JP2006010923A - Clear hard coat film, its manufacturing method, and antireflection film using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clear hard coat film and a method for manufacturing a clear hard coat film having an excellent antistatic function, physical properties of a film and flatness and free from interference irregularity or increase in haze even when a hard coat layer is formed in ≥1.2 m coating width, and to provide an antireflection film having excellent antireflection property using the above film. <P>SOLUTION: The method for manufacturing a clear hard coat film is carried out by applying at least two or more layers of clear hard coat layers in ≥1.2 m coating width on a transparent plastic substrate, wherein at least one layer of the layers contains an active energy ray curable resin. At least a coating liquid for the layer in the substrate side and a coating liquid for the layer in the surface side are simultaneously applied and layered into two or more layers, and then dried and cured. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a clear hard coat film, a method for producing the same, and an antireflection film using the same, and more specifically, clear hard having excellent antistatic function, film physical properties, and flatness and free from uneven interference and haze increase. The present invention relates to a coating film, a method for producing the same, and an antireflection film excellent in antireflection using the same.

  Image display devices such as liquid crystal display devices (LCDs) and plasma display panels (PDPs) tend to be increasingly larger, and the display surface is exposed to external light sources such as fluorescent lamps in order to increase its visibility. There is a demand not only for less reflection of the irradiated light beam, but also for the property of being hardly scratched (also called scratch resistance) by being located on the outermost surface.

  Reflection of light rays emitted from the external light source can be reduced by providing an antireflection film on the surface of the image display device. As the antireflection film, a single layer structure in which a low refractive index layer having a low refractive index is provided on a display surface or a multilayer film in which a transparent thin film of metal oxide is laminated has been conventionally used.

  As the antireflection film used for the antireflection laminate, a multilayer film in which transparent thin films of metal oxide are laminated is generally used, and a plurality of transparent thin films are used in order to lower the reflectance in a wide wavelength range. It is known that a transparent thin film of metal oxide is formed by a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method. A transparent thin film of metal oxide has excellent optical properties as an antireflection film, but the formation method by vapor deposition has low productivity and is not suitable for mass production. Instead of the vapor deposition method, a method of manufacturing an antireflection film by forming an optical functional layer on a transparent support by coating has also been proposed. In this case, it is common to form a metal oxide thin film by a sol-gel method, but there is also a method of forming a thin film by dispersing metal oxide fine particles in a binder solution in view of ease of adjusting the refractive index and stability. It has been taken. In this case, when the optical functional layer is formed by coating, the planarity of the transparent support is important because the optical functional layer is a thin film, particularly when it is wide.

  On the other hand, in the antireflection laminate, dust is easily attached due to static electricity or the like at the time of film production, a step of bonding to a polarizing plate or a display device, or panel production, and failure often occurs. Therefore, for the purpose of improving the conductivity, a conductive layer containing an ionic polymer compound or conductive fine particles (also referred to as an antistatic layer) may be provided on one surface of the support. The conductive layer is provided at a position closer to the substrate than the hard coat layer with a film thickness of about 0.2 μm, a method for imparting conductivity to the hard coat layer, and the medium refractive index of the antireflection laminate. A method of imparting conductivity to a layer or a high refractive index layer is known.

  Among the above methods, when the antistatic layer is provided on the side closer to the substrate than the hard coat layer, the antistatic property and the surface specific resistance reduction effect are small due to the distance between the antistatic layer and the surface. When a large amount of an antistatic agent is added to the antistatic layer in order to provide a sufficient antistatic function, there are disadvantages such as the film becomes brittle and cracks, scratches, etc. are likely to occur.

  Therefore, in order to maintain the scratch resistance while maintaining antistatic properties, an antistatic layer having a hard coat property may be provided, but when an active energy ray curable resin is mixed with a material having antistatic properties. Hard coat properties may be deteriorated, and cost may increase due to the use of expensive antistatic materials.

  In addition, a cured resin layer that imparts antistatic properties with a type of antistatic material in which fine particles and the like are dispersed is provided with a film thickness sufficient to provide sufficient hard coat properties and lower surface specific resistance. The rate also drops. In particular, inorganic antistatic materials are extremely superior in antistatic properties, but on the other hand, the cost is high and the cost increases due to the increase in film thickness.

  In order to obtain antistatic performance without lowering the transmittance and increasing haze, and to reduce costs, a hard coating property is provided by providing a general chargeable cured resin layer on the substrate side. And an antistatic cured resin layer may be further laminated on the surface side.

  However, drying and curing after applying the cured resin layer on the substrate side, and further drying and curing after applying the resin layer having antistatic performance on the surface side, the drying process passes twice. There is a problem that the flatness deteriorates, and a problem occurs when the antireflection laminate is applied. In particular, when the coating width is 1.2 m or more, the problem becomes more prominent.

  As a means to solve this problem, an anti-static UV curable resin containing an anti-static group in the molecule is laminated with the anti-static UV curable resin layer uncured, and two layers are cured simultaneously. Providing a cured resin layer is disclosed (for example, see Patent Document 1).

  However, although it contains a group having an antistatic function, the antistatic property is insufficient because it is a resin. Therefore, the antistatic performance can be further improved by using an inorganic antistatic agent as described above, but when an inorganic antistatic agent is used to form a cured resin layer, there is a color or haze. Many.

Further, when the surface side resin layer is laminated after curing the substrate side resin layer, an interface of the surface side resin layer / substrate side resin layer is generated, reflection occurs at this interface, and this reflected light is reflected on the substrate side resin layer. Interference with the reflected light at the interface and the reflected light on the outermost surface may cause interference unevenness, which is not preferable as an antireflection laminate. Furthermore, in the case where inorganic fine particles are dispersed in a cured resin, when coating is performed with a thin film thickness, the coating property and dispersion are disturbed on the surface of the substrate-side resin layer, resulting in unevenness and a decrease in transmittance or haze. There was a problem that it was easy to raise.
Japanese Patent No. 2877754

  The present invention has been made in view of the above problems, and the object thereof is to provide an excellent antistatic function, film physical properties, and flatness even when a hard coat layer is provided with a coating width of 1.2 m or more, and interference unevenness. Another object of the present invention is to provide a clear hard coat film having no haze increase and a method for producing the same, and an antireflection film excellent in antireflection using the same.

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

(Claim 1)
A method for producing a clear hard coat film comprising a clear hard coat layer having a coating width of 1.2 m or more on a transparent plastic substrate and comprising an active energy ray curable resin in at least one of the layers, A method for producing a clear hard coat film, comprising simultaneously applying two or more layers of at least a substrate-side layer coating solution and a surface-side layer coating solution, followed by drying and curing.

(Claim 2)
2. The method for producing a clear hard coat film according to claim 1, wherein immediately after the simultaneous multilayer coating is applied, active energy ray irradiation is performed so that the coating film is in a semi-cured state, followed by drying and curing.

(Claim 3)
The method for producing a clear hard coat film according to claim 1 or 2, wherein at least one of the clear hard coat layers containing the active energy ray-curable resin contains conductive metal oxide fine particles.

(Claim 4)
The conductive metal oxide fine particles are mainly composed of at least one element selected from the group consisting of Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W, and V. 4. The method for producing a clear hard coat film according to claim 3, wherein the method is a fine particle or a complex oxide fine particle.

(Claim 5)
The said active energy ray hardening resin has polyfunctional acrylate resin as a main component, The manufacturing method of the clear hard coat film of any one of Claims 1-4 characterized by the above-mentioned.

(Claim 6)
A clear hard coat film produced by the method for producing a clear hard coat film according to any one of claims 1 to 5.

(Claim 7)
An antireflection film comprising an antireflection layer on the surface of the clear hard coat film according to claim 6.

  According to the present invention, even if a hard coat layer is provided with a coating width of 1.2 m or more, a clear hard coat film having excellent antistatic function, film physical properties, flatness and free from uneven interference and haze increase, and a method for producing the same In addition, an antireflection film excellent in antireflection properties using the same can be provided.

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

  As a result of intensive studies, the inventor provided at least two clear hard coat layers with a coating width of 1.2 m or more on a transparent plastic substrate, and at least one of the layers contains an active energy ray curable resin. A method for producing a clear hard coat film, wherein at least two layers of a substrate-side layer coating solution and a surface-side layer coating solution are simultaneously applied, and then dried and cured. It has been found that the object of the present invention is achieved by a method for producing a coated film. In particular, immediately after the simultaneous multilayer coating, it is preferable to perform active energy ray irradiation so that the coating film is in a semi-cured state, and then to dry and cure.

  That is, a resin layer on the surface side is provided in a state where the resin layer on the substrate side is uncured, and in particular, the resin layer on the surface side is laminated on the substrate side resin layer without a drying step by wet on wet. This is a necessary condition for obtaining the effect of the present invention.

  This is because after the substrate side resin layer is applied, it is dried and cured, or transported to the application position of the surface side resin layer, and the substrate side resin layer touches the air, so that the surface of the substrate side resin layer is exposed. Oxygen may be taken in and curing inhibition may occur. In particular, when the surface-side resin layer is thinned, it is not preferable because the influence of oxygen taken into the surface of the substrate-side resin layer is significantly affected.

  In order to solve this problem, the present inventor achieved the best mixing of the interface by simultaneously layering the resin layer on the surface side on the substrate side resin layer by wet-on-wet without passing through the drying step as described above. Since it can be adjusted to the desired state, the film formation of the base resin layer and the surface resin layer can be controlled well while maintaining the dispersion of fine particles, and excellent antistatic effect, reduction in transmittance and increase in haze are suppressed. It has been found that can be. In particular, the resin layer on the substrate side and the resin layer on the surface side are irradiated with active energy rays immediately after the simultaneous multilayer coating, and the coating film is semi-cured and then dried and cured, so that By supplying radicals, inhibition of curing by oxygen can be prevented, and depending on the film thickness of the simultaneous layering, the ratio of the thickness of each layer, drying conditions, etc. If a layer containing fine particles and a layer containing no fine particles are completely mixed, the concentration of particles is relatively lowered, which is not preferable because the conductivity is lowered. Thus, it has been found that when an active energy ray is irradiated immediately after the simultaneous multilayer coating and the coating film is semi-cured, the fluidity of the coating film becomes small and the stacked layers can be prevented from being mixed more than necessary.

