2004-24967 A JP 2004-4777 A JP 2003-121620 A

  The present invention has been made in view of the above problems, and its purpose is to effectively prevent the reflection of external light and the decrease in contrast without deteriorating the sharpness of a high-definition image due to a reduction in pixel size or the like. An anti-glare film in which a desired fine concavo-convex structure can be formed effectively and stably with good productivity, and a method for producing the same, and an anti-glare anti-reflection film using the same, a polarizing plate, and a display device Is to provide.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
Forming a patterned first hard coat layer consisting of a water- and oil-repellent coating part and a non-coating part on the base film, and then applying any coating on the base film on which the first hard coat layer is formed A method for producing an antiglare film, wherein a second hard coat layer is formed in a convex or concave shape in a portion other than the first hard coat layer forming portion by applying a hard coat material by the method.

(Claim 2)
2. The method for producing an antiglare film according to claim 1, wherein a coating method for forming the first hard coat layer in a pattern comprising a coating part and a non-coating part is a flexographic printing method.

(Claim 3)
The height of the convex part or concave part of the second hard coat layer is 0.1 to 1.5 μm higher or lower than the first hard coat layer surface, and the long side of the convex part or concave part The method for producing an antiglare film according to claim 1 or 2, wherein the average center distance between adjacent convex portions or concave portions is 10 to 200 µm.

(Claim 4)
Either of the first hard coat layer and the second hard coat layer contains 5 to 50 mass% of fine particles having a particle diameter of 0.5 to 5 µm with respect to each layer. The manufacturing method of the anti-glare film of any one of Claims 1.

(Claim 5)
5. The prevention according to claim 1, wherein the base film is at least one selected from a cellulose ester film, a polyester film, a norbornene resin film, and a polycarbonate film. A method for producing a dazzling film.

(Claim 6)
The flexographic ink used for the first hard coat layer contains an actinic ray curable resin or a thermosetting resin. After flexographic printing, the actinic ray is irradiated or heated to cure the first hard coat layer. -The method for producing an antiglare film according to any one of claims 1 to 5, wherein the film is fixed.

(Claim 7)
The hard coat material used for the second hard coat layer contains an actinic ray curable resin or a thermosetting resin, and after the second hard coat layer is formed on the first hard coat layer by any coating method, The method for producing an antiglare film according to any one of claims 1 to 6, wherein the second hard coat layer is cured and fixed by irradiation with an actinic ray or heating.

(Claim 8)
An anti-glare film produced by the method for producing an anti-glare film according to claim 1.

(Claim 9)
An antiglare antireflection film, wherein at least a low refractive index layer is laminated on the surface of the antiglare film according to claim 8.

(Claim 10)
A polarizing plate comprising the antiglare film according to claim 8 or the antiglare antireflection film according to claim 9.

(Claim 11)
A display device comprising at least one of the antiglare film according to claim 8, the antiglare antireflection film according to claim 9, or the polarizing plate according to claim 10.

(Claim 12)
A rough structure composed of a first hard coat layer formed in a pattern comprising a coated part and a non-coated part on a base film, and a second hard coat layer formed on the non-coated part of the base film. An antiglare film having a surface.

  According to the present invention, it is possible to effectively prevent the reflection of external light and a decrease in contrast without deteriorating the sharpness of a high-definition image due to a reduction in pixel size, etc. An antiglare film formed stably and stably, and a method for producing the same, and an antiglare antireflection film, a polarizing plate and a display device using the film can be provided.

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

  The method for producing an antiglare film of the present invention uses a seamless resin plate, a transparent resin ink containing an actinic ray curable resin or a thermosetting resin, and has a long side of 5 on the surface of the base film by flexographic printing. A pattern-shaped water / oil-repellent first hard coat layer having a circular or elliptical non-printing portion of -100 μm and an average distance between adjacent non-printing portions of 10-200 μm is 0.1 in terms of film thickness after drying. 10 μm transfer printing. Next, irradiate with actinic light or heat to cure and fix, and then apply a second hard coat layer on it by a thin film coating method such as microgravure method, flexographic printing method, ink jet method, extrusion coating method, etc. At this time, since the first hard coat layer has water and oil repellency, the second hard coat layer is not applied on the first hard coat layer, and the second hard coat layer is patterned in a portion other than the first hard coat layer. A hard coat layer is formed. Next, after the solvent and the like are dried and removed, the second hard coat layer is cured and fixed by irradiating actinic rays or heating to form a second hard coat having a circular or elliptical shape having a long side of 5 to 100 μm. A second hard coat layer having a convex or concave shape of 0.1 to 1.5 μm with respect to the surface of the first hard coat layer having an average distance between adjacent patterns of 10 to 200 μm and a height, The substrate film is provided with a fine concavo-convex structure to impart antiglare properties.

  According to this method, an anti-glare film can be produced even at a printing speed of 10 m / min or more and 500 m / min, and reflection of external light can be achieved without deteriorating the sharpness of high-definition images. And an anti-glare film that can effectively and stably form a desired fine uneven structure with good productivity, an anti-glare anti-reflection film, a polarizing plate and a display device using the same Has been found to be obtained.

<< Formation of first hard coat layer and second hard coat layer >>
<Flexo printing>
First, flexographic printing that is preferably used when forming a patterned first hard coat layer composed of a coated portion and a non-coated portion having water and oil repellency on a base film will be described.

  In general, flexographic printing is a printing method using a relief printing plate made of a flexible rubber or resin and a solvent-based evaporation-drying ink mainly composed of water or alcohol. In addition to paper, printed materials have been frequently used for printing absorbent and non-absorbable films such as polyethylene, polyvinyl chloride, polypropylene, polystyrene and other stretched or unstretched resin films. On the other hand, a drum-type printing machine (single cylinder type, common impression cylinder type) is provided with four to six printing units around a single large impression cylinder at the center, and is a long belt-shaped printing medium. Has the feature of running and printing in a state of being wound around an impression cylinder. Therefore, it is suitable for printing on a plastic film or aluminum foil that is thin and easily stretched.

  As a result of intensive studies on the above-mentioned problems concerning the antiglare film, the present inventors have determined that the first hard coat layer having water and oil repellency by using flexographic printing on the surface of the base film is a pattern comprising an application part and a non-application part. In addition, the second hard coat layer is formed in a convex shape or a concave shape on the portion other than the coating portion of the first hard coat layer, thereby forming a fine concavo-convex structure while maintaining high productivity. It has been found that the above problem can be improved by forming. Some of the prior literatures describing the production method of the antiglare film mention the production by flexographic printing, but only mention the name of the method, and specifically suggest the present invention. Is not found.

  First, flexographic printing preferably used in the present invention will be described with reference to the drawings.

  1 and 2 are schematic views showing an example of flexographic printing according to the present invention.

  The substrate film 10 that runs continuously is sandwiched between a plate cylinder 3 constituted by an impression cylinder 5, a resin plate roll 2, and a seamless resin plate 1 that forms a fine uneven structure on the substrate film after transfer printing. The ink 8 is supplied to the plate cylinder 3 by the anilox roll 4 in which the transfer ink amount is adjusted, and transfer printing is performed on the base film.

  In flexographic printing, ink supply to the plate cylinder 3 is performed by the anilox roll 4, and the amount of ink on the anilox roll surface is generally controlled by the doctor blade method shown in FIG. 1 or the two-roll method shown in FIG. Known to. In the two-roll system shown in FIG. 2, the ink 8 is transferred from the ink pan to the anilox roll 4 by the fountain roll 7 and further supplied to the plate cylinder 3 to transfer the ink to the base film 10. In addition to adjusting the number of engraved lines of the anilox roll 4, the depth of the cell, and the shape of the ink 8 according to the method of FIG. 2, the nip pressure between the fountain roll 7 and the anilox roll 4 (which tends to fluctuate) The method shown in FIG. 1 is preferred in the present invention because the ink supply amount is controlled and there is a problem that the ink transfer amount is not stable.

  As another method, FIG. 3 shows a schematic diagram of flexographic printing in which ink is supplied by an extrusion coater.

  The ink 8 is directly extruded onto the seamless resin plate 1 mounted on the resin plate roll 2 by an extrusion coater 9, and is transferred and printed onto a base film 10 that is sandwiched between the plate cylinder 3 and the impression cylinder 5 and continuously running. In this apparatus, since there is no anilox roll, the amount of ink supplied depends on the accuracy of the extrusion coater.

  In the doctor blade system shown in FIG. 1, the amount of ink transferred to the plate cylinder 3 is determined by the number of engraved lines of the anilox roll 4 and the shape of the cell, and can be stabilized as the amount of ink transferred. The ink that fills the cells of the anilox roll scrapes excess ink on the surface of the anilox roll with a doctor blade. Therefore, the transferred ink is determined by the number of engraving lines, the shape of the cell, and the volume. Then, the anilox roll cell is subjected to, for example, copper plating on the surface of the iron cylinder as necessary, the cell is formed on the surface by engraving, and the surface processing with hardness is performed by nickel or chromium plating. The material of anilox roll includes a type in which the surface of the iron cylinder is plated with copper or the like, or a type with ceramic coating. In the present invention, however, the type is ceramic coated in terms of wear resistance and easy thinning of the number of engraving lines. Is preferred.

  FIG. 4 is a perspective view of the anilox roll.

  FIG. 5 is a perspective view for explaining an anilox cell.

  As shown in FIG. 4, the anilox roll 4 can be formed by chemical corrosion in the same manner as a gravure plate provided on a copper surface. It is desirable to provide the cell b by engraving. The surface of anilox roll is usually made by chrome plating after pressing with a mill, but it is sprayed with inorganic oxides such as chromium oxide and tungsten carbide from the viewpoint of wear resistance, corrosion resistance and ink transferability. Those formed are preferred.

  The sculpture shape of the anilox roll 4 is not particularly limited in addition to the lattice type cell, although there are shapes such as a helical type, a pyramid type, a diagonal type, a hexagonal honeycomb pattern, etc. A honeycomb pattern is preferable from the viewpoint of reproducibility of ink transfer during high-speed printing. The number of engraving lines and the depth d of the cell b shown in FIGS. 4 and 5 greatly affect the amount of ink transferred, and form a fine uneven structure on the antiglare film surface according to the present invention. It is preferable that 600 lines / 2.54 cm or more and the cell depth d is 5 to 30 μm. The selection of the engraving shape and the number of lines is considered in accordance with the type of substrate to be printed and the number of lines on the printing screen. However, a plastic film with a small number of lines is preferably used for a plastic film with low absorbability. And it is preferable that the bank a (non-recessed portion) of the cell should be small enough not to affect the wear resistance from the viewpoint that the ink charge amount can be increased. Specifically, the bank width w is set to 0.1 as the cell width. It is preferable to provide it at ˜0.5 times. The anilox roll controls the amount of ink supplied to the plate surface by flexing in flexographic printing. And abrasion and damage occur in the process of doctoring, which causes the cell to become shallow and the ink transfer amount to decrease. Therefore, compared with the conventional metal (iron or copper engraving, chrome plating finish), the ceramic anilox roll has little wear due to doctor ring and can greatly contribute to the repetitive stability of the uneven pattern.

  The present invention preferably uses a plate cylinder 3 on which a seamless resin plate 1 having a diameter of 50 to 1000 mm is mounted on a resin plate roll 2 and preferably an anilox roll 4 coated with ceramics by a flexographic printing apparatus as shown in FIG. First, a patterned first hard coat comprising an application part and a non-application part having water and oil repellency on the base film by transferring and printing ink onto the base film 10 and irradiating or heating with actinic rays The layer is formed.

  The material of the resin plate roll 2 is not particularly limited as long as it can maintain strength, and is preferably a metal such as iron, stainless steel, or aluminum, or a synthetic or natural rubber. A composite member may be used. In the present invention, the diameter of the resin plate roll 2 may be selected so that the diameter (roll diameter) when the seamless resin plate 1 is mounted on the resin plate roll 2 is in the range of 50 to 1000 mm. If the diameter of the seamless resin plate 1 is less than 50 mm, the rotation speed is too fast to maintain the strength, and the repetition cycle of the pattern composed of the water- and oil-repellent coated part and the non-coated part is short, resulting in an anti-glare effect. It may decrease and is not preferable. If the diameter exceeds 1000 mm, the apparatus becomes too large, which is expensive to operate and disadvantageous in terms of cost. In addition, uneven rotation tends to occur, and the accuracy of pattern formation decreases.

  The resin plate used in the seamless resin plate 1 of the present invention is preferably a photosensitive resin plate to which photopolymerization of a photoreactive substance polymer and a monomer is applied. This photosensitive resin plate is composed of a photopolymer, a monomer photopolymerized by exposure to ultraviolet light, a sensitizer that initiates photopolymerization between the polymer and the monomer, and a plasticizer that adjusts the physical properties of the plate material. The above pattern is engraved on the photosensitive resin plate by a conventional mask plate making, or directly applied by irradiating the photosensitive resin layer provided on the entire surface of the cylinder (axial core) by laser light. The pattern can also be engraved.

  As the photosensitive resin composition used in the present invention, those known for flexographic printing plates can be used. In general, a composition mainly composed of a binder polymer, at least one ethylenically unsaturated monomer and a photoinitiator is used. Furthermore, additives such as a sensitizer, a thermal polymerization inhibitor, a plasticizer, and a colorant can be included depending on the properties required for the photosensitive resin layer.

  As the binder polymer, for example, a thermoplastic elastomer obtained by polymerizing a monovinyl-substituted aromatic hydrocarbon monomer and a conjugated diene monomer is used. Examples of the monovinyl-substituted aromatic hydrocarbon monomer include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene and the like, and examples of the conjugated diene monomer include butadiene and isoprene. Specific examples include a styrene-butadiene-styrene block copolymer and a styrene-isoprene-styrene block copolymer.

  The at least one ethylenically unsaturated monomer is compatible with a binder polymer, for example, an ester of an alcohol such as t-butyl alcohol or lauryl alcohol with acrylic acid or methacrylic acid, or lauryl maleimide, cyclohexyl maleimide, benzyl Maleimide derivatives such as maleimide, or alcohol and fumaric acid esters such as dioctyl fumarate, and polyhydric alcohols such as hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate And esters of acrylic acid and methacrylic acid.

  Photoinitiators include aromatic ketones such as benzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylol benzoin methyl ether, α-methoxybenzoin methyl ether, 2,2-diethoxyphenylacetophenone, etc. These are selected from known photopolymerization initiators such as benzoin ethers and used in combination.

  The photosensitive resin layer can be prepared by various methods. For example, the raw materials to be blended can be dissolved and mixed in a suitable solvent such as chloroform, tetrachloroethylene, methyl ethyl ketone, toluene, etc., and coated on a suitable support with a coater. It can be cast into the plate as it is to evaporate the solvent. Moreover, it can knead | mix with a kneader or a roll mill, without using a solvent, and can shape | mold into the board of desired thickness with an extruder, an injection molding machine, a press.

  When the photosensitive resin sheet is wound around the resin plate roll, it is necessary to accurately cut and use the sheet so that there is no gap between the ends of the photosensitive resin in order to form a seamless resin plate. Usually, after the photosensitive resin plate is wound around the resin plate roll, the photosensitive resin is heated to a temperature higher than the softening point of the photosensitive resin, and the ends of the photosensitive resin are melt-bonded. The heating time is usually 20 minutes to 1 hour, and is determined based on the fact that the ends are fused according to the temperature and the softening point of the resin. Next, it is preferable for seamlessness that the surface of the photosensitive resin is polished by a grinder to completely eliminate the joint, and at the same time the accuracy is increased, and then the heating treatment is performed again above the softening point of the photosensitive resin. Although the time depends on the temperature, it is about 10 to 40 minutes, and is performed until the entire surface of the photosensitive resin becomes glossy. If the heating is continued for a long time, the accuracy of the printing plate is impaired, so it is desirable to process within one hour. In addition, a photosensitive resin layer can be applied seamlessly so that there is no direct seam on the base material such as rubber, polyester film, aluminum plate, steel plate, or aluminum resin plate roll that can be mounted on a cylinder.

  In the present invention, the rubber hardness of the seamless resin plate is preferably in the range of 30 to 80 degrees, and it is preferable that the rubber hardness of the resin plate be in this range in order to perform transfer printing of a fine uneven structure with accuracy and stability. Since the rubber hardness of the roll-shaped seamless resin plate 1 is also affected by the thickness of the resin plate, it is preferably in the range of 30 to 80 degrees in the resin plate having a thickness in the range of 0.5 to 10 mm. More preferably, it is in the range of 40 to 80 degrees.

