WO2008026539A1 - Particule fine composite, procede de production associe, composition de revetement contenant ladite particule et film optique - Google Patents

Particule fine composite, procede de production associe, composition de revetement contenant ladite particule et film optique Download PDF

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Publication number
WO2008026539A1
WO2008026539A1 PCT/JP2007/066545 JP2007066545W WO2008026539A1 WO 2008026539 A1 WO2008026539 A1 WO 2008026539A1 JP 2007066545 W JP2007066545 W JP 2007066545W WO 2008026539 A1 WO2008026539 A1 WO 2008026539A1
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group
composite fine
film
refractive index
coating composition
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PCT/JP2007/066545
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English (en)
Japanese (ja)
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Takanori Hattori
Hironobu Akutagawa
Tsuyoshi Yorino
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Nippon Shokubai Co., Ltd.
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Publication of WO2008026539A1 publication Critical patent/WO2008026539A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • COMPOSITE PARTICLE METHOD FOR PRODUCING THE SAME, COATING COMPOSITION AND OPTICAL FILM CONTAINING THE COMPOSITE PARTICLE
  • the present invention relates to composite fine particles and a method for producing the same. More specifically, the present invention relates to composite fine particles having excellent curability and capable of achieving both adhesion and dispersion stability and a simple production method thereof.
  • Patent Document 1 discloses the use of a composition containing particles obtained by modifying the surface of colloidal silica with methacryloxysilane and acrylate, as a photocurable coating material.
  • Patent Documents 2 and 3 disclose a method for producing reactive silica by reacting silica fine particles with an organic silane compound having a polymerizable unsaturated group.
  • any of the above techniques the amount of polymerizable functional groups that can be introduced onto the surface of the fine particles is insufficient, and as a result, the resulting reactive fine particles have insufficient wear resistance and curability. . Furthermore, any of the reactive fine particles obtained by the conventional technique has insufficient dispersion stability.
  • Patent Document 1 Japanese Patent Publication No. 62-21815
  • Patent Document 2 JP-A-9 100111
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-256753
  • the present invention has been made to solve the above-described conventional problems. It is an object of the present invention to provide composite fine particles having excellent curability and capable of achieving both adhesion and dispersion stability and a simple production method thereof.
  • the composite fine particle of the present invention has an inorganic core particle and an organic polymer bonded to at least a part of the surface of the core particle, and the organic polymer has a polymerizable functional group in its side chain.
  • the polymerizable functional group is bonded to the organic polymer main chain via a urethane bond.
  • the polymerizable functional group is an ethylenically unsaturated group.
  • the organic polymer is an acrylic polymer.
  • a method for producing composite microparticles comprises a step of reacting a silicon-containing polymer having a functional group having active hydrogen and a polysiloxane group in the side chain with an isocyanate compound having a polymerizable functional group; the reaction product, and hydrolysis And reacting with a metal compound capable of producing a metal oxide.
  • the polymerizable functional group is an ethylenically unsaturated group
  • the silicon-containing polymer is an acrylic polymer.
  • a coating composition contains the composite fine particles and a polyfunctional polymerizable compound.
  • a low refractive index coating composition is provided.
  • This low refractive index coating composition contains the composite fine particles and a polyfunctional polymerizable compound, and the organic polymer in the composite fine particles has a portion containing a fluorine atom.
  • these coating compositions further comprise a polymerization initiator and a solvent.
  • an optical film is provided.
  • This optical film includes a coating layer of the coating composition.
  • an antireflective film is provided.
  • the antireflection film includes a coating layer of the low refractive index coating composition.
  • a polarizing plate is provided.
  • the polarizing plate includes a polarizer and the antireflection film.
  • an optical filter for a plasma display is provided. This optical filter includes a support and an upper And an antireflection film.
  • an image display apparatus includes at least one selected from the antireflection film, the polarizing plate, and the optical filter.
  • the amount of functional group introduced into the composite fine particles can be remarkably increased as compared with the prior art.
  • the functional group and the organic polymer main chain are bonded via a specific bond (typically a urethane bond), so that the solubility and dispersibility in a solvent are mainly caused by the organic polymer main chain. Ensured and largely improved due to the specific bonds mentioned above. Therefore, composite fine particles having excellent curability (hardness, wear resistance, scratch resistance) and having both adhesion and dispersion stability can be obtained.
  • the composite fine particles of the present invention have inorganic core particles and an organic polymer bonded to at least a part of the surface of the core particles.
  • bonding of core particle and organic polymer means that a chemical bond is formed between the organic polymer and the core particle, which is not physically attached.
  • the chemical bond is generated means that, for example, when the composite fine particles are washed with a solvent, the organic polymer is not substantially detected in the washing solution.
  • the organic polymer has a polymerizable functional group in its side chain. In other words, the polymerizable functional group is not directly bonded to the core particle surface, and the organic polymer is interposed between the polymerizable functional group and the core particle.
  • the polymerizable functional group is an ethylenically unsaturated group. This is because it is easy to produce and the particles have excellent curability.
  • the inorganic core particle is a particle composed of any appropriate inorganic substance (for example, a simple metal, an inorganic oxide, an inorganic carbonate, an inorganic sulfate, or an inorganic phosphate).
  • the inorganic substance is preferably an inorganic oxide.
  • “inorganic oxide” refers to various oxygen-containing metal compounds in which a metal element forms a three-dimensional network mainly through bonding with oxygen atoms.
  • the metal element constituting the inorganic oxide for example, an element selected from Group III to V is preferred, and an element selected from Groups II to VI of the Periodic Table of Elements is preferred. Among these, an element selected from Si, Al, Ti, and Zr is particularly preferable.
  • Silica whose metal element is Si is most preferable. This is because it is easy to manufacture and easy to obtain.
  • the core particle may be composed of one inorganic oxide or may be composed of two or more inorganic oxides.
  • metals and semimetals may be collectively referred to as metals.
  • the core particles have any suitable shape (for example, spherical, needle-like, plate-like, scale-like, crushed granule).
  • the average particle size of the core particles is preferably 5 to 200 nm, more preferably 5 to; 100 nm, most preferably 5 to 50 nm.
  • the average particle diameter of the core particles is less than 5 nm, the surface energy of the composite fine particles becomes high and the composite fine particles are likely to aggregate. If the average particle diameter of the core particles exceeds 200 nm, the transparency of the resulting film may be lowered.
  • the variation coefficient (particle size distribution) of the particle diameter of the core particles is preferably 50% or less, more preferably 40% or less, and most preferably 30% or less. If the coefficient of variation exceeds 50% (if the particle size distribution of the core particles is too large), the resulting coating film surface becomes uneven and the smoothness of the coating film may be lost.
  • the organic polymer is bonded to at least a part of the surface of the core particle.
  • An organic polymer is bonded to the surface of the core particle, and an organic functional group (preferably an ethylenically unsaturated group) is introduced into the polymer side chain (that is, an organic polymer is interposed between the polymerizable functional group and the core particle).
  • an organic functional group preferably an ethylenically unsaturated group
  • a much larger amount of functional groups can be introduced into the composite particles than in the past.
  • a part of the organic polymer may be encapsulated in the core particles. In this case, moderate flexibility and toughness can be imparted to the core particles.
  • the presence or absence of an organic polymer in the core particle is determined by, for example, measuring the specific surface area of the core particle after pyrolyzing the organic polymer by heating the composite fine particles at 500 to 700 ° C, and calculating the theoretical value of the specific surface area of the core particle. By comparing with (calculated from the diameter of the core particle measured by TEM etc.), it can be confirmed.
  • the organic polymer is encapsulated in the core particle In this case, the thermal decomposition of the organic polymer generates a large number of pores in the core particle, so that the specific surface area of the core particle after the thermal decomposition becomes a value considerably larger than the theoretical value.
  • the organic polymer may have any suitable structure (eg, linear, branched, cross-linked structure).
  • organic polymers include acrylic polymers, styrene polymers, olefin polymers (eg, polyethylene, polypropylene), polyesters (eg, polyethylene terephthalate), and bull polymers (polyacetate butyl, polychlorinated butyl). , Polyvinylidene chloride, and copolymers thereof.
  • a polymer obtained by partially modifying these with a functional group such as an amino group, an epoxy group, a hydroxyl group, or a carboxyl group may be used.
  • An acrylic polymer is preferred.
  • the acrylic polymer has an appropriate coating film forming ability and is suitable for use in a film forming composition such as a paint.
