JP2010196014A - Anti-reflection film, and coating liquid of ultraviolet light-curable resin material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-reflection film equipped with a low refractive index layer at its outermost surface, and the coating liquid of an ultraviolet light-curable resin material composition suitable as a material for forming the low refractive index layer, in more detail, the coating liquid hardly developing a whitening phenomenon on forming the ultraviolet light-curable resin material composition layer by evaporating solvent from the coating liquid. <P>SOLUTION: This ultraviolet light-curable resin material composition for forming the low refractive index layer is prepared by dissolving or dispersing the ultraviolet light-curable resin material composition containing a fluorine-containing resin monomer and/or its oligomers, hollow or porous silica fine particles having ≤100 nm particle diameter and a polymerization initiator in a mixed solvent containing 0.1 to 20.0 mass% hydrophilic solvent for preventing the whitening, and having a higher boiling point than that of water and ≤35 dyn/cm (25°C) surface tension, and a main solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antireflection film having a low refractive index layer on the outermost surface and a coating liquid of an ultraviolet curable resin material composition suitable as a material for forming the low refractive index layer. The present invention relates to suppression of a whitening phenomenon that occurs when a solvent is evaporated from a liquid.

  In image display devices such as a liquid crystal display device (LCD), a plasma display device (PDP), an electroluminescence display device (ELD), and a cathode ray tube display device (CRT), in many cases, the outermost surface on the user side of the image display unit In addition, an antireflection layer is provided for preventing light other than light for displaying data from being reflected by the display screen and reaching the eyes of the user. The antireflection layer is provided in order to prevent reflection of external light to make the screen easier to see, and to improve the display image quality by raising the contrast.

  As a method of providing an antireflection layer on the display screen, a method of attaching an antireflection film having an antireflection layer on the surface of a transparent substrate film is generally used. The structure of the antireflection film includes a transparent base film provided with a low refractive index layer having a lower refractive index than that of the transparent base film, and a transparent base film that is refracted more than the transparent base film. There is one in which a high refractive index layer having a large refractive index is provided, and a low refractive index layer having a refractive index smaller than that of a transparent substrate film is provided thereon. In these antireflection films, the lower the refractive index of the low refractive index layer and the higher the refractive index of the high refractive index layer, the lower the reflectance. Therefore, the lower the refractive index of the low refractive index layer, the better.

As a material for forming such a low refractive index layer, a resin composition in which ultrafine particles having a refractive index smaller than that of a resin is dispersed in a binder resin has been proposed. For example, in Patent Document 1 described later, LiF (refractive index 1.4), MgF ₂ (refractive index 1.4), 3NaAlF ₄ (refractive index 1.4), and AlF ₃ (refractive index) are used as low refractive index ultrafine particles. 1.4), fine particles comprising Na ₃ AlF ₆ (cryolite, refractive index 1.33), SiO _x (x: 1.50 ≦ x ≦ 2.00, refractive index 1.35 to 1.48), etc. Are listed.

  The method of controlling the refractive index by dispersing ultrafine particles in the binder resin has the advantage that the refractive index of the resin composition can be easily controlled. However, it is generally difficult to disperse the ultrafine particles uniformly in the binder resin. Therefore, the antireflection film formed using such a resin composition has a drawback that it easily causes whitening, and it has been difficult to obtain an antireflection film having excellent transparency and antireflection performance. .

  Therefore, in Patent Document 1 described later, a resin layer having a controlled refractive index is formed on a transparent base film directly or via another layer, and at least one layer is made of a resin composition containing ultrafine particles. The layer formed on the outermost surface has a lower refractive index than the refractive index of the lower layer in direct contact with the layer, and the resin composition contains a carboxyl group-containing (meth) acrylate as part of the binder resin component. An ultrafine particle-containing antireflection film characterized by containing as a whole has been proposed. In addition, (meth) acrylate shall mean either an acrylate and a methacrylate.

  According to Patent Document 1, the carboxyl group-containing (meth) acrylate can contain ultrafine particles with good dispersibility. Moreover, although it is estimated that it has a carboxyl group in the same molecule, a binder resin having good adhesion to various plastic substrates and excellent wear resistance can be obtained. And even if it mixes with the polyfunctional acrylate which has a hydroxyl group and three or more acryloyl groups in a molecule | numerator, an acryloyl group density does not fall. As a result, the obtained ultrafine particle-containing antireflection film is suppressed in whitening and excellent in transparency, has a small haze value, and a low reflectance. Moreover, it is excellent also in hard performances, such as pencil hardness and abrasion resistance, and the adhesiveness between layers. A solvent is appropriately used for adjusting the viscosity of the resin material composition. Examples of the solvent include aromatic hydrocarbons, alcohols, ketones, ethers, ether esters, and the like, and these can be used in combination.

Patent Document 2 described below is an antireflection laminate in which a low refractive index layer having a refractive index of 1.45 or less is provided on a light-transmitting substrate,
The low refractive index layer comprises an ionizing radiation curable resin composition and silica fine particles having an outer shell layer, the inside of which is porous or hollow;
A part or all of the silica fine particles are formed by treating at least a part of the surface of the silica fine particles with a silane coupling agent having an ionizing radiation curable group.
Anti-reflection laminates have been proposed.

  At this time, the ionizing radiation curable group is preferably an acryloyl group and / or a methacryloyl group, and the silica fine particles are passed through the ionizing radiation curable group of the silane coupling agent introduced on the surface, The antireflection laminate is formed by forming a covalent bond by chemical reaction directly with the ionizing radiation curable resin composition and / or through the ionizing radiation curable group of the free silane coupling agent. It is said to be good.

  Patent Document 2 explains as follows.

  The silica fine particles whose inside is porous or hollow have voids occupied by air, and therefore have a small refractive index. For this reason, the refractive index of a coating film can be reduced effectively by addition of silica fine particles. Moreover, since a silane coupling agent having an ionizing radiation curable group is introduced into at least a part of the surface of the silica fine particles, the affinity with the binder component is improved, and the coating liquid and the coating film are applied. Silica fine particles can be uniformly dispersed. At this time, the ionizing radiation curable group of the silane coupling agent is covalently bonded by a chemical reaction directly with the ionizing radiation curable group of the binder component and / or through the ionizing radiation curable group of the free silane coupling agent. Therefore, even if the amount of silica fine particles relative to the resin composition is very large, a significant decrease in the hardness and strength of the coating film can be avoided and the refractive index is low. In addition, a low refractive index layer having excellent mechanical strength can be realized.