  If the rubber hardness of the resin plate is less than 30 degrees, the plate is too soft and it is difficult to form a desired fine concavo-convex structure, and the plate itself is easily worn, which is not preferable. When the rubber hardness of the resin plate exceeds 80 degrees, the plate cylinder rotates at a high speed and lacks flexibility when printing and the reproducibility of the ink transfer amount becomes poor. The rubber hardness is indicated by a value measured with a durometer or the like according to the method described in JIS K 6253.

  A mask plate making is used as a method for imprinting a pattern composed of a coating portion and a non-coating portion on a seamless resin plate. In mask plate making, a resin plate provided with a layer of a photosensitive resin material is covered with a negative film as an original mask and exposed. The photosensitive resin layer is cured or insolubilized by light, particularly ultraviolet energy having a wavelength of 350 to 450 nm. The uncured resin in the unexposed portion is maintained in a soluble state in water, an aqueous alkali solution, or an organic solvent such as alcohol. Therefore, by washing out the unexposed portion with a solvent corresponding to the unexposed portion (developing step), only the exposed portion remains and forms a relief plate (flexographic plate).

  Further, as a recent printing plate method, a complete endless plate can be produced by directly engraving a cured resin plate with a laser beam or an engraving machine based on a corrected image signal. Alternatively, an unexposed photosensitive resin plate is scanned with a laser beam modulated with a corrected image signal in the form of a cylinder and patterned, and then developed by a normal method, from the viewpoint of forming an endless plate.

  The first hard coat layer of the present invention is characterized in that it is formed in a pattern comprising a coated part and a non-coated part having water and oil repellency on the substrate film.

  The water / oil repellency in the present invention can be defined by the contact angle of the first hard coat layer with respect to tetradecane, and the contact angle is preferably 10 ° or more with respect to the water / oil repellency, more preferably 20 It should be more than °.

  The first hard coat layer ink of the present invention preferably contains a water / oil repellent component in order to exhibit water / oil repellency. The first hard coat layer ink of the present invention includes silicone oil, modified silicone oil, silicone surfactant, fluorine surfactant, fluorine resin, fluorine oligomer, fluorine modified silicone oil, and fluorine silane coupling agent. It is preferable to contain an oil repellent such as 0.1 to 50 parts by mass. More preferably, it is preferable to contain 0.1 parts by mass or more and 10 parts by mass or less of silicone oil and modified silicone oil. If the amount added is too large, the hard coat property may be impaired, and if it is too small, the water / oil repellent effect cannot be obtained. The type of water / oil repellent used depends on the second hard coat layer solvent applied on the first hard coat layer.

(Silicone oil or silicone surfactant)
Silicone oils used in the present invention can be broadly classified into straight silicone oils and modified silicone oils depending on the type of organic groups bonded to silicon atoms. Straight silicone oil refers to those bonded with a methyl group, a phenyl group, or a hydrogen atom as a substituent. A modified silicone oil is one having a component that is secondarily derived from a straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

Silicone oil Straight silicone oil 1-1. Non-reactive silicone oil: dimethyl, methylphenyl substitution, etc. 1-2. Reactive silicone oil: methyl hydrogen substitution, etc. Modified silicone oil Modified silicone oil was born by introducing various organic groups into dimethyl silicone oil 2-1. Non-reactive silicone oil: alkyl, alkyl / aralkyl, alkyl / polyether, polyether, higher fatty acid ester substitution, etc.
Alkyl / aralkyl-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with a long-chain alkyl group or a phenylalkyl group,
Polyether-modified silicone oil is a silicone-based polymer surfactant in which hydrophilic polyoxyalkylene is introduced into hydrophobic dimethyl silicone,
Higher fatty acid-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with higher fatty acid ester,
Amino-modified silicone oil is a silicone oil having a structure in which a part of methyl group of silicone oil is substituted with aminoalkyl group,
The epoxy-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is replaced with an epoxy group-containing alkyl group,
The carboxyl-modified or alcohol-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with a carboxyl group or a hydroxyl group-containing alkyl group 2-2. Reactive silicone oil: amino, epoxy, carboxyl, alcohol substitution, etc. Of these, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2000 to 50,000. If the number average molecular weight is less than 1,000, the drying property of the coating film decreases, and conversely, the number average molecular weight. When it exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

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

  The silicone surfactant used in the present invention is a surfactant obtained by substituting a part of the methyl group of the silicone oil with a hydrophilic group. The position of substitution includes a side chain of silicone oil, both ends, one end, both end side chains, and the like. Examples of the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.

  As the silicon surfactant, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.

  A nonionic surfactant is a generic term for surfactants that do not have a group capable of dissociating into ions in an aqueous solution. In addition to a hydrophobic group, a hydrophilic group includes a hydroxyl group of a polyhydric alcohol, a polyoxyalkylene chain (poly Oxyethylene) or the like as a hydrophilic group. The hydrophilicity becomes stronger as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. The nonionic surfactant according to the present invention is characterized by having dimethylpolysiloxane as a hydrophobic group.

  When a nonionic surfactant composed of a dimethylpolysiloxane having a hydrophobic group and a polyoxyalkylene having a hydrophilic group is used, the unevenness of the low refractive index layer and the antifouling property of the film surface are improved. It is thought that the hydrophobic group made of polymethylsiloxane is oriented on the surface and forms a film surface that is not easily soiled. This effect cannot be obtained by using other surfactants.

  Specific examples of these nonionic surfactants include, for example, Nippon Unicar Co., Ltd., silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ- 2163, FZ-2164, FZ-2166, FZ-2191 and the like.

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

  In addition, as a preferable structure of the nonionic surfactant in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. It is preferably a linear block copolymer. Since the main chain skeleton has a long chain length and a linear structure, it is excellent. This is considered to be due to the fact that one activator molecule can be adsorbed on the surface of the silica fine particle at a plurality of locations so as to cover the surface of the silica fine particle by being a block copolymer in which hydrophilic groups and hydrophobic groups are alternately repeated.

  Specific examples thereof include, for example, silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208 and the like manufactured by Nippon Unicar Co., Ltd.

  Among these silicone oils or silicone surfactants, those having a polyether group are preferred.

  Other surfactants may also be used in combination. For example, anionic surfactants such as sulfonates, sulfates, phosphates, etc., and ethers having polyoxyethylene chain hydrophilic groups Type, ether ester type nonionic surfactants and the like may be used in combination.

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

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

  Examples of the fluorine compound monomer or oligomer include the following compounds. These may be used alone, or may be copolymerized with the following monomer not containing fluorine and added to the first hard coat layer as a fluorine-modified resin.

_{C 7 F 15 CH 2 OCOCH =} CH 2, C 7 F 15 CH 2 OCOC (Me) = CH 2, CF 3 (CF 2) 2 CH 2 OCOC (Me) = CH 2, CF 3 (CF 2) 4 ( CH ₂ ) ₂ OCOC (Me) = CH ₂ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OCOC (Me) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ OCOC (Me) = CH ₂ , C ₈ F ₁₇ CH ₂ CH (OH) CH ₂ OCOC (Me) = CH ₂ , C ₈ F ₁₇ (CF ₂ ) ₁₁ OCOC (Me) = CH ₂ , C ₇ F ₁₅ CON (Et) (CH ₂ ) ₂ OCOC (Me) = CH ₂ , C ₆ F ₁₃ SO ₂ N (Me) (CH ₂ ) _{2 OCOCH = CH 2, C 8 F} 17 SO 2 N (Pr) (CH 2) 2 OCOCH = CH 2, C 8 F 17 SO 2 N (Me _{(CH 2) 2 OCOC (Me} ) = CH 2, C 8 F 17 SO 2 N (Me) (CH 2) 18 OCOCH 2 CH = CH 2, C 8 F 17 SO 2 N (CH 2 CH 2 OCOCH = CH ₂ ) ₂ , HCF ₂ (CF ₂ ) ₇ CH ₂ OCOC (Me) = CH ₂ , and other perfluoroalkyl group-containing (meth) acrylic acid esters;
Vinyl ether or allyl ether having a perfluoroalkyl group similar to the above, such as C ₇ F ₁₅ CH ₂ OCH═CH ₂ , C ₇ F ₁₅ CH ₂ OCH ₂ CH═CH ₂ , etc .;
Examples include vinyl sulfone having a perfluoroalkyl group similar to the case of the above (meth) acrylic acid ester such as C ₈ F ₁₇ SO ₂ NHCH ₂ SO ₂ CH═CH ₂ , wherein Me is a methyl group, Et is Ethyl group and Pr are propyl groups. ].

  Examples of the monomer not containing fluorine generally include styrene and derivatives thereof, acrylic acid, methacrylic acid, alkyl esters and amides thereof, and when 2-hydroxyethyl acrylate or methacrylate is used, an —OH group is contained in the polymer. Can be cured with polyisocyanate. Putting a dimethylsiloxane chain in these fluorine-modified resins is effective in bringing out fluorine on the surface, specifically, a method of copolymerizing polydimethylsiloxane having an acryloyl group or a methacryloyl group at the end, or As described above, dialcohol which can be a radical initiator and polydimethylsiloxane having both terminal alcohol groups via urethanization or dicarboxylic acid which can be a radical initiator and polydimethylsiloxane having both terminal epoxy groups By this reaction, a silicone-modified fluorine-containing polymer is obtained. Further, the fluorine-containing silicone-modified resin can be obtained by increasing the molecular weight of polydimethylsiloxane having both terminal alcohol groups and fluorine-containing alcohol with polyisocyanate. Specific examples of the fluorinated alcohol include the following.

C ₈ F ₁₇ C ₂ H ₄ OH, C ₆ F ₁₃ C ₂ H ₄ OH, (CF ₃ ) ₂ CFC ₁₀ F ₂₀ C ₂ H ₄ OH, C ₈ F ₁₇ C ₂ H ₄ OH, C ₁₀ F ₂₁ C _{2 H 4 OH, C 8 F} 17 SO 2 N (C 2 H 5) C 2 H 4 OH, C 8 F 17 SO 2 N (Me) C 2 H 4 OH, (CF 3) 2 CHOH.

  Furthermore, a fluorine-containing silicone-modified resin can be obtained by a reaction between a dimethylpolysiloxane having a silanol group and a fluoroalkylsilane. Moreover, the following are mentioned as a fluorine-type silane coupling agent.

CF ₃ CH ₂ CH ₂ Si (OMe) ₃
CF ₃ CH ₂ CH ₂ SiCl ₃
CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCl ₃
CF ₃ (CH ₂ ) ₅ CH ₂ CH ₂ Si (OMe) ₃
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃
CF ₃ (CH ₂ ) ₇ CH ₂ CH ₂ Si (OMe) ₃
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiMeCl ₂
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiMe (OMe) ₂
The refractive index of the ink is preferably in the range of 1.45 to 1.65, and the transmittance of the ink is preferably 80% or more, preferably 90% or more.

  The viscosity of the ink is preferably 0.1 to 10 Pa · s, more preferably 0.5 to 8 Pa · s at a measurement temperature of 40 ° C. If the viscosity is less than 0.1 Pa · s, the viscosity is too low to obtain a pattern having a desired shape, and if it exceeds 10 Pa · s, the fluidity of the ink is poor and the transferability of the ink is also unfavorable. The viscosity of the ink is not particularly limited as long as it is tested with a viscometer calibration standard solution specified in JIS Z 8809, and a rotary, vibration or capillary type viscometer can be used. . As a viscometer, it can be measured with a Saybolt viscometer, a Redwood viscometer, etc., for example, Tokimec Co., Ltd., conical plate type E type viscometer, Toki Sangyo E Type Viscometer, manufactured by Tokyo Keiki Co., Ltd. B-type viscometer BL, Yamaichi Denki Co., Ltd. FVM-80A, Nametor Kogyo Viscoliner, Yamaichi Denki Co., Ltd. VISCO MATE MODEL VM-1A, and the like.

  In any case, an ink within the above range can be obtained by adjusting the constitution of the ink composition. The main ink composition will be described below.

  First, the actinic ray curable resin preferably used in the present invention will be described.

  The actinic ray curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic ray curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, but a resin that is cured by irradiation with actinic rays other than ultraviolet rays and electron beams may be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. .

  An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or carboxyl group at the end of the polyester (see, for example, JP-A No. 59-151112).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  Examples of ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta. Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.

  As examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin, preferred examples of the epoxy actinic ray reactive compound are shown.

(A) Glycidyl ether of bisphenol A (this compound is obtained as a mixture having different degrees of polymerization by reaction of epichlorohydrin and bisphenol A)
(B) A compound having a glycidyl ether group by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OHs such as bisphenol A. (c) Glycidyl ether of 4,4'-methylenebisphenol (D) Epoxy compound of phenol formaldehyde resin of novolak resin or resol resin (e) Compound having alicyclic epoxide, for example, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) ) Adipate, bis (3,4-epoxy-6-cyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl pimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxy Rhohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3', 4'-epoxy-1 '-Methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3', 4'-epoxy-6'-methyl-1'-cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl- 5 ', 5'-spiro-3 ", 4" -epoxy) cyclohexane-meta-dioxane (f) diglycidyl ethers of dibasic acids such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, di Glycidyl hexahydrophthalate, diglycidyl Phthalate (g) Diglycidyl ether of glycol, such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol-propylene glycol) di Glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether (h) Glycidyl ester of polymer acid, for example, polyglycidyl ester of polyacrylic acid, polyester diglycidyl ester (i) Polyhydric alcohol Glycidyl ethers such as glycerin triglycidyl ether, trimethylolpropane triglyceride Dil ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl ether (j) As diglycidyl ether of 2-fluoroalkyl-1,2-diol, the low refractive index substance (K) Examples of the fluorine-containing alkane-terminated diol glycidyl ether include fluorine-containing epoxy compounds of the fluorine-containing resin of the low refractive index material, and the like. I can do it.

  The molecular weight of the said epoxy compound is 2000 or less as an average molecular weight, Preferably it is 1000 or less.

  When the above epoxy compound is cured with actinic rays, it is effective to use a compound having a polyfunctional epoxy group (h) or (i) in order to increase the hardness.

  The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy actinic light-reactive compound is a compound capable of releasing a cationic polymerization initiating substance upon irradiation with actinic light, and particularly preferably, cationic polymerization is initiated by irradiation. A group of double salts of onium salts that release potent Lewis acids.

  The actinic ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is a preferable actinic ray reactive resin because it is not affected by oxygen in the reaction system.

  The actinic ray-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or a photosensitizer that releases a substance that initiates cationic polymerization upon irradiation with actinic rays. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

  A typical example is a compound represented by the following general formula (a).

Formula (a)
[(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{w +} [MeX _v ] ^w-
In the formula, the cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), and R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeX _v ] ^w− of the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ⁻ ), tetra Examples thereof include fluoroarsenate (AsF ₄ ⁻ ) and tetrachloroantimonate (SbCl ₄ ⁻ ).

Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

  Among such onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, aromatic halonium salts described in JP-A-50-151996, 50-158680, etc. VIA group aromatic onium salts described in Kaisho 50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56-149402, Preference is given to oxosulfoxonium salts described in JP-A-57-192429, aromatic diazonium salts described in JP-B-49-17040, thiopyrilum salts described in US Pat. No. 4,139,655, and the like. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  In the case of an actinic ray reactive compound having an epoxy acrylate group, a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photosensitizer and photoinitiator used for the actinic ray reactive compound are sufficient to initiate the photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet reactive compound, Preferably they are 1 mass part-10 mass parts. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the actinic ray curable resin composition useful in the present invention, the photopolymerization initiator is generally 0.1 to 15 parts by mass with respect to 100 parts by mass of the actinic ray curable epoxy resin (prepolymer). Is more preferable, and addition of 1 mass part-10 mass parts is more preferable.

  An epoxy resin can be used in combination with the urethane acrylate type resin, polyether acrylate type resin, or the like. In this case, it is preferable to use an actinic ray radical polymerization initiator and an actinic ray cationic polymerization initiator in combination.

  In the present invention, an oxetane compound can also be used. The oxetane compound used is a compound having a three-membered oxetane ring containing oxygen or sulfur. Among them, a compound having an oxetane ring containing oxygen is preferable. The oxetane ring may be substituted with a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxyl group, an allyloxy group, or an acetoxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-methyl -3 chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, 3,3-dimethyloxetane and the like. In the present invention, any of a monomer, an oligomer and a polymer may be used.

