JP2012188547A - Organic-inorganic composite and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic-inorganic composite that has excellent appearance and excellent antifouling properties, and can form a transparent coating film and a transparent molded product, wherein the refractive indice of the coating film and molded product thus obtained can be easily controlled.SOLUTION: The organic-inorganic composite comprises: inorganic oxide particles (A); a polymer (B) formed by subjecting a radical polymerizable monomer to polymerization, having a molar weight dispersion degree of 2.3 or lower, and binding to the inorganic oxide particle; and 0.1-60 mass% of fluorine (C) based on the total mass.

Description

  The present invention relates to an organic-inorganic composite having improved antifouling properties and a method for producing the same. The present invention also relates to a coating material, a coating film, a molded body, an optical member, and an optical material using an organic-inorganic composite.

Conventionally, the refractive index of a coating film or a molded body formed from a polymer has been controlled by a method of introducing fluorine into the polymer. However, since a general fluororesin is produced by polymerizing a fluorine-containing gas or liquid under high-pressure conditions, labor is required for safety management, and its selling price is expensive. Moreover, when using these polymers as a coating material, it is necessary to dissolve in a special fluorine-based solvent, and the use is limited.
Also, there is a method of polymerizing a fluorine-containing radical polymerizable monomer to obtain a fluorine-containing polymer, but the strength tends to be low.

  Therefore, there is an attempt to disperse hollow silica particles as inorganic particles in the polymer without using a fluorine-based polymer. For example, Patent Document 1 describes a method of mixing a hollow silica sol and a fluorine-based polymer and performing UV curing. Patent Document 2 describes a mixture of pMMA-modified silica and a fluorine-containing polymer. Non-Patent Document 1 describes a substance obtained by grafting an organic polymer onto silica.

JP 2008-115329 A JP 2006-257308 A

Journal of Polymer Science: Part B: Polymer Physics, Vol. 40, 2667-2676 (2002)

  However, when the hollow silica particles are dispersed in the polymer as inorganic particles, the hollow silica particles are very expensive, and thus the raw material cost is very high. Further, there is a drawback that a desired refractive index cannot be obtained even if general silica particles are dispersed in an organic polymer instead of hollow silica, and the particles are easily soiled.

  The main object of the present invention is to form a transparent coating film or molded body having a good appearance and excellent antifouling property, and to easily improve the refractive index of the resulting coating film or molded body. It is an object to provide an organic-inorganic composite that can be controlled easily.

The present invention relates to the following.
[1]
(A) inorganic oxide particles, and (B) a polymer formed by polymerization of a radical polymerizable monomer and having a molecular weight dispersity of 2.3 or less and bonded to the inorganic oxide particles,
(C) An organic-inorganic composite containing 0.1 to 60% by mass of fluorine based on the total mass.
[2]
The organic-inorganic composite according to [1], wherein the glass transition temperature is −10 to 180 ° C.
[3]
The organic-inorganic composite according to [1] or [2], wherein the total content of bromine and chlorine is 0.001 to 5% by mass based on the total mass.
[4]
The organic-inorganic composite according to any one of [1] to [3], wherein the inorganic oxide particles are silica particles.
[5]
The organic-inorganic composite according to any one of [1] to [4], wherein the minimum width of the inorganic oxide particles is 1 to 70 nm.
[6]
The organic-inorganic composite according to any one of [1] to [5], wherein the inorganic oxide particles have a circularity of 0.7 to 1.
[7]
The organic-inorganic composite according to any one of [1] to [6], wherein L / D of the inorganic oxide particles is 5 or more.
[8]
The organic-inorganic composite according to any one of [1] to [7], wherein the inorganic oxide particles form a long-chain structure including a plurality of primary particles connected in a bead shape.
[9]
The organic-inorganic composite according to any one of [1] to [8], wherein the inorganic oxide particles have a refractive index of 1.4 to 1.6.
[10]
The organic-inorganic composite according to any one of [1] to [9], wherein the content of the inorganic oxide particles is 2 to 96% by mass based on the total mass.
[11]
The organic-inorganic composite according to any one of [1] to [10], wherein the content of the inorganic oxide particles is 1 to 94% by volume based on the total volume.
[12]
The organic-inorganic composite according to any one of [1] to [11], wherein the radical polymerizable monomer includes at least one fluorine-based monomer.
[13]
The organic-inorganic composite according to any one of [1] to [12], wherein the radical polymerizable monomer includes at least one monomer selected from the group consisting of acrylic acid esters and methacrylic acid esters.
[14]
In any one of [1] to [13], the radical polymerizable monomer includes an acrylic ester and a methacrylic ester, and the polymer is a copolymer of the acrylic ester and the methacrylic ester. The organic-inorganic composite as described.
[15]
The organic-inorganic composite according to any one of [1] to [14], wherein the polymer is a thermoplastic polymer.
[16]
The organic-inorganic composite according to any one of [1] to [15], wherein the polymer has a molecular weight dispersity of 1.0 to 1.9.
[17]
A step of producing surface-modified inorganic oxide particles by reacting inorganic oxide particles with a coupling agent having a polymerization initiating group, and living radical polymerization initiated by the polymerization initiating group, to the inorganic oxide particles. A method for producing an organic-inorganic composite according to any one of [1] to [16], comprising a step of forming a bonded polymer.
[18]
The production method according to [17], wherein the living radical polymerization is atom transfer radical polymerization.
[19]
The production method according to [17] or [18], wherein the polymerization initiating group contains a halogen atom.
[20]
The production method according to [19], wherein the halogen content of the surface-modified inorganic oxide particles is 0.02 to 10% by mass.
[21]
The coupling agent has at least one functional group selected from the group consisting of a phosphate group, a carboxy group, an acid halide group, an acid anhydride group, an isocyanate group, a glycidyl group, a chlorosilyl group, and an alkoxysilyl group. [17] The manufacturing method according to any one of [20].
[22]
The production method according to [21], wherein the functional group is a chlorosilyl group or an alkoxysilyl group.
[23]
The production method according to [22], wherein the coupling agent has one or two of the functional groups.
[24]
The coating material containing the organic-inorganic composite of any one of [1]-[16].
[25]
The coating material according to [24], further comprising an organic solvent.
[26]
[24] A coating film comprising the coating material according to [25].
[27]
The coating film according to [26], which has a refractive index of 1.05 to 1.43.
[28]
The coating film according to [26] or [27], wherein the pencil hardness is HB or higher.
[29]
The coating film according to any one of [26] to [28], wherein the water contact angle is 75 ° or more.
[30]
The coating film according to any one of [26] to [29], wherein the oil contact angle is 30 ° or more.
[31]
The coating film according to any one of [26] to [30], wherein the porosity is 2 to 60% by volume.
[32]
The molded object containing the organic-inorganic composite of any one of [1]-[16].
[33]
The molded product according to [32], wherein the particle dispersity is 0.6 or less.
[34]
The molded product according to [32] or [33], which has a refractive index of 1.05 to 1.43.
[35]
The molded object according to any one of [32] to [34], wherein the porosity is 2 to 60% by volume.
[36]
An optical member provided with the coating film of any one of [26]-[31], or the molded object of any one of [32]-[35].
[37]
An optical material comprising the organic-inorganic composite according to any one of [1] to [16].

  According to the present invention, it is possible to form a transparent coating film or molded body having a good appearance and excellent antifouling property, and easily control the refractive index of the obtained coating film or molded body. A possible organic-inorganic composite is provided.

  Since the organic-inorganic composite of the present invention has a uniform molecular weight of the polymer bonded to the inorganic oxide particles, a molded body and a coating film having a good appearance in which aggregation of particles is suppressed can be obtained.

  In the organic-inorganic composite of the present invention, a hollow silica particle and an ungrafted polymer are used, as in the technique of Patent Document 1, in that a fluorine-containing polymer is directly grafted onto an inorganic oxide particle. Compared to the case of mixing, it is advantageous in that aggregation of inorganic oxide particles is suppressed. Moreover, this invention can suppress manufacturing cost by using an inexpensive inorganic oxide particle instead of an expensive hollow silica particle.

  Patent Document 2 describes a composition composed of hollow silica surface-modified with a polymer and a binder component such as a fluorine-containing monomer. However, a film is formed only with hollow silica surface-modified with a polymer. First, a binder component is essential. As a result, the refractive index of the obtained low refractive index layer is 1.44 to 1.46, which is not much different from general general-purpose polymers. The rate is 1.4 or less. Similarly to Patent Document 1, since expensive hollow silica particles are used, the method of Patent Document 2 is different from the present invention.

It is a schematic diagram which shows the calculation method of the maximum length and minimum width | variety of inorganic oxide particle. It is a TEM photograph of beaded silica particles.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to this Embodiment, It can implement by changing variously within the range of the summary.

  The organic-inorganic composite according to the present embodiment includes (A) inorganic oxide particles and (B) a polymer formed by polymerization of a radical polymerizable monomer. This organic-inorganic composite preferably has film-forming properties alone. The “film forming property” here means the property that a coating film can be formed alone without being mixed with other binder components such as monomers.

[Inorganic oxide particles]
The inorganic oxide particles are not particularly limited as long as they are particles formed from an inorganic oxide that is an oxide of an element other than carbon, and two or more types of inorganic oxide particles are used in combination. Is also possible.

The particle porosity of the inorganic oxide particles is not particularly limited, but is generally 0 to 4% because the particle porosity of the inorganic oxide particles that are generally available at low cost is about 0 to 4%. Is preferable, and more preferably 0%.
The particle porosity is represented by “particle porosity (%) = (volume of void portion in particle) / (volume of entire particle) × 100”, and the measurement method of the particle porosity will be described in detail in Examples described later. Explained.

  The kind of the inorganic oxide particles is not particularly limited, but silica particles are preferable from the viewpoint of transparency of the coating film and the molded body and ease of controlling the refractive index.

  The minimum width of the inorganic oxide particles is not particularly limited, but is preferably 1 to 70 nm. When the minimum width is larger than 70 nm, when an organic-inorganic composite is used as an optical material, the transparency tends to decrease due to light scattering, and when it is less than 1 nm, the substance constituting the inorganic oxide particles is inherent. The characteristics of can change. From the same viewpoint, the average particle size of the inorganic oxide particles is more preferably 2 to 60 nm, still more preferably 5 to 50 nm, and particularly preferably 7 to 30 nm.

  When spherical particles are used as the inorganic oxide particles, the circularity is preferably 0.7-1. When the circularity is 0.7 to 1, evenness can be maintained even with a thin film. From the same viewpoint, the circularity is more preferably 0.8 to 1, and still more preferably 0.85 to 1. The method for measuring the circularity will be described in detail in the examples described later.

  When inorganic particles other than spherical particles are used, the maximum length L and the minimum width D are not particularly limited, but it is preferable that L / D ≧ 5 is satisfied from the viewpoint of refractive index control. L / D is more preferably 6 to 50, still more preferably 7 to 30, and particularly preferably 8 to 20. The measuring method of L / D will be described in detail in Examples described later.

  The shape and crystal shape of the inorganic oxide particles are not particularly limited, and may be various shapes such as a spherical shape, a crystal shape, a scale shape, a rod shape, a fiber shape, and a bead shape. Among them, the spherical shape is preferable for applications requiring strength and strict uniformity. Further, from the viewpoint of controlling the refractive index, a rod shape, a fiber shape, and a bead shape are preferable, a fiber shape or a bead shape is more preferable, and a bead shape is particularly preferable.

  The beaded inorganic oxide particles referred to here are those having a long chain structure including a plurality of primary particles connected in a bead shape, and the primary particles are connected and / or branched in a bead shape. Have.

  The bead-like inorganic oxide particles include those in which primary particles connected in a bead shape are branched. When rosary inorganic oxide particles are observed with an electron microscope such as SEM and TEM at a magnification of 50,000 to 100,000, among the primary particles present in the field of view, the above long chain is not a single primary particle. The number of primary particles having a structure having a branched structure and a branched structure is at least 50% or more, preferably 70% or more, more preferably 90 to 100%. Because of the steric hindrance of the beaded inorganic oxide particles, other beaded inorganic oxide particles cannot occupy the space closely, and as a result, a film with a higher porosity can be easily formed. Particularly preferred.

  The beaded inorganic oxide particles are not particularly limited as long as they are made of an inorganic oxide, but beaded silica particles are preferable from the viewpoint of easy availability. Specifically, for example, as shown in FIG. 2, there may be mentioned those having a long chain structure in which spherical colloidal silica is connected in a bead shape, and those in which the connected colloidal silica is branched. The bead-like silica particles are obtained by bonding primary particles composed of spherical colloidal silica with primary and primary particles intervening bivalent or higher metal ions. At least 3 or more, more preferably 5 or more, more preferably 7 or more primary particles are connected.

