JP2010202860A - Organic/inorganic composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic/inorganic composite, which is a polysiloxane-based organic/inorganic composite having high hardness that is higher in the surface than that of the interior and has both high surface hardness and anti-glare property or anti-Newton ring property. <P>SOLUTION: The organic/inorganic composite contains (a) a condensate of an organosilicon compound as a principal component, which is represented by formula (I) R<SB>n</SB>SiX<SB>4-n</SB>(wherein R represents an organic group wherein a carbon atom directly binds to Si, X represents a hydroxy group or the like, n represents 1 or 2, Rs may be the same or different when n represents 2, and Xs may be the same or different when (4-n) represents 2 or more), (b) at least one type of photosensitive compound that is sensitive to light with a wavelength of 350 nm or less selected from the group consisting of a metal chelate compound, a metal organic acid salt compound, and the like and/or a compound induced therefrom, (c) a cured product of a ultraviolet curing compound, and (d) a metal oxide particle. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic-inorganic composite containing metal oxide particles. More specifically, the present invention relates to an organic-inorganic composite in which the carbon content on the surface side is smaller than the carbon content on the inside and the surface is mineralized. Further, the present invention relates to an organic-inorganic composite having irregularities on the surface by containing metal oxide particles, and a composition for forming the same. The metal oxide particle-containing organic-inorganic composite of the present invention is suitably used as an antiglare film or an anti-Newton ring film in touch panels and various display screens.

  Currently, trifunctional silanes are mainly used as raw materials for commercially available silane-based coating agents, and polysiloxanes having appropriate hardness and flexibility are formed by such trifunctional silanes. However, a trifunctional silane film does not have sufficient hard coat properties. Therefore, the trifunctional silane is mixed with tetrafunctional silane or colloidal silica to supplement the hard coat properties. However, if the film is hardened, there is a problem in that it becomes easy to crack and the adhesiveness deteriorates.

  Examples of the silane-based coating agent include a composition for forming an antifouling film containing a trifunctional alkoxysilane compound having an epoxy group (see, for example, Patent Document 1). A silane-based coating agent containing a photocatalyst has also been proposed, and a film is cured using a photoacid generator, a crosslinking agent, a curing catalyst, or the like (see, for example, Patent Documents 2 and 3). Furthermore, a silane-based organic-inorganic composite gradient material having a component gradient structure in which the content of the metal compound in the material continuously changes in the depth direction from the surface of the material has also been proposed (for example, Patent Documents). 4).

  The inventors irradiate the organosilicon compound with ultraviolet light in the presence of the photosensitive compound, so that the surface has a very high hardness, the inside and the back side have appropriate hardness, and An organic-inorganic composite having excellent adhesion was provided (see Patent Document 5). However, further improvements have been desired in terms of adhesion to the substrate and moisture resistance.

  On the other hand, as a hard coat film, it is known to use an acrylate resin or the like as a UV curable resin. For example, Patent Document 6 discloses (meth) acrylic acid ester mixture (A), photopolymerization initiator (B), ethylenically unsaturated group-containing urethane oligomer (C), colloidal silica sol (D), and diluent (E). It is described that the hard coat film containing is good, and the obtained film has good pencil hardness, curl, and adhesion to the substrate.

  Patent Document 7 discloses (A) oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, and polymerizable unsaturated. A curable composition containing particles formed by bonding an organic compound containing a group, (B) a compound having a urethane bond and two or more polymerizable unsaturated groups in the molecule, and (C) a photopolymerization initiator. It has been described that it has excellent coating properties, and has high hardness and high refractive index on the surface of various base materials, as well as scratch resistance and adhesion between the base material and the low refractive index layer. It is described that an excellent coating film (film) can be formed.

  Further, Patent Document 8 discloses an ultraviolet ray comprising a mixture of a hydrolyzate of an organosilicon compound and metal oxide fine particles, (B) a polyfunctional acrylate or methacrylate, and (C) a photopolymerization initiator. The curable hard coat resin composition is described, and can bleed the surface of the antistatic agent, decrease in transparency, deteriorate moisture resistance, etc. within a practically acceptable range, and as a hard coat Satisfying the above functions (abrasion resistance, surface hardness, moisture resistance, solvent resistance, chemical resistance, etc.).

  However, hard coat films using these acrylate-based resins and the like are inferior to inorganic films in terms of wear resistance, and are therefore improved by adding a metal oxide sol with high hardness. However, in this method, the surface of the metal oxide particles is covered with a lot of resin, and a sufficient effect cannot be expected. In particular, in the case of an anti-glare film or an anti-Newton ring film that contains metal oxide particles having a large particle size to form irregularities on the surface of the film, if the surface of the metal oxide particles is not covered with a resin, There was a problem that metal oxide particles having a large particle size fall off.

  In response to these problems, the inventors have already blended a polysiloxane-based organic-inorganic composite with an ultraviolet curable compound, so that the surface has extremely high hardness, adhesion to the substrate, and moisture resistance. It has been found that an excellent organic-inorganic composite can be produced (Patent Document 9). However, the light reflection characteristics of the organic-inorganic composite have not been studied.

  Furthermore, conventionally, it has been known that an anti-glare hard coat film is formed by adding metal oxide fine particles to a hard coat composition and imparting irregularities to the surface of the hard coat (Patent Document 10). The surface of the hard coat film is an organic component such as a resin, and no anti-glare hard coat film having a mineralized surface has been known.

Japanese Patent Laid-Open No. 10-195417 JP 2002-363494 A JP 2000-169755 A JP 2000-336281 A WO 2006/088079 JP 2002-233501 A JP 2005-272702 A JP 2001-214092 A WO2008 / 069217 JP 2008-158536 A

  An object of the present invention is to provide an anti-glare property and an anti-Newton ring property to a polysiloxane-based organic-inorganic composite having a surface whose hardness is higher than that of the inside, and an organic material having both a high surface hardness and an anti-glare property and an anti-Newton ring property. It is to provide an inorganic composite.

  As a result of diligent research on the above problems, the present inventors have further added metal oxide particles to an organic-inorganic composite containing a polysiloxane-based organic-inorganic composite and an ultraviolet curable compound, so that the surface is improved. It has been found that an excellent organic-inorganic composite having an extremely high hardness and at the same time having an antiglare property and an anti-Newton ring property can be produced, and the present invention has been completed.

That is, the present invention
[1]
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And each X may be the same or different when (4-n) is 2 or more.)
b) At least one 350 nm or less selected from the group consisting of metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. A light-sensitive compound that is sensitive to light of a wavelength and / or a compound derived therefrom,
c) an organic-inorganic composite containing a cured product of an ultraviolet curable compound, and d) metal oxide particles, wherein the 10-point average roughness of the surface of the organic-inorganic composite is 0.1 μm to 5 μm. Organic-inorganic composites,
[2]
The organic-inorganic composite according to [1], wherein the carbon content on the surface of the organic-inorganic composite is 80% or less of the carbon content on the back side;
[3]
The organic-inorganic composite according to [1] or [2], wherein the metal in the compound of b) is Ti, Al, Zr or Sn,
[4]
The organic-inorganic composite according to [1] to [3], wherein the ultraviolet curable compound of c) is a (meth) acrylate ultraviolet curable compound,
[5]
The organic-inorganic composite according to any one of [1] to [4], wherein the metal oxide particles of d) are porous powders,
[6]
The primary particle diameter of the metal oxide particle of d) is 0.05 micrometer-0.2 micrometer, It is related with the organic-inorganic composite in any one of [1]-[4] characterized by the above-mentioned.