  • a film forming composition such as a paint.
  • the acrylic unit (repeating unit) in the acrylic polymer include a methyl (meth) acrylate unit and an ethyl (meth) acrylate unit. According to the acrylic polymer having such a repeating unit, the stain resistance of the coating can be improved.
  • the molecular weight (number average molecular weight) of the organic polymer is preferably 200,000 or less, more preferably (up to 50,000, most preferably (up to 3,000-30, 000). If it is within the range, a large amount of functional groups can be introduced into the side chain at appropriate intervals, so that composite fine particles having very excellent curability can be obtained, and the dispersion stability of the composite fine particles is also good. Can be maintained.
  • the organic polymer has a polymerizable functional group in its side chain.
  • the polymerizable functional group is not directly bonded to the surface of the core particle, and the organic polymer is interposed between the polymerizable functional group and the core particle.
  • the polymerizable functional group is an ethylenically unsaturated group.
  • the ethylenically unsaturated group include a terminal bur group, a aryl group, a (meth) acryl group, an ⁇ -substituted methacryl group, an ethylene group, and an acetylene group. These ethylenically unsaturated groups may be introduced singly into the organic polymer side chain, or may be introduced in combination of two or more.
  • the polymerizable functional group may be bonded via any appropriate bond that may be directly bonded to the organic polymer.
  • the polymerizable functional group is via a urethane bond.
  • the polymerizable functional group can be introduced with very high reaction efficiency without causing gelation or the like.
  • the content of the polymerizable functional group in the composite fine particles is preferably 0.1 to 5 mmol / g, more preferably 0.7 to 3 mmol / g, per lg of the composite fine particles. With such a content, composite fine particles having an excellent balance between curability and dispersion stability can be obtained.
  • Method 1 reacting a silicon-containing polymer having an active hydrogen-containing functional group and a polysiloxane group in the side chain with a metal compound capable of generating a metal oxide by hydrolysis; And reacting an isocyanate compound having a polymerizable functional group (preferably, an ethylenically unsaturated group) (Method 2).
  • Method 1 is preferred. This is because polymerizable functional groups with high reaction efficiency can be efficiently introduced into the side chains of the organic polymer on the surface of the composite fine particles. Below, for simplicity, Method 1 will be described with emphasis.
  • the main chain of the above silicon-containing polymer is mainly composed of carbon, and the carbon atom that participates in the main chain bond accounts for 50 to 100 mol% of the main chain, and the balance is N, 0, S, Si. Those made of an element such as P are preferred for reasons such as availability.
  • the structure and examples of the main chain of the silicon-containing polymer are as described for the organic polymer in Section B above.
  • the organic polymer described in item B is derived from the main chain of the silicon-containing polymer.
  • the functional group having active hydrogen include a hydroxyl group, a carboxyl group, an amino group, and a mercapto group. Hydroxyl groups are preferred. This is because the introduction of the silicon-containing polymer into the side chain is easy and the reactivity with the isocyanate compound is excellent.
  • the functional group may be bonded via any suitable group (for example, a methylene group) that may be directly bonded to the main chain of the silicon-containing polymer! /.
  • the content of the functional group in the silicon-containing polymer is preferably 10 to 80 mol%, It is preferably 30 to 60 mol%. Within such a range, composite fine particles having a polymerizable functional group with a desired content can be obtained.
  • the “polysiloxane group” refers to a group containing a number of siloxane bonds capable of forming core particles capable of obtaining the effects of the present invention. Therefore, the “polysiloxane group” is not only a group in which two or more Si atoms are linked in a linear or branched manner by a polysiloxane bond (Si—O—Si—O bond), but also a polyfunctional siloxane group. Also includes groups containing a single Si atom that constitutes a bond (eg, (linking chain) —R—Si— (OR), where R is any suitable substituent)
  • the polysiloxane group has a structure containing a polysiloxane bond and containing at least one Si—OR 1 group.
  • R 1 is at least one group selected from a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted acyl group, and when R 1 is plural in one molecule, R 1 May be the same or different.
  • the carbon number of the alkyl group or the acyl group as R 1 an appropriate number can be adopted depending on the purpose. The carbon number is preferably 1-5. This is because the hydrolysis rate of the 0 group is fast.
  • alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, tert-butyl group, and pentyl group.
  • acyl group having 1 to 5 carbon atoms include acetyl group and propionyl group.
  • substituent for the alkyl group or the acyl group include alkoxy groups such as methoxy group and ethoxy group; acyl groups such as acetyl group and propionyl group; and halogens such as chlorine and bromine.
  • R 1 is most preferably a methyl group, preferably a hydrogen atom, a methyl group or an ethyl group. This is because the hydrolysis / condensation rate of the 0 group is further increased.
  • the number of Si atoms contained in the polysiloxane group any appropriate number can be adopted depending on the purpose.
  • the average number of Si atoms per polysiloxane group is preferably 4 or more, more preferably 11 or more. This is because many Si—OR 1 groups can be contained.
  • the average number of — ⁇ ⁇ groups in one Si—OR group is preferably 5 or more, more preferably 20 or more, per molecule of silicon-containing polymer. Since the 0 group is a functional group capable of hydrolysis and / or condensation, the larger the number of groups, the more the reaction points for hydrolysis-condensation and the stronger the bond between the polymer and the core particle.
  • polysiloxane group examples include polymethylmethoxysiloxane group, polyethylene methoxysiloxane group, polymethylol ethoxy siloxane group, polyethylen ethoxy siloxane group, polyphenyl methoxy siloxane group, polyphenyl ethoxy siloxane. Groups.
  • Si — O— Si bond it is preferable that all the Si atoms in the polysiloxane group are bonded only to the ⁇ ⁇ ⁇ group except for the bond to the organic chain or the polysiloxane bond (Si — O— Si bond). Since the ionicity of the Si atom is further increased, and as a result, the hydrolysis / condensation rate of the 0 group is increased, and the reactive sites in the silicon-containing polymer are increased, resulting in core particles having a stronger skeleton. It is.
  • polysiloxane group examples include a polydimethoxysiloxane group, a polydiethoxysiloxane group, a polydiiso-propoxysiloxane group, and a poly n-butoxysiloxane group.
  • the Si atom in the polysiloxane group may be directly bonded to the organic chain (for example, a Si—C bond may be formed) or bonded via any appropriate group or atom. (For example, a Si—O—C bond may be formed).
  • the Si atom is directly bonded to the organic chain. This is because the binding site is less susceptible to undesired reactions (for example, hydrolysis and exchange reactions).
  • the content of the polysiloxane group in [0033] silicon-containing polymer preferably 0.5 5; 10 molar%, more preferably from 0.5 to 5 mol 0/0. Within such a range, core particles having a desired strength, shape, size and the like can be obtained.
  • the molecular weight (number average molecular weight) of the silicon-containing polymer is preferably 200,000 or less, more preferably ⁇ 50,000 or less, and particularly preferably ⁇ 10000 or 10,000. -30,000. If the molecular weight is too high, it may not dissolve in organic solvents. If the molecular weight is too low, the amount of polymerizable functional group introduced may be insufficient.
  • the silicon-containing polymer can be produced by any appropriate method. Specific examples include a method of radical (co) polymerizing a radical polymerizable monomer in the presence of a polymerizable polysiloxane.
  • the polymerizable polysiloxane is obtained by partially hydrolyzing and condensing a silane compound and a polymerizable functional group-containing silane coupling agent.
  • the silane compound may be any appropriate one as long as desired core particles are obtained.
  • Silane compounds can be employed. Specific examples of silane compounds include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, triethoxymethoxysilane, diethoxydimethoxysilane, tetraiso-propoxysilane, tetrabutoxysilane, trimethoxyhydro
  • Methoxysilane is particularly preferred. Silane compounds may be used alone or in combination of two or more.
  • polymerizable functional group-containing silane coupling agent examples include attaryloxypropyltrimethoxysilane, talyloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, and methacryloxypropyltriethoxysilane.
  • the polymerizable functional group-containing silane coupling agent may be used alone or in combination of two or more.
  • the hydrolysis / condensation reaction between the silane compound and the polymerizable functional group-containing silane coupling agent may be carried out under any appropriate conditions.
  • the hydrolysis / condensation reaction is performed in solution.
  • the solution is a solution in which a silane compound and a polymerizable functional group-containing silane coupling agent are dissolved in water and / or an organic solvent.