  Japanese Patent Application Laid-Open No. 2000-71392 discloses inorganic or organic fine particles in which a first hard coat layer and a second hard coat layer are laminated and any one of the hard coat layers satisfies an average particle size range of 0.01 to 10 μm. Hard coat films or sheets containing are described. In this case, it is described that the inorganic or organic fine particles that can be blended in the hard coat layer need to be fine particles that maintain good transparency in the active energy ray curable resin. Therefore, since the resin layer having antistatic properties can be thinned, the fine particles to be blended can be used even if they do not have so good transparency. In particular, the fine particles having antistatic properties as described above are often colored, and therefore the method of the present invention is particularly useful. As a result, according to the method of the present invention, it is possible to obtain a hard coat layer having very good antistatic properties, high transmittance and transparency, and low haze all at a high level. Further, the antistatic agent is often expensive, but according to this method, the layer containing the antistatic agent can be thinned, so that the cost can be reduced.

  In addition, in the conventional method in which the first hard coat layer is provided and then dried and cured, and then the second hard coat layer is laminated and then further dried and cured, flatness deterioration due to drying and curing is observed. However, according to the method of the present invention, since drying is performed only once, even when the coating width is 1.2 m or more, the flatness is not deteriorated, and a hardware capable of applying a precise antireflection layer is possible. A coated film can be provided.

  Hereinafter, the present invention will be described in detail.

  First, the clear hard coat layer according to the present invention will be described.

  The clear hard coat layer according to the present invention is characterized in that at least two or more layers containing an active energy ray-curable resin are provided on a transparent plastic substrate described later.

(Active energy ray curable resin)
The active energy ray curable resin used in the clear hard coat layer of the present invention is directly irradiated by active energy rays such as ultraviolet rays or electron beams, or indirectly undergoes a polymerization reaction by receiving the action of a photopolymerization initiator. A monomer or oligomer having two or more functional groups can be used.

  In the present invention, a layer containing an ultraviolet curable resin that is cured by ultraviolet rays is particularly preferable, and a clear hard coat film having excellent scratch resistance can be obtained.

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

  In general, UV-curable acrylic urethane-based resins are obtained by further reacting 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate, methacrylate) with a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, see JP-A-59-151110).

  The UV curable polyester acrylate resin can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer (see, for example, JP-A-59-151112). .

  Specific examples of the ultraviolet curable epoxy acrylate resin include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoinitiator added thereto (for example, JP-A-1- No. 105738). As this photoreaction initiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.

  In the present invention, it is particularly preferable to use an ultraviolet curable polyol acrylate resin, and examples of such a compound include polyfunctional acrylate resins. Here, the polyfunctional acrylate resin is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate resin include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipenta Lithritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, Tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol teto Methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient. Moreover, it is preferable that active energy ray cured resin has a hydroxyl group in a molecule | numerator.

  As the ultraviolet curable resin, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (manufactured by Asahi Denka Kogyo Co., Ltd.), or KOEI HARD A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT- 102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), or 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 Kogyo Co., Ltd.), or KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB Corporation), or 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.) or Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), or RCC-15C (Grace Japan Co., Ltd.) (Manufactured by company), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available ones can be used.

  Moreover, it is preferable to contain 2-30 mass% of photoinitiators with respect to active energy ray hardening resin for hardening acceleration | stimulation of active energy ray hardening resin. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

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

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

Specific examples of the anion [MeX _v ] ^-w of the compound represented by the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ^-), tetrafluoro arsenate titanate (AsF ₄ ^-), hexachloroantimonate (SbCl ₄ ^-) and the like. Furthermore, an anion of (OH ⁻ ) can also be used as the anion [MeX _v ] ^−w . Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

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

  For the active energy ray-curable resin layer, an alcohol-soluble acrylic resin having a molecular weight of 100 to 500,000 can be preferably used as the acrylic or methacrylic resin. Specifically, an alkyl (meth) acrylate polymer or an alkyl (meth) acrylate copolymer, for example, a copolymer such as n-butyl methacrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, is preferably used. The copolymer component is not limited to these. Commercially available products include Dianal BR-50, BR-51, BR-52, BR-60, BR-64, BR-65, BR-70, BR-73, BR-75, BR-76, BR-77. , BR-79, BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-89, BR-90, BR-93, BR-95, BR-96, BR -100, BR-101, BR-102, BR-105, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118 (above, Mitsubishi Can be used.

The acrylic resin or methacrylic resin preferably has a Tg (glass transition point) of 30 ° C. or lower. Tg is measured using a SOLIDS ANALYZER-RSAII manufactured by Rheometrics with a frequency of 100 rad / sec and a strain of 8.0 × 10 ⁻⁴ , and the temperature at which the peak value of tan δ reaches the glass transition. It can be obtained as a point (Tg).

  In the clear hard coat layer according to the present invention, the conductive metal oxide fine particles are dispersed in the base-side hard coat layer coating liquid or the surface-side hard coat layer coating liquid. It is preferable for imparting an antistatic function as an object. More preferably, a resin layer having no antistatic function is coated on the substrate side, and a resin layer having an antistatic function is coated on the surface side. With this configuration, the antistatic layer can be positioned near the surface, so that sufficient antistatic properties and surface resistivity reduction effects can be obtained, and a resin layer having no antistatic function is coated on the substrate side. As a result, sufficient hard coat properties can be imparted, so that it is possible to improve defects such as brittleness, cracks, and scratches that are easily generated when a large amount of conventional antistatic agents are added to the antistatic layer.

  The film thickness of the layer is preferably the resin layer on the substrate side> the resin layer on the surface side, the film thickness of the resin layer on the substrate side is in the range of 1 μm to 20 μm, and the film of the resin layer on the surface side The thickness is preferably in the range of 0.2 to 5 μm. More preferably, the thickness of the resin layer on the substrate side is 2 to 7 μm, and the thickness of the resin layer on the surface side is 0.5 to 3 μm. In the case of this configuration, since the resin layer having antistatic properties is thin, the fine particles to be blended can be used even if the transparency is not so good. In particular, the above structure is particularly useful in the case of fine particles having antistatic properties because they are often colored.

  Antistatic agent for the resin layer on the surface side is fine particles mainly composed of at least one element selected from the group consisting of Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W, and V. The content is preferably 10 to 90% by mass, and preferably 20 to 70% by mass, based on the solid content of the resin layer.

The surface specific resistance of the layer having an antistatic function of the present invention is preferably adjusted to 10 ¹¹ Ω / □ (25 ° C., 55% RH) or less, more preferably 10 ¹⁰ Ω / □ (25 ° C., 55 % RH) or less, and particularly preferably 10 ⁹ Ω / □ (25 ° C., 55% RH) or less.

  Here, although details of the measurement of the surface specific resistance value are described in the Examples, the sample was conditioned for 24 hours under the conditions of 25 ° C. and 55% RH, and a terraohm meter model VE-30 manufactured by Kawaguchi Electric Co., Ltd. was used. Use to measure.

The antistatic agent according to the present invention contains at least one element selected from the group consisting of Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W and V as a main component, and A conductive material having a volume resistivity of 10 ⁷ Ω · cm or less is preferably used.

  Examples of the antistatic agent include metal oxides and composite oxides having the above elements.

As an example of the metal oxide, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , or a composite oxide thereof is preferable. In particular, ZnO, In ₂ O ₃ , TiO ₂ and SnO ₂ are preferred. Examples of containing different atoms include, for example, addition of Al and In to ZnO, addition of Nb and Ta to TiO ₂ , and addition of Sb, Nb and halogen elements to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.

In addition, the volume resistivity of these metal oxide powders having conductivity is 10 ⁷ Ω · cm or less, particularly 10 ⁵ Ω · cm or less.

  As other antistatic agents, an ionic polymer compound can be used in combination.

  Examples of the ionic polymer compound include anionic polymer compounds such as those described in JP-B-49-23828, JP-A-49-23827, and JP-A-47-28937; JP-B-55-734, JP-A-50-54672 Ionene type polymers having a dissociating group in the main chain, as seen in JP-B Nos. 59-14735, 57-18175, 57-18176, 57-56059, etc .; No. 57-15376, No. 53-45231, No. 55-145783, No. 55-65950, No. 55-67746, No. 57-11342, No. 57-19735, No. 58-56858. No., JP-A 61-27853, 62-9346, and a cationic pendant type poly having a cationic dissociation group in the side chain. Over; and the like can be mentioned.

  Particularly preferred ionic polymer compounds include polymers having units of the following general formulas [1], [1a] and [1b].

In the formula, R ₃ , R ₄ , R ₅ and R ₆ each represent a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ and / or R ₅ and R ₆ are bonded to each other such as piperazine. A nitrogen-containing heterocycle may be formed. A, B and D are each a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, an arylene group, an alkenylene group, an arylenealkylene _{group, -R 7 COR 8 -, -} R 9 COOR 10 OCOR 11 -, - R 12 _{OCR 13 COOR 14 -, - R} 15 - (oR 16) m -, - R 17 CONHR 18 NHCOR 19 -, - R 20 OCONHR 21 NHCOR 22 - or -R ₂₅ NHCONHR ₂₄ NHCONHR ₂₅ - represents a. R ₇ , R ₈ , R ₉ , R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₉ , R ₂₀ , R ₂₂ , R ₂₃ and R ₂₅ are alkylene groups, R ₁₀ , R ₁₃ , R ₁₈ , R ₂₁ and R ₂₄ are each a linking group selected from a substituted or unsubstituted alkylene group, alkenylene group, arylene group, arylene alkylene group and alkylene arylene group, m represents a positive integer of 1 to 4, X ⁻ represents an anion.

