JP2006078538A - Antireflection film, its manufacturing method, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film which is inexpensive and has excellent scratch resistance and which is excellently mass-produced, and also to provide a method for manufacturing the film, and a polarizing plate and an image display device using the antireflection film. <P>SOLUTION: The method for manufacturing the antireflection film is characterized in that a low refractive index layer formed by a coating liquid containing an alkoxy silane compound or its hydrolyzed product is directly or indirectly provided on a transparent base film made of an organic polymer, and that the surface of the low refractive index layer is subjected to a flame plasma treatment. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antireflection film, a method for producing the same, a polarizing plate, and an image display device.

  Conventionally, various proposals have been made as a method for producing an antireflection film using a metal oxide thin film having excellent scratch resistance. The method for improving the hardness of the reflection film itself, and the adhesion between the base film and the reflection film have been proposed. A method for improvement has been proposed.

  For example, Japanese Patent No. 3435262 describes a technique for irradiating light in the state of a sol-gel coating solution, and improves the formulation of a low refractive index layer and improves the formulation of a hard coat layer by providing an adhesion layer. Have been proposed as techniques for improving the scratch resistance. JP-A-2002-182004, JP-A-2004-52028, JP-A-3508342, JP-A-2002-139602, JP-A-2002-282777, and other patents of anti-reflection films include transparent groups of organic polymers. Chemical material treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, alkali treatment and the like on the material film or organic polymer hard coat layer A technique for performing surface treatment of ozone oxidation treatment to improve the adhesion between the base material and the antireflection film is known, but is insufficient.

  On the other hand, the lower the refractive index, the lower the refractive index of the low refractive index layer, the lower the reflectance, and the lower the refractive index layer, the lower the refractive index, and the lower the refractive index layer. Japanese Laid-Open Patent Publication Nos. 2001-233611, 2003-201443, 2003-145686, etc. propose a technique for reducing the refractive index of the low refractive index layer by providing a gap in the low refractive index layer. When it is provided, the strength and adhesion of the low refractive index layer are lowered, and there is a problem that the scratch resistance is lowered.

In Patent Documents 1 to 4, the use of flame plasma treatment (flame treatment) for general films and antireflection films is known, but this method modifies the surface of the substrate (film), and on top of that, The purpose is to improve the adhesion with the thin film layer to be provided, and unlike the method of modifying the surface of the low refractive index layer proposed by the present invention, it could not be predicted that the effect of the present invention will be obtained.
JP 7-314629 A Japanese Patent Laid-Open No. 6-255042 Japanese Patent Laid-Open No. 2001-9799 JP 2000-356714 A

  An object of the present invention is to provide an antireflection film having excellent scratch resistance, low cost and mass productivity, a method for producing the same, a polarizing plate using the antireflection film, and an image display device.

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

(Claim 1)
A low refractive index layer formed by a coating solution containing an alkoxysilane compound or a hydrolyzate thereof is provided directly or indirectly on a transparent base film of an organic polymer, and flame plasma treatment is performed on the surface of the low refractive index layer. A method for producing an antireflection film, comprising:

(Claim 2)
The method for producing an antireflection film according to claim 1, wherein a hard coat layer mainly composed of an active energy ray curable resin is provided between the transparent base film and the low refractive index layer.

(Claim 3)
The method for producing an antireflection film according to claim 1, wherein 50% or more of the alkoxysilane compound is tetraethoxysilane.

(Claim 4)
The method for producing an antireflection film according to any one of claims 1 to 3, wherein the coating liquid containing the alkoxysilane compound or a hydrolyzate thereof contains silica-based fine particles having voids.

(Claim 5)
The method for producing an antireflection film according to claim 4, wherein the silica-based fine particles having voids are hollow spherical silica-based fine particles.

(Claim 6)
The said transparent base film is a cellulose-ester film, The manufacturing method of the antireflection film of any one of Claims 1-5 characterized by the above-mentioned.

(Claim 7)
A roller having a cooling means after providing a low refractive index layer formed of a coating solution containing an alkoxysilane compound or a hydrolyzate thereof directly or indirectly on one side of a long organic polymer transparent substrate film Anti-reflection, characterized by providing a heating means for heating the surface of the low refractive index layer which is conveyed on a roller so that the opposite surface of the low refractive index layer is at least partially wrapped around the surface, and the wound portion or the surface of the low refractive index layer before and after the wound portion A method for producing a film.

(Claim 8)
A process of carrying a roller after forming a low refractive index layer formed by a coating solution containing an alkoxysilane compound or a hydrolyzate thereof, directly or indirectly on one side of a transparent substrate film of a long organic polymer. A method for producing an antireflection film, comprising providing a plurality of heating means for heating the surface of the low refractive index layer that is provided and transported.

(Claim 9)
The method for producing an antireflection film according to claim 8, further comprising a cooling unit by blowing air between the plurality of heating units.

(Claim 10)
The method for producing an antireflection film according to any one of claims 7 to 9, wherein the heating means is flame plasma.

(Claim 11)
The method for producing an antireflection film according to any one of claims 7 to 9, wherein the heating means is a metallic heating roller having a surface temperature of 300 to 800 ° C.

(Claim 12)
It manufactures with the manufacturing method of the antireflection film of any one of Claims 1-11, The antireflection film characterized by the above-mentioned.

(Claim 13)
An image display device comprising the antireflection film according to claim 12 as an outermost surface.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an antireflection film excellent in scratch resistance, low cost and excellent in mass productivity, a manufacturing method thereof, a polarizing plate and an image display device using the antireflection film.

  As a result of intensive studies, the present inventor provided a low refractive index layer formed of a coating solution containing an alkoxysilane compound or a hydrolyzate thereof directly or indirectly on a transparent substrate film of an organic polymer, and the low refractive index It has been found that a method for producing an antireflection film, which is excellent in scratch resistance, low in cost and mass productivity, can be obtained by a method for producing an antireflection film in which the surface of the rate layer is subjected to flame plasma treatment.

  Moreover, after providing a low refractive index layer formed of a coating liquid containing an alkoxysilane compound or a hydrolyzate thereof directly or indirectly on one side of a long organic polymer transparent substrate film, a cooling means is provided. Production of an antireflection film provided with a heating means for heating the wound surface or the surface of the low refractive index layer before and after it is conveyed on the roller so that the opposite surface of the low refractive index layer is at least partially wrapped around the roller surface After providing a low refractive index layer formed by a coating solution containing an alkoxysilane compound or a hydrolyzate thereof directly or indirectly on one side of a method or a transparent substrate film of a long organic polymer, a roller Scratch resistance is provided by an antireflection film manufacturing method in which a process for transporting and a heating means for heating the surface of the low refractive index layer being transported are provided in multiple places Excellent, found that the production method of the anti-reflection film excellent in mass productivity can be obtained at low cost.

  About these effects, the sol-gel reaction is promoted by bringing the low refractive index layer formed by the coating liquid containing the alkoxysilane compound or the hydrolyzate thereof to a high temperature of 200 ° C. or more, and the glass is close to glassy. It is estimated that the strength of the film itself is increased and the adhesion with the layer in contact with the low refractive index layer is improved. In particular, when the layer in contact with the low refractive index layer is an organic polymer, it is presumed that the adhesion is improved because the portion in contact with the low refractive index layer is close to softening and melting at high temperatures.

  The present invention will be described in detail below.

[Heating means, cooling means]
In the present invention, the heating means used for heating the surface of the low refractive index layer is preferably a heating means capable of heating the surface of the low refractive index layer to 200 to 500 ° C. Specifically, a far infrared heater, a microwave ( Preferably, the wavelength is adjusted to the absorption wavelength of the low refractive index layer composition), flame plasma treatment (flame treatment), heating roller contact (direct or indirect), hot gas (air) spraying. Of these, flame plasma treatment and heating roller contact are preferred.

  The heating means is preferably capable of controlling ON / OFF of heating (ON / OFF of power source used, ON / OFF of supply of combustion gas, ON / OFF by adjusting the distance to the film, etc.). It also has temperature adjustment functions (electric power consumption adjustment, combustion gas supply adjustment, film distance adjustment, contact heat transfer distance adjustment with film, temperature detection means, feedback control means). It is preferable to obtain stable scratch resistance.

  The distance in the transport direction of the film heating unit by the heating means is preferably 1/3 or less of the distance in the transport direction of the cooling means. It is preferable to provide a plurality of heating means with a certain distance in the conveying direction. Preferably, it is 2 to 20 places, more preferably 3 to 10 places.

  It is preferable to provide a cooling means between the plurality of heating means. The cooling means is preferably a cooling means capable of maintaining the opposite surface temperature of the low refractive index layer at 150 ° C. or lower when the surface heating of the low refractive index layer is completed. Examples of the cooling medium include liquid (preferably water), gas-liquid circulating solvent (such as Freon gas and ammonia), and gas (air, gas, preferably air).