  Specific examples of the ultraviolet curable resin that can be used in the present invention include, for example, Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B. (Asahi Denka Kogyo Co., Ltd.), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T -102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX -9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, CR900 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB), RC-5015, RC-5016, RC-5020, RC -5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (above, Dainippon Ink & Chemicals, Inc.), Aurex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, Sanyo Chemical Industries, Ltd.) , SP-1509, SP-1507 (above, manufactured by Showa Polymer Co., Ltd.), RCC-15C (produced by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.) (Made by Co., Ltd.), or other commercially available products.

In the ink according to the present invention, a binder such as a known thermoplastic resin or a hydrophilic resin such as gelatin can be mixed with the actinic ray curable resin described above. These resins preferably have a polar group in the molecule. Examples of the polar _{group, -COOM, -OH, -NR 2,} -NR 3 X, -SO 3 M, -OSO 3 M, -PO 3 M 2, -OPO 3 M ( wherein, M represents a hydrogen atom, an alkali A metal or an ammonium group, X represents an acid forming an amine salt, R represents a hydrogen atom or an alkyl group).

  In order to initiate photopolymerization or photocrosslinking reaction of the actinic ray reactive compound used in the present invention, the actinic ray reactive compound alone is initiated, but the induction period of polymerization is long or the initiation of polymerization is slow. Therefore, it is preferable to use a photosensitizer or a photoinitiator, which can speed up the polymerization.

  When the ink which concerns on this invention contains actinic-light curable resin, it is preferable to use a photoreaction initiator and a photosensitizer at the time of irradiation of actinic light.

  Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. Moreover, when using a photoreactant for the synthesis | combination of an epoxy acrylate-type resin, sensitizers, such as n-butylamine, a triethylamine, a tri-n-butylphosphine, can be used.

  Further, when an ultraviolet curable resin is used as the actinic ray curable resin, an ultraviolet absorber may be included in the ultraviolet curable resin composition to the extent that does not hinder the photocuring of the ultraviolet curable resin. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

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

  Moreover, in order to improve the heat resistance of the pattern formed by flexographic printing, an antioxidant that does not suppress the photocuring reaction can be selected and used. For example, hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives and the like can be mentioned. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

The ink according to the present invention preferably contains an antistatic agent such as conductive fine particles such as SnO ₂ , ITO, ZnO, and crosslinked cationic polymer particles.

  In the present invention, it is also preferable to contain fine particles in the ink for adjusting the refractive index. For example, inorganic fine particles or organic fine particles can be added.

  Examples of the inorganic fine particles include silicon-containing compounds, silicon dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and Calcium phosphate and the like are preferable, and an inorganic compound containing silicon and zirconium oxide are more preferable, and silicon dioxide is particularly preferably used. These include particles having a shape such as a spherical shape, a flat plate shape, and an amorphous shape.

  As the fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.) can be used.

  As the fine particles of zirconium oxide, commercially available products such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  The organic fine particles include polymethacrylate methyl acrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicon resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, and melamine resin. Examples thereof include fine particles, polyolefin resin fine particles, polyester resin fine particles, polyamide resin fine particles, polyimide resin fine particles, and polyfluoroethylene resin fine particles.

  In the present invention, either the first hard coat layer or the second hard coat layer preferably contains the fine particles, and the average particle size is preferably 0.01 to 5 μm, more preferably 0.05 to 5 μm. And particularly preferably 0.5 to 5 μm. You may contain 2 or more types of microparticles | fine-particles from which a particle size and refractive index differ. Moreover, it is preferable that content is 5-50 mass% with respect to each layer. The refractive index of the fine particles preferably has a difference of 0.02 or more and 0.1 or less from the refractive index of the hard coat layer binder resin. When the second hard coat layer contains spherical fine particles having a particle size of 0.5 μm or more and 5 μm or less and a refractive index difference with the hard coat layer binder resin of 0.02 or more and 0.1 or less, the second hard coat layer portion This is particularly preferable in order to suppress glare due to the lens effect.

  In the present invention, when the pattern formed by flexographic printing contains an actinic ray curable resin, it is preferable to irradiate actinic rays after the ink is transferred onto a transparent substrate as an actinic ray irradiation method. The timing of irradiation can be determined in consideration of the pattern shape to be formed. For example, irradiation can be performed immediately after transfer printing to 2 minutes later.

  The term “immediately after transfer printing the ink on the transparent substrate” in the present invention specifically means that the ink starts to be irradiated within 0.001 to 2.0 seconds after transfer printing, more preferably 0. Between 0.001 and 1.0 seconds.

  In addition, irradiation with actinic rays immediately after the ink is transferred and printed may be performed so that the fluidity of the transferred and printed ink is lowered and a desired pattern shape can be formed, and may be in a half-cured state. In this case, it can be cured completely by irradiating an active light source separately installed on the downstream side. In the present invention, it is preferable to use an actinic radiation curable resin for forming the first hard coat layer and the second hard coat layer.

The actinic ray that can be used in the present invention can be used without limitation as long as it is a light source that activates the actinic ray curable resin formed in a pattern with ultraviolet rays, electron beams, γ rays, etc. Electron beams are preferable, and ultraviolet rays are particularly preferable in that they are easy to handle and high energy can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably 1 mJ / cm ² or more, more preferably 20 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

  In the present invention, the oxygen concentration in the atmosphere at the time of active ray irradiation is preferably 10% or less, particularly preferably 1% or less. In order to obtain this atmosphere, it is effective to introduce nitrogen gas or the like.

  Moreover, in this invention, in order to advance the hardening reaction of actinic light efficiently, a base film etc. can also be heated. The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method such as spraying hot air on the surface of transfer-printed ink. Moreover, you may heat continuously by using the back roll used on the opposite side across the base film of a flexographic printing part as a heat roll.

  The heating temperature cannot be generally specified depending on the type of actinic ray curable resin to be used, but is preferably in a temperature range that does not affect the base film such as thermal deformation, and is preferably 30 to 200 ° C. Furthermore, 50-120 degreeC is preferable, Most preferably, it is 70-100 degreeC.

  Next, a thermosetting resin that can be used in the ink of the present invention will be described.

  Examples of the thermosetting resin that can be used in the present invention include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, thermosetting polyimide resins, thermosetting polyamide imides, and the like.

As the unsaturated polyester resin, for example, orthophthalic acid resin, isophthalic acid resin, terephthalic acid resin, bisphenol resin, propylene glycol-maleic acid resin, dicyclopentadiene or derivatives thereof are introduced into the unsaturated polyester composition. Low styrene volatile resin with low molecular weight or added film-forming wax compound, low shrinkage with thermoplastic resin (polyvinyl acetate resin, styrene / butadiene copolymer, polystyrene, saturated polyester, etc.) Resin, unsaturated polyester brominated directly with Br ₂ , or reactive type such as copolymerization of het acid or dibromoneopentyl glycol, halides such as chlorinated paraffin, tetrabromobisphenol and antimony trioxide, phosphorus Compound combinations Additive-type flame retardant resin that uses sesame or aluminum hydroxide as an additive, toughness resin that is hybridized with polyurethane or silicone, or toughened with IPN (high strength, high elastic modulus, high elongation), etc. is there.

  Examples of the epoxy resin include glycidyl ether type epoxy resins including bisphenol A type, novolak phenol type, bisphenol F type, brominated bisphenol A type, glycidyl amine type, glycidyl ester type, cyclic aliphatic type, and heterocyclic epoxy type. Special epoxy resins containing

  As the vinyl ester resin, for example, an oligomer obtained by ring-opening addition reaction of an ordinary epoxy resin and an unsaturated monobasic acid such as methacrylic acid is dissolved in a monomer such as styrene. There are also special types such as vinyl monomers having vinyl groups at the molecular ends and side chains. Examples of vinyl ester resins of glycidyl ether type epoxy resins include bisphenol type, novolak type, brominated bisphenol type, etc., and special vinyl ester resins include vinyl ester urethane type, isocyanuric acid vinyl type, side chain vinyl ester type, etc. There is.

  The phenol resin is obtained by polycondensation using phenols and formaldehyde as raw materials, and there are a resol type and a novolac type.

  Examples of thermosetting polyimide resins include maleic acid-based polyimides such as polymaleimide amine, polyamino bismaleimide, bismaleimide / O, O'-diallyl bisphenol-A resin, bismaleimide / triazine resin, and nadic acid-modified polyimide. And acetylene-terminated polyimide.

  A part of the actinic ray curable resin described above can also be used as a thermosetting resin.

  In addition, you may use suitably the antioxidant and ultraviolet absorber which were described in the ink containing actinic-light curable resin for the ink which consists of a thermosetting resin used for this invention.

  In the present invention, when the pattern formed by flexographic printing contains a thermosetting resin, the heating method is preferably performed immediately after the ink is transferred onto the base film.

  The term “immediately after the transfer transfer of the ink in the present invention on the base film” is specifically preferably the heating of the ink at the same time as the transfer printing or within 5 seconds. Can be raised. For example, the base film can be wound on a heat roll, and the ink can be transferred by transfer printing, more preferably at the same time as transfer printing or for 2.0 seconds. In addition, if the distance between the nozzle part and the heating part is too close and heat is transferred to the head part, the nozzle part is clogged due to curing at the nozzle part, so care must be taken. Further, if the heating interval exceeds 5.0 seconds as necessary, a smooth fine uneven structure can be obtained by causing the flow-printed ink to flow and deform.

  The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method such as spraying hot air on the surface of transfer-printed ink. In addition, the back roll provided on the opposite side with the base film of the flexographic printing unit interposed therebetween may be continuously heated as a heat roll. The heating temperature cannot be generally defined by the type of thermosetting resin to be used, but is preferably in a temperature range that does not affect the heat deformation of the transparent substrate, preferably 30 to 200 ° C, Furthermore, 50-120 degreeC is preferable, Especially preferably, it is 70-100 degreeC.

  In the ink according to the present invention, any of the above-mentioned actinic ray curable resins and thermosetting resins can be used as the pattern forming composition, but preferably an actinic ray curable resin is used.

  The ink according to the present invention may contain 0 to 99.9% by mass of a solvent as necessary. For example, the actinic ray curable resin monomer component or the thermosetting resin monomer component may be dissolved or dispersed in an aqueous solvent, or an organic solvent may be used. An organic solvent having a low boiling point or a high boiling point can be appropriately selected and used, and the addition amount, type and composition of these solvents are preferably adjusted appropriately in order to adjust the viscosity of the ink.

  Examples of the solvent that can be used in the ink according to the present invention include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ketones such as diacetone alcohol Alcohols; aromatic hydrocarbons such as benzene, toluene, xylene; glycols such as ethylene glycol, propylene glycol, hexylene glycol; ethyl cellsolve, butylcellsolve, ethylcarbitol, butylcarbitol, diethylcellsolve, Glycol ethers such as diethyl carbitol and propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, amino acetate Esters and the like; dimethyl ether, and diethyl ether, water and the like, they can be used alone or in combination. Further, those having an ether bond in the molecule are particularly preferred, and glycol ethers are also preferably used.

  Specific examples of glycol ethers include, but are not limited to, the following solvents. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether Ac, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether Ac, ethylene glycol Examples thereof include diethyl ether, and Ac represents acetate. In the ink according to the present invention, among the above solvents, a solvent having a boiling point of less than 100 ° C. is preferably used. These solvents are desirably volatilized and dried as quickly as desired pattern shape is maintained after transfer printing. Alternatively, the pattern shape can be controlled by mixing different volatile solvents and changing the ratio.

  The second hard coat layer is composed of the actinic ray curable resin, photopolymerization initiator, thermoplastic resin, photoreaction initiator, photosensitizer, ultraviolet absorber, fine particles described in detail in the first hard coat layer. Further, a hard coat coating composition can be prepared by appropriately using a thermosetting resin and a solvent, and coating is performed on the first hard coat layer by any coating method.

  The coating method of the second hard coat layer is not particularly limited, but the hard coat coating composition may be a known gravure coater, dip coater, reverse coater, wire bar coater, die coater, ink jet method, flexographic printing method or the like. It is preferable to apply by a method.

  FIG. 6 shows that a first hard coat layer is formed by forming a first hard coat layer having water and oil repellency on a base film in a pattern comprising an application part and a non-application part, and further applying a second hard coat layer. It is the schematic diagram which showed a mode that the convex part of the 2nd hard-coat layer was formed in a layer non-formation part.

  The height of the convex part or concave part of the concavo-convex structure of the second hard coat layer of the present invention is 0.1 to 1.5 μm higher or lower than the surface of the first hard coat layer, and the long side of the convex part or concave part Is preferably 5 to 100 μm and the average center-to-center distance between adjacent convex portions or concave portions is 10 to 200 μm. The adjustment of the height, the length of the long side, and the distance is carried out by adjusting the pattern shape and printing thickness of the coated portion and the non-coated portion by the first hard coat layer, and the hard coat composition used for the second hard coat layer. It can be controlled by adjusting physical properties such as viscosity and adding fine particles.

  FIG. 7 is a schematic view of the concavo-convex structure formed by the second hard coat layer preferable for the present invention formed on the base film.

  FIG. 7A is a perspective view of a fine concavo-convex structure, and FIG. 7B is a cross-sectional view. The height of the fine concavo-convex structure is indicated by e in the figure, and refers to the difference in height between the top of the convex portion and the first hard coat layer, and the height is 0.1 to 1.5 μm, preferably 0. 2 to 1.2 μm. If it is less than 0.1 μm, the antiglare effect cannot be obtained, and if it exceeds 1.5 μm, the feeling of roughness increases in visibility, which is not preferable. The height of the convex part of the fine concavo-convex structure can be measured by a commercially available stylus type surface roughness measuring machine or a commercially available optical interference type surface roughness measuring machine. For example, the unevenness is measured two-dimensionally within a certain range by an optical interference type surface roughness measuring device, and the unevenness is color-coded as contour lines from the bottom side and displayed. Here, the height of each fine concavo-convex structure on the basis of the adjacent concave bottom is obtained and used as an average value.

  The long side of the convex portion or the concave portion is indicated by f in the figure (in this case, the convex portion). The average of the convex or concave long side is defined as the long side of the convex or concave when the height of the convex or concave is 5% higher or lower than the concave bottom or surface as a reference when color-coded as contour lines. Shown by value. At this time, the long side of the convex portion or concave portion of the fine concavo-convex structure of the present invention is preferably 5 to 100 μm, and if it is less than 5 μm, an antiglare effect cannot be obtained, and if it exceeds 100 μm, a feeling of roughness is visible. Since it increases, it is not preferable.

  The average center-to-center distance g between adjacent convex portions or concave portions (in this case, the convex portion) is the average distance between adjacent convex portions or concave centers with the vertex of the convex portion or concave portion as the center of the convex portion or concave portion. It is a thing. It is preferable that it is 10-200 micrometers, More preferably, it is 30-150 micrometers. Even if it is less than 10 μm or more than 200 μm, the antiglare effect is reduced, which is not preferable. The average distance between protrusions or recesses can be measured by a stylus type surface roughness measuring machine, for example, a fine uneven structure surface through a measuring needle having a diameter of 1 mm with a tip portion made of diamond having a conical shape with an apex angle of 55 degrees. It is possible to obtain knowledge as a surface roughness curve by scanning the upper side with a length of 3 mm in a certain direction, measuring the movement change in the vertical direction of the measuring needle in that case, and recording it. The average value can be obtained by measuring the distance between the recesses. Alternatively, it can be measured by an optical interference type surface roughness measuring machine as described above.

  The height, long side, and average center-to-center distance of the convex or concave portion of the fine concavo-convex structure can be obtained by calculating the average of those obtained by measuring 100 fine concavo-convex structures.

  The antiglare film surface having a fine relief structure according to the present invention preferably has a center line average roughness Ra defined by JIS B 0601 of 0.01 to 5 μm, preferably Ra of 0.07 to 1 μm. Most preferably, Ra is 0.1 to 0.5 μm. For example, Ra increases the anti-glare part, and vice versa. For example, Ra can be varied by 0.05 μm or more.

  The center line average roughness Ra defined in the present invention is defined by JIS B0601, and represents a value obtained by the following formula expressed in micrometers (μm).