  However, when A is an alkylene group, a hydroxyalkylene group or an arylenealkylene group, it is preferable that B is not an alkylene group, a hydroxylalkylene group or an arylenealkylene group.

E represents a group selected from a simple bond, —NHCOR ₂₆ CONH— or D. R ₂₆ represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group, arylene alkylene group, or alkylene arylene group.

Z ₁ and Z ₂ are linked to E in the form of a quaternary salt of a group of nonmetallic atoms (≡N ⁺ [X ⁻ ] — necessary for forming a 5-membered or 6-membered ring together with —N═C— group. May be).

  n represents an integer of 5 to 300.

  Among them, a quaternary ammonium cationic polymer having molecular crosslinking is particularly preferable, and a quaternary ammonium cationic polymer not containing chlorine ions and having molecular crosslinking is particularly preferably used from the viewpoint of environmental safety such as prevention of dioxin generation.

  Specific examples of the ionic polymer compound according to the present invention are given below, but the present invention is not limited thereto.

  The ionic polymer compound used in the present invention may be used alone or in combination with several kinds of ionic polymer compounds. The content of the ionic polymer compound in the resin layer on the surface side of the clear hard coat layer according to the present invention is 2 to 50% by mass, preferably 5 to 30% by mass, based on the solid content of the resin layer.

  Furthermore, in the present invention, in order to adjust the refractive index and to provide slipperiness, scratch resistance or antiglare properties, fine particles are added to a resin layer having no antistatic function and a resin layer having an antistatic function. It is preferable. In particular, it is preferable to add fine particles as a refractive index increasing agent in the active energy curable resin layer on the surface side. As the fine particles to be added, inorganic metal fine particles are preferable. For example, as the inorganic metal fine particles, silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, Mention may be made of talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  Further, the metal oxide fine particles used in the present invention may have a core / shell structure. In the core / shell structure, one shell may be formed around the core, or a plurality of shells may be formed. May be formed. The core region is preferably completely covered with the shell, but may be partially covered. For the core, titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, tin-doped indium oxide, antimony-doped tin oxide, etc. can be used. It is preferable that titanium is a main component.

  The shell is preferably formed from a metal oxide. Specifically, the shell preferably includes at least one selected from the group consisting of aluminum oxide, zirconium oxide, and silicon oxide, and silicon oxide is particularly preferable.

  Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, and melamine resin powder. Polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added to the ultraviolet curable resin composition. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical) and polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical).

  The average particle size of these fine particle powders is preferably 0.005 to 5 μm, and particularly preferably 0.01 to 4 μm. Moreover, it is preferable to contain 2 or more types of microparticles | fine-particles from which a particle size differs. The proportion of the ultraviolet curable resin composition and the fine particles is desirably blended so as to be 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.

  The refractive index of the hard coat layer according to the present invention is preferably 1.55 or more from the viewpoint of optical design for obtaining a low reflective film, 1.55 to 2.0, particularly 1.6 to It is preferably 1.7. The refractive index of a hard-coat layer can be adjusted with the refractive index and content of the microparticles | fine-particles or inorganic binder to add.

  Even if the hard coat layer formed in this way is a hard coat layer having a center line average roughness Ra of 1 to 50 nm as defined in JIS B 0601, an anti-glare layer having an Ra of about 0.1 to 1 μm. It may be.

  A method for coating the hard coat layer will be described.

  When the resin layer having no antistatic function on the substrate side is the first hard coat layer and the resin layer having the antistatic function on the surface side is the second hard coat layer, the first and second hard coat layer coating methods In the production stage, known methods such as a gravure coater, spinner coater, wire bar coater, roll coater, reverse coater, extrusion coater, air doctor coater, slit coater can be used.

  In the conventional method in which the first hard coat layer is applied, the layer is dried, and then the second hard coat layer is applied and UV cured / dried, flatness is deteriorated and interference fringes are generated between the layers. As can be seen, the present invention is a method of laminating a second hard coat layer wet-on-wet on a first hard coat layer without curing, and curing / drying the two layers simultaneously using ultraviolet light. It is.

  According to this coating method, the inhibition of curing by oxygen can be prevented by supplying radicals from the first hard coat layer, and drying can be performed after the first hard coat layer is coated or the coating position of the second hard coat layer is reached. When the first hard coat layer is exposed to air by being conveyed, it is possible to avoid inhibition of curing due to oxygen being taken into the surface of the first hard coat layer.

  In particular, when the antistatic layer of the present invention is applied to the second hard coat layer and the layer thickness is reduced, the influence of oxygen taken into the surface of the first hard coat layer is significantly affected. The system is an excellent system for achieving the object of the present invention.

  Furthermore, as described above, by laminating the second hard coat layer on the first hard coat layer without passing through the drying step, the interface mixing can be adjusted to the best state, Film formation without the influence of oxygen can be performed while maintaining the dispersion of fine particles, and a stronger film can be formed. Further, the interface between the first hard coat layer and the second hard coat layer is eliminated, and interference unevenness due to the interface can be prevented.

  In order to laminate the second hard coat layer on the first hard coat layer without a drying process, the layers are stacked one after another by an extrusion coater or simultaneously by a slot die having a plurality of slits. Multiple layers may be formed. In the present invention, simultaneous multi-layering by a slot die having a plurality of slits is preferable.

  Also, immediately after the simultaneous application of the coating solution for the first hard coat layer on the substrate side and the coating solution for the second hard coat layer on the surface side, irradiation with active energy rays is performed so that the coating film becomes semi-cured. It is preferable. By making the coating film semi-cured, the viscosity of the coating film can be increased. In the case of a coating solution having a relatively low viscosity, the diffusion of the metal oxide particles at the layer boundary can be suppressed. The layer can be formed without impairing the performance of the conductive particles.

  The irradiation of active energy rays immediately after coating may be performed by arranging a light source, which will be described later, in series with the coating machine and the coating direction, for example, a method of guiding and irradiating active energy rays through the glass fiber in the coating width direction. I can do it. The time from application to irradiation with active energy rays is preferably within 3 minutes, more preferably within 1 minute, and particularly preferably within 30 seconds.

Ultraviolet light is preferably used as the active energy ray source, and light sources such as a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, and a xenon arc can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. The irradiation time is preferably 0.5 seconds to 5 minutes, and more preferably 3 seconds to 2 minutes in view of the curing efficiency and work efficiency of the ultraviolet curable resin. In general, a high-pressure mercury lamp is used for curing a clear coating film that does not contain a filler, and a metal halide lamp is used for curing a thick film when it contains a filler. It is also possible to use an electron beam to cure the second hard coat layer. Specifically, the cockloftwald type, the bandecraft type, the resonant transformer type, the insulated core transformer type, the linear type, the dynamitron type, the high frequency An electron beam having an energy of 50 to 1000 KeV, preferably 100 to 300 KeV, emitted from various electron beam accelerators such as a mold can be used.

  As a solvent for coating the active energy ray-curable resin layer, for example, a hydrocarbon, an alcohol, a ketone, an ester, a glycol ether, or other solvent is appropriately selected, or these are mixed. Available. Preferably, propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether or propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass or more. The containing solvent is used.

  Next, the configuration of the antireflection film in which an antireflection layer is provided on the hard coat film of the present invention will be described.

  The basic structure of the antireflection film of the present invention will be described. For example, the antireflection film is made of transparent plastic substrate / hard coat layer / low refractive index layer, transparent plastic substrate / hard coat layer / high refractive index layer / low refractive index layer, transparent plastic substrate / hard coat layer / medium. It has a layer structure in the order of refractive index layer / high refractive index layer / low refractive index layer. The hard coat layer is a hard coat layer having at least two layers as described above, and the refractive index of the hard coat layer may have a refractive index of a medium refractive index layer or a high refractive index layer. The transparent support, the middle refractive index layer, the high refractive index layer, and the low refractive index layer have a refractive index that satisfies the following relationship.

  The refractive index of the low refractive index layer <the refractive index of the transparent plastic substrate <the refractive index of the medium refractive index layer <the refractive index of the high refractive index layer.

  In an antireflection film having a medium refractive index layer, a high refractive index layer, and a low refractive index layer, as described in JP-A No. 59-50401, the medium refractive index layer represents 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 possible to further reduce the average reflectance as an antireflection film.

(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 film.

  In addition, a layer configuration in the order of transparent plastic substrate / hard coat layer (antiglare layer) / high refractive index layer / low refractive index layer / high refractive index layer / 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.

<High refractive index layer and medium refractive index>
In the present invention, in order to reduce the reflectance, it is preferable to provide a high refractive index layer between the transparent plastic substrate or the transparent plastic substrate provided with 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 plastic substrate 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 medium refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent support 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 medium 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 medium 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 higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.

  In the present invention, the high refractive index layer is formed by applying and drying a coating solution containing a monomer, oligomer or hydrolyzate of an organic titanium compound represented by the following general formula (1). A layer of .55 to 2.5 is preferred.

General formula (1)
Ti (OR ¹ ) ₄
In the formula, R ¹ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O-i- _{C 3 H 7) 4, Ti} (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7) 4 2-10 mer, Ti (O-i-C 3 H 7) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These may be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ to 10-mer and Ti (On-C ₄ H ₉ ) ₄ to 10-mer are particularly preferable.

  In the present invention, it is preferable that the organic titanium compound is added to a solution in which water and an organic solvent described later are sequentially added to the coating solution for the high refractive index layer. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

Moreover, it is preferable that the quantity of water is the range of 0.25-3 mol with respect to 1 mol of organic titanium compounds. When the amount is less than 0.25 mol, hydrolysis and polymerization are not sufficiently progressed and the film strength is lowered. If it exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse TiO ₂ particles and white turbidity. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount. If the water content is 10% by mass or more with respect to the total amount of the coating solution, it is not preferable because the stability of the coating solution with time deteriorates and white turbidity occurs.