  The refractive index of the inorganic oxide particles is not particularly limited, but is preferably about 1.4 to 1.6 because a refractive index control effect is easily obtained. From the viewpoint of the balance between the refractive index design and the film formability, the refractive index of the inorganic oxide particles is more preferably 1.41 to 1.48, and still more preferably 1.42 to 1.46.

[Organic-inorganic composite]
The organic-inorganic composite of the present invention contains 0.1 to 60% by mass of fluorine based on the total mass of the organic-inorganic composite. Among these, considering the dispersibility in a general-purpose organic solvent and the balance between the refractive index control effect, water / oil repellency, and transparency, 1 to 50% by mass, more preferably 3 to 40% by mass, and still more preferably. It is 5-30 mass%.

  The glass transition temperature (hereinafter also referred to as “Tg”) of the organic-inorganic composite is not particularly limited, but it can be imparted with favorable film formability while suppressing stickiness, and is −10. It is preferable that it is -180 degreeC, More preferably, it is 0-160 degreeC, More preferably, it is 20-150 degreeC, Most preferably, it is 40-120 degreeC.

  The halogen content of the organic-inorganic composite refers to the total amount of bromine and chlorine contained in the organic-inorganic composite. The halogen content is not particularly limited, but is preferably 0.001 to 5% by mass on the basis of the total mass of the organic-inorganic composite because the film-forming property is good. More preferably, it is 0.01-2 mass%, More preferably, it is 0.1-1 mass%.

  The content of the inorganic oxide particles in the organic-inorganic composite is not particularly limited, but is preferably 2 to 96% by mass, more preferably 5 to 85%, from the viewpoint of the balance between refractive index control and strength. % By mass, particularly preferably 10 to 80% by mass. Further, from the viewpoints of refractive index control, film formability and moldability, the content of inorganic oxide particles is preferably 1 to 94% by volume, more preferably 4 to 79, based on the total volume of the organic-inorganic composite. % By volume, particularly preferably 7 to 66% by volume.

[polymer]
The polymer constituting the organic-inorganic composite is bonded to the surface of the inorganic oxide particle by a covalent bond via a coupling agent (coupling agent having a polymerization initiating group). This polymer contains one or more radically polymerizable monomers as monomer units. The organic-inorganic composite may contain a plurality of types of polymers composed of different monomer units.

  The polymerization form of the polymer is not particularly limited. For example, a homopolymer, a periodic copolymer, a block copolymer, a random copolymer, a gradient copolymer, a tapered copolymer, or a graft copolymer Is mentioned. Among these, a copolymer is preferable from the viewpoint of controlling physical properties such as Tg and refractive index.

  The polymer is preferably a copolymer of acrylic acid ester and methacrylic acid ester from the viewpoint of suppressing thermal decomposition. Moreover, since the said polymer is excellent in a moldability and workability, it is desirable that it is a thermoplastic polymer. The thermoplastic polymer here refers to a polymer that can be softened by heating to Tg or a melting point and can be molded, and is clearly distinguished from a curable polymer that does not have thermoplasticity. However, even if a curable polymer (crosslinkable polymer) is partially copolymerized, a thermoplastic polymer is the main component, and what exhibits thermoplasticity as a whole can be regarded as a thermoplastic polymer.

  The radical polymerizable monomer is preferably polymerizable by atom transfer radical polymerization (hereinafter also referred to as “ATRP”) or reversible addition / elimination chain transfer polymerization (hereinafter also referred to as “RAFT”).

  Examples of the monomer include ethylene, “dienes such as buta-1,3-diene, 2-methylbuta-1,3-diene, 2-chlorobuta-1,3-diene”, “styrene, α-methyl. Styrenes such as styrene, 4-methylstyrene, divinylbenzene, acetoxystyrene, 4-chloromethylstyrene 2,3,4,5,6-pentafluorostyrene, 4-aminostyrene "," methyl acrylate, ethyl acrylate " , N-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, octadecyl acrylate, benzyl acrylate, trimethylsilyl acrylate, 2- (dimethylamino) ethyl acrylate, acrylic Acid 2,2,2-trifluoroethyl, acrylic acid , 2,3,3, -tetrafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, acrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl, acrylic acid 1H, 1H , 3H-hexafluorobutyl, acrylic acid 1H, 1H, 5H-octafluoropentyl, acrylic acid esters such as 1H, 1H-heptafluorobutyl acrylate, ”“ methyl methacrylate, ethyl methacrylate, n-butyl methacrylate ” , Tert-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, octadecyl methacrylate, benzyl methacrylate, trimethylsilyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) methacrylate D Chill, 2,2,2-trifluoroethyl methacrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, 2,2,3,3 methacrylate , -Tetrafluoropropyl, methacrylic acid esters such as 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoropentyl methacrylate ”,“ 2-hydroxyethyl acrylate, 2-hydroxy methacrylate ” (Meth) acrylic acid derivatives such as ethyl, acrylamide, methacrylamide, N-cyclopropylacrylamide, N, N-dimethylacrylamide, N-hydroxymethylacrylamide, N-isopropylacrylamide, acrylonitrile, methacrylonitrile "," vinegar Vinyl, vinyl propionate, vinyl benzoate, vinyl esters such as vinyl butyrate ”,“ vinyl ethers such as vinyl methyl ether, vinyl ethyl ether ”,“ vinyl methyl ketone, vinyl hexyl ketone, vinyl ketones, N-vinyl pyrrole ” N-vinyl compounds such as N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone "," Allyl compounds such as allyl alcohol, allyl chloride, allyl acetate, vinyl chloride and vinylidene chloride "," vinyl fluoride And compounds having a fluorine alkyl group such as vinylidene fluoride ”and“ functional monomers such as glycidyl acrylate and glycidyl methacrylate ”. Among these, when emphasizing the transparency of the coating film or the molded product, it is preferable to select an acrylic ester or a methacrylic ester.

  Among the above monomers, from the viewpoint of providing refractive index control and imparting water / oil repellency, it is preferable to select at least one fluorine-based monomer, and since it is easily available, acrylic acid 2,2,2- Trifluoroethyl, acrylic acid 2,2,3,3-tetrafluoropropyl, acrylic acid 2,2,3,3,3-pentafluoropropyl, acrylic acid 1,1,1,3,3,3-hexa Fluoroisopropyl, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, and 1, More preferred is 1,1,3,3,3-hexafluoroisopropyl.

  Moreover, as a monomer which does not contain fluorine, since it is easily available, it is preferable to use at least one monomer selected from the group consisting of styrenes, acrylic acid esters and methacrylic acid esters. Among them, methyl acrylate, Monomers selected from ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate are preferred.

Specific examples of preferable monomers are shown below by chemical formulas.

  The shape of the polymer is not particularly limited, and examples thereof include a chain shape, a branched chain shape, a ladder shape, and a star shape. In addition, it is possible to introduce an arbitrary substituent or the like to improve the dispersibility and compatibility.

  The molecular weight of the polymer is not particularly limited, but the number average molecular weight (hereinafter also referred to as “Mn”) is preferably 500 to 500,000 g / mol, more preferably 5,000 to 200,000 g / mol, and still more preferably. Is 10,000 to 100,000 g / mol. When Mn is less than 500 g / mol, aggregation of inorganic oxide particles tends to occur, and when it exceeds 500,000 g / mol, characteristics as an inorganic oxide are hardly expressed, or the organic-inorganic composite The compatibility with other substances tends to decrease.

The degree of dispersion of the molecular weight of the polymer is determined by the following formula from the mass average molecular weight (hereinafter also referred to as “Mw”) and Mn.
Molecular weight dispersity = Mw / Mn
Mn and Mw here are polymethyl methacrylate equivalent values measured by gel permeation chromatography (GPC), as will be described in detail in the examples described later.

  In the present embodiment, the molecular weight dispersity is 2.3 or less. When the molecular weight dispersity is 2.3 or less, aggregation of the inorganic oxide particles is effectively suppressed. From the viewpoint of dispersibility, it is preferable that the molecular weight (chain length) of the polymer is uniform, that is, the degree of dispersion of the molecular weight is close to 1. From such a viewpoint, the degree of dispersion of the molecular weight is preferably 1.0 to 1.9, more preferably 1.0 to 1.7, and particularly preferably 1.0 to 1.5.

  The amount of the polymer bonded to the inorganic oxide particles in the present embodiment is determined by the method described later, and from the viewpoint of maintaining transparency, the amount is preferably 50% by mass or more, more preferably 70% by mass. As mentioned above, More preferably, it is 90 mass% or more.

[Coupling agent having a polymerization initiating group]
The coupling agent in this Embodiment is a compound used in order to connect the inorganic oxide particle surface and the above-mentioned polymer. The coupling agent is not particularly limited as long as it is a compound having a polymerization initiating group and a functional group that reacts with the surface of the inorganic oxide particles to form a bond. The inorganic oxide particle surface at this time may be formed from the inorganic oxide itself, or may be surface-treated. The surface treatment here is to modify the surface of the inorganic oxide particles with a functional group by chemical reaction, heat treatment, light irradiation, plasma irradiation, radiation irradiation or the like.

  The method for binding the coupling agent to the surface of the inorganic oxide particles is not particularly limited. For example, the method of reacting the hydroxyl group on the surface of the inorganic oxide particles with the coupling agent, or the inorganic oxide particles There is a method of reacting a functional group introduced by surface treatment of a surface with a coupling agent. It is also possible to connect a plurality of coupling agents by further reacting the coupling agent bonded to the inorganic oxide particles with a coupling agent. Depending on the type of coupling agent, water or a catalyst may be used in combination.

  The functional group of the coupling agent is not particularly limited. For example, when a bond is formed by reaction with a hydroxyl group on the surface of the inorganic oxide particle, a phosphate group, a carboxy group, an acid halide group, an acid anhydride group , Isocyanate group, glycidyl group, chlorosilyl group, alkoxysilyl group, silanol group, amino group, phosphonium group, sulfonium group and the like. Among these, from the viewpoint of the balance between the reactivity and the remaining amount of acid and coloring, preferred are an isocyanate group, a chlorosilyl group, an alkoxysilyl group, and a silanol group, and more preferred are a chlorosilyl group and an alkoxysilyl group. Among them, a chlorosilyl group is particularly preferable from the viewpoint of reactivity.

  The number of functional groups of the coupling agent is not particularly limited, but is preferably monofunctional or bifunctional, and particularly preferably monofunctional, because removal of by-products is easy.

  The polymerization initiating group possessed by the coupling agent is not particularly limited as long as it is a functional group having a polymerization initiating ability. For example, nitroxide-mediated radical polymerization (hereinafter also referred to as “NMP”), atom transfer radical polymerization (hereinafter also referred to as “ATRP”), reversible addition / elimination chain transfer polymerization (hereinafter referred to as “RAFT”). The polymerization initiating group used in the above).

  The polymerization initiating group in NMP is not particularly limited as long as it is a group to which a nitroxide group is bonded.

  The polymerization initiating group in ATRP is typically a group containing a halogen atom. It is preferable that the bond dissociation energy of the halogen atom is low. For example, a halogen atom bonded to a tertiary carbon atom, a halogen atom bonded to a carbon atom adjacent to an unsaturated carbon-carbon bond such as a vinyl group, a vinylidene group or a phenyl group, a hetero group such as a carbonyl group, a cyano group or a sulfonyl group. A preferable structure includes a group in which a halogen atom bonded directly to an atom-containing conjugated group or bonded to an atom adjacent thereto is introduced. More specifically, an organic halide group represented by the following general formula (1) and a halogenated sulfonyl group represented by the general formula (2) are preferable.

In formulas (1) and (2), R ₁ and R ₂ each independently have a hydrogen atom, a C 1-20 alkyl group that may have a substituent, or a substituent. An allyl group, an aryl group having 6 to 20 carbon atoms that may have a substituent, an alkylaryl group, or an alkylaryl group that may have a substituent, and Z represents a halogen atom.

The polymerization initiating group of the formula (1) may have a carbonyl group as shown in the following general formula (3). In the formula _(3), R 1, _{R 2} and Z have the same meanings as _R 1, _{R 2} and Z in the formula (1).

Specific examples of the polymerization initiating group of the formula (3) are shown in the following chemical formula.