  The measurement method of the center line average roughness (Ra) can be determined by measuring in the above environment after conditioning for 24 hours in a 25 ° C., 65% RH environment under conditions where the measurement samples do not overlap each other. . The non-overlapping conditions mentioned here are, for example, a method of winding with the edge portion of the sample raised, a method of stacking paper between the sample and the sample, a frame made of cardboard, etc., and fixing its four corners One of the methods. Examples of the measuring apparatus that can be used include a RSTPLUS non-contact three-dimensional micro surface shape measuring system manufactured by WYKO.

  Next, FIG. 8 shows an example of the formation of the first hard coat layer by flexographic printing preferably used in the present invention and the formation of the second hard coat layer by a coating method using a coater that is subsequently performed.

  In FIG. 8, the base film 502 fed out from the roll 501 is conveyed, and a patterned first hard coat layer comprising a coating portion and a non-application portion having water and oil repellency by flexographic printing in the flexographic printing portion A is provided. Painted. Here, the ink liquid is supplied from the ink supply tank 508 to the anilox roll 510, and the ink is transferred to the resin plate 509 having a pattern structure which is a flexographic printing unit. When the actinic ray curable resin is used for the transfer printed ink, the actinic ray irradiation unit 506A disposed after the resin plate 509 which is a flexographic printing unit is irradiated with actinic rays such as ultraviolet rays. Harden. When the ink uses a thermosetting resin, the ink is heated and cured by a drying zone 505A, for example, a heat plate. A method of heating the back roll 504A as a heat roll is also preferable.

  In the flexographic printing part A, the actinic ray irradiation part 506A and the resin plate 509 are arranged at an appropriate interval so that the irradiation light of the actinic ray irradiation part 506A does not directly affect the ink of the resin plate 509. It is preferable to install a light shielding wall or the like between the light irradiation unit 506A and the resin plate 509. Further, the resin plate 509 is covered with a heat insulating cover so that the heat of the drying zone 505A does not directly affect the ink of the resin plate 509, or the drying air in the drying zone 505A is blocked as shown in the figure. It is preferable to install such a partition.

  The base film 502 that has been cured to such an extent that the pattern formed by the transfer-printed ink can be maintained is cured by evaporating unnecessary organic solvent or the like in the drying zone 505A.

  Next, in the second hard coat layer application part B, the hard coat layer composition supplied from the coater 503 is applied to the surface of the first hard coat layer, and a concave or convex part is formed in the first hard coat layer non-formation part. To do. When the second hard coat layer contains an actinic ray curable resin, actinic rays are irradiated by the actinic ray irradiation units 506B and 506C. Further, it is dried and solidified by the drying zone 505B.

  In the actinic ray irradiation sections 506A, B, and C, it is preferable to irradiate the base film 502 on the back roll 504C whose temperature is controlled to 20 to 120 ° C. with actinic rays.

  The method for forming a patterned first hard coat layer comprising a coated portion and a non-coated portion by flexographic printing according to the present invention is formed while the substrate film is transferred at 1 to 500 m / min, preferably 10 to 300 m / min. It is preferable to do.

  The base film used for transfer printing of the ink is preferably free from unevenness in charging, and is preferably charged immediately before, or may be uniformly charged.

  Also, the anti-glare property such as haze and transmission sharpness is measured for the pattern formed by transfer printing of ink, and it is confirmed that it is a predetermined value, and when the deviation or fluctuation is confirmed, the result is fed back. It is preferable to adjust the ink and replace the resin plate.

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

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

  Although it will not specifically limit if it has said property, For example, cellulose ester-type films, such as a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, a polyester-type film, a polycarbonate Film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol Film, syndiotactic polystyrene film, polycarbonate film, nor Runen resin film, a polymethylpentene film, a polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, may be mentioned acrylic film or a glass plate or the like. Among these, a polycarbonate film, a polyester film, a norbornene resin film, and a cellulose ester film are preferable.

  Various polycarbonates can be used for the polycarbonate-based resin film preferably used in the present invention, but aromatic polycarbonate is preferable from the viewpoint of chemical properties and physical properties, and bisphenol A-based is particularly preferable. More preferably, bisphenol A derivatives obtained by introducing a benzene ring, cyclohexane ring, aliphatic hydrocarbon group, etc. into bisphenol A have anisotropy in the unit molecule obtained using a derivative introduced asymmetrically with respect to the central carbon. Polycarbonate with reduced structure is preferred. For example, two methyl groups in the central carbon of bisphenol A are substituted with benzene rings, and one hydrogen in each benzene ring of bisphenol A is asymmetrically substituted with respect to the central carbon with methyl groups, phenyl groups, etc. The polycarbonate obtained by using is mentioned.

  Specifically, 4,4′-dihydroxydiphenylalkane or a halogen-substituted product thereof is obtained by a phosgene method or a transesterification method. For example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylethane, Examples include 4,4'-dihydroxydiphenylbutane.

  The production method of the polycarbonate resin film used in the present invention is not particularly limited. That is, any of an extrusion method, a solvent casting method, a calendar method, and the like may be used. In the present invention, a uniaxially stretched film or a biaxially stretched film may be used, but in terms of excellent surface accuracy, a film produced by a solvent cast method has a small optical isotropy and anisotropy. Then, the film produced by the extrusion method is more preferable.

  The polycarbonate resin used in the present invention has a glass transition point (Tg) of 110 ° C. or higher and a water absorption rate (measured under conditions of 23 ° C. water for 24 hours) of 0.3% or less. Good to do. More preferably, Tg is 120 ° C. or higher and water absorption is 0.2% or less.

  Although it does not specifically limit as polyester which comprises the polyester-type resin which can be preferably used for this invention, It is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components.

  The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples include cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioether dicarboxylic acid, diphenylketone dicarboxylic acid, and phenylindanedicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.

  Among the polyesters having these as main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid as a dicarboxylic acid component and ethylene glycol as a diol component from the viewpoint of transparency, mechanical strength, dimensional stability, etc. And / or a polyester mainly composed of 1,4-cyclohexanedimethanol is preferred. Among them, a polyester mainly composed of polyethylene terephthalate or polyethylene-2,6-naphthalate, a copolymer polyester composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and two or more kinds of these polyesters A polyester having a mixture as a main constituent is preferred.

  As long as the polyester constituting the polyester film used in the present invention is within a range that does not impair the effects of the present invention, other copolymer components may be copolymerized or other polyesters may be mixed. Also good. Examples of these include the dicarboxylic acid components and diol components mentioned above, or polyesters composed thereof.

  For the purpose of improving the heat resistance of the film, a bisphenol compound, a compound having a naphthalene ring or a cyclohexane ring can be copolymerized. The copolymerization ratio is preferably 1 to 20 mol% based on the bifunctional dicarboxylic acid constituting the polyester.

  The norbornene-based resin film preferably used in the present invention is an amorphous polyolefin film having a norbornene structure, such as APO manufactured by Mitsui Petrochemical Co., Ltd., ZEONEX manufactured by Nippon Zeon Co., Ltd., manufactured by JSR Co., Ltd. ARTON etc.

  In the present invention, it is particularly preferable to use a cellulose ester film. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used. As a commercially available cellulose ester film, for example, Konica Minoltac, product names KC8UX2MW, KC4UX2MW, KC8UY, KC4UY, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5 (manufactured by Konica Minolta Opto, Inc.) From the viewpoint of production, cost, transparency, adhesiveness and the like are preferably used. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

  Hereinafter, the cellulose ester film particularly preferably used in the present invention will be described in more detail.

(Cellulose ester film)
The cellulose ester used in the present invention is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A Nos. 10-45804 and 08-231761 Further, mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.

  If the molecular weight of the cellulose ester is too small, the tear strength is reduced. However, if the molecular weight is too high, the viscosity of the cellulose ester solution becomes too high, and the productivity is lowered. The molecular weight of the cellulose ester is preferably 70000-200000 in terms of number average molecular weight (Mn), more preferably 100,000-200000.

  In the case of cellulose triacetate, those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate. When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average degree of acetylation is large, the solubility in a solvent is lowered and the productivity is lowered.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester containing the cellulose ester which satisfy | fills I) and (II) simultaneously.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
Of these, cellulose acetate propionate is preferably used, and it is particularly preferable that 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9. The portion that is not substituted with an acyl group is usually present as a hydroxyl group. These can be synthesized by known methods.

  As the cellulose ester, cellulose ester synthesized using cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cellulose ester synthesized from a cotton linter (hereinafter sometimes simply referred to as linter) alone or in combination.

  The cellulose ester film used in the present invention may be one produced by a solution casting method or one produced by a melt casting method, but is preferably at least stretched in the width direction, and particularly solution casting. It is preferable that the film is stretched 1.01 to 1.5 times in the width direction when the amount of the residual dissolution in the process is 3 to 40% by mass. More preferably, it is biaxially stretched in the width direction and the lengthwise direction, and when the amount of residual dissolution is 3 to 40% by mass, it is stretched by 1.01 to 1.5 times in the width direction and the lengthwise direction, respectively. It is desirable that By carrying out like this, the anti-glare film excellent in visibility can be obtained. Further, by performing biaxial stretching and knurling, it is possible to remarkably improve the deterioration of the winding shape during storage in the form of a roll of a long low-reflection film. The draw ratio at this time is particularly preferably 1.03 to 1.45.

  In the present invention, it is preferable to use a long film, and specifically, about 100 m to 5000 m is used. Moreover, 1.4 m or more is preferable and, as for the width | variety of a base film, it is more preferable that it is 1.4-4m.

  The cellulose ester film according to the present invention is preferably a transparent film having a light transmittance of 90% or more, more preferably 93% or more.

The cellulose ester film according to the present invention preferably has a thickness of 10 to 100 μm, and the moisture permeability is preferably 200 g / m ² · 24 hours or less at 25 ° C. and 90 ± 2% RH, Preferably, it is 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less.

  In particular, it is preferable that the film thickness is 10 to 60 μm and the moisture permeability is within the above range.

  Here, the moisture permeability of each sample was measured according to the method described in JIS Z 0208.

(Plasticizer)
When using a cellulose ester film for the base film used in the present invention, it is preferable to contain the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, a polyhydric alcohol ester plasticizer, and the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy Ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, and other trimellitic acid plasticizers include tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethylglycolate, butylphthalylbutylglycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid and a glycol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used. As the glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The polyhydric alcohol ester plasticizer comprises an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid. Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, 2-n-butyl-2-ethyl- Examples include 1,3-propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable. There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention. Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid. Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Examples of preferable alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof. Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. Aromatic monocarboxylic acids possessed by them, or their derivatives. Particularly preferred is benzoic acid. The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Further, all of the OH groups in the polyhydric alcohol may be esterified with carboxylic acid, or a part of the OH groups may be left as they are.

  These plasticizers are preferably used alone or in combination.

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

(UV absorber)
It is preferable to add an ultraviolet absorber to the base film used in the present invention.

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

  Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like. For example, but not limited to.

  As the benzotriazole ultraviolet absorber, a compound represented by the following general formula (1) is preferably used.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and are a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxyl group, acyloxy Represents a group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or 5- to 6-membered heterocyclic group, and R ₄ and R ₅ are closed to form a 5- to 6-membered carbocyclic ring May be.

  Moreover, these groups described above may have an arbitrary substituent.

  Although the specific example of the ultraviolet absorber used for this invention is given to the following, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba Specialty Chemicals)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba Specialty Chemicals)
As the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (2) is preferably used.

In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a —CO (NH) _n-1 —D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have m and n represent 1 or 2.

  In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group has, for example, carbon number An alkenyl group up to 16 represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents to alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, etc., hydroxyl groups, phenyl groups (this phenyl group is substituted with alkyl groups or halogen atoms, etc.) May be used).

  Specific examples of the benzophenone compound represented by the general formula (B) are shown below, but the present invention is not limited thereto.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber, which are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal, are preferable, and unnecessary coloring occurs. Less benzotriazole-based UV absorbers are particularly preferably used.

  Moreover, the ultraviolet absorber with the distribution coefficient described in Japanese Patent Application No. 11-295209 having a distribution coefficient of 9.2 or more is excellent in the surface quality of the film and in the coating property when used for the base film. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorber (or ultraviolet ray) described in the general formula (1) or general formula (2) of JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039. Absorbable polymers) are also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

(Fine particles)
In the present invention, the cellulose ester film preferably contains fine particles. Examples of the fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, and hydration. It is preferable to contain inorganic fine particles such as calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and crosslinked polymer fine particles. Of these, silicon dioxide is preferable because it can reduce the haze of the film. The average particle size of the secondary particles of the fine particles is in the range of 0.01 to 1.0 μm, and the content is preferably 0.005 to 0.3% by mass with respect to the cellulose ester. In many cases, fine particles such as silicon dioxide are surface-treated with an organic material, but such a material is preferable because it can reduce the haze of the film. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes (particularly alkoxysilanes having a methyl group), silazane, siloxane and the like. The larger the average particle size of the fine particles, the greater the mat effect, and on the contrary, the smaller the average particle size, the better the transparency. Therefore, the average particle size of the preferred primary particles is 5 to 50 nm, more preferably 7 to 16 nm. It is. These fine particles are usually present as aggregates in the cellulose ester film, and it is preferable to form irregularities of 0.01 to 1.0 μm on the surface of the cellulose ester film. Examples of the fine particles of silicon dioxide include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, etc. manufactured by Aerosil, preferably AEROSIL (Aerosil) 200V, R972, R972V, R974, R202, and R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, for example, AEROSIL (Aerosil) 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9 to 0.1. In the present invention, the fine particles may be dispersed together with cellulose ester, other additives, and an organic solvent at the time of preparing the dope, but in a sufficiently dispersed state like a fine particle dispersion separately from the cellulose ester solution. It is preferable to prepare the dope. In order to disperse the fine particles, it is preferably preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force. After that, it is preferable to disperse in a larger amount of organic solvent, merge with the cellulose ester solution, and mix with an in-line mixer to obtain a dope. In this case, an ultraviolet absorbent may be added to the fine particle dispersion to form an ultraviolet absorbent liquid.

  The deterioration inhibitor, the ultraviolet absorber and / or the fine particles may be added together with the cellulose ester and the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.

(Organic solvent)
The organic solvent useful for forming the dope of the cellulose ester film used in the present invention can be used without limitation as long as it dissolves cellulose ester and other additives simultaneously. For example, as the chlorinated organic solvent, methylene chloride, as the non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- Examples include 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, and nitroethane. Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used. Particularly preferred is methyl acetate.

  In addition to the organic solvent, the dope according to the present invention preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms. When the proportion of alcohol in the dope increases, the web gels, facilitating peeling from the metal support, and when the proportion of alcohol is small, the role of promoting dissolution of cellulose esters in non-chlorine organic solvent systems There is also. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, good drying properties, and no toxicity.

  The concentration of the cellulose ester in the dope is preferably adjusted to 15 to 40% by mass, and the dope viscosity is preferably adjusted to a range of 100 to 500 poise (P) in order to obtain good film surface quality.

《Anti-glare anti-reflection film》
In the present invention, it is preferable to provide an antiglare antireflection film by providing the following low refractive index layer on the surface having a fine uneven structure of the antiglare film having the first hard coat layer and the second hard coat layer.

  In particular, in the present invention, the low refractive index layer is preferably coated with a low refractive index layer coating solution containing hollow silica-based fine particles having an outer shell layer and porous or hollow inside.

<Low refractive index layer>
The refractive index of the low refractive index layer according to the present invention is preferably lower than the refractive index of the substrate film as the support, and is preferably in the range of 1.30 to 1.45 at 23 ° C. and a wavelength of 550 nm.

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

  The composition for forming a low refractive index layer used in the present invention comprises (a) an organosilicon compound represented by the following general formula (3) or a hydrolyzate thereof or a polycondensate thereof, and (b) an outer shell layer. It is preferable that hollow silica-based fine particles having a porous or hollow interior constitute the composition.

General formula (3) Si (OR) ₄
(In the formula, R is an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms.)
In addition, a silane coupling agent, a curing agent, and the like may be added as necessary.

[Hollow silica fine particles]
First, hollow silica-based fine particles having the outer shell layer represented by (b) and having a porous or hollow interior will be described.