  As the cooling method, a method of directly cooling the film (preferably air cooling) and a method of contacting a cooled roller with the film (water, air cooling, and a gas-liquid circulating solvent are preferable) are preferable. Most preferably, only air cooling is used, and a plurality of parts are preferably air cooled.

  In order to obtain a stable effect of the present invention, the air temperature used for cooling is preferably -20 to 80 ° C, and more preferably 0 to 50 ° C.

  At the time of heating the surface of the low refractive index layer, it is preferable to provide a means for cooling the opposite surface of the film and continuously provide a means for cooling the opposite surface of the film even after the heating is completed.

  The above is preferable for obtaining the effects of the present invention stably and in the best condition.

(Frame plasma treatment)
Flame plasma treatment is a surface treatment by generating plasma by performing flame (flame) treatment with a burner on the surface of the film to be surface treated. For example, paraffinic gas (city gas, natural gas, methane gas) Combustion gas such as propane gas and butane gas) and an oxidizing gas mixed therewith, for example, a mixed gas composed of air or oxygen (also using a combustion aid or an oxidizer, etc.) It is to treat the surface with a flame.

  Hereinafter, an embodiment of the present invention will be described based on FIG. 1, which is a schematic configuration diagram of a surface treatment apparatus 1.

  This apparatus has a conveying means 3 (in FIG. 1, the conveying means 3 of the conveying means 3) for continuously conveying a support 2 having a long low refractive index layer (hereinafter, the support having a low refractive index layer is simply referred to as a support). And a surface treatment apparatus 1 that performs a physical surface treatment on the support 2 continuously conveyed by the conveying means 3. The support 2 is surface-treated by the surface treatment apparatus 1 and then sent to the next step.

  The surface treatment apparatus 1 is an apparatus that performs physical surface treatment on the support 2 that is continuously conveyed. In the present embodiment, the surface treatment apparatus 1 is an apparatus that performs flame plasma treatment (flame treatment). The surface treatment apparatus 1 includes a rotary cooling drum 11 that rotates as the support 2 moves, and plasma processing means that performs plasma processing on the support 2 wound around the rotary cooling drum 11 (in the present embodiment). Is a plasma processing means for burning the combustion gas to perform the flame plasma processing (details will be described later in FIG. 2) 12, and an electric field between the support 2 on which the flame plasma processing is performed and the plasma processing means 12. An electric field generating means 13 for generating a gas, an introducing means 14 for introducing an inert gas into the combustion gas of the plasma processing means 12, and a static elimination prior to performing a static elimination process on the support 2 prior to flame plasma treatment by the plasma processing means 12. Means 15, and post-static elimination means 16 that performs static elimination treatment on the support 2 that has been subjected to flame plasma treatment by the plasma treatment means 12. It has.

  The rotary cooling drum 11 is a so-called backup roller, which is a roller that winds around the support 2 conveyed by the conveying means on its peripheral surface and rotates as the support 2 moves. Accordingly, the support 2 is in contact with the rotary cooling drum 11 and travels in the direction of the arrow. The rotary cooling drum 11 also has a function of cooling the support 2 on which the bill is mounted by flowing cooling water (water having a temperature of about 40 ° C. lower than the temperature of the flame emitted by the plasma processing means 12). is doing.

  The plasma processing means 12 is means for performing plasma processing, specifically, flame plasma processing, on the support 2 wound around the rotary cooling drum 11. By burning the combustion gas supplied by the plasma processing means 12, the generated plasma collides with the surface (low refractive index layer surface) of the support 2, and the surface of the support 2 is heated, modified, or so-called etched. Is called. The plasma processing means 12 is provided so as to face the rotary cooling drum 11 with a predetermined interval, thereby keeping the interval with the support 2 constant.

  The electric field generating means 13 is a means for generating a uniform electric field between the plasma processing means 12 and the support 2 on which the flame plasma treatment is performed, that is, the support wound around the rotary cooling drum 11. In the present embodiment, the plasma processing means 12 (specifically, the dielectric of the plasma processing means 12) is grounded (grounded), and the rotating cooling drum 11 (specifically, the dielectric of the rotating cooling drum 11) is supplied from the power source. Is applied to the support 2 before being subjected to the flame plasma treatment by charging means such as corona discharge, and the support 2 is uniformly charged. An electric field may be generated. The voltage applied to the support 2 by the electric field generating means 13 (applied via the rotary cooling drum 11) may be an alternating current or a direct current, but a high frequency alternating current is preferred, and either a positive or negative voltage may be used. There may be. Note that it is preferable that the charge amount of the support 2 by the electric field generating means 13 is set to 500 V or more in absolute value, whereby the damage to the support 2 can be suppressed and the reforming effect can be improved.

  As described above, in the present embodiment, when the flame plasma treatment is performed on the support 2 that is continuously conveyed, an electric field is generated, and thus generated plasma (particularly, an inert gas plasma described later). Can be efficiently caused to collide with the support 2, and the improvement effect can be improved.

  The introduction unit 14 is a unit that introduces an inert gas into the combustion gas (for example, city gas, natural gas, propane gas) of the plasma processing unit 12. The introduced inert gas is an inert gas after neon (Ne) having a mass larger than that of helium (He) (hereinafter simply referred to as an inert gas unless otherwise specified), for example, neon (Ne), argon ( Ar), xenon (Xe), etc., and particularly inexpensive argon (Ar) is preferable. The combustion gas into which the inert gas is introduced by the introducing unit 14 is supplied to the plasma processing unit 12 and is burned by the plasma processing unit 12, thereby generating an inert gas plasma. In addition, although the introduction means 14 of this Embodiment introduce | transduced the inert gas into the combustion gas by mixing an inert gas with a combustion gas, it is made to combust with the support body 2 currently conveyed continuously. An inert gas may be introduced into the combustion gas, or the inert gas may be introduced into the combustion gas by causing the inert gas to collide with a flame portion (frame portion) emerging from the plasma processing means 12.

  As described above, in the present embodiment, when flame plasma processing is performed on the support 2 that is continuously transported, the combustion gas of the flame plasma processing is used as neon (mass greater than the inert gas (helium (He)). Ne) and subsequent inert gas) can be generated to generate a plasma with a large mass, to perform a large etching on the support 2, to bring out the anchor effect more greatly, and to improve the effect. Can be improved. Furthermore, in this case, as compared with the case where an inert gas is not introduced, the plasma temperature can be lowered, and the accompanying effect that damage to the support 2 can be reduced can be obtained.

  The pre-static elimination means 15 is a static elimination means that performs static elimination treatment on the support 2 prior to flame plasma treatment by the plasma treatment means 12. This pre-charger 15 is disposed upstream of the plasma processing unit 12 in the transport direction of the support 2 and is non-uniform (plus / minus mixed) due to static electricity of the support 2 being continuously transported. This is a means for eliminating the polar charge (charging unevenness), whereby the flame plasma treatment can be stabilized. That is, as a result of the study by the present inventors, it has been found that if the support 2 to which flame plasma treatment is applied has uneven charging, stable flame plasma treatment cannot be performed. Therefore, it is effective to perform the static elimination treatment prior to the flame plasma treatment, and to perform a stable flame plasma treatment.

  Further, the pre-charger 15 may be a contact-type static eliminator such as a blower-type static eliminator that blows ion wind or a static eliminator brush, but sandwiches a plurality of positive and negative ion generating static elimination electrodes and the support 2. It is preferable to use a static eliminator in which the ion attracting electrode is opposed and a high-density static eliminator provided with a positive / negative direct current type static eliminator after the static eliminator (see, for example, JP-A-7-263173).

  The post neutralization unit 16 is a neutralization unit that performs neutralization processing on the support 2 that has been subjected to flame plasma processing by the plasma processing unit 12. Thereafter, the charge removal means 16 is disposed on the downstream side in the transport direction of the support 2 with respect to the plasma treatment means 12, and is a means for removing charge unevenness of the support 2 charged during the flame plasma treatment. Static electricity troubles in the process can be prevented.

  It should be noted that the charge removal process prior to the plasma process by the pre-charger 15 and the charge removal process after the plasma process by the post-charger 16 are not only applied to the flame plasma process but also to the plasma process including the glow discharge process. Plasma treatment can be performed.

  The conveying means 3 is means for continuously conveying the support 2, and a part of it is shown in FIG. 1. The rollers 31 and 32 of the transport unit 3 are rollers arranged so that the support 2 is in close contact with the rotary cooling drum 11 on the upstream and downstream sides in the transport direction of the support 2 with respect to the rotary cooling drum 11. The rollers 33 to 36 (and the roller 32) of the transport unit 3 are rollers that support and transport the surface-treated surface of the support 2 that has been surface-treated by the surface treatment apparatus 1.