The present invention also provides:
[7]
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And when the number of (4-n) is 2 or more, each X may be the same or different.)
b) At least one 350 nm or less selected from the group consisting of metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. A light-sensitive compound that is sensitive to light of a wavelength;
an organic-inorganic composite-forming composition comprising: c) an ultraviolet curable compound; and d) metal oxide particles having a particle diameter of 0.05 μm to 5 μm,
[8]
The composition for forming an organic-inorganic composite according to [7], wherein the metal in the compound of b) is Ti, Al, Zr or Sn,
[9]
The ultraviolet curable compound is 2 to 98% by mass with respect to the total mass of the organosilicon compound and / or its condensate, photosensitive compound, ultraviolet curable compound and metal oxide particles [7 ] Or the composition for forming an organic-inorganic composite according to [8],
[10]
The composition for forming an organic-inorganic composite according to any one of [7] to [9], wherein the metal oxide particles of d) are porous powders,
[11]
The primary particle diameter of the metal oxide particle of d) is 0.05 micrometer-0.2 micrometer, It is related with the composition for organic-inorganic composite formation in any one of [7]-[9] characterized by the above-mentioned.

Furthermore, the present invention provides
[12]
The organic-inorganic composite according to any one of [1] to [6], wherein the organic-inorganic composite is an antiglare film or an anti-Newton ring film,
[13]
The composition for forming an organic / inorganic composite according to any one of [7] to [11], wherein the composition for forming an organic / inorganic composite is a composition for an antiglare film or an anti-Newton ring film. .

  In this specification, “the minimum value of the carbon content between the film surface and the depth direction of 0.5 μm” is obtained when the carbon content in the depth direction from the film surface is measured by ESCA analysis. In the graph of carbon content, it means the minimum value of the measured value of carbon content for each depth from the film surface to the depth direction of 0.5 μm. The measurement can be performed by the method described in WO2008 / 069217.

  In addition, the carbon content on the back side of the organic-inorganic composite is a value when the carbon content reaches a constant depth even deeper than the depth at which the carbon content gradually increases from the film surface, and is not necessarily It may not be the value on the back side. In most films of the present invention, the carbon content is constant in the thickness direction of the film from the depth at which the carbon content is gradually increasing, and is not different from the value on the back surface.

  According to the present invention, an organic-inorganic composite having an extremely high hardness on the front surface, an appropriate hardness on the inner and rear surfaces, and excellent adhesion to the substrate and moisture resistance, and having anti-glare properties An organic-inorganic composite having anti-Newton ring properties can be provided.

Since the organic-inorganic composite of the present invention has a SiO ₂ -like structure having a high polarity on the surface, it has excellent interlayer adhesion when various films are laminated. Surface treatment by silane coupling treatment is also possible, and various treatments are easy, such as changing the surface to water / oil repellency, introducing an amino group, and providing plating adhesion. Moreover, since the surface slipperiness by the metal oxide particles is good, and the slipperiness and water / oil repellency can be compatible, it can be suitably used for the touch panel surface, for example.

  Furthermore, the organic-inorganic composite of the present invention has a property of good moisture resistance. In general, it was thought that when metal oxide particles were added to the hard coat film, the moisture resistance was inferior, but the organic-inorganic composite of the present invention had good moisture resistance despite containing the metal oxide particles. Show.

(Organic inorganic composite)
The organic-inorganic composite of the present invention is
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And each X may be the same or different when (4-n) is 2 or more.) Condensates of organosilicon compounds (hereinafter sometimes simply referred to as organosilicon compounds) As the main component,
b) At least one 350 nm or less selected from the group consisting of metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. A light-sensitive compound that is sensitive to light of a wavelength, and / or a compound derived therefrom,
c) A cured product of an ultraviolet curable compound, and d) metal oxide particles. The organic-inorganic composite of the present invention includes a photosensitizing compound and / or a derivative thereof dispersed in a non-bonded state in a condensate of an organosilicon compound, a photosensitizing compound and a condensate of an organosilicon compound, and And / or derivatives thereof (for example, those having a Si—OM bond (M represents a metal atom in the photosensitive compound)) and those having a mixed state thereof are included. .

Since the organic-inorganic composite of the present invention contains metal oxide particles, the surface thereof is not smooth but has irregularities. Specifically, the 10-point average roughness of the surface is 0.1 to 5 μm, and more preferably 0.5 to 2 μm. Specifically, the 10-point average roughness of the surface is JIS B
As shown in 0601, in the part extracted by the reference length from the cross-section curve, the average of the highest to the fifth highest peaks measured in the direction of the vertical magnification from the straight line parallel to the average line and not crossing the cross-section curve The difference between the value and the average value of the elevation of the bottom valley from the deepest to the fifth is expressed in μm. The average value of 10 measured values was defined as the 10-point average surface roughness. For the measurement of the 10-point average roughness, for example, a scanning probe microscope or a three-dimensional non-contact surface shape measurement system using optical interference can be used. Specifically, “SPI3800N (SPA400)” manufactured by Seiko Instruments Inc. can be used as a scanning probe microscope, and Ryoka System Co., Ltd. can be used as a three-dimensional non-contact surface shape measurement system using optical interference. Either method does not change the measured value.

(Organic silicon compound)
In formula (I) of the organosilicon compound of the present invention, R and X are as follows.
R represents an organic group in which a carbon atom is directly bonded to Si. Examples of the organic group include an optionally substituted hydrocarbon group, an optionally substituted hydrocarbon polymer group, and the like, and an optionally substituted hydrocarbon having 1 to 30 carbon atoms. A linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, an alkyl group having a longer chain than carbon number 10 or a cycloalkyl group having 3 to 8 carbon atoms which may be substituted An optionally substituted linear or branched alkenyl group having 2 to 10 carbon atoms or an optionally substituted cycloalkenyl group having 3 to 8 carbon atoms may be preferable, and may have an aromatic ring.

  Such an organic group may contain an oxygen atom, a nitrogen atom, or a silicon atom, or may be a group containing a polymer such as polysiloxane, polyvinyl silane, or polyacryl silane. Examples of the substituent include a halogen and a methacryloxy group. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group having 1 to 10 carbon atoms include linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl. Group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, nonyl Group, isononyl group, decyl group and the like, and examples of the long chain alkyl group having 10 carbon atoms include lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.

  Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  The straight chain or branched alkenyl group having 2 to 10 carbon atoms means a straight chain or branched alkenyl group having 2 to 10 carbon atoms having a carbon-carbon double bond at any one or more, for example, Ethenyl group, prop-1-en-1-yl group, prop-2-en-1-yl group, prop-1-en-2-yl group, but-1-en-1-yl group, but- 2-ene-1-yl group, but-3-en-1-yl group, but-1-en-2-yl group, but-3-en-2-yl group, penta-1-en-1- Yl group, penta-4-en-1-yl group, penta-1-en-2-yl group, penta-4-en-2-yl group, 3-methyl-but-1-en-1-yl group Hexa-1-en-1-yl group, hexa-5-en-1-yl group, hepta-1-en-1-yl group, hepta-6-ene 1-yl group, oct-1-en-1-yl group, oct-7-en-1-yl group.