  The organic solvent used in the present invention 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. The amount of these organic solvents used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.

  The monomer, oligomer or hydrolyzate thereof used in the present invention occupies 50.0% by mass to 98.0% by mass with respect to the solid content contained in the coating solution when used alone. It is desirable. The solid content ratio is more preferably 50% by mass to 90% by mass, and further preferably 55% by mass to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and middle refractive index layer in the present invention may contain metal oxide particles as fine particles, and may further contain a binder polymer.

  When the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness and uniform film of the particles It is possible to obtain a strong coating film having both flexibility.

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 weight 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 weight average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and more 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.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals and can further contain other elements. 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 fine particle dispersion and allowing the dispersion to stand 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 easy 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 combination in the high refractive index layer and 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 90% by mass, more preferably 10 to 85% by mass, and still more preferably 20 to 80% by mass. is there. In the case of containing fine particles, the proportion of the monomer, oligomer or hydrolyzate thereof described above is 1 to 50% by mass, preferably 1 to 40% by mass, based on the solid content contained in the coating liquid. More preferably, it is 1-30 mass%.

  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), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The 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.

  In the high refractive index layer and the medium refractive index layer in the present invention, it is preferable to use a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as polyolefin), and crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide, and melamine resin. Among them, 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. Further, it is further 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 ratio 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, 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 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 of forming a crosslinked polymer by a polymerization reaction simultaneously with or after application of the coating liquid.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable, and examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, 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 Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., 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, alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

(Low refractive index layer)
Examples of the low refractive index layer include a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorinated resin before crosslinking”), a low refractive index layer by a sol-gel method, or fine particles. And a binder polymer, and a low refractive index layer or the like having voids between or inside the fine particles is used. The low refractive index layer according to the present invention may be a low refractive index layer mainly using fine particles and a binder polymer. preferable. In particular, a low refractive index layer having voids inside the particles (also referred to as hollow fine particles) is preferable because the refractive index can be further lowered. However, if the refractive index of the low refractive index layer is low, it is preferable because the antireflection performance is improved, but it is difficult from the viewpoint of imparting strength to the low refractive index layer. From this balance, the refractive index of the low refractive index layer is preferably 1.45 or less, further preferably 1.30 to 1.50, more preferably 1.35 to 1.49, It is particularly preferably 1.35 to 1.45.

  Moreover, you may use combining the preparation method of the said low-refractive-index layer suitably.

  Preferred examples of the fluorine-containing 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.). The latter can introduce a crosslinked structure after copolymerization by adding a compound that reacts with a functional group in the polymer and one or more reactive groups. No. 147739. 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 with a crosslinking 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, it is a 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, the ionizing radiation curable type is used.

  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-containing 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-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins 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 cross-linked 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.

  It is preferable from the viewpoint of refractive index adjustment that the low refractive index layer containing a crosslinked fluorine-containing resin as a constituent component contains inorganic particles described later. The inorganic fine particles are preferably used after being subjected to a surface treatment. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent, etc.) is preferably used. When the inorganic fine particles are silica, treatment with a silane coupling agent is particularly effective.

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

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

The inorganic fine particles are preferably amorphous. The inorganic fine particles are preferably made of a metal oxide, nitride, sulfide or halide, more preferably a metal oxide or a metal halide, and most preferably a metal oxide or a metal fluoride. . As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb and Ni are preferable, and Mg, Ca, B and Si are more preferable. An inorganic compound containing two kinds of metals may be used. Specific examples of preferred inorganic compounds are SiO ₂ and MgF ₂ , and particularly preferred is SiO ₂ .

Particles having microvoids in the inorganic fine particles can be formed, for example, by crosslinking silica molecules forming the particles. Crosslinking silica molecules reduces the volume and makes the particles porous. (Porous) inorganic fine particles having microvoids are prepared by a sol-gel method (described in JP-A-53-112732 and JP-B-57-9051) or a precipitation method (described in APPLIED OPTICS, 27, 3356 (1988)). Can be directly synthesized as a dispersion. Further, the powder obtained by the drying / precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available porous inorganic fine particles (for example, SiO ₂ sol) may be used.

  These inorganic 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) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone) are preferable.

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

  Microvoids between particles can be formed by stacking at least two fine particles. When spherical particles having the same particle diameter (completely monodispersed) are closely packed, microvoids between particles with a porosity of 26% by volume are formed. When spherical fine particles having the same particle diameter are simply filled with cubic particles, microvoids between fine particles having a porosity of 48% by volume are formed. In an actual low-refractive index layer, the particle size distribution of fine particles and intra-particle microvoids exist, so the porosity varies considerably from the above theoretical value. When the porosity is increased, the refractive index of the low refractive index layer is lowered. When microvoids are formed by stacking fine particles, the size of the microvoids can be adjusted to an appropriate value (does not scatter light and cause no problem with the strength of the low refractive index layer) by adjusting the particle size of the fine particles. You can adjust. Furthermore, by making the particle diameters of the fine particles uniform, it is possible to obtain an optically uniform low refractive index layer in which the size of microvoids between particles is uniform. As a result, the low refractive index layer is microscopically a microvoided porous film, but can be made optically or macroscopically uniform. The interparticle microvoids are preferably closed in the low refractive index layer by fine particles and a polymer. The closed air gap also has an advantage that light scattering on the surface of the low refractive index layer is less than that of an opening opened on the surface of the low refractive index layer.

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

In the present invention, it is also a preferred embodiment to use SiO ₂ hollow fine particles.

The hollow fine particles referred to in the present invention are particles having a particle wall and a hollow inside. For example, SiO ₂ particles having microvoids inside the fine particles described above are further converted to organosilicon compounds (alkoxy such as tetraethoxysilane). These are particles formed by covering the surface with silanes and closing the pore entrance. Alternatively, the cavity inside the particle wall may be filled with a solvent or gas. For example, in the case of air, the refractive index of the hollow fine particles should be significantly lower than that of ordinary silica (refractive index = 1.46). (Refractive index = 1.44 to 1.34). By adding such hollow SiO ₂ fine particles, the refractive index of the low refractive index layer can be further reduced.

The method for preparing particles having microvoids in the inorganic fine particles may be in accordance with the methods described in JP-A Nos. 2001-167737 and 2001-233611. In the present invention, commercially available hollow SiO _Two fine particles can be used. Specific examples of commercially available particles include P-4 manufactured by Catalytic Chemical Industry Co., Ltd.

  The low refractive index layer preferably contains the polymer in an amount of 5 to 50% by mass. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treatment agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer (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, the above-described silane coupling agent is preferably used.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand 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 the coating of the low refractive index layer, by a polymerization reaction (further crosslinking reaction if necessary). 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 layers of the present invention, and scratch resistance can be improved by imparting slipperiness. As the slip agent, silicone 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, It can be mentioned oligo polyester or the like from the Le.

For example, the amount of slip agent to be used in the low refractive index layer is preferably ^{0.01mg / m 2 ~10mg / m 2} .

  In addition to the above-mentioned components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the antireflection film or its coating solution is a polymerization inhibitor, leveling agent, thickener, anti-coloring agent. An agent, an ultraviolet absorber, a silane coupling agent, an antistatic agent or an adhesion promoter may be added.

  Each layer of the antireflection film is applied by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (US Pat. No. 2,681,294). Can be formed. Two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, It is described in Asakura Shoten (1973).

  In the present invention, in the method for producing a low reflection laminate, when the prepared coating solution is applied to a support and then dried, it is preferably dried at 60 ° C. or higher, and may be dried at 80 ° C. or higher. Further preferred. Further, drying at a dew point of 20 ° C. or lower is preferable, and drying at 15 ° C. or lower is more preferable. Furthermore, drying is preferably started within 10 seconds after coating on the support, and combining with the above conditions is a preferable production method for obtaining the effects of the present invention.

(Transparent plastic substrate)
Next, the transparent plastic substrate that can be used in the present invention will be described.

  The transparent plastic substrate used in the present invention is easy to manufacture, has good adhesion to the active energy ray-curable resin layer, is optically isotropic, and is optically transparent. That is mentioned as a preferable requirement, and the following base film is preferably used.

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

  Although it will not specifically limit if it has said property, For example, a cellulose-ester type film, a polyester-type film, a polycarbonate-type film, a polyarylate-type film, a polysulfone (a polyether sulfone is also included) type film, a polyethylene terephthalate, polyethylene Polyester film such as naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, Polycarbonate film, cycloolefin polymer film (Arton (manufactured by JSR), Onex, Zeonea (above, ZEON Corporation), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate film, acrylic film, glass plate, etc. Can be mentioned. Among them, cellulose triacetate film, polycarbonate film, and polysulfone (including polyethersulfone) are preferable, and in the present invention, cellulose ester film (for example, Konica Katak product names KC8UX2MW, KC4UX2MW, KC8UY, KC4UNY, KC5UN, KC12UR (Konica Minolta) (Manufactured by Opt Co., Ltd.)) is preferably used from the viewpoints of production, cost, transparency, isotropy, adhesion and the like. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

The optical properties of the substrate film thickness direction retardation R _t is 0Nm～300nm, retardation R ₀ in the plane direction those 0nm~1000nm is preferably used.

  In the present invention, it is preferable to use a cellulose ester film as the substrate film. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used.

  In particular, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group or butyryl group is Y, a base film having a mixed fatty acid ester of cellulose in which X and Y are in the following ranges is preferably used.

2.3 ≦ X + Y ≦ 3.0
0.1 ≦ Y ≦ 1.2
In particular, 2.5 ≦ X + Y ≦ 2.85
It is preferable that 0.3 ≦ Y ≦ 1.2.

  When cellulose ester is used as the base film according to the present invention, the cellulose used as a raw material for the cellulose ester is not particularly limited, and examples thereof include cotton linter, wood pulp (derived from coniferous tree, derived from broadleaf tree), kenaf and the like. . Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic solvent such as acetic acid or an organic solvent such as methylene chloride, and It can be obtained by reacting with a cellulose raw material using a protic catalyst.