  • the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran and dioxane.
  • Ethers such as ethyl ether; methanol, ethanol, iso-propyl alcohol, n-butanol, ethylene glycol, propylene glycol, and other halogenated hydrocarbons such as methylene chloride and chloroform .
  • the organic solvents may be used alone or in combination of two or more.
  • the hydrolysis / condensation reaction may be carried out with or without a catalyst.
  • a catalyst is used.
  • the catalyst include an acidic catalyst and a basic catalyst.
  • the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as acetic acid, propionic acid, oxalic acid and p-toluenesulfonic acid; and acidic ion exchange resins.
  • Specific examples of basic catalysts include ammonia; organic amine compounds such as triethylamine, tripropylamine; sodium methoxide, sodium ethoxide, potassium methoxide.
  • Alkali metal compounds such as xoxide, potassium ethoxide, sodium hydroxide and potassium hydroxide; basic ion exchange resins and the like. Acidic catalysts are preferred. This is because partial hydrolysis is easy to control the condensation reaction.
  • the catalysts may be used alone or in combination of two or more.
  • the reaction temperature of the hydrolysis / condensation reaction is preferably 60 to 100 ° C, and the total reaction time is preferably 3 to 6 hours.
  • the reaction temperature may be controlled stepwise or may be changed in stages. As described above, a polymerizable polysiloxane is obtained.
  • a radically polymerizable monomer is radically (co) polymerized in the presence of the polymerizable polysiloxane to obtain a silicon-containing polymer.
  • the radical polymerizable monomer include acrylic monomers, styrene monomers, olefin monomers, bur monomers, and monomers that form polyesters (for example, dicarboxylic acids and diamines). Preference is given to acrylic monomers. This is because composite fine particles having an appropriate coating film forming ability can be obtained.
  • acrylic monomers include acrylic carboxylic acids such as (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryltridecyl (meth) acrylate, etc.
  • acrylic carboxylic acids such as (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth
  • (Meth) acrylic acid ester epoxy group-containing (meth) acrylic acid ester such as (meth) acrylic acid glycidyl; (meth) acrylonitrile, (meth) acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, diacetone acrylamide , (Meth) acrylic acid 2-ethyl sulfonate.
  • Acrylic monomers may be used alone or in combination of two or more. In the present invention, it is preferable to copolymerize the acrylic monomer and an acrylic monomer having a functional group containing active hydrogen.
  • a typical example of an acrylic monomer having a functional group containing active hydrogen is a hydroxyl group-containing acrylic monomer.
  • hydroxyl group-containing attalinole monomers include (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl, and force prolataton-modified hydroxyl (meth).
  • the ratio (molar ratio) of acrylic monomer / functional group (for example, hydroxyl group) -containing acrylic monomer in copolymerization is preferably 90/10 to 20/80, more preferably 70/30 to 40/60. It is.
  • the ratio of the functional group-containing acrylic monomer is too small, the amount of the polymerizable functional group introduced into the composite fine particles is insufficient, and as a result, the curability of the composite fine particles may be insufficient. If the ratio of the functional group-containing acrylic monomer is too large, the stability of the silicon-containing polymer may be insufficient.
  • the silicon-containing polymer is reacted with an isocyanate compound having a polymerizable functional group (preferably an ethylenically unsaturated group) to introduce a polymerizable functional group into the polymer side chain.
  • a polymerizable functional group derived from an isocyanate compound is introduced into the polymer side chain by an addition reaction between a functional group having active hydrogen (for example, a hydroxyl group) on the polymer side chain and an isocyanate group.
  • a functional group having active hydrogen for example, a hydroxyl group
  • the polymerizable functional group contained in the isocyanate group include an alicyclic group and a methacryloyl group.
  • a typical reaction scheme is as follows. Arbitrary appropriate conditions can be employ
  • the fine particles are obtained by reacting the silicon-containing polymer having a polymerizable functional group in the side chain with a metal compound capable of generating a metal oxide by hydrolysis.
  • a metal compound is converted into a metal oxide by hydrolysis, and further condensed with a polysiloxane group in the polymer side chain to form a three-dimensional network.
  • core particles having a strong skeleton are formed, and composite fine particles are obtained.
  • Specific examples of such metal compounds include metal halides, metal nitrates, metal sulfates, metal ammonium salts, organometallic compounds, alkoxy metal compounds, or derivatives thereof.
  • the metal compounds may be used alone or in combination of two or more.
  • the metal compound is a compound represented by the following general formula (1) or an derivative thereof:
  • M is a group III, group IV or group V metal element of the periodic table, preferably at least one metal element selected from Si, Al, Ti and Zr.
  • R 2 is each independently a hydrogen atom or a substituted or unsubstituted alkyl group or an acyl group.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group.
  • Specific examples of the acyl group include an acetyl group and a propionyl group.
  • R 2 is particularly preferably a hydrogen atom, a methyl group, or an ethyl group, and most preferably a methyl group . Hydrolysis of R 2 0 group 'Because the condensation rate is fast.
  • R 3 is independently a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group or aralkyl group.
  • the alkyl group is the same as described above.
  • Specific examples of the cycloalkyl group include a cyclohexyl group.
  • aryl groups include phenyl, tolyl, and xylyl groups.
  • Specific examples of the aralkyl group include a benzyl group.
  • Examples of the substituent for the alkyl group, cycloalkyl group, aryl group and aralkyl group include an alkoxy group such as a methoxy group and an ethoxy group, an amino group, a nitro group, an epoxy group, and a halogen.
  • n is the valence of the metal element M
  • m is an integer from !! to n.
  • metal compound methyltrimethoxysilane ⁇ Seto silane, dimethyl ⁇ Se Toki La silane, tetra i so proxy silane, tetrabutoxysilane, methylcarbamoyl Honoré trimethoxysilane, phenylalanine trimethoxysilane, phenylalanine triethoxysilane , Dimethoxydimethylsilane, dimethoxymethylenophenylenosilane, trimethinolemethoxysilane, trimethinoreethoxysilane, dimethinolegoxysilane, dimethoxydiethoxysilane, aroleminium trimethoxide, aluminum triethoxy Aluminum triisopropoxide, aluminum tributoxide, dimethylaluminum methoxide, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium,
  • the metal compound is particularly preferably a silane compound and a derivative thereof in which M is Si in the general formula (1). Most preferred are tetramethoxysilane and tetraethoxysilane. This is because it is easy to obtain and does not contain no, rogen, etc., and does not adversely affect the physical properties of the production equipment and the final product.
  • any appropriate condition can be adopted.
  • the reaction is performed in the presence of an organic solvent and / or water. Therefore, the composite fine particles are typically obtained in the form of a dispersion.
  • Specific examples of the solvent are as listed above.
  • the ratio of the core particle / organic polymer in the composite fine particles obtained as described above is preferably 90/10 to 40/60, more preferably 80/20 to 50/50. If the ratio of the core particles is too high, the amount of polymerizable functional groups introduced may be insufficient, and as a result, the curability of the composite fine particles may be insufficient. If the ratio of the organic polymer is too high, the resulting coating film may have insufficient hardness.
  • the coating composition of the present invention comprises composite fine particles, a polyfunctional polymerizable compound, and, if necessary, a polymerization initiator and a solvent.
  • a film is formed by the polymerization (curing) of the polymerizable functional group (typically an ethylenically unsaturated group) of the composite fine particle and the functional group of the polyfunctional polymerizable compound.
  • the composite fine particles are as described in the above items A to C.
  • the composite fine particles are contained in the composition at a ratio of preferably 20 to 500 parts by weight, and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable compound.
  • Specific examples of the polyfunctional polymerizable compound include polyfunctional (meth) acrylate and urethane (meth) acrylate.
  • Polyfunctional polymerizable compounds may be used alone or in combination of two or more.
  • any appropriate (meth) acrylate can be adopted as long as it has two or more (meth) acrylate groups in the molecule.
  • Specific examples include 1,6-hexanediol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate.
  • Examples of the urethane (meth) acrylate include compounds obtained by reacting a hydroxyl group-containing (meth) acrylate and a polyisocyanate.
  • Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) alkyl.
  • Hydroxyhexynole (meth) atalylate pentaerythritoloretriacrylate, pentaerythritoloretetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylol, propanediatalylate, etc. It is done.
  • the hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more.
  • the polyisocyanate may be any of aliphatic, aromatic and alicyclic.
