JP5230902B2 - Fluorine-containing curable coating liquid, fluorine-containing cured film, and anti-reflection material using fluorine-containing cured film - Google Patents

Description

  The present invention is applied to the surface of a plasma display panel (PDP), a liquid crystal display screen (LCD), etc., and can exhibit a low refractive index and a low reflectance of the film, and improve the scratch resistance and wear resistance of the film surface. The present invention relates to a fluorine-containing curable coating liquid, a fluorine-containing cured film, and a low reflection material using the fluorine-containing cured film.

  Electronic image display devices such as a cathode ray tube display (CRT), plasma display (PDP), and liquid crystal display (LCD) have little reflection of light emitted from an external light source such as a fluorescent lamp in order to improve the visibility. Is required. Therefore, a method is generally known in which an antireflection film formed by providing an antireflection layer on the surface of a transparent plastic film substrate is bonded to the display surface.

  Conventionally, in this antireflection film, the antireflection layer generally has a multilayer structure in which a plurality of layers of a high refractive index material and a low refractive index material are laminated in order to obtain high antireflection performance. If a material having a refractive index is used, an antireflection film having a low refractive index in a wide wavelength region can be obtained even in a single layer configuration. Since the antireflection film having a single layer structure has a simple layer structure as compared with that having a multilayer structure, it is excellent in productivity and cost performance. Low refractive index materials include resins containing fluorine atoms in the molecule. However, if the fluorine content is excessively increased to lower the refractive index, the intermolecular force of the fluorine itself is small. The contained molecules tend to be soft, resulting in a problem that the strength of the coating film is lowered and the coating film surface is easily damaged.

  Therefore, a low refractive index layer using hollow silica fine particles having a cavity inside in addition to the fluorine-containing resin has been proposed (see, for example, Patent Document 1). That is, a coating solution for a low refractive index layer is described in which a fluorine-containing resin having a polymerizable double bond, hollow silica fine particles, and reactive silicone are blended.

Furthermore, an antireflection laminate is proposed in which a low refractive index layer having a refractive index of 1.45 or less is provided on a light-transmitting substrate (see, for example, Patent Document 2). Such a low refractive index layer contains an ionizing radiation curable resin composition and silica fine particles that are surface-treated with a silane coupling agent having an ionizing radiation curable group and that are porous or hollow inside. Further, the low refractive index layer may contain a fluorine-based or silicon-based compound having compatibility with the ionizing radiation curable resin composition and the silica fine particles.
JP 2005-37904 A (pages 29 and 45) JP-A-2005-99778 (2nd page, 5th page, 6th page, 11th page, 13th page, 22nd page and 23rd page)

  However, in the fluorine-containing curable coating liquid described in Patent Document 1, although the low refractive index and low reflectance of the obtained film are achieved by the fluorine-containing resin and the hollow silica fine particles, the hollow silica fine particles themselves react on the surface. Therefore, the affinity (binding property) with the fluorine-containing resin having a polymerizable functional group is not sufficient. Furthermore, even if reactive silicone is copolymerized with a fluorine-containing resin having a polymerizable double bond to form a matrix, the hollow silica fine particles are not incorporated into the matrix but are separated as a dispersed phase. Accordingly, there is a problem that the strength and hardness of the film obtained by curing the fluorine-containing curable coating liquid is low, and as a result, the scratch resistance and wear resistance on the surface of the film are insufficient.

  On the other hand, the silica fine particles constituting the low refractive index layer described in Patent Document 2 are bonded to the ionizing radiation curable resin composition via the ionizing radiation curable group of the silane coupling agent introduced on the surface, and uniformly dispersed. Thus, the effect of improving the hardness of the coating film can be exhibited. That is, Patent Document 2 aims to provide an antireflection laminate having a low refractive index and excellent mechanical strength by using an ionizing radiation curable resin composition not containing fluorine and modified silica fine particles. (Page 6 of Patent Document 2) and is not intended to develop a function based on a fluorine compound. This is because when the fluorine content increases, the hardness and strength of the coating film decrease (page 5, paragraph 5 of Patent Document 2).

  Specifically, low-refractive-index layer formation of 12.85 parts by mass (64% by mass) of the surface-treated hollow silica sol and 1.43 parts by mass (36% by mass) of pentaerythritol triacrylate forming the ionizing radiation curable resin composition. The composition for use is disclosed (Examples 1 to 6 described on pages 22 and 23 of Patent Document 2). In this case, the proportion of the surface-treated hollow silica sol is excessively increased, in other words, the proportion of the ionizing radiation curable resin composition is excessively decreased, and the scratch resistance and abrasion resistance of the obtained coating film are decreased and fluorine is contained. Therefore, the effect of low refractive index and low reflectance based on fluorine cannot be obtained.

  In addition, although it describes that a fluorine-type compound is mix | blended as another component if necessary, since the content is a small amount of 0.01-10 mass% (refer to the 11th page and 13th page of patent document 2). ), The effect based on the fluorine-based compound is not sufficiently exhibited.

  Therefore, the object of the present invention is to exhibit low refractive index and low reflectance for the formed film, improve strength and hardness, and improve scratch resistance and wear resistance of the film surface. An object of the present invention is to provide a fluorine-containing curable coating liquid, a fluorine-containing cured film, and a reduced reflection material using the fluorine-containing cured film.

In order to achieve the above-mentioned object, the fluorine-containing curable coating liquid of the first invention in the present invention has a film-forming property, a fluorine-containing compound having a polymerizable double bond, and the following chemical formula (1): Hollow silica fine particles modified with the silane coupling agent shown, and the content of the hollow silica fine particles is 20 to 60% by mass in the total amount of the fluorine-containing compound and the hollow silica fine particles, The fluorine-containing compound having a polymerizable double bond includes a fluorine-containing monomer having a structure in which a fluorine atom is introduced into the molecule as a methylene fluoride group or a fluoride methine group, an ester solvent, and a ketone solvent. or at least one selected from fluorine-containing reactive polymer in an alcohol solvent having a polymerizable double bond in a soluble, the hollow silica fine particles is at least at 200 to 280 ° C. It is time hydrothermal treatment, the modified hollow silica fine particles is characterized in that the heat mass decrease in the thermal mass measurement in a temperature range of 200 to 500 ° C. is 2 mass% or more.

(In the formula, Z is a (meth) acryloyloxy group, R ¹ is an alkylene group having 1 to 4 carbon atoms, and R ² is a hydrogen atom, a methyl group or an ethyl group. )

Curable fluorine-containing coating solution of the second aspect, in the first aspect, is characterized in that it contains further fluorine (meth) acrylic acid ester represented by the following chemical formula (2).

(In the formula, X and Y are either a (meth) acryloyloxy group or a hydroxyl group, and at least one is a (meth) acryloyloxy group.)
Is.

In the fluorine-containing curable coating liquid of the third invention, in the first or second invention, the fluorine-containing compound is a fluorine-containing polyfunctional (meth) acrylate.
The fluorine-containing cured film of the fourth invention is obtained by curing the fluorine-containing curable coating liquid of any one of the first to third inventions.

The fluorine-containing cured film of the fifth invention is a film surface when water is allowed to stand for 30 minutes on the surface of the film obtained by curing the fluorine-containing curable coating liquid of any one of the first to third inventions. The change in reflectance at a light wavelength of 600 nm before and after being left in the portion where water is left is 0.3% or less.

The antireflection material of the sixth invention is characterized in that the fluorine-containing cured film of the fourth or fifth invention is formed on one side or both sides of the substrate directly or via layers having different refractive indexes. It is what.

According to the present invention, the following effects can be exhibited.
In the fluorine-containing curable coating liquid according to the first aspect of the invention, a hollow film modified with a fluorine-containing compound having a film forming property and having a polymerizable double bond and the silane coupling agent represented by the chemical formula (1) Silica fine particles are contained, and the content of the hollow silica fine particles is set to 20 to 60% by mass in the total amount of the fluorine-containing compound and the hollow silica fine particles. For this reason, when the (meth) acryloyloxy group of the silane coupling agent and the polymerizable double bond of the fluorine-containing compound are copolymerized, the hollow silica fine particles are integrally bonded to the fluorine-containing compound, and the fluorine-containing curable property. The strength and hardness of the coating obtained from the coating liquid can be improved, and the scratch resistance and wear resistance of the coating surface can be improved. In this case, since the content of the hollow silica fine particles modified with the silane coupling agent is higher than the conventional amount, the above effect can be sufficiently exhibited. Furthermore, a low refractive index and a low reflectance can be exhibited by the hollow part of fluorine and hollow silica fine particles with respect to the formed film.

Further, the modified hollow silica fine particles have a thermal mass reduction of 2% by mass or more in a thermal mass measurement in a temperature range of 200 to 500 ° C. As a result, scratch resistance and wear resistance can be improved.
The hollow silica fine particles are obtained by hydrothermal treatment at 200 to 280 ° C. for at least 5 hours. By this hydrothermal treatment, the outer shell of the hollow silica fine particles is densified, and moisture is hardly adsorbed on the surface. As a result, it is possible to improve the water resistance of the skin layer.

The curable fluorine-containing coating solution of the second aspect of the invention includes a fluorine-containing (meth) acrylic acid ester represented by the following Symbol Chemical Formula (2) further. For this reason, in addition to the effect of 1st invention, effects, such as antifouling property based on a fluorine, can be exhibited favorably.

In the fluorine-containing curable coating liquid of the third invention, since the fluorine-containing compound is a fluorine-containing polyfunctional (meth) acrylic acid ester, the formed film has a crosslinked structure. Therefore, in addition to the effects of the first or second invention, the strength and hardness of the coating can be improved.

The fluorinated cured film of the fourth invention, since those obtained by curing a curable fluorine-containing coating solution of the invention according to the first to third one of the third from the first for the fluorinated cured film The effect of the invention according to any of the above can be exhibited.