When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804. In addition, the cellulose ester used in the present invention is obtained by mixing and reacting the amount of the acylating agent in accordance with the degree of substitution. In the cellulose ester, these acylating agents react with hydroxyl groups of cellulose molecules. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

  The cellulose ester used in the present invention is a mixed fatty acid ester of cellulose in which a propionate group or a butyrate group is bonded in addition to an acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, or cellulose acetate propionate butyrate. Is particularly preferably used. The butyryl group forming butyrate may be linear or branched.

  Cellulose acetate propionate containing a propionate group as a substituent has excellent water resistance and is useful as a film for liquid crystal image display devices.

  The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably 70000 to 250,000, since it has a high mechanical strength when molded and an appropriate dope viscosity, and more preferably 80000 to 150,000.

  These cellulose esters are pressurized by applying a cellulose ester solution (dope) generally called a solution casting film forming method onto, for example, an endless metal belt for infinite transport or a support for casting of a rotating metal drum. It is preferable to manufacture the dope from a die by casting (casting).

  The organic solvent used for the preparation of these dopes is preferably capable of dissolving the cellulose ester and having an appropriate boiling point, for example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetoacetate, acetone, tetrahydrofuran 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2 -Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3 , 3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone, etc. It is possible, organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, acetone, methyl acetoacetate, and the like are preferable organic solvents (i.e., good solvent), and as.

  Moreover, as shown in the following film forming process, it is used from the viewpoint of preventing foaming in the web when the solvent is dried from the web (dope film) formed on the casting support in the solvent evaporation process. The boiling point of the organic solvent is preferably 30 to 80 ° C. For example, the good solvent described above has a boiling point of methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56.32 ° C), acetone (boiling point 56.56 ° C). 3 ° C.), ethyl acetate (boiling point 76.82 ° C.) and the like.

  Among the good solvents described above, methylene chloride or methyl acetate, which is excellent in solubility, is preferably used.

  It is preferable to contain 0.1 mass%-40 mass% of C1-C4 alcohol other than the said organic solvent. It is particularly preferable that the alcohol is contained at 5 to 30% by mass. After casting the dope described above onto a casting support, the solvent starts to evaporate and the alcohol ratio increases and the web (dope film) gels, making the web strong and peeling from the casting support. It is also used as a gelling solvent for facilitating the dissolution, and when these ratios are small, it also has a role of promoting the dissolution of the cellulose ester of the non-chlorine organic solvent.

  Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like.

  Of these solvents, ethanol is preferred because it has good dope stability, relatively low boiling point, good drying properties, and no toxicity. It is preferable to use a solvent containing 5% by mass to 30% by mass of ethanol with respect to 70% by mass to 95% by mass of methylene chloride. Methyl acetate can be used in place of methylene chloride. At this time, the dope may be prepared by a cooling dissolution method.

  The cellulose ester film used in the present invention is preferably at least stretched in the width direction, and is 1.01 times to the width direction when the residual solvent amount is 3% by mass to 40% by mass in the solution casting process. The film is preferably stretched 1.5 times. More preferably, biaxial stretching is performed in the width direction and the longitudinal direction, and when the residual solvent is 3% by mass to 40% by mass, the width direction and the longitudinal direction are 1.01 times to 1.5 times, respectively. It is desirable to be stretched. By doing in this way, the light diffusable film excellent in planarity and light diffusibility can be obtained.

  The residual solvent amount is represented by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass of the web (cellulose ester film containing the solvent) at an arbitrary point in time, and N is the mass when the web of M is dried at 110 ° C. for 3 hours.

  Furthermore, by performing biaxial stretching and knurling, it is possible to remarkably improve the deterioration of the winding shape during storage of the long optical film in the form of a roll.

  In the present invention, the biaxially stretched cellulose ester film is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

The cellulose ester film support according to the present invention preferably has a thickness of 10 μm to 100 μm, more preferably 40 μm to 80 μm, and moisture permeability conforms to JIS Z 0208 (25 ° C., 90% RH). The measured value is preferably 200 g / m ² · 24 hours or less, more preferably 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less. . In particular, it is preferable that the film thickness is 10 μm to 80 μm and the moisture permeability is within the above range.

  In the present invention, it is preferable to use a long film, and specifically, a film having a length of about 100 m to 5000 m is shown, which is usually provided in a roll shape. Moreover, it is preferable that the width | variety of a base film is 1.3-4 m.

  When a cellulose ester film is used for the antireflection film of the present invention, it is preferable to contain the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer or the like can be preferably used.

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

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

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

  For the long film for the antireflection film of the present invention, an ultraviolet absorber is preferably used.

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

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

  Specific examples of the benzotriazole-based ultraviolet absorbers include the following ultraviolet absorbers, but the present invention is not limited thereto.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- 4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
Moreover, although the following specific example is shown as a benzophenone series ultraviolet absorber, this invention is not limited to these.

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

  Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a long film, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

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

Moreover, in order to provide slipperiness to the cellulose-ester film used for this invention, the microparticles | fine-particles similar to what was described in the said active energy ray hardening-type resin layer can be used. Of these, SiO ₂ fine particles are preferred.

  The primary average particle diameter of the fine particles added to the cellulose ester film used in the present invention is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm. These fine particles preferably form secondary particles having a particle diameter of 0.1 to 5 μm and are contained in the cellulose ester film, and the preferable average particle diameter is 0.1 to 2 μm, more preferably 0.2 to 0.6 μm. Thereby, the unevenness | corrugation about 0.1-1.0 micrometer high can be formed in the film surface, and, thereby, appropriate slipperiness can be given to the film surface.

  The primary average particle diameter of the fine particles used in the present invention is measured by observing particles with a transmission electron microscope (magnification 500,000 to 2,000,000 times), observing 100 particles, and using the average value, the primary value is measured. The average particle size was taken.

  The apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter. A larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention. Are particularly preferably used.

SiO ₂ fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more are, for example, a mixture of vaporized silicon tetrachloride and hydrogen burned in air at 1000 to 1200 ° C. Can be obtained. For example, it is marketed by the brand name of Aerosil 200V and Aerosil R972V (above, Nippon Aerosil Co., Ltd. product), and can use them.

The apparent specific gravity described above is calculated by the following formula by measuring a weight of SiO ₂ fine particles in a graduated cylinder and measuring the weight at that time.

Apparent specific gravity (g / liter) = SiO ₂ mass (g) / SiO ₂ volume (liter)
Examples of the method for preparing the fine particle dispersion used in the present invention include the following three types.

<< Preparation Method A >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.

<< Preparation Method B >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a small amount of cellulose triacetate is added to the solvent and dissolved by stirring. The fine particle dispersion is added to this and stirred. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

<< Preparation Method C >>
Add a small amount of cellulose triacetate to the solvent and dissolve with stirring. Fine particles are added to this and dispersed by a disperser. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

Preparation method A is excellent in the dispersibility of SiO ₂ fine particles, and preparation method C is excellent in that the SiO ₂ fine particles are difficult to re-aggregate. Among them, the preparation method B described above is a dispersion of SiO ₂ particles, a preferred preparation method SiO ₂ particles have excellent reagglomeration hardly like, both.

《Distribution method》
The concentration of SiO ₂ when the SiO ₂ fine particles are mixed with a solvent and dispersed is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and most preferably 15 to 20% by mass. A higher dispersion concentration is preferable because liquid turbidity with respect to the added amount tends to be low, and haze and aggregates are improved.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

The addition amount of SiO ₂ fine particles to the cellulose ester relative to 100 parts by weight of cellulose ester, SiO ₂ fine particles is preferably 5.0 parts by 0.01 parts by weight, 0.05 parts by weight to 1.0 parts by weight is more Preferably, 0.1 mass part-0.5 mass part is the most preferable. The larger the added amount, the better the dynamic friction coefficient, and the smaller the added amount, the less aggregates.

As the disperser, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersion of SiO ₂ fine particles, a medialess disperser is preferred because of low haze. Examples of the media disperser include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure disperser is preferable. The high pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube. When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 9.807 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 19.613 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable.

  Examples of the high-pressure dispersing apparatus include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersing apparatuses such as homogenizer manufactured by Izumi Food Machinery. And UHN-01 manufactured by Sanwa Machinery Co., Ltd.

  In addition, casting a dope containing fine particles so as to be in direct contact with the casting support is preferable because a film having high slip properties and low haze can be obtained.

  Moreover, after peeling and drying after casting and winding up into a roll, the optical thin film layer according to the present invention is provided. Until processing or shipment, packaging is usually performed in order to protect the product from dirt, static electricity, and the like. The packaging material is not particularly limited as long as the above purpose can be achieved, but a material that does not hinder volatilization of the residual solvent from the film is preferable. Specific examples include polyethylene, polyester, polypropylene, nylon, polystyrene, paper, various non-woven fabrics, and the like. Those in which the fibers are mesh cloth are more preferably used.

  The cellulose ester film used in the present invention may have a multilayer structure by a co-casting method using a plurality of dopes.

  Co-casting is a sequential multilayer casting method in which two or three layers are configured through different dies, and a simultaneous multilayer casting method in which two or three slits are combined in a die having two or three slits. Any of the multilayer casting methods combining sequential multilayer casting and simultaneous multilayer casting may be used.

  In addition, the cellulose ester used in the present invention is preferably used as a support having a small amount of bright spot foreign matter when formed into a film. In the present invention, the bright spot foreign material is a structure in which two polarizing plates are arranged orthogonally (crossed Nicols), a cellulose ester film is arranged between them, and light from a light source is applied from one side to the other side. When the cellulose ester film is observed, the light from the light source appears to leak.

