JP2006299049A - Organic-inorganic compounded material and silylated derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic compounded material having a high transparency and a high refractive index, and useful as an optical material, and a silylated derivative useful as a raw material for the production of the organic-inorganic compounded material. <P>SOLUTION: This organic-inorganic compounded material consisting of an organic component and an inorganic component consisting of the silylated derivative obtained by reacting a silylation agent with any of a dispersed material obtained by hydrolyzing a metal alkoxide by 0.5 to ≤1 fold mol water based on the metal alkoxide in an organic solvent in the absence of an acid, a base or a dispersion stabilizer, a metal compound obtained by hydrolyzing the metal alkoxide by 1.0-1.7 fold mol water at 20-90°C and distilling off low boiling substances and a dispersed material obtained by hydrolyzing a metal alkoxide by 1.0 to ≤2.0 fold mol water based on the metal alkoxide in an organic solvent in the absence of an acid, a base or a dispersion stabilizer at ≤-20°C. The silylated derivative is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an organic-inorganic composite having high transparency and a high refractive index and useful as an optical material, and a silylated derivative useful as a raw material for producing the organic-inorganic composite.

Organic-inorganic composites (organic-inorganic hybrids, also referred to as organic-inorganic composite polymers) in which an inorganic component is combined in an organic polymer are attracting attention as a new industrial material having both properties of an organic polymer and an inorganic component. In particular, the use of this organic-inorganic composite for plastic lenses having a high refractive index has been studied.

In producing such an organic-inorganic composite for plastic lenses having a high refractive index, it is considered preferable to use titanium oxide as an inorganic component.

Examples of organic-inorganic composites using titanium oxide as an inorganic component include hydrolysis and dehydration condensation of metal alkoxides containing titanium alkoxides in the presence of organic monomers using acid or base as a catalyst described in Patent Document 1, for example. An organic-inorganic composite polymer in which the obtained metal oxide is mixed with an organic monomer and polymerized is known.

Patent Document 2 discloses a component A, which is a monomer composition containing a metal oxide that may have an organic group, obtained by hydrolysis and dehydration condensation of a metal alkoxide in the presence of a monomer; A method for producing a contact lens is described in which a monomer mixture containing component A and component B which is a monomer capable of polyaddition or polycondensation is polymerized.

However, in either case of Patent Documents 1 and 2, the metal alkoxide is hydrolyzed and dehydrated using an acid or base, and the solvent, water, acid or base is distilled off and subjected to bulk polymerization treatment. Since it was difficult to completely remove the water, acid, or base, there was a problem that these remained to affect the polymerization reaction. In particular, in order to perform solution polymerization in an organic solvent, it is necessary to use an acid, a base, or a dispersion stabilizer in order to cause the hydrolysis product of the metal alkoxide to exist stably in the solution. There is also a problem that it interferes with or adversely affects the physical properties of the product. Furthermore, the inorganic-organic composites using titanium oxide gel generally tend to have lower transmittance than inorganic-organic composites using other metal oxide gels, and titanium oxide is hydrolyzed and dehydrated. It can be said that it is agglomerated in a later concentration stage.

As related to the present invention, Patent Document 3 discloses a titanium alkoxide represented by the general formula: Ti (OR ″) ₄ (R ″ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms), One or more solvents selected from ether solvents, ketone solvents, and alcohol solvents in the presence or absence of an inorganic or organic acid as a catalyst, using 1.0 mole to 1.75 moles of water. High TiO ₂ content by hydrolysis at a temperature of 0 ° C. to 30 ° C. and further aging at a temperature of 60 ° C. to 120 ° C., or by further reaction with a chelating reagent or silylating agent. A method for obtaining solid polytitanoxane is described.
JP-A-8-157735 Japanese Patent Laid-Open No. 11-14949 JP 2000-86769 A

The present invention has been made in view of the above-described prior art, has an organic-inorganic composite having high transparency and a high refractive index, and useful as a lens material, and a raw material for producing the organic-inorganic composite. It is an object to provide a silylated derivative useful as:

As a result of diligent research to solve the above problems, the present inventor prepared a dispersion of a specific titanium compound obtained by hydrolyzing titanium alkoxide in the absence of an acid, a base and / or a dispersion stabilizer. Add a polymerizable monomer to this dispersion and perform a polymerization reaction, or add a silylating agent to the dispersion and perform a silylation reaction, then add a polymerizable monomer to the resulting reaction liquid By conducting a polymerization reaction, it was found that an organic-inorganic composite having high transparency and high refractive index and useful as an optical material or the like can be obtained, and the present invention has been completed.

Thus, according to the first aspect of the present invention, the following organic-inorganic composites (1) to (3) are provided. (1) An organic-inorganic composite comprising an inorganic component and an organic component, wherein the inorganic component is (A) a metal alkoxide in the absence of an acid, a base, and / or a dispersion stabilizer in an organic solvent. Obtained by hydrolyzing the metal alkoxide with less than 0.5 to 1 mol of water, and having a metal-oxygen bond that is stably dispersed without agglomerating in an organic solvent, or ( B) It is obtained from a metal compound obtained by hydrolyzing a metal alkoxide at 20 to 90 ° C. using 1.0 to 1.7 moles of water with respect to the metal alkoxide, and then distilling off a low-boiling substance. An organic-inorganic composite characterized by being an inorganic polymer.

(2) An organic-inorganic composite comprising an inorganic component and an organic component, wherein the inorganic component is (A) a metal alkoxide in the absence of an acid, a base, and / or a dispersion stabilizer in an organic solvent. A dispersoid having a metal-oxygen bond which is obtained by hydrolyzing the metal alkoxide with 0.5 to 1 times less moles of water and stably dispersed without aggregation in an organic solvent, (B ) A metal compound obtained by hydrolyzing a metal alkoxide at 20 to 90 ° C. using 1.0 to 1.7 moles of water with respect to the metal alkoxide, and then distilling off the low boiling point substance, or (C ) Hydrolysis in an organic solvent in the absence of acid, base, and / or dispersion stabilizer at −20 ° C. or less with 1.0 to 2.0 times less water than metal alkoxide. Metal that is obtained and stably dispersed without agglomeration in an organic solvent To one of the dispersoid having an iodine binding, characterized in that an inorganic polymer obtained silyl derivative obtained by reacting a silylating agent organic - inorganic composite.

(3) The organic component is at least one selected from the group consisting of acrylic resins, polyurethane resins, polythiourethane resins, resins mainly composed of diethylene glycol bisallyl carbonate, and resins obtained from epithio group-containing compounds. The organic-inorganic composite according to (1) or (2), wherein

According to the second aspect of the present invention, the following silylated derivative (4) is provided. (4) (A) A metal alkoxide is hydrolyzed in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer using 0.5 to 1 times less moles of water than the metal alkoxide. A dispersoid having a metal-oxygen bond which is stably dispersed without agglomerating in an organic solvent, and (B) 1.0 to 1.7 moles of water with respect to the metal alkoxide. Using a metal compound obtained by hydrolysis at 20 to 90 ° C. and then distilling off the low boiling point substance, or (C) in the absence of an acid, a base, and / or a dispersion stabilizer in an organic solvent, − It has a metal-oxygen bond that is obtained by hydrolysis using water at a temperature of 20 ° C. or less and less than 1.0 to 2.0 times moles of metal alkoxide and stably dispersed without aggregation in an organic solvent. Silica obtained by reacting any of the dispersoids with a silylating agent Derivatized.

The organic-inorganic composite of the present invention has high transparency and a high refractive index, and is useful as an optical material or the like. The silylated derivative of the present invention is a novel substance, has high transparency and high refractive index, and is useful as a raw material for producing the organic-inorganic composite of the present invention.

Hereinafter, the organic-inorganic composite of the present invention will be described in detail.

The organic-inorganic composite of the present invention is an organic-inorganic composite comprising an inorganic component and an organic component, and the inorganic component is any one of the following (I) or (II) inorganic polymers. It is characterized by. (I) (A) A metal alkoxide is hydrolyzed in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer using 0.5 to 1 times less moles of water than the metal alkoxide. A dispersoid having a metal-oxygen bond (hereinafter sometimes referred to as “metal compound (A)”), which is stably dispersed without agglomerating in an organic solvent, or (B) a metal alkoxide A metal compound (hereinafter referred to as “metal compound (B)”) obtained by hydrolysis at 20 to 90 ° C. using 1.0 to 1.7 moles of water with respect to the alkoxide, and then distilling off the low boiling point substance. Inorganic polymer obtained from (II) Metal compound (A), Metal compound (B), or (C) In an organic solvent, in the absence of an acid, a base, and / or a dispersion stabilizer, the temperature is -20 ° C. or less, and 1 for the metal alkoxide. A dispersoid having a metal-oxygen bond (hereinafter referred to as “metal compound (C)” obtained by hydrolysis using less than 0.0 to 2.0 moles of water and stably dispersed without aggregation in an organic solvent. ) "), And an inorganic polymer obtained from a silylated derivative obtained by reacting with a silylating agent.

(1) Metal compound (A) The metal compound (A) used in the present invention is 0.5 to 1 mole per mole of metal alkoxide in an organic solvent in the absence of acid, base, and / or dispersion stabilizer. A dispersoid having metal-oxygen bonds that are stably dispersed without agglomeration in an organic solvent, obtained by hydrolysis using less water.