  Generally, there are external flames and internal flames in the flame coming out of the burner, and the external flame part is a light blue part heated by the unreacted (cannot burn) gas of the internal flame part. It is said to be a gas flame, and is a portion where the temperature is high, and a non-blue flame portion is a relatively low temperature portion where the inner flame is low and the oxygen supply is low.

  A large amount of plasma is generated in the flame within 30 mm from the tip of the inner flame, and a support having a low refractive index layer with a restricted flame within 30 mm from the tip of the inner flame by restricting the flame by a shielding plate. The body surface (side surface of the low refractive index layer) can be treated, and plasma treatment by this can be performed.

  The time for which the flame is applied is within 0.001 to 2 seconds in terms of the time when the surface of the support to be treated comes into contact with the flame. Preferably, it is within 0.01 to 1 second. If the length is too long, the surface of the support is too violated. If the length is too short, the oxidation reaction hardly occurs and the adhesion is not improved.

  The burner used for this purpose only needs to be able to uniformly apply a flame to the surface of the support to be subjected to the plasma treatment. It is preferable to arrange a plurality of burners.

  The mixing ratio of the combustion gas and the oxidizing gas in the flame treatment varies depending on the type of gas. For example, in the case of propane gas and air, the preferable mixing ratio of propane gas / air is 1/15 to 1 / In the case of natural gas and air, the range is 1/6 to 1/10, preferably 1/7 to 1/9. The ratio of the size of the inner flame to the outer flame varies depending on the type of combustion gas, the type of oxidizing gas, the mixing ratio, the supply speed, and the like.

  As the apparatus for performing flame (flame) plasma treatment, the apparatus described in JP-A-9-355097 is preferably used.

  FIG. 2 is a detailed view of the plasma processing means 12 of FIG. As mentioned above, the flame coming out of the burner has an outer flame and an inner flame, and the outer flame part is a portion that is usually light blue in which the unreacted (non-combustible) gas of the inner flame part is heated. It is said to be a blue gas flame, which is a high temperature portion, and a non-blue flame portion is a relatively low temperature portion where the inner flame is low and the oxygen supply is low. Since this external flame has many flames that are not necessary for plasma processing and the external flame spreads, it becomes impossible to control the processing, so it is not necessary to install a shielding plate (external flame regulating device) C as shown in FIG. The external flame E ′ is placed outside the shielding plate (external flame regulating device) C to be avoided from the support, and the effective flame (regulated flame) G is the surface (low refractive index) of the low refractive index layer. The flame treatment is controlled by hitting the layer surface) to achieve the purpose. The figure shows a burner B, an external flame E, an internal flame I, an external flame E ′ shielded and spread outside the shielding plate, an effective flame G, an effective processing hole (slit) S, etc., and through an effective processing hole (slit) S. A mode that the effective flame G was applied to the surface of the sample film F was shown.

(Heating roller contact)
The heating roller contact is preferably a system in which the roller is made of a metal material (stainless steel, titanium), and the temperature is controlled by indirectly heating the roller with an electric heater (nichrome wire, ceramic heater, etc.). The heating roller contact method has low initial cost and running cost, and is excellent in safety without using a flame. The surface temperature of the heating roller is preferably 300 to 800 ° C. More preferably, it is 300-500 degreeC. The best temperature on the surface of the heating roller is closely related to the film contact time, and it is preferable that the surface temperature on the low refractive index layer side immediately after heating is 200 ° C. or higher and the surface temperature on the back surface side is 80 ° C. or lower. .

  An example of a heating roller contact type heating / cooling means is shown in FIG. In this apparatus, the opposite surface of the low refractive index layer can be cooled by the rotating cooling roller 42 and the cooling air (air cooling) 43 that are heated by the plurality of heating rollers 41 and the inside provided between the heating rollers is water-cooled. .

  As an example of other heating / cooling means, the low-refractive-index layer surface of the support with the low-refractive-index layer wound around the rotating cooling drum 42 in which the air 44 is sent to the nichrome wire heater 45 and the inside is cooled with water FIG. 4 shows an apparatus applied to the above. FIG. 5 shows a support with a low refractive index layer that is sent to a far-infrared ceramic heater 46, and is fed with a far-infrared ray and hot air around a rotary cooling drum 47 that is hollow and has fins inside and is air-cooled. It is a device that hits the surface of the low refractive index layer.

[Transparent substrate film]
The organic polymer transparent substrate film used as the substrate of the antireflection film in the present invention is not particularly limited. For example, polyester film, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, Cellulose acetate phthalate film, cellulose acetate propionate film (CAP film), cellulose triacetate, film made of cellulose esters such as cellulose nitrate or derivatives thereof, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Shinji Otectic polystyrene film, polycarbonate film, norbornene resin film, poly Chilpentene film, polyether ketone film, polyether sulfone film, polysulfone film, polyether ketone imide film, polyamide film, fluororesin film, nylon film, polymethyl methacrylate film, acrylic film, polyarylate film or polylactic acid film Examples of the present invention include cellulose ester films such as cellulose triacetate film (TAC film), polycarbonate (hereinafter sometimes abbreviated as PC) film, syndiotactic polystyrene film, and polyarylate film. The norbornene resin-based film and the polysulfone-based film are preferable because they have no transparency, mechanical properties, and optical anisotropy. Ether film (CAP film, TAC film), they are preferably used for film-forming property is excellent in easy workability among particularly preferred to use a TAC film.

  When the cellulose ester film is used, the cellulose ester film may be saponified before the coating layers of the present invention are applied. For example, after saponification treatment after film formation, an active energy ray-curable resin layer may be applied and further saponification treatment may be performed.

  Next, although a method for forming a TAC film will be described, CAP can also be formed in the same manner. A TAC film is generally made of a TAC flake raw material and a plasticizer dissolved in methylene chloride to form a viscous liquid, and the plasticizer is dissolved into a dope. From a extruder die, a metal such as stainless steel that rotates endlessly. It is cast on a belt (also referred to as a band), dried, peeled off from the belt in a freshly dried state, and dried from both sides by a transport device such as a roll and wound up to be manufactured. The PC film can be formed in the same manner as the TAC film.

  As the plasticizer, phosphoric acid esters or carboxylic acid esters are preferably used. Phosphoric esters include triphenyl phosphate (TPP) and tricresyl phosphate (TCP), biphenyl-diphenyl phosphate, dimethyl ethyl phosphate. Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diethyl hexyl phthalate (DEHP), ethyl phthalyl ethyl glycolate and the like. As the citrate ester, acetyltriethyl citrate (OACTE) and acetyltributyl citrate (OACTB) are used. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Phosphate ester plasticizers (TPP, TCP, biphenyl-diphenyl phosphate, dimethylethyl phosphate) and phthalate ester plasticizers (DMP, DEP, DBP, DOP, DEHP) are preferably used. In addition, a polymer compound having a weight average molecular weight of 1,000 to 100,000, such as a polyvinyl acetate copolymer, an aliphatic linear polyester, or a methyl methacrylate copolymer, can be added as a polymer plasticizer.

  Among these, triphenyl phosphate (TPP) and ethyl phthalyl ethyl glycolate are particularly preferably used. The addition amount of the plasticizer is usually 2 to 15% by mass in the film, more preferably 4 to 8% by mass.

  Also, the plasticizer can be added to the PC film.

  Furthermore, the protective film for polarizing plates excellent in light resistance can be obtained by containing a ultraviolet absorber in the TAC or PC film which is a base material useful for the present invention. Examples of ultraviolet absorbers useful in the present invention include salicylic acid derivatives (UV-1), benzophenone derivatives (UV-2), benzotriazole derivatives (UV-3), acrylonitrile derivatives (UV-4), benzoic acid derivatives (UV- 5) or an organic metal complex salt (UV-6), and (UV-1) is phenyl salicylate, 4-t-butylphenylsalicylic acid, etc., and (UV-2) is 2-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and the like (UV-3) include 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy-3'-5 ' -Di-butylphenyl) -5-chlorobenzotriazole and the like (UV-4) is 2-ethylhexyl-2-cyano- , 3'-diphenyl acrylate, methyl-α-cyano-β- (p-methoxyphenyl) acrylate, etc. (UV-5) is resorcinol-monobenzoate, 2 ', 4'-di-t-butylphenyl -3,5-t-butyl-4-hydroxybenzoate and the like (UV-6) include nickel bis-octylphenylsulfamide, ethyl-3,5-di-t-butyl-4-hydroxybenzyl phosphate And nickel salts of these.