  At this time, the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used. The occurrence of bright spot foreign matter is considered to be one of the causes of unacetylated cellulose contained in the cellulose ester. As countermeasures, the use of cellulose ester with a small amount of unacetylated cellulose, It can be removed and reduced by filtering the dissolved dope solution. Further, the thinner the film thickness, the smaller the number of bright spot foreign matter per unit area, and the lower the content of cellulose ester contained in the film, the fewer bright spot foreign matter.

The bright spot foreign matter having a bright spot diameter of 0.01 mm or more is preferably 200 pieces / cm ² or less, more preferably 100 pieces / cm ² or less, 50 pieces / cm ² or less, 30 pieces / cm. ² or less, preferably 10 pieces / cm ² or less, but it is particularly preferred that a 0.

Moreover, it is preferable that it is 200 pieces / cm < ² > or less also about 0.005 mm-0.01 mm bright spot, More preferably, it is 100 pieces / cm < ² > or less, 50 pieces / cm < ² > or less, 30 pieces / cm < ² > or less. The number is preferably 10 / cm ² or less, but particularly preferred is the case where the bright spot is zero. A thing with few also about a bright spot of 0.005 mm or less is preferable.

  When removing bright spot foreign matter by filtration, it is preferable to filter the composition in which a plasticizer is added and mixed, rather than filtering a cellulose ester dissolved alone, because the bright spot foreign matter removal efficiency is high. As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, and fluororesins such as tetrafluoroethylene resin are preferably used, but ceramics, metals and the like are also preferably used. The absolute filtration accuracy is preferably 50 μm or less, more preferably 30 μm or less, and 10 μm or less, and particularly preferably 5 μm or less.

  These can also be used in combination as appropriate. The filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.

  It is preferable to provide a backcoat layer on the surface opposite to the side on which the active energy ray-curable resin layer of the antireflection film of the present invention is provided. The back coat layer is provided in order to correct curl caused by providing an active energy ray-curable resin 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. The back coat layer is preferably applied also as an anti-blocking layer. In that case, it is preferable that fine particles are added to the back coat layer coating composition in order to provide an anti-blocking function.

  As fine particles added to the back coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxidation. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low haze, and silicon dioxide is particularly preferable.

  These fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (manufactured by Nippon Aerosil Co., Ltd.). . Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used. Examples of the polymer include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) 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 antireflection film used in the present invention preferably has a dynamic friction coefficient on the back side of the active energy ray-curable resin layer of 0.9 or less, particularly 0.1 to 0.9.

  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%.

  Specifically, the back coat layer is formed by applying a composition containing a solvent for dissolving or swelling a cellulose ester film. The solvent used may include a solvent to be dissolved and / or a solvent to be swollen in addition to a solvent to be swelled, a composition in which these are mixed at an appropriate ratio depending on the degree of curling of the transparent resin film and the type of resin, and This is done using the coating amount.

  In order to enhance the curl prevention function, it is effective to increase the mixing ratio of the solvent for dissolving the solvent composition to be used and / or the solvent for swelling, and to decrease the ratio of the solvent not to be dissolved. This mixing ratio is preferably (solvent to be dissolved and / or solvent to be swollen) :( solvent to be dissolved) = 10: 0 to 1: 9. Solvents that dissolve or swell the transparent resin 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, and ethylene 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).

  It is preferable to apply these coating compositions on the surface of the transparent resin 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. Is particularly preferably 5 to 30 μm. Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin Rubber resins such as polyvinyl acetal 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, Examples thereof include, but are not limited to, silicone resins and fluorine resins. For example, as an acrylic resin, 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, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (Mitsubishi Rayon Co., Ltd.) acrylic and The methacrylic monomers such as various homopolymers and copolymers were prepared as raw materials are commercially available, can also be selected preferred mono from this appropriate.

  Particularly preferred are cellulose resin layers such as diacetylcellulose and cellulose acetate propionate.

  The order of coating the backcoat layer may be before or after coating the active energy ray-curable resin layer of the cellulose ester film, but when the backcoat layer also serves as an antiblocking layer, it is desirable to coat it first. . Alternatively, the backcoat layer can be applied in two or more steps.

(Polarizer)
The hard coat film or antireflection film according to the present invention is extremely excellent as a polarizing plate protective film. The polarizing plate can be produced by a general method. Similarly, in the present invention, a completely saponified polyvinyl alcohol is formed on both sides of a polarizing film prepared by immersing and stretching the protective film for polarizing plate obtained by subjecting the hard coat film or antireflection film of the present invention to alkali saponification treatment in an iodine solution. Bond together using an aqueous solution. After making the hard coat film or antireflection film of the present invention, one side of the cellulose ester film may be saponified.

  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 cellulose ester film having a multilayer structure according to the present invention is bonded to form a polarizing plate. The antireflection film according to the present invention has low moisture permeability and excellent durability, although it is preferably bonded with a water-based adhesive mainly composed of completely saponified polyvinyl alcohol.

  The image display device using the polarizing plate of the present invention is excellent in durability and can display with high contrast over a long period of time.

(Image display device)
Various image display devices can be produced by incorporating the hard coat film or antireflection film of the present invention or a polarizing plate using the same into the image display device. Examples of the image display device include a liquid crystal image display device (reflective type, transflective type, transmissive type), an organic electroluminescence element, a plasma display, and the like. For example, in the forced deterioration treatment under high-temperature and high-humidity conditions, the antireflection film of the present invention or the polarizing plate using the same for the image display device is excellent in visibility and no problems caused by the antireflection film were observed. .

  Hereinafter, the present invention will be described more specifically by way of examples. However, the embodiments of the present invention are not limited to these examples.

  A chargeable resin layer (first clear hard coat layer) coating solution, an antistatic resin layer (second clear hard coat layer) coating solution, and a low refractive index layer coating solution were prepared with the following compositions.

<Charging resin layer 1>
The following materials were stirred and mixed to obtain a chargeable resin layer coating solution 1.

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku) 323 parts by mass Initiator; Irgacure 184 (manufactured by Ciba Specialty Chemicals) 36 parts by mass Leveling agent; FZ2207 (manufactured by Nihon Unicar) 10% propylene glycol Monomethyl ether solution 7 parts by mass Propylene glycol monomethyl ether 317 parts by mass Ethyl acetate 317 parts by mass <Charging resin layer 2>
The following materials were stirred and mixed to obtain a chargeable resin layer coating solution 2.

Sunrad H601R (manufactured by Sanyo Chemical) 360 parts by mass Propylene glycol monomethyl ether 320 parts by mass Ethyl acetate 320 parts by mass <Antistatic resin layer 1>
The following materials were stirred and mixed to obtain an antistatic resin layer coating solution 1.

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku) 226 parts by mass Initiator; Irgacure 184 (manufactured by Ciba Specialty Chemicals) 25 parts by mass Conductive fine particles; ELCOM V2504 (ITO sol, solid content 20%, (Catalyst Chemical)
540 parts by mass Leveling agent: FZ2207 (Nihon Unicar) 10% propylene glycol monomethyl ether solution 7 parts by mass Propylene glycol monomethyl ether 101 parts by mass Ethyl acetate 101 parts by mass <Antistatic resin layer 2>
The following materials were stirred and mixed to obtain an antistatic resin layer coating solution 2.

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku) 297 parts by mass Initiator; Irgacure 184 (manufactured by Ciba Specialty Chemicals) 33 parts by mass Conductive fine particles; ELCOM V2504 (ITO sol, solid content 20%, (Catalyst Chemical)
144 parts by mass Leveling agent: FZ2207 (Nihon Unicar) 10% propylene glycol monomethyl ether solution 7 parts by mass Propylene glycol monomethyl ether 259 parts by mass Ethyl acetate 259 parts by mass <Antistatic resin layer 3>
The following materials were stirred and mixed to obtain an antistatic resin layer coating solution 3.

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku) 275 parts by mass Initiator; Irgacure 184 (manufactured by Ciba Specialty Chemicals) 30 parts by mass Conductive fine particles; ELCOM V2504 (ITO sol, solid content 20%, (Catalyst Chemical)
270 parts by mass Leveling agent: FZ2207 (Nihon Unicar) 10% propylene glycol monomethyl ether solution 7 parts by mass Propylene glycol monomethyl ether 209 parts by mass Ethyl acetate 209 parts by mass <Antistatic resin layer 4>
The following materials were stirred and mixed to obtain an antistatic resin layer coating solution 4.

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku) 67 parts by mass Initiator; Irgacure 184 (manufactured by Ciba Specialty Chemicals) 7 parts by mass Conductive fine particles; ELCOM V2504 (ITO sol, solid content 20%, (Catalyst Chemical)
875 parts by mass Leveling agent; FZ2207 (Nihon Unicar) 10% propylene glycol monomethyl ether solution 5 parts by mass Propylene glycol monomethyl ether 23 parts by mass Ethyl acetate 23 parts by mass <Antistatic resin layer 5>
The following materials were stirred and mixed to obtain an antistatic resin layer coating solution 5.

Conductive fine particle dispersion (5% methanol dispersion of Exemplified Compound IP-24, average particle size 0.2 μm) 100 parts by mass Cellulose diacetate resin (trade name: Acetate Flakes L-AC, manufactured by Daicel Chemical Industries, Ltd.) 2 parts by mass Methanol 200 parts by mass Acetone 400 parts by mass Ethyl acetate 250 parts by mass Isopropyl alcohol 50 parts by mass <Antistatic resin layer 6>
The following materials were stirred and mixed to obtain an antistatic resin layer coating solution 6.

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku) 226 parts by mass Initiator; Irgacure 184 (manufactured by Ciba Specialty Chemicals) 25 parts by mass Conductive fine particles; SNAP (SbO ₂ dispersion, solid content 15% , Made by CI Kasei)
720 parts by mass Leveling agent: FZ2207 (Nihon Unicar) 10% propylene glycol monomethyl ether solution 7 parts by mass Propylene glycol monomethyl ether 11 parts by mass Ethyl acetate 11 parts by mass <Antistatic resin layer 7>
The following materials were stirred and mixed to obtain an antistatic resin layer coating solution 7.