  The polymerization initiating group in RAFT is not particularly limited as long as it is a group containing a sulfur atom that functions as a RAFT agent. Examples of such polymerization initiating groups include trithiocarbonate, dithioester, thioamide, thiocarbamate, dithiocarbamate, thiouranium, thiourea, dithiooxamide, thioketone and trisulfide.

Specific examples of suitable coupling agents include the following silane compounds.
3- (2-Bromoisobutyroxy) propyldimethylchlorosilane (Cas number: 370870-81-8)
Propionic acid, 2-bromo-2-methyl-, 3- (dichloromethylsilyl) propyl ester (Cas number: 1057260-39-5)
Propionic acid, 2-bromo-2-methyl-, 3- (trichlorosilyl) propyl ester (Cas number: 688359-84-4)
3- (methoxydimethylsilylpropyl) -2-bromo-2-methylpropionate (Cas number: 531505-27-8)
3- (Dimethoxymethylsilylpropyl) -2-bromo-2-methylpropionate (Cas number: 1186667-60-6)
3- (Trimethoxysilylpropyl) -2-bromo-2-methylpropionate (Cas number: 314021-97-1)
(3- (2-Bromoisobutyryl) propyl) dimethylethoxysilane (Cas number: 265119-86-6)
(3- (2-Bromoisobutyryl) propyl) methyldiethoxysilane (Cas number: 11866667-65-1)
Propionic acid, 2-bromo-2-methyl-, 3- (triethoxysilyl) propyl ester (Cas number: 880339-31-1)
Propionic acid, 2-bromo-, 3- (chlorodimethylsilyl) propyl ester (Cas number: 438001-36-6)
Propionic acid, 2-bromo-, 3- (trichlorosilyl) propyl ester (Cas number: 663174-64-9)
Propionic acid, 2-bromo-, 3- (methoxydimethylsilyl) propyl ester (Cas number: 861807-46-7)
(3- (2-Bromopropionyl) propyl) dimethylethoxysilane (Cas number: 265119-85-5)
(3- (2-Bromopropionyl) propyl) triethoxysilane (Cas number: 1233513-06-8)

[Method for producing organic-inorganic composite]
The organic-inorganic composite according to the present embodiment includes, for example, a step of producing surface-modified inorganic oxide particles by reacting inorganic oxide particles and a coupling agent having a polymerization initiating group, and a polymerization initiating group. And a step of forming a polymer bonded to the inorganic oxide particles by living radical polymerization that is started.

  By the reaction between the inorganic oxide particles and the coupling agent, surface-modified inorganic oxide particles in which the coupling agent is introduced onto the surface of the inorganic oxide particles are obtained. The reaction between the inorganic oxide particles and the coupling agent can be performed in a reaction solution in which they are dispersed or dissolved. If necessary, the reaction solution may be heated.

  The halogen content of the surface-modified inorganic oxide particles refers to the total amount of bromine and chlorine contained in the surface-modified inorganic oxide particles. The halogen content is not particularly limited, but is preferably 0.02 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably from the viewpoint of maintaining film formability. It is 0.3-3 mass%, Most preferably, it is 0.5-2.5 mass%.

  Living radical polymerization (hereinafter also referred to as “LRP”) is preferably selected from the viewpoint that the degree of dispersion of the molecular weight of the produced polymer can be reduced. There are NMP, ATRP, and RAFT as LRP. Among these, ATRP is particularly preferable from the viewpoints of the versatility of the polymerization initiator, the variety of applicable monomers, the polymerization temperature, and the like.

  The method of radical polymerization is not particularly limited, and for example, a bulk polymerization method or a solution polymerization method can be selected. Furthermore, from the viewpoint of productivity and safety, methods such as suspension polymerization, emulsion polymerization, dispersion polymerization, and seed polymerization may be employed.

  The polymerization temperature is not particularly limited and can be appropriately selected according to the polymerization method and the monomer type. For example, in the case of ATRP or RAFT, the polymerization temperature is preferably −50 ° C. to 200 ° C., more preferably 0 ° C. to 150 ° C., and particularly preferably 20 ° C. to 130 ° C. When the monomer contains an acrylic ester and / or a methacrylic ester, when the polymerization is performed at 50 to 130 ° C., it can be precisely polymerized in a relatively short time.

  The polymerization reaction may be performed without a solvent or in the presence of a solvent. When using a solvent, a solvent having good dispersibility of the surface-modified inorganic oxide particles and solubility of the polymerization catalyst is preferable. A solvent may be used independently or may be used in combination of multiple types.

  Although the usage-amount of a solvent is not specifically limited, For example, 0-2000 mass parts is preferable with respect to 100 mass parts of monomers, More preferably, it is 0-1000 mass parts. If the amount of the solvent is small, the reaction rate tends to be large, which is advantageous, but depending on the monomer species and the polymerization conditions, the viscosity of the polymerization solution tends to increase. Further, when the amount of the solvent is large, the viscosity of the polymerization solution is lowered, but the reaction rate is lowered. Therefore, it is preferable to appropriately adjust the blending ratio.

The polymerization reaction may be performed without a catalyst or using a catalyst, but it is preferable to use a catalyst from the viewpoint of productivity. The type of the catalyst is not particularly limited, but any catalyst may be appropriately used depending on the polymerization method, the monomer type, and the like. For example, in the case of ATRP, the type of catalyst may be appropriately selected from various commonly known types according to the polymerization method and the like. Specifically, for example, a metal catalyst containing Cu (0), Cu ⁺ , Cu ²⁺ , Fe ⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ or Ru ³⁺ can be used. Among these, in order to achieve a high degree of control of molecular weight and molecular weight distribution, a monovalent copper compound containing Cu ⁺ and zero-valent copper are particularly preferable. Specific examples thereof include Cu (0), CuCl, CuBr, Cu ₂ O and the like. And these copper compounds may be used in combination a small amount of divalent copper compound _(CuBr 2, CuCl _2, etc.). These may be used alone or in combination. Moreover, the usage-amount of a catalyst is 0.01-100 mol normally with respect to 1 mol of polymerization start groups, Preferably it is 0.01-50 mol, More preferably, it is 0.01-10 mol.

  The metal catalyst is usually used in combination with an organic ligand. Examples of the coordination atom to the metal include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom. Of these, a nitrogen atom and a phosphorus atom are preferable. Specific examples of the organic ligand include 2,2′-bipyridine and derivatives thereof, 1,10-phenanthroline and derivatives thereof, tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine ( Hereinafter, “PMDETA”), tris (dimethylaminoethyl) amine (hereinafter also referred to as “Me6TREN”), tris (2-pyridylmethyl) amine, triphenylphosphine, tributylphosphine, and the like can be given. When polymerizing acrylic acid esters and methacrylic acid esters, PMDETA, Me6TREN, 2,2′-bipyridine and one of its derivatives, 4,4′-di (5-nonyl) -2,2 ′ -Dipyridine (hereinafter also referred to as “dNbpy”) is preferable. Specific examples of the organic ligand are shown in the following chemical formula.

  The metal catalyst and the organic ligand may be added separately and mixed in the polymerization system, or may be mixed in advance and then added to the polymerization system. In particular, when using a copper compound, the former method is preferable.

  In the polymerization reaction, additives can be used as necessary in addition to the above. The type of additive is not particularly limited, and examples thereof include a dispersant / stabilizer and an emulsifier (surfactant).

  The dispersant / stabilizer is not particularly limited as long as it has the function, but polyhydroxystyrene, polystyrene sulfonic acid, vinylphenol- (meth) acrylic acid ester copolymer, styrene- (meth). Polystyrene derivatives such as acrylic acid ester copolymer, styrene-vinylphenol- (meth) acrylic acid ester copolymer; poly (meth) acrylic acid, poly (meth) acrylamide, polyacrylonitrile, potyethyl (meth) acrylate, polybutyl ( Poly (meth) acrylic acid derivatives such as (meth) acrylate; polyvinyl alkyl ether derivatives such as polymethyl vinyl ether, polyethyl vinyl ether, polybutyl vinyl ether, polyisobutyl vinyl ether; cellulose, methyl cellulose, cellulose acetate Cellulose derivatives such as cellulose nitrate, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose; polyvinyl acetate derivatives such as polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyvinyl acetate; polyvinyl pyridine, polyvinyl pyrrolidone, polyethyleneimine, poly Nitrogen-containing polymer derivatives such as 2-methyl-2-oxazoline; polyvinyl halide derivatives such as polyvinyl chloride and polyvinylidene chloride; various hydrophobic or hydrophilic dispersants such as polysiloxane derivatives such as polydimethylsiloxane, Stabilizers can be mentioned. These may be used alone or in combination.

  The emulsifier (surfactant) is not particularly limited as long as it has the function, but alkyl sulfate salts such as sodium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, and alkyl naphthalene. Anionic emulsifiers such as sulfonates, fatty acid salts, alkyl phosphates, alkylsulfosuccinates; Cationic emulsifiers such as alkylamine salts, quaternary ammonium salts, alkylbetaines, amine oxides; polyoxyethylene alkyl ethers, poly Nonionic series such as oxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester Agents and the like. These may be used alone or in combination.

[Coating material]
The coating material of the present embodiment is a material that includes the above-described organic-inorganic composite and is used to form a coating film. The form of the coating material may be liquid or solid. Solvent, additive, plasticizer, oil, emulsifier (surfactant), coupling agent, acid, alkali, monomer, oligomer, polymer, pigment, dye, fragrance, pigment Substances other than organic-inorganic composites such as may be included.

  As will be described later, the coating method is not particularly limited, but it is desirable to employ a wet coating method because it can be coated over a large area and the equipment cost can be reduced. For this purpose, the coating material is preferably a liquid in which the organic-inorganic composite is dispersed in a solvent.

  The solvent used here is not particularly limited, but a general-purpose organic solvent is preferable because the above-described organic-inorganic composite has good dispersibility and relatively high safety. These solvents may be used alone or in combination. From the viewpoint of film formability and safety, the evaporation rate of the organic solvent is preferably 20 to 600, more preferably 50 to 200, when butyl acetate is 100. From the same viewpoint, the boiling point of the organic solvent is preferably 75 to 200 ° C, more preferably 90 to 180 ° C.

  Specific examples of the organic solvent include ketones such as acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), diisopropyl ketone, cyclohexanone, and isophorone, and alcohols such as methanol, ethanol, butanol, 1-propanol, and 2-propanol. , Compounds containing benzene rings such as toluene, xylene, ethylbenzene, anisole, acetates such as ethyl acetate and butyl acetate, 2-methoxy-1-methylethyl acetate (PGMEA), methyl cellosolve, cellosolve, butyl cellosolve, propylene glycol mono Ethyl ether, methylmethoxybutanol, ethylene glycol, tetrahydrofuran (THF), cyclohexane, cyclohexanone, hexane, acetonitrile, 1,4-dioxane, di Chill acetamide, N, N-dimethylformamide and the like.

  Although the solid content concentration in the coating material is not particularly limited, it is preferably 1 to 70% by mass, more preferably 5 to 50% by mass based on the total mass of the coating material from the balance of dispersibility and film formability. %, Particularly preferably 10 to 20% by mass. The solid concentration may be adjusted by directly diluting the organic-inorganic composite as it is, or may be prepared by concentrating a dilute solution with an evaporator or the like.

[Coating film]
The coating film of the present embodiment is not particularly limited as long as it is a film obtained by coating the above-described coating material by a method described later. Generally, a substrate (for example, a PET film, a TAC film) is used. , Glass, metal, silicon wafer, LED, semiconductor, CD, DVD, etc.) refers to a film formed with a thickness of several nanometers to several centimeters.

  Coating methods include “dry coating methods such as vapor deposition, sputtering, ion plating” and “printing, slit coating, bar coating, wire coating, applicator coating, spin coating, blade coating, air knife coating, gravure coating, Generally known are "wet coating methods such as roll coating, spray coating, and dip coating". In addition to the methods described above, a coating film can be formed on the substrate by applying "molding methods such as film molding, laminate molding, injection molding, blow molding, compression molding, rotational molding, extrusion molding, stretch molding, etc." There is also a technique to form. These techniques can be used alone or in combination.

  The coating film according to the present embodiment has excellent transparency and optical characteristics, and the total light transmittance, which is an index thereof, is not particularly limited, but preferably 86 to 100%, More preferably, it is 88-100%, More preferably, it is 90-100%. Similarly, the haze value is not particularly limited, but is preferably 0 to 5%, more preferably 0 to 3%, and still more preferably 0 to 2%.