  The solvent used for dissolving and dispersing the solid component forming the low refractive index layer is not particularly limited, and various organic solvents such as alcohols, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons, Alternatively, a mixture of these can be used. However, when a coating solution is prepared using a ketone solvent, it can be easily and uniformly applied to the substrate surface, and after coating, the solvent evaporation rate is moderate and hardly causes uneven drying. It is preferable because a large-area coating film having a uniform thickness can be easily obtained.

Further, in Patent Document 3 described later, a low refractive index layer having an arithmetic average roughness Ra of 1 nm or more and less than 2 nm on at least one side of a light-transmitting base film, directly or via another layer. Is formed, the haze as the laminate is 0.4 or less, an antireflection film,
The low refractive index layer includes hollow silica fine particles or porous silica fine particles,
The resin composition for forming the low refractive index layer contains an organic solvent, a binder resin, hollow silica fine particles or porous silica fine particles in a ratio of 50% or more of a water-based organic solvent. Antireflection films have been proposed.

  Patent Document 3 explains as follows.

  If a coating composition containing 50% or more of an aqueous organic solvent is used, the reason why the low refractive index layer is excellent in transparency is probably because the organic solvent is porous silica fine particles or hollow silica. Good affinity with hydroxy groups present on the surface of silica fine particles, and the organic solvent improves the dispersibility of porous silica fine particles and hollow silica fine particles. As a result, porous silica fine particles and hollow silica This is because irregularities of the fine particles are hardly formed.

  As the aqueous organic solvent, methanol, ethanol, 2-propanol and 1-butanol can be used, and 1-butanol is particularly preferable. When 1-butanol is used, since the drying time of the coating film is longer than when other aqueous organic solvents are used, the coating film is formed slowly, and due to the leveling effect, porous silica fine particles and hollow silica are used. This is because the surface of the coating becomes smooth because the fine particles are more uniformly dispersed in the coating. Organic solvents other than water-based organic solvents that may be contained in less than 50% of organic solvents include ketones, esters, ethers, glycols, glycol ethers, aliphatic hydrocarbons , Halogenated hydrocarbons, aromatic hydrocarbons, N-methylpyrrolidone, dimethylformamide and the like.

  Further, in Patent Document 4 to be described later, a fluorine-containing compound having a film forming property and having a polymerizable double bond and hydrothermal treatment are performed, and modified by a silane coupling agent having a polymerizable double bond. And the modified hollow silica fine particles having a hollow portion porosity of 40 to 45% and an average particle diameter of 10 to 100 nm, the fluorine-containing compound in the total amount of the fluorine-containing compound and the modified hollow silica fine particles A fluorine-containing curable coating liquid characterized in that the content is 40 to 80% by mass and the content of the modified hollow silica fine particles is 60 to 20% by mass has been proposed.

  According to Patent Document 4, since the fluorine-containing curable coating liquid contains 40 to 80% by mass of the fluorine-containing compound, the refractive index can be lowered and the reflectance can be suppressed. Further, since the modified hollow silica fine particles are subjected to hydrothermal treatment, the outer shell is densified, and moisture is hardly adsorbed on the surface of the cured film. Furthermore, since the modified hollow silica fine particles are modified with a silane coupling agent having a polymerizable double bond, the polymerizable double bond of the silane coupling agent and the polymerizable double bond of the fluorine-containing compound are copolymerized. Thus, the hollow silica fine particles are integrally bonded to the fluorine-containing compound, and the strength and hardness of the cured film can be improved.

  In Patent Documents 1 to 3, since the resin material forming the low refractive index layer does not contain fluorine, the refractive index of the low refractive index layer cannot be made sufficiently small. Patent Document 2 describes that the low refractive index layer can contain an ionizing radiation curable resin composition and a silica-compatible fluorine-based compound, but the content is 0.01 to 10%. Since the amount is as small as mass%, the refractive index reduction effect based on fluorine content is not sufficient.

  On the other hand, as a result of studies by the present inventor, an ultraviolet curable resin material composition containing a fluorine-containing resin monomer and / or oligomer is dissolved or dispersed in a general organic solvent such as toluene, methyl ethyl ketone, or isopropyl alcohol. It has been found that in the liquid, whitening occurs in the ultraviolet curable resin material layer obtained by evaporating the solvent, and a low-refractive index layer with high transparency may not be obtained. This whitening phenomenon appears prominently when the relative humidity of the atmosphere is 40% or more. Whitening is caused by repelling and unevenness of the coating film surface. When whitening occurs, the original optical properties, scratch resistance, antifouling property, etc. of the ultraviolet curable resin composition are impaired. Patent Document 4 does not mention such a whitening phenomenon.

  The present invention has been made in view of such a situation, and an object thereof is an antireflection film having a low refractive index layer on the outermost surface, and an ultraviolet ray suitable as a material for forming the low refractive index layer. Specifically, the present invention provides a coating liquid for a curable resin material composition, and more specifically, to provide a coating liquid that hardly causes a whitening phenomenon that occurs when a solvent is evaporated from the coating liquid to form an ultraviolet curable resin material composition layer. is there.

That is, the present invention provides an ultraviolet curable resin material composition containing a fluorine-containing resin monomer and / or oligomer thereof, hollow or porous silica fine particles having a particle size of 100 nm or less, and a polymerization initiator.
80.0-99.9% by weight of the main solvent,
20.0 to 0.1% by mass in a mixed solvent containing a hydrophilic anti-whitening solvent having a boiling point higher than that of water and a surface tension of 35 dyn / cm (25 ° C.) or less. This relates to a coating liquid for ultraviolet curable resin material composition. In order to avoid confusion, the composition containing the monomer and / or oligomer before the curing treatment is referred to as a resin material composition, and the polymer after the curing treatment is referred to as a resin composition.

  In addition, the ultraviolet curable resin material composition coating liquid layer is applied directly or via a functional layer to the base film, and the mixed solvent evaporates from the coating liquid layer. This relates to an antireflection film in which a low refractive index layer is formed on the outermost surface of the base film by curing the conductive resin material composition layer.

  As a result of intensive studies by the present inventors, the ultraviolet curable resin material composition coating liquid of the present invention was applied to a transparent substrate directly or via a functional layer, and the mixed solvent was evaporated from the coating liquid layer. After that, when the obtained ultraviolet curable resin material composition layer is cured and a low refractive index layer is formed on the outermost surface of the transparent substrate, the whitening phenomenon hardly occurs. It was found that a low refractive index layer having excellent scratch resistance and antifouling properties can be obtained.