In the fluorine-containing cured film of the fifth invention, when water is left on the surface of the film obtained by curing the fluorine-containing curable coating liquid of any one of the first to third inventions , The change in reflectance at a light wavelength of 600 nm before and after being left in the water leaving portion is set to 0.3% or less. Therefore, in addition to the effects of the first to third aspects of the fluorine-containing cured film, water resistance can be imparted using a change in light reflectance as an index.

In the antireflection material of the sixth invention, the fluorine-containing cured film of the fourth or fifth invention is obtained by forming the fluorine-containing cured film of the fourth or fifth invention directly or on both sides of the base material through layers having different refractive indexes. . Therefore, the effects of the fourth or fifth invention can be exhibited with respect to the fluorinated cured film, and the antireflection material is preferably used as a display material such as a plasma display (PDP) or a liquid crystal display screen (LCD). it can.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The fluorine-containing curable coating liquid of this embodiment is a hollow silica fine particle modified with a fluorine-containing compound having a film forming property and a polymerizable double bond and a silane coupling agent represented by the following chemical formula (1) (Hereinafter also referred to as modified hollow silica fine particles). In the present invention, both acryl and methacryl are referred to as (meth) acryl.

(In the formula, Z is a (meth) acryloyloxy group, R ¹ is an alkylene group having 1 to 4 carbon atoms, and R ² is a hydrogen atom, a methyl group or an ethyl group.)
First, the said fluorine-containing compound is demonstrated. Fluorine atoms (also referred to simply as fluorine in the present invention) have a very low polarizability, so fluorine-containing monomers have low molecular cohesion and can obtain low surface energy properties after film formation, while film forming properties are improved. It has the property of being scarce. Here, the film formability represents the property that a fluorine-containing cured film (hereinafter also simply referred to as a film) is formed without being repelled when applied on a substrate such as a synthetic resin film. It is judged that a film having a uniform thickness can be formed with good thickness when the solution diluted in step 1 is applied to a substrate and heated to remove the solvent. For example, when the trifluoromethyl group is oriented, the critical surface tension is 6 dyn / cm, while the tetrafluoroethylene group is 18 dyn / cm, so that fluorine in the form of a methylene fluoride group or a fluorinated methine group is used. The film-formability is improved by introducing. Further, from the viewpoint of increasing the cohesive force of molecules, a technique of polymerizing is also effective. Therefore, as the fluorine-containing compound having the film forming property and having a polymerizable double bond, a fluorine-containing monomer having a structure in which a fluorine atom is introduced into the molecule as a methylene fluoride group or a fluorinated methine group, Examples thereof include a fluorine-containing reactive polymer that is soluble in a solvent and has a polymerizable double bond.

  In the fluorine-containing monomer having a structure in which the fluorine atom is introduced into the molecule as a methylene fluoride group or a fluorinated methine group, almost all of the fluorine atoms are introduced into the molecule as a methylene fluoride group or a fluorinated methine group. As long as it is a monomer, all known monomers can be used. That is, the polymerizable double bond may be either one (monofunctional) monomer, two or more (polyfunctional) monomers, or a mixture thereof. These fluorine-containing compounds can increase the strength and hardness of the film obtained by curing the fluorine-containing curable coating liquid, and can improve the scratch resistance and wear resistance of the film surface. Among the fluorine-containing compounds, a fluorine-containing polyfunctional (meth) acrylic acid ester is preferable because a crosslinked structure can be formed and the strength and hardness of the cured film are high.

  Specific examples of the fluorine-containing polyfunctional (meth) acrylic acid ester include, for example, 1,3-bis {(meth) acryloyloxy} -2,2-difluoropropane, 1,4-bis {(meth) acryloyloxy}. -2,2,3,3-tetrafluorobutane, 1,5-bis {(meth) acryloyloxy} -2,2,3,3,4,4-hexafluoropentane, 1,6-bis {(meta ) Acryloyloxy} -2,2,3,3,4,4,5,5-octafluorohexane, 1,7-bis {(meth) acryloyloxy} -2,2,3,3,4,4, 5,5,6,6-decafluoroheptane, 1,8-bis {(meth) acryloyloxy} -2,2,3,3,4,4,5,5,6,6,7,7-dodeca Fluorooctane, 1,9-bis {(meth) acrylo Ruoxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorononane, 1,10-bis {(meth) acryloyloxy} -2 , 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane, 1,11-bis {(meth) acryloyloxy} -2 , 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10-octadecafluoroundecane, 1,12-bis {(meth) acryloyl Oxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-eicosafluorododecane, 1, 8-bis {(meth) acryloyloxy} -2,7-dihydroxy 4,4,5,5-tetrafluorooctane, 1,7-bis {(me ) Acryloyloxy} -2,8-dihydroxy 4,4,5,5-tetrafluorooctane, 2,7-bis {(meth) acryloyloxy} -1,8-dihydroxy 4,4,5,5-tetrafluoro Octane, 1,10-bis {(meth) acryloyloxy} -2,9-dihydroxy 4,4,5,5,6,6,7,7-octafluorodecane, 1,9-bis {(meth) acryloyl Oxy} -2,10-dihydroxy 4,4,5,5,6,6,7,7-octafluorodecane, 2,9-bis {(meth) acryloyloxy} -1,10-dihydroxy 4,4 5,5,6,6,7,7-octafluorodecane, 1,2,7,8-tetrakis {(meth) acryloyloxy} -4,4,5,5-tetrafluorodecane, 1,2,8 , 9-Tetra Kiss {(meth) acryloyloxy} -4,4,5,5,6,6-hexafluorononane, 1,2,9,10-tetrakis {(meth) acryloyloxy} -4,4,5,5 6,6,7,7-octafluorodecane, 1,2,10,11-tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6,7,7,8,8-deca Fluoroundecane, 1,2,11,12-tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododecane, 1, 10-bis (α-fluoroacryloyloxy) -2,9-dihydroxy 4,4,5,5,6,6,7,7-octafluorodecane, 1,9-bis (α-fluoroacryloyloxy) -2 , 10-Dihydroxy 4,4,5,5,6 , 6,7,7-octafluorodecane, 2,9-bis (α-fluoroacryloyloxy) -1,10-dihydroxy 4,4,5,5,6,6,7,7-octafluorodecane, , 2,9,10-tetrakis (α-fluoroacryloyloxy) -4,4,5,5,6,6,7,7-octafluorodecane, 1,2,11,12-tetrakis (α-fluoroacryloyl) Oxy) -4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododecane and the like. In use, these are used alone or as a mixture.

  The fluorine-containing polyfunctional (meth) acrylic acid ester is produced by a known method. For example, a ring-opening reaction between a corresponding fluorine-containing epoxy compound and (meth) acrylic acid, a corresponding fluorine-containing polyhydric alcohol, or a fluorine-containing (meta) group having a hydroxyl group (hydroxyl group) obtained as an intermediate by the ring-opening reaction. ) Produced by an esterification reaction between an acrylic ester and (meth) acrylic chloride.

  The solvent-soluble fluorine-containing reactive polymer having a polymerizable double bond has a main chain derived from a fluorine-containing ethylenic monomer and has a reactive group for crosslinking and curing. As the solvent-soluble solvent, ester solvents such as ethyl acetate and propyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alcohol solvents such as isopropyl alcohol and 2-butanol are preferable. Examples of the reactive group include a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, and an epoxy group. Such a fluorine-containing reactive polymer that is soluble in a solvent and has a polymerizable double bond has a high molecular weight, so it has good film forming properties while containing fluorine, and is crosslinked and cured using reactive groups after film formation. By doing so, a solvent-insoluble cured layer can be obtained.

  Such a solvent-soluble fluorine-containing reactive polymer having a polymerizable double bond usually has a content of a group having a polymerizable double bond of 1 to 20% by mass, preferably 5 to 15% by mass. Weight) The average molecular weight is usually 1 to 500,000, preferably 3 to 200,000. Specific examples of the fluorine-containing reactive polymer include those disclosed in republished patent WO02 / 018457.

  The content of the fluorine-containing compound having film-forming properties and having a polymerizable double bond is preferably 40 to 80% by mass in the total amount (solid content) with the modified hollow silica fine particles. More preferably, it is -60 mass%. When the content of the fluorine-containing compound is less than 40% by mass, the strength and hardness of the film obtained by curing the fluorine-containing curable coating liquid tend to be insufficient, and the film surface has scratch resistance and abrasion resistance. descend. On the other hand, when the content exceeds 80% by mass, the content of the modified hollow silica fine particles is relatively decreased, the balance is deteriorated, the scratch resistance and wear resistance of the coating surface are lowered, and the reflectance of the coating is also increased.

Next, the hollow silica fine particles modified with the silane coupling agent represented by the chemical formula (1) will be described.
Since the hollow silica fine particles modified with the silane coupling agent contain air therein, the coating formed by curing the fluorine-containing curable coating liquid is reduced in refractive index and reflectance. In addition, it is possible to improve the scratch resistance and wear resistance of the film by using inorganic fine particles called silica fine particles. Examples of the silane coupling agent include γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, and γ-acryloyloxypropyltriethoxysilane.

The hollow silica fine particles are fine particles in which silica (silicon dioxide, SiO ₂ ) is formed in a substantially spherical shape and has a hollow portion in the outer shell, and the average particle diameter is about 10 to 100 nm. The thickness of the outer shell of the hollow silica fine particles is about 1 to 50 nm, and the proportion of the hollow portion in the hollow silica fine particles is 10 to 60%. The refractive index of the hollow silica fine particles is a low refractive index of 1.1 to 1.4.