  A C3-C8 cycloalkenyl group means a C3-C8 alkenyl group which has a carbon-carbon double bond in any one or more places and has a cyclic part, for example, 1-cyclopentene. Examples include a -1-yl group, a 2-cyclopenten-1-yl group, a 1-cyclohexen-1-yl group, a 2-cyclohexen-1-yl group, and a 3-cyclohexen-1-yl group.

Examples of the organic group having an aromatic ring include a C _6-10 aryl C _1-8 alkyl group such as a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, 5- Examples include a phenyl-n-pentyl group, an 8-phenyl-n-octyl group, and a naphthylmethyl group. Further, as C _6-10 aryl C _2-6 alkenyl group, styryl group, 3-phenyl-prop-1-en-1-yl group, 3-phenyl-prop-2-en-1-yl group, 4-phenyl -But-1-en-1-yl group, 4-phenyl-but-3-en-1-yl group, 5-phenyl-pent-1-en-1-yl group, 5-phenyl-pent-4- An en-1-yl group, an 8-phenyl-oct-1-en-1-yl group, an 8-phenyl-oct-7-en-1-yl group, a naphthylethenyl group, and the like can be given.

  Examples of the group having an oxygen atom include a group having an oxirane ring (epoxy group) such as an epoxy group, an epoxyalkyl group and a glycidoxypropyl group, an acryloxymethyl group, and a methacryloxymethyl group.

  Of the groups having an oxygen atom, the epoxyalkyl group is preferably a linear or branched epoxyalkyl group having 3 to 10 carbon atoms, such as an epoxymethyl group, an epoxyethyl group, an epoxy-n-propyl group, or an epoxyisopropyl group. , Epoxy-n-butyl group, epoxy isobutyl group, epoxy-t-butyl group, epoxy-n-pentyl group, epoxy isopentyl group, epoxy neopentyl group, epoxy-2-methylbutyl group, epoxy-2,2-dimethyl A propyl group, an epoxy-n-hexyl group, etc. are mentioned. Examples of the group having an oxygen atom other than the oxirane ring include a glycidoxypropyl group.

As the group having a nitrogen atom, a group having —NR ′ ₂ (wherein R ′ represents a hydrogen atom, an alkyl group or an aryl group, and each R ′ may be the same as or different from each other), or —N ═CR ″ ₂ (wherein R ″ represents a hydrogen atom or an alkyl group, and each R ″ may be the same as or different from each other), and the alkyl group is the same as described above. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthren-1-yl group.

For example, the group having —NR ′ ₂ includes a —CH ₂ —NH ₂ group, a —C ₃ H ₆ —NH ₂ group, a —CH ₃ —NH—CH ₃ group, and the like. -N = Examples of the group having a _{CR '' 2, -CH 2 -N} = CH-CH 3 _{group, -CH 2 -N = C (CH} 3) 2 _{group, -C 2 H 5 -N = CH} -CH ₃ groups etc. are mentioned.

Among the above groups, the group that is decomposed by irradiation with light having a wavelength of 350 nm or less includes a group having a vinyl group, a group having an oxirane ring, -NR ′ ₂ (wherein R ′ is a hydrogen atom, an alkyl group, or an aryl group). Each of R ′ may be the same as or different from each other, or —N═CR ″ ₂ (wherein R ″ represents a hydrogen atom or an alkyl group, and each R ″ May be the same or different from each other).

Here, as a group having a vinyl group, an ethenyl group (vinyl group), a prop-2-en-1-yl group, a but-3-en-1-yl group, a penta-4-en-1-yl group , Alkenyl groups such as hexa-5-en-1-yl group, hepta-6-en-1-yl group, octa-7-en-1-yl group, methacrylmethyl group, acryloxymethyl group, methacryloxymethyl And groups having a vinylcarbonyl group such as a group. Group having group having an oxirane ring, -NR 'group having _2, -N = CR' a _'2 are as described above.

  In the formula (I) of the organosilicon compound, n represents 1 or 2, and n = 1 is particularly preferable. When n is 2, each R may be the same or different. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  X represents a hydroxyl group or a hydrolyzable group. When (4-n) of formula (I) is 2 or more, each X may be the same or different. A hydrolyzable group is, for example, a group that can be hydrolyzed to form a silanol group or a siloxane condensate by heating at 25 ° C. to 100 ° C. in the presence of no catalyst and excess water. Specifically, an alkoxy group, an acyloxy group, a halogen group, an isocyanate group and the like can be mentioned, and an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 6 carbon atoms can be mentioned. preferable.

  Examples of the alkoxy group having 1 to 4 carbon atoms include a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, and the like. Examples of the acyloxy group include an acetyloxy group and a benzoyloxy group. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the isocyanate group include an isocyanate group bonded to an alkyl group, an isocyanate group bonded to a cycloalkyl group, an isocyanate group bonded to an aryl group, an isocyanate group bonded to an alkyl group substituted with a cycloalkyl group, and an aryl group. And an isocyanate group bonded to the alkyl group.

  Specifically, as the organosilicon compound, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, Pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyldimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane , Vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxetanemethoxy ) Propyltrimethoxysilane, oxacyclohexyltrimethoxysilane, methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, methyl-triglycidyloxysilane, methyltris (3-methyl-3-oxetanemethoxy) ) Silane, vinyltrichlorosilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldie Xysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- And dimethyl-butylidene) propylamine and N-phenyl-3-aminopropyltrimethoxysilane. These can be used alone or in combination of two or more.

Examples of the organosilicon compound having a hydrocarbon polymer group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl. (Meth) acrylate and other (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, fumaric acid and other carboxylic acids and maleic anhydride and other acid anhydrides; glycidyl (meth) acrylate and other epoxy compounds; diethylaminoethyl Amino compounds such as (meth) acrylate and aminoethyl vinyl ether; amino acids such as (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, and N-butoxymethyl (meth) acrylamide Compound: A compound in which a vinyl polymer obtained by copolymerizing a vinyl compound selected from acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate and the like is used as the R component of the formula (I) can be mentioned. .
In addition, the condensate of the organosilicon compound which is the main component in the organic-inorganic composite of the present invention is a method for producing the organic-inorganic composite of the present invention described later and / or the organosilicon compound in the composition for forming an organic-inorganic composite and / or It means that the condensate is further condensed.

(Photosensitive compound)
The photosensitive compound of the present invention is a compound that can remove the carbon component on the surface side by the action of light with a wavelength of 350 nm or less irradiated from the surface side, regardless of the mechanism, and preferably The minimum value of the carbon content between the film surface and the depth direction of 0.5 μm is 80% or less, more preferably 2 to 60%, still more preferably 2 to 40% of the carbon content on the film back side. Particularly preferably, a compound capable of removing the carbon component to a predetermined depth so that the removal amount gradually decreases from the surface side, that is, the carbon content from the surface to the predetermined depth. Refers to a compound that can form a gradually increasing film. Specific examples include compounds that absorb and excite light having a wavelength of 350 nm or less.
Here, the light having a wavelength of 350 nm or less is light using a light source having light of any wavelength of 350 nm or less, preferably a light source having light of any wavelength of 350 nm or less as a main component. That is, light using a light source having a wavelength of 350 nm or less with the largest component amount.