  Moreover, in order to improve the slipperiness, fine particles such as silica (average particle diameter of 0.005 to 0.2 μm) are added in an amount of 0.01 to 0.5% by mass in the dope when manufacturing these transparent base films. It can also be added. For example, Nippon Aerosil Co., Ltd. Aerosil 200V, Aerosil R972V, etc. can be added. The sliding property is measured with a steel ball, and it is desired that the coefficient of dynamic friction is 0.4 or less, preferably 0.2 or less.

[Hard coat layer]
In this invention, it is preferable to provide the hard-coat layer which has an active energy ray hardening resin as a main component between a transparent base film and the low-refractive-index layer mentioned later. Since the hard coat layer of the antireflection film of the present invention uses an active energy ray curable resin as a main component, the hard coat layer is also referred to as an active energy ray curable resin layer hereinafter. The active energy ray-curable resin layer refers to a layer mainly composed of a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams.

(Active energy ray curable resin)
As the active energy ray curable resin used for the hard coat layer, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin is cured and activated by irradiation with an active energy ray such as an ultraviolet ray or an electron beam. An energy ray curable resin layer is formed. In this invention, it is preferable that a hard-coat layer has acrylic type active energy ray hardening resin as a main component as a binder. Examples of the active energy ray-curable acrylate resin include acrylic urethane resins, polyester acrylate resins, epoxy acrylate resins, polyol acrylate resins, and the like.

  Acrylic urethane-based resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates including methacrylates) to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

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

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

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

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

  Examples of the resin monomer include common monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Among these, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolethane (meth) acrylate as the main component of the binder , An acrylic selected from dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate A system active energy ray-curable resin is preferred.

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

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  After the active energy ray-curable resin composition is applied and dried, it is cured by irradiating active energy rays, for example, ultraviolet rays.

  It is preferable to add inorganic or organic fine particles to the cured film layer thus obtained in order to prevent blocking and to improve scratch resistance and the like. Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, and the like, and examples of the organic fine particles include polymethacrylic acid. Methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder , Polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder, and the like, which can be added to the ultraviolet curable resin composition. The average particle diameter of these fine particle powders is preferably 0.005 μm to 1 μm, and particularly preferably 0.01 to 0.1 μm.

  As for the ratio of an active energy ray hardening resin composition and fine particle powder, it is desirable to blend so that it may become 0.1-10 mass parts to 100 mass parts of resin compositions.

  The layer formed by curing the active energy ray-curable resin thus formed is a clear hard coat layer having a center line average roughness Ra of 1 to 50 nm as defined in JIS B 0601. An antiglare layer of about 1 to 1 μm may be used.

  The refractive index of the hard coat layer is preferably within ± 0.005 with respect to the refractive index of the transparent substrate film in order to prevent interference unevenness, and more preferably within ± 0.002.

  An adhesion layer and an adhesive layer may be provided between the transparent substrate film and the hard coat layer. In this case, the film thickness should be 0.1 μm or less so as not to obstruct the effect of the present invention. Flame treatment, corona discharge, and plasma processing may be performed as pretreatment for applying the hard coat layer on the support. These hard coat layer layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active energy rays is usually 5 to 500 mJ / cm ² , preferably 5 to 100 mJ / cm ² , and particularly preferably 20 to 80 mJ / cm ² .

  Moreover, when irradiating an active energy ray, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying the tension is not particularly limited, and the tension may be applied in the conveying direction on the back roll, or the tension may be applied in the width direction or the biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  The ultraviolet curable resin layer composition coating solution may contain a solvent, or may be appropriately contained and diluted as necessary. Examples of the organic solvent contained in the coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), It can be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or a mixture thereof can be used. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  In addition, it is particularly preferable to add a silicon compound to the ultraviolet curable resin layer composition coating solution. For example, 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 2,000 to 50,000. When the number average molecular weight is less than 1,000, the coating film is dried. On the contrary, when the number average molecular weight exceeds 100,000, it tends to be difficult to bleed out on the surface of the coating film.

  Commercially available silicon compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (above, product names manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF3 2, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (trade name, manufactured by Toshiba Silicone Co., Ltd.) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Oil Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan) L series (for example, L7001, L-7006, L-7604, L-9000) manufactured by Nippon Unicar Co., Ltd. Y Over's, FZ series (FZ-2203, FZ-2206, FZ-2207) and the like, are preferably used.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

  As a method for applying the ultraviolet curable resin composition coating solution, the above-described methods can be used. The coating amount is suitably 1 to 40 μm as a wet film thickness, and preferably 3 to 20 μm. The dry film thickness is 1 to 20 μm, preferably 1.5 to 10 μm as described above.

The ultraviolet curable resin composition is preferably irradiated with ultraviolet rays during or after coating and drying, and the irradiation time for obtaining the necessary dose of active energy rays is preferably about 0.1 second to 1 minute. From the viewpoint of curing efficiency or work efficiency of the curable resin, 0.1 to 10 seconds is more preferable. Moreover, it is preferable that the illumination intensity of these active energy ray irradiation parts is 50-150 mW / m < ² >. When two layers of hard coat layers are applied, it is preferable to irradiate with ultraviolet rays in the state of being stacked.

[Back coat layer]
In the present invention, it is preferable to have a back coat layer on one side of the transparent substrate film.

  It is preferable to use a cellulose ester as one (binder) of the coating composition of the backcoat layer. As the cellulose ester, cellulose ester resins such as nitrocellulose, cellulose acetate propionate, diacetyl cellulose, cellulose acetate butyrate, and cellulose acetate propionate resin can be used. Of these, diacetylcellulose is particularly preferred.

  Other binders include, for example, vinyl chloride / vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride / vinyl acetate copolymer, vinyl chloride / chloride. Vinyl polymers such as vinylidene copolymer, vinyl chloride / acrylonitrile copolymer, ethylene / vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene / vinyl chloride copolymer, ethylene / vinyl acetate copolymer Polymers, copolymers of maleic acid and / or acrylic acid, acrylate copolymers, acrylonitrile / styrene copolymers, chlorinated polyethylene, acrylonitrile / chlorinated polyethylene / styrene copolymers, methyl methacrylate / butadiene / styrene Copolymer, acrylic resin, polyvinyl chloride Rubber resins such as ruacetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene / butadiene resin, butadiene / acrylonitrile resin, silicone Resin, fluorine resin, or the like can be used.

  As acrylic resins, Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M-4501 ( Manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR-80, BR- 82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, Acrylic and methacrylic monomers such as BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (manufactured by Mitsubishi Rayon Co., Ltd.) Various homopolymers and copolymers such as to produce a charge is preferably used.

  The back coat layer is provided in order to correct curling caused by providing a hard coat layer or other layers. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. In the antireflection film of the present invention, the backcoat layer is preferably applied also as an antiblocking layer, and fine particles are added to the backcoat layer coating composition in order to provide an antiblocking function. These fine particles added to the back coat layer include, as examples of inorganic compounds, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, oxidized Mention may be made of tin, indium oxide, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferred from the viewpoint of low haze, and silicon dioxide, especially hollow silica fine particles are preferred.

  These fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). . Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used. Examples of polymer fine particles include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. It is marketed by name and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large anti-blocking effect while keeping haze low.

  The fine particles contained in the backcoat layer are 0.1 to 50% by weight, preferably 0.1 to 10% by weight, based on the binder. When the back coat layer is provided, the increase in haze is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  It is preferable to use a plasticizer as one of the coating compositions for the backcoat layer. As the plasticizer, the plasticizer described in the section of the transparent substrate film can be used.

  The organic solvent used for the back coat layer has an anti-curl function in addition to the function as a solvent. The imparting of the anti-curl function is specifically performed by applying a composition containing a solvent for dissolving or swelling a transparent substrate film used as an antireflection film substrate. As an organic solvent to be used, in addition to a solvent to be dissolved or a mixture of solvents to be swollen, it may further contain a solvent that is not dissolved, and a composition in which these are mixed at an appropriate ratio depending on the degree of curl of the transparent substrate film and the type of resin. And using the coating amount.

  In order to strengthen the curl prevention function, it is effective to increase the mixing ratio of the solvent that dissolves the solvent composition to be used or the solvent that swells and to decrease the ratio of the solvent that does not dissolve. This mixing ratio is preferably (solvent to be dissolved or solvent to be swollen) :( solvent not to be dissolved) = 10: 0 to 1: 9.

  Examples of the solvent for dissolving or swelling the transparent substrate film contained in such a mixed composition include, for example, dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene. There are chloride, tetrachloroethane, trichloroethane, chloroform and the like. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanol, and hydrocarbons (toluene, xylene).

  These coating compositions are applied to the surface of the transparent substrate film with a wet film thickness of 1 to 100 μm using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. Although it is preferable, it is especially preferable that it is 5-30 micrometers.

  The order in which the backcoat layer is applied may be before or after the hard coat layer of the transparent substrate film is applied, but when the backcoat layer also serves as an antiblocking layer, it is preferably applied first. Further, the back coat layer can be applied in two or more times.