  The refractive index of the coating film or molded body according to the present embodiment needs to be less than 1.46 from the viewpoint of preventing reflection. When a higher antireflection effect is expected, the refractive index is preferably 1.05 to 1.43, more preferably 1.05 to 1.4, and still more preferably 1.05 to 1.35. When the refractive index is 1.46 or more, the antireflection effect decreases.

  Moreover, since it is easy to achieve a desired refractive index, it is useful as an optical material or an optical member. Typical examples include an antireflection film and a hard coat film.

  Although the hardness of the coating film which concerns on this Embodiment is not specifically limited, The pencil hardness becomes like this. Preferably it is HB or more, More preferably, it is F or more.

  The water contact angle of the coating film according to the present embodiment is an index of water repellency, and the value is not particularly limited, but is preferably 75 ° or more, more preferably 80 ° or more, and still more preferably 90. More than °. This is because, when the contact angle is 75 ° or more, an adhesion suppressing effect and good wiping properties are expressed with respect to aqueous stains. This function is particularly useful when the coating film is the outermost layer.

  The oil contact angle of the coating film according to the present embodiment is an index of water repellency, and the value is not particularly limited, but is preferably 30 ° or more, more preferably 45 ° or more, and still more preferably 60. More than °. This is because when the contact angle is 30 ° or more, an adhesion suppressing effect is exhibited against oily dirt. In particular, when the contact angle is 60 ° or more, the oil-based magic ink is repelled, so that characters cannot be normally written on the film, and the traces can be easily wiped off. This function is particularly useful when the coating film is the outermost layer.

[Porosity of coating film]
The coating film of this Embodiment contains the organic-inorganic composite of this invention, and may have a space | gap.

  The term “void” in the coating film of the present invention means a microvoid formed between two or more adjacent organic-inorganic composites forming the coating film. The term “particle void” means pores formed inside the inorganic oxide particles themselves, and is distinguished from “void”.

  The size of the void is not particularly limited, but is preferably a size that does not scatter light, and specifically, for example, preferably 1 to 200 nm, more preferably 2 to 100 nm, still more preferably. 5 to 70 nm. That is, even a film having voids can be regarded as an optically or macroscopically uniform film. For this reason, the ratio of the voids based on the apparent volume of the coating film microporous film, that is, the porosity is determined by the refractive index (> 1) of the organic-inorganic composite material forming the microporous film and the refractive index of the void ( It can be calculated based on the volume average with the refractive index of air: 1.00).

  The proportion of voids formed between the organic-inorganic composite (porosity) is preferably 2 to 60% by volume based on the volume of the coating film. If the porosity is less than 2% by volume, the effect of lowering the refractive index of the film tends to be reduced. Moreover, when the porosity exceeds 60 volume%, there exists a tendency for the intensity | strength of a film | membrane to fall.

[Molded body]
The molded body of the present embodiment is obtained by molding the above-described organic-inorganic composite into a predetermined shape. The molding method is not particularly limited, but usually, the organic-inorganic composite is given a stimulus such as temperature, pressure, light (visible light, ultraviolet ray, infrared ray, near infrared ray, etc.), electron beam, plasma, shock wave, etc. It is common to shape into a shape. For example, general polymer material molding methods such as injection molding, extrusion molding, compression molding, cast molding, and spin coating can be employed. Moreover, the shape is not limited at all, and can take various forms such as a block shape, a pellet shape, a plate shape, and a film shape. During molding, solvents, additives, plasticizers, fats and oils, emulsifiers (surfactants), coupling agents, acids, alkalis, monomers, oligomers, polymers, pigments, dyes, fragrances, pigments, explosives / explosives, fertilizers, pharmaceuticals Add a pharmaceutical additive, quasi-drug, food, food additive, seasoning, inorganic particles, curing agent, curing accelerator, acid generator, cation generator, etc. to prepare a molding composition. Molding is not limited at all.

The particle dispersion degree of the molded body according to the present embodiment is a value reflecting the dispersion state of the inorganic oxide particles in the molded body. The degree of particle dispersion is not particularly limited, but is desirably 0.6 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less, from the viewpoint of the transparency of the molded body. The particle dispersity is calculated by the following equation based on the measurement result obtained by observing the compact using a scanning transmission electron microscope or the like, measuring the distance between the centers of gravity of adjacent particles in the observed image.
Particle dispersity = (Average deviation of the distance between the center of gravity between adjacent inorganic oxide particles) / (Distance between the center of gravity between adjacent inorganic oxide particles)

  The molded body according to the present embodiment has excellent transparency and is easy to achieve a desired refractive index, and thus is useful as an optical member. Examples of the optical member include a lens, an optical waveguide, an optical disc, an antireflection film, and a conductive film.

[Porosity of molded body]
The molded body of the present embodiment may contain the organic-inorganic composite and have voids.

  The term “void” in the molded article of the present invention means a microvoid formed between two or more adjacent organic-inorganic composite particles forming the molded article. The term “particle void” means pores formed inside the inorganic oxide particles themselves, and is distinguished from “void”.

  The ratio of the voids formed between the organic-inorganic composite (porosity) is preferably 2 to 60% by volume on the basis of the volume of the molded body for the same reason as the porosity of the coating film described above.

[Optical materials]
The optical material according to the present embodiment contains the above-described organic-inorganic composite and is used to form an optical member. The optical material can be suitably used as, for example, an antireflection film, a coating material, or a hard coating agent.

  The coating film, molded article, optical member, and optical material according to the present embodiment are various organic resins, colorants, leveling agents, lubricants, surfactants, silicone compounds, within the scope of the present invention, It may contain a reactive diluent, a non-reactive diluent, an antioxidant, a light stabilizer and the like. Also commonly used as additives for plastics (plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, foaming agents, antibacterial / antifungal agents, fillers, antifogging agents, crosslinking agents, etc.) Substances can be blended. Other substances may be included. Other substances include solvents, fats and oils, processed oils, natural resins, synthetic resins, pigments, dyes, dyes, release agents, preservatives, adhesives, deodorizers, flocculants, cleaning agents, deodorizers, and pH adjusters. , Photosensitive material, ink, electrode, plating solution, catalyst, resin modifier, plasticizer, softener, agrochemical, insecticide, fungicide, pharmaceutical raw material, emulsifier / surfactant, rust inhibitor, metal compound, filler, Cosmetics / pharmaceutical raw materials, dehydrating agent, desiccant, antifreeze, adsorbent, colorant, rubber, foaming agent, colorant, abrasive, mold release agent, flocculant, antifoaming agent, curing agent, reducing agent, flux agent, Film treatment agent, casting raw material, mineral, acid / alkali, shot agent, antioxidant, surface coating agent, additive, oxidant, explosives, fuel, bleach, light emitting element, fragrance, concrete, fiber (carbon fiber, Aramid fiber, glass fiber, etc.), glass, metal, excipient Disintegrants, binders, fluidizing agents, gelling agents, stabilizers, preservatives, buffering agents, suspending agents, thickeners, and the like.

  The organic resin is not particularly limited, and examples thereof include an epoxy resin, an acrylic resin, a polyester resin, and a polyimide resin.

  The colorant is not particularly limited as long as it is a substance used for the purpose of coloring. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine-based various organic systems Examples thereof include inorganic pigments such as pigments, titanium oxide, lead sulfate, chromium yellow, zinc yellow, chromium vermilion, valve shells, cobalt purple, bitumen, ultramarine, carbon black, chromium green, chromium oxide, cobalt green and the like. These colorants may be used alone or in combination.

  The leveling agent is not particularly limited. For example, oligomers having a molecular weight of 4,000 to 12,000 consisting of acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, Examples include hydrogenated castor oil and titanium-based coupling agents. These leveling agents may be used alone or in combination.

  The lubricant is not particularly limited, and hydrocarbon lubricants such as paraffin wax, micro wax, polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, stearylamide, Higher fatty acid amide lubricants such as palmitylamide, oleylamide, methylene bisstearamide, ethylene bisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri- , Or higher fatty acid ester lubricants such as tetra-stearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, arachi Metal soaps that are metal salts such as magnesium, calcium, cadmium, barium, zinc, lead such as acid, behenic acid, ricinoleic acid, naphthenic acid, and natural waxes such as carnauba wax, candelilla wax, beeswax, and montan wax . These lubricants may be used alone or in combination.

  The surfactant refers to an amphiphilic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent. Moreover, the kind is not specifically limited, For example, a silicone type surfactant, a fluorine type surfactant, etc. are mentioned. Surfactants may be used alone or in combination.

  The silicone-based compound is not particularly limited, and examples thereof include a silicone resin, a silicone condensate, a silicone partial condensate, a silicone oil, a silane coupling agent, a silicone oil, a polysiloxane, and the like. Those modified by introducing an organic group into the side chain are also included. The modification method is not particularly limited. For example, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification, carboxyl modification, phenol modification, silanol modification, polyether modification. , Polyether / methoxy modification, diol modification and the like.

  The reactive diluent is not particularly limited. For example, alkyl glycidyl ether, monoglycidyl ether of alkylphenol, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, alkanoic acid glycidyl ester, ethylene glycol diglycidyl ether , Propylene glycol diglycidyl ether and the like, and the non-reactive diluent is not particularly limited, and examples thereof include high-boiling solvents such as benzyl alcohol, butyl diglycol and propylene glycol monomethyl ether.

  Antioxidant is not particularly limited, for example, organic phosphorus antioxidants such as triphenyl phosphate, phenylisodecyl phosphite, organic sulfur antioxidants such as distearyl-3,3′-thiodipropinate, And phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol.

  The light stabilizer is not particularly limited, and examples thereof include ultraviolet absorbers such as benzotriazole, benzophenone, salicylate, cyanoacrylate, nickel, and triazine, hindered amine light stabilizers, and the like.

  Applications of the organic-inorganic composite and the molded body according to the present embodiment are not limited to optical applications. For example, electronic materials (such as insulators, AC transformers, switchgears and circuit units, package of various parts, IC / LED / semiconductor sealing materials, generators, motors and other rotating machine coils, windings, etc. Impregnation, printed wiring board, insulation board, medium-sized insulators, coils, connectors, terminals, various cases, electrical components, etc.), paint (corrosion-proof paint, maintenance, ship paint, corrosion-resistant lining, primer for automobiles and home appliances, Beverages and beer cans, outer surface lacquer, extrusion tube coating, general anticorrosion coating, maintenance equipment, lacquer for woodwork products, automotive electrodeposition primer, other industrial electrodeposition coating, beverage and beer can inner surface lacquer, coil coating, drum Can inner surface coating, acid-resistant lining, wire enamel, insulating coating, automotive primer, various metal products for beautiful and anticorrosive coating , Pipe interior / exterior coating, electrical component insulation coating, etc.), composite materials (pipes and tanks for chemical plants, aircraft materials, automobile parts, various sports equipment, carbon fiber composite materials, aramid fiber composite materials, etc.), civil engineering and building materials ( Floor materials, paving materials, membranes, anti-slip and thin-layer paving, concrete jointing / raising, anchor embedding adhesion, precast concrete bonding, tile bonding, crack repair of concrete structures, pedestal grout leveling, water supply and sewerage facilities Corrosion-resistant and waterproof coating, corrosion-resistant laminated lining of tanks, corrosion-resistant coating of iron structures, mastic coating of exterior walls of buildings, etc.), adhesive (metal, glass, ceramics, cement concrete, wood, plastic, etc.) Adhesives, adhesives for assembling automobiles, railway vehicles, aircraft, etc., manufacturing prefabricated composite panels Adhesives, etc .: Including one-component, two-component, and sheet types), aircraft / automobile / plastic molding jigs (resin molds such as press molds, stretched dies, matched dies, vacuum molding / blow molding molds, master models , Casting patterns, laminated jigs, jigs for various inspections, etc.), modifiers / stabilizers (fiber resin processing, stabilizers for polyvinyl chloride, additives to synthetic rubber, etc.).

  The organic-inorganic composite, the coating material, the coating film, and the molded body according to the present embodiment are a substrate material, a die bond material, a chip coating material, a laminated plate, an optical fiber, an optical waveguide, an optical filter, an adhesive for electronic components, It can also be used for applications such as coating materials, sealing materials, insulation materials, photoresists, encap materials, potting materials, optical transmission layers and interlayer insulation layers, printed wiring boards, laminates, light guide plates, and antireflection films. is there.

  Examples of the present embodiment will be described below more specifically. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

  Evaluation of physical properties in Examples and Comparative Examples was performed according to the following procedure.