  It cannot be said that the cause of the whitening phenomenon that occurs when the solvent is evaporated from the conventional coating liquid layer and the mechanism that the whitening phenomenon is less likely to occur when the mixed solvent, which is a feature of the present invention, is not completely elucidated. However, since the whitening phenomenon is remarkable when the relative humidity in the atmosphere is 40% or more, there is no doubt that moisture in the atmosphere is related to the whitening phenomenon. Therefore, it is considered as follows.

  In the process where the solvent evaporates from the coating layer, the solvent vapor diffuses while being mixed with the surrounding air in a complicated manner. In this process, a part of the moisture in the air that is entrained in the solvent vapor flow is applied to the coating liquid. Contact layer. Moisture is not compatible with fluorine-containing resin monomers and / or oligomers thereof and solvents with low polarity. For this reason, when a solvent having a small polarity is used alone, moisture adheres to the surface of the hollow or porous silica fine particles, and causes whitening. When a highly polar solvent is used alone, the water has affinity with the solvent and is once taken into the solvent. However, as the solvent evaporates, the remaining water adheres to the surface of the hollow or porous silica fine particles, causing whitening.

  On the other hand, in the present invention, the mixed solvent containing the hydrophilic whitening prevention solvent is used. For this reason, water | moisture content is once taken in in the said mixed solvent by affinity with the said whitening prevention solvent. As evaporation of the mixed solvent from the coating liquid layer proceeds, the boiling point of the anti-whitening solvent is higher than that of water, and the anti-whitening solvent is less likely to evaporate than water, so that it is taken into the mixed solvent. The water that has been evaporated evaporates faster than the anti-whitening solvent and is returned to the atmosphere again. Since the surface tension of the anti-whitening solvent is as small as 35 dyn / cm (25 ° C.) or less, the anti-whitening solvent does not easily wet the surface of the hollow or porous silica fine particles during this time, and the moisture taken into the mixed solvent is There is little contact with the surface of the hollow or porous silica fine particles. As a result, moisture hardly adheres to the surface of the hollow or porous silica fine particles to cause whitening, and the whitening phenomenon is prevented.

  In order for the action of the whitening prevention solvent to be effective, the blending amount of the whitening prevention solvent needs to be 0.1% by mass or more of the mixed solvent. Originally, whitening hardly occurs under low-humidity conditions, and even a blending amount of about 0.1% by mass is effective. On the other hand, even if the anti-whitening solvent is effective in preventing the whitening phenomenon, the performance of the ultraviolet curable resin material composition as a solvent is inferior to that of the main solvent. For example, since the whitening prevention solvent has a high boiling point, if the blending amount is too large, the time required for evaporation of the solvent becomes longer, or the temperature required for evaporation increases, so that the production efficiency decreases. Further, the whitening prevention solvent remains in the low refractive index layer, the hardness of the low refractive index layer is lowered, and the scratch resistance is likely to deteriorate. Therefore, the blending amount of the whitening prevention solvent is preferably 20.0% by mass or less of the mixed solvent. In summary, the blending amount of the whitening prevention solvent is preferably 0.1 to 20.0% by mass of the mixed solvent.

  As described above, if the low refractive index layer is formed using the ultraviolet curable resin material composition coating liquid of the present invention, whitening does not occur, haze is small, scratch resistance, and antifouling properties are excellent. It was found that a low refractive index layer was obtained. Since the low refractive index layer contains the fluorine-containing resin monomer and / or oligomer thereof and the hollow or porous silica fine particles, an extremely small refractive index can be realized.

  The antireflection film of the present invention is an antireflection film having excellent antireflection performance because the low refractive index layer is formed on the outermost surface of the base film. Moreover, the ultraviolet curable resin material composition coating liquid of the present invention is also preferably used for forming a low refractive index layer in places where it is difficult to apply an antireflection film, such as the surface of a plastic molded product or a coated product. Can do.

It is a fragmentary sectional view which shows the structure of the antireflection film based on embodiment of this invention, and an antireflection hard coat film.

  In the ultraviolet curable resin material composition coating liquid of the present invention, the main solvent is a monohydric alcohol having 4 carbon atoms, and the whitening prevention solvent is an ether or ketone having 6 or more carbon atoms having a hydrophilic group. It is good.

  Moreover, it is good that the compounding quantity of the said fluorine-containing resin monomer and / or its oligomer in the said ultraviolet curable resin material composition is 10-50 mass%.

  Moreover, it is good that the compounding quantity of the said hollow or porous silica fine particle in the said ultraviolet curable resin material composition is 30-70 mass%. The hollow or porous silica fine particles are preferably surface-treated with an organic dispersant having a (meth) acryloyl group, a vinyl group, or an epoxy group at the terminal. In addition, a (meth) acryloyl group shall mean either an acryloyl group or a methacryloyl group.

  Moreover, it is good that the compounding quantity of the said polymerization initiator in the said ultraviolet curable resin material composition is 0.1-10.0 mass%.

  The ultraviolet curable resin material composition preferably contains a monomer having two or more (meth) acryloyl groups and / or an oligomer thereof.

Moreover, it is good for the said ultraviolet curable resin material composition to contain the (meth) acrylic resin monomer which has a hydrophilic group, and / or its oligomer. At this time, the hydrophilic group may be a hydroxy group —OH, a carboxy group —COOH, and / or an amino group —NH ₂ .

  Moreover, it is good for the said ultraviolet curable resin material composition to contain a 0.01-10 mass% leveling agent. In this case, a silicone oligomer having one or more (meth) acryloyl groups, vinyl groups, or epoxy groups is suitable as the leveling agent.

  In the antireflection film of the present invention, a hard coat layer having a refractive index larger than that of the base film is provided as the functional layer on the base film, and the low refractive index layer is provided by being laminated on the hard coat layer. It is good to have.

  Hereinafter, the ultraviolet curable resin material composition and the antireflection film according to the preferred embodiments of the present invention will be described more specifically with reference to the drawings. However, the present invention is not limited to these examples. .

  Fig.1 (a) is a fragmentary sectional view which shows the structure of the antireflection film 10 based on embodiment of this invention. In the antireflection film 10, a low refractive index layer 2 having a refractive index smaller than that of the base film 1 is formed on the base film 1 made of polyethylene terephthalate, etc. It is configured. The antireflection film 10 has a single layer structure, but has a sufficiently high antireflection performance because it includes the low refractive index layer 2 having a small refractive index. Since the antireflection film 10 has a simple layer structure as compared with a multilayer structure, the antireflection film 10 is excellent in productivity and cost performance.