  The modification of the hollow silica fine particles with the silane coupling agent is performed as follows. First, for example, the above-mentioned silane coupling agent is added to and mixed with hollow silica fine particles dispersed in an organic solvent, and distilled water is added to this mixture to perform ordinary hydrolysis and condensation reactions. The solid content of the hollow silica fine particles is preferably 1 to 70% by mass, and more preferably 15 to 40% by mass. In this case, the order of adding the silane coupling agent is not particularly limited. As for the compounding quantity of the distilled water to mix, it is desirable that it is 3-5 times by mass with respect to a silane coupling agent. The operation for carrying out the hydrolysis reaction and the condensation reaction is carried out by refluxing the organic solvent for 3 to 7 hours under normal pressure with stirring.

  Examples of the organic solvent include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, Amides such as dimethylacetamide and N-methylpyrrolidone are mentioned. These organic solvents can be used alone or in combination of two or more. The resulting modified hollow silica fine particles can be isolated by centrifugation or the like, but can also be subjected to a subsequent step while the organic solvent is present.

  The content of hollow silica fine particles (referred to as modified hollow silica fine particles) obtained by modification in this way is 20 to 60% by mass and 40 to 60% by mass in the total amount with the fluorine-containing compound. Is desirable. When the content is less than 20% by mass, the content of the modified hollow silica fine particles is small, and it becomes impossible to sufficiently reduce the refractive index and the reflectance of the resulting film, and the scratch resistance and Wear resistance is reduced. On the other hand, when it exceeds 60% by mass, the excessive modified hollow silica fine particles cannot react with the fluorine-containing compound, and the polymer remains, so that the scratch resistance and wear resistance of the fluorine-containing cured film surface tend to decrease. Indicates. As a result of the copolymerization and bonding of the (meth) acryloyloxy group contained in the silane coupling agent of the modified hollow silica fine particles and the polymerizable double bond of the fluorine-containing compound, the function of the modified hollow silica fine particles and the fluorine-containing compound are obtained. Are expressed synergistically and continuously.

The modified hollow silica fine particles will be further described. The modified hollow silica fine particles are produced by subjecting the surface of the hollow silica fine particles having an average particle diameter of 5 to 100 nm and a specific surface area of 50 to 1000 m ² / g with the silane coupling agent. Is done. Specifically, an organosilyl group (monoorganosilyl, diorganosilyl, or triorganosilyl group) is bonded to the surface of the hollow silica fine particle by a hydrolysis reaction between the silanol group on the surface of the hollow silica fine particle and the silane coupling agent. In addition, it has an organic group directly bonded to a large number of silicon atoms on its surface.

  Since the modified hollow silica fine particles are modified by the silane coupling agent, an excellent effect not found in conventional silica fine particles or hollow silica fine particles can be exhibited. This excellent effect is mainly based on the fact that the modified hollow silica fine particles are excellent in compatibility with the fluorine-containing compound. For this reason, when the modified hollow silica fine particles are mixed with a fluorine-containing compound, aggregation of the modified hollow silica fine particles can be suppressed, and a film having no transparency and excellent transparency can be obtained. Further, in the film, the polymerizable double bond group of the silane coupling agent and the fluorine-containing compound is chemically bonded to form a strong film, so that the scratch resistance and wear resistance of the film can be dramatically improved. . In addition, since the modified hollow silica fine particles contain a hollow portion (cavity) inside, the coating obtained by curing the coating liquid combined with the fluorine-containing compound has a lower refractive index and lower reflectance than the conventional coating. .

Specifically, the hollow silica fine particles used as the raw material for the modified hollow silica fine particles can be produced through the following first to fourth steps.
That is, in the first step, an aqueous solution of silicate or an acidic silicate solution and an aqueous solution of an alkali-soluble inorganic compound in an alkaline aqueous solution having a pH of 10 or more, or an alkaline aqueous solution having a pH of 10 or more in which seed particles are dispersed as necessary. At the same time, a core particle dispersion is prepared in which the molar ratio of silica to an inorganic compound other than silica is in the range of 0.3 to 1.0.

Next, in the second step, a silica source is added to the core particle dispersion to form a first silica coating layer on the core particle surface.
Next, in the third step, an acid is added to the dispersion in which the first silica coating layer is formed to remove a part or all of the elements constituting the core particles.

  Finally, in the fourth step, an aqueous alkali solution and an organosilicon compound or a partial hydrolyzate thereof are added to the dispersion of the hollow silica fine particles obtained in the third step, and the second silica coating layer is formed on the hollow silica fine particles. Form.

  Furthermore, it is preferable to add a fifth step in which the hollow silica fine particle dispersion obtained in the fourth step is hydrothermally treated at 200 ° C. for at least 5 hours. By this hydrothermal treatment, hollow silica fine particles having a dense outer shell can be obtained. By densifying the outer shell, it becomes difficult to adsorb moisture, and the water resistance of the hollow silica fine particles can be improved. As a result, the modified hollow silica fine particles obtained by modifying the hollow silica fine particles and the fluorine-containing compound It is possible to improve the water resistance of a film obtained by curing a fluorine-containing curable coating liquid in combination. The upper limit of the hydrothermal treatment temperature is preferably 280 ° C. Even when the temperature exceeds 280 ° C., the outer shell of the hollow silica fine particles is not further densified, and the hollow silica fine particles may aggregate instead. The hydrothermal treatment time varies depending on the hydrothermal treatment temperature, but is preferably 5 hours or more and 20 hours or less, more preferably 10 hours or more and 20 hours or less. A hydrothermal treatment time of less than 5 hours is not preferable because the outer shell cannot be sufficiently densified. On the other hand, if it exceeds 20 hours, the outer shell of the hollow silica fine particles is not further densified, and the productivity of the hollow silica fine particles is reduced, which is not industrially preferable.

  In the method for producing modified hollow silica fine particles, an organosol having a silica concentration of 1 to 70% by mass is prepared, and the silane coupling agent and the alkali catalyst are added within a range of 30 to 300 ° C. The said silane coupling agent is made to react with hollow silica fine particles on the conditions whose quantity is 0.1-50 mass%. In the method for producing an organosol, a silica sol composed of hollow silica fine particles prepared using water as a dispersion medium is solvent-substituted to obtain an organosol. An organic solvent is used as the type of solvent for solvent substitution. The type of organic solvent is not particularly limited as long as it does not adversely affect the surface coating of the hollow silica fine particles by the silane coupling agent. As examples of such organic solvents, solvents such as alcohols, glycols, esters, ketones, nitrogen compounds, and aromatics can be used. Usually, alcohols such as methanol, ethanol and isopropyl alcohol are selected.

  The addition amount of the silane coupling agent is usually 1 to 50 parts by mass and preferably 3 to 25 parts by mass with respect to 100 parts by mass of the hollow silica fine particles. If the amount added is less than 1 part by mass, the proportion of untreated hollow silica fine particles increases, and if it exceeds 50 parts by mass, the silane coupling agent becomes excessive, which is not economical.

  The kind of the alkali catalyst is not particularly limited, and ammonia, an alkali metal hydroxide, an amine compound, and the like are preferably used. These alkalis may be added in the form of an aqueous solution. The addition amount of the alkali catalyst is not particularly limited, and is preferably 20 to 2000 ppm with respect to the organosol in which the hollow silica fine particles are dispersed, although it depends on the kind of the alkali catalyst. When this addition amount is less than 20 ppm, the reaction of the silane compound on the surface of the hollow silica fine particles may not sufficiently proceed. On the other hand, when it exceeds 2000 ppm, the dispersibility when the hollow silica fine particles are dispersed in the binder may be reduced due to the excess alkali, and there is a problem that the alkali catalyst remains in the composition. .

  The amount of water in the reaction solution is preferably 10 to 50% by mass, more preferably 10 to 40% by mass, based on the amount of silica. If the moisture content is in the range of 10 to 50% by mass, the surface of the hollow silica fine particles reacts with the silane coupling agent to effect surface treatment effectively. When the water content is less than 10% by mass, the surface treatment efficiency is low and stable surface treatment is not performed, and when it exceeds 50% by mass, the tendency of the silane coupling agents to react with each other increases, resulting in the surface treatment of the hollow silica fine particles. It becomes insufficient.

  About reaction temperature when making a silane coupling agent react with hollow silica fine particles, if it is less than 30 degreeC, reaction rate will be slow and it is not practical. On the other hand, when the boiling point of the solvent of the organosol is exceeded, the evaporation of the solvent may cause an increase in the water content, etc., but this is not preferable. However, when the reaction is performed using a pressure vessel, the temperature is up to 300 ° C. Can be reacted. The reaction temperature is preferably in the temperature range from 40 ° C. to less than the boiling point of the solvent.

  The reaction time for reacting the silane coupling agent with the hollow silica fine particles is less than 0.1 hour, and the reaction may not sufficiently proceed, which is not practical. On the other hand, even if the reaction is carried out for more than 100 hours, no improvement is seen in the yield and the like, and it is not necessary to continue the reaction further. This reaction time is preferably 3 to 30 hours. The surface-treated hollow silica fine particles may be further substituted with an organic solvent using the same method as described above, if necessary.

  The average particle diameter of the modified hollow silica fine particles is preferably 5 to 100 nm. Modified hollow silica fine particles having an average particle diameter in this range can obtain a transparent film. It is difficult to produce modified hollow silica fine particles having an average particle size of less than 5 nm. On the other hand, when the thickness exceeds 100 nm, light scattering is increased, and reflection is increased in the thin film, so that the antireflection function cannot be exhibited. A more preferable average particle diameter range of the modified hollow silica fine particles is 30 to 80 nm.

The specific surface area of the modified hollow silica fine particles is preferably in the range of 50 to 1000 m ² / g in order to obtain the dispersibility and stability of the modified hollow silica fine particles in the solvent or film formation. When the specific surface area is less than 50 m ² / g, it is difficult to obtain modified hollow silica fine particles having a low refractive index. On the other hand, when it exceeds 1000 m ² / g, the dispersion stability of the modified hollow silica fine particles is lowered, which is not desirable. A more preferable range of the modified hollow silica fine particles is 50 to ²⁰⁰ m ² / g.