<Observation of shape of inorganic oxide particles>
(1) 0.1 g of organic-inorganic composite and 9.9 g of chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) were weighed in a sample bottle, and a rotor was put therein. The contents were stirred with a stirrer for 30 minutes and then subjected to ultrasonic treatment for 30 minutes to obtain a sample solution.
(2) The sample solution was dropped on a grid (“STEM100Cu grid” manufactured by Oken Shoji Co., Ltd.) and air-dried to form an organic-inorganic composite film.
(3) The organic-inorganic composite on the grid was observed in a transmission mode of a high-resolution scanning transmission electron microscope (hereinafter also referred to as “HR-STEM”) (manufactured by Hitachi, Ltd., “HD-2300A”). , Took a picture. However, an arbitrary measurement magnification was selected according to the size and shape of the inorganic oxide particles.
(4) The photographed HR-STEM image was processed with image analysis software (“A Image-kun” manufactured by Asahi Kasei Engineering Co., Ltd.), and the shape of 200 inorganic oxide particles was observed.

<Particle porosity>
In the above shape observation, when voids were observed in the inorganic oxide particles, the particle porosity was calculated according to the following formula.
Particle porosity (%) = (volume of void portion in inorganic oxide particle) / (volume of entire inorganic oxide particle) × 100

<Circularity of inorganic oxide particles>
(1) 0.1 g of organic-inorganic composite and 9.9 g of chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) were weighed in a sample bottle, and a rotor was put therein. The contents were stirred with a stirrer for 30 minutes and then subjected to ultrasonic treatment for 30 minutes to obtain a sample solution.
(2) The sample solution was dropped on a grid (“STEM100Cu grid” manufactured by Oken Shoji Co., Ltd.) and air-dried to form an organic-inorganic composite film.
(3) The organic-inorganic composite on the grid was observed in HR-STEM transmission mode and photographed. However, an arbitrary measurement magnification was selected according to the size and shape of the inorganic oxide particles.
(4) The photographed HR-STEM image was processed by the image analysis software, and the “equivalent circle diameter” and “peripheral length” of the inorganic oxide particles (particle outer diameter) were calculated. Based on the calculated equivalent circle diameter and circumference, the circularity of each of the 200 inorganic oxide particles was determined according to the following formula. The case where the circularity was 0.5 or more was determined as “A”, and the case where the circularity was less than 0.5 was determined as “B”.
Circularity = (circumference length obtained from equivalent circle diameter) / (peripheral length) (10)
Here, (circumferential length obtained from equivalent circle diameter) = (equivalent circle diameter) × π.
(5) Of the circularity of 200 inorganic oxide particles, numerical values of the upper 5% and lower 5% are removed, and the average value of the remaining 90% is obtained, and the value is defined as the circularity of the inorganic oxide particles. .

<L / D of inorganic oxide particles>
(1) 0.1 g of organic-inorganic composite and 9.9 g of chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) were weighed in a sample bottle, and a rotor was put therein. The contents were stirred with a stirrer for 30 minutes and then subjected to ultrasonic treatment for 30 minutes to obtain a sample solution.
(2) The sample solution was dropped on a grid (“STEM100Cu grid” manufactured by Oken Shoji Co., Ltd.) and air-dried to form an organic-inorganic composite film.
(3) The organic-inorganic composite on the grid was observed in HR-STEM transmission mode and photographed. However, an arbitrary measurement magnification was selected according to the size and shape of the inorganic oxide particles.
(4) The HR-STEM image was processed by the image analysis software, and the “maximum length” and “minimum width” of the outer diameter of each of the 200 inorganic oxide particles were calculated. FIG. 1 is a schematic diagram showing a method for calculating the maximum length and the minimum width of each inorganic oxide particle. As shown in FIG. 1, “maximum length” refers to the maximum value of the distance between any two points on the circumference of the inorganic oxide particles in the HR-STEM image, and “minimum width” refers to inorganic oxidation. It refers to the width of the inorganic oxide particles in a direction perpendicular to the direction in which the product particles exhibit the maximum length. Here, when branching was confirmed in the inorganic oxide particles, as shown in FIG. 1, the branch portion was not used in the calculation, and only the trunk portion was used in the calculation.
(5) The obtained maximum length L and minimum width D were substituted into the following formula, and L / D of each of 200 inorganic oxide particles was obtained.
L / D = (maximum length) / (minimum width) (11)
(6) Of the L / D of 200 inorganic oxide particles, the numerical values of the upper 5% and lower 5% are removed, the average value of the remaining 90% is obtained, and the value is calculated as the L / D of the inorganic oxide particles. It was.

<Refractive index of inorganic oxide particles>
The refractive index of the inorganic oxide particles was determined by the following method using a standard refractive liquid (manufactured by Cargill). However, when a standard refractive liquid having a desired refractive index was not available, a reagent with a known refractive index was substituted.
(1) The dispersion liquid of inorganic oxide particles was taken in an evaporator and the dispersion medium was evaporated.
(2) This was dried with a vacuum dryer at 120 ° C. to obtain powder.
(3) Two to three drops of a standard refractive liquid with a known refractive index was dropped on the glass plate, and the above powder was mixed therewith.
(4) The operation of (3) above was performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid became transparent was taken as the refractive index of the inorganic oxide particles.

<Measurement of halogen content of surface-modified inorganic oxide particles>
The halogen content of the surface-modified inorganic oxide particles was determined by the following procedure by combustion treatment and subsequent ion chromatography.
(1) The sample was burned in an oxygen stream using a quartz combustion tube, and the generated gas was absorbed in an absorbing solution (3% hydrogen peroxide solution).
(2) The absorbing solution was appropriately diluted, and the amount of bromine ion and chlorine ion in the absorbing solution was measured with an ion chromatograph (manufactured by Daionex, "ICS-2000").
(3) From the measured total amount of bromine ion and chlorine ion, the total amount of bromine ion and chlorine ion with respect to the mass of the surface-modified inorganic oxide was determined as the halogen content.

<Specific gravity of polymer>
Measured according to ASTM D792.

<Polymer molecular weight and molecular weight dispersion>
The molecular weight of the polymer and the degree of dispersion of the molecular weight were determined by “decomposition method” or “addition method”. When the organic-inorganic composite was easily dispersed in toluene, measurement was performed by the “decomposition method”, and when it was poorly soluble, measurement was performed by the “addition method”.

[Decomposition method]
(Preprocessing)
As a pretreatment for measuring the molecular weight of the polymer bonded to the inorganic oxide particles, the hydrofluoric acid treatment (hereinafter also referred to as “HF treatment”) was performed on the organic-inorganic composite according to the following procedure. .
(1) 2 mL of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 mg of phase transfer catalyst (in a Teflon (registered trademark) or a resin container containing a Teflon (registered trademark) rotor Aldrich “Alquat 336”) was added and stirred to obtain a solution in which the phase transfer catalyst was dissolved in toluene.
(2) A 200 mg sample of an organic-inorganic composite was added to the solution and dissolved by stirring.
(3) Further, 2 mL of hydrofluoric acid (manufactured by Wako Pure Chemical Industries, Ltd., concentration: 46 to 48%) is added to the obtained solution, and the mixture is stirred at room temperature for 24 hours. Separated.
(4) The above solution was neutralized with an aqueous solution of calcium carbonate (Wako Pure Chemical Industries, Ltd.). At this time, if the phase separation is poor, a solution obtained by further adding 2 mL of toluene and centrifuging may be used.

(Molecular weight measurement)
About the sample solution obtained by the said pre-processing, the measurement of the gel permeation chromatography (GPC) was performed on condition of the following. From the measurement results, the number average molecular weight (Mn) and the mass average molecular weight (Mw) in terms of polymethyl methacrylate of the main peak are based on a calibration curve created using polymethyl methacrylate standard (manufactured by Sowa Kagaku Co., Ltd.). Asked.
・ Equipment: “HLC-8220GPC” manufactured by Tosoh Corporation
-Detector: RI detector-Mobile phase: Tetrahydrofuran-Flow rate: 0.35 mL / min-Column: Two "TSKgel GMHXL" manufactured by Tosoh Corporation were connected.
-Column temperature: 40 ° C

(Dispersion of molecular weight)
The number average molecular weight (Mn) and mass average molecular weight (Mw) in terms of polymethyl methacrylate were substituted into the following formula to determine the degree of dispersion of the molecular weight of the polymer. The case where the molecular weight dispersity was 1.9 or less was determined as “A”, and the case where the molecular weight dispersity exceeded 1.9 was determined as “B”.
Dispersion degree of molecular weight = Mw / Mn (12)

[Addition method]
Pretreatment was performed by the following method, and “molecular weight measurement” and “molecular weight dispersity” were obtained by the same method as the above-mentioned “decomposition method”.
(Preprocessing)
The “molecular weight” and “molecular weight dispersity” of the polymer bonded to the inorganic oxide particles were determined according to the following procedure. Separately from the examples, the organic-inorganic composite was synthesized with the polymerization initiator added as a sample for measuring the molecular weight, and the polymer by-produced by the addition of the polymerization initiator was measured. The “molecular weight” and “dispersity of molecular weight” of the bound polymer were considered.
(1) Synthesis of Sample for Measuring Molecular Weight (1-1) The raw materials for the organic-inorganic composite were blended in the same manner as in the examples.
(1-2) A polymerization initiator was added to the above solution so as to be monomer: polymerization initiator = 100: (0.01 to 0.25) (mol ratio). The polymerization initiator was blended so as to have a bromine content of about 10 to 20% with respect to the bromine content in the polymerization liquid of the examples.
Polymerization initiator: ethyl 2-bromoisobutyrate (EBIB): manufactured by Aldrich (1-3) A catalyst solution was added to the above solution, and a measurement sample (organic-inorganic composite and secondary electrolyte was added in the same manner as in the examples) Polymer mixture) was polymerized.
(1-4) The flask was immersed in an ice bath and quickly cooled, then poured into hexane, stirred and allowed to stand. Thereafter, the supernatant was discarded.
(1-5) Hexane was added again to the remaining precipitate and allowed to stand, and the supernatant was discarded. This operation was further repeated 8 times, and the remaining precipitate was dried in the same manner as in the example.
(2) To 1 g of the molecular weight measurement sample obtained in (1) above, 10 mL of a solvent (for example, MIBK) was added and stirred for 24 hours.
(3) A suitable amount of THF was added to the above solution, and the solution stirred for 1 hour was centrifuged.
(4) The supernatant liquid after centrifugation was measured by the same method as the “decomposition method” described above, and “molecular weight” and “dispersion degree of molecular weight” were determined.