The metal compound (A) is a dispersoid that is stably dispersed without aggregation in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer. Here, the dispersoid means fine particles dispersed in the dispersion system, and specific examples thereof include colloidal particles.

In the present invention, the state of being stably dispersed without agglomeration represents a state in which a dispersoid having a metal-oxygen bond is not condensed and not separated heterogeneously in an organic solvent, preferably transparent. A homogeneous state.

Transparent means a state in which the transmittance in visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, the optical path length of the quartz cell is 1 cm, and the control sample is organic. It represents a state that represents a transmittance of 80 to 100%, preferably expressed as a spectral transmittance measured under the condition of using a solvent and a light wavelength of 550 nm.

Specifically as a metal atom of the metal alkoxide used for manufacture of a metal compound (A), the alkali metal element from the 2nd period of a periodic table to the 6th period, an alkaline-earth metal element, a 3B group element, a periodic rule Illustrates a combination of one or more metals selected from the group consisting of Group 4B and Group 5B elements, transition metal elements, and lanthanoid elements from the 3rd period to the 6th period of the table be able to. Of these, titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, and lead are preferable, and titanium is particularly preferable.

Although it does not restrict | limit especially as an alkoxy group of a metal alkoxide, From points, such as the availability of a raw material and production efficiency, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, 2-ethylhexyl group, etc. The C1-C8 alkoxy group of these is preferable. The number of alkoxy groups to be bonded is not particularly limited, and depends on the type and valence of metal atoms, the number of metal atoms contained in one molecule, and the like. When there are a plurality of alkoxy groups, the bonded alkoxy groups may all be the same or of different types.

Specific examples of the metal alkoxide include silicon alkoxides such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (i-OC ₃ H ₇ ) ₄ , and Si (t-OC ₄ H ₉ ) ₄ ; Titanium alkoxides such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (i-OC ₃ H ₇ ) ₄ , Ti (OC ₄ H ₉ ) ₄ ; Zr (OCH ₃ ) ₄ , Zr (OC _{2 H 5) 4, Zr (} OC 3 H 7) 4, Z
r (OC4H9) 4 or the like zirconium _{alkoxide; Al (OCH 3) 3,} Al (OC 2 H 5) 3, Al (O-i-C 3 H 7) 3, Al (OC 4 H 9) 3 , etc. Aluminum Alkoxide; Germanium alkoxide such as Ge (OC ₂ H ₅ ) ₄ ; In (OCH ₃ ) ₃ , In (OC ₂ H ₅ ) ₃ , In (Oi-C ₃ H ₇ ) ₃ , In (OC ₄ H ₉ ) Indium alkoxides such as ₃ ; Tin alkoxides such as Sn (OCH ₃ ) ₄ , Sn (OC ₂ H ₅ ) ₄ , Sn (Oi-C ₃ H ₇ ) ₄ , Sn (OC ₄ H ₉ ) ₄ ; Ta _{(OCH 3) 5, Ta (} OC 2 H 5) 5, Ta (O-i-C 3 H 7) 5, Ta (OC 4 H 9) ₅ such as tantalum _{alkoxide; W (OCH 3) 6,} W ( OC ₂ H _{5) 6 W (O-i-C 3} H 7) 6, W (OC 4 H 9) tungsten alkoxides ₆ such; Zn _{(OC 2} H ₅₎ zinc ₂ such _{alkoxide; Pb (OC 2 H 5)} 4 , etc. Lead Alkoxides; and the like.

Moreover, the partial hydrolyzate of the above metal alkoxide is also included in the metal alkoxide used in the present invention. In addition, a composite alkoxide obtained by a reaction between two or more metal alkoxides, or a composite obtained by reacting one or more metal alkoxides with one or more metal salts. It may be an alkoxide. Furthermore, it is also possible to use these in combination.

Specifically, as a composite alkoxide obtained by reaction between two or more kinds of metal alkoxides, a composite alkoxide obtained by reaction of an alkali metal or alkaline earth metal alkoxide and a transition metal alkoxide, or a Group 3B element The complex alkoxide as a complex salt obtained by combining these can be illustrated.

More _{specifically, BaTi (Or) 6, SrTi} (Or) 6, BaZr (Or) 6, SrZr (Or) 6, LiNb (Or) 6, LiTa (Or) 6, LiVO (Or) 4, MgAl 2 (Or) ₆ , (Or) ₃ SiOAl (Or ′) ₂ , (Or) ₃ SiOTi (Or ′) ₃ , (Or) ₃ SiOZr (Or ′) ₃ , (Or) ₃ SiOB (Or ′) ₂ , ( Or) ₃ SiONb (Or ′) ₄ , (Or) ₃ SiOTa (Or ′) _{4 and the} like. Here, r and r ′ each independently represents an alkyl group.

In addition, as a composite alkoxide obtained by reaction of one or more metal alkoxides with one or more metal salts, chloride, nitrate, sulfate, acetate, formate, oxalate, etc. The compound obtained by reaction with a metal salt and an alkoxide can be illustrated.

The metal alkoxide is used by dissolving or dispersing in a suitable organic solvent. The concentration of the metal alkoxide in the organic solvent is not particularly limited as long as it has a fluidity capable of suppressing rapid heat generation and can be stirred, but is usually 5 to 30% by weight.

The organic solvent to be used is not particularly limited as long as it is inert to the hydrolysis reaction of the metal alkoxide. Specifically, alcohol solvents such as methanol, ethanol and isopropyl alcohol; halogenated hydrocarbon solvents such as methylene chloride and chloroform; hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene, xylene and chlorobenzene; tetrahydrofuran and diethyl And ether solvents such as ether and dioxane; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; Further, silicones such as methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, methylphenylpolysiloxane, etc. used in the dispersion medium of titanium dioxide dispersion described in JP-A-9-208438 Can also be illustrated. These solvents can be used alone or in combination of two or more.

Among these, in order to perform the hydrolysis reaction using water at a low temperature as described later, a solvent that has high water solubility and does not solidify at a low temperature is preferable. Specifically, a lower alcohol solvent or an ether solvent. Preferred examples include aromatic hydrocarbon solvents.

When the metal alkoxide is not uniformly mixed with the organic solvent, for example, 1,2-bis- (2-ethylhexyloxycarbonyl) -1-ethanesulfonic acid sodium, polyoxyethylene (6) nonylphenyl ether, etc. It is preferable to add a surfactant, or to perform stirring treatment, ultrasonic treatment, etc. to make the solution uniform.

The amount of the organic solvent used is usually 10 to 5,000 parts by weight, preferably 100 to 3,000 parts by weight, based on 100 parts by weight of the metal alkoxide. If the amount is less than 10 parts by weight, the produced fine particles may grow in a combined state, and particle size control may be difficult. On the other hand, if the amount exceeds 5,000 parts by weight, the solution may be too dilute and it may be difficult to produce fine particles. There is.

The water used for the hydrolysis of the metal alkoxide is not particularly limited as long as it is neutral, but pure water, distilled water or ion-exchanged water with a low impurity content is preferable from the viewpoint of suppressing side reactions.

The amount of water used in the reaction is not particularly limited, but specifically, 0.5 to 1.5 times mol, preferably less than 0.5 to 1.0 times mol, of the metal alkoxide is exemplified. Can do.

As a method for adding water, any of a method of continuously adding the entire amount of water to be used and a method of adding in a plurality of divided portions may be used. As will be described later, when water is added in a plurality of times, the temperature at the time of addition may be changed. For example, the first addition of water can be performed at −25 ° C. to −20 ° C., and the second addition can be performed at −80 ° C. to −70 ° C.

Moreover, water can also be diluted and used for a suitable organic solvent. By using diluted water in the organic solvent, local heat generation at the time of dropping of water can be prevented, and the metal alkoxide can be homogeneously hydrolyzed. As the organic solvent used for diluting water, those compatible with water are preferable. For example, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol and the like can be mentioned.

In the hydrolysis reaction of the metal alkoxide with water, an acid, a base or a dispersion stabilizer may be added. Acids and bases are used as a deflocculant to disperse precipitates formed by condensation, and metal alkoxides and multimers of generated metal alkoxides are hydrolyzed and dehydrated to produce colloidal particles and other dispersoids. The catalyst is not particularly limited as long as it functions as a catalyst for the production and as a dispersant for the produced dispersoid.

Examples of the acid include mineral acids such as hydrochloric acid, nitric acid, boric acid, and borohydrofluoric acid; organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid; diphenyl And a photoacid generator that generates an acid by light irradiation, such as iodonium hexafluorophosphate and triphenylphosphonium hexafluorophosphate. Examples of the base include triethanolamine, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, ammonia, dimethylformamide, phosphine and the like.

The dispersion stabilizer is an agent having the effect of stably dispersing the dispersoid in the dispersion medium, and examples thereof include anti-caking agents such as a peptizer, a protective colloid, and a surfactant. Specific examples thereof include polyvalent carboxylic acids such as glycolic acid, gluconic acid, lactic acid, tartaric acid, citric acid, malic acid, and succinic acid; hydroxycarboxylic acids; phosphoric acids such as pyrophosphoric acid and tripolyphosphoric acid; acetylacetone, methyl acetoacetate, Ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate, 2,4-hexanedione, 2,4-heptanedione, 3,5 -A polydentate ligand compound having a strong chelating ability with respect to metal atoms such as heptanedione, 2,4-octanedione, 2,4-nonanedione, 5-methyl-hexanedione, and the like.