  • polyisocyanate examples include methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2, 2, 4-trimethinolate, dicyclohexylenomethane diisocyanate. , Tolylene diisocyanate, phenolic diisocyanate, methylene bisphenyl diisocyanate and the like. Polyisocyanates that are non-yellowing urethanes are preferred. Polyisocyanates can be used alone or in combination of two or more.
  • hydroxyl group-containing (meth) acrylate and polyisocyanate Any appropriate combination can be adopted depending on the purpose. Preferred is a combination of 2-hydroxyethyl acetylate and isophorone diisocyanate, and a combination of 2-hydroxyethyl oleate and 2,2,4 trimethylhexamethylene diisocyanate.
  • urethane (meth) acrylate for example, the ratio of hydroxyl group in hydroxyl group-containing (meth) acrylate and isocyanate group in polyisocyanate (hydroxyl group: isocyanate group) Is weighed to a molar ratio of 1: 0 ⁇ 8 to 1: 1 and placed in a reaction vessel, and a catalytic amount of an organic tin compound such as di-n-butyltin dilaurate is added to inhibit polymerization of nitroidroquinone, etc. An agent may be further added, followed by heating and stirring at a reaction temperature of 30 to 120 ° C, preferably 50 to 90 ° C.
  • the reaction temperature is preferably raised stepwise.
  • the reaction product may contain an oligomerized urethane (meth) acrylate.
  • urethane (meth) acrylates include the KAYARAD ureatanate series (manufactured by Nippon Kayaku Co., Ltd.), Shimitsu series (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and the New Frontier R-1000 series ( Daiichi Kogyo Seiyaku Co., Ltd.), UA-306H, UF-8001 (Kyoeisha Chemical Co., Ltd.), NK Oligo U Series, NK Oligo UA Series (Shin Nakamura Chemical Co., Ltd.), and the like.
  • any appropriate type of initiator may be employed depending on the purpose.
  • the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.
  • the polymerization initiators may be used alone or in combination of two or more.
  • a photopolymerization initiator is preferred.
  • Specific examples of the photopolymerization initiator include benzoin compounds, acetophenone compounds, benzophenone compounds, anthraquinone compounds, phosphine oxide compounds, xanthone compounds, thixanthone compounds, and ketal compounds.
  • Benzoin benzoin methyl ethereol, benzoin ethyleno ethere, benzoin isopropinore etherol, benzoin n butyl ether, benzoin isobutyl ether, acetophenone, dimethylacetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2, 2— Diethoxy-2-phenyl-2-acetophenone, 2-hydroxy-1-2-methyl 1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-phenyl [4 (methylthio) phenyl] — 2—morpholinopropane 1-one, 1— [4— (2-hydroxyethoxy) phenyl]-2 hydroxy-1-methyl 1-propane-1-one, 2-hydroxy-1- 1— ⁇ 4— [4— (2-hydroxy-2-methylpropionyl) benzyl] phenyl ⁇ 2-methylpropan 1-one, 2-benzyl-1-2
  • the polymerization initiator is preferably contained in the composition in a ratio of 0.;! To 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the solid content of the coating composition.
  • any suitable solvent can be adopted as long as the composite fine particles and the polyfunctional polymerizable compound can be dispersed.
  • Specific examples of the solvent include those listed in the above section C.
  • the coating composition of the present invention may further contain any appropriate monofunctional polymerizable compound depending on the purpose.
  • the monofunctional polymerizable compound include acrylamide, (meth) toxylmethyl (meth) acrylate, isobornyloxychetyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl ( (Meta) Atalylate, Ethyl Jetylene Mido, dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentagen (meth) acrylate, dicyclopentenyloxychetyl (meth) acrylate, N, N— Dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxychetyl (meth) acrylate, tetrahydr
  • the coating composition of the present invention may further contain any appropriate additive depending on the purpose.
  • additives include leveling agents, pigments, pigment dispersants, UV absorbers, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, peroxide decomposers, fillers.
  • a silicone compound may be used as the antifouling agent. Any appropriate type of silicone compound can be adopted as the silicone compound depending on the purpose. Only one silicone compound may be used, or two or more silicone compounds may be used in combination.
  • the silicone compound preferably has a hydroxyl group (one OH).
  • the number of hydroxyl groups may be one or more. Hydroxyl groups may be present at both ends of the polysiloxane main chain. However, it may be provided at one end. Moreover, you may have in the side chain couple
  • a silicone compound described in Chemical Formulas 3 to 10 of JP-A-8-208998 a silicone compound described in General Formula (2) (a structure having hydroxyl groups at both ends of a polysiloxane main chain)
  • the silicone compound described in the general formula (3) structure having a hydroxyl group at one end of the polysiloxane main chain
  • the silicone compound described in the general formula (4) (bonded to the polysiloxane main chain! /, Structure having a hydroxyl group in the side chain).
  • R and R are alkylene groups having 1 to 8 carbon atoms.
  • R and R are alkyl groups or phenyl groups having 1 to 8 carbon atoms, and each R
  • R may be the same or different.
  • R is an alkylene group having 1 to 8 carbon atoms.
  • R is an alkyl group or phenyl group having 1 to 8 carbon atoms, and each R may be the same or different.
  • R is an alkylene group having 1 to 8 carbon atoms.
  • the silicone compound preferably has a (meth) attayloxy group at both ends of the polysiloxane main chain via a polyether chain.
  • a silicone compound represented by the general formula (5) can be mentioned.
  • R is H or CH.
  • R and R are alkylene groups having 1 to 8 carbon atoms.
  • R is an alkyl group having 1 to 8 carbon atoms or phenyl
  • Each R may be the same or different.
  • X is an alkylene group having 1 to 5 carbon atoms.
  • the coating composition of the present invention may further contain any appropriate organic or inorganic fine particles.
  • organic or inorganic fine particles are used for imparting a function (for example, refractive index adjustment, conductivity, antiglare property) according to the purpose to the obtained coating layer.
  • fine particles useful for increasing the refractive index of the coating layer and imparting conductivity include zinc oxide, titanium oxide, zirconium oxide, aluminum oxide, tin oxide, tin-doped indium oxide, antimony-doped tin oxide, indium-doped zinc oxide, Examples include indium oxide and antimony oxide.
  • the fine particles useful for lowering the refractive index of the coating layer include magnesium fluoride, silica, and hollow silica.
  • Specific examples of the fine particles useful for imparting antiglare properties include inorganic particles such as calcium carbonate, barium sulfate, talc and kaolin in addition to the above fine particles; silicon resin, melamine resin, benzoguanine resin, acrylic resin, polystyrene resin And their copolymer resins, etc. And organic fine particles. These fine particles may be used alone or in combination of two or more.
  • the coating composition of the present invention includes, for example, a hard coating agent such as a transfer foil film, a plastic optical component, a touch panel, a film-type liquid crystal element, and a plastic molding, a low refractive index coating agent for an antireflection film, and a light diffusing agent. It can be suitably used as a film coating agent.
  • the coating composition of the present invention can be suitably used as a low refractive index coating agent.
  • a low refractive index coating composition such a composition is referred to as a “low refractive index coating composition”.
  • the refractive index at a wavelength of 550 nm of a 0.1 ⁇ m-thick film formed by the low refractive index coating composition of the present invention preferably (preferably 1 ⁇ 25—1.40, more preferred (preferably 1 25 to 1. 35.
  • the composite fine particles of the present invention due to voids in the composite fine particles and / or in the film formed from the low refractive index coating composition containing the composite fine particles, Such a refractive index appears.
  • the organic polymer has a portion containing a fluorine atom. It is preferable. This is because the refractive index of the composite fine particles is lowered and the refractive index of the coating film can be further lowered.
  • Such composite fine particles can be obtained by copolymerizing a radical polymerizable monomer containing a fluorine atom when producing a silicon-containing polymer.
  • the radically polymerizable monomer containing a fluorine atom can be copolymerized in a proportion of preferably 3 to 95 parts by weight, more preferably 5 to 80 parts by weight, based on 100 parts by weight of the total amount of the radically polymerizable monomers. If it is less than 3 parts by weight, the refractive index may not be sufficiently contributed. If it exceeds 95 parts by weight, the particles tend to aggregate.
  • an acrylic monomer having a perfluoroalkyl group is preferred.
  • fluoroalkyl group examples include perfluoromethyl group, perfluoroethyl group, norfluorobutyl group, perfluorohexyl group, perfluorooctyl group, nitrofluorodecyl group, perfluorododecinole group. Group, perfluorotetradecinole group is preferable.