  In order to produce the antireflection film 10, first, the ultraviolet curable resin material composition is dissolved or dispersed in the mixed solvent to prepare a coating liquid containing the ultraviolet curable resin material composition. Next, after the ultraviolet curable resin material composition coating liquid is deposited on the base film 1 by a coating method, a printing method, or an immersion method, the mixed solvent is evaporated at a predetermined temperature, A layer of the ultraviolet curable resin material composition is formed. At this time, since the mixed solvent contains the whitening prevention solvent, the whitening phenomenon can be suppressed as described above. Next, this layer is irradiated with ultraviolet rays and cured, and the low refractive index layer 2 is formed in contact with the base film 1.

  In the mixed solvent, the main solvent may be a monohydric alcohol having 4 carbon atoms, such as 2-methyl-2-propanol (tert-butyl alcohol). When these are used, the time required for the solvent to evaporate from the coating liquid layer is longer than when isopropyl alcohol or the like is used. Therefore, the hollow or porous silica fine particles are made into an ultraviolet curable resin material by a leveling effect. The time for uniformly dispersing in the composition layer is ensured, and the flatness of the surface of the ultraviolet curable resin material composition layer is improved.

As the whitening prevention solvent, ethers or ketones having 6 or more carbon atoms having a hydrophilic group, for example, 2-butoxyethanol (also referred to as ethylene glycol monobutyl ether; hereinafter abbreviated as butyl cellosolve) are preferable. Hydrophilic groups include hydroxy group —OH, carboxy group —COOH, amino group —NH ₂ and the like. As for the compounding quantity in the said mixed solvent of the said whitening prevention solvent, 0.1-20.0 mass% is desirable. If it is less than 0.1% by mass, the action as a whitening prevention solvent is insufficient, and whitening of the low refractive index layer 2 may not be suppressed. On the other hand, when the content is more than 20.0% by mass, the anti-whitening solvent may remain in the low refractive index layer 2 and the mechanical properties of the low refractive index layer 2 such as scratch resistance are deteriorated.

  Further, instead of butyl cellosolve, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) or tripropylene glycol monomethyl ether may be used as a whitening prevention solvent. Also, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monobutyl ether ( Butyl triglycol), dipropylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monoisopropyl ether, tripropylene glycol monoisopropyl ether, and methyl glycol can also be used.

  The main solvent is preferably polar and can dissolve or disperse all the components of the ultraviolet curable resin material composition. The boiling point of the main solvent is preferably about 50 to 100 ° C., and the evaporation rate is not too fast or too slow.

  The material of the base film 1 is not particularly limited, and examples thereof include polyethylene terephthalate (PET) resin, triacetyl cellulose (TAC) resin, and cycloolefin polymer (COP) resin. Base films made of these resins are excellent in scratch resistance, transparency, heat resistance, and the like.

  The ultraviolet curable resin material composition contains at least a fluorine-containing resin monomer and / or an oligomer thereof, hollow or porous silica fine particles having a particle diameter of 100 nm or less, and a polymerization initiator.

  The fluorine-containing addition-polymerizable monomer and / or oligomer thereof may be contained, for example, as a constituent component of OPTOOL AR110 (trade name; manufactured by Daikin Industries, Ltd.). Optool AR110 is an amorphous fluororesin material composition comprising a combination of a functional group-containing fluorine-containing monomer, a crosslinking group-containing fluorine-containing monomer, and an adhesive group-containing monomer. This amorphous fluororesin has both low refractive index properties and scratch resistance, adhesion with different materials, solubility of resin materials in general-purpose solvents, and coating solutions in which resin materials are dissolved in solvents The applicability of is optimized. The hydrocarbon group in the monomer and / or oligomer thereof does not have to be substituted for all hydrogen atoms with fluorine atoms, and may partially contain hydrogen atoms.

  The blending amount of the fluorine-containing resin monomer and / or oligomer thereof is desirably 10 to 50% by mass of the ultraviolet curable resin material composition. The reason is that if it is less than 10% by mass, the refractive index of the low refractive index layer becomes too high, and it is difficult to obtain a desired antireflection effect. On the other hand, if it exceeds 50% by mass, it is difficult to obtain a low refractive index layer having sufficient hardness and scratch resistance.

  The ultraviolet curable resin material composition preferably contains a monomer having two or more (meth) acryloyl groups and / or an oligomer thereof. When two or more (meth) acryloyl groups are contained per monomer molecule, a crosslinked structure can be formed between the polymer chains, so that the mechanical strength and hardness of the resin composition formed by polymerization are improved. The monomer and / or oligomer having the (meth) acryloyl group preferably contains three or more (meth) acryloyl groups per monomer molecule. Thereby, the crosslinked structure formed between the polymer chains can be further increased, and the mechanical strength and hardness of the resin composition can be further improved. As the (meth) acrylic monomer containing three or more (meth) acryloyl groups per monomer molecule, for example, pentaerythritol tetraacrylate which is a tetraacrylate of tetra (hydroxymethyl) methane (also known as pentaerythritol) is suitable. . The structural formula is shown below.

(Chemical Formula 1) Structural formula of pentaerythritol tetraacrylate:

Moreover, it is good for the said ultraviolet curable resin material composition to contain the (meth) acrylic resin monomer which has a hydrophilic group, and / or its oligomer. In this case, the hydrophilic group may be a hydroxy group —OH, a carboxy group —COOH, and / or an amino group —NH ₂ . The (meth) acrylic resin monomer and / or oligomer thereof having a hydrophilic group is considered to have affinity with moisture taken into the resin material by the hydrophilic group, suppress repelling and separation, and prevent whitening. For example, pentaerythritol triacrylate, which is a triacrylate of pentaerythritol, is suitable as the (meth) acrylic monomer having three or more (meth) acryloyl groups per monomer molecule and having a hydrophilic group. The structural formula is shown below.

(Chemical Formula 2) Structural formula of pentaerythritol triacrylate:

  As for the compounding quantity of a pentaerythritol triacrylate, 1.0-50.0 mass% of the said ultraviolet curable resin material composition is desirable. When it is less than 1.0% by mass, a sufficient crosslinking density cannot be obtained. On the other hand, when it is more than 50.0% by mass, the refractive index of the low refractive index layer 2 becomes too large.