As a method of performing a hydrolysis reaction between a metal alkoxide and water, (a) a method of adding water to an organic solvent solution of the metal alkoxide, (b) a metal alkoxide is added to a mixed solvent of water and an organic solvent. Although the method etc. are mentioned, since the metal compound (A) can be obtained with a sufficient yield, the method of (a) is preferable. In particular, 0.5 times to 1.0 times the amount of water with respect to the metal alkoxide is slowly added to a solution in which the metal alkoxide is dissolved or dispersed in an organic solvent at −20 ° C. or lower, and the reaction solution is added. A method in which the temperature is naturally raised (first step) and then refluxed (second step) is particularly preferable.

In the first step, it is considered that the low temperature hydrolysis reaction of the metal alkoxide mainly proceeds. For example, when titanium tetraisopropoxide is used as the metal alkoxide, a dispersion of fine particles having a loose crystal-like cage (chain) structure (metastable structure) is obtained in the first step.

The dropping temperature of water depends on the stability of the metal alkoxide used. Usually, the temperature is −20 ° C. or lower, but depending on the type of metal alkoxide, it may be more preferable to carry out in a temperature range of −50 ° C. to −100 ° C. Thus, by dripping water at low temperature, the dispersion liquid of a particulate metal compound (A) can be obtained.

The dropping time of water depends on the reaction scale and the like, but is usually 10 minutes to 3 hours, preferably 15 minutes to 1 hour. After completion of the dropwise addition, the reaction solution is preferably warmed to room temperature and stirred for 1 to 24 hours for aging.

In the second step, a solution containing the metal compound (A) is obtained by refluxing at the reflux temperature of the organic solvent using the reaction liquid obtained in the first step. In this step, the dropped water is completely used for hydrolysis, and a metal compound (A) is produced by a polycondensation reaction (dehydration and dealcoholization reaction). The reflux time is not particularly limited, but is usually 30 minutes to 5 hours, preferably 1 to 3 hours.

The solution containing the metal compound (A) obtained in the second step is a solution in which fine particles of the metal compound (A) are uniformly dispersed in an organic solvent. The fine particles of the metal compound (A) as a dispersoid are monodisperse having an average particle size of 0.3 to 5 nm, preferably 0.5 to 3 nm, and a particle size distribution of 0.1 to 50 nm.

By allowing the reaction solution obtained in the second step to stand at a temperature of room temperature or lower, crystals of the metal compound (A) are precipitated. This can be isolated by filtering out the precipitated crystals. The isolated metal compound (A) is stable and excellent in dispersibility in various organic solvents.

The metal compound (A) used in the present invention is preferably a titanium compound, and the titanium compound is spatially arranged in a molecule with six titanium atoms located at the apex of a pentagonal pyramid and five titanium compounds. More preferably, it is a titanium compound having a molecular structure including a pentagonal arrangement in which atoms are located at the apexes, and the pentagonal pyramid and the 5P are formed in one molecule through the bottom surface of a pentagonal pyramid (a pentagonal surface). It is more preferable that the squares face each other, and it is particularly preferable that the bottom surface of the pentagon and the pentagons face each other with a certain angle.

The metal compound (A) used in the present invention is preferably such that each metal atom constituting the molecular structure is cross-linked with a cross-linked oxygen atom. The bridging oxygen atom includes a μ ₂ type bridging oxygen atom that binds to only two metal atoms, a μ ₃ type bridging oxygen atom that binds to three metal atoms, and a μ ₄ type bridging oxygen atom that binds to _four metal atoms. The metal compound (A) preferably has at least a μ ₃ type bridging oxygen atom.

The metal compound (A) used in the present invention preferably contains a metal atom in which a metal atom is crosslinked by a bridging oxygen atom and an alkoxy group is bonded.

Specific examples of the metal compound (A) used in the present invention include those described in WO03 / 014022 and Japanese Patent Application No. 2004-258621.

(2) Metal Compound (B) The metal compound (B) used in the present invention hydrolyzes a metal alkoxide at 20 to 90 ° C. using 1.0 to 1.7 times moles of water with respect to the metal alkoxide. Then, the low boiling point substance is distilled off.

Specific examples of the metal alkoxide to be used include those listed as the metal alkoxide used as a raw material in the section of the metal compound (A).

The metal compound (B) hydrolyzed at least one of the metal alkoxides at 20 to 90 ° C. using 1.0 to 1.7 moles of water with respect to the metal alkoxide, and transesterified if necessary. Thereafter, low-boiling substances such as a solvent, by-product alcohol, and unreacted metal alkoxide are obtained by distilling off under reduced pressure. The method for transesterification is not particularly limited, and a known method can be used.

The metal compound (B) used in the present invention is preferably a titanium compound, and particularly preferably a ladder-shaped polytitanoxane represented by the following structural formula (i) or (ii).

上記式（ｉ）及び(ii)中、Ｒは、水素原子及び炭素数１〜１８の炭化水素基よりなる群から選ばれる一種または二種以上である。ただし、水素原子は全Ｒの１５％を超えない。

In said formula (i) and (ii), R is 1 type, or 2 or more types chosen from the group which consists of a hydrogen atom and a C1-C18 hydrocarbon group. However, hydrogen atoms do not exceed 15% of the total R.

Examples of the hydrocarbon group represented by R include alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl; cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl; vinyl, propenyl, and butenyl. Alkenyl groups such as a group; aryl groups such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group; Among these, a C1-C6 alkyl group is preferable.

M and n represent the degree of condensation of the ladder-shaped polytitanoxane. Specifically, m and n each independently represent an integer of 1 to 90. When m and n are in the range of 1 to 90, the titanium compound is soluble in an organic solvent.

The titanium compound having the ladder structure is described in detail in Japanese Patent Application Laid-Open No. 1-129032.

(3) Metal compound (C) The metal compound (C) used in the present invention is 1 to metal alkoxide at −20 ° C. or less in the absence of an acid, a base, and / or a dispersion stabilizer in an organic solvent. It is a dispersoid having a metal-oxygen bond which is obtained by hydrolysis using water of less than 0.0 to 2.0 times mol and stably dispersed without aggregation in an organic solvent.

The metal compound (C) is a dispersoid that is stably dispersed without aggregation in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer. Here, the dispersoid means fine particles dispersed in the dispersion system, and specific examples thereof include colloidal particles.

Examples of the organic solvent in which the dispersoid is dispersed include those exemplified as those capable of dispersing the metal compound (A). Among these, in order to perform the hydrolysis reaction using water at a low temperature as described later, a solvent that has high water solubility and does not solidify at a low temperature is preferable. Specifically, a lower alcohol solvent or an ether solvent. Etc. can be preferably exemplified.

The particle size of the metal compound (C) that is a dispersoid is not particularly limited, but in order to obtain a high transmittance in visible light, the particle size is preferably in the range of 1 to 100 nm, more preferably 1 to 50 nm, Is preferably in the range of 1 to 10 nm.

As the metal alkoxide and the organic solvent used for the production of the metal compound (C), those similar to the metal alkoxide and the organic solvent listed as those used for the production of the metal compound (A) can be used. Of these, titanium alkoxide is preferable as the metal alkoxide.

The metal compound (C) is a metal alkoxide in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer, at −20 ° C. or less, preferably in the range of −50 to −100 ° C. It can manufacture by hydrolyzing using 1.0-2.0 times less water with respect to it.

Moreover, after hydrolyzing at arbitrary temperature using the quantity of water set when manufacturing the said metal compound (A), the quantity of water is further added under the temperature conditions of -20 degrees C or less. By carrying out the reaction, the metal compound (C) can also be produced.

The reaction of metal alkoxide with water is a method of adding water diluted with an organic solvent to an organic solvent solution of metal alkoxide, or adding a metal alkoxide or diluted solution of an organic solvent into an organic solvent in which water is suspended or dissolved. However, a method of adding water later is preferable.

The concentration of the metal alkoxide or water in the organic solvent is not particularly limited as long as it has a fluidity capable of suppressing rapid exotherm and can be stirred, but is usually a concentration range of 5 to 30% by weight of the metal alkoxide. It is preferable to carry out.

The reaction temperature depends on the stability of the metal alkoxide and is not particularly limited as long as it is a temperature of −20 ° C. or lower. However, depending on the type of the metal alkoxide, the addition of water to the metal alkoxide is −50 ° C. to − It may be preferable to carry out in a temperature range of 100 ° C. Furthermore, after adding water at a low temperature and aging for a certain period of time, hydrolysis and dehydration condensation can be further performed at the reflux temperature of the solvent used from room temperature.

By adding water at a low temperature of −20 ° C. or less, the metal alkoxide is hydrolyzed at a high concentration without adding a dispersion stabilizer such as a multidentate coordination compound and stabilizing the metal alkoxide hydrolyzate. -A polymerization reaction can be performed, and a high-concentration dispersion liquid that does not contain unnecessary organic substances such as a multidentate coordination compound can be obtained. Specific examples of the metal compound (C) are described in WO03 / 014022.

(4) Silylated derivative (metal compound (D)) The metal compound (D) used in the present invention is a silylating agent in any of the metal compound (A), the metal compound (B), or the metal compound (C). Is a silylated derivative obtained by reacting The metal compound (D) is preferably a titanium compound.