  • Such monomers may be used alone or in combination of two or more.
  • F Specific examples of the acrylic monomer having a nitrogen atom include 2,2,2-trifluoroethylol (meth) acrylate and perfluorooctyl cetyl (meth) acrylate.
  • the composite fine particles are preferably 100 to 500 parts by weight, more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable compound. Contained in the composition. If it is 100 parts by weight or less, there is a possibility that voids in the coating are not filled with the polyfunctional polymerizable compound and the refractive index is not lowered. If it is 500 parts by weight or more, the scratch resistance of the film may be insufficient.
  • the optical film of the present invention includes a coating layer of the coating composition.
  • coating composition includes both the coating composition described in the above section D-1 and the low refractive index coating composition described in the section D-2.
  • this optical film includes a substrate and a coating layer.
  • the coating layer is typically formed by applying the above coating composition, followed by drying and curing.
  • a typical example of the base material is a plastic film. Specific examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene phenol, polypropylene vinyl, cellophane, dicetinoresenololose phenol, triacetyl cellulose film, acetylenoresenobutyl butyrate.
  • the substrate may be subjected to any appropriate surface treatment depending on the purpose.
  • surface treatment include surface concavo-convex treatment by sandblasting, solvent treatment, etc .; surface oxidation treatment such as corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment; resin composition
  • primer treatment with a product for example, primer treatment with a product.
  • any appropriate application method can be adopted. Specific examples include spin coating, dipping, spraying, slide coating, single coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, and bead coating.
  • any appropriate method and conditions may be employed as the drying and curing method.
  • the solvent is evaporated and dried at 0 to 200 ° C., followed by curing with heat and / or radiation.
  • radiation it is preferable to use ultraviolet rays or electron beams.
  • the coating composition of the present invention is used, a curing treatment with ultraviolet rays is particularly preferable.
  • the dose of ultraviolet ray is preferably 10; a 100 mJ / cm 2, more preferably from 100 to 2000 mJ / cm 2.
  • the ultraviolet irradiation is performed in a state where part or all of the atmosphere is replaced with an inert gas. As a result, oxygen inhibition at the surface can be suppressed.
  • the inert gas nitrogen gas is preferable.
  • the thickness of the coating layer to be formed is a force that can vary depending on the purpose, preferably 50 nm to 100 ⁇ m.
  • optical film examples include a hard coat film, an antiglare film, an antireflection film, a polarizing plate, an optical filter, a light diffusion film, and the like used in a show window, an automotive glass, and an image display device. It is done.
  • image display device include a liquid crystal display device (LCD), a cathode ray tube display device (CRT), a plasma display panel (PDP), and an electoric luminescence display (ELD).
  • LCD liquid crystal display device
  • CTR cathode ray tube display device
  • PDP plasma display panel
  • ELD electoric luminescence display
  • the optical film of the present invention is a hard coat film.
  • the hard coat film is a film imparted with physical strength by applying the above coating composition to a substrate and then drying and curing to form a hard coat layer.
  • the thickness of the hard coat layer can be appropriately designed according to the application.
  • Hard coat The thickness of the layer is preferably;! -10 m, more preferably 1-5111.
  • the strength of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more, in a pencil hardness test according to JIS K5400.
  • the hard coat film further comprises any suitable coating layer on the surface of the hard coat layer, which may contain any suitable additive in the substrate and / or hard coat layer. Also good.
  • the coating layer may be a single layer or two or more layers. By using an additive and / or a coating layer, for example, antistatic properties, antifouling properties, slip properties, antiglare properties and the like can be imparted.
  • antiglare properties can be imparted by forming irregularities on the surface of the hard coat layer.
  • the hard coat layer imparted with the antiglare property can be suitably used, for example, as an antiglare layer of an antireflection film.
  • a film having a hard coat layer imparted with antiglare properties can be suitably used, for example, as an antiglare film.
  • such a hard coat film can be used as a base material for an antireflection film.
  • the optical film of the present invention is an antireflection film.
  • the antireflection film is a laminate having a low refractive index layer formed by applying the low refractive index coating composition on at least one side of a substrate and then drying and curing.
  • the low refractive index layer may be formed through another layer which may be directly formed on the substrate.
  • the other layer may be one layer or two or more layers. Specific examples of the other layer include a layer having a refractive index different from that of the low refractive index layer.
  • the refractive index of the other layers is often larger than the refractive index of the low refractive index layer. By providing such a layer, reflection can be reduced in a wider wavelength range.
  • the low refractive index layer can be preferably formed as the outermost layer of the antireflection film. Therefore, specific examples of the preferred laminated structure of the antireflection film include: base material / low refractive index layer, base material / high refractive index layer / low refractive index layer, base material / medium refractive index layer / high refractive index layer / low Examples include a refractive index layer.
  • the high refractive index layer means a layer having a higher refractive index than the low refractive index layer, and the middle refractive index layer is higher than the low refractive index layer and has a high refractive index. A layer having a lower refractive index than the layer.
  • the thickness of the medium refractive index layer or the high refractive index layer is preferably 0.05. ⁇ 0.20 111.
  • the refractive index of the medium refractive index layer or the high refractive index layer is preferably 1.45 to 2.00. More specifically, the refractive index of the medium refractive index layer is preferably 1.45 to 1.80, and the refractive index of the high refractive index layer is preferably 1.60 to 2.00.
  • the middle refractive index layer or the high refractive index layer may be formed from a composition comprising a polyfunctional polymerizable compound and high refractive index fine particles. Specific examples of the polyfunctional polymerizable compound include polyfunctional (meth) acrylate and urethane (meth) acrylate.
  • a representative example of the high refractive index fine particles is metal oxide fine particles.
  • Specific examples include zinc oxide, titanium oxide, zirconium oxide, aluminum oxide, tin oxide, tin-doped indium oxide, indium-doped zinc oxide, indium oxide, and antimony oxide.
  • the refractive index of the medium refractive index layer or the high refractive index layer can be controlled.
  • the medium refractive index layer or the high refractive index layer can also function as an antistatic layer.
  • the medium refractive index layer or the high refractive index layer has a refractive index such as titanium oxide or zirconium oxide formed by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD). High vapor deposition film of inorganic oxide can be obtained.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the antireflection film of the present invention may have still another layer having any appropriate function depending on the purpose.
  • the further other layer is provided at any appropriate position of the laminate according to the purpose.
  • Specific examples of the other layers include a hard coat layer, an antiglare layer, an antistatic layer, and an antifouling layer.
  • the hard coat layer is preferably formed using a coating agent containing a polyfunctional polymerizable compound.
  • Specific examples of the polyfunctional polymerizable compound include polyfunctional (meth) acrylate and urethane (meth) acrylate.
  • the antiglare layer is preferably formed using a coating agent containing particles and a polyfunctional polymerizable compound.
  • Various inorganic particles, organic particles, and organic / inorganic composite particles can be used as the particles.
  • the hard coat layer and antiglare layer described in the above section E-2 can also be used as the hard coat layer and antiglare layer.
  • the antistatic layer prevents dust from adhering to the antireflection film by preventing the generation of static electricity and / or when the antireflection film is incorporated into an image display device. Prevent external static electricity failure.
  • Antistatic layer performance includes antireflection The surface resistance after formation of the stop film, preferably 10 ⁇ / mouth or less. Even if the surface resistance is 10 12 ⁇ / mouth or more, the adhesion of dust and dust can be improved to some extent as compared with the case where no antistatic layer is provided.
  • the antistatic layer is generally formed from an antistatic resin composition containing a film-forming component (typically a resin component) and an antistatic agent. Any appropriate resin capable of forming a film can be adopted as the resin component. Specific examples of antistatic agents include quaternary ammonium salts, pyridinium salts, and cationic antistatic agents having cationic groups such as primary to tertiary amino groups; sulfonate groups, sulfate ester bases, phosphate esters.
  • Anionic antistatic agents having anionic groups such as bases and phosphonic acid groups; Amphoteric antistatic agents such as amino acids and amino amino sulfates; Nonionic antistatic agents such as amino alcohols, glycerin, and polyethylene glycol
  • a surfactant-type antistatic agent such as an organometallic compound (for example, tin or titanium alkoxide) or a metal chelate compound (for example, an acetylethylacetonate salt of an organometallic compound); and the above-described antistatic agent And high molecular weight antistatic agents.