  Examples of the photosensitive compound in the organic-inorganic composite of the present invention include metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. It is preferably at least one compound selected from the group consisting of: a hydrolyzate and / or a condensate, and particularly a hydrolyzate and / or condensate of a metal chelate compound. Examples of the compound derived therefrom include those obtained by further condensing a condensate of a metal chelate compound. As described above, the photosensitive compound and / or derivative thereof may be chemically bonded to the organosilicon compound, dispersed in a non-bonded state, or a mixed state thereof.

  The metal chelate compound is preferably a metal chelate compound having a hydroxyl group or a hydrolyzable group, and more preferably a metal chelate compound having two or more hydroxyl groups or hydrolyzable groups. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more. Further, as the metal chelate compound, β-ketocarbonyl compounds, β-ketoester compounds, and α-hydroxyester compounds are preferable. Specifically, methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, acetoacetic acid β-ketoesters such as n-butyl, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane Β-diketones such as -2,4-dione, nonane-2,4-dione and 5-methyl-hexane-2,4-dione; hydroxycarboxylic acids such as glycolic acid and lactic acid; Is mentioned.

  The metal organic acid salt compound is a compound composed of a salt obtained from a metal ion and an organic acid. Examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid, benzoic acid; sulfonic acid, sulfinic acid, thiophenol. Organic compounds exhibiting acidity such as sulfur-containing organic acids such as phenol compounds, enol compounds, oxime compounds, imide compounds, aromatic sulfonamides, and the like.

  In addition, the metal compound having two or more hydroxyl groups or hydrolyzable groups excludes the metal chelate compound and the metal organic acid salt compound, and examples thereof include metal hydroxides and metal alcoholates. .

  Examples of the hydrolyzable group in the metal compound, metal chelate compound or metal organic acid salt compound include an alkoxy group, an acyloxy group, a halogen group, and an isocyanate group, and an alkoxy group having 1 to 4 carbon atoms and 1 to 1 carbon atoms. An acyloxy group of 4 is preferred. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.

  Such a hydrolyzate and / or condensate of a metal compound is obtained by hydrolyzing 0.5 mol or more of water with respect to 1 mol of a metal compound having two or more hydroxyl groups or hydrolyzable groups. It is preferable that it is a thing hydrolyzed using 0.5-2 mol water.

  Further, the hydrolyzate and / or condensate of the metal chelate compound is preferably hydrolyzed using 5 to 100 mol of water with respect to 1 mol of the metal chelate compound, More preferably, it is hydrolyzed with water.

  The hydrolyzate and / or condensate of the metal organic acid salt compound is preferably one hydrolyzed using 5 to 100 mol of water with respect to 1 mol of the metal organic acid salt compound. More preferably, it is hydrolyzed with ˜20 mol of water.

  Moreover, as a metal in these metal compounds, metal chelate compounds or metal organic acid salt compounds, titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), germanium (Ge), indium (In), Examples include tin (Sn), tantalum (Ta), zinc (Zn), tungsten (W), lead (Pb), etc. Among these, titanium (Ti), zirconium (Zr), aluminum (Al), tin (Sn) ) Is preferred, and titanium (Ti) is particularly preferred. These may be used alone or in combination of two or more.

(UV curable compound)
The ultraviolet curable compound of the present invention is a compound or resin having a functional group that undergoes a polymerization reaction upon irradiation with ultraviolet rays in the presence of a photopolymerization initiator, and is a (meth) acrylate compound, an epoxy resin, or an acrylate compound. There are vinyl compounds excluding compounds. The number of functional groups is not particularly limited as long as it is 1 or more.

As acrylate compounds, polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, polycarbonate diacrylate, tripropylene glycol di (Meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, siloxane polymer having (meth) acryloyloxy group, and the like, preferably polyester ( (Meth) acrylate, polyurethane (meth) acrylate, and epoxy poly (meth) acrylate, more preferably polyurethane Meth) acrylate.
The molecular weight is not limited as long as it dissolves in the organic-inorganic composite-forming composition, but is usually 500 to 50,000, preferably 1,000 to 10,000 as the weight average molecular weight.
Further, a polymer obtained by causing a polymerization reaction by ultraviolet irradiation is a cured product.

The epoxy (meth) acrylate can be obtained, for example, by an esterification reaction between an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolak epoxy resin and acrylic acid.
The polyester (meth) acrylate is obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends with acrylic acid, obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol. Alternatively, it can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with acrylic acid.
Urethane (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol with diisocyanate and an acrylate monomer having a hydroxyl group, and examples of the polyol include polyester polyol, polyether polyol, and polycarbonate diol. .

  As a commercial item of the urethane (meth) acrylate used by this invention, Arakawa Chemical Industries Co., Ltd. brand name: Beam set 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM-90, for example. Product name: Photomer 6008, 6210, Shin-Nakamura Chemical Co., Ltd. Product name: NK Oligo U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA, U -324A, U-4H, U-6H, manufactured by Toagosei Co., Ltd .: Aronix M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, Kyoeisha Chemical Co., Ltd. Product name: AH-600, AT606, UA-306H, Nippon Kayaku Co., Ltd. Product name: Kayarad UX-2201, UX-2301, UX -3204, UX-3301, UX-4101, UX-6101, UX-7101, trade names manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Purple light UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV-7000 , UV-7600B, UV-2010B, manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB, UN- 3320HC, UN-3320HS, H-61, HDP-M20, Daicel UCB Co., Ltd. trade name: Ebecryl 6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866 , 5129, 6602, 8301 etc. You can.

  Examples of vinyl compounds other than acrylate compounds include N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl acetate, styrene, and unsaturated polyester. Epoxy resins include hydrogenated bisphenol A diglycidyl ether, 3,4 -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) And methyl) adipate.

(Photopolymerization initiator)
Examples of the photopolymerization initiator of the present invention include (a) a compound that generates cationic species by light irradiation, and (b) a compound that generates active radical species by light irradiation.
As a compound that generates a cationic species by light irradiation, for example, an onium salt having a structure represented by the following formula (II) can be given as a preferred example.
This onium salt is a compound that releases a Lewis acid by receiving light.
_{^{[R 1 a R 2 b R}} 3 c R 4 d W] + e [ML e + f] -e (II)
(In the formula (II), the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N≡N—, and R ¹ , R ² , R ³ and R ⁴ are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. M is , A metal or metalloid constituting the central atom of the halide complex [ML _{e + f} ], for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. L is a halogen atom such as F, Cl, Br, etc., e is the net charge of the halide complex ion, and f is the valence of M. )

Specific examples of the anion (ML _{e + f} ) in the above formula (II) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarce. Nate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.
An onium salt having an anion represented by the formula [ML _f (OH) ⁻ ] can also be used. Furthermore, perchlorate ion (ClO ₄ ⁻ ), trifluoromethane sulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluene sulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene sulfonate The onium salt which has other anions, such as an acid anion, may be sufficient. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of compounds that generate active radical species by light irradiation include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, and benzaldehyde. Fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1 -(4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxa , Diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. .

  The blending amount of the photopolymerization initiator used in the present invention is preferably 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the solid content of the (meth) acrylate-based ultraviolet curable compound. Is more preferable.

  In the present invention, a sensitizer can be added as necessary. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and 4,4′-bis ( Diethylamino) benzophenone and the like can be used.