Examples of the silylating agent to be used include silicon compounds represented by the following formula (3), N, O-bis (trimethylsilyl) acetamide, N, N′-bis (trimethylsilyl) urea, hexamethyldisilazane compounds, and the like. A silicon compound represented by the following formula (3) is preferred.

In formula (3), R ³ represents a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon group containing a linking group, or a halogenated hydrocarbon group containing a linking group, which may have a substituent.

Examples of the hydrocarbon group for R ³ include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and an aryl group.

When R ³ is a hydrocarbon group having a substituent, examples of the substituent of the hydrocarbon group include a carboxyl group, an amide group, an imide group, an ester group, a hydroxyl group, and an epoxy group. The number of substituents in the hydrocarbon group is preferably 1 to 3.

When R ³ is a halogenated hydrocarbon group, a group in which two or more of the hydrogen atoms in the alkyl group are substituted with halogen atoms is preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Of these, a fluorinated alkyl group in which the halogen atom is a fluorine atom is preferable.

When R ³ is a fluorinated alkyl group, a fluorinated alkyl group having a linear structure or a branched structure is more preferable, and a fluorinated alkyl group having a branched structure in which the branched portion is a short chain having about 1 to 4 carbon atoms. Particularly preferred.

When R ³ is a fluorinated alkyl group, R ³ is preferably a fluorinated alkyl group in which one or more fluorine atoms are bonded to the terminal carbon atom, and a CF ₃ group portion in which _three fluorine atoms are bonded to the terminal carbon atom. The fluorinated alkyl group is more preferable.

The number of fluorine atoms in the fluorinated alkyl group is [(number of fluorine atoms in fluorinated alkyl group) / (number of hydrogen atoms present in alkyl group having the same carbon number corresponding to fluorinated alkyl group) × 100]. When expressed in%, 60% or more is preferable, and 80% or more is particularly preferable.

The fluorinated alkyl group has a perfluoroalkyl moiety in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms at the terminal portion, and — (CH ₂ ) _h — (h is 1) between the metal atom and the fluorinated alkyl group. The group in which the group which is an integer of ˜6 and an integer of 2 to 4 is preferable) is preferable. The preferred embodiment of the group is the same when R ³ is a halogenated hydrocarbon group having a substituent or a linking group.

When R ³ is a monovalent hydrocarbon group containing a linking group or a halogenated hydrocarbon group containing a linking group, the linking group may be —O—, —S—, —COO— or —CONR ⁴ — (R ⁴ represents a hydrogen atom or an alkyl group.) And the like. Examples of the bonding position of the linking group include a terminal portion bonded to a carbon atom between a hydrocarbon group or a halogenated hydrocarbon and a metal atom of the hydrocarbon group or the halogenated hydrocarbon group.

Among these, from the viewpoint of water repellency and durability, R ³ is particularly preferably a methyl group, a fluorinated alkyl group, or a fluorinated alkyl group having a linking group. Specific examples of the fluorinated alkyl group having R ³ or a fluorinated alkyl group having a linking group include the following groups.

_{CF 3 -CF 3 CF 2 - (} CF 3) 2 CF- (CF 3) 3 C-CF 3 (CH 2) 2 -CF 3 (CF 2) 3 (CH 2) 2 -CF 3 (CF 2) 5 _{(CH 2) 2 -CF 3 (} CF 2) 7 (CH 2) 2 -CF 3 (CF 2) 3 (CH 2) 3 -CF 3 (CF 2) 5 (CH 2) 3 -CF 3 (CF 2 ) ₇ (CH ₂ ) ₃ —CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ —CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ —CF ₃ (CF ₂ ) ₇ O (CF ₂ ) ₂ (CH ₂ ) ₂ -CF ₃ (CF ₂ ) ₇ CONH (CH ₂ )
_{2 -CF 3 (CF 2) 7} CONH (CH 2) 3 -CF 3 (CF 2) 3 O [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 -

_{CH 3 (CF 2) 7 (} CH 2) 2 -CH 3 (CF 2) 8 (CH 2) 2 -CH 3 (CF 2) 9 (CH 2) 2 -CH 3 (CF 2) 10 (CH 2) _{2 -CH 3 (CF 2) 11} (CH 2) 2 -CH 3 (CF 2) 12 (CH 2) 2 -CH 3 (CF 2) 7 (CH 2) 3 -CH 3 (CF 2) 9 (CH _{2) 3 -CH 3 (CF 2} ) 11 (CH 2) 3 -CH 3 CH 2 (CF 2) 6 (CH 2) 2 -CH 3 CH 2 (CF 2) 8 (CH 2) 2 -CH 3 CH _{2 (CF 2) 10 (CH} 2) 2 -CH 3 (CF 2) 4 O (CF 2) 2 (CH 2) 2 -CH 3 (CF 2) 7 (CH 2) 2 O (CH 2) 3 - _{CH 3 (CF 2) 8 (} CH 2) 2 O (CH 2) 3 -CH _{3 (CF 2) 9 (CH} 2) 2 O (CH 2) 3 -CH 3 CH 2 (CF 2) 6 (CH 2) 2 O (CH 2) 3 -CH 3 (CF 2) 6 CONH (CH 2 ) ₃ —CH ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₃ —CH ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) _m −

In the formula (3), a represents any integer of 0 to 3, and when a is 2 or more, R ³ may be the same or different. In order to form a high-density thin film, a is preferably 1. However, a + b = 4.

X represents a hydroxyl group or a hydrolyzable group. Specifically, a hydroxyl group; an alkoxy group having 1 to 12 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group; hydroxyimino group, hydroxyamino group, enoxy group, amino group, carbamoyl group, etc. Examples thereof include a group containing a nitrogen atom; a halogen atom such as a chlorine atom or a bromine atom;

Specific examples of the compound represented by the formula (3) include trimethylsilanol, triethylsilanol, t-butyldimethylsilanol, triphenylsilanol,

Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrachlorosilane, tetrabromosilane, dimethyl Dichlorosilane, tetrakis (diethylamino) silane, 4-aminobutyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, benzyltrichlorosilane, benzyltriethoxysilane, t-butylphenyldichlorosilane, 2 -Chloroethyltriethoxysilane, 3-chloropropyltrichlorosilane, 8-bromooctyltrichlorosilane, 3-bromopropyltrichlorosilane , (3,3,3-trifluoropropyl) dichlorosilane, (3,3,3-trifluoropropyl) trichlorosilane, chloromethyltrichlorosilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, allyltrichlorosilane, allyltriethoxysilane, vinylmethyldiacetoxysilane, vinylmethylbis (methylethylketoximine) silane, 3- Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrichlorosilane, 3-acryloxypropyltrimethoxysilane,

_{CH 3 CH 2 O (CH 2} ) 15 Si (OCH 3) 3 CF 3 CH 2 O (CH 2) 15 Si (OCH 3) 3 CH 3 (CH 2) 2 Si (CH 3) 2 (CH 2) 15 Si (OCH ₃ ) ₃ CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃ CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃ CF ₃ (CF ₂ ) _{5 (CH 2) 2 Si (} OCH 3) 3 CF 3 (CF 2) 7 - (CH = CH) 3 -Si (OCH 3) 3 CH 3 CH2O (CH 2) 15 Si (OC 2 H 5) 3 CH _{3 (CH 2) 2 Si (} CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3 CH 3 (CH 2) 6 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) ₃ CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃ CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃ CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H) _{5) 3 CF 3 COO (CH} 2) 15 Si (OCH 3) 3 CF 3 (CF 2) 9 (CH 2) 2 Si (OC 2 H 5) 3 CF 3 (CF 2) 7 (CH 2) 2 Si (OC ₂ H ₅ ) ₃ CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OC ₂ H ₅ ) ₃ CF _{3 (CF 2) 9 (CH 2} ) 2 Si (OCH 3) 3 CF 3 (CF 2) 5 (CH 2) 2 Si (OCH 3) 3 CF 3 (CF 2) 7 (CH 2) 2 Si (CH 3 _{) (OC 2 H 5) 2} CF 3 (C _{2) 7 (CH 2) 2} Si (CH 3) (OCH 3) 2 CF 3 (CF 2) 7 (CH 2) 2 Si (CH 3) 2 (OC 2 H 5) CF 3 (CF 2) 7 ( _{CH 2) 2 Si (CH 3} ) 2 (OCH 3)

CF ₃ (CH ₂ ) ₂ SiCl ₃ CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ SiCl ₃ CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ SiCl ₃ CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ SiCl ₃ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ SiCl ₃ CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ SiCl ₃ CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ SiCl ₃ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ SiCl ₃ CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ SiCl ₃ CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ SiCl ₃ CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ SiCl ₃

_{CF 3 (CF 2) 3 (} CH 2) 2 Si (CH 3) Cl 2 CF 3 (CF 2) 5 (CH 2) 2 Si (CH 3) Cl 2 CF 3 (CH 2) 2 Si (CH 3) Cl ₂ CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ CF ₃ (CF
_{2) 4 (CF 2) 2} (CH 2) 3 Si (CH 3) Cl 2 CF 3 (CF 2) 4 (CH 2) 2 O (CH 2) 3 Si (CH 3) Cl 2 CF 3 (CF 2 ₇ CONH (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ CH ₃ (CH ₂ ) ₇ SiCl ₃

