KR20090061659A - Oxide fine particle-containing organic-inorganic hybrid polymer composition and method for producing the same - Google Patents

Abstract

Disclosed is an oxide fine particle-containing organic-inorganic hybrid polymer composition, which is obtained by mixing (A) a silicon oxide fine particle and/or a metal oxide fine particle with (B) an organic-inorganic hybrid polymer, which is obtained by a hydrolysis/condensation reaction of at least one silane compound (b1) selected from the group consisting of at least one organosilane represented by the formula (1) below, hydrolysis products of the organosilane and condensation products of the organosilane, and a polymer (b2) having a silyl group containing a silicon atom bonded with a hydrolyzable group and/or a hydroxyl group, in an organic solvent in the presence of a basic compound, an acidic compound or a metal chelate compound, thereby dispersing the oxide fine particle (A) into the organic solvent. R1nSi(OR2)4-n (1) (In the formula, R1 represents a monovalent organic group having 1-8 carbon atoms; R2 represents an alkyl group having 1-5 carbon atoms or an acyl group having 1-6 carbon atoms; and n represents an integer of 0-2.)

Description

OXIDE FINE PARTICLE-CONTAINING ORGANIC-INORGANIC HYBRID POLYMER COMPOSITION AND METHOD FOR PRODUCING THE SAME

The present invention relates to an organic inorganic hybrid polymer composition in which silicon oxide fine particles and / or metal oxide fine particles are highly dispersed in an organic solvent comprising an organic inorganic hybrid polymer and a cured body thereof.

Conventionally, as a means for imparting various functions to a siloxane material having excellent durability, a binder having a siloxane skeleton (hereinafter also referred to as a "siloxane-based binder"), silicon oxide fine particles and various metal oxide fine particles (hereinafter, these are collectively referred to as "oxides" Complex with the fine particles " At this time, the siloxane binder and the oxide fine particles are often manufactured in the form of a dispersion containing them. By the way, since a siloxane binder is hard to melt | dissolve in water, it is necessary to use the organic solvent as a dispersion medium, On the other hand, since oxide fine particles are easy to aggregate in an organic solvent, it disperse | distributes in a water medium in many cases. For this reason, in order to finely disperse oxide fine particles in an organic solvent, phosphoric acid having an organic group having 6 or more carbon atoms, sulfonic acid or carboxylic acid (see Patent Document 1 below), an organic compound having an oxyalkylene group, a phosphoric acid having an oxyalkylene group, or the like It was necessary to use ester (refer patent document 2 below) or the silane compound (refer patent document 3) which has an oxyalkylene group.

However, in the method of finely dispersing the oxide fine particles in an organic solvent using these compounds, when the oxide fine particles and the siloxane binder are combined, the dispersibility of the dispersion is good, but the compatibility between the compound and the siloxane binder is poor, For example, when a solvent was removed and a coating film was formed, the coating film might whiten. In addition, even when controlling the film forming conditions and the like to form a transparent coating film, phosphoric acid and the like having an oxyalkylene group and a compound having an organic group having 6 or more carbon atoms remain in the coating film. There was a case.

On the other hand, although the silicon oxide fine particles have an organic solvent dispersion which maintains dispersibility at its surface charge, the dispersion has good dispersion stability, but when mixed with a siloxane binder, the silicon oxide fine particles aggregate and whiten or crack. This may occur.

Moreover, when the dispersion liquid containing a silane monomer and oxide fine particles was previously manufactured, and this silane monomer was hydrolyzed and condensed, and the siloxane binder was formed, the dispersion liquid obtained was low and transparency of the coating film was also low (patent document 3 of FIG. See comparative example).

This problem is not an exception in the case where the organic inorganic hybrid polymer is used as the siloxane binder and complexed with the oxide fine particles, and a transparent coating can not be obtained while having the function of the oxide fine particles.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-283822

Patent Document 2: Japanese Patent Laid-Open No. 2005-185924

Patent Document 3: Japanese Patent Laid-Open No. 2004-99879

<Start of invention>

Problems to be Solved by the Invention

The present invention is intended to solve the problems according to the prior art as described above, and a polysiloxane-based cured body having various functions and excellent transparency and outdoor weather resistance, and an organic-inorganic hybrid polymer composition in which oxide fine particles are highly dispersed, from which such a cured body is obtained. And its production method.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said problem, the present inventors hydrolyzed and condensed the polymer which has a silyl group containing the silicon atom couple | bonded with a silane compound, a hydrolysable group, and / or a hydroxyl group previously, and manufactured an organic inorganic hybrid polymer, In the organic solvent containing this organic inorganic hybrid polymer, in the presence of a basic compound, an acidic compound, or a metal chelate compound, an oxide fine particle is processed, and the organic inorganic inorganic particle in which the oxide fine particle was highly disperse | distributed in the organic solvent containing an organic inorganic hybrid polymer It discovered that a hybrid polymer composition was obtained, and also found that the hardened | cured material obtained from this composition was excellent in transparency and weather resistance, and also excellent in flexibility and traceability to a base material, and came to complete this invention.

That is, the oxide fine particle-containing organic inorganic hybrid polymer composition according to the present invention is in the presence of a basic compound, an acidic compound or a metal chelate compound in an organic solvent.

(A) silicon oxide fine particles and / or metal oxide fine particles, and

(B) at least one silane compound (b1) selected from the group consisting of at least one organosilane represented by the following formula (1), a hydrolyzate of the organosilane and a condensate of the organosilane, and a hydrolyzable group And / or an organic-inorganic hybrid polymer obtained by hydrolyzing and condensing a polymer (b2) having a silyl group containing a silicon atom bonded to a hydroxyl group, is obtained by dispersing the oxide fine particles (A) in an organic solvent. do.

R ¹ _n Si (OR ² ) _4-n

(Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two are present, they may be the same or different from each other, and R ² is each independently an alkyl group having 1 to 5 carbon atoms or 1 to 6 carbon atoms). Acyl group, n is an integer of 0 to 2)

It is preferable to mix the said oxide fine particle (A) and the said organic inorganic hybrid polymer (B) in presence of a basic compound.

It is preferable to mix the said oxide fine particle (A) and the said organic inorganic hybrid polymer (B) with a bead mill.

It is preferable to mix 1-1000 weight part of said organic inorganic hybrid polymers (B) in conversion of a complete hydrolysis condensate with respect to 100 weight part of said oxide fine particles (A).

The weight ratio (Wb1 / Wb2) of the silane compound (b1) and the polymer (b2) to the content (Wb1) of the total hydrolysis condensate conversion of the silane compound (b1) and the content (Wb2) of the solid content conversion of the polymer (b2) It is preferable to hydrolyze and condense in the range of 5/95 to 95/5 (but Wb1 + Wb2 = 100).

In the said polymer (b2), it is preferable that content of the silyl group containing the silicon atom couple | bonded with the hydrolysable group and / or the hydroxyl group is 0.1-2 weight% in conversion to silicon atom content.

The cured product according to the present invention is obtained from the oxide fine particle-containing organic inorganic hybrid polymer composition.

Coating composition according to the invention is characterized in that it comprises the oxide fine particle-containing organic inorganic hybrid polymer composition.

The laminate according to the present invention is characterized by having an organic substrate and a coating film obtained from the coating composition provided on the organic substrate.

Effect of the Invention

According to the present invention, a composition in which oxide fine particles are highly dispersed in an organic solvent containing an organic inorganic hybrid polymer is obtained without using phosphoric acid having an organic group having 6 or more carbon atoms or a compound having an oxyalkylene group. This composition is excellent in dispersion stability and can form the transparent hardened | cured material containing an oxide fine particle and the said organic inorganic hybrid polymer. Since this hardened | cured material does not contain the said compound substantially, even if it is left to stand in the environment irradiated with the ultraviolet-ray, such as outdoors for a long time, it is hard to yellow. Moreover, it is excellent in flexibility and followability with respect to a base material by the action of the said organic inorganic hybrid polymer. . Moreover, hardened | cured material using zinc oxide fine particles, cerium oxide fine particles, and rutile titanium oxide fine particles as oxide fine particles is useful as a material of an ultraviolet cut.

Best Mode for Carrying Out the Invention

The oxide fine particle-containing organic inorganic hybrid polymer composition according to the present invention contains the oxide fine particle (A) and the organic inorganic hybrid polymer (B) in an organic solvent without using phosphoric acid or the like having an organic group having 6 or more carbon atoms or a compound having an oxyalkylene group. It can obtain by mixing in presence of a basic compound, an acidic compound, or a metal chelate compound, and performing a dispersion process.