  The hollow or porous silica fine particles reduce the refractive index of the low refractive index layer 2. The refractive index of the hollow or porous silica fine particles is preferably 1.1 to 1.4. The blending amount of the hollow or porous silica fine particles is desirably 30 to 70% by mass of the composition. When it is less than 30% by mass, sufficient reflection characteristics cannot be obtained. On the other hand, if it exceeds 70% by mass, mechanical properties such as scratch resistance deteriorate. The surface of the fine particles is preferably surface-treated with an organic dispersant having a (meth) acryl group, vinyl group, or epoxy group at the terminal. In this case, the organic dispersant is polymerized with the surrounding (meth) acrylic group-containing monomer / oligomer in the curing step of the coating liquid layer, and the whole is integrated including the hollow or porous silica fine particles. Flexibility is improved.

  As the polymerization initiator, a known material may be appropriately selected and used. The blending amount of the polymerization initiator is preferably 0.1 to 10% by mass of the solid content. When the blending amount is less than 0.1% by mass, the photocurability is insufficient and it is substantially unsuitable for industrial production. On the other hand, if the blending amount is more than 10% by mass, odor may remain in the low refractive index layer 2 when the amount of irradiation light is small.

  The leveling agent spreads on the surface of the coating liquid layer in the process of forming the coating film, uniformizes the evaporation of the solvent from the coating film surface, prevents floating mottle, and smoothes the surface. As a result, it functions to impart antifouling properties to the low refractive index layer 2 and improve the mechanical properties of the low refractive index layer 2 such as scratch resistance. The blending amount of the leveling agent in the ultraviolet curable resin material composition is preferably 0.01 to 10.0% by mass. When the blending amount is less than 0.01% by mass, sufficient leveling properties may not be obtained. On the other hand, when there are more compounding quantities than 10.0 mass%, there exists a tendency for coating property to worsen.

  As leveling agents, silicone oligomers containing one or more (meth) acryloyl groups, vinyl groups or epoxy groups are preferred. For example, X-22-2426 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) which is methacryl-modified dimethyl silicone at one end, or Silaplane FM7725 (trade name; manufactured by Chisso Corporation) which is methacryl-modified dimethyl silicone at both ends is suitable. is there. Moreover, as a leveling agent, X-22-174DX (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) which is methacryl-modified dimethyl silicone at one end, and X-22-164E (trade name: Shin-Etsu Chemical Co., Ltd.) which is methacryl-modified dimethyl silicone at both ends. EBECRYL 350 (trade name; manufactured by Daicel Cytec), which is silicon diacrylate, can also be used.

  FIG.1 (b) is a fragmentary sectional view which shows the structure of the antireflection hard coat film 20 based on another example of embodiment of this invention. In the antireflection hard coat film 20, a hard coat layer 3 having a refractive index larger than that of the base film is provided as the functional layer on the base film 1 made of polyethylene terephthalate or the like, corresponding to claim 13. The low-refractive index layer 2 is provided on the hard coat layer 3 to form an antireflection hard coat film. The hard coat layer 3 also serves as a high refractive index layer.

  In order to obtain high antireflection performance, it is common to use a multilayer structure in which a plurality of layers of a high refractive index material and a low refractive index material are laminated as in the antireflection hard coat film 20. At this time, if the high refractive index layer also serves as the function of the hard coat layer 3, both high antireflection performance and hard coat performance can be easily obtained, which is preferable.

  In order to produce the antireflection hard coat film 20, first, an ultraviolet curable resin material composition for forming the hard coat layer 3 is dissolved or dispersed in an appropriate solvent, and a coating liquid containing the ultraviolet curable resin material composition is prepared. Prepare. Next, after applying the coating liquid onto the base film 1 by a coating method, a printing method, an immersion method, or the like, the solvent is evaporated at a predetermined temperature to form a layer of the ultraviolet curable resin material composition. . Next, the layer is irradiated with ultraviolet rays and cured, and the hard coat layer 3 is formed in contact with the base film 1. Thereafter, similarly to the antireflection film 10, the low refractive index layer 2 is laminated on the hard coat layer 3.

  Examples of the ultraviolet curable resin material composition for forming the hard coat layer 3 include dipentaerythritol hexaacrylate (refractive index = 1.49) and dimethylol tricyclodecane diacrylate (refractive index = 1.50). Those containing an acrylic monomer having two or more acryloyl groups in the molecule and a photopolymerization initiator such as 1-hydroxycyclohexyl phenyl ketone are preferred. In addition, a leveling agent that improves flatness may be included. This resin material composition is used after being dissolved in a solvent such as cyclohexanone.

  Examples of the present invention will be described below. In this example, the antireflection hard coat film 20 described with reference to FIG. 1B in the embodiment was produced, and the characteristics thereof were examined. In addition, this invention is not limited to the following Example at all.

[Example 1]
First, as a material for forming the hard coat layer 3, dipentaerythritol hexaacrylate (trade name KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), dimethylol tricyclodecane diacrylate (trade name: Light acrylate DCP-A; manufactured by Kyoeisha Chemical Co., Ltd.) ) And 1-hydroxycyclohexyl phenyl ketone (trade name IRGACURE 184; manufactured by Ciba Japan Co., Ltd.) was prepared using cyclohexanone as a solvent. Next, a TAC film having a thickness of 80 μm (manufactured by Fuji Film Co., Ltd.) was used as the base film 1, and the coating solution was applied onto the film using a coil bar. After the application, heat treatment was performed in an oven to evaporate the solvent. Then, ultraviolet rays were irradiated in a nitrogen atmosphere to form an acrylic hard coat layer 3 having a thickness of 7 μm.

  Next, a coating liquid in which an ultraviolet curable resin material composition, which is a material for forming the low refractive index layer 2, is dissolved or dispersed in a mixed solvent of 98.5% by mass at a concentration of 1.5% by mass. Prepared. The compounding amount of each component in the ultraviolet curable resin material composition and the compounding amount of each component in the mixed solvent are as follows.