_{CH 3 (CF 2) 7 (} CH 2) 2 SiCl 3 CH 3 (CF 2) 7 (CH 2) 2 Si (CH 3) Cl 2 CH 3 (CF 2) 7 (CH 2) 2 Si (OCH 3) ₃ CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (NCO) ₃ CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ SiCl ₃ CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) _{3 CH 3 (CF 2) 8 (} CH 2) 2 Si (NCO) 3 CH 3 (CF 2) 9 (CH 2) 2 SiCl 3 CH 3 (CF 2) 9 (CH 2) 2 Si (OCH 3) 3 CH _{3 (CF 2) 9 (CH} 2) 2 Si (NCO) 3 CH 3 CH 2 (CF 2) 6 (CH 2) 2 SiCl 3 CH 3 CH 2 (CF 2) 6 (CH 2) 2Si (OCH3) 3CH ₃ CH _{(CF 2) 6 (CH 2} ) 2 Si (NCO) 3 CH 3 CH 2 (CF 2) 8 (CH 2) 2 SiCl 3 CH 3 CH 2 (CF 2) 8 (CH 2) 2 Si (OCH 3) ₃ CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) ₃ CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ SiCl ₃ CH ₃ (CF ₂ ) 4 _O (CF ₂ ) ₂ (CH ₂ ) ₂ SiCl ₃ CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ SiCl ₃ CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ O (CH ₂ ) ₃ SiCl ₃ CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ O (CH ₂ ) ₃ SiCl ₃ CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ O (CH ₂ ) ₃ SiCl ₃ CH ₃ (CF ₂ ) ₆ CONH (CH ₂ ) ₃ Si _{l 3 CH 3 (CF 2)} 8 CONH (CH 2) 3 SiCl 3 CH 3 (CF 2) 3 O [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 SiCl ₃

The silylating agent need not be a monomolecular compound typified by the compound represented by the formula (3). For example, the compound represented by the formula (3) or the like can be obtained using the same method or the like. The obtained partially hydrolyzed polycondensation product may be used. In this case, the partially hydrolyzed polycondensation product refers to a condensate in a state before becoming a metal oxide state.

The addition amount of the silylating agent is not particularly limited, but for the metal compound (A), the metal compound (B) or the metal compound (C) (hereinafter, these may be collectively referred to as “metal compound”), Usually, it is 0.01-10 times mole, Preferably it is 0.1-1.0 times mole.

In the silylation reaction, a predetermined amount of a silylating agent is added to a reaction solution for preparing a metal compound or a solution in which a metal compound is dissolved or dispersed in an organic solvent, and the temperature is in a temperature range from 0 ° C. to the boiling point of the solvent used. , By stirring for several minutes to several tens of hours.

As described above, the metal compound (D) (silylated derivative) can be obtained. The structure of the resulting metal compound (D) can be determined and confirmed by known analytical means such as NMR spectrum measurement, mass spectrum measurement, and molecular weight measurement.

The metal compound (D) of the present invention is a novel substance, and has a high refractive index and transparency. As will be described later, an organic-inorganic composite useful as an optical material or the like can be obtained by compounding with a polymer. Can be manufactured.

(5) Inorganic polymer The inorganic polymer constituting the inorganic component of the organic-inorganic composite of the present invention is obtained from at least one of the metal compound (A), metal compound (B) or metal compound (D) described above. . The inorganic polymer can be obtained by polycondensation of at least one of the metal compound (A), the metal compound (B), or the metal compound (D) as described later.

(6) Organic Component The organic component of the organic-inorganic composite of the present invention is not particularly limited as long as it can be combined with the inorganic polymer to form an organic-inorganic composite. Examples thereof include acrylic resins, polyurethane resins, polythiourethane resins, resins mainly composed of diethylene glycol bisallyl carbonate, and resins obtained from epithio group-containing compounds.

Examples of acrylic resins include homopolymers composed of one type of acrylic monomer, copolymers composed of two or more types of acrylic monomers, copolymers of acrylic monomers and monomers copolymerizable with acrylic monomers, etc. Is mentioned.

Examples of acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth ) Monofunctional (meth) acrylic esters such as cyclohexyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate;

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin di (meth) acrylate, 2,2-bis [4-((meth) acryloxy) phenyl] propane, 2, And polyfunctional (meth) acrylic acid esters such as 2-bis [4-((meth) acryloxyethoxy) phenyl] propane; (meth) acrylamide derivatives such as (meth) acrylamide; and the like. Here, (meth) acryl means either acrylic or methacrylic (the same applies hereinafter).

Examples of monomers copolymerizable with acrylic monomers include styrene monomers such as styrene, methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene, divinylbenzene, α-methylstyrene; acrylonitrile Nitrile monomers such as methacrylonitrile; unsaturated carboxylic acid anhydrides such as maleic anhydride; unsaturated carboxylic acid amides such as N-substituted maleimide; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hydrogenated bisphenol A Epoxy monomers such as diglycidyl ether; acryloyl morpholine, methacryloyl morpholine, 2,2-bis [4- (acryloxy) phenyl] propane, 2,2-bis [4- (methacryloxy) Butoxy) phenyl] acryloyl monomers such as propane; N- vinylpyrrolidone and vinyl-based monomer; diallyl phthalate, diallyl isophthalate, allyl compounds such as diallyl terephthalate; and the like, etc. can be mentioned and the like.

The polyurethane-based resin is a resin obtained by a reaction between a polyisocyanate compound and a polyhydroxy compound, and the polythiourethane resin is a resin obtained by a reaction between a polyisocyanate compound and a polythiol compound.

The polyisocyanate compound is not particularly limited, and specific examples thereof include the following. Hydrogenated 2,6-tolylene diisocyanate, hydrogenated meta and paraphenylene diisocyanate, hydrogenated 2,4-tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated metaxylylene diisocyanate, hydrogenated paraxylylene diisocyanate, isophorone diisocyanate, etc. Alicyclic isocyanate compounds of: meta and paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, meta and paraxylylene diisocyanate, meta and para tetra Isocyanate compounds having an aromatic ring such as methylxylylene diisocyanate, 2,6-naphthalene diisocyanate, 1,5-naphthalene diisocyanate; hexamethylene dii Sorbate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate burette reaction product; hexamethylene diisocyanate trimer, lysine diisocyanate, lysine triisocyanate, 1,6,6 11-undecane triisocyanate triisocyanate compound having no alicyclic ring or aromatic ring such as triphenylmethane triisocyanate;

Diphenyl disulfide-4,4′-diisocyanate, 2,2′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3, 3′-dimethyldiphenyl disulfide-6,6′-diisocyanate, 4,4′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethoxydiphenyl disulfide-4,4′-diisocyanate Narate, 4,4′-dimethoxydiphenyldisulfide-3,3′-diisocyanate, diphenylsulfone-4,4′-diisocyanate, diphenylsulfone-3,3′-diisocyanate, benzylidenesulfone-4,4 '-Diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldi Phenylmethanesulfone-2,4′-diisocyanate, 4,4′-dimethoxydiphenylsulfone-3,3′-diisocyanate, 3,3′-dimethoxy-4,4′-diisocyanatodibenzylsulfone, 4,4′-dimethyldiphenylsulfone-3,3′-diisocyanate, 4,4′-di-tert-butyldiphenylsulfone-3,3′-diisocyanate, 4,4′-dimethoxybenzeneethylene disulfone 3,3′-diisocyanate, 4,4′-dichlorodiphenylsulfone-3,3′-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester, 4-methoxy- 3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester, 4-methyl-3-isocyanatobenzenesulfo Nilanilide-3′-methyl-4′-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4′-diisocyanate, 4,4′-dimethoxybenzenesulfonyl-ethylenediamine-3,3′-diisocyanate, 4- Methyl-3-isocyanatobenzenesulfonylanilide-4-methyl-3'-isocyanate, thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanatomethyl, 1,4-dithiane-2,5 -Diisocyanate, 1,4-dithian-2,5-diisocyanatomethyl, 1,4-dithian-2,3-diisocyanatomethyl, 1,4-dithian-2-isocyanatomethyl-5-isocyanate Natopropyl, 1,3-dithiolane-4,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanatomethi 1,3-dithiolane-2-methyl-4,5-diisocyanatomethyl, 1,3-dithiolane-2,2-diisocyanatoethyl, tetrahydrothiophene-2,5-diisocyanate, tetrahydrothiophene-2 , 5-diisocyanatomethyl, tetrahydrothiophene-2,5-diisocyanatoethyl, tetrahydrothiophene-3,4-diisocyanatomethyl and the like;

Polyhydroxy compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, pentaerythritol, diethylene Pentaerythritol, tripentaerythritol, triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, bicyclo [4,3,0] -Nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, (Ii) aliphatic polyols such as [3,4] octanediol, butylcyclohexanediol; dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, Aromatic polyols such as tetrabromobisphenol A;

Addition reaction product of aliphatic polyol or aromatic polyol and alkylene oxide such as ethylene oxide or propylene oxide; bis- [4- (hydroxyethoxy) phenyl] sulfide, bis- [4- (2-hydroxypropoxy) Phenyl] sulfide, bis- [4- (2,3-dihydroxypropoxy) phenyl] sulfide, bis- [4- (4-hydroxycyclohexyloxy) phenyl] sulfide, bis- [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide and compounds obtained by adding an average of 3 molecules or less of ethylene oxide and / or propylene oxide per hydroxyl group to these compounds;

Di- (2-hydroxyethyl) sulfide, 1,2-bis- (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithian-2,5-diol, bis (2, 3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone (trade name bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4′-thiobis Polyols containing sulfur atoms such as (6-tert-butyl-3-methylphenol), 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane; and the like.

Polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexane Dithiol, 1,2,3-propanetrithiol, tetrakis (mercaptomethyl) methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4- Dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimerca 1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1, 2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2- Mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol Tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethyl thio) -3 aliphatic thiols such as mercapto propane;

1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethoxy) benzene, 1,3-bis (mercaptomethoxy) benzene 1,4-bis (mercaptomethoxy) benzene, 1,2-bis (mercaptoethoxy) benzene, 1,3-bis (mercaptoethoxy) benzene, 1,4-bis (mercaptoethoxy) benzene, 1,2,3 -Trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptoben 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercapto) Ethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethoxy) benzene, 1,2,4-tris (Mercaptomethoxy) benzene, 1,3,5-tris (mercaptomethoxy) benzene, 1,2,3-tris (mercaptoethoxy) benzene, 1,2,4-tris (mercaptoethoxy) benzene, 1,3,5 -Tris (mercaptoethoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercap Benzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4 5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercapto) Ethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptomethoxy) benzene, 1,2,4,5-tetrakis (mercaptomethoxy) benzene, 1 , 2,3,4-Tetrakis (mercaptoethoxy) benzene, 1,2,3,4-tetrakis (mercaptoethoxy) Benzene, 1,2,4,5-tetrakis (mercaptoethoxy) benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluene Dithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2, 2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane Aromatic thiols;

2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, 2,3 Halogen-substituted aromatic thiols such as chlorine-substituted products and bromine-substituted products such as 1,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene;

1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (Mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5 -Tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5-the Lakis (mercaptomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethyl) Thio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene and the like, and aromatic thiols containing sulfur atoms in addition to mercapto groups such as these nuclear alkylated products;

Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, 1,2, -Bis (mercaptomethylthio) ethane, 1,2- (2-mercaptoethylthio) ethane, 1,2- (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis ( 2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 2-mercaptoethylthio-1,3- Propanedithiol, 1,2,3-tris (mercaptomethylthio) propyl Bread, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) ) Methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) Disulfides, bis (mercaptopropyl) disulfides and the like, and esters of these thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate) ), Hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), Hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl Disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ester -Terbis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5 -Diol bis (3-mercaptopropionate), thioglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4'-thiodibutyric acid bis (2-mercaptoethyl ester) ), Dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 4,4′-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodi Bis (2,3-dimercaptopropyl ester) ropionate, bis (2,3-dimercaptopropyl ester) dithiodiglycolate, dithiodipropionic acid (2,3-dimercaptopropyl ester), 4-mercaptomethyl- Mercapto groups such as 3,6-dithiaoctane-1,8-dithiol, bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol, bis (1,3-dimercapto-2-propyl) sulfide In addition to aliphatic thiols containing sulfur atoms;

3,4-thiophenedithiol, tetrahydrothiophene-2,5-dimercaptomethyl, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,4-dithiane, 2,5-dimercapto And heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as methyl-1,4-dithiane.

Among the polyurethane resins and / or polythiourethane resins, those used as lens base materials are conventionally known. Specific examples of known publications disclosing this include, for example, JP-A-58-127914, JP-A-57-136601, JP-A-01-163012 and JP-A-03-236386. JP, 03-283121, JP 04-159275, JP 05-148340, JP 06-065193, JP 06-256459, JP 06-313801, JP-A-06-192250, JP-A-07-063902, JP-A-07-104101, JP-A-07-118263, JP-A-07-118390, JP-A-07-316250, JP JP 60-199016, JP 60-217229, JP 62-236818, JP 62-255901, JP 62-267316, JP 63-130615, JP 63-130614, JP 63-046213, JP 63-245421 JP, 63-265201, JP 01-090167, JP 01-090168, JP 01-090169, JP 01-090170, JP 01-096208. JP-A-01-152019, JP-A-01-045611, JP-A-01-213601, JP-A-01-026622, JP-A-01-054021, JP-A-01-31118, Kohei 01-295201, JP-A-01-302202, JP-A-02-153302 JP-A-01-295202, JP-A-02-802, JP-A-02-032161, JP-A-02-058517, JP-A-02-167330, JP-A-02-270859, Japanese Unexamined Patent Publication Nos. 03-84031, 03-084021, 03-124722, 04-78801, 04-117353, 04-117354, 04 JP-A-256558, JP-A-05-78441, JP-A-05-273401, JP-A-05-09801, JP-A-05-080201, JP-A-05-297201, JP-A-05-320301. JP, 05-208950, JP 06-072989, JP JP-A-06-256342, JP-A-06-122748, JP-A-07-165859, JP-A-07-118357, JP-A-07-242722, JP-A-07-247335, JP-A-07. -252341, JP-A-08-73732, JP-A-08-092345, JP-A-07-228659, JP-A-08-3267, JP-A-07-252207, JP-A-07-324118. And Japanese Patent Application Laid-Open No. 09-208651.

Examples of the resin mainly composed of diethylene glycol bisallyl carbonate include a homopolymer of diethylene glycol bisallyl carbonate and a copolymer obtained by reacting diethylene glycol bisallyl carbonate with a copolymerizable monomer.

Examples of the monomer copolymerizable with diethylene glycol bisallyl carbonate include the acrylic monomers, acryloyl monomers, styrene monomers, nitrile monomers, unsaturated acid anhydrides, unsaturated acid amides, and allyl compounds.

Copolymers of diethylene glycol bisallyl carbonate and other monomers are known. Examples thereof include JP 54-41965 A, JP 51-125487 A, and JP 01-503809 A. Are described in the above.

The resin obtained from the epithio group-containing compound is a resin obtained by polymerizing a monomer having an epithio group or a monomer mixture containing the monomer as a raw material.

Examples of the monomer having an epithio group include 1,3 and 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4 -(Β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, etc. An episulfide compound having an alicyclic skeleton;

1,3 and 1,4-bis (β-epithiopropylthio) benzene, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β-epithiopropylthio) ) Phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithio) An episulfide compound having an aromatic skeleton such as propylthio) phenyl] sulfine and 4,4-bis (β-epithiopropylthio) biphenyl;

2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, 2,5-bis ( episulfide compounds having a dithian ring skeleton such as β-epithiopropylthioethyl) -1,4-dithian, 2,3,5-tri (β-epithiopropylthioethyl) -1,4-dithiane;

2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-epithiopropylthio) propane, 1,2-bis [(2-β-epithiopropylthioethyl) thio]- 3- (β-epithiopropylthio) propane, tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, bis- (β-epithiopropyl) ) Epithio compounds having an aliphatic skeleton such as sulfide;

Of the resins obtained from epithio group-containing compounds, those used as plastic lens substrates are conventionally known. Specific examples thereof include JP 09-071580, JP 09-110979, JP 09-255781, JP 03-081320, JP 11-140070, and JP 11-11. No. 183702, JP-A-11-189592, JP-A-11-180977, JP-T-01-810575, and the like.

Moreover, the radical polymer which has a urethane structure or a thiourethane structure in a molecule | numerator can be illustrated as another example. Specific examples of such a polymer include a linear alkane compound having 3 to 6 carbon atoms having at least two mercapto groups in the molecule, at least one isocyanate group and at least one (meta ) A radical polymer using a monomer obtained by reacting a compound having an acryloyl group can be exemplified. The (meth) acryloyl group means both an acryloyl group and a methacryloyl group.

Examples of linear alkane compounds having 3 to 6 carbon atoms having at least two mercapto groups in the molecule, which is one of the raw materials for radically polymerizable compounds having a thiourethane bond, include 1,2,3-trimethyl Mercaptopropane, 1,2,3-trimercaptobutane, 1,2,4-trimercaptobutane, 1,2,3,4-tetramercaptobutane, 1,2,3-trimercaptopentane, 1,2,4 -Trimercaptopentane, 1,2,3,4-tetramercaptopentane, 1,2,3-trimercaptohexane, 1,2,4-trimercaptohexane, 1,2,5-trimercaptohexane, 2,3 , 4-trimercaptohexane, 2,3,5-trimercaptohexane, 3,4,5-trimercaptohexane, 1,2,3,4-tetramercaptohexane 1,2,3,5-tetramercaptohexane, 1,2,4,5-tetramercaptohexane, 2,3,4,5-tetramercaptohexane, 1,2,3,4,5-pentamercaptohexane, etc. Is mentioned.

Examples of another raw material having at least one isocyanate group and at least one (meth) acryloyl group in the molecule include acryloyl isocyanate, methacryloyl isocyanate, 2-isocyanatoethyl acrylate, 2-isocyanato Examples include ethyl methacrylate, 2-isocyanatopropyl acrylate, and 2-isocyanatopropyl methacrylate.

The polymerization reaction is carried out using a known radical or cationic polymerization initiator when the organic monomer is a radical or cationic polymerizable organic monomer. When the organic monomer is an organic monomer capable of polyaddition or polycondensation, polymerization is carried out by adding a known amine compound or organometallic compound.

Among the catalysts for the polyaddition or polycondensation reaction, dibutyltin dichloride and dibutyltin dilaurate are particularly preferable. These catalysts may be used alone or in combination of two or more. In addition, when performing radical photopolymerization, a well-known sensitizer can also be added for the reactivity improvement.