[Oxide Fine Particles (A)]

The oxide fine particles (A) used in the present invention are silicon oxide fine particles and / or metal oxide fine particles. The metal oxide fine particles are not particularly limited as long as the metal oxide fine particles are oxide fine particles of a metal element, but for example, antimony oxide, zirconium oxide, anatase titanium oxide, rutile titanium oxide, brookite titanium oxide, zinc oxide, and tantalum oxide Indium oxide, hafnium oxide, tin oxide, niobium oxide, aluminum oxide, cerium oxide, scandium oxide, yttrium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, The metals such as holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, ruthetium oxide, calcium oxide, gallium oxide, lithium oxide, strontium oxide, tungsten oxide, barium oxide, magnesium oxide and their complexes, and indium-tin composite oxide Metal oxide fine particles, such as an oxide of 2 or more types of composites, are mentioned. Moreover, as said oxide fine particle (A), the oxide fine particle which coat | covered the surface of the composite oxide fine particle of a silicon oxide and a metal oxide with the metal oxide fine particle with silicon oxide can also be used.

In this invention, an oxide fine particle can also be used individually by 1 type or in mixture of 2 or more types. The oxide fine particles (A) can be appropriately selected according to the function to be imparted, but, for example, TiO ₂ fine particles are preferable in the case of providing high refractive index, and ZrO _{2 in} the case of achieving both transparency and high refractive index in the ultraviolet region. Fine particles are preferred. Moreover, when providing a UV cut function, cerium oxide fine particles and zinc oxide fine particles are preferable. Moreover, when giving electroconductivity, antimony oxide dope tin oxide fine particle and indium-tin type | system | group composite oxide fine particle are preferable.

The primary average particle diameter of the oxide fine particles (A) is preferably 0.1 to 100 nm, more preferably 0.1 to 70 nm, particularly preferably 0.1 to 50 nm. If the primary average particle diameter of oxide fine particles (A) exists in the said range, the hardened | cured material excellent in light transmittance can be obtained.

Such oxide fine particles (A) may be added in a state of powder not dispersed in a solvent or in a state of dispersion dispersed in a polar solvent such as isopropyl alcohol or in a nonpolar solvent such as toluene. The oxide fine particles (A) before the addition may be aggregated to form secondary particles. In the present invention, in view of the solubility of the organic inorganic hybrid polymer (B), an appropriate organic solvent can be appropriately selected, and it is preferable to use powder. Moreover, the manufacturing method of this invention is especially effective when adding in the state of powder.

[Organic Inorganic Hybrid Polymer (B)]

The organic-inorganic hybrid polymer (B) used in the present invention is prepared by hydrolysis and condensation reaction of a specific silane compound (b1) and a polymer (b2) containing a specific silyl group. More specifically, it is prepared by adding a catalyst and water for promoting the hydrolysis-condensation reaction to a mixture containing the silane compound (b1) and the polymer (b2) containing a silyl group.

(Silane compound (b1))

The silane compound (b1) used for this invention is organosilane (henceforth "organosilane (1)") represented by following formula (1), the hydrolyzate of organosilane (1), and organosilane (1 At least one silane compound selected from the group consisting of condensates, and among these three silane compounds, only one silane compound may be used, or any two kinds of silane compounds may be mixed and used, or Three types of all silane compounds can also be mixed and used. In addition, when organosilane (1) is used as a silane compound (b1), organosilane (1) may be used by 1 type | mold k or may use 2 or more types together. In addition, the hydrolyzate and condensate of the said organosilane (1) may be formed from 1 type of organosilane (1), or may be formed using 2 or more types of organosilane (1) together.

<Formula 1>

R ¹ _n Si (OR ² ) _4-n

(Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two are present, they may be the same or different from each other, and R ² is each independently an alkyl group having 1 to 5 carbon atoms or 1 to 6 carbon atoms). Acyl group, n is an integer of 0 to 2)

The hydrolyzate of the organosilane (1) may be hydrolyzed at least one of the OR ² groups contained in the organosilane (1) 2 to 4, for example, one OR ² group is hydrolyzed Or two or more OR ² groups hydrolyzed, or a mixture thereof.

The condensate of the organosilane (1) is a condensation of silanol groups in the hydrolyzate produced by the hydrolysis of the organosilane (1) to form a Si-O-Si bond. In the present invention, it is not necessary that all of the silanol groups are condensed, and the condensate is a condensed product of at least some of the silanol groups, most of the silanol groups (including all), and mixtures thereof. Include.

In Formula 1, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl Alkyl groups such as groups, t-butyl groups, n-hexyl groups, n-heptyl groups, n-octyl groups, and 2-ethylhexyl groups;

Acyl groups such as an acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group and caproyl group;

Vinyl group, allyl group, cyclohexyl group, a phenyl group, an epoxy group, glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, an isocyanate group, etc. are mentioned.

Moreover, as R <^1> , the substituted derivative of the said organic group, etc. are mentioned. As a substituent of the substituted derivative of R <^1> , a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, glycidoxy group, 3, 4- epoxycyclohexyl group, (meth) acryloxy group, urea Pottery, ammonium base, etc. are mentioned. However, the number of carbon atoms of R ¹ composed of these substituted derivatives is preferably 8 or less including carbon atoms in the substituent. When a plurality of R ¹ 's are present in Formula 1, they may be the same or different.

As R <^2> which is a C1-C5 alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group etc. are mentioned, for example. As R <^2> which is a C1-C6 acyl group, an acetyl group, a propionyl group, butyryl group, valeryl group, a caproyl group, etc. are mentioned, for example. In the case where a plurality of R ² 's are present in Formula 1, they may be the same or different.

Specific examples of such organosilanes (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane. (N = 0 in Formula 1); Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i- Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyl Remethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane , 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- ( Trialkoxysilanes such as (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane (n = 1 in Formula 1);

Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di -i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimeth Methoxysilane, di-n-hexyl diethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyl diethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di- dialkoxysilanes (n = 2 in the formula 1) such as n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane;

Methyl triacetyloxysilane (n = 1 in Formula 1), dimethyldiacetyloxysilane (n = 2 in Formula 1), etc. are mentioned.

In these, the trifunctional silane compound whose n = 1 in General formula (1) is mainly used. In view of the stability of the organic-inorganic hybrid polymer composition according to the present invention, the trifunctional silane compound is preferably used in combination with a bifunctional silane compound having n = 2. Trialkoxysilanes are particularly preferable as the trifunctional silane compound, and dialkoxysilanes are preferable as the bifunctional silane compound.

In the case of using the trifunctional silane compound and the bifunctional silane compound together, the trifunctional silane compound / 2 functional silane compound is preferably 95/5 to 10/90, more preferably, in terms of the weight ratio of the respective fully hydrolyzed condensates. Is 90/10 to 30/70, particularly preferably 85/15 to 40/60. However, the sum (complete hydrolysis condensate conversion) of a trifunctional silane compound and a bifunctional silane compound shall be 100. When the content of the trifunctional silane compound is too high, the dispersibility of the oxide fine particles may be inferior in that it becomes easy to aggregate, and when the content of the trifunctional silane compound is too small, the functional groups required for the dispersion of the oxide fine particles decrease. The dispersibility of oxide fine particles may be inferior. In addition, in this specification, a complete hydrolysis condensate means that the -OR group of a silane compound hydrolyzes 100%, becomes a SiOH group, and also fully condenses and becomes a siloxane structure.

In this invention, although 1 type of organosilane (1) may be used independently as a silane compound (b1), 2 or more types of organosilane (1) can also be used together. When two or more kinds of organosilanes (1) used as the silane compound (b1) are averaged and represented by the above formula (1), the averaged n (hereinafter also referred to as "average value of n") is preferably 0.5 to 1.9, more preferably. Preferably from 0.6 to 1.7, particularly preferably from 0.7 to 1.5. When the average value of n is less than the said minimum, the storage stability of an organic-inorganic hybrid polymer composition may fall, and when exceeding the said upper limit, the curability of a hardened | cured material (coating film) may be inferior.

The average value of n can be adjusted to the said range by using together the bifunctional to tetrafunctional silane compound suitably, and adjusting the compounding ratio suitably.

This also applies to the case where a hydrolyzate or a condensate is used as the silane compound (b1).

In this invention, although organosilane (1) can also be used as a silane compound (b1), the hydrolyzate and / or condensate of organosilane (1) can be used. When organosilane (1) is used as a hydrolyzate and / or a condensate, what was produced by previously hydrolyzing and condensing organosilane (1) can also be used, but will be mentioned later as an organic-inorganic hybrid polymer (B) It is preferable to add water, hydrolyze and condense the organosilane (1) and water to prepare the hydrolyzate and / or condensate of the organosilane (1).

As for the condensate of the said organosilane (1), the weight average molecular weight (henceforth "Mw") of polystyrene conversion measured by the gel permeation chromatography method (GPC method) becomes like this. Preferably it is 300-100,000, More preferably, Is 500 to 50,000.

When using the condensate of organosilane (1) as a silane compound (b1) in this invention, you may manufacture from the said organosilane (1), and may use the condensate of the organosilane commercially available. . Commercially available condensates of organosilanes include MKC silicates manufactured by Mitsubishi Chemical Corporation, ethyl silicates manufactured by Cole Coat, silicone resins manufactured by Toray Dow Corning Silicone Co., Ltd., and silicones manufactured by GE Toshiba Silicone Co., Ltd. Resins, silicone resins and silicone oligomers manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group-containing polydimethylsiloxanes manufactured by Dow Corning Asia Co., Ltd. and silicone oligomers manufactured by Nippon Unicar Co., Ltd .; These commercially available condensates of organosilanes may be used as they are or may be used by condensation.