  • Antistatic agents can also be used. Further, metal oxide fine particles such as zinc oxide, titanium oxide, tin oxide, tin-doped indium oxide, antimony-doped tin oxide, indium-doped zinc oxide, indium oxide, and antimony oxide can be used.
  • the hard coat layer and the antiglare layer can be used as an antistatic layer.
  • the antireflection film of the present invention is preferably as the total light transmittance is higher and / or as the haze is lower. Therefore, the layers that make up the antireflection film (laminate) should be as transparent as possible! /.
  • the optical film of the present invention is a polarizing plate.
  • the polarizing plate has a polarizer and the antireflection film provided on at least one of the polarizers.
  • the antireflection film also serves as a protective film for the polarizing plate.
  • Any suitable polarizer can be used as long as it has a polarization function (a function of passing only light having a polarization plane in a certain direction).
  • a typical example of a polarizer is a polybulal alcohol polarizing film.
  • the polybulal alcohol-based polarizing film is typically a stretched film of a polybulal alcohol-based film containing a dichroic substance (typically iodine or a dichroic dye).
  • Polyuric alcohol-based polarizing film is formed by forming a polyvinyl alcohol aqueous solution and uniaxially stretching it while dyeing it by immersing it in, for example, an iodine solution, or uniaxially stretching after dyeing, and is preferably durable with a boron compound. What has been sex-treated is used!
  • the polarizing plate of the present invention can be produced by any appropriate method.
  • the antireflective film of the present invention is treated with an alkali and bonded to both sides of the above-described polybulualcohol polarizing film using a completely saponified polybulualcohol adhesive (water-soluble adhesive).
  • the alkali treatment refers to a treatment in which the antireflection film is immersed in a high-temperature strong alkaline solution in order to improve the wettability of the adhesive and improve the adhesiveness.
  • a peelable protective film for example, a film made of polyester resin such as polyethylene terephthalate
  • a peelable protective film for example, a film made of polyester resin such as polyethylene terephthalate
  • the optical film of the present invention is an optical filter for a plasma display (PDP).
  • An optical filter for PDP typically has a support and an antireflection film provided on the support.
  • a specific example of the support is glass.
  • the antireflection film is preferably the antireflection film described in the above section E-3.
  • the PDP optical filter further includes a near-infrared absorbing film, an electromagnetic wave shielding film and / or a visible light absorbing film on the support. These films are typically provided between the support and the antireflection film.
  • PDP emits near-infrared light with a wavelength of 800 nm or higher during plasma discharge; Inducing malfunction of Kong is a problem! Such a problem can be reduced or eliminated by providing a near-infrared absorbing film.
  • the PDP performs plasma discharge in a gas mainly composed of a rare gas (especially neon) sealed inside the panel, and R, G, Since the phosphor of B emits light, electromagnetic waves unnecessary for the operation of the PDP are simultaneously emitted during this light emission process. By providing an electromagnetic wave shielding film, such problems can be reduced or eliminated.
  • the near-infrared absorbing film is typically formed from a composition containing a near-infrared absorbing dye and a binder.
  • a near-infrared absorbing dye include cyanine-based, polymethine-based, squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, and dimonium-based pigments.
  • Any appropriate resin can be adopted as the noinder.
  • a resin capable of forming a highly transparent film is preferred.
  • polyolefin resin such as polyethylene
  • styrene resin such as polyethylene
  • bur resin such as a (meth) acrylate ester polymer
  • polyamide resin such as nylon
  • polyurethane resin such as polyurethane resin
  • polyester resin such as polyethylene
  • polycarbonate resin such as polycarbonate resin
  • the electromagnetic wave shielding film a film obtained by patterning a metal mesh on a film by a technique such as etching or printing, and smoothed with a resin; a metal was deposited on a fiber mesh
  • a film in which a material is embedded in a resin examples include a film in which a material is embedded in a resin.
  • the PDP optical filter of the present invention may further have a shock absorbing layer.
  • the shock absorbing layer may be used instead of the support. It is preferable to use it instead of the support.
  • the shock absorbing layer is used to protect the PDP from external shocks.
  • the material constituting the shock absorbing layer include ethylene acetate butyl copolymer, acrylic resin, polychlorinated bur, urethane resin, and silicon resin. Details of the material constituting the shock absorbing layer are described in, for example, Japanese Patent Application Laid-Open No. 2004-246365 or Japanese Patent Application Laid-Open No. 2004-264416.
  • the PDP optical filter of the present invention may have any appropriate configuration (laminated structure) depending on the purpose.
  • Typical configurations include antireflection film / near infrared absorption film / support Examples include a holder, an antireflection film / near infrared absorption film / electromagnetic wave shielding film / support, and an antireflection film / electromagnetic wave shielding film / near infrared absorption film / support.
  • an optical filter for PDP having the configuration of an antireflection film / near infrared absorption film / support can be produced by the following method: (i) The above composition on the support side surface of the antireflection film Is applied and dried to form a laminate of an antireflection film / near-infrared absorbing film, and the laminate is laminated to a support, or (ii) the composition is applied to a support and dried. Then, a method of forming a support / near infrared absorption film laminate and laminating an antireflection film on the laminate. In the lamination, the same film to be laminated may be bonded with an adhesive or an adhesive, and the respective films may be bonded by heating and melting.
  • an anchor coat layer for example, a highly polar polymer such as polyethyleneimine, oxazoline polymer, polyester, cellulose, etc.
  • physical treatment eg, corona treatment, plasma treatment
  • the optical filter for PDP of the present invention may be used by being mounted on the front side of the PDP, and may be used by being bonded together with an adhesive or pressure sensitive adhesive.
  • the image display device of the present invention includes the optical film.
  • the image display device of the present invention includes at least one selected from the antireflection film, the polarizing plate, and the optical filter.
  • the image display device has the antireflection film on the outermost surface thereof. According to such an embodiment, external light reflection can be satisfactorily reduced.
  • the image display device includes the antireflection film on one or more surfaces of a component provided therein and having an interface with air. According to such an embodiment, it is possible to reduce the reflected light inside the apparatus with a force S.
  • the polymerizable agent to the composite fine particles is obtained.
  • the amount of active group introduced can be greatly increased compared to the conventional method.
  • composite fine particles having excellent curability hardness, wear resistance, scratch resistance
  • gelation occurs when a large amount is introduced, and it is substantially impossible to introduce a large amount of functional groups. It was impossible.
  • a polymerizable functional group is produced by reacting an active hydrogen-containing functional group (preferably a hydroxyl group) in the side chain of a silicon-containing polymer (which eventually becomes an organic polymer) with an isocyanate compound. It becomes possible to introduce a large amount of groups.
  • the polymerizable functional group is located away from the core particle via an organic polymer that is not directly bonded to the core particle, and the organic polymer main chain is flexible, so that The reaction rate of the polymerizable functional group at the time is very high. As a result, a film having very excellent hardness can be obtained.
  • the polymerizable functional group is bonded to the organic polymer main chain via a urethane bond.
  • solubility and dispersibility in a solvent are ensured mainly due to the organic polymer main chain, and adhesion is largely improved mainly due to the urethane bond. Therefore, composite fine particles that can achieve both adhesion and dispersion stability can be obtained. Furthermore, by having excellent adhesion, volume shrinkage after curing can be significantly reduced.
  • oxygen groups are unevenly distributed on the surface of the composite fine particles, thereby inhibiting oxygen inhibition. It is less susceptible to the effects of aging, and the curability during thin film formation is improved.
  • a pencil grabbing test was conducted in accordance with JIS—K5400, and an evaluation was made based on scratches.
  • the haze meter (Nippon Denshoku Co., Ltd., NDH2000) was used for measurement.
  • the appearance of the coating film surface was visually observed to evaluate the coating film unevenness. ⁇ indicates that no coating unevenness is observed, ⁇ indicates that coating unevenness is observed, and X indicates that significant coating unevenness is observed.
  • the reflectance was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV3700), and the luminous reflectance was obtained from the measurement result of the reflectance.
  • the refractive index at a wavelength of 550 nm of the coating film (coating layer) was obtained from the measured value of the film by the nonlinear least square method.
  • the internal temperature was raised to about 80 ° C over 2 hours and kept at the same temperature until methanol no longer flowed out. Furthermore, the reaction was allowed to proceed further by holding at a pressure of 2.67 X 10 kPa and a temperature of 90 ° C until methanol no longer flowed out. After the reaction mixture was cooled again to room temperature, Amberlyst 15 was filtered off to obtain a polymerizable polysiloxane (M-1) having a number average molecular weight of 1,800.