<Ultraviolet curable resin material composition>
OPTOOL AR-110 36.2% by mass
Pentaerythritol tetraacrylate (crosslinking agent) 12.1% by mass
Hollow silica fine particles (particle size 50-60 nm) 45% by mass
1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) 4.8% by mass
X-22-2426 (leveling agent) 2.0 mass%
<Mixed solvent>
Butyl cellosolve (anti-whitening solvent) 3.0% by mass (1.97 times the mass of the composition)
t-Butyl alcohol (main solvent) 97.0% by mass (63.7 times the mass of the composition)

  As described above, OPTOOL AR110 (trade name; manufactured by Daikin Industries, Ltd.) is an amorphous fluorine composed of a combination of a functional group-containing fluorine-containing monomer, a crosslinking group-containing fluorine-containing monomer, and an adhesive group-containing monomer. It is a resin material composition. This amorphous fluororesin has both low refractive index properties and scratch resistance, adhesion with different materials, solubility of resin materials in general-purpose solvents, and coating solutions in which resin materials are dissolved in solvents The applicability of is optimized. Pentaerythritol tetraacrylate (trade name A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.) is a tetraacrylate of tetra (hydroxymethyl) methane (also known as pentaerythritol) as described above. This molecule has four acryloyl groups in the molecule and functions as a cross-linking agent that connects the polymer chains. The hollow silica fine particles are hollow fine particles having a particle diameter of 50 to 60 nm, and the thickness of the silica shell is approximately 7 nm. The refractive index of the hollow silica fine particles is 1.1 to 1.4. The hollow silica fine particles were used after being surface-treated in advance with an organic dispersant having a terminal acryloyl group (trade name KBM-5103; manufactured by Shin-Etsu Chemical Co., Ltd.). 1-hydroxycyclohexyl phenyl ketone (trade name IRGACURE 184; manufactured by Ciba Japan) is a photopolymerization initiator. X-22-2426 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) is a silicone leveling agent that improves the flatness of the surface of the coating layer and improves the scratch resistance and antifouling property of the surface of the low refractive index layer 2. is there.

  In Example 1, butyl cellosolve was blended in the mixed solvent at a concentration of 3.0% by mass. The content of butyl cellosolve in the coating liquid corresponds to 1.97 times the mass of the ultraviolet curable resin material composition.

Next, the coating liquid was applied onto the hard coat layer 3 formed on the base film 1 using a coil bar. After the application, heat treatment was performed at 80 ° C. for 1 minute 30 seconds to evaporate the solvent. Thereafter, ultraviolet rays are irradiated with an intensity of 300 mJ / cm ^{2 in} a nitrogen atmosphere, and a low refractive index layer 2 having a thickness of 100 nm is laminated on the hard coat layer 3 to produce an antireflection hard coat film 20. did. At this time, the relative humidity of the atmosphere was 63%.

  The whitening prevention effect was confirmed by haze measurement using HM-150 (trade name; manufactured by Murakami Color Research Laboratory Co., Ltd.) and visual observation in a dark room. Moreover, the reflectance of the antireflection hard coat film 20 was measured using a spectrophotometer V-550 (trade name; manufactured by JASCO Corporation). In the scratch resistance test, steel wool (Nippon Steel Wool Co., Ltd. Bonstar # 0000) was reciprocated 5 or 10 times on the surface of the low refractive index layer 2 while applying a load, and the presence or absence of scratches was visually confirmed. The antifouling properties were evaluated by the repellent and wiping properties of oily magic (Mackey black) and the fingerprint wiping properties.

The antireflection hard coat film 20 obtained in Example 1 was not whitened in the low refractive index layer 2, and the visual appearance was good. The characteristics are shown below.
<Optical characteristics>
Haze: 0.2%
Total light transmittance: 95.7%
Minimum reflectance: 0.51% (at 601 nm)
Luminous reflectance (Y value): 0.6%
<Mechanical properties>
Scratch resistance: Even when steel wool was reciprocated 10 times while applying a load of 400 g / cm ² , the surface of the low refractive index layer 2 was not damaged.
Antifouling properties: repels oil-based magic and good wiping performance of oil-based magic and fingerprints.

[Example 2]
In Example 2, butyl cellosolve was blended in the mixed solvent at a concentration of 8.0% by mass. The content of butyl cellosolve in the coating liquid corresponds to 5.25 times the mass of the ultraviolet curable resin material composition. The compounding amount of each component in the ultraviolet curable resin material composition and the compounding amount of each component in the mixed solvent are as follows.

<Ultraviolet curable resin material composition>
OPTOOL AR-110 32.4% by mass
Pentaerythritol tetraacrylate 10.8% by mass
Hollow silica fine particles (particle size 50-60 nm) 50% by mass
1-hydroxycyclohexyl phenyl ketone 4.8% by mass
FM7725 (leveling agent) 2.0% by mass
<Mixed solvent>
Butyl cellosolve 8.0% by mass (5.25 times the mass of the composition)
t-butyl alcohol 92.0% by mass (60.41 times the mass of the composition)

  Using the above coating liquid, an antireflection hard coat film 20 was produced in the same manner as in Example 1. At this time, the relative humidity of the atmosphere was 53%.

The antireflection hard coat film 20 obtained in Example 2 was not whitened in the low refractive index layer 2, and the visual appearance was good. The characteristics are shown below.
<Optical characteristics>
Haze: 0.3%
Total light transmittance: 94.9%
Minimum reflectance: 0.43% (at 651 nm)
Luminous reflectance (Y value): 0.86%
<Mechanical properties>
Scratch resistance: Even when steel wool was reciprocated 10 times while applying a load of 400 g / cm ² , the surface of the low refractive index layer 2 was not damaged.
Antifouling properties: repels oil-based magic and good wiping performance of oil-based magic and fingerprints.

[Example 3]
In Example 3, butyl cellosolve was blended in the mixed solvent at a concentration of 4.0% by mass. The content of butyl cellosolve in the coating liquid corresponds to 2.63 times the mass of the ultraviolet curable resin material composition. The compounding amount of each component in the ultraviolet curable resin material composition and the compounding amount of each component in the mixed solvent are as follows.

<Ultraviolet curable resin material composition>
OPTOOL AR-110 40.3% by mass
Pentaerythritol tetraacrylate 13.4% by mass
Hollow silica fine particles (particle size 50-60 nm) 40% by mass
1-hydroxycyclohexyl phenyl ketone 4.8% by mass
FM7725 1.5 mass%
<Mixed solvent>
Butyl cellosolve 4.0% by mass (2.63 times the mass of the composition)
t-butyl alcohol 96.0% by mass (63.04 times the mass of the composition)

  Using the above coating liquid, an antireflection hard coat film 20 was produced in the same manner as in Example 1. At this time, the relative humidity of the atmosphere was 65%.