(Low refractive index layer)
The antireflection film of the present invention has a low refractive index layer formed by a coating solution containing an alkoxysilane compound or a hydrolyzate thereof directly or indirectly on a transparent substrate film. Further, as described above, a hard coat layer is provided between the transparent substrate film and the low refractive index layer, and an antireflection layer (low refractive index layer, high refractive index layer) provided directly or indirectly on the hard coat layer. In addition, a transparent conductive layer, an antistatic layer, an antifouling layer and the like can be further formed. The antireflective film of the present invention may not have a medium refractive index layer and a high refractive index layer, but has a low refractive index via another optical layer such as a medium refractive index layer and a high refractive index layer on the hard coat layer. It is preferable to have a layer. The present invention is particularly effective when the lower refractive index layer is mainly composed of an organic polymer resin.

(Alkoxysilane compound or hydrolyzate thereof)
Various sol-gel materials can be used as the binder of the low refractive index layer. As such a sol-gel material, metal alcoholates (alcolates such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. Of these, alkoxysilanes, organoalkoxysilanes and hydrolysates thereof are preferred. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In particular, 50% or more of the alkoxysilane compound is preferably tetraethoxysilane.

  In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.), containing fluoroalkyl ether group It is also preferable to use a run-compound. In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

(Silica fine particles with voids)
The low-refractive index layer preferably contains silica-based fine particles having voids (having an outer shell layer and the inside is porous or hollow), in particular, hollow spherical silica-based fine particles.

  The hollow spherical 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 content is a solvent, gas or porous Cavity particles filled with a substance. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or 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 diameter of such hollow spherical fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The hollow spherical fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and are in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. Is desirable. These hollow spherical 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, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use a silicate monomer or oligomer having a low polymerization degree, which is a coating liquid component described later. In some cases, the composite particles enter the inside of the composite particles and the internal porosity 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, if 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. .

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

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

  In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used in 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 spherical fine particles, for example, the method for preparing complex 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 spherical 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. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. 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 And 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. Can do. 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 the 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. It grows on the top and particle growth occurs. 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 through 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. Further, 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. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  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 composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. 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 together using a silicic acid liquid and the said alkoxysilane.

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, An alkoxysilane represented by a hydrocarbon group such as an acryl group, 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. In addition, you may use a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane. 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 (mass) ratio in the low refractive index layer coating solution of hollow spherical silica-based fine particles having an outer shell layer and porous or hollow inside is preferably 20 to 60% by mass. The refractive index of the low refractive index layer is preferably 1.30 to 1.50, more preferably 1.35 to 1.49. Therefore, the content (mass) ratio of the hollow spherical silica-based fine particles is preferably 20% by mass or more for lowering the refractive index, and when it exceeds 60% by mass, the matrix component is decreased and the film strength becomes insufficient.

  The film thickness (nm) of the low refractive index layer is 550 / (4 × refractive index of the low refractive index layer) × 0.85 to 550 / (4 × refractive index of the low refractive index layer) × 1.15. preferable.

  The low refractive index layer can be formed by coating by dispersing a metal oxide powder in a binder resin dissolved in a solvent, coating and drying, a method using a polymer having a crosslinked structure as a binder resin, Examples include a method of forming a layer by containing a saturated monomer and a photopolymerization initiator and irradiating active energy rays.

  In the present invention, an antireflection layer is provided on a transparent substrate film provided with a hard coat layer, and at least one of the antireflection layers is a low refractive index layer.

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

Transparent base film / hard coat layer / low refractive index layer Transparent base film / antistatic layer / hard coat layer / low refractive index layer Transparent base film / antiglare hard coat layer / low refractive index layer Transparent base film / Antistatic layer / Anti-glare hard coat layer / Low refractive index layer Transparent base film / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Transparent base film / Hard coat layer / High refractive index Index layer / Low refractive index layer / High refractive index layer / Low refractive index layer Transparent base film / Antistatic layer / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer Transparent base film / Antiproof Dazzle hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer Transparent substrate film / antiglare hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer / antifouling layer The medium refractive index layer and the high refractive index layer will be described later.

(Fluorine resin)
As the binder for the low refractive index layer, a fluorine resin that is crosslinked by heat or ionizing radiation (hereinafter, also referred to as “fluorine resin before crosslinking”) is preferably used.

  Preferred examples of the fluorine-based resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (produced by Osaka Organic Chemicals) or M-2020 (produced by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). In the latter, it is possible to introduce a crosslinked structure by adding a compound having a group that reacts with a functional group in the polymer and another reactive group after copolymerization, as disclosed in JP-A-10-25388 and 10-147739 In the issue. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is crosslinked by heating by a cross-linking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, the thermosetting type In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, etc., it is an ionizing radiation curable type. .

  Further, in addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-based resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-based resin before crosslinking is commercially available and can be used. Examples of commercially available fluororesins before cross-linking include Cytop (Asahi Glass), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR), etc. Can be mentioned.

  The low refractive index layer containing a crosslinked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

  The low refractive index layer containing a crosslinked fluororesin as a constituent component contains the silica-based fine particles described above.

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

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Particles when made of SiO _2, surface treatment with a silane coupling agent can be particularly effectively conducted. As a specific example of the silane coupling agent, a silane coupling agent described later is preferably used.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

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

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

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

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

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

  Moreover, it is preferable to add a slipping agent to the low refractive index layer or other refractive index layer according to the present invention, and scratch resistance can be improved by imparting slipperiness. As the slip agent, silicon oil or a wax-like substance is preferably used. For example, a compound represented by the following general formula is preferable.

General formula R ₁ COR ₂
In the formula, R ₁ represents a saturated or unsaturated aliphatic hydrocarbon group having 12 or more carbon atoms. An alkyl group or an alkenyl group is preferable, and an alkyl group or alkenyl group having 16 or more carbon atoms is more preferable. R ₂ represents —OM ₁ group (M ₁ represents an alkali metal such as Na or K), —OH group, —NH ₂ group, or —OR ₃ group (R ₃ represents a saturated or unsaturated group having 12 or more carbon atoms. R ₂ represents a saturated aliphatic hydrocarbon group, preferably an alkyl group or an alkenyl group, and R ₂ is preferably an —OH group, —NH ₂ group, or —OR ₃ group. Specifically, higher fatty acids such as behenic acid, stearamide, and pentacoic acid, or derivatives thereof, and carnauba wax, beeswax, and montan wax containing many of these components as natural products can also be preferably used. Polyorganosiloxane as disclosed in JP-B-53-292, higher fatty acid amide as disclosed in US Pat. No. 4,275,146, JP-B 58-33541, British patent No. 927,446 or JP-A-55-126238 and 58-90633, higher fatty acid esters (fatty acids having 10 to 24 carbon atoms and 10 to 24 carbon atoms). Esters of alcohols), and higher fatty acid metal salts as disclosed in U.S. Pat. No. 3,933,516, dicarboxylic acids having up to 10 carbon atoms as disclosed in JP-A-51-37217 A polyester compound comprising an acid and an aliphatic or cycloaliphatic diol, a dicarboxylic acid disclosed in JP-A-7-13292, Mention may be made of oligo polyester or the like from the Le.

For example, the addition amount of the slip agent used for the low refractive index layer is preferably 0.01 to 10 mg / m ² .

[Medium refractive index layer, High refractive index layer]
In the present invention, in order to reduce the reflectance, it is preferable to provide a high refractive index layer between the transparent substrate film provided with the transparent substrate film or the hard coat layer and the low refractive index layer. In addition, it is more preferable to provide an intermediate refractive index layer between the transparent base film and the high refractive index layer in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent substrate film and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of the high refractive index layer and the middle refractive index layer 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 haze of the high refractive index layer and the middle refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more, with a pencil hardness of 1 kg.

  In an antireflection laminate having a medium refractive index layer, a high refractive index layer, and a low refractive index layer, as described in JP-A-59-50401, the medium refractive index layer has the following formula (1): When the refractive index layer satisfies the following mathematical formula (2) and the low refractive index layer satisfies the following mathematical formula (3), it is preferable that the average reflectance as the antireflection laminate can be further reduced.

(Hλ / 4) × 0.7 <n ₃ d ₃ <(hλ / 4) × 1.3 (1)
In formula (1), h is a positive integer (generally 1, 2 or 3), n ₃ is the refractive index of the medium refractive index layer, and d ₃ is the film thickness (nm) of the medium refractive index layer. It is. Further, λ is a wavelength, which is a value in the range of 350 to 800 (nm).