  • a mixed solution (raw material solution B) of 5 g of 25% aqueous ammonia, 15 g of methanol and 10 g of deionized water was added dropwise from the dropping port b over 2 hours.
  • a distillation column, a cooling pipe connected to this, and an outlet are provided instead of the cooling pipe.
  • the temperature inside the flask is raised to 70 ° C under a pressure of 40 kPa, and ammonia, methanol, and butyl acetate are solidified. Distillation was carried out until the content reached 30% to obtain a dispersion (S-1) in which composite fine particles were dispersed in butyl acetate.
  • the resulting composite fine particles had an average particle size of 22. lnm and an inorganic core particle / organic polymer ratio of 61/39. Evaluation was performed by the following method.
  • Elemental analysis was performed on the composite fine particle dispersion (S-1) dried at 130 ° C for 24 hours under a pressure of 1.33 X 10 kPa, and ash was determined as the content of inorganic core particles in the composite fine particles.
  • Composite fine particle dispersion (S-1) Using a solution of lg diluted with 99 g of n-butyl acetate, the particles were photographed with a transmission electron microscope, and the diameters of 100 randomly selected particles were read. The average was determined as the average particle size.
  • Dipentaerythritol hexaatalylate (DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.)
  • DPE-6A Dipentaerythritol hexaatalylate
  • Irgacure 907 photopolymerization initiator
  • S-l composite fine particle dispersion
  • Example 11 The above coating composition was applied to a polyethylene terephthalate film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd .: thickness 1 88 m) using a bar coater. The coated layer was dried at 100 ° C. for 15 minutes and then cured by irradiating 250 mj / cm 2 of ultraviolet light with a high pressure mercury lamp to form a hard coat layer having a thickness of 2.8 m. The hard coat layer thus obtained was evaluated for pencil hardness, steel wool resistance, haze, total light transmittance and appearance, and the evaluation results are shown in Examples 2 to 11 and Comparative Examples described later! The results are shown in Table 2.
  • silane compound A 30 parts, MEK-ST (manufactured by Nissan Chemical Co., Ltd., methyl ethyl ketone dispersed colloidal silica, silica concentration 30%) 233 parts, isopropyl alcohol 5 parts and ion-exchanged water 3 parts under nitrogen flow
  • the liquid was stirred at 80 ° C. for 3 hours, then 18 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a colorless transparent dispersion (S-2).
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-2) was used and the formulation shown in Table 1 was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-3) was used and the formulation shown in Table 1 was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • 3-particyloxypropyltrimethoxysilane (KBM-5103, Shin-Etsu Chemical Co., Ltd.) 28 parts, MEK-ST (Nissan Chemical Co., Ltd., methyl ethyl ketone-dispersed colloidal silica, silica concentration 30 %) 400 parts and 8 parts of 0.002 N hydrochloric acid were added and stirred for 24 hours to obtain a dispersion (S-4).
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-4) was used and the formulation shown in Table 1 was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • a composite fine particle dispersion (S-5) was prepared in the same manner as in Example 1 except that the amount of the unsaturated group-containing silicon-containing polymer (P-2) used in the butyl acetate solution was changed from 10 g to 4 g. Obtained.
  • the obtained composite fine particles had an average particle size of 15.3 nm and an inorganic core particle / organic polymer ratio of 80/20.
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-5) was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • a silicon-containing polymer was obtained in the same manner as in Reference Example 2, except that Rataton-modified metatalylate (Daicel Chemical Industries, Plaxel FM-1) was used instead of 2-hydroxyethyl methacrylate. .
  • This silicon-containing polymer had a number average molecular weight of 15,000 and a weight average molecular weight of 29,000.
  • a solution in which the unsaturated group-containing silicon-containing polymer was dissolved in butyl acetate was obtained in the same manner as in Reference Example 3 except that this silicon-containing polymer was used.
  • This unsaturated group In the same manner as in Example 11 except that the solution containing the containing silicon containing silicon polypolymer solution was used in the same manner as in Example 11, the composite composite fine particles were obtained.
  • a fractional dispersion ((SS--66)) was obtained.
  • the obtained composite composite fine particles have a mean average particle size of 2233 .. 55nnmm, and the ratio ratio of inorganic inorganic cocoa granules // organic organic polypolymer is Was at 6611 // 3399. .
  • Example 11 In the same manner as in Example 11 except that this is the case where the dispersion dispersion ((SS—66)) is used, The composition composition was prepared to form a hard cocoate layer. .
  • the hardened coco coat layer here was used for the evaluation value in the same manner as in Example 11 of practical implementation. .
  • the results are shown in Table 22 below. .
  • a solution in which the unsaturated group-containing silicon-containing polymer was dissolved in butyl acetate was obtained in the same manner as in Reference Example 3 except that isocyanate (Power Lens BEI, Showa Denko) was used.
  • a composite fine particle dispersion (S-7) was obtained in the same manner as in Example 1 except that this unsaturated group-containing silicon-containing polymer solution was used.
  • the obtained composite fine particles had an average particle size of 25.2 nm and an inorganic core particle / organic polymer ratio of 61/39.
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-7) was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-8) was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • a composite fine particle dispersion (S-9) was obtained in the same manner as in Example 1 except that this unsaturated group-containing silicon-containing polymer (P-4) was used.
  • the resulting composite fine particles had an average particle size of 32. Onm and an inorganic core particle / organic polymer ratio of 61/39.
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-9) was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • a composite fine particle dispersion (S-10) was obtained in the same manner as in Example 1 except that this unsaturated group-containing silicon-containing polymer (P-6) was used.
  • the resulting composite fine particles had an average particle size of 18.6 nm and an inorganic core particle / organic polymer ratio of 61/39.
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-10) was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • a silicon-containing polymer (P--) was prepared in the same manner as in Reference Example 2 except that the amount of 2,2'-azobis (2-methylbutyronitrile) was changed to 2.5 g force and 1.8 g. 7) was obtained.
  • This silicon-containing polymer (P-7) had a number average molecular weight of 23,000 and a weight average molecular weight of 39,000.
  • a solution in which the unsaturated group-containing silicon-containing polymer (P-8) was dissolved in butyl acetate was obtained in the same manner as in Reference Example 3 except that this silicon-containing polymer (P-7) was used.
  • This unsaturated group-containing silicon-containing A composite fine particle dispersion (S11) was obtained in the same manner as in Example 1 except that the base polymer (P-8) was used.
  • the obtained composite fine particles had an average particle size of 30.5 nm and an inorganic core particle / organic polymer ratio of 61/39.
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-11) was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • a silicon-containing polymer (P-9) was used in the same manner as in Reference Example 2 except that the amount of 2,2'-azobis (2 methylbutyronitrile) was changed to 2.5 g force and 3.5 g. )
  • This silicon-containing polymer (P-9) had a number average molecular weight of 6,000 and a weight average molecular weight of 15,000.
  • a solution in which the unsaturated group-containing silicon-containing polymer (P-10) was dissolved in butyl acetate was obtained in the same manner as in Reference Example 3 except that this silicon-containing polymer (P-9) was used.
  • a composite fine particle dispersion (S-12) was obtained in the same manner as in Example 1 except that this unsaturated group-containing silicon-containing polymer (P-10) was used.
  • the obtained composite fine particles had an average particle size of 17.4 nm and an inorganic core particle / organic polymer ratio of 61/39.
  • a coating composition was prepared and a hard coat layer was formed in the same manner as in Example 1 except that this dispersion (S-12) was used. This hard coat layer was subjected to the same evaluation as in Example 1. The results are shown in Table 2.
  • Coating was performed in the same manner as in Example 1 except that urethane atarylate (DPHA-40H, Nippon Kayaku Co., Ltd.) was used instead of dipentaerythritol hexaatalylate and the formulation shown in Table 1 was used. A composition was prepared and a hard coat layer was formed. Examples of this hard coat layer The same evaluation as 1 was used. The results are shown in Table 2.
  • urethane atarylate DPHA-40H, Nippon Kayaku Co., Ltd.
  • a 500 ml four-necked flask equipped with a stirrer, two dripping ports (dropping port a and dripping port b), and a thermometer was charged with 200 g of butyl acetate and 50 g of methanol, and the internal temperature was adjusted to 40 ° C.