(Metal oxide particles)
Examples of the metal oxide particles of the present invention include silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, and cobalt oxide particles. Examples of the shape of the particles include a spherical shape, a porous powder, a scale shape, and a fiber shape, and a porous powder shape is more preferable. By being porous, even if the aggregate particle diameter is 1 μm or more, it can be uniformly dispersed while in the coating liquid. Examples of the porous particles include silicia manufactured by Fuji Silysia Chemical Ltd. Silane-coupled particles such as Admafine SQ surface treatment series manufactured by Admatechs can also be used. The size of the particles is not particularly limited as long as the antiglare property and the anti-Newton ring property are obtained, but the aggregated particle diameter is preferably 1 μm to 5 μm, and more preferably 2 μm to 3 μm. The addition amount is preferably 2 wt% to 10 wt%, and more preferably 3 wt% to 5 wt% as the solid content of the composition.
As the metal oxide particles of the present invention, colloidal metal oxide particles having a primary particle size of 0.05 to 0.2 μm can also be used. The primary particles here are particles that can be observed with an electron microscope. Colloidal silica and the like are well known as the particles, and include IPA-ST-ZL manufactured by Nissan Chemical Industries. The addition amount is preferably 10 wt% to 40 wt%, and more preferably 15 wt% to 30 wt%. Since this particle is a colloidal dispersion, a uniform dispersion can be easily obtained by simply mixing it with the coating liquid, and there are few problems of non-uniformity due to sedimentation. In addition, since this particle has a particle size of less than visible light, anti-glare property and anti-Newton ring property cannot be obtained if it is uniformly dispersed in the coating film, but this effect is recognized in this coating composition. It is a unique phenomenon. As shown in the comparative example, only a clear coating film was obtained even when mixed only with the UV curable resin.

  The metal-inorganic particle-containing organic-inorganic composite of the present invention contains metal oxide particles, so that irregularities occur on the surface of the organic-inorganic composite, resulting in irregular reflection of light, and the antiglare property is expressed. Good surface slipperiness. In addition, metal oxide particles are exposed on the surface of the film, and because there is a surface that is not coated with organic resin, silane coupling treatment made of water and oil repellent is possible. Function and slipperiness are improved. Furthermore, it is possible to control the distance between the films when the films are overlapped by the unevenness of the surface, and to suppress the generation of Newton rings (light interference fringes) (anti-Newton ring property).

(Application of composition for forming organic-inorganic composite)
Examples of the substrate on which the organic-inorganic composite of the present invention can be formed include metals, ceramics, glass, and plastics. Among these, plastic is preferably used, and specifically, a plastic substrate for a touch panel can be used. Conventionally, it has been difficult to form a thin film on a plastic substrate, and it has been limited to inorganic substrates such as glass. However, the thin film of the present invention can easily form a film even if it is difficult to form a plastic substrate. Suitable for optical components. Examples of such plastic include polycarbonate resin, acrylic resin, polyimide resin, polyester resin, epoxy resin, liquid crystal polymer resin, and polyether sulfone.

  Moreover, as a coating method of the composition for forming an organic / inorganic composite, a known coating method can be used. For example, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, A gravure printing method, a silk screen method, an inkjet method, etc. can be mentioned. Moreover, it does not restrict | limit especially as a film thickness to form, For example, it is about 0.05-200 micrometers.

  As a drying process of the film | membrane formed by apply | coating the composition for organic-inorganic composite formation, it is preferable to carry out for about 1 to 120 minutes at 40-200 degreeC, for example, for 60 to 120 degreeC, about 10 to 60 minutes. More preferably.

(Method for producing organic-inorganic composite)
As a method for producing the organic-inorganic composite of the present invention, an organic silicon compound and / or a condensate thereof is 350 nm in the presence of a photosensitive compound, an ultraviolet curable compound, metal oxide particles, and a photopolymerization initiator. The method of irradiating the light containing the following wavelengths can be mentioned, The organic-inorganic composite formation composition mentioned later can be used.

Irradiation with light having a wavelength of 350 nm or less can be performed using a known apparatus such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp, and the irradiation light is in the range of 150 to 350 nm. It is preferable that it is the light which has the light of any one of these wavelengths as a main component, and it is more preferable that it is the light which has the light of any wavelength in the range of 250-310 nm as a main component. As long as it is sensitive to wavelengths in this range and does not react to light exceeding 350 nm, preferably 310 nm, it is hardly affected by sunlight. Moreover, as an irradiation light quantity of the light to irradiate, about 0.1-100 J / cm < ² > is mentioned, for example, When film hardening efficiency (relation between irradiation energy and a film hardening degree) is considered, 0.2-20 J / cm preferably ² mm, and more preferably about 0.5~10J / cm ^2.
Note that irradiation with light having a wavelength of 350 nm or less is irradiation using a light source having light of any wavelength of 350 nm or less, preferably a light source having light of any wavelength of 350 nm or less as a main component. Irradiation used, that is, irradiation using a light source having a wavelength of 350 nm or less with the largest component amount.

  The organosilicon compound used in the production method of the present invention is preferably a condensate, and the average particle diameter is preferably 50 nm or less, and more preferably 20 nm or less. The photosensitive compound used in the production method of the present invention is preferably a hydrolyzate and / or condensate, particularly preferably a hydrolyzate and / or condensate of a metal chelate compound, and its average particle size The diameter is preferably 20 nm or less, and more preferably 10 nm or less. Thereby, the transparency of the organic-inorganic composite (organic-inorganic composite-based thin film) can be improved. These average particle diameters can be measured using, for example, HPPS manufactured by Malvern Instruments Ltd.

(Composition for forming organic-inorganic composite)
The organic-inorganic composite-forming composition of the present invention is
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And when the number of (4-n) is 2 or more, each X may be the same or different.)
b) At least one photosensitivity selected from the group consisting of metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. Compound,
The composition is not particularly limited as long as it is a composition containing c) an ultraviolet curable compound and d) metal oxide particles having a particle diameter of 0.05 μm to 5 μm, and may further contain water and / or a solvent. preferable. The organosilicon compound and the photosensitive compound represented by the formula (I) are the same as those described above. The ultraviolet curable compound and the metal oxide particles are the same as those described above, but the metal oxide particles preferably have a particle size of 0.05 μm to 5 μm.

  The solvent to be used is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane and cyclopentane. Ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethyl sulfoxide And the like; alcohols such as methanol and ethanol; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate; and the like. These solvents can be used alone or in combination of two or more.

  The solid content (organosilicon component, photosensitive compound component, ultraviolet curable compound and metal oxide particles) in the organic-inorganic composite-forming composition of the present invention is preferably 1 to 75% by mass, More preferably, it is 10-60 mass%. The ultraviolet curable compound is 2 to 98% by mass, preferably 5 to 95% by mass with respect to the total mass of the organosilicon compound and / or its condensate, photosensitive compound, ultraviolet curable compound and metal oxide particles. is there.

  As the content of the photosensitive compound, although depending on the type, generally 0.01 to 0.5 molar equivalent of a metal atom in the photosensitive compound with respect to Si in the organosilicon compound, Preferably it is 0.05-0.2 molar equivalent.

  A tetrafunctional silane or colloidal silica can be added to the composition for forming an organic-inorganic composite of the present invention for the purpose of improving the hardness of the resulting coating film. Examples of the tetrafunctional silane include tetraaminosilane, tetrachlorosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrabenzyloxysilane, tetraphenoxysilane, tetra (meth) acryloxysilane, tetrakis [2 -(Meth) acryloxyethoxy] silane, tetrakis (2-vinyloxyethoxy) silane, tetraglycidyloxysilane, tetrakis (2-vinyloxybutoxy) silane, tetrakis (3-methyl-3-oxetanemethoxy) silane be able to. Examples of the colloidal silica include water-dispersed colloidal silica and organic solvent-dispersed colloidal silica such as methanol or isopropyl alcohol.