(Silyl group-containing polymer (b2))

A polymer (b2) containing a specific silyl group (hereinafter, also referred to as a "specific silyl group-containing polymer (b2)") used in the present invention is a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter "specific" Silyl group ”). It is preferable that this specific silyl group containing polymer (b2) has a specific silyl group in the terminal and / or side chain of a polymer molecular chain.

When the hydrolyzable group and / or hydroxyl group in this specific silyl group co-condense with the said silane compound (b1), an organic-inorganic hybrid polymer (B) is formed and this organic-inorganic hybrid polymer (B) and oxide fine particles (A ) Is mixed and dispersed in the presence of a basic compound, an acidic compound or a metal chelate compound in an organic solvent, whereby the oxide fine particles (A) are highly dispersed in the organic solvent. This is condensed on the surface of the oxide fine particles (A) by a catalytic action such as a basic compound by hydrolysis and / or hydroxyl groups in the specific silyl group remaining in the organic inorganic hybrid polymer (B), and the surface of the oxide fine particles (A) It is guessed because it becomes hydrophobic and it becomes easy to disperse | distribute an oxide fine particle (A) in an organic solvent.

The content of the specific silyl group in the specific silyl group-containing polymer (b2) is usually 0.1 to 2% by weight, preferably 0.3 to 1.7% by weight, based on the amount of silicon atoms, relative to the polymer before introducing the specific silyl group. If the specific silyl group content in the specific silyl group-containing polymer (b2) is less than the lower limit, the specific silyl group remaining in the covalent bonding site with the silane compound (b1) or the organic inorganic hybrid polymer (B) decreases. , The effect of the mixed dispersion treatment may not be obtained. On the other hand, when the said upper limit is exceeded, gelation may arise at the time of storage of a composition.

It is preferable that the said specific silyl group is group represented by following formula (3).

(Wherein X represents a hydrolyzable group or hydroxyl group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxy group, an amino group, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or 1 to C carbon atoms). 10 aralkyl group, i is an integer of 1 to 3)

Such specific silyl group containing polymer (b2) can be manufactured by the method of following (I) and (II), for example.

(I) A hydrosilane compound having a specific silyl group represented by the formula (3) (hereinafter simply referred to as "hydrosilane compound (I)") is a vinyl polymer having a carbon-carbon double bond (hereinafter referred to as "unsaturated vinyl polymer To the carbon-carbon double bond in the above).

(II) A method of copolymerizing a silane compound represented by the following formula (4) (hereinafter referred to as "unsaturated silane compound (II)") and another vinyl monomer.

(Wherein, X, R ^5, i are each and X, R ^5, i and consent for Formula 3, R ⁶ represents an organic group having a polymerizable double bond)

As hydrosilane compound (I) used for the method of said (I), For example, Halogenated silanes, such as methyldichlorosilane, trichlorosilane, phenyldichlorosilane; Alkoxysilanes such as methyldimethoxysilane, methyldiethoxysilane, phenyldimethoxysilane, trimethoxysilane and triethoxysilane; Acyloxysilanes, such as methyldiacetoxysilane, phenyl diacetoxysilane, and triacetoxysilane; Aminooxysilanes, such as methyl diamine silane, a triamioxy silane, and dimethyl-aminooxysilane, etc. are mentioned. These hydrosilane compounds (I) can be used individually or in mixture of 2 or more types.

In addition, the unsaturated vinyl polymer used for the method of said (I) will not be specifically limited if it is other than the polymer which has a hydroxyl group, For example, the method of following (I-1), (I-2), or a combination thereof, etc. It can manufacture.

(I-1) After (co) polymerizing a vinyl monomer having a functional group (hereinafter referred to as "functional group (α)"), the functional group (α) in the (co) polymer may react with the functional group (α). A method of producing an unsaturated vinyl polymer having a carbon-carbon double bond in the side chain of the polymer molecular chain by reacting a functional group (hereinafter referred to as "functional group (β)") with an unsaturated compound having a carbon-carbon double bond. .

(I-2) A radical polymerization initiator (for example, 4,4'-azobis-4-cyano valeric acid or the like) having a functional group (α) is used, or a functional group is used for both the radical polymerization initiator and the chain transfer agent. Using a compound having (α) (for example, 4,4'-azobis-4-cyanovaleric acid, dithioglycolic acid, and the like), vinyl-based monomers are (co) polymerized to form one of the polymer molecular chains. After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or a chain transfer agent at one or both ends, the functional group (β) and a carbon-carbon double bond are bonded to the functional group (α) in the (co) polymer. A method of producing an unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of the polymer molecular chain by reacting an unsaturated compound having a compound.

As reaction of functional group ((alpha)) and functional group ((beta)) in the method of (I-1) and (I-2), for example, esterification reaction of a carboxyl group and a hydroxyl group, ring-opening esterification of a carboxylic anhydride group and a hydroxyl group Reaction, ring-opening esterification reaction of carboxyl group and epoxy group, amidation reaction of carboxyl group and amino group, ring-opening amidation reaction of carboxylic anhydride group and amino group, ring-opening addition reaction of epoxy group and amino group, urethanization reaction of hydroxyl group and isocyanate group, these Combinations of reactions, and the like.

As a vinyl monomer which has a functional group ((alpha)), For example, unsaturated carboxylic acids, such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; Unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxyethyl vinyl ether Hydroxyl group-containing vinyl monomers such as these; Amino group-containing vinyl monomers such as 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 2-aminoethyl vinyl ether; 1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylic Imide, 1,1-dimethyl-1- (2'-phenyl-2'-hydroxyethyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2'-hydroxy-2'- Amine imide group-containing vinyl monomers such as phenoxypropyl) amine (meth) acrylimide; And epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate and allyl glycidyl ether. The vinyl monomer which has these functional groups ((alpha)) can be used individually or in mixture of 2 or more types.

As another vinylic monomer copolymerizable with the vinylic monomer which has a functional group ((alpha)), for example, styrene, (alpha) -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2 -Hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene Aromatic vinyl monomers such as 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, and 1-vinylnaphthalene;

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, amyl (meth) acrylate, i-amyl ( (Meth) acrylate compounds, such as meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, and cyclohexyl methacrylate;

Divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylic Rate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanedioldi (meth) acrylate, hexanedioldi (meth) acrylate, trimethyl Polyfunctional monomers such as all propane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate;

(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N'-methylenebisacrylamide, diacetone Acid amide compounds such as acrylamide, maleic acid amide and maleimide;

Vinyl compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl esters;

1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2 Aliphatic conjugated dienes such as substituted straight chain conjugated pentadienes substituted with substituents such as -cyano-1,3-butadiene, isoprene, alkyl group, halogen atom and cyano group, and linear and branched conjugated hexadiene;

Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;

Fluorine atom-containing monomers such as trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate;

4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- Piperidine monomers such as (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine;

2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methacryloxyethylphenyl) Ultraviolet absorbing monomers such as -2H-benzotriazole, 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone, and 2-hydroxy-4- (acryloyloxyethoxy) benzophenone;

Dicaprolactone etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

As an unsaturated compound which has a functional group ((beta)) and a carbon-carbon double bond, for example, the vinyl monomer same as the vinyl monomer which has a functional group ((alpha)), and the said hydroxyl-containing vinyl monomer and a diisocyanate compound are made to react by equimolar. Isocyanate group containing unsaturated compound obtained, etc. are mentioned.

Moreover, as unsaturated silane compound (II) used for the method of said (II),

Can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

Moreover, as another vinylic monomer copolymerized with an unsaturated silane compound, the vinylic monomer which has a functional group ((alpha)) illustrated in the method of said (I-1), another vinylic monomer, etc. are mentioned, for example.

As a manufacturing method of the said specific silyl group containing polymer (b2), for example, the method of superposing | polymerizing by adding each monomer collectively, the method of superposing | polymerizing by adding the remainder continuously or intermittently after superposing | polymerizing a part of monomers, Or the method of continuously adding a monomer from the start of superposition | polymerization, etc. are mentioned. Moreover, these polymerization methods can also be combined.

Solution polymerization is mentioned as a preferable polymerization method. The solvent used for the solution polymerization is not particularly limited as long as it can produce a specific silyl group-containing polymer (b2). Examples thereof include alcohols, aromatic hydrocarbons, ethers, ketones, and esters. Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, Triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, diacetone alcohol, etc. are mentioned. Examples of the aromatic hydrocarbons include benzene, toluene and xylene, and ethers include tetrahydrofuran and dioxane. Ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and the like. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate. Can be. These organic solvents may be used individually by 1 type, or may mix and use 2 or more types.