<Amount of “polymer bonded to inorganic oxide particles” of organic-inorganic composite>
(1) 10 g of an organic-inorganic composite was weighed into a sample bottle, MIBK was added to make 100 mL, a rotor was added, and the contents were stirred with a stirrer for 24 hours.
(2) In a separate sample bottle, 10 mL of the above solution was weighed, THF was added to dilute to 100 mL, a rotor was added, and the contents were further stirred with a stirrer for 24 hours.
(3) The above solution was transferred to a centrifuge tube and treated with a centrifuge at 6600 rpm for 30 minutes.
(4) About the supernatant liquid after centrifugation, the gel permeation chromatography (GPC) was measured on condition of the following, and the free polymer in an organic-inorganic composite was measured. From the measurement results, the peak top molecular weight (Mp) in terms of polymethyl methacrylate of the main peak was determined based on a calibration curve created using polymethyl methacrylate standard (manufactured by Soka Kagaku Co., Ltd.).
・ Equipment: “HLC-8220GPC” manufactured by Tosoh Corporation
-Detector: RI detector-Mobile phase: Tetrahydrofuran-Flow rate: 0.35 mL / min-Column: Two "TSKgel GMHXL" manufactured by Tosoh Corporation were connected.
-Column temperature: 40 ° C
(5) The peak of Mp> 800 obtained above was quantified as a free polymer. When quantifying, select the “quantitative standard substance” with the closest Mp from the following, create a calibration curve, and calculate the amount (% by mass) of the free polymer in the organic-inorganic complex in terms of the quantitative standard substance. did. Moreover, when there were a plurality of peaks, the total amount thereof was determined and used as the amount (% by mass) of the free polymer.
(5-1) Quantitative reference material: polymethyl methacrylate (manufactured by Soka Kagaku Co., Ltd.)
・ Polymethyl methacrylate "PMMA850 (Mp = 860)"
・ Polymethyl methacrylate "PMMA2K (Mp = 2,000)"
・ Polymethyl methacrylate "PMMA7K (Mp = 7,500)"
・ Polymethyl methacrylate "PMMA11K (Mp = 11,800)"
・ Polymethyl methacrylate "PMMA21K (Mp = 20,850)"
・ Polymethyl methacrylate "PMMA30K (Mp = 33,500)"
・ Polymethyl methacrylate "PMMA45K (Mp = 46,300)"
・ Polymethyl methacrylate "PMMA85K (Mp = 87,800)"
・ Polymethyl methacrylate "PMMA110K (Mp = 107,000)"
・ Polymethyl methacrylate "PMMA135K (Mp = 130,000)"
・ Polymethyl methacrylate "PMMA135K (Mp = 130,000)"
・ Polymethyl methacrylate "PMMA190K (Mp = 185,000)"
・ Polymethyl methacrylate "PMMA225K (Mp = 240,000)"
・ Polymethyl methacrylate "PMMA320K (Mp = 322,000)"
・ Polymethyl methacrylate "PMMA680K (Mp = 670,000)"
(6) Measurement of amount of polymer in organic-inorganic composite (amount of polymer and free polymer bonded to inorganic oxide) When the organic-inorganic composite was heated under the following conditions by a thermogravimetric apparatus The weight loss (mass%) was measured at n = 3, and the average value was defined as “the amount of polymer in the organic-inorganic composite (polymer and free polymer bonded to inorganic oxide particles)”.
・ Equipment: Shimadzu Corporation, “TGA-50”
・ Atmosphere: Nitrogen stream containing 1% oxygen ・ Sample container: Aluminum pan ・ Temperature program: Start at 25 ° C. → Temperature rise at 20 ° C./min→Reach 500 ° C. → Hold at 500 ° C. for 1 hour From “the amount of free polymer (% by mass)” and “the amount of polymer in the organic-inorganic composite (the amount of polymer and free polymer bonded to inorganic oxide particles) (% by mass)”, “ The amount (% by mass) of the polymer bonded to the inorganic oxide particles was calculated.
Amount of polymer bonded to inorganic oxide particles (mass%) = (A−B) / A × 100 (13)
Here, A: the amount of polymer in the organic-inorganic composite (amount of polymer and free polymer bonded to inorganic oxide particles) (mass%), and B: the amount of free polymer (mass%).

<Measurement of Tg of Organic-Inorganic Composite>
The Tg of the organic-inorganic composite was determined under the following conditions using a differential scanning calorimeter (DSC).
・ Device: “Diamond DSC” manufactured by PerkinElmer
・ Temperature program: Start at -40 ℃ → Hold for 20 minutes → Increase temperature at 20 ℃ / minute → 200 ℃

<Measurement of halogen content of organic-inorganic composite>
The halogen content of the organic-inorganic composite was determined by the same method as described above in “Measurement of halogen content of surface-modified inorganic oxide particles”.

<Measurement of fluorine content of organic-inorganic composite>
The fluorine content was determined by the following procedure by combustion treatment and subsequent ion chromatography.
(1) The sample was burned using a quartz combustion tube under an oxygen stream. At this time, the sample may be used after being dissolved and / or diluted as necessary.
(2) Gas generated by combustion was absorbed in an ice-cooled absorption liquid (0.2% NaOH aqueous solution).
(3) The absorbing solution was appropriately diluted, and the amount of fluorine ions in the absorbing solution was measured with an ion chromatograph (manufactured by Daionex, "ICS-2000"). From the measured amount of fluorine ions, the amount of fluorine ions relative to the mass of the organic-inorganic composite was determined as the fluorine content.

<Measurement of inorganic oxide particle content of organic-inorganic composite>
The mass loss when the organic-inorganic composite was heated under the following conditions was determined by a thermogravimetric apparatus.
・ Equipment: Shimadzu Corporation, “TGA-50”
・ Atmosphere: Nitrogen stream containing 1% oxygen ・ Sample container: Aluminum pan ・ Temperature program: Start at 25 ° C. → Temperature rises at 20 ° C./min→Area reaches 500 ° C. → Holds at 500 ° C. for 1 hour. The average value thereof was defined as the content of inorganic oxide particles in the organic-inorganic composite. The mass% and volume% values were calculated as follows.
(1) Mass%
The measured weight loss (mass%) was substituted into the following formula to calculate the content (mass%) of inorganic oxide particles.
Inorganic oxide particle content (mass%) = 100-mass loss (mass%)
(2) Volume%
(2-1) Calculation of polymer mass and volume The measured mass loss (mg) was regarded as the polymer mass (mg), and the value was substituted into the following formula to calculate the polymer volume (μL). .
Polymer volume (μL) = {mass of polymer (mg)} / {specific gravity of polymer}
(2-2) Calculation of mass and volume of inorganic oxide particles The measured mass loss (mg) was substituted into the following formula to calculate the mass (mg) of the inorganic oxide particles.
Mass of inorganic oxide particles (mg) = sample amount (mg) −mass loss (mg)
By substituting the mass of the inorganic oxide particles into the following formula, the volume (μL) of the inorganic oxide particles was calculated.
Volume of inorganic oxide particles (μL) = {mass of inorganic oxide particles (mg)} / {density of inorganic oxide particles (g / cm ³ )}
(2-3) Calculation of inorganic oxide particle content (% by volume) The value obtained as described above was substituted into the following formula to calculate the inorganic oxide particle content (% by volume).

<Production of coating material>
An arbitrary solvent was added to the organic-inorganic composite, the mixture was stirred at room temperature for 24 hours, and subjected to ultrasonic treatment for 1 hour to prepare a solvent dispersion of the organic-inorganic composite, which was used as a coating material. In addition, the ultrasonication and the concentration process by an evaporator were added as needed.

<Solid content concentration of coating material>
The solid content concentration of the coating material was determined by the following procedure.
(1) The coating material was weighed in a weighing bottle, and the content mass (mass A) was recorded.
(2) The weighing bottle was air-dried under a nitrogen stream until the fluidity of the contents disappeared.
(3) The weighing bottle was dried at 105 ° C. under vacuum for 24 hours, and then cooled to room temperature in a desiccator.
(4) The weight of the weighing bottle was measured and the mass (mass B) of the contents was recorded.
(5) Solid content was calculated | required with the following formula | equation.
Solid content (mass%) = (mass B) / (mass A) × 100

<Preparation of coating film>
A coating film was prepared by the following procedure.
(1) An appropriate amount of the above-mentioned coating material is weighed.
(2) The coating material of (1) was placed on a PET film or a TAC film, and quickly coated with a bar coater. However, the bar coater was appropriately selected so that the coating film thickness after drying was about 3 μm.
PET film: “Cosmo Shine 4100” manufactured by Toyobo Co., Ltd. (thickness 100 μm, total light transmittance 90%, haze 0.9%)
TAC film: manufactured by Fuji Film Co., Ltd. (thickness 80 μm, total light transmittance 93%, haze 0.7%)
(3) After air drying for 1 hour, what was dried for 1 hour with an explosion-proof blower dryer at 100 ° C. was used as a coating film.

<Appearance of coating film and molded body>
The above-mentioned coating film and the molded body described later are visually observed, and a case where the aggregation of particles is not substantially observed is determined as pass ("A"), and a case where the aggregation of particles is observed is rejected (" B ").

<Refractive index measurement>
Using a refractive index measuring device, the refractive index of the coating film and the molded body described later were measured under the following conditions.
-Equipment: "METEL 2010 PRISM COUPLER" manufactured by Metricon
・ Mode: coating film is measured in single film mode, molded body is measured in bulk mode ・ Measurement wavelength: 633 nm

<Measurement of total light transmittance and haze>
Using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., “NDH 5000W”), the total light transmittance and haze of the coating film were measured according to “JIS K7105: Plastic Optical Properties Test Method”.

<Measurement of pencil hardness>
Using an electric pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusyo Co., Ltd.) and with a load of 500 g, “JIS K5600-5-4: Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 4: According to the “scratch hardness (pencil method)”, the pencil hardness of the coating film or molded product was measured.

<Measurement of contact angle>
Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle (contact angle with respect to water) and the oil contact angle (contact angle with respect to n-hexadecane) of the coating film were measured by the droplet method.

<Porosity of coating film>
The porosity of the low refractive index layer was calculated from the following calculated refractive index and the actually measured refractive index.
[Calculation of calculated refractive index]
The Maxwell-Garnett equation was used to obtain the calculated refractive index of the obtained organic-inorganic composite. The refractive index of the polymer was determined by synthesizing a polymer having the same composition as the polymer in the organic-inorganic composite and measuring the refractive index. As the refractive index of the inorganic oxide particles, the value of the refractive index measured by the method described in the section “Refractive index of inorganic oxide particles” is used, and the volume fraction of the inorganic oxide particles is expressed as “organic-inorganic composite”. A value obtained by dividing the inorganic oxide particle content (% by volume) measured by the method described in the section “Measurement of inorganic oxide particle content of body” by 100 was used.
[Maxwell-Garnett equation]
(N _a ²⁻ n _m ² ) / (n _a ² + 2n _m ² ) = q (n _p ² −n _m ² ) / (n _p ² + 2n _m ² )
... (15)
In the formula (15), n _a is organic - inorganic composite calculation refractive index of the refractive index of n _m is a polymer, n _p is the refractive index of the inorganic oxide particles, q is the volume fraction of the inorganic oxide particles Respectively.
[Calculation of porosity of coating film]
The measured refractive index of the coating film having voids is obtained by adding the product of the refractive index and volume fraction of the void (refractive index of air 1.00) to the product of the refractive index and volume fraction of the organic-inorganic composite. It becomes the value. Therefore, the porosity was calculated by the following formula. Organic - calculating the refractive index of the inorganic composite n _a, and substitutes the measured refractive index n _b of the coating film to the following formula to determine the porosity.
Porosity (%) = (n _a −n _b ) / (n _a −1) × 100 (16)
Wherein (16), n _a is organic - represents calculated refractive index of the inorganic composite, n _b is the measured refractive index of the coating film respectively.

<Production of molded body>
Using a compression molding machine, the organic-inorganic composite was vacuum hot pressed under the following conditions to produce a molded body having a thickness of about 50 to 100 μm.
・ Equipment: “SFV-30” manufactured by Shinto Metal Industries Co., Ltd.
-Temperature: 100-255 ° C

<Particle dispersion degree of the molded product>
(1) An ultrathin section was prepared from the molded body.
(2) The ultrathin section was observed in the HR-STEM scanning mode and photographed. However, an arbitrary measurement magnification was selected according to the size and shape of the inorganic oxide particles.
(3) The above HR-STEM image is processed with the above image analysis software, and for each of 500 inorganic oxide particles, the degree of dispersion of each particle is determined by the distance between centers of gravity method according to the following formula, and the average value is obtained as a compact The degree of particle dispersion was determined as follows. The smaller the particle dispersity, the more uniformly the particles are dispersed. When the particle dispersity ≦ 0.6, variations in physical properties can be suppressed.
Particle dispersity = (average deviation of distance between centroids between adjacent inorganic oxide particles) / (distance between centroids between adjacent inorganic oxide particles) (17)

<Raw materials>
The contents of the raw materials used in the examples and comparative examples are shown in the following (1) to (8).
(1) Inorganic oxide particle solution (1-1) 20 nm spherical SiO ₂ solution / trade name: “MIBK-ST” manufactured by Nissan Chemical Industries, Ltd.
・ SiO ₂ content: 31% by mass
・ Particle porosity: 0%
-Refractive index: 1.45
・ Circularity: 0.96
・ Minimum width D: 18nm
・ L / D = 1
(1-2) 50 nm spherical SiO ₂ solution / trade name: “MEK-ST-L” manufactured by Nissan Chemical Industries, Ltd.
・ SiO ₂ content: 30% by mass
・ Particle porosity: 0%
-Refractive index: 1.45
・ Circularity: 0.95
・ Minimum width D: 48nm
・ L / D = 1.1
(1-3) Beaded SiO ₂ solution / trade name: “MEK-ST-UP” manufactured by Nissan Chemical Industries, Ltd.
・ SiO ₂ content: 20% by mass
・ Particle porosity: 0%
-Refractive index: 1.45
・ Minimum width D: 12 nm
・ L / D = 14
A long chain structure formed by connecting spherical silica in a rosary shape. FIG. 2 shows a TEM photograph of the beaded silica particles.

(2) Silane compound (2-1) 3- (2-bromoisobutyroxy) propyldimethylchlorosilane (hereinafter also referred to as “BPS”)
BPS represented by the following chemical formula (10) was synthesized with reference to a known method (JP 2006-063042 A).