The antireflection hard coat film 20 obtained in Example 3 was not whitened in the low refractive index layer 2, and the visual appearance was good. The characteristics are shown below.
<Optical characteristics>
Haze: 0.4%
Total light transmittance: 94.4%
Minimum reflectance: 0.52% (at 587 nm)
Luminous reflectance (Y value): 0.63%
<Mechanical properties>
Scratch resistance: Even when steel wool was reciprocated 10 times while applying a load of 500 g / cm ² , the surface of the low refractive index layer 2 was not damaged.
Antifouling property: The oil-based magic was repelled, and the oil-based magic and fingerprint wiping properties were good.

Further, the following tests were conducted.
Ethanol wipe test: The surface of the low refractive index layer 2 was wiped with steel wool (Bencot M-1) containing ethanol while applying a load of 500 g / cm ² , and the fluctuation of the pure water contact angle before and after that was measured by CA-X. (Trade name; manufactured by Kyowa Interface Chemical Co., Ltd.). Even when the ethanol wipe was performed 500 times, there was no change in the pure water contact angle.
Pencil hardness: measured using a Clemens type scratch hardness tester (trade name HA-301-E; manufactured by Tester Sangyo Co., Ltd.) while applying a load of 750 g / cm ² . The pencil hardness was 2H.
Initial adhesion: The result of the cross hatch test was 100/100, which was good.

[Example 4]
In Example 4, butyl cellosolve was blended in the mixed solvent at a concentration of 6.0% by mass. The content of butyl cellosolve in the coating liquid corresponds to 3.37 times the mass of the ultraviolet curable resin material composition. The compounding amount of each component in the ultraviolet curable resin material composition and the compounding amount of each component in the mixed solvent are as follows.

<Ultraviolet curable resin material composition>
OPTOOL AR-110 34.6% by mass
Pentaerythritol tetraacrylate 8.65% by mass
Hollow silica fine particles (particle size 50-60 nm) 50% by mass
1-hydroxycyclohexyl phenyl ketone 4.8% by mass
FM7725 2.0 mass%
<Mixed solvent>
Butyl cellosolve 6.0% by mass (3.37 times the mass of the composition)
t-Butyl alcohol 96.0% by mass (52.77 times the mass of the composition)

  Using the above coating liquid, an antireflection hard coat film 20 was produced in the same manner as in Example 1. At this time, the relative humidity of the atmosphere was 54%.

The antireflection hard coat film 20 obtained in Example 4 was not whitened in the low refractive index layer 2, and the visual appearance was good. The characteristics are shown below.
<Optical characteristics>
Haze: 0.4%
Total light transmittance: 95.7%
Minimum reflectance: 0.34% (at 559 nm)
Luminous reflectance (Y value): 0.40%
<Mechanical properties>
Scratch resistance: Even when steel wool was reciprocated 10 times while applying a load of 300 g / cm ² , the surface of the low refractive index layer 2 was not damaged.
Antifouling property: Although it does not repel oily magic, the oily magic and fingerprint wiping properties were good.

Ethanol wipe test: Even if the ethanol wipe was performed 500 times while applying a load of 500 g / cm ² , the pure water contact angle did not change.
Pencil hardness: The pencil hardness was 2H.
Initial adhesion: The result of the cross hatch test was 100/100, which was good.

[Example 5] to [Example 10]
In Examples 5 to 10, the amount of hollow silica fine particles and the type of the leveling agent, the change in characteristics depending on the amount, and the whitening prevention effect due to the amount of butyl cellosolve were investigated. Other than that was carried out similarly to Example 1, the antireflection hard coat film 20 was produced, and the characteristic was investigated.

[Comparative Example 1]
In Comparative Example 1, no butyl cellosolve was added to the solvent. Otherwise, a hard coat film was produced in the same manner as in Example 1, and the characteristics thereof were examined. The compounding amount of each component in the ultraviolet curable resin material composition and the compounding amount of the solvent are as follows.

<Ultraviolet curable resin material composition>
OPTOOL AR-110 32.8% by mass
Pentaerythritol tetraacrylate 10.9% by mass
Hollow silica fine particles (particle size 50-60 nm) 50% by mass
1-hydroxycyclohexyl phenyl ketone 4.8% by mass
X-22-22426 1.5 mass%
<Solvent>
t-Butyl alcohol 100.0% by mass (66.67 times the mass of the composition)

  Using the above coating solution, an antireflection hard coat film was produced in the same manner as in Example 1. At this time, the relative humidity of the atmosphere was 55%.

In the antireflection hard coat film obtained in Comparative Example 1, whitening and repelling in the low refractive index layer 2 were observed, and the visual appearance was poor. The characteristics are shown below.
<Optical characteristics>
Haze: 5.2%
Total light transmittance: 94.1%
In addition, mechanical properties such as scratch resistance and antifouling properties deteriorated.

Tables 1 and 2 are tables showing the compositions of the ultraviolet curable resin material composition and the mixed solvent and the evaluation results in Examples 1 to 10 and Comparative Example 1, respectively. In Table 2, the term “SW Max” indicates the maximum load (g / cm ² ) at which no scratch was generated on the surface of the low refractive index layer 2 in the scratch resistance test using steel wool.

[Example 11]
In Example 11, pentaerythritol triacrylate was used instead of pentaerythritol tetraacrylate. This molecule functions as a (meth) acrylic resin monomer having two or more (meth) acryloyl groups per molecule and a hydrophilic group, corresponding to claims 7-9. That is, it functions as a cross-linking agent that forms a cross-linked structure between polymer chains when the ultraviolet curable resin material composition layer is cured, and also functions to hydrate the remaining water molecules and hydrophilic groups to suppress whitening.

  The compounding amount of each component in the ultraviolet curable resin material composition and the compounding amount of each component in the mixed solvent are as follows. Butyl cellosolve was blended in the mixed solvent at a concentration of 6% by mass. The content of butyl cellosolve in the coating liquid corresponds to 3.37 times the mass of the ultraviolet curable resin material composition.

<Ultraviolet curable resin material composition>
OPTOOL AR-110 36.2% by mass
A-TMM-3 12.1% by mass
Hollow silica fine particles (particle size 50-60 nm) 45% by mass
1-hydroxycyclohexyl phenyl ketone 4.8% by mass
FM7725 2.0 mass%
<Mixed solvent>
Butyl cellosolve 6.0% by mass (3.37 times the mass of the composition)
t-Butyl alcohol 96.0% by mass (52.77 times the mass of the composition)

  A-TMM-3 (trade name; manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of pure pentaerythritol triacrylate. A-TMM-3 is obtained by changing a part of pentaerythritol into an ester with acrylic acid, and contains 37% by mass of pentaerythritol triacrylate. Instead of A-TMM-3, A-TMM-3L (trade name; manufactured by Shin-Nakamura Chemical Co., Ltd., a mixture containing 55% triacrylate), or A-TMM-3LN (trade name; Shin-Nakamura Chemical Co., Ltd.) Or a mixture containing 57% of triacrylate).