  In the modified hollow silica fine particles, the amount of the silane coupling agent bonded to the hollow silica fine particles by the modification treatment can be easily known by a thermal mass measurement method (TG). This thermal mass measurement method (Thermogravimetry Analysis) measures the mass change of the sample with respect to the temperature rise (or fall) of the sample, and the mass change curve with respect to the temperature change is called a TG curve. ing.

  The modified hollow silica fine particles preferably exhibit a mass loss of 2% by mass or more in thermal mass measurement in a temperature range of 200 to 500 ° C. In a fluorine-containing curable film formed by blending modified hollow silica fine particles having a thermal mass reduction of less than 2% by mass, whitening occurs and scratch resistance and wear resistance are insufficient. About thermal mass reduction | decrease, what shows the thermal mass reduction | decrease of 3 mass% or more in a temperature range 200-500 degreeC is further more preferable. However, if the thermal mass reduction exceeds 10% by mass, the reaction between the particles tends to occur, so that the stability as the sol of the modified hollow silica fine particles and the stability as the fluorine-containing cured coating liquid are not preferable. .

  The water resistance of a fluorine-containing cured film can be evaluated by the reflectance of the film. In a film having no water resistance, when water droplets are left on the film for 30 minutes, moisture is adsorbed and the refractive index increases, resulting in an increase in the reflectance of light on the film surface. In the fluorine-containing curable film obtained by using hollow silica fine particles that have been subjected to hydrothermal treatment for 5 hours or more, even when water droplets are left on the film for 30 minutes, the change in light reflectance on the film surface before and after being left is left. , 0.3% or less.

  The fluorine-containing curable coating liquid preferably further contains a fluorine-containing (meth) acrylic acid ester represented by the following chemical formula (2) that does not have film-forming properties.

(In the formula, X and Y are either a (meth) acryloyloxy group or a hydroxyl group, and at least one is a (meth) acryloyloxy group.)
Although the above fluorine-containing (meth) acrylic acid ester itself does not exhibit film-forming properties, it exhibits affinity for the fluorine-containing compound having the film-forming properties and does not deteriorate the film-forming properties. . For this reason, the fluorine-containing curable coating liquid can exhibit excellent film forming properties. Moreover, the fluorine-containing (meth) acrylic acid ester represented by the chemical formula (2) having no film-forming property is a component that can exhibit high antifouling properties. Furthermore, since the fluorine-containing (meth) acrylic acid ester has a polymerizable double bond, it has the film-forming property, and undergoes a copolymerization reaction with a fluorine-containing compound having a polymerizable double bond, Become.

Such fluorine-containing (meth) acrylic acid ester has a fluoroalkyl group having 10 carbon atoms having a trifluoromethyl group (CF _3- ) at its terminal, and this fluorine-containing (meth) acrylic acid ester is a small amount. A trifluoromethyl group is oriented on the surface. In particular, the trifluoromethyl group is sufficiently oriented on the surface even in a film made of a fluorine-containing compound having a film forming property and a high fluorine content having a polymerizable double bond. Therefore, the obtained fluorine-containing cured film can exhibit properties such as antifouling property and low refractive index. On the other hand, in the fluorine-containing (meth) acrylic acid ester having a fluoroalkyl group having 9 or less carbon atoms, the terminal trifluoromethyl group is not sufficiently oriented on the surface, and the effect cannot be obtained. The fluorine-containing (meth) acrylic acid ester having a fluoroalkyl group having 11 or more carbon atoms is difficult to produce and obtain. In other words, only fluorine-containing (meth) acrylate having a C10 fluoroalkyl group exhibits a specific function compared to other fluorine-containing (meth) acrylates having fluoroalkyl groups of other chain lengths. It can be done.

  Specifically, as the fluorine-containing (meth) acrylic acid ester represented by the chemical formula (2), 1- (meth) acryloyloxy-2-hydroxy-4,4,5,5,6,6,7,7,8 , 8, 9, 9, 10, 10, 11, 11, 12, 12, 13, 13, 13-heneicosafluorotridecane, 2- (meth) acryloyloxy-1-hydroxy-4, 4, 5, 5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane and 1,2-bis (meta Acrylyloxy 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotri A decane etc. are mentioned. These fluorine-containing (meth) acrylic acid esters can be used alone or as a mixture.

  The content of the fluorine-containing (meth) acrylic acid ester represented by the chemical formula (2) is preferably 0.5 to 30% by mass with respect to the total amount of the fluorine-containing compound and the modified hollow silica fine particles. When this content is less than 0.5% by mass, the antifouling property of the fluorine-containing cured film surface is lowered, and when it exceeds 30% by mass, it is difficult to obtain a transparent uniform and good fluorine-containing cured film. Tend to be.

  In addition, a solvent may be contained in the fluorine-containing curable coating liquid as long as the reaction is not inhibited for the purpose of adjusting the viscosity of the coating liquid and surface leveling after coating. Examples of the solvent include alcohol solvents such as methanol, ethanol, isopropanol, 2-butanol and isobutanol, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Furthermore, in the fluorine-containing curable coating liquid, for the purpose of adjusting the fluorine content, polyfunctional (meth) acrylic acid esters not containing fluorine, such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (Meth) acrylate and the like can be mixed and used at a ratio of 60% by mass or less. If this blending amount exceeds 60% by mass, the refractive index of the film is increased, which is not preferable when used, for example, as a low reflection material.

  The film is obtained by polymerizing and curing the fluorine-containing curable coating liquid with high energy rays such as an electron beam, or polymerizing and curing the fluorine-containing curable coating liquid in the presence of a thermal decomposition type polymerization initiator or a photopolymerization initiator. Can be obtained. In these, the method of apply | coating the fluorine-containing sclerosing | hardenable coating liquid which added the photoinitiator to the base-material surface, and irradiating an ultraviolet irradiation in inert gas atmosphere to the formed film | membrane and polymerizing and hardening is preferable.

  Any photopolymerization initiator may be used as long as it has a polymerization initiating ability by ultraviolet irradiation. Specifically, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morphe Acetophenone polymerization initiators such as linopropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2- Benzoin-based polymerization initiators such as dimethoxy 1,2-diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ′, Benzophenone polymerization initiators such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2 Chlorothioxanthone, 2,4-diethyl thioxanthone thioxanthone polymerization initiator such as and the like, but not limited thereto. These photopolymerization initiators can be used alone or as a mixture.

  The blending ratio of the photopolymerization initiator is preferably 0.1 to 20% by mass with respect to the solid content in the fluorine-containing curable coating liquid. When the blending ratio of the photopolymerization initiator is less than 0.1% by mass, the polymerization curing of the fluorine-containing curable coating liquid becomes insufficient, and when it exceeds 20% by mass, the refractive index of the film after polymerization curing increases. Therefore, it is not preferable. The kind of ultraviolet lamp used for ultraviolet irradiation is not particularly limited as long as it is generally used. For example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like is used.

  As the conditions for ultraviolet irradiation, the irradiation amount is preferably 10 mJ or more, more preferably 100 mJ or more. The upper limit of the irradiation amount is determined according to a conventional method in this type of ultraviolet irradiation. When the irradiation dose is less than 10 mJ, sufficient hardness cannot be obtained for the film obtained after polymerization and curing. Further, post-curing by ultraviolet irradiation may be performed after the polymerization curing. In order to obtain good polymerization curability, it is preferable to suppress the oxygen concentration at the time of ultraviolet irradiation to 1000 ppm or less by blowing an inert gas such as nitrogen or argon at the time of polymerization curing and post-curing. The film after curing has a refractive index of preferably 1.5 or less, particularly preferably 1.45 or less in consideration of uses such as a low reflection material, and the lower limit thereof is about 1.3. The film thickness is preferably 50 to 200 nm. When this film thickness is less than 50 nm or exceeds 200 nm, the anti-reflection effect decreases.

  Next, by forming the fluorine-containing cured film on one or both surfaces of the substrate directly or via a plurality of functional layers, a low-refractive-index layer can be obtained as an outermost surface. This anti-reflection material may be one in which one or more functional layers are provided between the low refractive index layer and the substrate. Examples of the functional layer include a layer made of a high refractive index material, a hard coat layer, an antistatic layer, an ultraviolet ray preventing layer, an antiglare layer for antiglare, a near infrared ray preventing layer, and an electromagnetic wave shielding layer. When a layer made of a high refractive index material is provided as a functional layer in order to enhance the antireflection effect, the high refractive index material preferably has a refractive index of 1.55 or more, and the film thickness is 50 to 500 nm. Is preferred. The low-refractive index material layer and the high-refractive index material layer may be provided one by one on the substrate, but a plurality of layers may be provided. When providing a plurality of layers, the outermost layer is provided with the low refractive index layer. By laminating layers having different refractive indexes with an optical film thickness of about 100 nm, the interface reflection light generated at the thin film interface interferes with the reflection light on the outermost surface to cancel out, thereby producing a dereflection effect. it can. Therefore, layers having different refractive indexes are laminated on the substrate surface in order from the substrate side, and a low refractive index layer made of a fluorine-containing cured film is provided on the outermost surface.

  In order to further improve the surface hardness of the anti-reflection material, a hard coat layer can be provided as a functional layer. The material for the hard coat layer is not particularly limited, and a normal hard coat resin formed from a polyfunctional monomer having two or more polymerizable unsaturated groups can be used. The film thickness of the hard coat layer is preferably 1 to 10 μm, more preferably 3 to 7 μm.