(2-2) 1,1,1,3,3,3-hexamethyldisilazane (hereinafter also referred to as “HMDS”): Tokyo Chemical Industry Co., Ltd. (3) Catalyst (3-1) Copper bromide (I) (CuBr): Wako Pure Chemical Industries, Ltd. (3-2) Copper bromide (II) (CuBr ₂ ): Wako Pure Chemical Industries, Ltd. (4) Ligand N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (hereinafter also referred to as “PMDETA”): Aldrich (5) Monomer The following monomers were all bubbled with nitrogen for 1 hour or more after removing the polymerization inhibitor through an alumina column. And used after deoxygenation treatment. When an alumina column cannot be used, the polymerization inhibitor may be removed by a known method such as distillation.
(5-1) Methyl methacrylate (hereinafter also referred to as “MMA”): manufactured by Tokyo Chemical Industry Co., Ltd. (5-2) Ethyl acrylate (hereinafter also referred to as “EA”): manufactured by Tokyo Chemical Industry Co., Ltd. (5-3) 2,2,2-trifluoroethyl methacrylate (hereinafter also referred to as “TFEMA”): manufactured by Tokyo Chemical Industry Co., Ltd. (5-4) 2,2,3,3,3-methacrylic acid Pentafluoropropyl (hereinafter also referred to as “PFPMA”): manufactured by Kanto Chemical Co., Inc. (6) Solvent, etc. (6-1) Methanol: Wako Pure Chemical Industries, Ltd. (6-2) Methyl isobutyl ketone (hereinafter “ MIBK "): Wako Pure Chemical Industries, Ltd. (6-3) methyl ethyl ketone (hereinafter also referred to as" MEK "): Wako Pure Chemical Industries, Ltd. (6-4) Tetrahydrofuran (hereinafter," THF ") Tomo .): Wako Pure Chemical Industries, Ltd. (6-5) Hexane: Wako Pure Chemical Industries, Ltd. (7) Methanol-water mixed solution (7-1) Methanol-water mixed solution-1: 77% by volume of methanol And a mixed solution (7-2) of methanol-water mixed solution-2: 80% by volume of methanol and 20% by volume of ion-exchanged water (8) polymerization Initiator (8-1) Ethyl 2-bromoisobutyrate (hereinafter also referred to as “EBIB”): manufactured by Aldrich

<Synthesis of Surface Modified Inorganic Oxide Particles-1 (BPS Modification—Synthesis of ₂₀ nm SiO ₂ Particles)>
According to the following procedure, BPS modified -20NmSiO ₂ particles (BPS is bound to the surface, 20nmSiO ₂ particles) was synthesized.
(1) A cooling pipe was connected, and the inside of the two-necked flask containing the rotor was replaced with nitrogen.
(2) Under nitrogen, 88% by volume of 20 nm SiO ₂ solution was introduced into the flask, and further 2% by volume of BPS was introduced, and stirring was started.
(3) The flask was immersed in an 85 ° C. oil bath and reacted for 36 hours with stirring.
(4) After cooling the reaction solution to room temperature, 10 vol% HMDS was introduced under nitrogen.
(5) After stirring at room temperature for 2 hours, the reaction was carried out by stirring at 80 ° C. for 8 hours, and the reaction solution was cooled to room temperature.
(6) The reaction solution was transferred to a centrifuge tube and centrifuged at 10,000 rpm, 10 ° C. for 30 minutes using a centrifuge (manufactured by Kubota Corporation, model: 7700).
(7) The supernatant liquid in the centrifuge tube was added to and mixed with the methanol-water mixed solution-2, and after standing, the supernatant liquid was discarded.
(8) Nitrogen was blown into the precipitate to volatilize the remaining liquid, a small amount of THF was added, and the precipitate was dissolved in THF by stirring.
(9) The above solution was added to methanol, stirred and allowed to stand, and then the supernatant was discarded.
(10) Methanol was added to the remaining precipitate, stirred and allowed to stand, and then the supernatant was discarded. This operation was further repeated 10 times.
(11) Air was dried overnight while blowing nitrogen into the precipitate, thereby volatilizing the liquid and obtaining a solid.
(12) The solid was dried at 80 ° C. under vacuum for 24 hours to obtain BPS-modified silica particles.
(13) The halogen content was 1.6% by mass. Since no chlorine was detected, the bromine content is shown as the halogen content.

<Synthesis of Surface Modified Inorganic Oxide Particles-2 (BPS Modification-Synthesis of 50 nm SiO ₂ Particles)>
The 20NmSiO ₂ particle solution was changed to 50NmSiO ₂ particle solution, except for the following modifications to the amount, in the same manner as in the above <Synthesis of surface modified inorganic oxide particles -1>, BPS reforming the -50nmSiO ₂ particles were synthesized.
Blending amount: 50 nm SiO ₂ particle solution (82 mass%), BPS (9 mass%), HMDS (9 mass%)
The halogen content was 0.6% by mass.

<Synthesis of Surface Modified Inorganic Oxide Particles-3 (BPS Modification—Synthesis of Beaded SiO ₂ Particles)>
The 20NmSiO ₂ particle solution was changed to beaded SiO ₂ particle solution, except for the following modifications to the amount, in the same manner as in the above <Synthesis of surface modified inorganic oxide particles -1>, BPS reformer - was synthesized beaded SiO ₂ particles.
Blending amount: bead-like SiO ₂ particle solution (86% by mass), BPS (7% by mass), HMDS (7% by mass)
The halogen content was 2.0% by mass.

[Example 1]
The organic-inorganic composite A was produced according to the following procedure according to the formulation in Table 1. The concentration of each component is a numerical value based on the total amount of all components. The evaluation results of the obtained organic-inorganic composite A are shown in Table 2.
(1) to the Schlenk flask containing a rotor, added CuBr and CuBr _2, and three times to purged with nitrogen inside the flask from the vacuum treatment, and the inner atmosphere of the flask was deoxygenated, a small amount of MIBK nitrogen Introduced below and stirred.
(2) A catalyst solution was prepared by adding PMDETA to the above solution and stirring at 60 ° C.
(3) A BPS modified-20 nm SiO ₂ particle was charged into another Schlenk flask with a condenser connected and a rotor.
(4) A cooling tube was connected to the Schlenk flask, and the inside of the flask was subjected to vacuum treatment and then replaced with nitrogen three times to deoxygenate the inside of the flask.
(5) Introduce the remaining solvent (MIBK) into the flask under nitrogen, treat with an ultrasonic cleaner for 10 minutes, introduce further monomers (MMA, TFEMA), soak in an oil bath at 60 ° C., and stir did.
(6) Furthermore, after introducing the catalyst solution prepared above under nitrogen, the reaction solution was stirred for 25 minutes to carry out a polymerization reaction.
(7) Immerse the flask in an ice bath and quickly cool it, then add it to methanol (in the case where it is difficult to precipitate solids only with methanol, hexane may be used) and stir. When it was difficult to sink, it was separated by centrifugation and allowed to stand.
(8) After standing, the supernatant was discarded, and then methanol was added again to the remaining precipitate and left standing, and the supernatant was discarded. This operation was further repeated 8 times.
(9) Air was dried overnight while blowing nitrogen into the remaining precipitate, thereby volatilizing the liquid and obtaining a solid.
(10) The solid was dried at 80 ° C. for 24 hours under vacuum to obtain an organic-inorganic composite A.
(11) The Tg of the organic-inorganic composite A was measured by the method described above and found to be 83 ° C.
(12) The halogen content of the organic-inorganic composite A was measured by the above-mentioned method and found to be 0.8% by mass. Since no chlorine was detected, the bromine content is shown as the halogen content.
(13) The fluorine content of the organic-inorganic composite A was measured by the above-mentioned method and found to be 6% by mass.
(14) When the number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polymer constituting the organic-inorganic composite A were measured by the above-described methods, Mn = 35,500 and Mw = 52,500. . Further, when the molecular weight dispersity (Mw / Mn) was calculated, it was found that Mw / Mn = 1.48, and the polymer chain having a uniform chain length was bonded to the inorganic oxide particles.
(15) When the amount of the free polymer of the organic-inorganic composite A was measured, no free polymer was detected, and the amount of the polymer bonded to the inorganic oxide particles was 100% by mass.
(16) When the inorganic oxide particle content of the organic-inorganic composite A was measured by the above method, the inorganic oxide particle content was 55% by mass and 42% by volume.
(17) Organic-inorganic composite A and MIBK were mixed so that the solid content was about 10% by mass, and a coating material was obtained by the method described above.
(18) Using the coating material, coating and drying were performed on a PET film by the method described above to obtain a coating film. When the appearance of the obtained coating film was visually confirmed, no aggregation of the inorganic oxide particles was observed, and the transparency was maintained.
(19) When the total light transmittance and haze of the coating film were measured by the above-described method, the total light transmittance was 91% and the haze was 0.5%.
(20) When the refractive index of the coating film was measured by the above-mentioned method, it was 1.44, which was lower than the refractive index of 1.48 of 20 nmSiO ₂ -g-pMMA in Comparative Example 1. From this, it was found that the refractive index can be controlled.
(21) Further, the pencil hardness of the coating film measured by the above method is F, and the strength is higher than the pencil hardness (B) of the coating film of p (TFEMA-co-MMA) in Comparative Example 2. I knew it was up.
(22) As a result of evaluating the contact angle of the coating film by the method described above, the water contact angle was 105 ° and the oil contact angle was 40 °.
(23) When the porosity of the coating film was determined by the method described above, it was 0%.
(24) Using the above-described coating material, using a TAC film instead of a PET film, and producing and evaluating a coating film by the same method as described above, results were as good as the PET film. was gotten.
(25) The organic-inorganic composite A was molded by the method described above to obtain a molded body. When the external appearance of the obtained molded body was visually confirmed, no aggregation of inorganic oxide particles was observed, and transparency was maintained. Furthermore, it was 1.45 when the refractive index of the molded object was measured by the above-mentioned method. Also as compared with the refractive index 1.48 of 20nmSiO ₂ -g-pMMA of Comparative Example 1 showed low values. From this, it was found that the refractive index can be controlled.
(26) When the particle dispersity of the molded body was calculated by the above method, the particle dispersity was 0.14, and it was confirmed that the dispersibility of the particles was good.

[Example 2]
An organic-inorganic composite B was produced and evaluated in the same manner as in Example 1 except that the polymerization reaction conditions were changed to 60 ° C. and 20 hours according to the formulation in Table 1. The evaluation results of the obtained organic-inorganic composite B are shown in Table 2. Since no chlorine was detected, the bromine content is shown as the halogen content.
When the number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polymer constituting the organic-inorganic composite B were measured by the above-mentioned methods, Mn = 12,000, Mw = 201,600, Mw / Mn = 1. It was found that the polymer chain having a uniform chain length was bonded to the inorganic oxide particles.
Using the organic-inorganic composite B, a molded body was obtained by the method described above. When the external appearance of the obtained molded body was visually confirmed, no aggregation of inorganic oxide particles was observed, and transparency was maintained. Furthermore, when the refractive index was measured by the above-mentioned method, it was 1.39, which was significantly lower than the refractive index of 1.48 of 20 nmSiO ₂ -g-pMMA in Comparative Example 1. From this, it was found that the refractive index of the molded body can be controlled by forming the organic-inorganic composite.
Also, the water repellency and oil repellency, which are indicators of the antifouling property of the coating film, were significantly improved as compared with Comparative Example 1. An attempt was made to write characters on the surface of the molded body with an oil-based pen (manufactured by Zebra Co., Ltd., “Mackey”). Further, when the ink trace was wiped with a nonwoven fabric for electronic materials (“Bencot” manufactured by Asahi Kasei Fibers Co., Ltd.), the ink trace was completely wiped off.

[Example 3]
An organic-inorganic composite C was produced and evaluated in the same manner as in Example 1 except that the polymerization reaction conditions were 75 ° C. and 25 hours in accordance with the formulation in Table 1. The evaluation results of the obtained organic-inorganic composite C are shown in Table 2. Since no chlorine was detected, the bromine content is shown as the halogen content.
When the number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polymer constituting the organic-inorganic composite C were measured by the above method, Mn = 38,000, Mw = 65,700, Mw / Mn = 1. It was found that the polymer chain having a uniform chain length was bonded to the inorganic oxide particles.
Using the organic-inorganic composite C, a coating film and a molded body were obtained by the method described above. When the external appearance of the obtained coating film and the molded product was visually confirmed, no aggregation of inorganic oxide particles was observed, and transparency was maintained. Furthermore, when the refractive index was measured by the above-mentioned method, it was 1.43, which was lower than the refractive index of 1.48 of 50 nm SiO ₂ -g-pMMA in Comparative Example 3. From this, it was found that the refractive index of the coating film and the molded body can be controlled by forming the organic-inorganic composite.
In addition, the water repellency and oil repellency, which are indicators of the antifouling property of the coating film, were also significantly improved as compared with Comparative Example 3.