(Jλ / 4) × 0.7 <n ₄ d ₄ <(jλ / 4) × 1.3 (2)
In formula (2), j is a positive integer (generally 1, 2 or 3), n ₄ is the refractive index of the high refractive index layer, and d ₄ is the film thickness (nm) of the high refractive index layer. It is. Further, λ is a wavelength, which is a value in the range of 350 to 800 (nm).

(Kλ / 4) × 0.7 <n ₅ d ₅ <(kλ / 4) × 1.3 (3)
In Equation (3), k is a positive odd number (generally 1), n ₅ is the refractive index of the low refractive index layer, and d ₅ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 350 to 800 (nm).

  Moreover, in this invention, it is also preferable to give an unevenness | corrugation to a hard-coat layer or a high refractive index layer, and to set it as an anti-glare antireflection laminated body.

  In addition, a layer structure in the order of a transparent support, a hard coat layer (antiglare layer), a high refractive index layer, a low refractive index layer, a high refractive index layer, and a low refractive index layer is also a preferable configuration. An antiglare property can be imparted to the low refractive index layer on the surface, and an antiglare layer may be provided on the surface.

  The high refractive index layer and medium refractive index layer used in the present invention preferably contain a polymer containing a (meth) acrylate compound as a polymerization component as a binder component and contain metal oxide particles.

The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The mass average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The mass average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, further preferably 10 to 100 nm, and preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  The layer having a higher refractive index than the transparent base film, that is, the metal oxide particles used for the high refractive index layer and the middle refractive index layer are selected from Ti, Ta, Zr, Sn, Sb, Zn, Nb, In, and Al. Metal oxide fine particles having at least one kind of element are preferred. Specific examples include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide.

  In the middle refractive index layer, metal oxide fine particles containing at least one element selected from Zr, Sn, Sb, Zn, Nb, and In are preferable because they can impart an antistatic function. Specifically, ITO and antimony oxide are preferable.

  Titanium oxide fine particles are formed in the high refractive index layer, in particular, the core is formed from titanium oxide (rutile type, anatase type, amorphous type, etc., rutile type titanium oxide is preferable), and the shell is formed from oxides of zirconium oxide, silica or alumina. Titanium oxide fine particles having a core-shell structure are preferred.

  The metal oxide particles are mainly composed of oxides of these metals, can further contain other elements, and fine particles imparted with conductivity are also preferably used. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, a silane coupling agent is most preferable.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-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.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surfaces of the organic titanium compound and the metal oxide particles described above are likely to react and a stronger film is formed. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for this hydrolysis can also be used for the hydrolysis / polymerization of the organic titanium compound.

  In the present invention, the treatment may be performed by combining two or more kinds of surface treatments. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in the high refractive index layer or the middle refractive index layer.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume, more preferably 10 to 60% by volume, and still more preferably 20 to 55% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium 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 particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, 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.

  The high refractive index layer and medium refractive index layer used in the present invention is also a preferred embodiment in which other binder is used in combination with a polymer having a (meth) acrylate compound as a polymerization component. As the other binder, a polymer having a crosslinked structure is preferable. Examples of the polymer having a crosslinked structure include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as polyolefin), crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. . Among these, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Moreover, it is more preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono). Of these, sulfonic acid groups and phosphoric acid groups are preferred. Here, the anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated. The linking group that binds the anionic group and the polymer chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked polymer which is a preferable binder polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. In this case, the proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. preferable. The repeating unit may have two or more anionic groups.

  The crosslinked polymer having an anionic group may contain other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure). Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. The benzene ring has a function of increasing the refractive index of the high refractive index layer. The amino group, the quaternary ammonium group, and the benzene ring can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.

  In the crosslinked polymer containing a repeating unit having an amino group or a quaternary ammonium group as a constituent unit, the amino group or quaternary ammonium group may be directly bonded to the polymer chain, or may be a side chain via a linking group. May be bonded to the polymer chain, but the latter is more preferred. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, and more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably a carbon number. 1 to 6 alkyl groups. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer chain is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Is preferred. When the crosslinked polymer includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, more preferably 0.08 to 30% by mass, Most preferably, it is 0.1-28 mass%.

  The cross-linked polymer is prepared by blending a monomer for generating a cross-linked polymer to prepare a coating solution for forming a high refractive index layer and a medium refractive index layer, and is generated by a polymerization reaction simultaneously with or after coating of the coating solution. Is preferred. Each layer is formed with the production of the crosslinked polymer. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The monomer having an anionic group is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to the inorganic fine particles. The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid in the coating solution. The monomer having an amino group or a quaternary ammonium group is preferably used in an amount of 3 to 33% by mass based on the monomer having an anionic group. These monomers can be made to function effectively before application of the coating liquid by a method in which a crosslinked polymer is produced by a polymerization reaction simultaneously with or after application of the coating liquid.

  In the present invention, the monomer preferably used is most preferably a monomer having two or more ethylenically unsaturated groups. Examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol). Di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, di Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate Polyester polyacrylate), vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), Examples include acrylamide (eg, methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator mentioned later used in order to form the binder polymer of a hard-coat layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers. The coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application | coating, and may additionally process the thermosetting reaction of the formed polymer.

  For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. . Polymers having other cyclic (aromatic, heterocyclic, and alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

  Moreover, it is preferable to add the silicon compound described in the section of the hard coat layer to the middle and high refractive index layers.

  Among them, the organic solvent for diluting the high refractive index layer is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, 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 mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, 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 and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

  Each layer of the antireflection layer can be formed by coating by 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 or an extrusion coating method. it can.

  In the case of the high refractive index layer composition according to the present invention, the surface of the high refractive index layer is applied after the high refractive index layer is applied and dried, after the active energy ray irradiation, and before the low refractive index layer is applied. On the other hand, even if it is manufactured in a manufacturing process in which the members of the manufacturing apparatus are in contact, the occurrence of bright spot foreign matter is small.

〔Polarizer〕
A polarizing plate using the antireflection film of the present invention will be described.

  The polarizing plate can be produced by a general method. The back surface side of the antireflection film of the present invention is subjected to alkali saponification treatment, and a completely saponified polyvinyl alcohol aqueous solution is used on at least one surface of a polarizing film prepared by immersing and stretching the treated antireflection film in an iodine solution. It is preferable to bond them together. The antireflection film may be used on the other surface, or another polarizing plate protective film may be used. In contrast to the 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, a phase difference of 20 to 70 nm, and Rt of 70 to 400 nm. preferable. These can be prepared, for example, by the methods described in JP-A No. 2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. By using in combination with the antireflection film of the present invention, a polarizing plate having excellent planarity and a stable viewing angle expansion effect can be obtained.

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

  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. On the surface of the polarizing film, one side of the antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

<Image display device>
By incorporating the polarizing plate into an image display device, various image display devices with less interference unevenness and excellent visibility can be manufactured. The antireflection film of the present invention is a reflective, transmissive, transflective LCD or TN, STN, OCB, HAN, VA (PVA, MVA), IPS, etc. Preferably used. Further, the antireflection film of the present invention has extremely little interference unevenness and is 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, a large-screen display device with a 30-inch screen or more has the effect that there is little interference unevenness and eyes are not tired even during long-time viewing.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these aspects. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
[Production of cellulose ester film]
A cellulose ester solution (dope) was prepared using the following cellulose ester, plasticizer, ultraviolet absorber, fine particles and solvent, and a cellulose ester film 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.)
1.0kg
UV absorber (Tinuvin 171 manufactured by Ciba Specialty Chemicals Co., Ltd.)
1.0kg
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 (referred to as a web after casting on a stainless steel belt) is dried by applying hot air of 44 ° C., and the residual solvent in the peeling is peeled off at 120%. The tension was applied so that the longitudinal draw ratio was 1.1 times, and then the web end was gripped with a tenter while the residual solvent amount was 35% to 10%, and 1.1% in the width direction. It extended | stretched so that it might become a draw ratio of 2 times. After stretching, the width is maintained for several seconds, and after the tension in the width direction is relaxed, the width is released and further conveyed for 20 minutes in a third drying zone set at 125 ° C., and dried. A cellulose ester film having a width of 1.5 m and a film thickness of 50 μm was produced.

[Formation of hard coat layer 1]
On the surface of the cellulose ester film (the B surface side; the surface in contact with the support mirror surface such as a stainless steel band used in the casting film forming method; the support side), the following coating liquid 1 for hard coat layer has a pore size of 0. A hard coat layer coating solution 1 is prepared by filtration through a 4 μm polypropylene filter, which is applied using a micro gravure coater, dried at 90 ° C., and then the illuminance of the irradiated part is 100 mW / cm ² using an ultraviolet lamp. Then, the coating layer was cured with an irradiation amount of 80 mJ / cm ² to form a hard coat layer 1 having a thickness of 5 μm.