  The method for forming each layer is not particularly limited, and a commonly applied coating method such as a roll coating method, a dip coating method, a spin coating method, or the like is employed. In the anti-reflective material, an antiglare layer can be provided between the anti-reflective layer and the substrate in order to further provide antiglare properties. The anti-glare layer is an anti-glare layer, which is formed by a method that forms uniform and fine irregularities on the surface of the layer or a method that mixes fine particles with different refractive indexes in the layer, scatters the light, and the light incident on the layer It is designed not to return straight. The thickness of the antiglare layer is preferably 1 to 10 μm, more preferably 3 to 7 μm. The method for forming the antiglare layer is not particularly limited, and a commonly used method, for example, a method of coating a resin liquid containing fine particles, or a method of making the surface uneven by using an embossing roll after coating, etc. is adopted. Is done.

  Although it does not specifically limit as said base material, A film form or a sheet form is preferable and a film form is preferable from the point of mass production. Examples of the material constituting the base material include synthetic resins such as polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), triacetyl cellulose (TAC), polyolefin, polyamide, and polyvinyl chloride (PVC). Etc.

  The anti-reflective material is applied to ordinary films and sheets with anti-reflection treatment, so it is suitable for plasma display panels (PDP), flat CRTs, liquid crystal display screens (LCD), field emission displays (FED), and surface electric field displays (SED). By sticking to the surface of a typical flat electronic display, the reflection of a fluorescent lamp or the like coming from the background can be reduced. Further, it is possible to reduce the adhesion of dirt during use, and to improve the wiping property of the adhered dirt. Visibility can be remarkably improved by these effects, so that eyestrain and the like can be reduced.

  Now, the operation of the present embodiment will be described. A fluorine-containing curable coating liquid is prepared by mixing a fluorine-containing compound having film-forming properties and having a polymerizable double bond and the modified hollow silica fine particles. Is done. The obtained fluorine-containing curable coating liquid is applied onto a substrate and, for example, irradiated with ultraviolet rays, the fluorine-containing curable coating liquid is polymerized and cured to form a fluorine-containing cured film. In this process, the polymerizable double bond of the fluorine-containing compound and the (meth) acryloyloxy group of the silane coupling agent are copolymerized and cured, and the modified hollow silica fine particles are bonded to the fluorine-containing compound to be contained in the copolymer. Embedded in. Therefore, the action of the modified hollow silica fine particles having air inside and the low refractive index and low reflectivity of fluorine, the action of the polymerized and cured fluorine-containing compound and the silica fine particles as inorganic fine particles such as strength and hardness Is demonstrated synergistically and continuously.

The effects exhibited by the above embodiment will be described collectively below.
-The fluorine-containing curable coating liquid of this embodiment has a film-forming property, a hollow compound modified with a fluorine-containing compound having a polymerizable double bond and the silane coupling agent represented by the chemical formula (1) Silica fine particles are contained, and the content of the hollow silica fine particles is set to 20 to 60% by mass in the total amount of the fluorine-containing compound and the hollow silica fine particles. For this reason, when the (meth) acryloyloxy group of the silane coupling agent and the polymerizable double bond of the fluorine-containing compound are copolymerized, the hollow silica fine particles are integrally bonded to the fluorine-containing compound, and the fluorine-containing curable property. The strength and hardness of the coating obtained from the coating liquid can be improved, and the scratch resistance and wear resistance of the coating surface can be improved. In this case, since the content of the hollow silica fine particles modified with the silane coupling agent is higher than the conventional amount, the above effect can be sufficiently exhibited. Furthermore, the formed film can exhibit a low refractive index and a low reflectance based on fluorine and hollow silica fine particles.

  The hollow silica fine particles are obtained by hydrothermal treatment at 200 ° C. for at least 5 hours, so that the outer shell of the hollow silica fine particles is densified, and moisture and solvent are hardly adsorbed on the surface. Therefore, the water resistance and solvent resistance of the film obtained by curing the fluorine-containing curable coating liquid can be improved. In this case, when water droplets are allowed to stand for 30 minutes on the surface of the film, the change in light reflectance on the surface of the film before and after being left is 0.3% or less. The desired water resistance and solvent resistance can be imparted to the conductive film.

  On the other hand, in the coating made of the hollow silica fine particles described in Patent Documents 1 and 2 described above, since the hollow silica itself is very easy to absorb moisture, if water droplets are left on the coating, moisture is adsorbed. End up. When moisture is adsorbed, the refractive index of the portion increases, so that the reflectance of light on the surface of the film increases, and a spot-like mark (water mark) that can be visually recognized is formed on the film. . Such generation of water marks on the film is fatal as an antireflection film to be bonded to the surface of the electronic image display device, and the appearance is remarkably impaired and the antireflection performance is deteriorated.

  In addition, the fluorine-containing curable coating liquid exhibits a fluorine-based antifouling property by containing the fluorine-containing (meth) acrylic acid ester represented by the chemical formula (2) having no film-forming property. Can do.

  -Furthermore, since the fluorine-containing compound is a fluorine-containing polyfunctional (meth) acrylic acid ester, the formed film can have a crosslinked structure, and the strength and hardness of the film can be improved. .

  The antireflection material is obtained by forming the fluorine-containing cured film on one surface or both surfaces of the substrate directly or on the outermost surface via a plurality of functional layers. The antireflection material is excellent in the strength and hardness of the fluorine-containing cured film, has a low refractive index and a low reflectance, and is excellent in antifouling properties. Therefore, plasma display (PDP), liquid crystal display (LCD), field emission display (FED), surface electric field display (SED) and other flat electronic displays or display covers such as picture frames and museums, showcases, etc. It can use suitably for the surface of.

Hereinafter, the embodiment will be described more specifically with reference to production examples, examples , reference examples, and comparative examples. In addition, the part in each example represents a mass part.
(Production Example 1, production of a film having a hard coat layer on the surface)
50 parts of photopolymerizable urethane acrylate [trade name: Purple light UV7600B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.], 20 parts of dipentaerythritol hexaacrylate [trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.], photopolymerization initiator [Product name: IRGACURE 184, manufactured by Ciba Specialty Chemicals] 3 parts and 30 parts of isopropanol (IPA) were mixed to obtain a coating solution for a hard coat layer.

This was coated on a triacetyl cellulose (TAC) film [trade name: KC8UY, manufactured by Konica Minolta Opto Co., Ltd.] having a thickness of 80 μm by a spin coating method so that the dry film thickness was about 4 μm. A TAC film having a hard coat layer formed on the surface by irradiating 400 mJ of ultraviolet light using an ultraviolet irradiation apparatus (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) on this to harden the coating liquid for hard coat layer. This was abbreviated as HC-TAC).
(Production Example 2, production of modified hollow silica fine particles)
IPA-dispersed hollow silica sol [trade name: ELCOM NY-1001 SIV, solid content concentration 20% by mass, average particle size 60 nm, refractive index 1.32, manufactured by Catalysts & Chemicals, Inc.] 2000 parts, γ-acryloyloxypropyltrimethoxy 70 parts of silane [trade name: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.] and 80 parts of distilled water were mixed to obtain a coating solution for a modified hollow silica sol. Thereafter, the mixture was heated under reflux (reaction temperature: 77 ° C.) for 4 hours to conduct a hydrolysis reaction and a condensation reaction. By this operation, modified hollow silica fine particles (sol) were obtained.
(Production Example 3, production of fluorine-containing compound having a polymerizable double bond)
In a four-necked flask, 104 parts of perfluoro- (1,1,9,9-tetrahydro-2,5-bisfluoromethyl-3,6-dioxanonenol) and bis (2,2,3,3, 4,4,5,5,6,6,7,7-dodecafluoroheptanoyl) peroxide 11 parts by weight of 8% by weight perfluorohexane was added. The hollow portion was purged with nitrogen, and then stirred at 20 ° C. for 24 hours under a nitrogen stream to obtain a highly viscous solid. A solution obtained by dissolving the obtained solid in diethyl ether was poured into perfluorohexane, followed by separation and vacuum drying to obtain a colorless and transparent polymer.

When this polymer was analyzed by ¹⁹ F-NMR (nuclear magnetic resonance spectrum), ¹ H-NMR, and IR (infrared absorption spectrum), it was found to be a fluorine-containing polymer having a hydroxyl group at the end of the side chain consisting of the structural unit of allyl ether. It was. The number average molecular weight measured by GPC (gel permeation chromatograph) was 72,000, and the mass average molecular weight was 118,000.

  5 parts of the obtained hydroxyl group-containing fluorine-containing allyl ether polymer, 43 parts of methyl ethyl ketone (MEK) and 1 part of pyridine were charged into a four-necked flask and cooled to 5 ° C. or lower with ice. And what melt | dissolved 1 part of (alpha) -fluoroacrylic acid fluoride in 9 parts of MEK was dripped over 10 minutes, stirring under nitrogen stream. And the solution of the fluorine-containing reactive polymer which has a polymerizable double bond was obtained.

The solid content of the obtained MEK solution was 13%, and as a result of analysis by ¹⁹ F-NMR, the introduction rate of α-fluoroacryloyl group was 40 mol%.
(Production Example 4, production of fluorine-containing polyfunctional (meth) acrylic acid ester)
In a reactor equipped with a stirrer, a cooling pipe, and a gas introduction pipe, 314.2 g (1 mol) of 1,4-bis (2 ′, 3′-epoxypropyl) perfluorobutane, 216.2 g (3 mol) of acrylic acid, tetraethylammonium 4.4 g of bromide and 0.44 g of tert-butylcatechol were charged and gradually heated to 95-100 ° C. in an oil bath. And it stirred at the temperature for 4 hours, and cooled to room temperature. The obtained reaction solution was dissolved in 500 ml of chloroform and washed 3 times with a 10% aqueous sodium carbonate solution and 3 times with a saturated saline solution. Chloroform was distilled off under reduced pressure, and the resulting yellow crystals were further purified by column chromatography using an ethyl acetate / n-hexane mixed solvent (volume ratio 1: 2) as a developing solvent, and further produced by distilling off the solvent under reduced pressure. Product A was obtained. Product A was a mixture of compounds having the structures shown in the following chemical formulas (3), (4) and (5).