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate) (manufactured by Nippon Kayaku) 148 parts by mass Initiator; Irgacure 184 (manufactured by Ciba Specialty Chemicals) 16 parts by mass Conductive fine particles; ELCOM V2504 (ITO sol, solid content 20%, (Catalyst Chemical)
450 parts by mass High refractive agent: RTSPNB15WT% -G0 (Titanium oxide fine particle dispersion, solid content 15%, manufactured by CI Kasei Kogyo Co., Ltd.) 300 parts by mass Leveling agent: FZ2207 (Nihon Unicar) 10% propylene glycol monomethyl ether Solution 6 parts by mass Propylene glycol monomethyl ether 40 parts by mass Ethyl acetate 40 parts by mass <Low refractive index layer>
(Preparation of tetraethoxysilane hydrolyzate)
29 g of tetraethoxysilane and 55 g of ethanol were mixed, and after adding 16 g of a 1.6 mass% aqueous solution of acetic acid thereto, a tetraethoxysilane hydrolyzate was prepared by stirring at 25 ° C. for 20 hours.

(Preparation of low refractive index layer composition a: sol-gel formulation)
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 382 parts by mass Isopropyl alcohol 384 parts by mass To this mixed solvent, 226 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass was slowly added and mixed. After mixing and stirring
2 parts by mass of a 10% propylene glycol monomethyl ether solution of a linear dimethyl silicone-EO block copolymer (FZ-2207: manufactured by Nihon Unicar) was slowly added and mixed to obtain a low refractive index layer composition a.

(Preparation of low refractive index layer composition b: hollow fine particle formulation)
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 377 parts by mass Isopropyl alcohol 379 parts by mass To this mixed solvent, 226 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by mass was slowly added and mixed. After mixing and stirring
Silicon dioxide fine particle dispersion (solid content 20% by mass) (P-4 manufactured by Catalytic Chemical Industry Co., Ltd.)
12 parts by mass A 10% propylene glycol monomethyl ether solution of a linear dimethyl silicone-EO block copolymer (FZ-2207: manufactured by Nihon Unicar) was slowly added and mixed to obtain a low refractive index layer composition b.

<Comparative example 1>
Uncoated base unwinding-coating 1 (first coater)-drying 1 (drying zone 1)-coating 2 (second coater)-drying 2 (drying zone 2)-UV irradiation-coated base winding can be performed continuously. In a test plant, coating was performed on one side of a 80 μm-thick cellulose triacetate film (Konica Minolta Opto Konicakatak KC8UX2MW, refractive index 1.49, acetyl group substitution degree 2.88) under the following conditions. A coated film was produced.

・ Base width 1.4m, coating width 1.3m
(First pass)
・ Coating speed 10m / min
-1st coater: 1 slot extrusion coater-Coating solution: Chargeable resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 3.0 μm.

・ Drying zone 1: 1m, drying temperature 80 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 80 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 80 ° C
-Drying zone 2-4: 2m, drying temperature 80 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
(2nd pass)
・ Coating speed 10m / min
-1st coater: 1 slot extrusion coater-Coating solution: Antistatic resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 2.0 μm.

・ Drying zone 1: 1m, drying temperature 80 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 80 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 80 ° C
-Drying zone 2-4: 2m, drying temperature 80 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
<Comparative example 2>
In Comparative Example 1, immediately after coating the first coater coating solution in the first pass, UV irradiation (adjusting the output of the UV lamp to adjust to 30 mJ / cm ² ) was performed with a UV irradiation lamp provided close to the coating machine. A second pass of coating, drying and UV irradiation were performed in the same manner except that the film was semi-cured and not dried.

<Comparative Example 3>
Using the same test plant and base film as Comparative Example 1, a hard coat film was produced under the following conditions.

・ Base width 1.4m, coating width 1.3m
(First pass)
・ Coating speed 10m / min
-1st coater: 1 slot extrusion coater Coating solution: Chargeable resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 3.0 μm.

・ Drying zone 1: 1m, drying temperature 30 ℃
・ Second coater: 1 slot extrusion coater Coating solution: Antistatic resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 2.0 μm.

・ Drying zone 2-1: 1m, drying temperature 80 ℃
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 80 ° C
-Drying zone 2-4: 2m, drying temperature 80 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
<Comparative example 4>
A hard coat film was produced in the same manner as in Comparative Example 3 except that the temperature of the drying zone 1 was changed to 80 ° C. in Comparative Example 3.

<Comparative Example 5>
In Comparative Example 3, immediately after coating the coating solution of the first coater, UV irradiation (adjusting the output of the UV lamp to adjust to 30 mj / cm ² ) was performed with a UV lamp provided close to the coating machine, and the coating film was semi-cured. After that, in the same manner as in Comparative Example 3, coating with a second coater, drying, and UV irradiation were performed to produce a hard coat film.

<Example 1>
Using the same test plant and base film as Comparative Example 1, a hard coat film was produced under the following conditions.

・ Base width 1.4m, coating width 1.3m
(First pass)
・ Coating speed 10m / min
First coater: 2-slot extrusion coater A two-slot extrusion coater was used and wet coating was simultaneously performed by wet on wet.

  The film thickness was set according to the flow rate when applied as a single layer.

(First slot; base resin layer)
-Coating solution: Chargeable resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 3.0 μm.

(Second slot; surface side resin layer)
-Coating solution: Antistatic resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 2.0 μm.

・ Drying zone 1: 1m, drying temperature 80 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 80 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 80 ° C
-Drying zone 2-4: 2m, drying temperature 80 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
<Example 2>
A hard coat film was produced in the same manner as in Example 1 except that the second slot in Example 1 and the thickness of the surface-side resin layer after drying and curing were adjusted to 0.4 μm.

<Example 3>
In Example 1, the first slot; the thickness of the base-side resin layer after drying and curing was adjusted to 5.0 μm, and the second slot; the thickness of the surface-side resin layer after drying and curing was set to 4.0 μm. A hard coat film was produced in the same manner as in Example 1 except that the adjustment was performed.

<Example 4>
In Example 1, the first slot; the thickness of the base-side resin layer after drying and curing is adjusted to 1.5 μm, and the second slot; the thickness of the surface-side resin layer after drying and curing is set to 1.0 μm. A hard coat film was produced in the same manner as in Example 1 except that the adjustment was performed.

<Example 5>
A hard coat film was produced in the same manner as in Example 1 except that the second slot in Example 1 and the surface-side resin layer coating solution was changed to the antistatic resin layer coating solution 2.

<Example 6>
A hard coat film was produced in the same manner as in Example 1 except that the second slot in Example 1; the surface-side resin layer coating solution was changed to the antistatic resin layer coating solution 3.

<Example 7>
A hard coat film was prepared in the same manner as in Example 1 except that the second slot in Example 1 and the surface-side resin layer coating solution was changed to the antistatic resin layer coating solution 4.

<Example 8>
A hard coat film was prepared in the same manner as in Example 1 except that the second slot in Example 1 and the surface-side resin layer coating solution was changed to the antistatic resin layer coating solution 6.

<Example 9>
A hard coat film was prepared in the same manner as in Example 1 except that the second slot in Example 1 and the surface-side resin layer coating solution was changed to the antistatic resin layer coating solution 7.

<Example 10>
In Example 1, the first slot; the substrate-side resin layer coating solution was changed to the chargeable resin layer coating solution 2 and the film thickness after drying and curing was adjusted to 4.0 μm, the second slot; the surface-side resin layer coating A hard coat film was produced in the same manner as in Example 1 except that the solution was changed to an antistatic resin layer coating solution 7 and the film thickness after drying and curing was adjusted to 1.0 μm.

<Example 11>
Using the same test plant and base film as in Example 1, a hard coat film was produced under the following conditions.

・ Base width 1.4m, coating width 1.3m
(First pass)
・ Coating speed 10m / min
First coater: 2-slot extrusion coater A two-slot extrusion coater was used and wet coating was simultaneously performed by wet on wet.

  The film thickness was set according to the flow rate when applied as a single layer.

(First slot; base resin layer)
-Coating solution: Antistatic resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 1.0 μm.

(Second slot; surface side resin layer)
-Coating solution: Chargeable resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 3.0 μm.

・ Drying zone 1: 1m, drying temperature 80 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 80 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 80 ° C
-Drying zone 2-4: 2m, drying temperature 80 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
The refractive index of the first-pass resin layer sample was measured by the following measurement method and found to be 1.52.

<Example 12>
In Example 1, immediately after applying the first coater coating solution in the first pass, UV irradiation (adjusting the output of the UV lamp so as to be 30 mJ / cm ² ) was performed by a UV irradiation lamp provided close to the coating machine. After semi-curing the coating film, drying and UV irradiation were carried out in the same manner as in Example 1 to obtain a hard coat film.

<Example 13>
Using the same test plant and base film as in Example 1, an antireflection film was produced under the following conditions.

・ Base width 1.4m, coating width 1.3m
(First pass)
・ Coating speed 10m / min
First coater: 2-slot extrusion coater A two-slot extrusion coater was used and wet coating was simultaneously performed by wet on wet.

  The film thickness was set according to the flow rate when applied as a single layer.

(First slot; base resin layer)
-Coating solution: Chargeable resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 3.0 μm.

(Second slot; surface side resin layer)
-Coating solution: Antistatic resin layer coating solution 1
The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 2.0 μm.

・ Drying zone 1: 1m, drying temperature 80 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 80 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 80 ° C
-Drying zone 2-4: 2m, drying temperature 80 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
The refractive index of the first-pass resin layer sample was measured by the following measurement method and found to be 1.52.

(2nd pass)
・ Coating speed 10m / min
-1st coater: 1 slot extrusion coater-Coating solution: Low refractive index layer coating solution a
The flow rate of the coating solution was adjusted so that the film thickness after drying was 90 nm.