The polymerization reaction can be performed by either solution polymerization or bulk polymerization, and the polymerization can be performed by heating or irradiating a mixture of an organic component and an inorganic component.

(7) Production of organic-inorganic composite As a method for producing the organic-inorganic composite of the present invention, a metal compound (A), a metal compound (B) or a metal compound (D) and an organic monomer are mixed. The organic polymer is polymerized to form an organic polymer, and at the same time, the metal compound (A), the metal compound (B), or the metal compound (D) is polycondensed to form an inorganic polymer. A method for obtaining a body: a metal compound and an organic polymer are mixed, and the metal compound (A), the metal compound (B), or the metal compound (D) is polycondensed to form an inorganic polymer. And the like.

More specifically, (i) a method in which an organic polymer and a metal compound (A), a metal compound (B) or a metal compound (D) are mixed in an organic solvent or in a bulk and processed by molding; (ii) an organic solvent A method in which a metal compound (A), a metal compound (B) or a metal compound (D) is prepared, an organic monomer is added, solution polymerization or bulk polymerization is performed, and (iii) a metal in an organic solvent. An alkoxide and an organic monomer are mixed, and a predetermined amount of water is added for hydrolysis to prepare an organic monomer and a metal compound (A), a metal compound (B), or a metal compound (D), and solution polymerization Or (iv) a method of forming by processing by bulk polymerization, (iv) a method of mixing an organic polymer and a metal alkoxide in an organic solvent, adding a predetermined amount of water to perform hydrolysis, and (v) a metal. Compound (A), Organic solvent containing organic polymer in organic solvent solution containing metal compound (B) or metal compound (D) (or reaction solution prepared from metal compound (A), metal compound (B) or metal compound (D)) Examples thereof include a method of dropping and mixing the solution and molding.

In the above method (iii), when a polycondensate is used as the organic polymer, the monomer unstable to water is prepared as a metal compound (A), a metal compound (B) or a metal compound (D). It is preferable to add after this.

Since the organic-inorganic composite of the present invention has a high refractive index and a high visible light transmittance, it is preferably used as an optical material. The optical material includes an ultraviolet absorber, a dye, a pigment, etc. for improving light absorption characteristics, an antioxidant, an anti-coloring agent, etc. for improving weather resistance, A release agent or the like can be appropriately added as desired. Here, examples of the ultraviolet absorber include benzotriazole, benzophenone, and salicylic acid, and examples of the dye and pigment include anthraquinone and azo. Examples of antioxidants and anti-coloring agents include monophenol-based, bisphenol-based, polymer-type phenol-based, sulfur-based, and phosphorus-based agents, and examples of mold release agents include fluorine-based surfactants and silicone-based surfactants. , Acidic phosphates, higher fatty acids and the like.

The optical material obtained from the organic-inorganic composite of the present invention is a raw material for producing optical products such as optical plastic lenses such as spectacle lenses, prisms, optical fibers, recording medium substrates, filters, and glass and vases. Useful. Among these, the optical material obtained from the organic-inorganic composite of the present invention is suitably used for optical plastic lenses, particularly spectacle lenses.

In addition, the optical material of the present invention is applied to the surface of a lens or glass without performing cast polymerization, and is hardened by performing an operation such as light irradiation as necessary to protect the surface, It can also be used as a raw material for a multilayer antireflection film for preventing reflection. The application method is not particularly limited, and any method such as dip coating, spin coating, flow coating, roller coating, and brush coating can be employed.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.

(Production Example 1) Four-necked flask with 100 g (0.35 mol) of titanium tetraisopropoxide (manufactured by Nippon Soda Co., Ltd., trade name: A-1, purity 99.9%, titanium oxide equivalent concentration 28% by weight) The solution was dissolved in 370 g of toluene (manufactured by Nacalai Tesque), purged with nitrogen gas, and then cooled in a methanol bath to which dry ice was added, and the temperature was set to -20 ° C. Separately prepared a mixed solution of 5.73 g (H ₂ 0 / Ti = 0.9 mol / mol) of distilled water (collected from ADBANTEC GS-200) diluted with 51.7 g of isopropyl alcohol (manufactured by Nacalai Tesque) The mixture was added dropwise over 30 minutes while stirring at 25 to -20 ° C. After completion of the dropwise addition, the reaction solution was continuously stirred and gradually heated to room temperature over 1.5 hours, and further refluxed at 80 ° C. for 2.5 hours to obtain a colorless and transparent sol solution. Next, white crystals precipitated from the reaction solution were collected by filtration and dried in vacuo.

The obtained crystals were subjected to ¹ H-NMR and ¹³ C-NMR measurements and X-ray structural analysis. The obtained crystals were dissolved in C ₆ D ₆ and ¹ H-NMR and ¹³ C-NMR spectra were measured as internal standard TMS. The measured ¹ H-NMR chart is shown in FIG. 1, and the ¹³ C-NMR chart is shown in FIG. 1 and 2, the horizontal axis represents the chemical shift (δppm).

The crystal structure and molecular structure of the obtained crystal were determined by measurement using a rapid single crystal X-ray analyzer (Rigaku R-AXIS RAPID). The final R value in the structural analysis refinement was 4%. Composition formula: C ₅₄ H ₁₂₆ O ₃₁ Ti ₁₁ · C ₇ H ₈ (Molecular weight = 1890.58) Crystal system: orthorhombic system (Pca2 ₁ ) Lattice constants: a = 26.40ｂ, b = 14.23Å, c = 24.00Å, α = β = γ = 90 °, Z = 4

From the above measurement results, the obtained crystal has a unit containing 4 molecules in which 18 isopropoxy groups are bonded to a cage structure (cage-like titania) in which 11 titanium atoms are bridged by oxygen atoms. The cell was found to exist. The cage-like titania spatially includes an arrangement in which six titanium atoms are located at the apex of a pentagonal pyramid and an arrangement consisting of a pentagon in which five titanium atoms are located at the apex, and the bottom of the pentagonal pyramid and the pentagonal shape are It had a structure that faced and faced at an angle of about 36 °. This structure is shown in FIG. In FIG. 3, 1 represents a titanium atom, and 2 represents an oxygen atom. The crystal obtained as described above is defined as a titanium compound (A1).

(Production Example 2) 284 g (1 mol) of titanium tetraisopropoxide (manufactured by Nippon Soda Co., Ltd., trade name: A-1, purity 99.9%, titanium oxide equivalent concentration 28% by weight) was charged into a four-necked flask. The mixture was heated and held at 80 ° C. with good mixing. Into this, a mixed solution of 27 g of water and 405 g of isopropanol was gradually added, and then the temperature was raised to 85 ° C. and stirred for 1 hour under reflux to ripen the reaction. After cooling the reaction solution, the solvent isopropanol was removed using a rotary evaporator, and the low boiling point product was distilled using a vacuum pump to obtain a white solid substance. The molecular weight of the obtained white solid substance was measured by the freezing point depression method, and the results of elemental analysis were as follows.

で示されるラダー状ポリチタノキサンと推定された。 以上のようにして得られた結晶をチタン化合物（Ｂ１）とする。

It was presumed to be a ladder-like polytitanoxane represented by The crystal obtained as described above is defined as a titanium compound (B1).

Production Example 3 Titanium tetraisopropoxide (A-1 manufactured by Nippon Soda Co., Ltd .: purity 99.9%, titanium oxide equivalent concentration 28% by weight) 7.87 g (27.7 mmol) in a four-necked flask After dissolving in tetrahydrofuran and substituting with nitrogen gas, the solution was cooled in a methanol bath (about −74 ° C.) to which dry ice was added. After cooling for about 20 minutes, distilled water diluted with tetrahydrofuran (0.8 g as distilled water: 44.4 mmol) was added with stirring. At this time, the total weight of tetrahydrofuran was 32.12 g. The amount of water added at this time is H ₂ O / Ti = 1.6 molar ratio. Then, when the temperature was gradually returned to room temperature, a pale yellow transparent tetrahydrofuran solution containing a hydrolyzate of titanium isopropoxide was obtained. The solution obtained as described above is used as a dispersion of titanium compound (C1).

(Example 1) 1.89 g of crystals of the titanium compound (A1) and 7.1 g (18 mol) of octadecyltrimethoxysilane were dissolved in 20 ml of toluene, and the whole volume was stirred at reflux for 3 hours. The reaction solution was cooled to room temperature, washed with saturated brine, and separated three times. After drying the organic layer from anhydrous sodium sulfate, the solvent toluene was removed using a rotary evaporator, and the low boiling point was distilled using a vacuum pump to obtain a white solid substance. The obtained white substance is a silylated derivative of the titanium compound (A1). This is referred to as a titanium compound (D1).

(Example 2) In Example 1, except that the titanium compound (B1) is used in place of the titanium compound (A1), a silylation reaction is performed using octadecyltrimethoxysilane in the same manner as in Example 1, and the titanium compound ( A silylated derivative of B1) was obtained. This is referred to as a titanium compound (D2).

(Example 3) In Example 1, except that the titanium compound (C1) is used instead of the titanium compound (A1), a silylation reaction is performed using octadecyltrimethoxysilane in the same manner as in Example 1, and the titanium compound ( A silylated derivative of C1) was obtained. This is referred to as a titanium compound (D3).