( Reference Example 1)
50 parts of the modified hollow silica sol obtained in Production Example 2 in terms of solid content, 50 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 3 in terms of solid content, 2-methyl-1- [4- Methylthiophenyl] -2-morpholinopropan-1-one [trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.] and 2000 parts of isopropyl alcohol were mixed to obtain a fluorine-containing curable coating solution. .

  This fluorine-containing curable coating solution was applied on the HC-TAC of Production Example 1 by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. After that, under a nitrogen atmosphere, ultraviolet rays of 400 mJ are irradiated using an ultraviolet irradiation device (made by Eye Graphics, 120W high-pressure mercury lamp), the fluorine-containing curable coating liquid is cured, and a coating film (film) is formed. A reflecting material (hereinafter abbreviated as a reduced reflection TAC film) was obtained.

The obtained anti-reflection TAC film was subjected to measurement of reflectance, scratch resistance, abrasion resistance, contact angle with water on the film surface and evaluation of antifouling property by the methods described below, and the results are shown in Table 1. Show.
(1) Measurement of reflectance A spectrophotometer [trade name: U-best50, manufactured by JASCO Corporation] with a back surface roughened with sandpaper and a 5 ° specular reflection measuring device in order to remove the back surface reflection of the measurement surface. ] Was used to read the reflectance (%) at a wavelength of 600 nm.
(2) Evaluation of scratch resistance The surface of the anti-reflection film was fixed with # 0000 steel wool at the tip of an eraser abrasion tester manufactured by Honko Seisakusho, and applied with a load of 2.5 N (250 gf) and 1 N (100 gf). The scratches on the surface after reciprocating the top 10 times were visually observed and evaluated according to the following 6 grades A to E.

A: No scratch, A ': 1-3 scratches, B: 4-10 scratches, C: 11-20 scratches, D: 21-30 scratches, E: 31 or more (3) Abrasion resistance Evaluation Shiranell [manufactured by Kowa Co., Ltd.] is attached to the tip of the Eraser abrasion tester manufactured by Honko Seisakusho, and it is rubbed back and forth on the surface of the anti-reflection film under a load of 10.0 N (1000 gf) until scratches are made. The number of rubs was recorded.
(4) Measurement of contact angle A static contact angle meter (°) with respect to distilled water was measured using a static contact angle meter (trade name: CA-A, manufactured by WA Interface Chemical Co., Ltd.).
(5) Evaluation of antifouling property Marked on the surface of the antireflection film with a marker [Zebra Co., Ltd., trade name: McKee, abbreviated as McKee in Tables 1 to 3]. Thereafter, the antifouling property was evaluated by the following three-stage evaluation.

◎: When there is ink repellency and can be wiped, ○: When there is no ink repellency, but when wiping is possible, △: When there is no ink repellency and cannot be wiped off ( Reference Example 2)
50 parts of the modified hollow silica sol obtained in Production Example 2 in terms of solid content, 50 parts of Product A obtained in Production Example 4, 5 parts of Irgacure 907, and 2000 parts of isopropyl alcohol are mixed and fluorine-containing curable. A coating solution was obtained.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. The obtained anti-reflection TAC film was subjected to measurement of reflectance, scratch resistance, abrasion resistance, contact angle to water on the film surface and evaluation of antifouling property by the method described in Reference Example 1, and the results are shown. It is shown in 1.
( Reference Example 3)
50 parts of the modified hollow silica sol obtained in Production Example 2 in terms of solid content, 1,2,9,10-tetrakis (acryloyloxy) -4,4,5,5,6,6,7,7-octafluoro 50 parts of decane (hereinafter abbreviated as OD4A), 5 parts of Irgacure 907 and 2000 parts of isopropyl alcohol were mixed to obtain a fluorine-containing curable coating solution.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. The obtained anti-reflection TAC film was subjected to measurement of reflectance, scratch resistance, abrasion resistance, contact angle to water on the film surface and evaluation of antifouling property by the method described in Reference Example 1, and the results are shown. It is shown in 1.
( Reference Example 4)
50 parts of the modified hollow silica sol obtained in Production Example 2 in terms of solid content, 50 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 3 in terms of solid content, 1-acryloyloxy-2-hydroxy- 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane (below) 4 parts, 2-methyl-1- [4-methylthiophenyl] -2-morpholinopropan-1-one [trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.] 5 parts And 2000 parts of isopropyl alcohol were mixed and the fluorine-containing curable coating liquid was obtained.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. With respect to the obtained reduced reflection TAC film, measurement of reflectance, scratch resistance, abrasion resistance, contact angle with water on the film surface and evaluation of antifouling property were carried out by the following methods, and the results are shown in Table 1.
( Reference Example 5)
50 parts of the modified hollow silica sol obtained in Production Example 2 in terms of solid content, 50 parts of Product A obtained in Production Example 4, 4 parts of DHPA, 5 parts of Irgacure 907, and 2000 parts of isopropyl alcohol were mixed. A fluorine curable coating solution was obtained.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. The obtained anti-reflection TAC film was subjected to measurement of reflectance, scratch resistance, abrasion resistance, contact angle to water on the film surface and evaluation of antifouling property by the method described in Reference Example 1, and the results are shown. It is shown in 1.
( Reference Example 6)
50 parts of the modified hollow silica sol obtained in Production Example 2, 50 parts of OD4A, 4 parts of DHPA, 5 parts of Irgacure 907 and 2000 parts of isopropyl alcohol were mixed to obtain a fluorine-containing curable coating solution.

  This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film.

The obtained anti-reflection TAC film was subjected to measurement of reflectance, scratch resistance, abrasion resistance, contact angle to water on the film surface and evaluation of antifouling property by the method described in Reference Example 1, and the results are shown. It is shown in 1.

From the results shown in Table 1, in Reference Examples 1 to 6, the evaluation of the scratch resistance could be maintained at A to C. Furthermore, in Reference Examples 1-6, 70 times or more was able to be achieved about abrasion resistance. In Reference Examples 1 to 6, the reflectance could be maintained at 0.8 to 1.8%. Furthermore, in Reference Examples 4 to 6, since DHPA having no film forming property was blended, the contact angle could be increased as compared with Reference Examples 1 to 3, and the antifouling property could be improved.
( Reference Examples 7-12)
In Reference Examples 7 to 9, fluorine-containing curable coating liquids were obtained by changing the blending ratio of the modified hollow silica sol obtained in Production Example 2 and the product A as shown in Table 2. And it implemented similarly to the reference example 2, and obtained the low reflection TAC film. The obtained anti-reflection TAC film was subjected to measurement of reflectance, scratch resistance, abrasion resistance, contact angle to water on the film surface and evaluation of antifouling property by the method described in Reference Example 1, and the results are shown. It is shown in 2.

In Reference Examples 10 to 12, 4 parts by mass of DHPA was blended with the compositions of Reference Examples 7 to 9 to obtain fluorine-containing curable coating solutions. And it implemented similarly to Reference Examples 7-9, and obtained the antireflection TAC film. The obtained anti-reflection TAC film was subjected to measurement of reflectance, scratch resistance, abrasion resistance, contact angle to water on the film surface and evaluation of antifouling property by the method described in Reference Example 1, and the results are shown. It is shown in 2.

From the results in Table 2, in Reference Example 7, the blending ratio of the product A was increased, so that the reflectance was slightly increased, and the scratch resistance and abrasion resistance were also excellent. In Reference Examples 8 and 9, the reflectance, scratch resistance, and wear resistance were good in good balance. In Reference Examples 10 to 12, since DHPA having no film forming property was blended, the contact angle could be increased and the antifouling property could be improved as compared with Reference Examples 7 to 9.
(Comparative Example 1)
IPA-dispersed hollow silica sol [trade name: ELCOM NY-1001 SIV, solid content concentration 20% by mass, average particle size 60 nm, refractive index 1.32, manufactured by Catalyst Chemicals Co., Ltd.] 50 parts in terms of solid content, in Production Example 3 50 parts of the obtained solvent-soluble fluorine-containing reactive polymer in terms of solid content, 5 parts of Irgacure 907 and 2000 parts of isopropyl alcohol were mixed to obtain a fluorine-containing curable coating solution.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. The obtained anti-reflection TAC film was subjected to measurement of reflectance, scratch resistance, abrasion resistance, contact angle with water on the film surface and evaluation of antifouling properties, and Table 3 shows the results.
(Comparative Examples 2 to 5)
In Comparative Examples 2 and 4, except that by changing the content of the modified hollow silica sol product A in Reference Example 2 was conducted in the same manner as in Reference Example 2. In Comparative Examples 3 and 5, except that by changing the content of the modified hollow silica sol product A in Reference Example 5 was conducted in the same manner as in Reference Example 5. The resulting anti-reflection TAC film was evaluated for reflectivity, scratch resistance, abrasion resistance, contact angle with water on the film surface and antifouling property, and the results are shown in Table 3.

From the results shown in Table 3, the evaluation for scratch resistance was E in Comparative Example 1 because the hollow silica was not modified. In Comparative Examples 4 and 5, excess modified hollow silica could not react with the fluorine-containing compound, no improvement in scratch resistance was observed, and E. In Comparative Examples 2 and 3, the content of the modified hollow silica was small and could not sufficiently contribute to the improvement of scratch resistance, and B was 1.0N and D was 2.5N. The abrasion resistance was 10 times or less in Comparative Example 1, 30 to 50 times in Comparative Examples 2 and 3, and 10 to 20 times in Comparative Examples 4 and 5. Further, the reflectance reached 2.5% in Comparative Examples 2 and 3 because the content of the modified hollow silica was small.
(Production Example 5, production of hollow silica sol A)
As a first step, 100 g of silica sol having an average particle diameter of 5 nm and a silica (SiO ₂ ) concentration of 20% by mass and 1900 g of pure water were mixed to prepare a reaction mother liquor and heated to 80 ° C. The reaction pH of the mother liquor is 10.5, 1.17 mass% of sodium silicate solution 9,000g as SiO ₂ in the reaction mother liquor, Al ₂ O ₃ as 0.83 wt% of aqueous sodium aluminate solution 9, 000 g was added simultaneously. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate and remained almost unchanged thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ primary particle dispersion (core particle dispersion) having a solid content concentration of 20% by mass.