In addition, in the said polymerization, a well-known thing can be used for a polymerization initiator, a molecular weight modifier, a chelating agent, and an inorganic electrolyte.

In this invention, other specific silyl group containing polymers, such as a specific silyl group containing epoxy resin and a specific silyl group containing polyester resin, besides the specific silyl group containing polymer superposed | polymerized as mentioned above as specific silyl group containing polymer (b2), Can also be used. The specific silyl group-containing epoxy resin is, for example, in epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic polyglycidyl ether and aliphatic polyglycidyl ester. The epoxy group can be produced by reacting aminosilanes having a specific silyl group, vinylsilanes, carboxysilanes, glycidylsilanes and the like. Moreover, the said specific silyl group containing polyester resin can be manufactured by making aminosilane, carboxysilane, glycidylsilane, etc. which have a specific silyl group, for example in the carboxyl group and hydroxyl group contained in a polyester resin. .

Mw of polystyrene conversion measured by the GPC method of a specific silyl group containing polymer (b2) becomes like this. Preferably it is 2,000-100,000, More preferably, it is 3,000-50,000.

In this invention, a specific silyl group containing polymer (b2) can be used individually or in mixture of 2 or more types.

(catalyst)

In the present invention, a catalyst is added to the mixture of the silane compound (a) and the specific silyl group-containing polymer (b) in order to promote the hydrolysis and condensation reaction of the silane compound (b1) or the specific silyl group-containing polymer (b2). It is desirable to. By adding a catalyst, the crosslinking degree of the organic-inorganic hybrid polymer (B) obtained can be raised, and the molecular weight of the polysiloxane produced | generated by the polycondensation reaction of organosilane (1) becomes large, As a result, strength, long-term durability, etc. This excellent cured product can be obtained, and the thickening and coating of the coating film also becomes easy. In addition, the addition of the catalyst promotes the reaction between the silane compound (b1) and the specific silyl group-containing polymer (b2) to form a reaction site (alkoxy group) sufficient for the organic inorganic hybrid polymer (B). When the organic inorganic hybrid polymer (B) and the oxide fine particles (A) are mixed and dispersed in an organic solvent in the presence of a basic compound or the like, the oxide fine particles (A) are highly dispersed in the organic solvent. It is assumed that this is because the organic inorganic hybrid polymer (B) is condensed on the surface of the oxide fine particles (A), the surface of the oxide fine particles (A) becomes hydrophobic, and the oxide fine particles (A) are easily dispersed in the organic solvent. .

As a catalyst used in order to accelerate such hydrolysis and condensation reaction, a basic compound, an acidic compound, a salt compound, and a metal chelate compound are mentioned, for example.

(Basic compound)

Examples of the basic compound include alkoxides of alkali metals such as ammonia (including aqueous ammonia solution), organic amine compounds, sodium hydroxide and potassium hydroxide, alkali earth metal hydroxides, and alkali metals such as sodium methoxide and sodium ethoxide. have. Among them, ammonia and organic amine compounds are preferred.

Examples of the organic amines include alkylamines, alkoxyamines, alkanolamines, and arylamines.

Alkylamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutyl And alkylamines having an alkyl group having 1 to 4 carbon atoms such as amine, trimethylamine, triethylamine, tripropylamine, and tributylamine.

Examples of the alkoxy amine include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxy And alkoxyamines having an alkoxy group having 1 to 4 carbon atoms such as ethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine and butoxybutylamine.

Alkanolamines include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, and N-ethylethanol Amine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N -Dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine, N, N-diethylpropanolamine, N , N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine, N, N -Dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N- Propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyl Dibutanolamine, N-propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl ) Butanolamine, N- (aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methanolamine, N -(Aminopropyl) ethanolamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (ami Butyl) ethanolamine, N- (aminobutyl) propanol amine, N- (aminobutyl) butanol alkanolamine having an alkyl group of 1 to 4 carbon atoms such as an amine.

Examples of the arylamines include aniline and N-methylaniline.

Moreover, as organic amine of that excepting the above, Tetraalkyl ammonium hydroxide, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; Tetraalkylethylenediamines such as tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine and tetrabutylethylenediamine; Methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylaminobutylamine, propylaminomethylamine, propylaminoethylamine, Alkylaminoalkylamines such as propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine and butylaminobutylamine; Polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-phenylenediamine and p-phenylenediamine; Pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene and the like.

These basic compounds may be used individually by 1 type, or may mix and use 2 or more types. Among them, triethylamine, tetramethylammonium hydroxide and pyridine are particularly preferred.

(Acid compound)

Examples of the acidic compound include organic acids and inorganic acids. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, methylmalonic acid, adipic acid, and sebacic acid. , Lactic acid, butyric acid, melic acid, arachidonic acid, sikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, Dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, methanesulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like. As said inorganic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, etc. are mentioned, for example.

These acidic compounds may be used individually by 1 type, or may mix and use 2 or more types. Among these, maleic acid, maleic anhydride, methanesulfonic acid and acetic acid are particularly preferable.

(Salt compound)

Examples of the salt compound include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminic acid, and carbonic acid.

(Metal chelate compound)

As said metal chelate compound, an organometallic compound and / or its partial hydrolyzate (henceforth an organic metal compound and / or its partial hydrolyzate are collectively called "organic metal compounds") are mentioned.

As said organometallic compounds, for example

A compound represented by the following formula a (hereinafter referred to as "organic metal compound (a)"),

M (OR ⁷ ) _r (R ⁸ COCHCOR ⁹ ) _s

(Wherein M represents one or more metal atoms selected from the group consisting of zirconium, titanium and aluminum, and R ⁷ and R ⁸ are each independently a methyl group, an ethyl group, n-propyl group, i-propyl group, n- C1-C6 monovalent hydrocarbon groups, such as a butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, a cyclohexyl group, and a phenyl group, R <^9> is said C1-C6 Monovalent hydrocarbon groups or methoxy groups, ethoxy groups, n-propoxy groups, i-propoxy groups, n-butoxy groups, sec-butoxy groups, t-butoxy groups, lauryloxy groups, stearyloxy groups, etc. An alkoxyl group having 1 to 16 carbon atoms, r and s are each independently an integer of 0 to 4, satisfying the relationship of (r + s) = (valence of M))

An organometallic compound of tetravalent tin in which 1 to 10 alkyl groups of 1 to 10 carbon atoms are bonded to one tin atom (hereinafter referred to as an "organic tin compound"), or

These partial hydrolysates etc. are mentioned.

Moreover, as organometallic compounds, tetraalkoxy titanium, such as tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxytitanium, tetra-n-butoxy titanium; Methyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, i-propyltriethoxysilane, n-hexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, 3 -Chloropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) -aminopropyltrimethoxysilane, 3- (2-aminoethyl) -Aminopropyltriethoxysilane, 3- (2-aminoethyl) -aminopropylmethyldimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimeth Trialkoxysilanes such as oxysilane, 3-glycidoxypropyltriethoxysilane and 3-ureidopropyltrimethoxysilane; Dimethyldiethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-octyldiethoxysilane, di-n Titanium alcoholate, such as dialkoxysilanes, such as -cyclohexyl dimethoxysilane and diphenyldimethoxysilane, and its condensate can be used.

As the organometallic compound (a), for example, tetra-n-butoxy zirconium, tri-n-butoxy ethylacetoacetate zirconium, di-n-butoxy bis (ethylacetoacetate) zirconium, n-part Organic zirconium compounds such as oxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium and the like;

Tetra-i-propoxytitanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium Organic titanium compounds such as;

Tri-i-propoxy aluminum, di-i-propoxy ethylacetoacetate aluminum, di-i-propoxy acetylacetonato aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy Organic aluminum compounds such as bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonate bis (ethylacetoacetate) aluminum.

As an organotin compound, for example

Carboxylic acid type organic tin compounds, such as these;

Mercaptied organic tin compounds such as these;

Sulfide type organic tin compounds such as these;

Chloride type organic tin compounds such as these;

Reaction products of organic tin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and ester compounds such as these organic tin oxides and silicates, dimethyl maleate, diethyl maleate, and dioctyl phthalate;

Etc. can be mentioned.

These metal chelate compounds may be used individually by 1 type, or may mix and use 2 or more types. Among them, tri-n-butoxy ethylacetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-i-propoxy ethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum Or these partial hydrolysates are preferred.

The catalyst may also be used in combination with a zinc compound or other reaction retardant.

The amount of the catalyst used is usually 0.001 to 100 parts by weight, preferably 100 parts by weight of the silane compound (b1) (in terms of complete hydrolysis condensate of the organosilane (1)) when the catalyst is other than organometallic compounds. It is preferably 0.01 to 80 parts by weight, more preferably 0.1 to 50 parts by weight. When the catalyst is an organometallic compound, it is usually 100 parts by weight or less, preferably 0.1 to 80 parts by weight, based on 100 parts by weight of the silane compound (b1) (in terms of fully hydrolyzed condensate of the organosilane (1)), More preferably, it is 0.5-50 weight part. When the usage-amount of the said catalyst exceeds the said upper limit, the storage stability of a composition may fall, or the crosslinking degree of an organic-inorganic hybrid polymer (B) may become high too much.