In addition, in the composition for forming an organic-inorganic composite of the present invention, in order to express various properties such as coloring of the obtained coating film, thickening of the coating film, prevention of UV transmission to the base, imparting corrosion resistance, and heat resistance. It is also possible to add and disperse the filler separately.
Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments, and particulate and fibrous or scale-like metals and alloys other than pigments, and oxides, hydroxides, carbides, nitrides thereof, and the like. Examples thereof include sulfides. Specific examples of this filler include particulate, fibrous or scale-like iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, Manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, carbonic acid Magnesium, Barium sulfate, Bentonite, Mica, Zinc green, Chromium green, Cobalt green, Viridian, Guinea green, Cobalt chrome green, Shale green, Green earth, Manganese green, Pigment green, Ultramarine, Bitumen, Rock ultramarine, Cobalt blue, Cerulean Blue, copper borate, molybdenum blue, copper sulfide, koval Purple, Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Lead Sulfide, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium red, chrome vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, sulfuric acid Examples thereof include lead, graphite, bone black, diamond black, thermostatic black, vegetable black, potassium titanate whisker, and molybdenum disulfide.

  The composition for forming an organic-inorganic composite of the present invention includes other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium Additives such as coupling agents, dyes, dispersants, thickeners and leveling agents can also be added.

(Method for preparing composition for forming organic-inorganic composite)
As a method for preparing the composition for forming an organic-inorganic composite of the present invention, water and / or a solvent are added as necessary, and an organic silicon compound, a photosensitive compound, an ultraviolet curable compound, and metal oxide particles are mixed. .

Specifically, for example, a photosensitive compound is mixed with a solvent, a predetermined amount of water is added, (partial) hydrolysis is performed, and then an organosilicon compound is added (partial) to hydrolyze. On the other hand, an ultraviolet curable compound is dissolved in a solvent, a photopolymerization initiator is added, and then both solutions are mixed.
These four components can be mixed at the same time. Also, regarding the method of mixing the organosilicon compound and the photosensitive compound, after mixing the organosilicon compound and the photosensitive compound, water is added (partial) hydrolysis. And a method of separately (partially) hydrolyzing an organosilicon compound and a photosensitive compound. It is not always necessary to add water or a solvent, but it is preferable to add (partly) a hydrolyzate by adding water. The amount of the predetermined amount of water depends on the type of the photosensitive compound. For example, when the photosensitive compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, the amount of water is 1 mol of the metal compound. It is preferable to use 0.5 mol or more of water, and more preferably 0.5 to 2 mol of water. Further, when the photosensitive compound is a metal chelate compound or metal organic acid salt compound, it is preferable to use 5 to 100 mol of water with respect to 1 mol of the metal chelate compound or metal organic acid salt compound, and 5 to 20 mol. More preferably, the water is used.
The addition of metal oxide particles can be performed at the end of the above process. Specifically, for example, the particles may be added directly to the solution prepared in the above step or may be added after being dispersed in an organic solvent such as alcohol. It can be set as the composition for organic-inorganic composite formation of this invention by stirring after addition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.

[Example 1]
1. Synthesis of Photosensitive Compound Diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda, T-50, solid content in terms of titanium oxide: 16.5% by weight) 303.03 g was ethanol / ethyl acetate (= 50/50: weight) %) Was dissolved in 584.21 g of mixed solvent, and 112.76 g of ion-exchanged water (10 times mol / mol of titanium oxide) was added with stirring. This solution was stirred for 2 hours while being heated to 40 ° C. to be hydrolyzed. Next, the solution was filtered to obtain a yellow transparent titanium oxide nano-dispersion [A-1] having a titanium oxide equivalent concentration of 5% by weight. The average particle size of titanium oxide was 4.1 nm and was monodispersed.

2. Preparation of organosilicon compound As an organosilicon compound, 179.91 g [B-1] of vinyltrimethoxysilane (KBE-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) and 301.55 g of 3-methacryloxypropyltrimethoxysilane [B-2 ] Liquid [C-1] in which (vinyltrimethoxysilane / 3-methacryloxypropyltrimethoxysilane = 50/50: molar ratio) (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was mixed was used.
Next, 431.05 g of [A-1] and 481.47 g of [C-1] were mixed so that the element ratio (Ti / Si = 1/9) was obtained, and 87.48 g (2 2 mol / mol of organosilicon compound) was added, and the mixture was heated to 70 ° C. and stirred for 3 hours to prepare a liquid [D-1].

3. Preparation of UV curable compound solution Mixing ethanol / ethyl acetate (= 50/50: wt%) as UV curable compound, urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry, purple light UV7600B) to be 40 wt% Dissolved in solvent. As a photopolymerization initiator, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Ciba -4 parts of Irgacure 127) manufactured by Specialty Chemicals was added to the solid content of the urethane acrylate oligomer to prepare a solution [E-1].

4). Preparation of the composition for forming an organic-inorganic composite The above-mentioned [D-1] solution 732.57 g and [[D-1] / [E-1] so that the solid content ratio is 70% by weight / 30% by weight = [D-1] / [E-1]. The E-1] liquid 267.43g was mixed and the coating-film formation solution [F-1] was produced.

5). Addition of Metal Oxide As a metal oxide, SYLYSIA310P (average particle diameter of 2.7 μm agglomerated silica powder) manufactured by Fuji Silysia Chemical Ltd. was added and dispersed at a ratio of 4% by weight to the solid content of [F-1]. G-1] was produced.

[Comparative Example 1]
As an ultraviolet curable compound, a mixed solvent of ethanol / ethyl acetate / 2-butanol (= 60/20/20:% by weight) of urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry, purple light UV7600B) so as to be 40% by weight. Dissolved in. As a photopolymerization initiator, 4-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173, manufactured by Ciba Specialty Chemicals) was added to this solution as a photopolymerization initiator in an amount of 4% by weight based on the solid content of the urethane acrylate oligomer. To obtain a solution [E-2]. SYLYSIA310P (average particle size: 2.7 μm agglomerated silica powder) manufactured by Fuji Silysia Chemical Co., Ltd. was added as a metal oxide in a proportion of 4% by weight with respect to the solid content of [E-2] and dispersed [G-2 ] Was produced.

[Comparative Example 2]
[A-1] 453.09 g and [C-1] 454.95 g were mixed so that the element ratio (Ti / Si = 1/9) was obtained, and 91.96 g of ion-exchanged water (2 times mol / mol) was added. Mole of organosilicon compound) was added, and the solution [D-1] was heated to 70 ° C. and stirred for 3 hours. As a metal oxide, SYLYSIA310P (average particle size of 2.7 μm agglomerated silica powder) manufactured by Fuji Silysia Chemical Ltd. was added and dispersed at a ratio of 4% by weight to the solid content of [D-1] [G-3 ] Was produced.

(Test Example A)
A-1. Coating Film Formation A coating film forming composition [G-1 to 3] was dip-formed on a glass substrate and heated at 150 ° C. for 5 minutes in a hot air circulation dryer. Subsequently, a condensing type high-pressure mercury lamp (UV light mainly composed of 365 nm, 313 nm, and 254 nm wavelengths, manufactured by Eye Graphics, one lamp type, 120 W / cm, lamp height 9.8 cm, conveyor speed 5 m / Minutes), an ultraviolet ray with an integrated irradiation amount of 2000 mJ / cm ² was irradiated to obtain a thin film.