Next, as a second step, 500 g of this SiO ₂ .Al ₂ O ₃ primary particle dispersion is sampled, 1,700 g of pure water is added and heated to 98 ° C., and while maintaining this temperature, a concentration of 0.5 50,400 g of mass% sodium sulfate was added, and then 3,000 g of a sodium silicate aqueous solution with a concentration of 1.17 mass% as SiO ₂ and 9,000 g of a sodium aluminate aqueous solution with a concentration of 0.5 mass% as Al ₂ O ₃ Was added to obtain a composite oxide fine particle dispersion (fine particle dispersion in which the first silica coating layer was formed on the core particles). And this was wash | cleaned with the ultrafiltration membrane, and it was set as the complex oxide fine particle dispersion liquid of solid content concentration 13 mass%.

  As a third step, 1,125 g of pure water was added to 500 g of this composite oxide fine particle dispersion, and concentrated hydrochloric acid (35.5%) was added dropwise to adjust the pH to 1.0, followed by dealumination. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and washed to obtain a dispersion of silica-based fine particles (1) having a solid content concentration of 20% by mass.

As a fourth step, a mixture of 1500 g of an aqueous dispersion of silica-based fine particles (1) having a solid content concentration of 20% by mass, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water is heated to 35 ° C. After that, 104 g of ethyl silicate (SiO ₂ 28 mass%) was added to form a silica coating (second silica coating layer). Subsequently, while adding 5 L of pure water, it was washed with an ultrafiltration membrane to prepare a dispersion of silica-based fine particles (2) having a solid content concentration of 20% by mass.

Finally, as a fifth step, the dispersion of silica-based fine particles (2) was again hydrothermally treated at 200 ° C. for 1 hour. Then, it washed with the ultrafiltration membrane, adding 5 L of pure water, and adjusted solid content concentration to 20 mass%. Then, using an ultrafiltration membrane, the dispersion medium of this dispersion was replaced with ethanol to obtain an organosol having a solid content concentration of 20% by mass. This organosol was an organosol in which hollow silica fine particles having an average particle diameter of 46 nm and a specific surface area of 130 m ² / g were dispersed (hereinafter referred to as “hollow silica sol A”).

The average particle size and specific surface area were measured by the following methods.
(Average particle size)
Using a particle size distribution measuring device (PAR-III, manufactured by Otsuka Electronics Co., Ltd.), the average particle size was measured by a dynamic light scattering method using laser light.
(Specific surface area)
A sample obtained by drying 50 ml of sol at 110 ° C. for 20 hours was measured by a nitrogen adsorption method (BET method) using a specific surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12).
(Production Example 6, production of hollow silica sol B)
Production was performed in the same manner as in Production Example 5 except that the dispersion of silica-based fine particles (2) was hydrothermally treated at 200 ° C. for 11 hours to obtain an organosol having a SiO ₂ concentration of 20 mass%. This organosol was an organosol in which hollow silica fine particles having an average particle size of 45 nm and a specific surface area of 120 m ² / g were dispersed (hereinafter referred to as “hollow silica sol B”).
(Production Example 7, production of modified hollow silica sol α)
The hollow silica sol A (silica solid content: 20 wt%) was prepared 200 g, an ultrafiltration membrane, subjected to solvent substitution to methanol, SiO ₂ minutes organosol 100 g (water content of 20% by weight SiO ₂ minutes 0.5 mass%) was prepared. Thereto, 28% aqueous ammonia solution was added to 100 g of the organosol so as to be 100 ppm as ammonia, and mixed well. 3.6 g was added to prepare a reaction solution. This was heated to 50 ° C. and heated at 50 ° C. for 6 hours with stirring. After completion of the heating, the reaction solution was cooled to room temperature, and further the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain an organosol composed of coated hollow fine particles having a SiO ₂ concentration of 20% by mass.

This organosol has an average particle diameter of 47 nm, a specific surface area of 110 m ² / g, and a TG mass reduction rate of 3.2% of hollow silica fine particles dispersed therein (hereinafter referred to as “modified hollow silica sol α”). )Met. TG was measured by the following method.

Differential thermal mass measurement method (TG / DTA)
Differential thermothermal mass simultaneous measurement was performed using a differential thermothermal mass simultaneous measurement apparatus (manufactured by Rigaku Corporation, Thermoplus TG8110). In addition, TG represents a thermogravimetry analysis (Thermogravimetry Analysis) and DTA represents a differential scanning calorimetry (differential scanning calorimetry). The measurement conditions are a temperature range of room temperature to 500 ° C. under a temperature rise rate of 10 ° C./min in an air atmosphere.

In addition, about the sample for differential thermothermal mass simultaneous measurement methods (TG / DTA), after removing the solvent of the organosol prepared as mentioned above, it wash | cleans thoroughly with hexane, and it dries under reduced pressure after removing hexane. It dried with the machine and it used for the measurement as a powder sample.
(Production Example 8, production of modified hollow silica sol β)
In Production Example 7, an organosol composed of coated hollow fine particles having a SiO ₂ concentration of 20% by mass was obtained in the same manner as in Production Example 7 except that hollow silica sol B was used instead of hollow silica sol A. This organosol has an average particle diameter of 47 nm, a specific surface area of 103 m ² / g, and a sol in which hollow silica fine particles having a mass reduction ratio of TG of 3.3% are dispersed (hereinafter referred to as “modified hollow silica sol β”). )Met.
(Production Example 9, production of modified hollow silica sol γ)
In Production Example 7, the SiO ₂ concentration was 20 mass in the same manner as in Production Example 7 except that the amount of γ-acryloyloxypropyltrimethoxysilane [trade name: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.] was changed to 1.8 g. % Organosol consisting of coated hollow fine particles was obtained. This organosol has an average particle size of 46 nm, a specific surface area of 109 m ² / g, and a TG mass reduction ratio of 1.4% of hollow silica fine particles dispersed therein (hereinafter referred to as “modified hollow silica sol γ”). )Met.
( Reference Example 13)
50 parts of the modified hollow silica sol α obtained in Production Example 7 in terms of solid content, 50 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 3 in terms of solid content, 2-methyl-1- [4 -Methylthiophenyl] -2-morpholinopropan-1-one [trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.] and 2000 parts of isopropyl alcohol were mixed to obtain a fluorine-containing curable coating solution. It was.

  This fluorine-containing curable coating solution was applied on the HC-TAC of Production Example 1 by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. After that, under a nitrogen atmosphere, ultraviolet rays of 400 mJ are irradiated using an ultraviolet irradiation device (made by Eye Graphics, 120W high-pressure mercury lamp), the fluorine-containing curable coating liquid is cured, and a coating film (film) is formed. A reflecting material (hereinafter abbreviated as a reduced reflection TAC film) was obtained.

About the obtained reduced reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with respect to water, antifouling property and evaluation of water resistance of the film were carried out by the methods described below. The results are shown in Table 4.
(1) Measurement of reflectance The reflectance was measured by the same measurement method as in Reference Example 1.
(2) Evaluation of scratch resistance The scratch resistance was evaluated by the same measurement method and evaluation criteria as in Reference Example 1.
(3) Evaluation of Abrasion Resistance Abrasion resistance was evaluated by the same measurement method as in Reference Example 1.
(4) Measurement of contact angle The static contact angle (°) was measured by the same method as in Reference Example 1.
(5) Evaluation of antifouling property The antifouling property was evaluated by the same method as in Reference Example 1.
(6) Water resistance of the film After leaving the distilled water to stand for 30 minutes on the surface of the obtained film, the moisture is wiped off with Kimwipe (Wiper S-200, manufactured by Crecia Co., Ltd.), and the surface of the film before and after leaving the distilled water to stand. The difference in reflectance at a light wavelength of 600 nm was measured.
○: Reflectance difference is less than 0.3%, Δ: Reflectance difference is 0.3 to 0.5%, and X: Reflectance difference is greater than 0.5%.
( Reference Example 14)
50 parts of the modified hollow silica sol α obtained in Production Example 7 in terms of solid content, 50 parts of Product A obtained in Production Example 4, 5 parts of Irgacure 907, and 2000 parts of isopropyl alcohol are mixed and fluorine-containing cured. A characteristic coating solution was obtained.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 4.
( Reference Example 15)
50 parts of the modified hollow silica sol α obtained in Production Example 7 in terms of solid content, 50 parts of OD4A, 5 parts of Irgacure 907 and 2000 parts of isopropyl alcohol were mixed to obtain a fluorine-containing curable coating solution.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 4.
( Reference Example 16)
50 parts of the modified hollow silica sol α obtained in Production Example 7 in terms of solid content, 50 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 3 in terms of solid content, 4 parts of DHPA, 2-methyl-1 -[4-Methylthiophenyl] -2-morpholinopropan-1-one [trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.] and 2000 parts of isopropyl alcohol were mixed to prepare a fluorine-containing curable coating. A liquid was obtained.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 4.
( Reference Example 17)
50 parts of the modified hollow silica sol α obtained in Production Example 7 in terms of solid content, 50 parts of Product A obtained in Production Example 4, 4 parts of DHPA, 5 parts of Irgacure 907 and 2000 parts of isopropyl alcohol were mixed. A fluorine-containing curable coating solution was obtained.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 4.
( Reference Example 18)
50 parts of the modified hollow silica sol α obtained in Production Example 7, 50 parts of OD4A, 4 parts of DHPA, 5 parts of Irgacure 907 and 2000 parts of isopropyl alcohol were mixed to obtain a fluorine-containing curable coating solution.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. At this time, the film-forming property of the fluorine-containing curable coating liquid was good. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 4.
(Reference Example 19)
In Reference Example 13, a reduced reflection TAC film was obtained in the same manner as in Reference Example 13 except that modified hollow silica sol γ was used instead of modified hollow silica sol α. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 4.
(Example 20)
In Reference Example 13, a reduced reflection TAC film was obtained in the same manner as in Reference Example 13 except that modified hollow silica sol β was used instead of modified hollow silica sol α. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 4.
(Example 21)
In Reference Example 16, a reduced reflection TAC film was obtained in the same manner as in Reference Example 16 except that modified hollow silica sol β was used instead of modified hollow silica sol α. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 4.