  The hollow silica-based fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having cavities inside, and the contents are solvent, gas or porous It is a hollow particle filled with a porous material. The low refractive index layer may contain either (I) composite particles or (II) hollow particles, or may contain both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such hollow fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The hollow fine particles to be used are appropriately selected according to the thickness of the transparent coating to be formed, and may be in the range of 2/3 to 1/10 of the thickness of the transparent coating such as the low refractive index layer to be formed. desirable. These hollow fine particles 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 (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use silicate monomers and oligomers with a low polymerization degree, which are coating liquid components described later. In some cases, the inside of the composite particle enters the inside and the porosity of the inside is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, when the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. In addition, components other than silica may be contained. Specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, particles having a small pore volume and a low refractive index cannot be obtained. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a low refractive index. is there.

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

  Incidentally, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Examples of the porous substance include those composed of the compounds exemplified for the porous particles. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow fine particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. As an alkali metal silicate, sodium silicate (water glass) or potassium silicate is used. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium Salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. I can do it. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When using a seed particle dispersion, the pH of the seed particle dispersion is adjusted to 10 or higher, and then an aqueous solution of the compound is added to the above-mentioned alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. Particle deposition occurs on the top. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of the silica and the inorganic compound other than silica in the first step is calculated by converting the inorganic compound to silica into an oxide (MO _X ), and the molar ratio of MO _X / SiO ₂ is 0.05 to 2.0, Preferably it is in the range of 0.2-2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing the hollow particles, the molar ratio of MO _X / SiO ₂ is desirably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded via oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Moreover, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore, the silica coating layer described later is formed without reducing the pore volume. I can do it. Note that when the amount of the inorganic compound to be removed is small, it is not always necessary to form a protective film because the particles are not broken.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor comprising a silica protective film, a solvent in the silica protective film, and an undissolved porous solid, and the hollow particles When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organic silicon compound used for the silica protective film formed of the general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, such as acrylic group An alkoxysilane represented by a hydrocarbon group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film using a silicic acid liquid and the said alkoxysilane together.

Third step: Formation of silica coating layer In the third step, the porous particle dispersion prepared in the second step (in the case of hollow particles, the hollow particle precursor dispersion) contains a fluorine-substituted alkyl group-containing silane compound. By adding a hydrolyzable organosilicon compound or silicic acid solution, the surface of the particles is coated with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, A hydrocarbon group such as an acryl group or an alkoxysilane represented by n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. A silicic acid solution may be used in combination with the alkoxysilane for forming a coating layer. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.

  The content of the hollow silica-based fine particles having an outer shell layer and porous or hollow inside is preferably 10 to 50% by mass. In order to obtain the effect of a low refractive index, the content is preferably 15% by mass or more, and when it exceeds 50% by mass, the binder component is decreased and the film strength becomes insufficient.

(Silicon compound)
In the organosilicon compound represented by the general formula (3), R represents an alkyl group having 1 to 4 carbon atoms.

  Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

  As a method of adding to the low refractive index layer, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these tetraalkoxysilane, pure water, and alcohol is added to the dispersion of the hollow silica fine particles. The silicic acid polymer produced by hydrolyzing tetraalkoxysilane is deposited on the surface of the hollow silica fine particles. At this time, tetraalkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  In the present invention, the low refractive index layer may contain a fluorine-substituted alkyl group-containing silane compound represented by the following general formula (4).

  The fluorine-substituted alkyl group-containing silane compound represented by the general formula (4) will be described.

In the formula, R ^{1 to} R ⁶ are alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, 6 to 12 carbon atoms, preferably 6 carbon atoms. 10 to 10 aryl groups, 7 to 14 carbon atoms, preferably 7 to 12 alkylaryl groups, arylalkyl groups, 2 to 8 carbon atoms, preferably 2 to 6 alkenyl groups, or 1 to 6 carbon atoms, preferably 1 to 3 alkoxy groups, a hydrogen atom or a halogen atom.

Rf represents-(C _a H _b F _c )-, a is an integer of 1 to 12, b + c is 2a, b is an integer of 0 to 24, and c is an integer of 0 to 24. Such Rf is preferably a group having a fluoroalkylene group and an alkylene group. Specifically, as such a fluorine-containing silicone compound, (MeO) ₃ SiC ₂ H ₄ C ₂ F ₄ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (MeO) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H Examples include methoxydisilane compounds represented by ₄ Si (OC ₂ H ₅ ) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ , and the like.

  If the fluorine-containing alkyl group-containing silane compound is included as a binder, the transparent film itself is hydrophobic, so the transparent film is not sufficiently densified and is porous or cracked. Even if it has a void or a void, entry into the transparent film by chemicals such as moisture, acid and alkali is suppressed. Furthermore, fine particles such as metals contained in the conductive layer which is the substrate surface or the lower layer do not react with chemicals such as moisture, acid and alkali. For this reason, such a transparent film has excellent chemical resistance.

  In addition, when a fluorine-substituted alkyl group-containing silane compound is included as a binder, not only the hydrophobic property but also the slipperiness (low contact resistance) is obtained, and thus a transparent film having excellent scratch strength can be obtained. I can do it. Furthermore, when the binder contains a fluorine-substituted alkyl group-containing silane compound having such a structural unit, when the conductive layer is formed in the lower layer, the shrinkage of the binder is equal to or close to that of the conductive layer. Since it is a thing, the transparent film excellent in adhesiveness with the conductive layer can be formed. Furthermore, when the transparent film is heat-treated, the conductive layer is not peeled off due to the difference in shrinkage rate, and a portion having no electrical contact is not generated in the transparent conductive layer. For this reason, sufficient electroconductivity can be maintained as a whole film.

  A transparent film containing a fluorine-substituted alkyl group-containing silane compound and hollow silica-based fine particles having the outer shell layer and being porous or hollow inside has high scratch strength and is evaluated by eraser strength or nail strength. The film strength is high, the pencil hardness is high, and a transparent film excellent in strength can be formed.

  The low refractive index layer according to the present invention may contain a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, 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- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  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-mercaptopropylmethyldimeth Shishiran, .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, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents 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 its hydrolyzate.

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

  The low refractive index layer preferably contains 5 to 80% by mass of binder as a whole. The binder has a function of adhering the hollow silica fine particles and maintaining the structure of the low refractive index layer including voids. The usage-amount of a binder is adjusted so that the intensity | strength of a low refractive index layer can be maintained, without filling a space | gap.

(solvent)
The low refractive index layer according to the present invention preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The content of the organic solvent is preferably 1 to 4% by mass of the solid content concentration in the low refractive index layer coating composition. The organic solvent is preferably 1% by mass or more in order to prevent coating unevenness and achieve a uniform film thickness, and if it exceeds 4% by mass, the drying load increases, which is not preferable because the size of the drying apparatus is increased and the time is increased.

<High refractive index layer>
In the present invention, in order to improve antireflection properties, it is preferable to provide the following high refractive index layer below the low refractive index layer.

  The high refractive index layer preferable for the present invention preferably contains (c) metal oxide fine particles having an average particle diameter of 10 to 200 nm, (d) a metal compound, and (e) an ionizing radiation curable resin.

(Metal oxide fine particles)
The high refractive index layer of the present invention preferably contains metal oxide fine particles. The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the above can be used, and these metal oxide fine particles are doped with a trace amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta. May be. A mixture of these may also be used. In the present invention, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. It is preferably used as a main component, and particularly preferably indium tin oxide (ITO).

  The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles may be measured from an electron micrograph by a scanning electron microscope (SEM) or the like, or measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. May be. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  Specifically, the refractive index of the high refractive index layer is preferably higher than the refractive index of the base film as a support, and is preferably in the range of 1.50 to 1.70 when measured at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index of the high refractive index layer is that the kind and addition amount of the metal oxide fine particles are dominant, so that the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, More preferably, it is 1.85 to 2.50.

  The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . For this reason, the surface modification amount with a preferable organic compound is 0.1 mass%-5 mass% with respect to metal oxide particle, More preferably, it is 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent mentioned later is preferable. Two or more kinds of surface treatments may be combined.

  The thickness of the high refractive index layer containing the metal oxide fine particles is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm.

  The ratio of the metal oxide fine particles to be used and a binder such as ionizing radiation curable resin, which will be described later, varies depending on the type of metal oxide fine particles, the particle size, etc. The latter one is preferable.

  The amount of the metal oxide fine particles used in the present invention is preferably 5% by mass to 85% by mass in the high refractive index layer, more preferably 10% by mass to 80% by mass, and most preferably 20% to 75% by mass. preferable. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained, and if it is too large, the film strength deteriorates.

  The metal oxide fine particles are supplied to a coating solution for forming a high refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (for example, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  In the present invention, metal oxide fine particles having a core / shell structure may be further contained. One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

  For the core, titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, tin-doped indium oxide, antimony-doped tin oxide, etc. can be used. Titanium may be the main component.

  The shell is preferably formed of a metal oxide or sulfide containing an inorganic compound other than titanium oxide as a main component. For example, an inorganic compound mainly composed of silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc sulfide, or the like is used. Of these, alumina, silica, and zirconia (zirconium oxide) are preferable. A mixture of these may also be used.

  The coating amount of the shell with respect to the core is 2 to 50% by mass as an average coating amount. Preferably it is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles decreases, and when the coating amount is too small, the light resistance is deteriorated. Two or more kinds of metal oxide fine particles may be used in combination.

  The titanium oxide used as a core can use what was produced by the liquid phase method or the gaseous-phase method. As a method for forming the shell around the core, for example, U.S. Pat. No. 3,410,708, JP-B-58-47061, U.S. Pat. No. 2,885,366, and U.S. Pat. No. 1, British Patent No. 1,134,249, US Pat. No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. I can do it.

(Metal compound)
As the metal compound used in the present invention, a compound represented by the following general formula (5) or a chelate compound thereof can be used.

Formula (5) _An MB _xn
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the above formula (5) includes an alkoxide having two or more alkoxyl groups bonded directly to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxide, zirconium alkoxide, or chelate compounds thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Moreover, since titanium alkoxide has the effect of accelerating the reaction of the ultraviolet curable resin and metal alkoxide, the physical properties of the coating film can be improved by adding a small amount.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against moisture mixing and is excellent in the effect of reinforcing the coating film.

  The addition amount of the metal compound is preferably adjusted so that the content of the metal oxide derived from the metal compound contained in the high refractive index layer is 0.3 to 5% by mass. If it is less than 0.3% by mass, the scratch resistance is insufficient, and if it exceeds 5% by mass, the light resistance tends to deteriorate.

(Ionizing radiation curable resin)
The ionizing radiation curable resin is added as a binder for the metal oxide fine particles to improve the film formability and physical properties of the coating film. As the ionizing radiation curable resin, a monomer or oligomer having two or more functional groups that cause polymerization reaction directly by irradiation of ionizing radiation such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator is used. Can be used. Examples of the functional group include a group having an unsaturated double bond such as a (meth) acryloyloxy group, an epoxy group, and a silanol group. Among these, radically polymerizable monomers and oligomers having two or more unsaturated double bonds can be preferably used. You may combine a photoinitiator as needed. Examples of such ionizing radiation curable resins include polyfunctional acrylate compounds and the like, and the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. It is preferable that it is a compound chosen from these. Here, the polyfunctional acrylate compound is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate preferred. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  The addition amount of the ionizing radiation curable resin is preferably less than 50% by mass in the solid content in the high refractive index composition.

  In order to accelerate the curing of the ionizing radiation curable resin according to the present invention, the photopolymerization initiator and the acrylic compound having two or more polymerizable unsaturated bonds in the molecule are in a mass ratio of 3: 7 to 1: 9. It is preferable to contain.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof.

(solvent)
Examples of the organic solvent used for coating the high refractive index layer of the present invention include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol). , Cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexane Triol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether) , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine) , Ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide) Etc.), heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.) ), Sulfones (for example, sulfolane, etc.), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

(Anti-fouling layer)
The antiglare film or antiglare antireflection film of the present invention preferably has an antifouling layer on the outermost layer.

  The antifouling layer preferable for the present invention preferably contains a fluorine-containing silane compound in the antifouling layer forming composition, and is prepared by coating a silane compound solution having a fluoroalkyl group or a fluoroalkyl ether group. In particular, the fluorine-containing silane compound is preferably silazane or alkoxysilane.

  In addition, among the silane compounds having the fluoroalkyl group or the fluoroalkyl ether group, the fluoroalkyl group in the silane compound is bonded to Si atoms at a ratio of 1 or less to one Si atom, and the remaining Is preferably a silane compound which is a hydrolyzable group or a siloxane bond group.

  The hydrolyzable group here is a group such as an alkoxy group, for example, and becomes a hydroxyl group by hydrolysis, whereby the silane compound forms a polycondensate.

  For example, the silane compound is usually reacted with water (in the presence of an acid catalyst if necessary) in the range of room temperature to 100 ° C. while distilling off by-produced alcohol. As a result, the alkoxysilane is (partially) hydrolyzed to cause a partial condensation reaction, and can be obtained as a hydrolyzate having a hydroxyl group. The degree of hydrolysis and condensation can be adjusted as appropriate depending on the amount of water to be reacted, but in the present invention, water is not actively added to the silane compound solution used for antifouling treatment, and after preparation, It is preferable to dilute and use the solid content concentration of the solution in order to cause a hydrolysis reaction mainly by moisture in the air during drying.

  Preferably, in the composition for forming an antifouling layer, the silane compound having a fluoroalkyl group is represented by the following general formula (6), and the concentration of the silane compound is diluted to 0.01 to 5% by mass. Use antifouling treatment.

Formula _{(6) CF 3 (CF 2} ) m (CH 2) n -Si- (ORa) 3
Here, m is an integer of 1-10. n is an integer of 0-10. Ra represents the same or different alkyl group.

  In the compound represented by the general formula (6), Ra has 3 or less carbon atoms and is preferably an alkyl group consisting of only carbon and hydrogen, for example, a group such as methyl, ethyl, isopropyl and the like.

Examples of the silane compound having a fluoroalkyl group or fluoroalkyl ether group preferably used in the present invention include CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ). ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₄ H ₉ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC _{3 H 7) 3, CF 3} (CF 2) 7 (CH 2) 2 Si (OCH 3) (OC 3 H 7) 2, CF 3 (CF 2) 7 _{CH 2) 2 Si (OCH 3} ) 2 OC 3 H 7, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 (OCH 3) 2, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 ( OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₃ H ₇ ) ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , C ₇ F ₁₅ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₅ ( _{CH 2) 2 Si (CH 3} ) (OCH 3) 2, CF 3 (CF 2) 5 (CH 2) 2 Si (CH 3) (OC 3 H 7) 2, CF 3 (CF 2) 2 O (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ), C ₇ F ₁₅ CH ₂ O (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ O (CH ₂ ) ₃ Si Examples include (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCHO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , but not limited thereto.

  Examples of the fluorine-based silane compound include KP801M and X-24-9146 manufactured by Shin-Etsu Chemical Co., Ltd., GE Toshiba Silicones Co., Ltd. XC98-A5382, XC98-B2472, Daikin Industries, Ltd. OPTOOL DSX, and FG5010 manufactured by Fluoro Technology Co., Ltd. As the compound for surface treatment, perfluoroalkylsilazane, perfluoroalkylsilane, or perfluoropolyether group-containing silane compound, particularly perfluoroalkyltrialkoxysilane, perfluoropolyethertrialkoxysilane, Examples include perfluoropolyether ditrialkoxysilane.

  When these silane compounds are used, they are diluted to 0.01 to 10% by mass, preferably 0.03 to 5% by mass, more preferably 0.05 to 2% by mass in an organic solvent not containing fluorine. It is preferable to use in.

  In the present invention, an organic solvent containing no fluorine is preferably used to prepare the silane compound solution, and the following may be mentioned.

  As a solvent of the coating composition for the antifouling layer used in the present invention, propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, propylene glycol mono (C1-C4). Specific examples of the alkyl ether include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether and the like. The propylene glycol mono (C1 to C4) alkyl ether ester includes propylene glycol monoalkyl ether acetate, specifically, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. Propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, etc., alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol, t-butanol, cyclohexanol , Ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetone, esters such as ethyl acetate, methyl acetate, ethyl lactate, isopropyl acetate, amyl acetate and ethyl butyrate, hydrocarbons such as benzene, toluene and xylene, dioxane, N, N-dimethylformamide and other solvents. Alternatively, these solvents are used by being appropriately mixed. The solvent to be mixed is not particularly limited to these.

  Particularly preferred solvents are one or more organic solvents selected from ethanol, isopropyl alcohol, propylene glycol, and propylene glycol monomethyl ether.