A-2. Pencil hardness A pencil hardness test was performed in accordance with the pencil method of JIS K5600-5-4.

A-3. Adhesiveness An adhesiveness test was performed in accordance with the cross-cut method of JIS K5600-5-6. The case where peeling was not observed was marked with ◯, and the case where peeling was seen was marked with x.

A-4. Anti-glare performance The case where the outline of the fluorescent lamp reflected on the surface of the coating film was clearly visible was rated as x, and the case where the outline of the fluorescent lamp was blurred due to the anti-glare effect of the coating film was rated as ◯.

A-5. Humidity resistance A constant temperature and humidity chamber (LH-30 manufactured by Nagano Kagaku Kikai Seisakusho) was set to a temperature of 60 ° C. and a humidity of 95% RH, and the coating film was allowed to stand for 1000 hours in the bath. ○: No abnormal appearance, ×: Peeling occurred

  The test results are shown in Table 1 below.

[Example 2]
1. Synthesis of Photosensitive Compound Diisopropoxybisacetylacetonatotitanium (manufactured by Nippon Soda, T-50, solid content in terms of titanium oxide: 16.5% by weight) 303.03 g was added to ethanol / ethyl acetate / 2-butanol (= 60 / 20/20: wt%) was dissolved in 584.21 g of mixed solvent, and 112.76 g of ion-exchanged water (10-fold mol / mol of titanium oxide) was added with stirring. This solution was stirred for 2 hours while being heated to 40 ° C. to be hydrolyzed. Next, the solution was filtered to obtain a yellow transparent titanium oxide nano-dispersion [A-1] having a titanium oxide equivalent concentration of 5% by weight. The average particle size of titanium oxide was 4.1 nm and was monodispersed.

2. Preparation of organosilicon compound As an organosilicon compound, 264.76 g [B-1] vinyltrimethoxysilane (KBE-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) and 190.19 g 3-methacryloxypropyltrimethoxysilane [B-2 The liquid [C-2] obtained by mixing (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) (vinyltrimethoxysilane / 3-methacryloxypropyltrimethoxysilane = 70/30: molar ratio) was used.
Next, [A-1] 453.09 g and [C-2] 454.95 g were mixed so that the element ratio (Ti / Si = 1/9) was obtained, and ion-exchanged water was further added to 91.96 g (2 2 mol / mol of organosilicon compound) was added, and the solution [D-2] was heated to 70 ° C. and stirred for 3 hours.

3. Preparation of ultraviolet curable compound solution As an ultraviolet curable compound, ethanol / ethyl acetate / 2-butanol (= 60/20/20) was used so that urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry, purple light UV7630B) would be 40% by weight. : Wt%) mixed solvent. As a photopolymerization initiator, 4-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173, manufactured by Ciba Specialty Chemicals) was added to this solution as a photopolymerization initiator in an amount of 4% by weight based on the solid content of the urethane acrylate oligomer. To obtain a solution [E-3].

4). Preparation of composition for forming organic-inorganic composite [D-2] solution and [E-3] so that the solid content ratio is 10% by weight / 90% by weight = [D-2] / [E-3] ] Solution was mixed to prepare a coating film forming solution [F-2].

5). Addition of Metal Oxide As a metal oxide, SYLYSIA310P (average particle diameter of 2.7 μm agglomerated silica powder) manufactured by Fuji Silysia Chemical Ltd. was added and dispersed at a ratio of 4% by weight to the solid content of [F-2]. G-4] was produced.

[Comparative Example 3]
As a metal oxide, SYLYSIA310P (average particle size of 2.7 μm agglomerated silica powder) manufactured by Fuji Silysia Chemical Ltd. was added and dispersed at a ratio of 1% by weight with respect to the solid content of [F-2], and [G-5] was dispersed. Produced.

(Test Example B)
B-1. Coating Film Formation The coating film forming composition [G-4] was formed on a 188 μm thick PET film (Toyobo Cosmo Shine A4300) with a bar coater and heated at 60 ° C. for 3 minutes in a hot air circulation dryer. did. Subsequently, a condensing type high-pressure mercury lamp (UV light mainly composed of 365 nm, 313 nm, and 254 nm wavelengths, manufactured by Eye Graphics, one lamp type, 120 W / cm, lamp height 9.8 cm, conveyor speed 5 m / Min), a thin film was obtained by irradiating ultraviolet rays with an integrated dose of 300 mJ / cm ² .

B-2. Adhesiveness An adhesiveness test was performed in accordance with the cross-cut method of JIS K5600-5-6. The case where peeling was not observed was marked with ◯, and the case where peeling was seen was marked with x.

B-3. Anti-Newton ring performance The formed PET film was bonded so that the coated surface faced the glass substrate, and the PET film was pressed from the body coated surface side with a finger to be in close contact. This portion was observed under a three-wavelength fluorescent lamp. The case where Newton's ring was generated was indicated as x, and the case where Newton's ring was not visible was indicated as ○.

  The test results are shown in Table 2 below.

[Example 3]
As a metal oxide, SYLYSIA310P (average particle size: 2.7 μm agglomerated silica powder) manufactured by Fuji Silysia Chemical Co. was added in the same manner as in Example 2 except that it was added at a ratio of 2% by weight to the solid content of [F-2]. Coating agent [G-6] was obtained.

[Example 4]
As a metal oxide, SYLYSIA310P (average particle size of 2.7 μm agglomerated silica powder) manufactured by Fuji Silysia Chemical Co. was added in the same manner as in Example 2 except that it was added at a ratio of 5% by weight to the solid content of [F-2]. Coating agent [G-7] was obtained.

[Comparative Example 4]
As a metal oxide, SYLYSIA310P (average particle size of 2.7 μm agglomerated silica powder) manufactured by Fuji Silysia Chemical Ltd. was added in the same manner as in Example 2 except that it was added at a ratio of 1% by weight to the solid content of [F-2]. Coating agent [G-8] was obtained.

(Test Example C)
C-1. Coating Film Formation The coating film forming composition [G-4] was formed on a 188 μm thick PET film (Toyobo Cosmo Shine A4300) with a bar coater and heated at 60 ° C. for 3 minutes in a hot air circulation dryer. did. Subsequently, a condensing type high-pressure mercury lamp (UV light mainly composed of 365 nm, 313 nm, and 254 nm wavelengths, manufactured by Eye Graphics, one lamp type, 120 W / cm, lamp height 9.8 cm, conveyor speed 5 m / Min), a thin film was obtained by irradiating ultraviolet rays with an integrated dose of 300 mJ / cm ² .

C-2. Measurement of 10-point Average Roughness The surface shape of the obtained coating film was observed using a scanning probe microscope “SPI3800N (SPA400)” manufactured by Seiko Instruments Inc.

  The test results are shown in Table 3 below.