[Example 4]
An organic-inorganic composite D was produced and evaluated in the same manner as in Example 1 except that the polymerization reaction conditions were 60 ° C. and 10 minutes in accordance with the formulation in Table 1. The evaluation results of the obtained organic-inorganic composite D are shown in Table 2. Since no chlorine was detected, the bromine content is shown as the halogen content.
When the number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polymer constituting the organic-inorganic composite D were measured by the above method, Mn = 9,500, Mw = 15,400, Mw / Mn = 1. It was found that the polymer chain having a uniform chain length was bonded to the inorganic oxide particles.
Using the organic-inorganic composite D, a coating film was obtained by the method described above. When the appearance of the obtained coating film was visually confirmed, no aggregation of the inorganic oxide particles was observed, and the transparency was maintained. Furthermore, when the refractive index was measured by the above-mentioned method, it was 1.39, which was significantly lower than the refractive index of 1.48 of 20 nmSiO ₂ -g-pMMA in Comparative Example 1. Furthermore, the porosity determined from the value of refractive index was 13%. From this, it was found that the refractive index of the coating film can be controlled by forming the organic-inorganic composite.
Also, the water repellency and oil repellency, which are indicators of the antifouling property of the coating film, were significantly improved as compared with Comparative Example 1.

[Example 5]
An organic-inorganic composite E was produced and evaluated in the same manner as in Example 3 except that the polymerization reaction conditions were 75 ° C. and 12 hours in accordance with the formulation in Table 1. The evaluation results of the obtained organic-inorganic composite E are shown in Table 2. Since no chlorine was detected, the bromine content is shown as the halogen content.
When the number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polymer constituting the organic-inorganic composite E were measured by the above methods, Mn = 14,200, Mw = 21,900, Mw / Mn = 1. It was found that the polymer chain having a uniform chain length was bonded to the inorganic oxide particles.
Using the organic-inorganic composite E, a coating film was obtained by the method described above. When the appearance of the obtained coating film was visually confirmed, no aggregation of the inorganic oxide particles was observed, and the transparency was maintained. Furthermore, when the refractive index was measured by the above-mentioned method, it was 1.38, which was significantly lower than the refractive index of 1.48 of 50 nm SiO ₂ -g-pMMA in Comparative Example 3. Furthermore, the porosity determined from the value of the refractive index was 14%. From this, it was found that the refractive index of the coating film can be controlled by forming the organic-inorganic composite.
In addition, the water repellency and oil repellency, which are indicators of the antifouling property of the coating film, were also significantly improved as compared with Comparative Example 3.

[Example 6]
An organic-inorganic composite F was produced and evaluated in the same manner as in Example 5 except that the polymerization reaction conditions were 75 ° C. and 10 hours in accordance with the formulation in Table 1. The evaluation results of the obtained organic-inorganic composite F are shown in Table 2. Since no chlorine was detected, the bromine content is shown as the halogen content.
When the number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polymer constituting the organic-inorganic composite F were measured by the above method, Mn = 8,700, Mw = 13,800, Mw / Mn = 1. It was found that the polymer chain having a uniform chain length was bonded to the inorganic oxide particles.
Using the organic-inorganic composite F, a coating film was obtained by the method described above. When the appearance of the obtained coating film was visually confirmed, no aggregation of the inorganic oxide particles was observed, and the transparency was maintained. Furthermore, when the refractive index was measured by the above-mentioned method, it was 1.33, which was significantly lower than the refractive index 1.48 of 20 nmSiO ₂ -g-pMMA in Comparative Example 1. Furthermore, the porosity determined from the refractive index value was 25%. From this, it was found that the refractive index of the coating film can be controlled by forming the organic-inorganic composite.
Also, the water repellency and oil repellency, which are indicators of the antifouling property of the coating film, were significantly improved as compared with Comparative Example 1.

[Comparative Example 1]
An organic-inorganic composite α was produced and evaluated in the same manner as in Example 1 except that the polymerization reaction conditions were set at 60 ° C. for 20 minutes in accordance with the formulation shown in Table 1. The evaluation results of the obtained organic-inorganic composite α are shown in Table 2. Since no chlorine was detected, the bromine content is shown as the halogen content.
When the number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polymer constituting the organic-inorganic complex α were measured by the above-described methods, Mn = 28,900, Mw = 40,200, Mw / Mn = 1. It was found that the polymer chain having a uniform chain length was bonded to the inorganic oxide particles.
Using the organic-inorganic composite α, a coating film and a molded body were obtained by the method described above. When the appearance of the obtained coating film was visually confirmed, no aggregation of the inorganic oxide particles was observed, and the transparency was maintained. Furthermore, when the refractive index was measured by the above-mentioned method, it was 1.48, almost the same refractive index as pMMA, and the refractive index was significantly higher than that of Example 1.
In addition, the water repellency and oil repellency, which are indicators of antifouling properties of the coating film, were also significantly lower than those of Example 1 and were found to be inferior in antifouling properties.

[Comparative Example 2]
EBIB was added as a polymerization initiator in place of the BPS-modified ₂₀ nm SiO ₂ particles of Example 1, and p (TFEMA-co-MMA) was synthesized according to the formulation in Table 1. It manufactured and evaluated by the method similar to Example 1 except having made the polymerization reaction conditions into 60 degreeC and 30 minutes. The evaluation results of the obtained p (TFEMA-co-MMA) are shown in Table 2.
When the number average molecular weight (Mn) and mass average molecular weight (Mw) of p (TFEMA-co-MMA) were measured by the above-mentioned methods, Mn = 72,900, Mw = 94,000, Mw / Mn = 1.29. It was a polymer with a uniform chain length.
Using p (TFEMA-co-MMA), a coating film was obtained by the method described above. When the appearance of the obtained coating film was visually confirmed, no aggregation was observed and the transparency was maintained. Furthermore, when the refractive index was measured by the above-mentioned method, it was 1.47, almost the same refractive index as that of pMMA, and the refractive index was significantly higher than that of Example 1.
It was also found that the pencil hardness of the coating film and the like was B, and the strength was insufficient.

[Comparative Example 3]
An organic-inorganic composite β was produced and evaluated in the same manner as in Example 3 except that the polymerization reaction conditions were set at 60 ° C. for 3 hours in accordance with the formulation in Table 1. Table 2 shows the evaluation results of the obtained organic-inorganic composite β.
When the number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polymer constituting the organic-inorganic composite β were measured by the above-described methods, Mn = 41,900, Mw = 67,000, Mw / Mn = 1. It was found that the polymer chain having a uniform chain length was bonded to the inorganic oxide particles.
Using the organic-inorganic composite β, a coating film was obtained by the method described above. When the appearance of the obtained coating film was visually confirmed, no aggregation of the inorganic oxide particles was observed, and the transparency was maintained. Furthermore, when the refractive index was measured by the above-mentioned method, it was 1.48, which was substantially the same as that of pMMA, and the refractive index was significantly higher than that of Example 3.
In addition, the water repellency and oil repellency, which are indicators of the antifouling property of the coating film, were also significantly lower than those of Example 3, indicating that the antifouling property was poor.

  Regarding the comprehensive judgment in Table 2, the case where the judgment is acceptable is indicated as “A”, and the case where the judgment is unacceptable is indicated as “B”. From the experimental results shown in Table 2, organic-inorganic that is excellent in antifouling property and can control the refractive index of a coating film or a molded article by bonding a polymer chain containing fluorine to the surface of the inorganic oxide particles. It became clear that the composite could be manufactured.

  The organic-inorganic composite and molded body of the present invention are useful as, for example, optical materials and coating materials.

Claims (37)

(A) inorganic oxide particles, and (B) a polymer formed by polymerization of a radical polymerizable monomer and having a molecular weight dispersity of 2.3 or less and bonded to the inorganic oxide particles,
(C) An organic-inorganic composite containing 0.1 to 60% by mass of fluorine based on the total mass.   The organic-inorganic composite according to claim 1, wherein the glass transition temperature is -10 to 180 ° C.   The organic-inorganic composite according to claim 1 or 2, wherein the total content of bromine and chlorine is 0.001 to 5 mass% based on the total mass.   The organic-inorganic composite according to any one of claims 1 to 3, wherein the inorganic oxide particles are silica particles.   The organic-inorganic composite according to any one of claims 1 to 4, wherein the inorganic oxide particles have a minimum width of 1 to 70 nm.   The organic-inorganic composite according to any one of claims 1 to 5, wherein the inorganic oxide particles have a circularity of 0.7 to 1.   The organic-inorganic composite according to any one of claims 1 to 6, wherein L / D of the inorganic oxide particles is 5 or more.   The organic-inorganic composite according to any one of claims 1 to 7, wherein the inorganic oxide particles form a long-chain structure including a plurality of primary particles connected in a bead shape.   The organic-inorganic composite according to any one of claims 1 to 8, wherein the inorganic oxide particles have a refractive index of 1.4 to 1.6.   The organic-inorganic composite according to any one of claims 1 to 9, wherein the content of the inorganic oxide particles is 2 to 96% by mass based on the total mass.   The organic-inorganic composite according to any one of claims 1 to 10, wherein the content of the inorganic oxide particles is 1 to 94% by volume based on the total volume.   The organic-inorganic composite according to any one of claims 1 to 11, wherein the radical polymerizable monomer includes at least one fluorine-based monomer.   The organic-inorganic composite according to any one of claims 1 to 12, wherein the radical polymerizable monomer includes at least one monomer selected from the group consisting of acrylic acid esters and methacrylic acid esters.   The said radically polymerizable monomer contains acrylic acid ester and methacrylic acid ester, The said polymer is a copolymer polymer of the said acrylic acid ester and the said methacrylic acid ester, The any one of Claims 1-13. Organic-inorganic composite.   The organic-inorganic composite according to any one of claims 1 to 14, wherein the polymer is a thermoplastic polymer.   The organic-inorganic composite according to any one of claims 1 to 15, wherein the polymer has a molecular weight dispersity of 1.0 to 1.9.   The step of producing surface-modified inorganic oxide particles by reacting inorganic oxide particles with a coupling agent having a polymerization initiating group, and living radical polymerization initiated by the polymerization initiating group, to the inorganic oxide particles. A method for producing an organic-inorganic composite according to any one of claims 1 to 16, comprising a step of forming a polymer that is bonded.   The production method according to claim 17, wherein the living radical polymerization is atom transfer radical polymerization.   The production method according to claim 17 or 18, wherein the polymerization initiating group contains a halogen atom.   The manufacturing method of Claim 19 whose halogen content of the said surface modification inorganic oxide particle is 0.02-10 mass%.   The coupling agent has at least one functional group selected from the group consisting of a phosphoric acid group, a carboxy group, an acid halide group, an acid anhydride group, an isocyanate group, a glycidyl group, a chlorosilyl group, and an alkoxysilyl group. Item 21. The production method according to any one of Items 17 to 20.   The production method according to claim 21, wherein the functional group is a chlorosilyl group or an alkoxysilyl group.   The production method according to claim 22, wherein the coupling agent has one or two of the functional groups.   The coating material containing the organic-inorganic composite of any one of Claims 1-16.   The coating material according to claim 24, further comprising an organic solvent.   A coating film comprising the coating material according to claim 24 or 25.   27. The coating film according to claim 26, having a refractive index of 1.05 to 1.43.   The coating film according to claim 26 or 27, wherein the pencil hardness is HB or more.   The coating film according to any one of claims 26 to 28, wherein the water contact angle is 75 ° or more.   The coating film according to any one of claims 26 to 29, wherein the oil contact angle is 30 ° or more.   The coating film according to any one of claims 26 to 30, wherein the porosity is 2 to 60% by volume.   The molded object containing the organic-inorganic composite of any one of Claims 1-16.   The molded object of Claim 32 whose particle dispersion degree is 0.6 or less.   The molded product according to claim 32 or 33, wherein the refractive index is 1.05 to 1.43.   The molded product according to any one of claims 32 to 34, wherein the porosity is 2 to 60% by volume.   An optical member provided with the coating film of any one of Claims 26-31, or the molded object of any one of Claims 32-35.   The optical material containing the organic-inorganic composite of any one of Claims 1-16.