  Among these solvents, those having a boiling point of less than 100 ° C. (low boiling solvent) such as methanol, ethanol and isopropyl alcohol, and boiling points of 100 ° C. or more such as propylene glycol monomethyl ether and n-butyl alcohol. (Boiling point solvent) is preferably used in combination, and in particular, those having a boiling point of 60 to 98 ° C. and those having a boiling point of 100 to 160 ° C. are preferably used in combination. The ratio of the low boiling point solvent and the high boiling point solvent when used in combination is preferably 98.0% by mass or more and the high boiling point solvent is 0.5 to 2% by mass in the composition.

  In the antifouling layer forming composition used in the present invention, it is preferable to add an acid to adjust the pH to 5.0 or less. Since the acid promotes hydrolysis of the silane compound and acts as a catalyst for the polycondensation reaction, the polycondensation film of the silane compound can be easily formed on the surface of the substrate, and the antifouling property can be improved. The pH is preferably in the range of 1.5 to 5.0. If the pH is 1.5 or less, the acidity of the solution is too strong, and the container or the piping may be damaged. Preferably it is the range of pH2.0-4.0.

  In the present invention, it is preferable not to positively add water to the silane compound solution used for the antifouling treatment, but to cause a hydrolysis reaction by moisture in the air after the preparation, mainly at the time of drying. Therefore, it is used when the solid content concentration of the solution is diluted. If too much water is added to the treatment liquid, the pot life is shortened accordingly.

  In the present invention, sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, boric acid, hydrofluoric acid, preferably an inorganic acid such as hydrochloric acid and nitric acid, an organic acid having a sulfo group (also referred to as a sulfonic acid group) or a carboxyl group, For example, acetic acid, polyacrylic acid, benzenesulfonic acid, p-toluenesulfonic acid, methylsulfonic acid and the like are used. The organic acid is more preferably a compound having a hydroxyl group and a carboxyl group in one molecule. For example, a hydroxydicarboxylic acid such as citric acid or tartaric acid is used. The organic acid is more preferably a water-soluble acid. For example, in addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaloacetic acid, pyruvin. Acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D-gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are preferably used. Also, benzoic acid, hydroxybenzoic acid, atorvaic acid and the like can be used as appropriate.

  The addition amount is 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the partial hydrolyzate of the silane compound. Further, the amount of water added is not limited as long as the partial hydrolyzate can theoretically be hydrolyzed by 100%, and an amount equivalent to 100% to 300%, preferably an amount equivalent to 100% to 200% is added. Good.

  By using a fluorine-containing silane compound, it is not only preferable in terms of lowering the refractive index of the antifouling layer and imparting water and oil repellency, but also has an effect of being highly scratch resistant and particularly excellent in blocking between films. .

  In the present invention, it is also preferable to use a composition obtained by further adding an alkoxysilane or an alkylalkoxysilane to a fluorine-free organic solvent solution containing the silane compound having a fluoroalkyl group.

  As examples of these alkoxysilanes and alkylalkoxysilanes, any known silane compounds may be used.

  Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), dialkyldialkoxysilane, and the like.

  These alkoxysilanes and alkylalkoxysilanes can be used in the range of 0.01 to 15% by mass in addition to the fluorine-containing silane compound when preparing the coating composition for the antifouling layer. In the same manner, by performing hydrolysis and condensation in the same manner, an integrated film is formed by polycondensation with the fluorine-containing silane compound.

  By using these alkoxysilanes and alkylalkoxysilanes in admixture with the fluorine-containing silane compound, the film strength is increased, and there are further effects in scratch resistance and prevention of blocking when stacked.

  Furthermore, it is also possible to use a composition formed by adding 0.01 to 5% by mass of a silicon isocyanate compound to a silane compound solution having a fluoroalkyl group or a fluoroalkyl ether group. The strength is further improved, and further effects can be obtained by preventing the surface from being scratched and suppressing sticking (blocking) when the films are stacked.

As the silicon isocyanate compound used in the present invention, Si (NCO) ₄ , CH ₃ Si (NCO) ₃ , (CH ₃ ) ₂ Si (NCO) ₂ , (CH ₃ ) ₃ SiNCO, CH ₂ = CHSi (NCO) ₃ , C ₂ H ₅ Si (NCO) ₃ , and the like. Si (NCO) ₄ and CH ₃ Si (NCO) ₃ are preferable, and Si (N) is preferred from the viewpoint of environmental safety, which is an object of the present invention. NCO) ₄ is more preferred.

  By mixing these silicon isocyanate compounds in the above amounts in the antifouling layer-forming composition, the crosslinking reaction with the silane compound can be performed more completely, and the effect of improving the film properties is great. These compounds do not participate in the hydrolysis, but react with a hydroxyl group (silanol group) formed by hydrolysis to complement the condensation of the silanol groups and make the film strong.

  The organic solvent that does not contain fluorine may be used as it is as the organic solvent when using these silicon isocyanate compounds. However, among the above-mentioned organic solvents, when the silicon isocyanate compound is mixed and used, ethanol, isopropyl Particularly preferred are solvents such as alcohol, propylene glycol, toluene, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and butyl acetate.

  Moreover, when mixing and using a silicon isocyanate compound, pH should just be 7.0 or less, and the range of 2.0-7.0 is good. When the pH is 7.0 or more, the reaction with the silanol group is difficult to proceed. Among them, the pH is preferably in the range of 3.0 to 6.0.

  The refractive index of the antifouling layer is preferably 1.30 to 1.50, more preferably 1.35 to 1.49. When it is 1.30 or less, the film hardness cannot be obtained, and when it is 1.50 or more, the surface reflectance increases. The antifouling layer comprising a resin formed from a hydrolyzed polycondensate of a silane compound containing a fluoroalkyl group preferably has a dynamic friction coefficient in the range of 0.03 to 0.25.

  The antifouling layer coating composition thus obtained is applied on the low refractive index layer to form an antifouling layer. As a coating method, any method may be used, and a method using a normal dip coater, gravure coater, reverse roll coater, extrusion coater, etc. may be mentioned.

(Formation of antireflection layer)
In the present invention, the method for providing the antireflection layer is not particularly limited, but it is preferably formed by coating.

  In the present invention, a step of forming a fine concavo-convex structure on the base film by the first hard coat layer and the second hard coat layer, and sequentially coating using the above-described high refractive index layer composition and low refractive index layer composition It is preferable to produce an antireflection layer. It is also preferable to coat the antifouling layer.

  Although the structure of a preferable anti-glare antireflection film is shown below, it is not limited to these.

  Here, the hard coat layer means the first hard coat layer and the second hard coat layer according to the present invention.

Base film / hard coat layer / low refractive index layer Base film / hard coat layer / high refractive index layer / low refractive index layer Base film / antistatic layer / hard coat layer / low refractive index layer Base film / charge Prevention layer / hard coat layer / high refractive index layer / low refractive index layer base film / hard coat layer / low refractive index layer / antifouling layer base film / hard coat layer / high refractive index layer / low refractive index layer / Antifouling layer Base film / antistatic layer / hard coat layer / low refractive index layer / antifouling layer Base film / antistatic layer / hard coat layer / high refractive index layer / low refractive index layer / antifouling layer Preferably, after the hard coat layer is formed, the surface of the hard coat layer is subjected to a surface treatment, and the low refractive index layer according to the present invention is formed on the surface of the hard coat layer subjected to the surface treatment. It is also preferable to subject the low refractive index layer to a surface treatment before providing the antifouling layer.

  Examples of the surface treatment include cleaning methods, alkali treatment methods, flame plasma treatment methods, high frequency discharge plasma methods, electron beam methods, ion beam methods, sputtering methods, acid treatments, corona treatment methods, atmospheric pressure glow discharge plasma methods, and the like. The alkali treatment method and the corona treatment method are preferable, and the alkali treatment method is particularly effective.

The corona treatment is a treatment performed by applying a high voltage of 1 kV or more between the electrodes under atmospheric pressure and discharging it. An apparatus commercially available from Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. Can be used. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency. As one electrode (A electrode) of the corona treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is carried out stably and uniformly. A commercially available one can also be used, and the material is preferably a roll made of aluminum, stainless steel, or a metal thereof, and a roll lined with ceramics, silicon, EPT rubber, hyperon rubber, or the like. It is done. The frequency used for the corona treatment used in the present invention is a frequency of 20 kHz to 100 kHz, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it is difficult to perform stable processing, resulting in uneven processing. Will occur. The output of the corona treatment is 1 to 5 w · min. / M ² but ² to 4 w · min. An output of / m ² is preferred. The distance between the electrode and the film is 5 mm or more and 50 mm or less, preferably 10 mm or more and 35 mm or less. When the gap is opened, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. If the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film comes into contact with the electrodes and scratches are generated.

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

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

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

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

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

  Each layer of the antireflection layer uses a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a micro gravure coating method and an extrusion coating method on a base film. And can be formed by coating. At the time of application, the base film is preferably wound up in a roll shape after being unwound from a state wound in a roll shape with a width of 1.4 to 4 m, performing the above-described application, drying and curing treatment. .

  Furthermore, the anti-glare antireflection film of the present invention is obtained by laminating the antireflection layer on the base film and then heat-treating it in the range of 50 to 150 ° C. and 1 to 30 days in the state of being wound in a roll. It is preferable to manufacture by the manufacturing method to perform. The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C, it is preferably a period of 3 days or more and less than 30 days, and if it is 150 ° C, a range of 1 to 3 days is preferable. Usually, it is preferable to set it at a relatively low temperature so that the heat treatment effect on the outside of the winding, the center of the winding, and the core is not biased, and it is preferable to carry out at around 50 to 80 ° C. for about 3 to 7 days.

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

  When winding an optical film coated with a functional thin film in a roll shape, the winding core may be of any material as long as it is a cylindrical core, but preferably a hollow plastic core. The plastic material may be any heat-resistant plastic that can withstand the heat treatment temperature, and examples thereof include resins such as phenol resin, xylene resin, melamine resin, polyester resin, and epoxy resin. A thermosetting resin reinforced with a filler such as glass fiber is preferable.

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

  In this way, when the heat treatment is performed in a state where the functional thin film is coated on the long plastic film substrate and the roll wound around the plastic core is wound, it is preferable to rotate the roll. The rotation is preferably a speed of 1 rotation or less per minute, and may be continuous or intermittent. Moreover, it is preferable to perform rewinding of the roll once or more during the heating period.

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

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

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

  In the case of a dedicated carriage having a rotation function, it is preferable that the optical film roll can be rotated during movement and storage. In this case, rotation is effective as a countermeasure against black bands that occur when the storage period is long. Function.

(Polarizer)
The polarizing plate can be produced by a general method. Using a fully saponified polyvinyl alcohol aqueous solution on at least one surface of a polarizing film prepared by subjecting the back side of the antiglare film and the antiglare antireflection film of the present invention to alkali saponification treatment and immersion drawing in an iodine solution It is preferable to stick them together. The film may be used on the other surface, or another polarizing plate protective film may be used. Commercially available cellulose ester films (for example, Konica Minoltac KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, preferably Konica Minolta) Used. In contrast to the antiglare film and the antiglare antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, 30 to 300 nm, and Rt of 70 to 400 nm. It is preferable to have a phase difference. These can be produced, for example, by the method described in JP-A-2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. By using in combination with the antiglare film and the antiglare antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound.

  Further, ethylene-modified polyvinyl alcohol having an ethylene unit content of 1 to 4 mol%, a polymerization degree of 2000 to 4000, and a saponification degree of 99.0 to 99.99 mol% is also preferably used. Among them, an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 ° C. is preferably used. The difference in hot water cutting temperature between two points 5 cm away in the TD direction of the film is more preferably 1 ° C. or less in order to reduce color spots, and two points separated 1 cm in the TD direction of the film. In order to reduce color spots, it is more preferable that the difference in hot water cutting temperature between them is 0.5 ° C. or less.

  A polarizing film using this ethylene-modified polyvinyl alcohol film is excellent in polarizing performance and durability, and has few color spots, and is particularly preferably used for a large liquid crystal display device.

  As the ethylene-modified polyvinyl alcohol (ethylene-modified PVA) used in the present invention, an ethylene-vinyl ester polymer obtained by copolymerizing ethylene and a vinyl ester monomer is saponified, and the vinyl ester unit is converted into a vinyl alcohol unit. Can be used. Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like. Of these, vinyl acetate is preferably used.

  The ethylene unit content (ethylene copolymerization amount) in the ethylene-modified PVA is 1 to 4 mol%, preferably 1.5 to 3 mol%, more preferably 2 to 3 mol%.

  When the content of the ethylene unit is within this range, the polarization performance and durability performance are improved, and color spots are reduced, which is preferable.

  Furthermore, the following monomers can be copolymerized with a vinyl ester monomer in ethylene-modified polyvinyl alcohol. When copolymerizing with a vinyl ester monomer, the preferred range is 15 mol% or less, more preferably 5 mol% or less.

  Examples of monomers copolymerizable with such vinyl ester monomers include olefins having 3 to 30 carbon atoms such as propylene, 1-butene and isobutene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, Acrylic acid esters such as n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc. Methacrylic acid and salts thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-methacrylic acid 2- Ethylhexyl, dodecyl methacrylate, methacrylate Methacrylic acid esters such as octadecyl acid; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acrylamidopropyldimethylamine and its salt, N- Acrylamide derivatives such as methylolacrylamide and its derivatives; methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid and its salts, methacrylamidepropyldimethylamine and its salts, N-methylolmethacrylamide and its Methacrylamide derivatives such as derivatives; N-vinyl such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone Mido; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; acrylonitrile, methacrylonitrile, etc. Nitriles; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid and its salts or esters; itaconic acid and its salts or its Esters; Vinylsilyl compounds such as vinyltrimethoxysilane; N-vinylamines such as isopropenyl acetate, N-vinylformamide, N-vinylacetamide, and N-vinylpyrrolidone Mention may be made of mids.

  The degree of polymerization of the ethylene-modified PVA constituting the polarizing film is 2000 to 4000 from the viewpoint of polarization performance and durability, preferably 2200 to 3500, and particularly preferably 2500 to 3000. When the degree of polymerization is less than 2000, the polarizing performance and durability performance of the polarizing film are lowered, which is not preferable. Moreover, it is preferable that the polymerization degree is 4000 or less because color spots of the polarizing film are hardly generated.

  The degree of polymerization of ethylene-modified PVA is the weight average degree of polymerization determined from GPC measurement. This weight average degree of polymerization is a value obtained by performing GPC measurement at 40 ° C. using hexafluoroisopropanol (HFIP) in which 20 mmol / liter sodium trifluoroacetate is added to the mobile phase using monodispersed PMMA as a standard. is there.

  The saponification degree of the ethylene-modified PVA constituting the polarizing film is 99.0 to 99.99 mol% from the viewpoint of the polarizing performance and durability of the polarizing film, more preferably 99.9 to 99.99 mol%. Particularly preferred is .95 to 99.99 mol%.

  Although it does not specifically limit as a method to manufacture an ethylene modified PVA film, The casting film forming method and the melt extrusion film forming method are preferable from a viewpoint of obtaining a favorable ethylene modified PVA film. The obtained ethylene-modified PVA film is subjected to drying and heat treatment as necessary.

  Examples of the solvent for dissolving the ethylene-modified PVA used in producing the ethylene-modified PVA film include dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, and triethylene. Glycol, tetraethylene glycol, trimethylolpropane, ethylenediamine, diethylenetriamine, glycerin, water and the like can be mentioned, and one or more of these can be used. Among these, dimethyl sulfoxide, water, or a mixed solvent of glycerin and water is preferably used.

  The ratio of ethylene-modified PVA in the ethylene-modified PVA solution or water-containing ethylene-modified PVA used in producing the ethylene-modified PVA film varies depending on the degree of polymerization of ethylene-modified PVA, but is preferably 20 to 70% by mass. 25-60 mass% is more preferable, 30-55 mass% is further more preferable, and 35-50 mass% is the most preferable. If the proportion of ethylene-modified PVA exceeds 70% by mass, the viscosity of ethylene-modified PVA containing ethylene-modified PVA solution or water becomes too high, making filtration and defoaming difficult when preparing a stock solution of the film. It is difficult to obtain a film without any defects. On the other hand, when the proportion of the ethylene-modified PVA is lower than 20% by mass, the viscosity of the ethylene-modified PVA solution or the ethylene-modified PVA containing water becomes too low, and it becomes difficult to produce a PVA film having a target thickness. Further, this ethylene-modified PVA solution or ethylene-modified PVA containing water may contain a plasticizer, a surfactant, a dichroic dye, or the like as necessary.