[Reference example]
Formation of coating film: The coating film forming composition [G-3] was formed on a soda-lime glass substrate having a thickness of 1.1 mm by using dip coating. At this time, the dip pulling speed was set between 10 and 100 cm / min. This coating film was heated at 150 ° C. for 3 minutes in a hot air circulation dryer. Subsequently, a condensing type high-pressure mercury lamp (UV light mainly composed of 365 nm, 313 nm, and 254 nm wavelengths, manufactured by Eye Graphics, one lamp type, 120 W / cm, lamp height 9.8 cm, conveyor speed 5 m / Minutes), an ultraviolet ray with an integrated irradiation amount of 2000 mJ / cm ² was irradiated to obtain a thin film.
Measurement of 10-point average roughness: The surface shape of the obtained coating film was observed using a scanning probe microscope “SPI3800N (SPA400)” manufactured by Seiko Instruments Inc.

  The test results are shown in Table 4 below.

[Example 5]
1. Synthesis of Photosensitive Compound Diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda Co., Ltd., T-50, solid content in terms of titanium oxide: 16.5% by weight) was dissolved in 304.23 g of ethanol and then stirred. Then, 112.76 g of ion-exchanged water (10-fold mol / mol of titanium oxide) was added. This solution was stirred for 2 hours while being heated to 40 ° C. to be hydrolyzed. Next, the solution was filtered to obtain a yellow transparent titanium oxide nano-dispersion [A-2] having a titanium oxide equivalent concentration of 5% by weight. The average particle size of titanium oxide was 4.1 nm and was monodispersed.

2. Preparation of organosilicon compound As an organosilicon compound, 264.76 g [B-1] vinyltrimethoxysilane (KBE-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) and 190.19 g 3-methacryloxypropyltrimethoxysilane [B-2 The liquid [C-2] obtained by mixing (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) (vinyltrimethoxysilane / 3-methacryloxypropyltrimethoxysilane = 70/30: molar ratio) was used.
Next, [A-2] 453.09 g and [C-2] 454.95 g were mixed so that the element ratio (Ti / Si = 1/9) was obtained, and ion-exchanged water was further added to 91.96 g (2 The liquid [D-3] was prepared by adding 24 moles / mole of the organosilicon compound and stirring for 24 hours.

3. Preparation of UV curable compound solution As an UV curable compound, urethane acrylate oligomer (manufactured by Nippon Gosei Kagaku Kogyo, purple light UV7600B) was dissolved in methyl isobutyl ketone so as to be 40% by weight. As a photopolymerization initiator, 4 parts of Irgacure 907 manufactured by Ciba Specialty Chemicals was added to this solution based on the solid content of the urethane acrylate oligomer to prepare a solution [E-1].

4). Preparation of composition for forming organic-inorganic composite [D-3] and [E-1] so that the solid content ratio is 10% by weight / 90% by weight = [D-3] / [E-1] ] Solution was mixed to prepare a coating film forming solution [F-3].

5). Addition of Metal Oxide As a metal oxide, SiO ₂ dispersion sol IPA-ST-ZL (average particle size 0.07 μm-0.1 μm) manufactured by Nissan Chemical Industries, Ltd., 20 wt.% Relative to the solid content of [F-3] % Was added and dispersed to prepare [G-9].

[Comparative Example 5]
As an ultraviolet curable compound, urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry, purple light UV7600B) was dissolved in methyl isobutyl ketone so as to be 40% by weight. As a photopolymerization initiator, 4 parts of Darocure 907 manufactured by Ciba Specialty Chemicals was added to the solid content of the urethane acrylate oligomer as a photopolymerization initiator to prepare a solution [E-1]. To this, as a metal oxide, SiO ₂ dispersion sol IPA-ST-ZL (average particle size 0.07 μm-0.1 μm) manufactured by Nissan Chemical Industries, 30 wt% relative to the solid content of [F-3] [G-10] was prepared by adding and dispersing at a ratio.

(Test Example D)
D-1. Coating Film Formation The coating film forming composition [G-9] was formed on a PET film (Toyobo Cosmo Shine A4300) having a thickness of 188 μm with a bar coater, and heated at 100 ° C. for 3 minutes with a hot air circulation dryer. Heated. Subsequently, by a condensing high-pressure mercury lamp (UV light mainly composed of light of 365 nm, 313 nm, and 254 nm, manufactured by Eye Graphics, 120 W / cm, lamp height 9.8 cm, conveyor speed 5 m / min), A thin film was obtained by irradiating with an ultraviolet ray having an integrated irradiation amount of 350 mJ / cm ² .
D-2. Pencil hardness A pencil hardness test was performed in accordance with the pencil method of JIS K5600-5-4.
D-3. Scratch resistance Steel wool # 0000 (trade name: Bonstar Nippon Steel Wool) was used, and a load of 200 g was applied, and the scratches after rubbing the surface of the coating film 20 times were evaluated.
D-4. Haze rate The haze rate of the coating film was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.).
D-5. Planar roughness The surface of the coating film was observed using a three-dimensional non-contact surface shape measurement system (manufactured by Ryoka System) using an optical interference method, and the calculated 10-point average roughness R _ZJIS was used.

  The test results are shown in Table 5 below.

Claims (13)

a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And each X may be the same or different when (4-n) is 2 or more.)
b) At least one 350 nm or less selected from the group consisting of metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. A light-sensitive compound that is sensitive to light of a wavelength and / or a compound derived therefrom,
c) an organic-inorganic composite containing a cured product of an ultraviolet curable compound, and d) metal oxide particles, wherein the 10-point average roughness of the surface of the organic-inorganic composite is 0.1 μm to 5 μm. A characteristic organic-inorganic composite. The organic-inorganic composite according to claim 1, wherein the carbon content on the surface of the organic-inorganic composite is 80% or less of the carbon content on the back surface side. The organic-inorganic composite according to claim 1 or 2, wherein the metal in the compound of b) is Ti, Al, Zr or Sn. The organic-inorganic composite according to claim 1, wherein the ultraviolet curable compound of c) is a (meth) acrylate-based ultraviolet curable compound. The organic-inorganic composite according to any one of claims 1 to 4, wherein the metal oxide particles of d) are porous powders. The organic-inorganic composite according to any one of claims 1 to 4, wherein the primary particle diameter of the metal oxide particles of d) is 0.05 µm to 0.2 µm. a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And when the number of (4-n) is 2 or more, each X may be the same or different.)
b) At least one 350 nm or less selected from the group consisting of metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. A light-sensitive compound that is sensitive to light of a wavelength;
An organic-inorganic composite-forming composition comprising: c) an ultraviolet curable compound; and d) metal oxide particles having a particle size of 0.05 μm to 5 μm. The composition for forming an organic-inorganic composite according to claim 7, wherein the metal in the compound of b) is Ti, Al, Zr or Sn. The ultraviolet curable compound is 2 to 98% by mass with respect to the total mass of the organosilicon compound and / or condensate thereof, the photosensitive compound, the ultraviolet curable compound and the metal oxide particles. The composition for forming an organic-inorganic composite according to 7 or 8. The composition for forming an organic-inorganic composite according to any one of claims 7 to 9, wherein the metal oxide particles of d) are porous powders. The composition for forming an organic-inorganic composite according to any one of claims 7 to 9, wherein the primary particle diameter of the metal oxide particles of d) is 0.05 µm to 0.2 µm.
The organic-inorganic composite according to any one of claims 1 to 6, wherein the organic-inorganic composite is an antiglare film or an anti-Newton ring film. The composition for forming an organic-inorganic complex according to any one of claims 7 to 11, wherein the composition for forming an organic-inorganic complex is a composition for an antiglare film or an anti-Newton ring film.