(water)

In the present invention, water is added to the mixture of the silane compound (b1) and the specific silyl group-containing polymer (b2), and the silane compound (b1) and the specific silyl group-containing polymer (b2) are co-condensed to form an organic-inorganic hybrid polymer (B ) Is preferred.

The amount of water added at this time is usually 0.1 to 1.0 mol, preferably 0.2 to 0.8 mol, and more preferably 0.25 to 0.6 mol with respect to 1 mol of all the OR ² groups in the silane compound (b1). If the amount of water added is in the above range, gelation is unlikely to occur, and the composition exhibits good storage stability. Moreover, when the addition amount of water exists in the said range, the organic-inorganic hybrid polymer (B) fully crosslinked is obtained, and the hardened | cured material excellent in mechanical strength can be obtained by using the composition containing such an organic-inorganic hybrid polymer (B).

(Organic solvent)

In the present invention, the silane compound (b1) and the specific silyl group-containing polymer (b2) can also be subjected to hydrolysis and condensation reaction in an organic solvent. Under the present circumstances, the organic solvent used at the time of manufacture of the said silyl group containing polymer (b2) can be used as it is. Moreover, in order to adjust solid content concentration at the time of organic-organic hybrid polymer (B) manufacture, you may add an organic solvent as needed. Moreover, the organic solvent used at the time of manufacture of the said silyl group containing polymer (b2) can be removed, and an organic solvent can also be added newly.

The organic solvent is such that the solid concentration in the preparation of the organic inorganic hybrid polymer (B) is preferably in the range of 10 to 60% by weight, more preferably 15 to 50% by weight, particularly preferably 20 to 40% by weight. Can be added. In addition, when the solid content concentration at the time of manufacturing an organic-inorganic hybrid polymer (B) is in the said range using the organic solvent used at the time of manufacture of the said silyl group containing polymer (b2) as it is, an organic solvent may or may not be added. have.

The reactivity of a silane compound (b1) and a specific silyl group containing polymer (b2) can be adjusted by adjusting solid content concentration at the time of manufacturing an organic inorganic hybrid polymer (B). When solid content concentration at the time of organic-inorganic hybrid polymer (B) manufacture becomes less than the said minimum, the reactivity of a silane compound (b1) and a specific silyl group containing polymer (b2) may fall. It may gelatinize when solid content concentration at the time of organic-organic hybrid polymer (B) manufacture exceeds the said upper limit. In addition, solid content in solid content concentration here is the total amount of usage-amount (Wb1) of complete hydrolysis-condensation product conversion of a silane compound (b1), and the usage-amount (Wb2) of solid content conversion of a specific silyl group containing polymer (b2).

The organic solvent is not particularly limited as long as the components can be uniformly mixed, but alcohols, aromatic hydrocarbons, ethers, ketones exemplified as organic solvents used in the production of the specific silyl group-containing polymer (b2), Ester etc. are mentioned. In addition, these organic solvents may be used individually by 1 type, or may mix and use 2 or more types.

(Stability improver)

In the present invention, in order to improve the storage stability and the like of the organic inorganic hybrid polymer composition, particularly the organic inorganic hybrid polymer (B), after the organic inorganic hybrid polymer (B) is produced, it is preferable to add a stability enhancer as necessary. . The stability improving agent used in the present invention is at least one selected from the group consisting of? -Diketones,? -Ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds, and oxyaldehyde compounds represented by the following general formula (6): Compound.

R ¹⁰ COCH ₂ COR ¹¹

(In formula, R <^10> is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, It denotes a carbon number of 1 to 6 monovalent hydrocarbon groups of 1 group and the like, R ¹¹ is a C 1 -C 6 monovalent hydrocarbon group, or a methoxy group, an ethoxy group, n- propoxy, i- propoxy, n- butoxy An alkoxyl group having 1 to 16 carbon atoms, such as a period, sec-butoxy group, t-butoxy group, lauryloxy group and stearyloxy group)

When organometallic compounds are used as said catalyst, it is preferable to add the stability improving agent represented by the said General formula (6). By using a stability improver, a stability improver is coordinated with the metal atom of organometallic compounds, and this coordination suppresses the excessive cocondensation reaction of a silane compound (b1) and a specific silyl-group containing polymer (b2), and the organic inorganic hybrid obtained It is thought that the storage stability of a polymer composition, especially an organic inorganic hybrid polymer (B), can be improved further.

As such a stability improving agent, for example, acetylacetone, methyl acetoacetate, acetoacetate, acetoacetic acid-n-propyl, acetoacetic acid-i-propyl, acetoacetic acid-n-butyl, acetoacetic acid-sec-butyl, acetoacetic acid- t-butyl, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methylhexane-2 , 4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10-phenanthrol Lean, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithione, methionine, salicylaldehyde and the like. Among these, acetylacetone and ethyl acetoacetate are preferable.

In addition, a stability improving agent may be used individually by 1 type, or may mix and use 2 or more types.

The amount of the stability improving agent used in the present invention is usually 2 mol or more, preferably 3 to 20 mol, with respect to 1 mol of the organometallic compound of the organometallic compounds. When the amount of the stability improver is less than the above lower limit, the effect of improving the storage stability of the composition to be obtained may be insufficient.

(Method for producing organic inorganic hybrid polymer (B))

The organic inorganic hybrid polymer (B) used for this invention can be manufactured by cocondensing a silane compound (b1) and a specific silyl group containing polymer (b2). Especially preferably, it can manufacture by adding a catalyst for hydrolysis / condensation reaction and water to a mixture of a silane compound (b1) and a specific silyl group containing polymer (b2), and cocondensing.

At this time, the weight ratio (Wb1 / Wb2) of the content (Wb1) of the silane compound (b1) and the content (Wb2) of the specific silyl group-containing polymer (b2) is Wb1 + Wb2 = 100, which is 5/95 to 95/5. , Preferably 15/85 to 85/15. In addition, Wb1 is a complete hydrolysis-condensation conversion value of a silane compound (b1), and Wb2 is a solid content conversion value of a specific silyl group containing polymer (b2). When the weight ratio (Wb1 / Wb2) is in the above range, a cured product having excellent transparency and weather resistance can be obtained. In addition, when Wb1 / Wb2 is preferably 5/95 to 50/50, more preferably 15/85 to 40/60, it is preferable to the organic substrate even if the surface of the organic substrate such as an acrylic plate is not treated with a primer or the like. Expresses adhesion.

It is preferable to specifically manufacture an organic inorganic hybrid polymer (B) by the method of following (1)-(3).

(1) Water in the above range is added to the mixture of the silane compound (b1), the specific silyl group-containing polymer (b2), and the catalyst for the hydrolysis / condensation reaction, at a temperature of 40 to 80 캜 and a reaction time of 0.5 to 12 hours. The silane compound (b1) and the specific silyl group-containing polymer (b2) are cocondensed to prepare an organic inorganic hybrid polymer (B). Then, other additives, such as a stability improver, can also be added as needed.

(2) Using organosilane (1) as the silane compound (b1), water in an amount in the above range is added thereto, and the valence of the organosilane (1) at a temperature of 40 to 80 ° C. and a time of 0.5 to 12 hours. A decomposition and condensation reaction is performed. Subsequently, the specific silyl group-containing polymer (b2) and the catalyst for the hydrolysis-condensation reaction are added and mixed, and the condensation reaction is further performed at a temperature of 40 to 80 ° C. and a reaction time of 0.5 to 12 hours to form an organic inorganic hybrid polymer (B). To prepare. Then, other additives, such as a stability improver, can also be added as needed.

(3) Water in the above ranges was added to the mixture of the silane compound (b1), the specific silyl group-containing polymer (b2), and the catalyst for the hydrolysis-condensation reaction, at a temperature of 40 to 80 ° C. and a reaction time of 0.5 to 12 hours. The silane compound (b1) and the specific silyl group-containing polymer (b2) are hydrolyzed and condensed to produce an organic inorganic hybrid polymer (B). Then, other additives, such as a stability improver, can also be added as needed.

In view of ensuring the storage stability of the organic-inorganic hybrid polymer (B) obtained above and the stability of the dispersion of the metal oxide fine particles thereafter, washing with water may be performed as a decatalyst step after hydrolysis condensation. When using a basic compound as a hydrolysis-condensation catalyst especially, it is more preferable to wash with water after neutralizing with an acidic compound after reaction.

The acidic compound used for neutralization can use the above-mentioned acidic compound. The use amount of the acidic compound is usually 0.5 to 2.0 moles, preferably 0.8 to 1.5 moles, more preferably 0.9 to 1.3 moles with respect to 1 mole of the basic compound used for hydrolysis condensation. When dissolving an acidic compound in water and using it, it is 10-500 weight part normally, Preferably it is 20-300 part, with respect to a total of 100 weight part of a silane compound (b1) and a specific silyl group containing polymer (b2). Preferably in 30 to 200 parts of water. After neutralization, the mixture was stirred and mixed sufficiently to stand, and after confirming phase separation of the aqueous phase and the organic solvent phase, water of the lower layer was removed.