  When producing an ethylene-modified PVA film, it is preferable to add a polyhydric alcohol as a plasticizer. Examples of the polyhydric alcohol include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, trimethylolpropane, etc., and one or more of these are used. can do. Among these, diglycerin, ethylene glycol, and glycerin are preferably used because of the effect of improving stretchability.

  As addition amount of a polyhydric alcohol, 1-30 mass parts is preferable with respect to 100 mass parts of ethylene modified PVA, 3-25 mass parts is more preferable, 5-20 mass parts is the most preferable. When the amount is less than 1 part by mass, the dyeability and stretchability may be lowered. When the amount is more than 30 parts by mass, the ethylene-modified PVA film becomes too flexible and the handleability may be lowered.

  When producing an ethylene-modified PVA film, it is preferable to add a surfactant. The type of the surfactant is not particularly limited, but an anionic or nonionic surfactant is preferable. As the anionic surfactant, for example, a carboxylic acid type such as potassium laurate, a sulfate type such as octyl sulfate, and a sulfonic acid type anionic surfactant such as dodecylbenzenesulfonate are preferable. Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether, alkylphenyl ether types such as polyoxyethylene octylphenyl ether, alkyl ester types such as polyoxyethylene laurate, and polyoxyethylene laurylamino. Alkylamine type such as ether, alkylamide type such as polyoxyethylene lauric acid amide, polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether, alkanolamide type such as oleic acid diethanolamide, polyoxyalkylene allyl phenyl ether, etc. Nonionic surfactants such as allyl phenyl ether type are preferred. These surfactants can be used alone or in combination of two or more.

  As addition amount of surfactant, 0.01-1 mass part is preferable with respect to 100 mass parts of ethylene modified PVA, and 0.02-0.5 mass part is further more preferable. If the amount is less than 0.01 parts by mass, the effect of improving the film forming property and the peelability is hardly exhibited, and if the amount is more than 1 part by mass, the surfactant elutes on the surface of the ethylene-modified PVA film and causes blocking. May decrease.

  The ethylene-modified PVA film before stretching used for producing the polarizing film preferably has a thickness of 10 to 50 μm, and more preferably 20 to 40 μm. If the thickness is smaller than 10 μm, the film strength is too low to perform uniform stretching, and color spots of the polarizing film are likely to occur. When the thickness exceeds 50 μm, when a polarizing film is produced by uniaxially stretching an ethylene-modified PVA film, a thickness change is likely to occur due to neck-in at the end, and color spots of the polarizing film are easily emphasized, which is not preferable.

  In order to produce a polarizing film from the ethylene-modified PVA film of the present invention, for example, the ethylene-modified PVA film may be dyed, uniaxially stretched, fixed, and dried, and further heat treated as necessary. There is no restriction | limiting in particular in the order of operation of a uniaxial stretching and a fixing process. Moreover, you may perform uniaxial stretching twice or more.

  Dyeing can be performed before uniaxial stretching, during uniaxial stretching, or after uniaxial stretching. As a dye used for dyeing, iodine-potassium iodide, a dichroic dye, or the like can be used in one kind or a mixture of two or more kinds. Ordinary dyeing is generally performed by immersing the PVA film in a solution containing the above-mentioned dye, but the processing conditions and processing method are particularly limited, such as mixing with the PVA film to form a film. is not.

  For uniaxial stretching, wet stretching or dry heat stretching can be used, using warm water such as an aqueous boric acid solution (in a solution containing the dye or in a fixing treatment bath described later) or an ethylene-modified PVA film after water absorption. Can be done in air. The stretching temperature is not particularly limited, and is preferably 30 to 90 ° C. when the ethylene-modified PVA film is stretched (wet stretching) in warm water, and 50 to 180 ° C. is preferable when it is dry-heat stretched. Further, the stretching ratio of uniaxial stretching (total stretching ratio in the case of multi-stage uniaxial stretching) is preferably 4 times or more, and most preferably 5 times or more from the viewpoint of the polarization performance of the polarizing film. The upper limit of the stretching ratio is not particularly limited, but it is preferably 8 times or less because uniform stretching is easily obtained. 5-20 micrometers is preferable and, as for the thickness of the film after extending | stretching, 5-15 micrometers is more preferable.

  Fixing treatment is often performed for the purpose of strengthening the adsorption of the dye to the ethylene-modified PVA film. Usually, boric acid and / or boron compounds are added to the treatment bath used for the fixing treatment. Moreover, you may add an iodine compound in a processing bath as needed.

  It is preferable to perform the drying process of the obtained polarizing film at 30-150 degreeC, and it is more preferable to carry out at 50-150 degreeC.

  The polarizing film obtained as described above is usually used as a polarizing plate with a polarizing plate protective film bonded to both sides or one side. Examples of the adhesive used for pasting include a PVA-based adhesive and a urethane-based adhesive. Among them, a PVA-based adhesive is preferably used.

(Display device)
By incorporating the polarizing plate of the present invention into a display device, the display device of the present invention having various visibility can be manufactured. The antiglare film and antiglare antireflection film of the present invention are reflective, transmissive, transflective LCD or TN, STN, OCB, HAN, VA (PVA, MVA), IPS. It is preferably used in LCDs of various drive systems such as. Further, the antiglare film and the antiglare antireflection film of the present invention are excellent in flatness and are preferably used for various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper. In particular, in a large-screen display device having a screen size of 30 or more, especially 30 to 54, there is no white spot in the periphery of the screen, and the effect is maintained for a long time, and a remarkable effect is obtained in the MVA liquid crystal display device. Is recognized. In particular, there was little color unevenness, glare and wavy unevenness, which is the object of the present invention.

  In the display device according to the present invention, the fine concavo-convex structure formed on the surface of the antiglare film or the antiglare antireflection film has an elliptical convex part, and the long side direction of the elliptical convex part is a display. It is also preferable that the display device is arranged in the vertical direction or the horizontal direction.

  The elliptical shape here means that the proportion of the ellipse defined by the following formula is in the range of 0.50 to 0.85, and the shape in the range of 0.60 to 0.80 is 60% by number or more. Say that included.

Ellipse ratio = (short axis of ellipse) / (long axis of ellipse)
According to the inventor's study, in a display device using an antiglare film or an antiglare antireflection film, it is a convex part close to a perfect circle or an irregular convex part using conventional fine particles, and its For a display device whose long side direction is not a fixed direction on the display, the shape of the convex portion of the fine concavo-convex structure formed by flexographic printing of the present invention is an elliptical shape, and the long side direction of the elliptical shape is the display side It has been found that the display device arranged in the vertical direction or the horizontal direction can further reduce the glare on the surface in addition to the anti-glare effect. This is because the long sides of the convex portions of the fine concavo-convex structure are arranged in the vertical direction or the horizontal direction of the display, which contributes to a reduction in glare because the scattered light is in a certain direction. It is presumed that the effect of reducing the glare is increased because the directionality of the scattered light can be further enhanced by the elliptical shape of the portion. In flexographic printing, since the pattern shape of the fine concavo-convex structure meeting such a purpose can be freely produced as a printing plate, the formation of the fine concavo-convex structure can be easily controlled.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
[Production of Cellulose Ester Film 1]
A cellulose ester solution (dope) was prepared using the following cellulose ester, plasticizer, ultraviolet absorber, fine particles and solvent, and a cellulose ester film 1 was prepared by a solution casting film forming method.

Cellulose ester (cellulose triacetate, acetyl group substitution degree 2.9, Mn = 16000, Mw / Mn = 1.8) 100 kg
Plasticizer (trimethylolpropane tribenzoate) 5kg
Plasticizer (ethyl phthalyl ethyl glycolate) 5kg
UV absorber (Tinubin 109, manufactured by Ciba Specialty Chemicals Co., Ltd.)
1.0 kg
UV absorber (Tinuvin 171 manufactured by Ciba Specialty Chemicals Co., Ltd.)
1.0 kg
Fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) 0.3kg
Solvent (methyl acetate) 440kg
Solvent (ethanol) 110kg
A cellulose ester solution (dope) was prepared using the above cellulose ester, plasticizer, ultraviolet absorber, fine particles and solvent.

  That is, the solvent was put into an airtight container, the remaining materials were put in order with stirring, and completely dissolved and mixed while heating and stirring. The fine particles were added dispersed in a part of the solvent. After the temperature was lowered to the temperature at which the solution was cast and allowed to stand overnight, a defoaming operation was performed, and then the solution was Azumi Filter Paper No. Filtration using 244 gave a cellulose ester solution.

  Next, the cellulose ester solution whose temperature was adjusted to 33 ° C. was fed to a die and uniformly cast from a die slit onto a stainless steel belt. The cast part of the stainless steel belt was heated from the back with hot water of 37 ° C. After casting, the dope film on the metal support (which is called a web after casting on the stainless steel belt) is dried by applying hot air of 44 ° C., and the residual solvent in the peeling is peeled off at 120 mass%. The web end is gripped with a tenter while the residual solvent amount is from 35% by mass to 10% by mass, and is stretched in the width direction. It extended | stretched so that it might become 1.1 times the draw ratio. After stretching, the width is maintained for several seconds, then the tension in the width direction is relaxed, then the width is released, and further transported for 20 minutes in the third drying zone set at 125 ° C. for drying. The cellulose ester film 1 having a width of 1.5 m, a film thickness of 80 μm, and a length of 3000 m was produced.

[Preparation of antiglare hard coat film 1 by adding fine particles]
On the surface of the cellulose ester film 1 (B surface side; surface in contact with a support mirror surface such as a stainless steel band used in the casting film forming method; support side), the following coating solution 1 for hard coat layer has a pore diameter of 20 μm. A hard coat layer coating solution is prepared by filtration through a polypropylene filter, and this is applied using a micro gravure coater, dried at 90 ° C., and then irradiated with an ultraviolet lamp with an illuminance of 0.1 W / cm ^2. Thus, the coating layer was cured with an irradiation amount of 0.1 J / cm ² to form an antiglare hard coat layer having a thickness of 5 μm, thereby producing an antiglare hard coat film 1. As a result of measuring the 100 convex portions using the optical interference type surface roughness measuring instrument for the formed irregularities, the average height of the convex portions is 0.52 μm, the long sides of the convex portions are highly variable, and the convex portions The average center-to-center distance was 75 μm, and the variation was in the range of ± 13%.

(Hard coat layer coating solution 1)
The following materials were stirred and mixed to obtain hard coat layer coating solution 1.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 200 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
25 parts by weight Propylene glycol monomethyl ether 110 parts by weight Ethyl acetate 110 parts by weight Synthetic silica fine particles Average particle size 1.8 μm 40 parts by weight Surfactant (silicone surfactant; FZ2207 (manufactured by Nippon Unicar)) 10% by weight propylene glycol monomethyl ether Solution) 0.6 parts by mass in solid content [Preparation of antiglare hard coat film 2 by embossing]
In the production of the cellulose ester film 1, a roll provided with a mold after the stretching treatment by a tenter (after forming the unevenness, the height of the convex part is 1 μm, the convex part size (long side) is 10 μm, and the distance between the convex parts is 50 μm. A B-side of the film (the side in contact with the stainless steel band support is the B-side, with the film containing the solvent sandwiched between the concavo-convex forming part consisting of a fine roll and the back roll, and the opposite side is the A side. In the same manner, except that a hot roll provided with a mold on the side is pressed, a back roll is placed on the A side, and irregularities are formed on the B side by passing between both rolls. An embossed cellulose ester film 2 was produced. In addition, the static elimination wire was installed in the uneven | corrugated formation vicinity vicinity, and charging of the film was suppressed. As a result of measuring 100 convex portions using the optical interference type surface roughness measuring instrument for the formed irregularities, the average height of the convex portions was 0.47 μm, the long sides of the convex portions were highly variable, and the convex portions The average distance between centers was 68 μm, and the variation was in the range of ± 15%.

On the surface of the embossed cellulose ester film 2 (B side; surface in contact with a mirror surface of a support such as a stainless steel band used in the casting film forming method; support side), the following coating liquid 2 for hard coat layer Is filtered through a polypropylene filter having a pore size of 20 μm to prepare a hard coat layer coating solution, which is applied using a micro gravure coater, dried at 90 ° C., and then irradiated with an ultraviolet lamp with an illuminance of 0.1 W. / in cm ^2, thereby curing the coated layer to irradiation dose as 0.1 J / cm ^2, to prepare an antiglare hard coat film 2 to form an antiglare hard coat layer having a thickness of 5 [mu] m.

(Hard coat layer coating solution 2)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Ethyl acetate 50 parts by mass Propylene glycol monomethyl ether 50 parts by mass Silicon compound 0.4 parts by mass (BYK-307 (manufactured by Big Chemie Japan))
[Preparation of antiglare hard coat films 3 to 15 by flexographic printing]
Using the apparatus of FIG. 8, on the surface of the cellulose ester film 1 produced as described above (A surface side; surface in contact with a mirror surface of a support such as a stainless steel band used in the casting film forming method; support side), the following The hard coat layer coating solution 3 is filtered through a polypropylene filter having a pore diameter of 20 μm to prepare a hard coat layer coating solution, which is not formed with the first hard coat layer forming portion of the fine uneven pattern by flexographic printing using the manufacturing apparatus of FIG. Copies were printed.

At that time, using a seamless resin plate under the laser engraving condition 3 having the following specifications, a fine concavo-convex structure was formed by flexographic printing in the flexographic printing part A of FIG. After printing, the film was dried at 90 ° C. in a drying zone 505A, and then cured using an ultraviolet lamp 506A at an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² . The average thickness of the first hard coat layer was 2 μm, and the average center-to-center distance between adjacent first hard coat layer non-forming portions was 10 μm.

(Seamless resin plate specifications)
Photosensitive resin plate: Core-shell type microgel obtained by reacting 98 parts of 2-hydroxyethyl acrylate and 1 part of butanediol diacrylate, 20 parts of methacrylic acid and 80 parts of N-butyl acrylate A photosensitive resin composition obtained by mixing 71 g of (core / shell = 2/1), 25 g of trimethylolpropane ethoxytriacrylate and 4 g of 2,2-dimethoxy-2-phenylacetophenone on a polyester film having a thickness of 2 mm After coating, the substrate was exposed at 1000 mJ / cm with ultraviolet light having a wavelength of 360 nm to obtain a printing original plate for laser engraving. Next, the fine concavo-convex structure was engraved under the following laser engraving conditions, and mounted on the resin plate roll while evacuating as shown in FIG. 1. When the whole was heated at 120 ° C. for 20 minutes, the joints disappeared and a seamless resin plate was obtained. .

  The resin plate diameter was 500 mm, and the rubber hardness of the resin plate was 50. Rubber hardness was measured with a durometer according to the method described in JIS K 6253.

(Laser engraving condition 1)
Carbon dioxide laser output: 300 W, 50% output Engraving image: A fine concavo-convex structure was engraved on the resin plate so that the concavo-convex height was 1 mm, the recess size (long side) was 30 μm, and the distance between the recess centers was 80 μm.

Anilox roll: 800 lines / 2.54 cm, cell volume 4 ml / m ² (manufactured by Neurong Co., Ltd., honeycomb pattern)
Ink supply: Steel doctor blade method (see Fig. 1)
(Laser engraving condition 2)
In the same manner as in laser engraving condition 1, a fine concavo-convex structure was engraved on the resin plate so that the concavo-convex height was 1.5 mm, the recess size (long side) was 50 μm, and the center distance between the recesses was 100 μm.

(Laser engraving condition 3)
In the same manner as in laser engraving condition 1, a fine concavo-convex structure was engraved on the resin plate so that the concavo-convex height was 1.5 mm, the recess size (long side) was 3 μm, and the center distance between the recesses was 10 μm.

(Laser engraving condition 4)
In the same manner as in laser engraving condition 1, a fine uneven structure was engraved on the resin plate so that the unevenness height was 1.5 mm, the recess size (long side) was 120 μm, and the distance between the recess centers was 220 μm.