(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) 226 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 25 parts by mass Silicone surfactant; FZ2207 (manufactured by Nippon Unicar) 10% propylene glycol monomethyl Ether solution 2 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass [Formation of hard coat layers 2 to 4]
Using the following coating liquids 2 to 4 for hard coat layer, hard coat layers 2 to 4 were formed on the cellulose ester film in the same manner as the formation of hard coat layer 1.

(Hard coat layer coating solution 2)
The following materials were stirred and mixed to obtain hard coat layer coating solution 2.

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 226 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 25 parts by mass Silicone surfactant; FZ2207 (manufactured by Nippon Unicar) 10% propylene glycol monomethyl 2 parts by mass of ether solution Titanium oxide fine particles (average particle size of about 0.5 μm) 25% of solid content of coating solution
101 parts by mass of propylene glycol monomethyl ether 101 parts by mass of ethyl acetate (hard coat layer coating solution 3)
Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 226 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 25 parts by mass Silicone surfactant; FZ2207 (manufactured by Nippon Unicar) 10% propylene glycol monomethyl Ether solution 2 parts by mass Antimony oxide fine particles (Nippon Seiko Co., Ltd., average particle size of about 0.03 μm)
Amount of refractive index 1.61 Propylene glycol monomethyl ether 101 parts by weight Ethyl acetate 101 parts by weight (hard coat layer coating solution 4)
Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 226 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 25 parts by mass Silicone surfactant; FZ2207 (manufactured by Nippon Unicar) 10% propylene glycol monomethyl Ether solution 2 parts by mass Titanium oxide fine particles (average particle size of about 0.05 μm) Amount of refractive index 1.61 Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass [Formation of hard coat layer 5]
On the surface of the cellulose ester film (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 hard coat layer coating solution 5 (lower layer) and the above Using the hard coat layer coating solution 3 (upper layer), simultaneous multilayer coating, drying, and ultraviolet irradiation were performed to form a hard coat layer 5 (two layers).

(Hard coat layer coating solution 5)
Instead of the silica-based fine particles P-2 (hollow spherical fine particles) prepared as described below, the antimony oxide fine particles of the hard coat layer coating solution 3 were used as the hard coat layer coating solution 5.

<Preparation of silica-based fine particles P-2>
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% 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% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02% 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 with a solid content concentration of 20%. (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 3.5%) 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 formed with the first silica coating layer having a solid content of 13% by washing with an ultrafiltration membrane, 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%) is added. The surface of the porous particles on which the silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, a dispersion of silica-based fine particles (P-2) having a solid content concentration of 20% 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 / SiO ₂ (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.

[Coating of back coat layer]
The following backcoat layer coating solution was prepared by filtering with a filter having a particle capture efficiency of 3 μm of 99% or more and 0.5 μm or less of particle capture efficiency of 10% or less. This back coat layer coating solution was applied to the surface opposite to the surface on which the hard coat layer was applied with an extrusion coater so that the wet film thickness was 15 μm, and dried at 90 ° C. for 30 seconds.

(Backcoat layer coating solution)
Diacetylcellulose (acetyl group substitution degree 2.4) 0.5 parts by mass Acetone 70 parts by mass Methanol 20 parts by mass Propylene glycol monomethyl ether 10 parts by mass Ultrafine silica Aerosil 200V (manufactured by Nippon Aerosil Co., Ltd.) 0.002 parts by mass or more Thus, a hard coat film with a back coat layer was produced.

(Surface modification)
The hard coat layer surface of the part of the hard coat film with the back coat layer produced above was subjected to flame plasma (FP) treatment using the flame plasma treatment apparatus shown in FIG. The treatment conditions were such that the contact time between the flame and the film was about 0.01 seconds, the ratio of the contact area of the outer flame to the maximum area of the inner flame was 5, and the distance from the tip of the inner flame was 5 mm. The inner flame maximum area is a value obtained by multiplying the width of the center of the inner flame I in FIG. 2 by the processing width of the film, and the contact area of the outer flame is the treatment of the effective flame G (also outer flame). It is a value obtained by multiplying the width in contact with the film to be processed and the processing width of the film.

A part of the hard coat film with a back coat layer was immersed in a 1.5 mol / l NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali (Alk) treatment, washed with water, and then washed with 0.5% H _2. It was neutralized by immersing in an aqueous SO ₄ solution at room temperature for 30 seconds, washed with water and dried.

[Formation of medium refractive index layer / high refractive index layer]
The following medium refractive index layer coating solution is applied onto the hard coat layer of the above-modified hard coat film with a back coat layer using a bar coater, dried at 60 ° C., and then cured by irradiating with ultraviolet rays. The intermediate refractive index layer is coated with the following high refractive index layer coating solution using a bar coater, dried at 60 ° C., and then irradiated with ultraviolet rays to cure the coated layer. Formed respectively.

(Preparation of titanium dioxide dispersion)
Titanium dioxide (primary particle mass average particle size: 50 nm, refractive index: 2.70) 30 parts by mass, anionic diacrylate monomer (PM21, Nippon Kayaku Co., Ltd.) 4.5 parts by mass, cationic methacrylate monomer ( DMAEA (manufactured by Kojin Co., Ltd.) 0.3 parts by mass and 65.2 parts by mass of methyl ethyl ketone were dispersed with a sand grinder to prepare a titanium dioxide dispersion.

(Preparation of medium refractive index layer coating solution)
47 parts by mass of the above titanium dioxide dispersion electroconductive ITO fine particles (ELCOM V2504, ITO sol, solid content 20%, manufactured by catalytic conversion) 3 parts by mass Dipentaerythritol hexaacrylate (matrix) 50 parts by mass Irgacure 184 (photopolymerization initiator) 3 parts by mass γ-methacryloxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503, silane coupling agent) 10 parts by mass Poly-n-butyl methacrylate (matrix) 5 parts by mass Propylene glycol monomethyl ether (PGME) 720 parts by mass Isopropyl alcohol 1470 parts by weight Methyl ethyl ketone (MEK) 250 parts by weight (Preparation of coating solution for high refractive index layer)
70 parts by mass of the titanium dioxide dispersion 1.5 parts by mass of tetra (n) butoxytitanium γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503)
3 parts by mass Silicone surfactant; FZ2207 (Nihon Unicar) 10% propylene glycol monomethyl ether solution 2 parts by mass Isopropyl alcohol 555 parts by mass Propylene glycol monomethyl ether (PGME) 278 parts by mass Methyl ethyl ketone (MEK) 93 parts by mass [Low refractive index Formation of layers 1 to 4]
Next, the following low refractive index layer coating is applied on the hard coat layer of the hard coat film with the back coat layer subjected to the surface modification and on the high refractive index layer surface of the film on which the medium refractive index layer and the high refractive index layer are formed. Liquids 1 to 4 were applied with an extrusion coater, dried at 80 ° C. for 5 minutes, then thermally cured at 120 ° C. for 5 minutes, further cured by irradiation with ultraviolet rays, and a low refractive index so that the thickness was 95 nm. Layers 1-4 were formed.

(Preparation of low refractive index layer coating solution 1)
Si (OCH ₃ ) ₄ is used as a matrix, silicone surfactant (FZ2207, manufactured by Nihon Unicar, 10% propylene glycol monomethyl ether solution) is added to the matrix at 3.0%, and 1.0 mol / L-HCl is used as a catalyst. Then, a coating solution 1 having a low refractive index diluted with an organic solvent (propylene glycol monomethyl ether: isopropyl alcohol = 1: 1 mixture) was prepared.

(Preparation of low refractive index layer coating solution 2)
Si (OC ₂ H ₅ ) ₄ is used as a matrix, silicone surfactant (FZ2207, manufactured by Nihon Unicar, 10% propylene glycol monomethyl ether solution) is added to the matrix by 3.0%, and 1.0 mol / L-HCl is added. Using the catalyst, a low refractive index coating solution 2 was further diluted with an organic solvent (propylene glycol monomethyl ether: isopropyl alcohol = 1: 1 mixture).

(Preparation of low refractive index layer coating solution 3)
Si (OC ₂ H ₅ ) ₄ as a matrix, silicone surfactant (FZ2207, manufactured by Nihon Unicar, 10% propylene glycol monomethyl ether solution) is 3.0% with respect to the matrix, and silica-based fine particles P-2 are 40%. A low refractive index coating solution 3 was prepared by adding 1.0 mol / L-HCl as a catalyst and further diluting with an organic solvent (propylene glycol monomethyl ether: isopropyl alcohol = 1: 1 mixture).

(Preparation of low refractive index layer coating solution 4)
A silicone surfactant (50% Si (OC ₂ H ₅ ) ₄ and 50% (CH ₃ O) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (OCH ₃ ) ₃ ) was used as a matrix. FZ2207, manufactured by Nihon Unicar, 10% propylene glycol monomethyl ether solution) is added to the matrix at 3.0%, the silica-based fine particles P-2 are added at 40%, and 1.0 mol / L-HCl is used as a catalyst. A low refractive index coating solution 4 diluted with an organic solvent (propylene glycol monomethyl ether: isopropyl alcohol = 1: 1 mixture) was prepared.