Water used for the water washing after neutralization is 10-500 weight part normally, Preferably it is 20-300 part, More preferably, 30 with respect to a total of 100 weight part of a silane compound (b1) and a specific silyl group containing polymer (b2). To 200 parts.

Water washing is performed by adding water, stirring sufficiently, standing still, confirming phase separation of the aqueous phase and the organic solvent phase, and then removing the water in the lower layer. The number of washing times is preferably one or more times, more preferably two or more times.

On the other hand, when using a metal chelate compound as a hydrolysis condensation catalyst, it is preferable to add the said stability improving agent after reaction.

The weight average molecular weight of the organic-inorganic hybrid polymer (B) obtained by the above method is usually 3,000 to 200,000, preferably 4,000 to 150,000, and more preferably 5,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography.

[Oxide Fine Particle-Containing Organic Inorganic Hybrid Polymer Composition]

The oxide fine particle-containing organic inorganic hybrid polymer composition according to the present invention contains the oxide fine particle (A) and the organic inorganic hybrid polymer (B) in an organic solvent without using phosphoric acid or the like having an organic group having 6 or more carbon atoms or a compound having an oxyalkylene group. It can obtain by mixing in presence of a basic compound, an acidic compound, or a metal chelate compound, and performing a dispersion process.

(Organic solvent)

As said organic solvent, the organic solvent illustrated in the said organic inorganic hybrid polymer (B) is mentioned. Among these organic solvents, organic solvents other than alcohols, for example, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, toluene, xylene, ethyl acetate, in that the dispersion stability of the oxide fine particle-containing organic inorganic hybrid polymer composition is good. , Butyl acetate and mixtures thereof are preferred. Moreover, it is preferable to use these organic solvents in the state which removed the water beforehand and removes moisture.

Although the usage-amount of the said organic solvent will not be restrict | limited especially if it is an amount which can disperse | distribute an oxide fine particle (A) uniformly, The solid content concentration of the obtained oxide fine particle containing organic-inorganic hybrid polymer composition becomes like this. Preferably it is 5-80 weight%, More preferably, Is 7 to 70% by weight, particularly preferably 10 to 60% by weight.

(Basic compounds, acidic compounds and metal chelate compounds)

As said basic compound, an acidic compound, and a metal chelate compound, the compound illustrated in the said organic inorganic hybrid polymer (B) is mentioned. Among these basic compounds, acidic compounds and metal chelate compounds, basic compounds and acidic compounds are preferable, basic compounds are more preferable, organic amine compounds are more preferable, triethylamine, tetramethylammonium hydroxide and pyridine are particularly preferred. desirable.

The basic compound, acidic compound or metal chelate compound is usually 0.001 to 20 parts by weight, preferably 0.005 to 10 parts by weight, based on 100 parts by weight of the oxide fine particles (A) in the oxide fine particle-containing organic inorganic hybrid polymer composition of the present invention. More preferably 0.01 to 5 parts by weight, still more preferably 0.01 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight. When the basic compound, acidic compound or metal chelate compound is in the above range, the composition of oxide fine particle-containing polysiloxane shows good dispersion stability.

(Method for producing oxide fine particle-containing organic inorganic hybrid polymer composition)

In the oxide fine particle-containing organic inorganic hybrid polymer composition, an oxide fine particle (A), an organic inorganic hybrid polymer (B), a basic compound, an acidic compound, or a metal chelate compound are added to an organic solvent, and these are sufficiently mixed to form an oxide fine particle (A). Can be prepared by dispersing in an organic solvent. At this time, it is preferable to use well-known dispersers, such as a ball mill, a sand mill (bead mill, a high share bead mill), a homogenizer, an ultrasonic homogenizer, a nanomizer, a propeller mixer, a high share mixer, a paint shaker, and especially high dispersion Fine particle dispersion ball mill and sand mill (bead mill, high share bead mill) are preferably used. As described above, when the oxide fine particles (A) and the organic inorganic hybrid polymer (B) are mixed in the presence of a basic compound, an acidic compound or a metal chelate compound, the oxide fine particles are formed by the catalytic action of the basic compound, the acidic compound or the metal chelate compound. It is guessed that the condensation reaction of an organic-inorganic hybrid polymer (B) advances on the surface of (A), and the surface of an oxide fine particle (A) becomes hydrophobic and it becomes easy to disperse | distribute in an organic solvent easily.

The oxide fine particle-containing organic inorganic hybrid polymer composition of the present invention is preferably 1 to 1000 parts by weight, more preferably 1 to 1000 parts by weight, based on 100 parts by weight of the oxide fine particles (A) in terms of complete hydrolysis condensate. Preferably it is 5 to 900 parts by weight, particularly preferably 10 to 800 parts by weight.

Further, the oxide fine particle-containing organic inorganic hybrid polymer composition is a composition in which the oxide fine particles (A) are highly dispersed at a volume average dispersion particle diameter of 300 nm or less, preferably 200 nm or less, more preferably 150 nm or less.

[Hardening body]

By coating the oxide fine particle dispersion of the present invention on a substrate or the like, and removing the solvent by drying to cure the polyfunctional polysiloxane, a cured product (film) having excellent transparency can be formed. Since this hardened | cured material contains the organic-inorganic hybrid polymer (B), it is excellent in weatherability, flexibility, and followability with respect to a base material. Moreover, when the said base material is an organic base material, the adhesiveness of a base material and a hardening body further improves by treating the surface of an organic base material with a primer etc. In particular, the weight ratio (Wb1 / Wb2) of the content (Wb1) of the silane compound (b1) and the content (Wb2) of the specific silyl group-containing polymer (b2) is preferably 50/50 to 95/5, more preferably 60 When the organic-inorganic hybrid polymer (B) of / 40 to 85/15 is used, the effect by the primer treatment is large. As said primer, the solution containing the said specific silyl group containing polymer (b2) is mentioned.

Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In addition, "part" and "%" in an Example and a comparative example show a "weight part" and "weight%" unless there is particular notice. In addition, various measurements in the Example and the comparative example were performed by the following method.

(GPC measurement)

The weight average molecular weight of the specific silyl group containing polymer and the organic inorganic hybrid polymer was shown as the polystyrene conversion value measured on the following conditions by the gel permeation chromatography.

Equipment: HLC-8120C (manufactured by Tosoh Corporation)

Column: TSK-gel MultiporeH _XL- M (manufactured by Tosoh Corporation)

Eluent: THF, flow rate 0.5 mL / min, loading 5.0%, 100 μL

[Dispersibility 1]

The appearance of the obtained composition was visually observed. The volume average dispersion particle diameter of the composition which does not show the sedimentation of microparticles | fine-particles was measured with the micro track ultra-fine particle size distribution meter ("UPA150" by Nikkiso Corporation), and the following reference | standard evaluated.

A: No sedimentation sedimentation. Volume average dispersion particle diameter ≤ 200 nm.

B: No sedimentation sedimentation. 200 nm <volume average dispersion particle size ≤ 300 nm.

C: No sedimentation sedimentation. 300 nm <volume average dispersion particle diameter.

D: There is separation sedimentation.

[Dispersibility 2]

The dispersibility was also evaluated by the following criteria. That is, the external appearance of the obtained composition was visually observed. The volume average dispersion particle diameter of the composition which does not show the sedimentation of microparticles | fine-particles was measured with the micro track ultra-fine particle size distribution meter ("UPA150" by Nikkiso Corporation), and the following reference | standard evaluated.

AA: No sedimentation sedimentation. Volume average dispersion particle diameter ≤ 150 nm.

A: No sedimentation sedimentation. 150 nm <volume average dispersion particle size≤200 nm.

B: No sedimentation sedimentation. 200 nm <volume average dispersion particle size ≤ 300 nm.

C: No sedimentation sedimentation. 300 nm <volume average dispersion particle diameter.

D: There is separation sedimentation.

[Coating transparency]

The obtained composition was applied onto a quartz glass plate so that the dry film thickness was 5 μm, and then dried and cured at 100 ° C. for 1 hour to prepare a cured product having a film thickness of 5 μm on the quartz glass plate. The spectral transmittance at wavelength 500-700 nm of this hardened | cured material was measured with the ultraviolet visible spectrophotometer, and the following reference | standard evaluated.

A: The light transmittance is more than 90%.

B: Light transmittance is 70% or more and 90% or less.

C: The light transmittance is less than 70%.

(Yellowness)

The obtained composition was applied onto a quartz glass plate so that the dry film thickness was 5 μm, and then dried and cured at 100 ° C. for 1 hour to prepare a cured product having a film thickness of 5 μm on the quartz glass plate. The light transmittance of 450 nm in wavelength of this hardened | cured material was measured with the ultraviolet visible spectrophotometer, and the following reference | standard evaluated.