From the results shown in Table 4, in Reference Examples 13 to 18, the scratch resistance evaluation could be maintained at A to C. Furthermore, in Reference Examples 13-18, 80 times or more was able to be achieved about abrasion resistance. Moreover, in Reference Examples 13 to 18, the reflectance could be maintained at 0.7 to 1.7%. Furthermore, in Reference Examples 16 to 18, since DHPA having no film forming property was blended, the contact angle could be increased as compared with Reference Examples 13 to 15, and the antifouling property could be improved. In Reference Example 19, although the hollow silica fine particles are modified, the mass reduction ratio of the modified hollow silica fine particles due to TG is 1.4%. Therefore, the scratch resistance evaluation is C to D, and the wear resistance evaluation is also performed. It was weak with 50-60 times. In Examples 20 and 21, since the modified hollow silica sol β excellent in water resistance was used, the water resistance of the film could be improved.
( Reference Examples 22 to 27)
In Reference Examples 22 to 27, the blending ratio of the modified hollow silica sol α obtained in Production Example 7 and the product A was changed as shown in Table 5 to obtain a fluorinated curable coating liquid. And it implemented like Reference Example 14 and obtained the low reflection TAC film. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 5.

In Reference Examples 25 to 27, 4 parts by mass of DHPA was blended with the compositions of Reference Examples 22 to 24 to obtain fluorine-containing curable coating liquids. And it implemented like Reference Examples 22-24, and obtained the antireflection TAC film. With respect to the obtained anti-reflection TAC film, the reflectance, scratch resistance, abrasion resistance, measurement of the contact angle of the film surface with water, antifouling property and evaluation of the water resistance of the film are carried out by the method described in Reference Example 13, The results are shown in Table 5.

From the results of Table 5, in Reference Example 22, since the blending ratio of the product A was increased, the scratch resistance and abrasion resistance were excellent except that the reflectance was slightly increased. In Reference Examples 23 and 24, the reflectance, scratch resistance, and wear resistance were good in good balance. In Reference Examples 25 to 27, since DHPA having no film forming property was blended, the contact angle could be increased and the antifouling property could be improved as compared with Reference Examples 22 to 24.
(Comparative Example 6)
50 parts of the hollow silica sol A obtained in Production Example 5 in terms of solid content, 50 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 3 in terms of solid content, 5 parts of Irgacure 907 and isopropyl alcohol 2000 Parts were mixed to obtain a fluorine-containing curable coating solution.

This fluorine-containing curable coating solution was applied on the HC-TAC by a dip coating method so that the dry film thickness was about 0.1 μm. Thereafter, a coating film was formed by irradiating with 400 mJ ultraviolet rays using an ultraviolet irradiation device (120 W high-pressure mercury lamp, manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to obtain a reduced reflection TAC film. The resulting anti-reflection TAC film was measured for reflectivity, scratch resistance, abrasion resistance, contact angle with water on the film surface, antifouling property and water resistance of the film, and the results are shown in Table 6. .
(Comparative Examples 7 to 10)
In Comparative Examples 7 and 9, except that by changing the content of the modified hollow silica sol α with the product A in reference example 14, was carried out in the same manner as in Reference Example 14. In Comparative Examples 8 and 10, except that by changing the content of the modified hollow silica sol α with the product A in reference example 17, was carried out in the same manner as in Reference Example 17. The resulting anti-reflection TAC film was measured for reflectivity, scratch resistance, abrasion resistance, contact angle with water on the film surface, antifouling property and water resistance of the film, and the results are shown in Table 6. .

From the results shown in Table 6, the scratch resistance evaluation was E in Comparative Example 6 because the hollow silica was not modified. In Comparative Examples 9 and 10, excess modified hollow silica could not react with the fluorine-containing compound, and no improvement in scratch resistance was observed. In Comparative Examples 7 and 8, the content of the modified hollow silica was small and could not sufficiently contribute to the improvement of scratch resistance, and B was 1.0N and D was 2.5N. Further, the abrasion resistance was 10 times or less in Comparative Example 6, 30 to 50 times in Comparative Examples 7 and 8, and 10 to 20 times in Comparative Examples 9 and 10. Further, the reflectance reached 2.5% in Comparative Examples 7 and 8 because the content of the modified hollow silica was small.

In addition, this embodiment can also be changed and embodied as follows.
-In order to improve the adhesiveness with respect to the substrate surface, a compound having a hydroxyl group, a carboxyl group or the like can be blended in the fluorine-containing curable coating liquid.

-A fluorine-based graft copolymer or a fluorine-based block copolymer can also be blended in the fluorine-containing curable coating liquid.
-Fillers, pigments, thickeners, plasticizers and the like can also be added to the fluorine-containing curable coating liquid.

  -3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- as fluorine-containing silane coupling agent in fluorine-containing curable coating liquid Heptadecafluorodecyltrimethoxysilane, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyltrimethoxysilane and the like can also be blended.

-The cavity of the modified hollow silica fine particles may contain gas components other than air, for example, organic solvent vapor, water vapor and the like.
Further, the technical idea that can be grasped from the embodiment will be described below.

The hollow silica fine particles modified by the silane coupling agent are obtained by mixing the silane coupling agent and the hollow silica fine particles in a solvent and performing a hydrolysis reaction and a condensation reaction. Item 4. The fluorine-containing curable coating solution according to any one of Items 3 to 3 . When comprised in this way, in addition to the effect of the invention which concerns on any one of Claims 1-3 , a silane coupling agent can be easily combined with hollow silica microparticles by reaction.

The film-forming fluorine-containing compound having a polymerizable double bond is a fluorine-containing monomer having a structure in which fluorine atoms are introduced into the molecule as a methylene fluoride group or a fluorinated methine group. The fluorine-containing curable coating liquid according to any one of claims 1 to 3 . When comprised in this way, in addition to the effect of the invention which concerns on any one of Claims 1-3 , the film-forming property of a fluorine-containing curable coating liquid can be improved.

- has a film forming property, the fluorine-containing compound having a polymerizable double bond, claim 1 is a fluorine-containing reactive polymer having a polymerizable double bond in a solvent soluble in any of claims 3 The fluorine-containing curable coating liquid described. When configured in this manner, in addition to the effects of the invention according to any one of claims 1 to 3 , the film formability is good, the film can be crosslinked and cured after film formation, and the strength and hardness of the fluorine-containing cured film Can be improved.

The fluorine-containing curable coating solution according to any one of claims 1 to 3 , wherein the hydrothermal treatment is performed at 200 to 280 ° C for 5 to 20 hours. In such a configuration, in addition to the effect of the invention according to any one of claims 1 to 3, it is possible to perform the hydrothermal treatment of the hollow silica fine particles sufficiently.

The fluorine-containing curable coating liquid according to any one of claims 1 to 3 , wherein the hollow silica fine particle is an organosol that is hydrothermally treated in the form of an aqueous dispersion and then solvent-substituted with an organic solvent. In such a configuration, organosol is easily compatible with the fluorine-containing compound, in addition to the effect of the invention according to any one of claims 1 to 3, improving the binding properties of the hollow silica fine particles to the fluorinated compound Can be made.

Claims (6)

The film contains a fluorine-containing compound having a polymerizable double bond and hollow silica fine particles modified with a silane coupling agent represented by the following chemical formula (1), and the content of the hollow silica fine particles Is 20 to 60% by mass in the total amount of the fluorine-containing compound and the hollow silica fine particles,
The fluorine-containing compound having a film forming property and having a polymerizable double bond includes a fluorine-containing monomer having a structure in which a fluorine atom is introduced into a molecule as a methylene fluoride group or a fluorinated methine group, and an ester solvent. , At least one selected from a fluorine-containing reactive polymer that is soluble in a ketone solvent or an alcohol solvent and has a polymerizable double bond,
The hollow silica fine particles are hydrothermally treated at 200 to 280 ° C. for at least 5 hours ,
The modified hollow silica fine particles have a thermal mass reduction in a thermal mass measurement in a temperature range of 200 to 500 ° C. of 2% by mass or more.
(In the formula, Z is a (meth) acryloyloxy group, R ¹ is an alkylene group having 1 to 4 carbon atoms, and R ² is a hydrogen atom, a methyl group or an ethyl group.) The fluorine-containing curable coating liquid according to claim 1 , further comprising a fluorine-containing (meth) acrylic acid ester represented by the following chemical formula (2).
(In the formula, X and Y are either a (meth) acryloyloxy group or a hydroxyl group, and at least one is a (meth) acryloyloxy group.) The fluorine-containing curable coating liquid according to claim 1 or 2 , wherein the fluorine-containing compound is a fluorine-containing polyfunctional (meth) acrylic acid ester. A fluorine-containing cured film obtained by curing the fluorine-containing curable coating liquid according to any one of claims 1 to 3 . If claims 1 was left claim 3 of any water on the surface of the cured-obtained film of the curable fluorine-containing coating liquid according to an item 30 min, before and after standing in the left part of the water of the coating surface And a change in reflectance at a light wavelength of 600 nm is 0.3% or less. A fluorine-containing cured film according to claim 4 or 5 is formed on the outermost surface directly or via a plurality of functional layers on one side or both sides of a substrate.