(Example 4) 1.89 g of crystals of the titanium compound (A1) and 2.38 g (18 mol) of t-butyldimethylsilanol were dissolved in 20 ml of toluene and refluxed for 2 hours. After cooling the reaction solution to room temperature, the solvent toluene was removed using a rotary evaporator, and the low-boiling product was distilled using a vacuum pump to obtain a white solid substance. The solid material was further washed with isopropyl alcohol. Let the obtained compound be a titanium compound (D4).

(Example 5) In Example 4, a silylation reaction was performed using t-butyldimethylsilanol in the same manner as in Example 4 except that the titanium compound (B1) was used instead of the titanium compound (A1), and the titanium compound was used. A silylated derivative of (B1) was obtained. This is referred to as a titanium compound (D5).

(Example 6) In Example 4, except that the titanium compound (C1) is used in place of the titanium compound (A1), a silylation reaction is performed using t-butyldimethylsilanol in the same manner as in Example 4 to obtain a titanium compound. A silylated derivative of (C1) was obtained. This is referred to as a titanium compound (D6).

(Example 7) 52.42 g of tetrahydrofuran was added to 0.29 g of the crystal of the titanium compound (A1), and dissolved by stirring. On the other hand, 1.61 g of 2,5-bismercapto-1,4-dithiane (BMMD), 1.61 g of 2,5- (bisisocyanatomethyl) -1,4-dithiane (BIMD) and dibutyltin dilaurate A solution obtained by adding 04 g to 8.03 g of tetrahydrofuran was shaken and stirred in a hot bath at 60 ° C. for 1 hour to prepare a tetrahydrofuran solution containing a polymer of BMMD and BIMD. Next, a predetermined amount of this tetrahydrofuran solution was added dropwise over 10 minutes to the tetrahydrofuran solution containing the crystals of the titanium compound (A1). After completion of the dropwise addition, 40.33 g of tetrahydrofuran was further added to this solution, followed by stirring, whereby an organic polymer containing a titanium compound (A1) as a starting material as an inorganic component and a polymer of BMMD and BIMD as an organic component was used.
A clear solution containing an inorganic composite was obtained.

Using this transparent solution, a transparent thin film was formed by spin coating on a 30 mm × 15 mm silicon wafer. The refractive index, average Abbe number, and film thickness at a wavelength of 587.6 nm of this thin film were measured with a measuring device (SENTECH SE800). The measurement results are shown in Table 1.

(Example 8) In Example 7, the inorganic polymer using the titanium compound (B1) as a starting material was inorganic in the same manner as in Example 7 except that the titanium compound (B1) was used instead of the titanium compound (A1). As a component, a transparent solution containing an organic-inorganic composite containing a polymer of BMMD and BIMD as an organic component was obtained.

Using this transparent solution, a transparent thin film was formed by spin coating on a 30 mm × 15 mm silicon wafer. The refractive index, average Abbe number, and film thickness at a wavelength of 587.6 nm of this thin film were measured with a measuring device (SENTECH SE800). The measurement results are shown in Table 1.

(Example 9) In Example 7, an inorganic polymer using a titanium compound (C1) as a starting material was inorganic in the same manner as in Example 7 except that the titanium compound (C1) was used instead of the titanium compound (A1). As a component, a transparent solution containing an organic-inorganic composite containing a polymer of BMMD and BIMD as an organic component was obtained.

Using this transparent solution, a transparent thin film was formed by spin coating on a 30 mm × 15 mm silicon wafer. The refractive index, average Abbe number, and film thickness at a wavelength of 587.6 nm of this thin film were measured with a measuring device (SENTECH SE800). The measurement results are shown in Table 1.

（実施例１０） 実施例１で得たチタン化合物（Ａ１）１ｇにトルエン１８９ｇを加え攪拌し溶解した。他方、ポリメチルメタクリレート（ＰＭＭＡ）（和光純薬社製、Ｃａｔ．Ｎｏ．１３８−０２７３５）１ｇにトルエン９ｇを加え溶解させた。両液を所定割合になるように混合し、室温で１時間攪拌することにより、チタン化合物（Ａ１）から得られた無機高分子を無機成分とし、ＰＭＭＡを有機成分とする有機−無機複合体を含有する透明溶液を得た。

(Example 10) To 1 g of the titanium compound (A1) obtained in Example 1, 189 g of toluene was added and stirred to dissolve. On the other hand, 9 g of toluene was added to 1 g of polymethyl methacrylate (PMMA) (manufactured by Wako Pure Chemicals, Cat. No. 138-02735) and dissolved. An organic-inorganic composite containing the inorganic polymer obtained from the titanium compound (A1) as an inorganic component and PMMA as an organic component by mixing both liquids at a predetermined ratio and stirring at room temperature for 1 hour. A clear solution containing was obtained.

Using this transparent solution, a transparent thin film was formed by spin coating on a 30 mm × 15 mm silicon wafer. The thickness of the thin film was 20-30 nm. The refractive index at 587.6 nm of this thin film was measured with a measuring device (SENTECH SE800). The measurement results are shown in FIG.

In FIG. 4, the horizontal axis represents the addition ratio (% by weight) of the titanium compound (A1), and the vertical axis represents the refractive index (nd) of the thin film at a wavelength of 587.6 nm. The refractive index when the addition ratio (wt%) of the titanium compound (A1) is 0 wt% (the leftmost in FIG. 4) is the refractive index of PMMA, and the addition ratio (wt%) of the titanium compound (A1) is 100. The refractive index of weight% (the rightmost end in FIG. 4) represents the refractive index of the thin film of inorganic polymer obtained from the titanium compound (A1).

(Example 11) In Example 10, it replaces with a titanium compound (A1), and except using a titanium compound (D5), it carries out similarly to Example 10, and makes the inorganic polymer obtained from the titanium compound (D5) inorganic. A transparent solution containing an organic-inorganic composite containing PMMA as an organic component was obtained.

(Example 11) In Example 10, it replaces with a titanium compound (A1), and except using a titanium compound (D6), it carries out similarly to Example 9, and makes the inorganic polymer obtained from the titanium compound (D6) inorganic. A transparent solution containing an organic-inorganic composite containing PMMA as an organic component was obtained.

1 is a ¹ H-NMR chart of a titanium compound (A1) crystal obtained in Example 1. FIG. 1 is a ¹³ C-NMR chart of a titanium compound (A1) crystal obtained in Example 1. FIG. 1 is a view showing a molecular structure constituting a unit cell of a titanium compound (A1) crystal obtained in Example 1. FIG. The content ratio (horizontal axis: wt%) of the titanium compound (A1) in the organic-inorganic composite obtained in Example 10 and 587 of the thin film formed from the transparent solution containing this organic-inorganic composite. It is a graph which shows the relationship with the refractive index in 6 nm (vertical axis: nd).

Claims (4)

  An organic-inorganic composite comprising an inorganic component and an organic component, wherein the inorganic component is a metal alkoxide in the presence of (A) an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer. A dispersoid having a metal-oxygen bond obtained by hydrolysis using 0.5 to 1 times less mole of water than the alkoxide and stably dispersed without agglomerating in an organic solvent, or (B) a metal An inorganic polymer obtained from a metal compound obtained by hydrolyzing an alkoxide at 20 to 90 ° C. using 1.0 to 1.7 moles of water with respect to the metal alkoxide and then distilling off a low-boiling point substance. An organic-inorganic composite characterized in that   An organic-inorganic composite comprising an inorganic component and an organic component, wherein the inorganic component is a metal alkoxide in the presence of (A) an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer. A dispersoid having a metal-oxygen bond, which is obtained by hydrolysis using less than 0.5 to 1 mol of water relative to the alkoxide, and stably dispersed without agglomeration in an organic solvent, (B) metal alkoxide A metal compound obtained by hydrolyzing at 20 to 90 ° C. using 1.0 to 1.7 moles of water with respect to the metal alkoxide, and then distilling off the low boiling point substance, or (C) an organic solvent In the presence of acid, base, and / or dispersion stabilizer in the presence of 1.0 to 2.0 times less than the molar amount of water relative to the metal alkoxide at -20 ° C or lower, Metal-oxygen bonds stably dispersed without aggregation in organic solvents To one of the dispersoid having, characterized in that an inorganic polymer obtained silyl derivative obtained by reacting a silylating agent organic - inorganic composite.   The organic component is at least one selected from the group consisting of acrylic resins, polyurethane resins, polythiourethane resins, resins mainly composed of diethylene glycol bisallyl carbonate, and resins obtained from epithio group-containing compounds. The organic-inorganic composite according to claim 1 or 2.   (A) It is obtained by hydrolyzing a metal alkoxide in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer using 0.5 to 1 times less water than the metal alkoxide. A dispersoid having a metal-oxygen bond that is stably dispersed without agglomerating in an organic solvent, and (B) 20 to 20 times the metal alkoxide in an amount of 1.0 to 1.7 times moles of water. -20 ° C. or lower in the absence of an acid, base and / or dispersion stabilizer in a metal compound obtained by hydrolysis at −90 ° C. and then distilling off the low boiling point substance, or (C) an organic solvent The dispersoid having a metal-oxygen bond obtained by hydrolysis using 1.0 to less than 2.0 moles of water with respect to the metal alkoxide and stably dispersed without agglomeration in an organic solvent. One of them is a silylation catalyst obtained by reacting with a silylating agent. Body.

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