A: The light transmittance is more than 90%.

B: Light transmittance is 70 to 90%.

C: The light transmittance is less than 70%.

[Weather resistance]

5 parts of i-butyl alcohol solutions (solid content concentration of about 10%) of dioctyl tin dimaleate ester were added to 100 parts of obtained compositions, and the acrylic plate (primary) which surface-treated the solution which stirred sufficiently as needed. An engineering test service was manufactured, and a brand name: Acrylite # 001) was applied so as to have a dry film thickness of 2 μm, and then dried at 80 ° C. for 30 minutes to form a cured product (cured film). In addition, the primer treatment was an i-butyl alcohol solution of dioctyl tin dimaleate ester (solid content concentration of about 10%) in 100 parts by weight of a solution containing the specific silyl group-containing polymer (b2-1) obtained in Preparation Example 1-1 below. 10 parts of) were added, and the solution which was sufficiently stirred was applied by applying the dry coating film to 1 µm.

About the obtained hardened | cured material, 2,000 hours of irradiation tests were performed with the sunshine weather meter (made by Suga Shikeki Co., Ltd.) based on JISK5400, visual appearance was observed by visual observation, and the following reference | standard evaluated. Moreover, the tape peeling test was done using Nichiban Co., Ltd. cellophane tape (brand name: Cello tape (registered trademark) No. 405), and adhesiveness was evaluated based on the following reference | standard.

(Appearance) A: There is no crack, there is no peeling of a film, and there is no change before and after irradiation test.

       B: No peeling of the film, but some cracks

       C: No peeling of the film, but cracks on the whole surface

       D: There is peeling of the film

(Adhesiveness) AA: No peeling off of the film in the entire portion to which the tape is bonded

          A: Less than 5% of the places where the film was peeled out of the portion to which the tape was bonded.

          B: 5-50% of the places where the film was peeled out of the portion to which the tape was bonded.

          C: The part from which the film peeled was more than 50% in the part which adhered the tape.

[Production of Specific Silyl Group-Containing Polymer (b2)]

<Production Example 1-1>

55 parts of methyl methacrylate, 5 parts of 2-ethylhexyl acrylate, 5 parts of cyclohexyl methacrylate, 10 parts of γ-methacryloxypropyl trimethoxysilane, and glycidyl meta to a reactor equipped with a reflux condenser and a stirrer 20 parts of acrylate, 5 parts of 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 75 parts of i-butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol were added and mixed. Then, the mixture was warmed to 80 ° C while stirring. The solution which melt | dissolved 3 parts of azobisisovaleronitrile in 8 parts of xylene was dripped at this mixture over 30 minutes, and it was made to react at 80 degreeC for 5 hours. 36 parts of methyl ethyl ketones were added after cooling, and the solution containing the specific silyl group containing polymer (b2-1) whose solid content concentration is 35%, Mw measured by GPC method is 12,000, and the silicon content in solid content is 1.1 weight%. Got.

<Manufacture example 1-2>

A solid content concentration of 35%, a Mw of 13,000, and a silicon content of solids of 1.1 were the same as in Production Example 1-1 except that 20 parts of 2-hydroxyethyl methacrylate was used instead of 20 parts of glycidyl methacrylate. The solution containing the specific silyl group containing polymer (b2-2) which is weight% was obtained.

<Manufacture example 1-3>

30 parts of methyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of γ-methacryloxypropyl trimethoxysilane, 20 parts of glycidyl methacrylate, 4- (meth) to the reactor equipped with a reflux cooler and a stirrer ) Acryloyloxy-2,2,6,6-tetramethylpiperidine 10 parts, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole 20 parts, i 75 parts of butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol were added and mixed, followed by heating to 80 ° C. while stirring. The solution which melt | dissolved 4 parts of azobisisovaleronitrile in 10 parts of xylene was dripped at this mixture over 30 minutes, and it was made to react at 80 degreeC for 5 hours. After cooling, 83 parts of methyl ethyl ketone was added, the solution containing the specific silyl group-containing polymer (b2-3) having a solid content concentration of 30%, a Mw of 10,000 and a silicon content of 1.1% by weight in the solid content measured by the GPC method. Got.

<Manufacture example 1-4>

75 parts of methyl methacrylate, 5 parts of 2-ethylhexyl acrylate, 5 parts of cyclohexyl methacrylate, 10 parts of γ-methacryloxypropyl trimethoxysilane, 4- (meth) in a reactor equipped with a reflux cooler and a stirrer 5 parts of acryloyloxy-2,2,6,6-tetramethylpiperidine, 75 parts of i-butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol were added and mixed, followed by warming to 80 ° C while stirring. . The solution which melt | dissolved 3 parts of azobisisovaleronitrile in 8 parts of xylene was dripped at this mixture over 30 minutes, and it was made to react at 80 degreeC for 5 hours. After cooling, 35 parts of methyl ethyl ketone was added to obtain a specific silyl group-containing polymer (b2-4) solution having a solid content concentration of 35%, a Mw of 8,000 measured by the GPC method, and a silicon content of 1.1% by weight in solid content.

[Production of Organic Inorganic Interpolymer (B)]

<Manufacture example 2-1>

In a reactor equipped with a stirrer and a reflux condenser, 24 parts of methyltrimethoxysilane and 10 parts of dimethyldimethoxysilane as the silane compound (b1), and the specific silyl group-containing polymer (b2-1) as the specific silyl group-containing polymer (b2) 118 parts of a solution containing 10 parts of i-propyl alcohol as an organic solvent (e) and 2 parts of a 75% dilution solution of i-propyl alcohol of di-i-propoxy ethylacetoacetate aluminum as a hydrolysis-condensation reaction catalyst were added and mixed. It heated up at 50 degreeC, stirring. After 6 parts (corresponding to 0.48 mol with respect to 1 mol of all OR ² groups in the silane compound (b1)) were added dropwise thereto over 30 minutes, the reaction was carried out at 60 ° C for 4 hours, and the Mw measured by the GPC method was The solution containing 13,000 organic inorganic hybrid polymers (B-1) was obtained. Thereafter, 2 parts of acetylacetone was added as a stability improver, the mixture was stirred for 1 hour, and then cooled to room temperature, 129 parts of methyl isobutyl ketone were added as a diluting solvent, and the solid content concentration was adjusted to 20% by weight.

<Production Example 2-2 to 2-9>

Except having changed each component into the component shown in following Table 1, it carried out similarly to manufacture example 2-1, and the solution containing organic-inorganic hybrid polymer (B-2)-(B-9) (all the solid content concentration 20weight%) ) Was prepared. The results are shown in Table 1.

Example 1

100 parts by weight of the powdered rutile titanium oxide fine particles (primary average particle diameter: 30 nm), 500 parts by weight of the solution containing the organic inorganic hybrid polymer (B-1) (100 parts by weight in terms of solid content), and triethylamine 0.1 weight part and 400 weight part of methyl isobutyl ketones are put into a container, 2000 weight part of 0.1 mm diameter zirconia beads are added, it stirs at 1500 rpm using a bead mill for 1 hour, and disperse | distributes microparticles | fine-particles, solid content concentration 20 weight% of oxide fine particle containing organic inorganic hybrid polymer composition (1) was obtained. The results of evaluating the properties of this composition are shown in Table 2A.

Example 2

An organic-inorganic hybrid polymer composition containing metal oxide fine particles having a solid content concentration of 20% by weight in the same manner as in Example 1, except that 100 parts by weight of powdered zinc oxide fine particles (primary average particle diameter: 20 nm) were used instead of the rutile titanium oxide fine particles (2 ) Was prepared. The result of having evaluated the characteristic of this composition is shown in Table 2a.

Example 3

An organic-inorganic hybrid polymer composition containing metal oxide fine particles having a solid content concentration of 20% by weight in the same manner as in Example 1, except that 100 parts by weight of powdered zirconium oxide fine particles (primary average particle diameter: 20 nm) were used instead of the rutile titanium oxide fine particles (3 ) Was prepared. The result of having evaluated the characteristic of this composition is shown in Table 2a.

Example 4

An organic-inorganic hybrid polymer composition (4) containing metal oxide fine particles having a solid content concentration of 20% by weight was prepared in the same manner as in Example 2, except that 0.1 part by weight of methanesulfonic acid was used instead of triethylamine. The result of having evaluated the characteristic of this composition is shown in Table 2a.

Example 5

In the same manner as in Example 2 except that 500 parts by weight of the solution containing the organic inorganic hybrid polymer (B-2) (100 parts by weight in terms of solid content) was used instead of the solution containing the organic inorganic hybrid polymer (B-1). The organic-inorganic hybrid polymer composition (5) containing metal oxide fine particles of 20 weight% of solid content concentration was prepared. The result of having evaluated the characteristic of this composition is shown in Table 2a.