・ Drying zone 1: 1m, drying temperature 80 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 80 ° C.
-Drying zone 2-2: 2m, drying temperature 90 ° C
-Drying zone 2-3: 2m, drying temperature 100 ° C
-Drying zone 2-4: 2m, drying temperature 80 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
It was 1.45 as a result of measuring the refractive index of the 2nd pass low refractive index layer with the following measuring method.

<Example 14>
In Example 14, the second slot of the first coater in the first pass; the surface side resin layer coating solution is changed to the antistatic resin layer coating solution 7, and the low refractive index layer coating solution of the second pass first coater is applied to the low refractive index layer. An antireflection laminate was produced in the same manner as in Example 12 except that the liquid b was used.

  The refractive index of the first-pass resin sample was 1.60, and the refractive index of the low-refractive index layer in the second pass was 1.37.

<Comparative Example 6>
On the hard coat film prepared in Comparative Example 1, the second-pass coating liquid (low refractive index layer coating liquid a) of Example 14 was applied, dried and UV cured in the same manner as in Example 14 to produce an antireflection film. did.

<Comparative Example 7>
In Comparative Example 1, the coating solution for the first pass is the antistatic resin layer coating solution 5 and the film thickness is 0.2 μm. The coating solution for the second pass is the charging resin layer coating solution 1 and the film thickness is 4.0 μm. A hard coat film was produced in the same manner as in Comparative Example 1 except that the above was changed.

<Comparative Example 8>
In Comparative Example 1, except that the coating solution for the first pass was the antistatic resin layer coating solution 5, the temperature of the drying zones 1 and 2 was 30 ° C., and the coating solution for the second pass was the charging resin layer coating solution 1. A hard coat film was produced in the same manner as in Comparative Example 1.

<Comparative Example 9>
In Comparative Example 3, the coating solution for the first coater was made antistatic resin layer coating solution 5 to make the film thickness 0.2 μm, and the coating solution for the second coater was made chargeable resin layer coating solution 1 to make the film thickness 4.0 μm. A hard coat film was produced in the same manner as in Comparative Example 3 except that it was changed.

<Example 15>
In Example 1, the first slot; the substrate-side resin layer coating solution is made antistatic resin layer coating solution 5 to a film thickness of 0.2 μm, and the second slot; the surface-side resin layer coating solution is applied to the charging resin layer. A hard coat film was produced in the same manner as in Example 1 except that the liquid 1 was changed to a film thickness of 4.0 μm.

<Comparative Example 10>
A hard coat film was produced in the same manner as in Comparative Example 1 except that the base width was 1.2 m and the coating width was 1.1 m in Comparative Example 1.

<Comparative Example 11>
A hard coat film was produced in the same manner as in Comparative Example 2 except that the base width was 1.2 m and the coating width was 1.1 m in Comparative Example 2.

<Comparative example 12>
A hard coat film was produced in the same manner as in Comparative Example 3 except that the base width was 1.2 m and the coating width was 1.1 m in Comparative Example 3.

<Comparative Example 13>
A hard coat film was produced in the same manner as in Comparative Example 4 except that the base width was 1.2 m and the coating width was 1.1 m in Comparative Example 4.

<Comparative example 14>
A hard coat film was produced in the same manner as in Comparative Example 5 except that the base width was 1.2 m and the coating width was 1.1 m in Comparative Example 5.

<Example 16>
A hard coat film was produced in the same manner as in Example 1 except that the base width was 1.2 m and the coating width was 1.1 m in Example 1.

<Example 17>
A hard coat film was produced in the same manner as in Example 12 except that the base width was 1.2 m and the coating width was 1.1 m in Example 12.

  The following evaluation was performed about the obtained sample.

"Evaluation methods"
(Refractive index)
The refractive index of the resin layer was determined from the measurement result of the spectral reflectance of the resin layer provided on the cellulose triacetate film. Spectral reflectance is FE-3000 (manufactured by Otsuka Electronics Co., Ltd.), and after roughening the back side of the measurement side of the sample, light absorption treatment is performed with a black spray to prevent reflection of light on the back side. Measurements were made. The spectral reflectance was analyzed and fitted with FE-3000 software to obtain the refractive index.

  The refractive index of the low refractive index layer was determined in the same manner as the above resin layer from the spectral reflectance of the low refractive index layer provided on the resin layer whose refractive index and film thickness were already measured.

(Surface specific resistance)
Each of the above samples was conditioned at 25 ° C. and 55% RH for 24 hours, and measured using a Teraohm Meter Model VE-30 manufactured by Kawaguchi Electric Co., Ltd. The electrodes used for the measurement were measured by placing two electrodes (parts in contact with the sample at 1 cm × 5 cm) in parallel with an interval of 1 cm, contacting the sample with the electrodes, and multiplying the measured value by five times. The value was defined as the surface specific resistance value Ω / □.

(Scratch resistance)
Place the sample on a smooth table, apply a load of 200 g per cm ² on # 0000 steel wool, rub the sample surface (side with the resin layer) 10 times, and rub 1 cm in the direction perpendicular to the rubbing direction. The number of scratches generated in the range of was visually counted.

(Haze)
The haze of the sample was measured using a turbidimeter (NDH2000, Nippon Denshoku). The measurement was performed with a D65 light source by a method based on JIS K 7136 (haze).

(Interference unevenness)
About the said sample, the A4 size sample which prevented the reflection of the light in the back surface by light-absorbing the back surface in the side which provided the resin layer with the black spray was created.

  The sample surface was irradiated obliquely with a three-wavelength fluorescent lamp (a table lamp with FL20SS • EX-N / 18 (manufactured by Matsushita Electric Industrial Co., Ltd.)), and the interference fringes visible at that time were visually evaluated.

○: Interference unevenness is not visible ○ △: Interference unevenness is slightly visible △: Interference unevenness is clearly visible △: Interference unevenness is clearly visible and slightly noticeable ×: Interference unevenness is very conspicuous (Flatness index: Small unevenness Evaluation)
Laser displacement meter: Keyence Corporation, Model: LT-8100, Resolution: 0.2 μm, Scan with a laser displacement meter in the width direction to measure fine undulations on the surface, flatness of hard coat film Evaluated.

  The measuring method is that the film is placed on a flat and horizontal table, both ends of the width are fixed to the table with tape, and the measuring camera is set in parallel with the table on a moving rail made by Sigma Kogyo Co., Ltd. And the sample film were set so that the distance between them was 25 mm, and scanning was performed at a moving speed of 5 cm / min. The value obtained by the measurement is the state and size of minute irregularities on the film surface.

A: Unevenness due to film deformation is less than 0.5 μm ○: Unevenness due to film deformation is less than 0.5 to 1.0 μm Δ: Unevenness due to film deformation is less than 1.0 to 3.0 μm ×: Due to film deformation Concavities and convexities are 3.0 μm or more (flatness; visual evaluation)
Cut each sample into a size of 90cm in width and 100cm in length, and arrange five 50W fluorescent lamps at a height of 1.5m so that the sample stage can be illuminated from a 45 ° angle. Each film sample was placed, and the unevenness that appeared to be reflected on the film surface was visually observed and judged as follows. By this method, it is possible to determine “tsun” and “wrinkle”.

◎: All five fluorescent lamps looked straight ○: Fluorescent lamps appear to be bent slightly △: Fluorescent lamps appear to be slightly bent overall ×: Fluorescent lamps appear to swell greatly (Reflectance)
Using a spectrophotometer (U-3310, manufactured by Hitachi, Ltd.), 10 arbitrary samples were sampled from the samples of Examples 13 and 14 and Comparative Example 6, and the back surface on the side provided with the antireflection layer was roughened. After the treatment, light absorption treatment is performed with a black spray to prevent reflection of light on the back surface, and the reflection spectrum in the visible light region (380 nm to 780 nm) is measured under the condition of regular reflection at 5 degrees. Values and variability were determined.

  From the measurement result of this reflection spectrum, based on JIS-Z-8701 and CIE1931, the Y value in a C light source and a 2 degree visual field was made into the reflectance.

  The obtained evaluation results are shown in Table 1 below.

  From the above table, it can be seen that the hard coat film examples 1 to 17 according to the present invention have good electrical conductivity, and scratch resistance, interference unevenness, haze, and flatness are superior to the comparative example.

  Moreover, Examples 13 and 14 in which a low refractive index layer is applied to the hard coat film according to the present invention are good antireflection films with low reflectance and little variation. In particular, it can be seen that Example 14 containing a hard coat member having a refractive index of 1.55 or more and containing hollow fine particles has a lower reflectance and is preferable. On the other hand, it was found that the antireflection film of Comparative Example 6 had a large variation in reflectivity, and the flatness of the hard coat film as a base material was poor, so that there was a problem in applying a precise antireflection layer.

Claims (7)

A method for producing a clear hard coat film comprising a clear hard coat layer having a coating width of 1.2 m or more on a transparent plastic substrate and comprising an active energy ray curable resin in at least one of the layers, A method for producing a clear hard coat film, comprising simultaneously applying two or more layers of at least a substrate-side layer coating solution and a surface-side layer coating solution, followed by drying and curing. 2. The method for producing a clear hard coat film according to claim 1, wherein immediately after the simultaneous multilayer coating is applied, active energy ray irradiation is performed so that the coating film is in a semi-cured state, followed by drying and curing. The method for producing a clear hard coat film according to claim 1 or 2, wherein at least one of the clear hard coat layers containing the active energy ray-curable resin contains conductive metal oxide fine particles. The conductive metal oxide fine particles are mainly composed of at least one element selected from the group consisting of Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, W, and V. 4. The method for producing a clear hard coat film according to claim 3, wherein the method is a fine particle or a complex oxide fine particle. The said active energy ray hardening resin has polyfunctional acrylate resin as a main component, The manufacturing method of the clear hard coat film of any one of Claims 1-4 characterized by the above-mentioned. A clear hard coat film produced by the method for producing a clear hard coat film according to any one of claims 1 to 5. An antireflection film comprising an antireflection layer on the surface of the clear hard coat film according to claim 6.