  • a mixed solution (raw material liquid A) of 10 g of a butyl acetate solution of unsaturated group-containing silicon-containing polymer (P-12), 13 g of tetramethoxysilane and 5 g of butyl acetate was added from the dripping port a.
  • Dipentaerythritol hexaatalylate (DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.)
  • DPE-6A Dipentaerythritol hexaatalylate
  • lg photopolymerization initiator
  • S-13 composite fine particle dispersion
  • This coating composition was applied to a polyethylene terephthalate (PET) film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd .: thickness 188 ⁇ m) in the same manner as in Example 1 to form a hard coat layer.
  • PET polyethylene terephthalate
  • the low refractive index coating composition was applied to the hard coat layer side of the laminate of PET PET / hard coat layer using a bar coater.
  • the coated layer was dried at 100 ° C. for 15 minutes and then cured by irradiating 750 mj / cm 2 with a high-pressure mercury lamp to form a low refractive index layer having a thickness of about lOOnm.
  • the film thickness was adjusted between 90 and 120 nm so that the reflectance spectrum at a wavelength between 400 nm and 800 nm was minimized at a wavelength of 550 nm.
  • the obtained low refractive index layer was evaluated for refractive index, luminous reflectance, haze, total light transmittance, steel wool resistance and pencil hardness. The evaluation results are shown in Table 4 together with the results of Examples 13 to; 17 and Comparative Examples 4 to 5 described later.
  • a low refractive index coating composition was prepared in the same manner as in Example 12 except that (S-1) was used instead of the composite fine particle dispersion (S-13).
  • a low refractive index layer was formed in the same manner as in Example 12 except that this low refractive index coating composition was used.
  • the obtained low refractive index layer was subjected to the same evaluation as in Example 12. The results are shown in Table 4.
  • a composite fine particle dispersion (S-14) was obtained in the same manner as in Example 12 except that the silicon-containing polymer (P-11) was used instead of the unsaturated group-containing silicon-containing polymer (P-12).
  • a low refractive index layer was formed in the same manner as in Example 12 except that the composite fine particle dispersion (S-14) was used. It was. The obtained low refractive index layer was subjected to the same evaluation as in Example 12. The results are shown in Table 4.
  • a low refractive index layer was formed in the same manner as in Example 12 except that the composite fine particle dispersion (S-4) was used.
  • the obtained low refractive index layer was subjected to the same evaluation as in Example 12. The results are shown in Table 4.
  • Example 12 In the same manner as in Example 12, except that the amount of butyl acrylate was changed from 140 g to 50 g and the amount of perfluorooctylethyl methacrylate was changed from 60 g to 150 g. A polymer was obtained. This silicon-containing polymer had a number-average molecular weight of 14,000 and a weight-average molecular weight of 28,000. A composite fine particle dispersion (S-15) was obtained in the same manner as in Example 12 except that this silicon-containing polymer was used. A low refractive index layer was formed in the same manner as in Example 12 except that the composite fine particle dispersion (S-15) was used. The obtained low refractive index layer was subjected to the same evaluation as in Example 12. The results are shown in Table 4.
  • a silicon-containing polymer was obtained in the same manner as in Example 12, except that butyl acrylate was not used and the amount of perfluorooctylethyl methacrylate was changed from 60 g to 200 g. .
  • This silicon-containing polymer had a number average molecular weight of 13,000 and a weight average molecular weight of 27,000.
  • a composite fine particle dispersion (S-16) was obtained in the same manner as in Example 12 except that this silicon-containing polymer was used.
  • a low refractive index layer was formed in the same manner as in Example 12 except that the composite fine particle dispersion (S-16) was used. The obtained low refractive index layer was subjected to the same evaluation as in Example 12. The results are shown in Table 4.
  • Example 12 In the same manner as in Example 12, except that the amount of butyl acrylate was changed from 140 g to 80 g, and the amount of 2-hydroxyethyl methacrylate was changed from 84 g to 204 g. A silicon polymer was obtained. This silicon-containing polymer had a number average molecular weight of 15,000 and a weight average molecular weight of 29,000. Using this silicon-containing polymer, an unsaturated group-containing silicon-containing polymer was obtained in the same manner as in Example 12, except that the amount of talylloxchichinoleisocyanate used was changed from 59 g to 201 g.
  • Example 17 Using this unsaturated group-containing silicon-containing polymer Except that, a composite fine particle dispersion (S-17) was obtained in the same manner as in Example 12. A low refractive index layer was formed in the same manner as in Example 12 except that the composite fine particle dispersion (S-17) was used. The obtained low refractive index layer was subjected to the same evaluation as in Example 12. The results are shown in Table 4.
  • Example 17 Using this unsaturated group-containing silicon-containing polymer Except that, a composite fine particle dispersion (S-17) was obtained in the same manner as in Example 12. A low refractive index layer was formed in the same manner as in Example 12 except that the composite fine particle dispersion (S-17) was used. The obtained low refractive index layer was subjected to the same evaluation as in Example 12. The results are shown in Table 4. Example 17
  • a low refractive index was obtained in the same manner as in Example 12 except that urethane atarylate (DPHA-40H, Nippon Kayaku Co., Ltd.) was used instead of dipentaerythritol hexaatalylate and the formulation shown in Table 3 was adopted.
  • a coating composition was prepared.
  • a low refractive index layer was formed in the same manner as in Example 12 except that this low refractive index coating composition was used.
  • the obtained low refractive index layer was subjected to the same evaluation as in Example 12. The results are shown in Table 4.
  • the hard coat layer obtained using the composite fine particles of the present invention is excellent in the balance of hardness, scratch resistance and appearance (unevenness, haze, light transmittance).
  • the low refractive index layer obtained using the composite fine particles of the present invention achieves a good low refractive index and is excellent in the balance of hardness, reflectance and transmittance.
  • the composite fine particles of the present invention are excellent in dispersion stability, in addition to obtaining a coating film having the above-described excellent characteristics, and causing no aggregation or the like in the dispersion state.
  • the composite fine particles and the coating composition of the present invention include a transfer foil film, a plastic optical component, a touch panel, a film-type liquid crystal element, a hard coating agent such as a plastic molding, a low refractive index coating agent for an antireflection film, and a light diffusing agent. It can be suitably used as a film coating agent.

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Abstract

L'invention concerne une particule fine composite présentant en même temps des propriétés d'adhérence et de stabilité de dispersion ainsi qu'une excellente aptitude au traitement thermique. L'invention concerne également un procédé simple de production de cette particule fine composite. L'invention concerne en particulier une particule fine composite comprenant un noyau inorganique et un polymère organique lié à au moins une partie de la surface du noyau. Le polymère organique contient un groupe insaturé par éthylène dans une chaîne latérale. Ce groupe insaturé est de préférence lié à la chaîne principale du polymère organique par une liaison uréthane. Le polymère organique est de préférence un polymère acrylique.
PCT/JP2007/066545 2006-09-01 2007-08-27 Particule fine composite, procede de production associe, composition de revetement contenant ladite particule et film optique WO2008026539A1 (fr)

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WO2009139463A1 (fr) 2008-05-16 2009-11-19 日本電気株式会社 Particule fine d'oxyde métallique, procédé permettant de la produire et composition de résine
JP5887834B2 (ja) * 2011-10-28 2016-03-16 Dic株式会社 含フッ素重合性樹脂、それを用いた活性エネルギー線硬化性組成物及びその硬化物
JP2014016607A (ja) * 2012-06-13 2014-01-30 Ube Exsymo Co Ltd 反射防止材料
KR102293731B1 (ko) * 2014-10-16 2021-08-27 삼성디스플레이 주식회사 표시 장치용 윈도우 및 이를 포함하는 표시 장치
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JP6482414B2 (ja) * 2015-07-03 2019-03-13 富士フイルム株式会社 光学フィルム、それを用いた偏光板および液晶表示装置
JP6413130B2 (ja) * 2016-08-25 2018-10-31 レッド・スポット・ペイント・アンド・ヴァーニッシュ・カンパニー・インコーポレーテッド 脂肪族ウレタンアクリレート樹脂を含むｕｖ硬化性被覆組成物
JP7360249B2 (ja) * 2019-03-29 2023-10-12 太陽ホールディングス株式会社 ポリマー被覆無機フィラー、及び、これを含む樹脂組成物、ドライフィルム、硬化物、電子部品
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