(Hard coat layer coating solution 3)
Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) 170 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (Ciba Specialty Chemicals))
10 parts by mass Propylene glycol monomethyl ether 100 parts by mass Ethyl acetate 100 parts by mass Oil-repellent surfactant (polydimethylsiloxane; KF96 (manufactured by Shin-Etsu Chemical))
0.5 parts by mass The above composition was mixed and stirred to prepare hard coat coating solution 3.

(Hard coat layer coating solution 4)
Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 170 parts by mass Trimethylolpropane triacrylate 30 parts by mass Cross-linked polystyrene monodisperse particles (average particle size 3.5 μm, SX-350H manufactured by Soken Chemical Co., Ltd.) 20 Mass parts Photopolymerization initiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.))
10 parts by mass Propylene glycol monomethyl ether 100 parts by mass Ethyl acetate 100 parts by mass Oil-repellent surfactant (polydimethylsiloxane; KF96 (manufactured by Shin-Etsu Chemical))
0.5 parts by mass The above composition was mixed and stirred to prepare hard coat coating solution 4.

On the first hard coat layer thus prepared, the following hard coat layer coating solution 5 is applied by a reduced pressure extrusion method in the second hard coat layer application part B and dried at 90 ° C. in the drying zone 505B. An anti-glare hard coat using an ultraviolet lamp 506B and having an ultraviolet illuminance of 0.1 W / cm ² and an irradiation dose of 0.1 J / cm ² and a second hard coat layer thickness of 2.5 μm. Film 3 was obtained.

(Hard coat layer coating solution 5)
Dipentaerythritol hexaacrylate 70 parts by weight Trimethylolpropane triacrylate 30 parts by weight Photoinitiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals)) 4 parts by weight Surfactant (silicone surfactant; FZ2207 (Nihon Unicar) Made))
0.5 parts by mass Propylene glycol monomethyl ether 50 parts by mass Methyl ethyl ketone 500 parts by mass The viscosity of the coating solution was 3 ° C as a result of measurement using a B-type viscometer BL manufactured by Tokyo Keiki Co., Ltd.

(Hard coat layer coating solution 6)
Dipentaerythritol hexaacrylate 55 parts by mass Trimethylolpropane triacrylate 25 parts by mass Photoinitiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals)) 4 parts by mass Cross-linked polystyrene monodisperse particles (average particle size 3.5 μm, Soken) SX-350H manufactured by Chemical Co., Ltd.) 20 parts by mass surfactant (silicone surfactant; FZ2207 (manufactured by Nihon Unicar))
0.5 parts by mass Propylene glycol monomethyl ether 50 parts by mass Methyl ethyl ketone 50 parts by mass (hard coat layer coating solution 7)
Dipentaerythritol hexaacrylate 55 parts by mass Trimethylolpropane triacrylate 20 parts by mass Photoreaction initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals)) 4 parts by mass True spherical silicone fine particles (average particle size: 3.0 μm GE Toshiba) Silicone Tospearl 130) 25 parts by mass Surfactant (silicone surfactant; FZ2207 (Nihon Unicar))
0.5 parts by mass Propylene glycol monomethyl ether 50 parts by mass Methyl ethyl ketone 50 parts by mass Similarly, the laser engraving conditions and the hard coat layer coating solution used for the first and second hard coat layers are changed and shown in Table 1. Antiglare hard coat films 4 to 18 were produced. Table 1 shows the height of the formed recesses or projections, the long sides of the recesses or projections, and the average center distance between the recesses or projections. (In Table 1, concave / convex portions indicate concave portions or convex portions)
The following evaluation was performed about the produced anti-glare hard coat films 1-18.

<Evaluation>
(Anti-glare effect)
In an office with a window, each film was spread on a desk, and fluorescent lighting on the ceiling and reflection of external light on the film were evaluated as follows.

5: The outline of the fluorescent lamp and the external light are blurred and I don't care about the reflection at all 4: Between 5 and 3 3: The outline of the fluorescent lamp and the reflection of the external light are slightly recognized 2: 3: 1 Middle of 1: The outline of the fluorescent lamp and the external light are understood and the reflection is worrisome (glare)
About the produced film, the glare was determined visually.

5: I don't know the glare at all. 4: I can understand the glare very slightly. 3: I can see a slight glare. 2: Between 3 and 1. 1: I'm worried about the glare.
About the produced film, the cloudiness was determined visually.

5: White turbidity is not worrisome at all 4: Intermediate between 5 and 3 3: White turbidity is somewhat worrisome 2: Intermediate between 3 and 1 1: White turbidity is quite worrisome

  From Table 1, the antiglare hard coat film 1 imparted with a fine concavo-convex structure by addition of fine particles is in the midst of improving the glare, probably due to dispersion of fine particle dispersibility. The antiglare hard coat film 2 imparted with a fine concavo-convex structure by embossing was inferior in the antiglare effect and glare. Further, the height and size of the fine concavo-convex structure differed between the head and tail of the antiglare hard coat film, and when the mold was observed, clogging was caused by the film dissolved in a part of the mold.

  With respect to Comparative Examples 1 and 2, the antiglare hard coat films 7 to 18 produced by flexographic printing in which the formed irregularities are within the scope of claim 3 of the present invention are either antiglare effect or glare. It is clear that is excellent. In addition, it was found that the height and size of the fine concavo-convex structure at the head and tail of the antiglare hard coat film were uniform and had high uniformity and production stability.

  The antiglare hard coat film 3 of the present invention is too fine to form the unevenness and has a slightly less antiglare effect than the antiglare hard coat films 7 to 18, and the antiglare hard coat film 4 is uneven. The interval was too wide, and the antiglare effect was slightly low. The antiglare hard coat film 5 has a slightly small anti-glare effect because the difference in height of the unevenness is too small, and the antiglare hard coat film 6 has a too high unevenness, so that the cloudiness becomes too high and the visibility is low. Had fallen.

Example 2
Next, the following surface treatment was performed on the hard coat surfaces of the antiglare hard coat films 1 to 18 produced in Example 1.

<surface treatment>
Alkaline treatment: Each antiglare hard coat film was immersed in a 1.5 mol / l-NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali treatment, washed with water, and then into a 0.5 mass% -H ₂ SO ₄ aqueous solution. It was immersed for 30 seconds at room temperature to neutralize, washed with water and dried.

[Preparation of antiglare antireflection film]
Next, the following low refractive index layers were coated on the hard coat layers of the antiglare hard coat films 1 to 18.

(Preparation of antireflection layer: low refractive index layer)
The following low refractive index layer coating composition 1 is applied by an extrusion coater, dried at 100 ° C. for 1 minute, cured by irradiation with ultraviolet rays of 0.1 J / cm ² , and further thermally cured at 120 ° C. for 5 minutes. A low refractive index layer was provided so as to have a thickness of 95 nm, and antiglare and antireflection films 1 to 18 were produced. The refractive index of this low refractive index layer was 1.37.

  Moreover, about the produced anti-glare antireflection film, a spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm using a spectrophotometer (manufactured by JASCO Corporation). Since the antireflection performance is better as the reflectance is smaller in a wide wavelength region, the minimum reflectance at 450 to 650 nm is obtained from the measurement result. In the measurement, the back surface on the observation side was roughened, and then light absorption processing was performed using a black spray to prevent reflection of light on the back surface of the film, and the reflectance was measured. As a result of the measurement, all of the antiglare antireflection films had a reflectance of 0.7 to 1.2 and showed good results.

(Preparation of low refractive index layer coating composition 1)
<Preparation of tetraethoxysilane hydrolyzate A>
Hydrolyzate A was prepared by mixing 289 g of tetraethoxysilane and 553 g of ethanol, adding 157 g of 0.15% aqueous acetic acid solution thereto, and stirring in a water bath at 25 ° C. for 30 hours.

Tetraethoxysilane hydrolyzate A 110 parts by mass Hollow silica-based fine particle (P-2 below) dispersion 30 parts by mass KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass Linear dimethyl silicone-EO block copolymer (FZ-2207, manufactured by Nippon Unicar Co., Ltd.) 10% propylene glycol monomethyl ether solution 3 parts by mass Propylene glycol monomethyl ether 400 parts by mass Isopropyl alcohol 400 parts by mass <Preparation of hollow silica-based fine particle P-2 dispersion>
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO2 concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al 2 O 3 were simultaneously added to the mother liquor. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass. (Process (a))
1700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicic acid solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles in which 3000 g (concentration of 3.5% by mass) was added to form a first silica coating layer was obtained. (Process (b))
Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid that has been washed with an ultrafiltration membrane to form a first silica coating layer having a solid concentration of 13% by mass, and concentrated hydrochloric acid (35.5%) is further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al from which some of the constituent components of the core particles forming the first silica coating layer were removed. A dispersion of ₂ O ₃ porous particles was prepared (step (c)). A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water is heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) is added. The surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Subsequently, a hollow silica-based fine particle (P-2) dispersion having a solid content concentration of 20% by mass in which the solvent was replaced with ethanol using an ultrafiltration membrane was prepared.

  The thickness of the first silica coating layer of the hollow silica-based fine particles was 3 nm, the average particle size was 47 nm, MOx / SiO2 (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter was measured by a dynamic light scattering method.

[Preparation of polarizing plate]
Subsequently, a polarizing plate was produced using each antiglare antireflection film 1-18.

  A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.

  Then, according to the following processes 1-5, the polarizing film, the said glare-proof antireflection film 1-18, and the cellulose ester film KC8UCR-5 (made by Konica Minolta Opto Co., Ltd.) on the back side were bonded together, and the polarizing plate was produced. The polarizing plate protective film on the back side was a cellulose ester film having a retardation, and retardation values were Ro = 43 nm and Rt = 132 nm.

  Step 1: Soaked in a 1 mol / L sodium hydroxide solution at 50 ° C. for 60 seconds, then washed with water and dried to obtain a saponified cellulose ester film bonded to the polarizing film.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Lightly wipe off the excess adhesive adhering to the polarizing film in Step 2, place it on the cellulose ester film treated in Step 1, and then stack and arrange so that the antireflection layer is on the outside did.

Step 4: The antiglare antireflection film, the polarizing film, and the cellulose ester film sample laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm ² and a conveyance speed of about 2 m / min.

  Process 5: A sample obtained by bonding the polarizing film, the cellulose ester film, and the antiglare antireflection films 1 to 18 produced in Process 4 in a dryer at 80 ° C. is dried for 2 minutes to produce polarizing plates 1 to 18. did.

<Production of liquid crystal display device>
A liquid crystal panel was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The polarizing plate of the surface previously bonded of the commercially available 32-inch liquid crystal television (MVA type cell) was peeled off, and the produced polarizing plates 1 to 18 were each bonded to the glass surface of the liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the cellulose ester film having a retardation is on the liquid crystal cell side, and the absorption axis is in the same direction as the polarizing plate previously bonded. It carried out so that it might face, and produced the liquid crystal display devices 1-18, respectively.

<Evaluation>
The obtained liquid crystal display devices 1 to 18 are observed in the environment as shown in FIG. 9, and the anti-glare effect, glare, and the blackness when the following visibility and moving images are displayed are respectively shown below. Visual evaluation was made according to the criteria. In addition, 10 40W fluorescent lamps (FLR40S-EX-D / M manufactured by Matsushita Electric) were installed on the ceiling. Moreover, it evaluated in the state which external light inserts from a window.

(Visibility and black spots when displaying video)
As described above, a moving image of a TV program was displayed on the same display in an environment where artificial lighting by a fluorescent lamp and external light from a window were inserted from the ceiling, and a comparative experiment was performed. A moving image was observed at a position 1 m away from the front of the display, and sensory evaluation was performed.

5: I don't mind the reflection of the fluorescent lamp at the top of the screen, and the center of the screen looks black even when there is external light. Middle 3: Slight reflection of fluorescent light at the top of the screen is observed, and the center of the screen is slightly tired after observation if there is external light 2: Intermediate between 1: 3 and 1: 1: Fluorescence at the top of the screen The reflection of the light is recognized, the center of the screen lacks black spots due to the influence of external light, and eyes are tired when looking at the structure of the antiglare antireflection film / liquid crystal display device and the evaluation results are shown in Table 2 below. Shown in

  From Table 2, the liquid crystal display device 1 provided with fine concavo-convex structure by the addition of fine particles was inferior in visibility because the dispersion of fine particles was uneven and the improvement of contrast and glare was halfway. The liquid crystal display device 2 provided with a fine concavo-convex structure by embossing has difficulty in forming a uniform concavo-convex structure, and is inferior in visibility and glare.

  On the other hand, the liquid crystal display devices 3 to 18 using the antiglare antireflection film produced under the conditions of the present invention are excellent in the antiglare effect, glare, visibility and blackness. Is clear. In particular, the liquid crystal display devices 7 to 18 were excellent.

It is a schematic diagram which shows an example of the flexographic printing which concerns on this invention. It is a schematic diagram of the flexographic printing by a two-roll system. It is a schematic diagram of the flexographic printing which supplies ink with an extrusion coater. It is a perspective view of an anilox roll. It is a perspective view for demonstrating the cell of an anilox. It is the schematic diagram which showed formation of the 1st hard coat layer and the 2nd hard coat layer. It is a schematic diagram of the uneven structure by the 2nd hard-coat layer formed on the base film. It is an example of the manufacturing apparatus of 2nd hard-coat layer formation by the coating method using the 1st hard-coat layer by the flexo printing of this invention, and a coater. It is the figure which showed typically the environment at the time of observation when an anti-glare antireflection film is applied to a liquid crystal display device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Seamless resin plate 2 Resin plate roll 3 Plate cylinder 4 Anilox roll 5 Impression cylinder 6 Doctor blade 7 Fan ten roll 8 Ink 9 Extrusion coater 10,502 Base film e Convex part height f Convex part size (long side)
g Distance between convex parts (average center distance)
DESCRIPTION OF SYMBOLS 11 1st hard-coat layer 12 Fine concavo-convex structure A Flexo printing part B 2nd hard-coat layer application part 501 Film roll 503 Coater 504A, B, C Back roll 505A, B Drying zone 506A, B Actinic ray irradiation part 508 Ink supply tank 509 Flexo resin plate 510 Anilox roll

Claims (12)

Forming a patterned first hard coat layer consisting of a water- and oil-repellent coating part and a non-coating part on the base film, and then applying any coating on the base film on which the first hard coat layer is formed A method for producing an antiglare film, wherein a second hard coat layer is formed in a convex or concave shape in a portion other than the first hard coat layer forming portion by applying a hard coat material by the method. 2. The method for producing an antiglare film according to claim 1, wherein a coating method for forming the first hard coat layer in a pattern comprising a coating part and a non-coating part is a flexographic printing method. The height of the convex part or concave part of the second hard coat layer is 0.1 to 1.5 μm higher or lower than the first hard coat layer surface, and the long side of the convex part or concave part The method for producing an antiglare film according to claim 1 or 2, wherein the average center distance between adjacent convex portions or concave portions is 10 to 200 µm. Either of the first hard coat layer and the second hard coat layer contains 5 to 50 mass% of fine particles having a particle diameter of 0.5 to 5 µm with respect to each layer. The manufacturing method of the anti-glare film of any one of Claims 1. 5. The prevention according to claim 1, wherein the base film is at least one selected from a cellulose ester film, a polyester film, a norbornene resin film, and a polycarbonate film. A method for producing a dazzling film. The flexographic ink used for the first hard coat layer contains an actinic ray curable resin or a thermosetting resin. After flexographic printing, the actinic ray is irradiated or heated to cure the first hard coat layer. -The method for producing an antiglare film according to any one of claims 1 to 5, wherein the film is fixed. The hard coat material used for the second hard coat layer contains an actinic ray curable resin or a thermosetting resin, and after the second hard coat layer is formed on the first hard coat layer by any coating method, The method for producing an antiglare film according to any one of claims 1 to 6, wherein the second hard coat layer is cured and fixed by irradiation with an actinic ray or heating. An anti-glare film produced by the method for producing an anti-glare film according to claim 1. An antiglare antireflection film, wherein at least a low refractive index layer is laminated on the surface of the antiglare film according to claim 8. A polarizing plate comprising the antiglare film according to claim 8 or the antiglare antireflection film according to claim 9. A display device comprising at least one of the antiglare film according to claim 8, the antiglare antireflection film according to claim 9, or the polarizing plate according to claim 10. A rough structure composed of a first hard coat layer formed in a pattern comprising a coated part and a non-coated part on a base film, and a second hard coat layer formed on the non-coated part of the base film. An antiglare film having a surface.

Images