[Surface treatment of low refractive index layer]
The surface of the low refractive index layer produced above is shown in FIGS. 1 and 3 to 5 using flame plasma (FP), heating roller, nichrome wire heater and air blowing, far infrared ceramic heater and air heating (cooling) means. The surface treatment was performed. In addition, the number of each heating (cooling) means was set to five, and only the heating roller was set to 1, 2, 3, 5, 10, 20, 30.

[Evaluation of antireflection film]
The antireflection films 1 to 33 thus produced were measured for reflectivity and evaluated for scratch resistance (immediate and wet heat resistance) by the following methods.

(Reflectance)
The reflectance of the antireflection film was measured using a micro-reflection spectral film thickness meter (FE-3000 manufactured by Otsuka Electronics Co., Ltd.), and the average reflectance in the wavelength range of 400 to 700 nm was measured. If the reflectance is 3.0% or less, there is no practical problem, but it is preferably 2.0% or less, and more preferably 1.5% or less.

(Scratch resistance immediately)
A load of 200 g / cm ² was applied to # 0000 steel wool (SW) in an environment of 23 ° C. and 55% RH on the antireflection film, and the number of scratches per 1 cm width was measured after 10 reciprocations. In addition, the number of scratches is measured at a place where the number of scratches is the largest among the portions where the load is applied. If it is 10 / cm or less, there is no practical problem, but 5 / cm or less is preferable, and 3 / cm or less is more preferable.

(Abrasion resistance / wet heat resistance)
The antireflection film was put into a thermo-machine at 60 ° C. and 90% RH for 500 hours and subjected to wet heat treatment, and then measured by the same method as the above scratch resistance / immediate. The evaluation criteria are the same as the scratch resistance and immediate.

  The results of evaluation of reflectance and scratch resistance are shown in Table 1.

  From Table 1, it can be seen that the antireflection film of the present invention is excellent in scratch resistance.

  Sample No. When the film surface temperature immediately after contacting the heating roller was measured at 13, the low refractive index side = 243 ° C., the back surface side (cooling) = 63 ° C., and the cooling air temperature was about 50 ° C.

  Furthermore, as a result of conducting an experiment in which the surface temperature of the heating roller was changed, the heating efficiency is low at 200 ° C. or lower, and the effect of the present invention is reduced. At 250 ° C., a certain degree of effect can be obtained by increasing the one-time contact distance (time) with the low refractive index layer. At 300 ° C. or higher, a sufficient effect for the purpose of the present invention can be obtained by adjusting one contact distance (time) with the low refractive index layer. On the high temperature side, 500 ° C. or lower is preferable because it is easy to adjust the temperature of the heating roller using an electric heater. Above 800 ° C, a short contact distance (time) is the best state, and it is affected by temperature fluctuations (up and down hunting even if adjusted to a constant value). I understood.

Example 2
Polarizing plates were produced as follows using the antireflection film produced in Example 1, and these polarizing plates were incorporated into a liquid crystal display panel (image display device) to evaluate visibility.

  In accordance with the following method, a polarizing plate was prepared using an antireflection film and one cellulose triacetate film used as a support for the film as a polarizing plate protective film.

(A) Production of Polarizing Film A long 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 long polarizing film.

(B) Production of Polarizing Plate Next, according to the following steps 1 to 5, the polarizing film and the polarizing plate protective film were bonded together to produce a polarizing plate.

  Step 1: The cellulose triacetate film and the antireflection film were immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried. A surface of the antireflection film provided with the antireflection layer was previously protected with a peelable protective film (PET).

  Similarly, the cellulose triacetate film was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried.

  Process 2: The above-mentioned polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% for 1 to 2 seconds.

  Step 3: Excess adhesive adhered to the polarizing film in Step 2 was lightly removed, and it was sandwiched between the cellulose triacetate film and the antireflective film that had been subjected to alkali treatment in Step 1, and laminated.

Process 4: It bonded together at the speed | rate of about 2 m / min with the pressure of 20-30 N / cm < ² > with the two rotating rollers. At this time, care was taken to prevent bubbles from entering.

  Step 5: The sample prepared in Step 4 in a dryer at 80 ° C. was dried for 2 minutes to prepare the polarizing plate of the present invention.

  The polarizing plate on the outermost surface of a commercially available liquid crystal display panel (NEC color liquid crystal display MultiSync LCD1525J: model name LA-1529HM) was carefully peeled off, and the polarizing plate of the present invention having the polarization direction was attached thereto.

  The liquid crystal panel obtained as described above is placed on a desk 80 cm high from the floor, and a daylight direct fluorescent lamp (FLR40S • D / MX Matsushita Electric Industrial Co., Ltd.) is placed on the ceiling 3 m high from the floor. 10 sets of 40W × 2 pieces were arranged at 1.5 m intervals. At this time, when the evaluator is in front of the display surface of the liquid crystal panel, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling from the evaluator's overhead to the rear. The liquid crystal panel was tilted by 25 ° from the vertical direction with respect to the desk, and a fluorescent lamp was reflected so that the visibility of the screen (visibility) was evaluated as follows.

A: You don't have to worry about the movement of the nearest fluorescent light, and you can clearly read characters with a font size of 8 or less. B: The reflection of a nearby fluorescent light is a little anxious, but you don't care about the distance. Can manage to read characters with a font size of 8 or less C: It is difficult to read characters with a font size of 8 or less. I was worried, and I could not read characters with a font size of 8 or less in the part of the reflection. As a result of the evaluation, the sample of the present invention was B or more, which was better than the comparative sample.

It is the schematic of a flame plasma processing apparatus. It is detail drawing of a plasma processing means. It is the schematic of a heating roller processing apparatus. It is the schematic of a nichrome wire heating and ventilation cooling device. It is the schematic of a far-infrared ceramic heater and a ventilation cooling device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Surface treatment apparatus 2 Support body 3 Conveyance means 4 Application | coating means 11 Rotating cooling drum 12 Plasma processing means 13 Electric field generation means 14 Introduction means 15 Pre-neutralization means 16 Post-neutralization means B Burner C Shielding plate E, E 'Outer flame I Inner flame G Effective flame R Roller S Effective processing hole (slit)

Claims (13)

A low refractive index layer formed by a coating solution containing an alkoxysilane compound or a hydrolyzate thereof is provided directly or indirectly on a transparent base film of an organic polymer, and flame plasma treatment is performed on the surface of the low refractive index layer. A method for producing an antireflection film, comprising: The method for producing an antireflection film according to claim 1, wherein a hard coat layer mainly composed of an active energy ray curable resin is provided between the transparent base film and the low refractive index layer. The method for producing an antireflection film according to claim 1, wherein 50% or more of the alkoxysilane compound is tetraethoxysilane. The method for producing an antireflection film according to any one of claims 1 to 3, wherein the coating liquid containing the alkoxysilane compound or a hydrolyzate thereof contains silica-based fine particles having voids. The method for producing an antireflection film according to claim 4, wherein the silica-based fine particles having voids are hollow spherical silica-based fine particles. The said transparent base film is a cellulose-ester film, The manufacturing method of the antireflection film of any one of Claims 1-5 characterized by the above-mentioned. A roller having a cooling means after providing a low refractive index layer formed of a coating solution containing an alkoxysilane compound or a hydrolyzate thereof directly or indirectly on one side of a long organic polymer transparent substrate film Anti-reflection, characterized by providing a heating means for heating the surface of the low refractive index layer which is conveyed on a roller so that the opposite surface of the low refractive index layer is at least partially wrapped around the surface, and the wound portion or the surface of the low refractive index layer before and after the wound portion A method for producing a film. A process of carrying a roller after forming a low refractive index layer formed by a coating solution containing an alkoxysilane compound or a hydrolyzate thereof, directly or indirectly on one side of a transparent substrate film of a long organic polymer. A method for producing an antireflection film, comprising providing a plurality of heating means for heating the surface of the low refractive index layer that is provided and transported. The method for producing an antireflection film according to claim 8, further comprising a cooling unit by blowing air between the plurality of heating units. The method for producing an antireflection film according to any one of claims 7 to 9, wherein the heating means is flame plasma. The method for producing an antireflection film according to any one of claims 7 to 9, wherein the heating means is a metallic heating roller having a surface temperature of 300 to 800 ° C. It manufactures with the manufacturing method of the antireflection film of any one of Claims 1-11, The antireflection film characterized by the above-mentioned. An image display device comprising the antireflection film according to claim 12 as an outermost surface.

Images