  In the same manner as in Example 1, first, a TAC film having a thickness of 80 μm was used as the base film 1, and an acrylic hard coat layer 3 having a thickness of 7 μm was formed on this film. Next, a coating solution obtained by dissolving or dispersing the ultraviolet curable resin material composition in the mixed solvent was applied onto the hard coat layer 3 using a coil bar. After coating, the paint film was breathed three times. Thereafter, in the same manner as in Example 1, an antireflection hard coat film 20 was produced.

The antireflection hard coat film 20 obtained in Example 11 had no whitening in the low refractive index layer 2 and the visual appearance was good. The characteristics are shown below.
<Optical characteristics>
Haze: 0.5%
Total light transmittance: 95.4%
Minimum reflectance: 0.48% (at 581 nm)
Luminous reflectance (Y value): 0.58%
<Mechanical properties>
Scratch resistance: Even when the steel wool was reciprocated 10 times while applying a load of 300 g / cm ² , the surface of the low refractive index layer 2 was not damaged.
Antifouling properties: repels oil-based magic and good wiping performance of oil-based magic and fingerprints.

[Example 12] and [Example 13]
In Examples 12 and 13, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and tripropylene glycol monomethyl ether were used in place of butyl cellosolve as anti-whitening solvents, respectively. Except this, it carried out similarly to Example 11, and produced the anti-reflective hard coat film 20, and investigated the characteristic.

Tables 3 and 4 are tables showing the composition of the ultraviolet curable resin material composition and the mixed solvent in Examples 11 to 13 and the evaluation results. In Table 4, the term “SW Max” indicates the maximum load (g / cm ² ) in which no scratch was generated on the surface of the low refractive index layer 2 in the scratch resistance test using steel wool.

  From Examples 1 to 13 and Comparative Example 1, it was revealed that butyl cellosolve functions as an anti-whitening solvent and a good antireflection film without whitening can be obtained even in a high humidity environment.

  Although the present invention has been described based on the embodiments and examples, it is needless to say that the present invention is not limited to these examples and can be appropriately changed without departing from the gist of the invention. .

  The antireflection film of the present invention can be suitably used as an antireflection film for various displays such as liquid crystal televisions, organic EL televisions, personal computers and portable game machines. Moreover, the ultraviolet curable resin material composition of the present invention can be suitably used for forming an antireflection layer on the surface of a plastic molded product or a coated product.

DESCRIPTION OF SYMBOLS 1 ... Base film, 2 ... Low refractive index layer, 3 ... Hard-coat layer (high refractive index layer),
10 ... Antireflection film, 20 ... Antireflection hard coat film

JP-A-8-244178 (Claims 1, 2-5 and 10) Japanese Patent Laying-Open No. 2005-99778 (claims 1, 3 and 10, pages 6-8, 10, 14 and 15 and FIG. 1) Japanese Patent Laying-Open No. 2005-283611 (Claim 1, pages 3-7) JP 2008-115329 A (claims 1, 4, 5, 7-9 and 12 pages)

Claims (13)

An ultraviolet curable resin material composition containing a fluorine-containing resin monomer and / or oligomer thereof, hollow or porous silica fine particles having a particle diameter of 100 nm or less, and a polymerization initiator,
80.0-99.9% by weight of the main solvent,
0.1 to 20.0% by mass in a mixed solvent containing a hydrophilic anti-whitening solvent having a boiling point higher than that of water and a surface tension of 35 dyn / cm (25 ° C.) or less. An ultraviolet curable resin material composition coating liquid.   The ultraviolet curable resin material composition according to claim 1, wherein the main solvent is a monohydric alcohol having 4 carbon atoms, and the whitening prevention solvent is an ether or ketone having 6 or more carbon atoms having a hydrophilic group. Coating liquid.   The ultraviolet curable resin material composition coating liquid according to claim 1, wherein a blending amount of the fluorine-containing resin monomer and / or an oligomer thereof in the ultraviolet curable resin material composition is 10 to 50% by mass.   The ultraviolet curable resin material composition coating liquid according to claim 1, wherein a blending amount of the hollow or porous silica fine particles in the ultraviolet curable resin material composition is 30 to 70% by mass.   2. The ultraviolet curable resin material composition coating according to claim 1, wherein the hollow or porous silica fine particles are surface-treated with an organic dispersant having a (meth) acryloyl group, a vinyl group, or an epoxy group at a terminal. liquid.   The ultraviolet curable resin material composition coating liquid of Claim 1 whose compounding quantity of the said polymerization initiator in the said ultraviolet curable resin material composition is 0.1-10.0 mass%.   The ultraviolet curable resin material composition coating liquid according to claim 1, wherein the ultraviolet curable resin material composition contains a monomer having two or more (meth) acryloyl groups and / or an oligomer thereof.   The ultraviolet curable resin material composition coating liquid according to claim 1, wherein the ultraviolet curable resin material composition contains a (meth) acrylic resin monomer having a hydrophilic group and / or an oligomer thereof. The ultraviolet curable resin material composition coating liquid according to claim 8, wherein the hydrophilic group is a hydroxy group —OH, a carboxy group —COOH, and / or an amino group —NH ₂ .   The ultraviolet curable resin material composition coating liquid according to claim 1, wherein the ultraviolet curable resin material composition contains 0.01 to 10% by mass of a leveling agent.   The ultraviolet curable resin composition according to claim 10, wherein the leveling agent is a silicone oligomer having one or more (meth) acryloyl groups, vinyl groups, or epoxy groups.   The layer of the ultraviolet curable resin material composition coating liquid according to any one of claims 1 to 11 is applied directly or via a functional layer to a base film, and the mixed solvent is applied from the coating liquid layer. The antireflective film in which a low refractive index layer is formed on the outermost surface of the base film by curing the obtained ultraviolet curable resin material composition layer after evaporating.   The hard coat layer having a larger refractive index than the base film is provided as the functional layer on the base film, and the low refractive index layer is provided by being laminated on the hard coat layer. Antireflection film.

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