Example 6

In the same manner as in Example 2 except that 500 parts by weight of the solution containing the organic inorganic hybrid polymer (B-3) (100 parts by weight in terms of solid content) was used instead of the solution containing the organic inorganic hybrid polymer (B-1). The organic-inorganic hybrid polymer composition (6) containing metal oxide fine particles of 20 weight% of solid content concentration was prepared. The result of having evaluated the characteristic of this composition is shown in Table 2a.

Example 7

In the same manner as in Example 2 except that 500 parts by weight of the solution containing the organic inorganic hybrid polymer (B-4) (100 parts by weight in terms of solids) was used instead of the solution containing the organic inorganic hybrid polymer (B-1). The organic-inorganic hybrid polymer composition (7) containing metal oxide fine particles of 20 weight% of solid content concentration was prepared. The result of having evaluated the characteristic of this composition is shown in Table 2a.

[Examples 8 to 12]

It carried out except having used 500 weight part (100 weight part of solid content conversion) solutions containing organic inorganic hybrid polymers (B-5)-(B-9) instead of the solution containing organic inorganic hybrid polymer (B-1). In the same manner as in Example 2, metal oxide fine particle-containing organic inorganic hybrid polymer compositions (8) to (12) having a solid content concentration of 20% by weight were prepared. The result of having evaluated the characteristic of this composition is shown in Table 2a.

Comparative Example 1

100 parts by weight of powdered rutile titanium oxide fine particles (primary average particle diameter: 30 nm), 500 parts by weight of a solution containing the organic inorganic hybrid polymer (B-1) (100 parts by weight in terms of solid content), and polyoxyethylene 9 parts by weight of alkyl phosphate ester (manufactured by Kusumoto Kasei Co., Ltd., trade name: PLADD ED151), 5 parts by weight of acetylacetone, and 400 parts by weight of methyl isobutyl ketone are placed in a container, and 0.1 mm in diameter of zirconia beads 2000 weight part was added, and it stirred for 1 hour at 1500 rpm using the bead mill, and disperse | distributed microparticles | fine-particles, and obtained the oxide fine particle containing organic inorganic hybrid polymer composition (C1) of 20 weight% of solid content concentration. The results of evaluating the properties of this dispersion are shown in Table 2b below.

Comparative Example 2

In the same manner as in Example 1 except that triethylamine was not used, the powdered rutile titanium oxide fine particles were dispersed in methyl isobutyl ketone, but the titanium oxide fine particles precipitated.

Comparative Example 3

Powder rutile titanium oxide fine particles were dispersed in methyl isobutyl ketone in the same manner as in Example 1 except that a solution containing an organic inorganic hybrid polymer (B-1) was used, but the titanium oxide fine particles precipitated.

[Comparative Example 4]

Online in which titanium oxide fine particles dispersing anatase type titanium oxide fine particles in the water dispersion (Ishihara Sangyo Co., Ltd. Preparation "STS-01", TiO ₂ concentration: 30% by weight, a volume average dispersed particle diameter of the titanium oxide fine particles: 60 nm, organic Dispersant: 0% by weight) 300 parts by weight in a container, to which 500 parts by weight of a solution containing the organic inorganic hybrid polymer (B-1) (100 parts by weight in terms of solid content) and 400 parts by weight of methyl isobutyl ketone are added. Further, 2000 parts by weight of 0.1 mm diameter zirconia beads were added to the mixture, and the fine particles were dispersed by stirring at 1500 rpm for 1 hour using a bead mill, but the titanium oxide fine particles precipitated.

[Comparative Example 5]

Instead of a solution containing an organic inorganic hybrid polymer (B-1), a solution containing 100 parts by weight of polysiloxane (manufactured by GE Toshiba Silicone Co., Ltd., trade name: XR31-B2733) having Mw = 20,000 and 400 parts by weight of methyl isobutyl ketone was prepared. Except having used, it carried out similarly to Example 1, and obtained metal oxide fine particle containing polysiloxane composition (C5) of 20 weight% of solid content concentration. The results of evaluating the properties of this composition are shown in Table 2b.

Claims (15)

In an organic solvent in the presence of a basic compound, an acidic compound or a metal chelate compound (A) silicon oxide fine particles and / or metal oxide fine particles, and (B) at least one silane compound (b1) selected from the group consisting of at least one organosilane represented by the following formula (1), a hydrolyzate of the organosilane and a condensate of the organosilane, and a hydrolyzable group And / or oxide fine particles obtained by mixing an organic inorganic hybrid polymer obtained by hydrolyzing and condensing a polymer (b2) having a silyl group containing a silicon atom bonded to a hydroxyl group, and dispersing the oxide fine particles (A) in an organic solvent. Organic Inorganic Interpolymer Polymer Composition. <Formula 1> R ¹ _n Si (OR ² ) _4-n (Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two are present, they may be the same or different from each other, and R ² is each independently an alkyl group having 1 to 5 carbon atoms or 1 to 6 carbon atoms). Acyl group, n is an integer of 0 to 2) The oxide fine particle-containing organic inorganic hybrid polymer composition according to claim 1, wherein the oxide fine particles (A) and the organic inorganic hybrid polymer (B) are mixed in the presence of a basic compound. The oxide fine particle-containing organic inorganic hybrid polymer composition according to claim 1 or 2, wherein the oxide fine particles (A) and the organic inorganic hybrid polymer (B) are mixed by a bead mill. The method according to any one of claims 1 to 3, wherein 1 to 1000 parts by weight of the organic-inorganic hybrid polymer (B) is mixed in terms of complete hydrolysis condensate with respect to 100 parts by weight of the oxide fine particles (A). An oxide fine particle-containing organic inorganic hybrid polymer composition. The solid content of the content (Wb1) and the polymer (b2) of the said silane compound (b1) and a polymer (b2) in terms of complete hydrolysis-condensation product of a silane compound (b1). Oxide fine particle-containing organic inorganic hybrid, characterized in that the weight ratio (Wb1 / Wb2) of the content (Wb2) in terms of conversion is hydrolyzed and condensed in a range of 5/95 to 95/5 (where Wb1 + Wb2 = 100). Polymer composition. The content of the silyl group containing the silicon atom bonded to the hydrolyzable group and / or the hydroxyl group in the polymer (b2) is 0.1 to 2 weight, according to any one of claims 1 to 5. %, The oxide fine particle containing organic inorganic hybrid polymer composition characterized by the above-mentioned. Hardened | cured material obtained from the oxide fine particle containing organic-inorganic hybrid polymer composition in any one of Claims 1-6. The coating composition containing the oxide fine particle containing organic-inorganic hybrid polymer composition in any one of Claims 1-6. The laminated body which has an organic base material and the coating film obtained from the coating composition of Claim 8 provided on the said organic base material. At least one silane compound (b1) selected from the group consisting of at least one organosilane represented by the following formula (1), a hydrolyzate of the organosilane and a condensate of the organosilane, a hydrolyzable group and / or After hydrolysis and condensation reaction of the polymer (b2) which has the silyl group containing the silicon atom couple | bonded with the hydroxyl group, the organic-inorganic hybrid polymer (B) is produced, The above-mentioned organic inorganic hybrid polymer (B) and the silicon oxide fine particles and / or the metal oxide fine particles (A) are mixed in the presence of a basic compound, an acidic compound or a metal chelate compound in an organic solvent. Process for the preparation of the polymer composition. <Formula 1> R ¹ _n Si (OR ² ) _4-n (Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and when two are present, they may be the same or different from each other, and R ² is each independently an alkyl group having 1 to 5 carbon atoms or 1 to 6 carbon atoms). Acyl group, n is an integer of 0 to 2) The method for producing an oxide fine particle-containing organic inorganic hybrid polymer composition according to claim 10, wherein the oxide fine particles (A) and the organic inorganic hybrid polymer (B) are mixed in the presence of a basic compound. The method for producing an oxide fine particle-containing organic inorganic hybrid polymer composition according to claim 10 or 11, wherein the oxide fine particles (A) and the organic inorganic hybrid polymer (B) are mixed by a bead mill. The method according to any one of claims 10 to 12, wherein 1 to 1000 parts by weight of the organic-inorganic hybrid polymer (B) is mixed in terms of complete hydrolysis condensate based on 100 parts by weight of the oxide fine particles (A). A method for producing an oxide fine particle-containing organic inorganic hybrid polymer composition. The solid content of the content (Wb1) and polymer (b2) of the said silane compound (b1) and polymer (b2) in terms of complete hydrolysis-condensation product of a silane compound (b1). Oxide fine particle-containing organic inorganic hybrid, characterized in that the weight ratio (Wb1 / Wb2) of the content (Wb2) in terms of conversion is hydrolyzed and condensed in a range of 5/95 to 95/5 (where Wb1 + Wb2 = 100). Process for the preparation of the polymer composition. The content of the silyl group containing the silicon atom bonded to the hydrolyzable group and / or the hydroxyl group in the polymer (b2) is 0.1 to 2 wt% according to any one of claims 10 to 14. %, The manufacturing method of the oxide fine particle containing organic inorganic hybrid polymer composition characterized by the above-mentioned.