JPH07178335A - Organic polymer combined inorganic fine particle, its production and dispersed body and film forming composition containing the same - Google Patents

Abstract

PURPOSE:To provide an organic polymer combined inorganic fine particle and the producing method, which has fine average particle diameter, is narrow in particle diameter distribution and excellent in dispersion stability and affinity to an organic matrix at the time of using for coating material or molding material as an additive, and a dispersed body and film forming composition containing the organic polymer combined inorganic fine particle. CONSTITUTION:The organic polymer combined inorganic fine particulate is obtained by fixing an organic polymer on the surface of an inorganic fine particle and has 5-200nm average particle diameter and <=50% coefficient of variation of particle diameter. And the combined fine particle is obtained, for example, by hydrolyzing and condensing the organic polymer (P) having at least one polysiloxane group bonded in one molecule and at least one of Si-OR<1> group in the polysiloxane group individually or with a hydrolyzable metallic compound (G).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic polymer composite inorganic fine particle useful as an additive to various paints, molding materials, etc., a method for producing the same, a dispersion of the organic polymer composite inorganic fine particle dispersed in various dispersion media, and The present invention relates to a film-forming composition useful as various paints, surface treatment agents, coating agents, adhesives, pressure-sensitive adhesives, sealing agents, etc. containing the above-mentioned fine particles.

[0002]

2. Description of the Related Art Conventionally, various inorganic fine particles have been used as additives for various paints and molding materials for the purpose of imparting properties such as strength, flame retardancy, hiding power, heat resistance, surface hardness and rust resistance. It is put to practical use. However, the performance is not sufficient, and in order to solve this problem, the surface modification of the inorganic fine particles using an organic polymer or the like is carried out by various methods to improve the affinity between the inorganic fine particles and the organic medium. ing.

For example, JP-A-3-271114 describes fine particles obtained by treating fine silica particles having a particle diameter of 5 to 300 nm with a silyl etherified polymer. In addition, Tsubokawa et al. Found that the particle size obtained by the vapor phase method is several tens of n.
After introducing a polymerizable functional group or a polymerization initiating group to the surface of the silica fine particles of m, the silica fine particles were subjected to radical polymerization or surface treatment with a silyl group-containing polymer coupling agent to report an experiment for obtaining silica fine particles grafted with an organic polymer. ("Surface" Vol. 28, No. 4, 286-29
8 pages, 1990).

Further, in Japanese Patent Laid-Open No. 5-115772, a polymerizable functional group is introduced into the surface of silica fine particles having a particle diameter of several tens nm obtained by a gas phase method, and then emulsion polymerization is carried out to obtain a polymer on the silica surface. Of fine particles having an average particle diameter of 100 nm or less grafted by the above are described. On the other hand, JP-A-4
No. 180921 discloses that the particle size is 10 to 5000 n.
A method is described in which the surface of the colloidal silica of m is treated with a coupling agent in advance and then with an acid group-containing polymer to obtain polymer-modified silica fine particles. In addition, Yoshinaga et al. Reported an example of silica fine particles surface-modified with an organic polymer by treating monodisperse silica fine particles with an alkoxysilyl group-containing polymer (“Journal of the Fiber Society”, Vol. 49, No. 3). , 130th to 136th
P., 1993).

Apart from these, a number of methods are known for producing inorganic fine particles as a base material, and a hydrolyzable organometallic compound is hydrolyzed and condensed in a reaction solution such as water and alcohol. There is a typical way to do it. For example, Japanese Patent Publication No. 1-59974 discloses a method of hydrolyzing an organosilicon compound such as a hydrolyzable alkoxysilane without hydrolyzing the concentrations of water and ammonia in the reaction solution. A method for obtaining fine silica particles having good monodispersity in particle size is described. Further, in JP-A-63-77940, a mixed solution of an organic solvent such as methyltrialkoxysilane is used as an upper layer and an aqueous solution of ammonia or amine and / or a mixed solution of ammonia or amine and an organic solvent is used as a lower layer. , A method for obtaining polymethylsilsesquioxane powder having a substantially spherical shape and a particle size distribution within a range of ± 30% of the average particle size by hydrolyzing and condensing methyltrialkoxysilane or the like at these interfaces. ing. Further, Japanese Patent Publication No. 5-4325 discloses an average particle size of 0.05 to 20.
A method for producing high-purity true spherical silica fine particles in which the particle diameter is in the range of 1.0 to 1.5 and the true specific gravity of the particles is controlled in the range of 1.20 to 2.10. Has been done.

Acrylic polyols and polyester polyols, which are resin components contained in conventional film-forming compositions, are excellent in weather resistance and processability, but a film-forming composition containing these is applied. The surface hardness of the subsequent coating is low,
It had the drawback of being easily scratched. Therefore, for the purpose of improving the above-mentioned drawbacks, and further for the purpose of imparting properties such as strength, flame retardancy, hiding power, heat resistance, and rust resistance of the film-forming composition, various coatings containing various inorganic fine particles. And other film forming compositions have been produced.

However, its performance is not sufficient.
For example, the dispersibility of the inorganic fine particles is poor, or the adhesion between the inorganic fine particles and the resin used in the film-forming composition is not sufficient, and a minute gap is created at the interface between the two, and water penetrates into this space. Therefore, there is a problem that the weather resistance of the coating is significantly reduced. In order to solve such a problem, a film-forming composition using inorganic fine particles surface-modified with an organic polymer or the like by various methods is used, and an organic material such as a coating resin in the film-forming composition is used. The affinity between the medium and the inorganic fine particles has been improved. For example, there is a film-forming composition containing inorganic fine particles that have been surface-treated with a coupling agent in advance and then surface-treated with an acid group-containing polymer or an alkoxysilyl group-containing polymer. In addition, JP-A-4-
No. 173882 discloses an acrylic polyol resin, 2
Examples thereof include a binder such as an isocyanate compound having one or more functional groups, an inorganic organosol, and a solvent-containing acrylic resin-based coating composition, and it is described that weatherability is improved by using this composition.

[0008]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention
After a detailed study, after the inorganic fine particles were surface-treated with a coupling agent in advance, the surface treatment was carried out with an acid group-containing polymer, or when the surface treatment was carried out with an alkoxysilyl group-containing polymer, if the particles were not dried, That the polymer and the inorganic fine particles do not bond and a drying step is essential,
It has been found that such a drying treatment causes aggregation of the inorganic fine particles and cross-linking between the fine particles due to the polymer, so that the particle size distribution of the fine particles becomes wider than that before the surface treatment. In particular,
When inorganic fine particles having an average particle diameter of 200 nm or less were used, the aggregation thereof became remarkable, and it became clear that the average particle diameter of the finally obtained fine particles after the surface treatment was larger than 200 nm. When the fine particles after the surface treatment thus obtained are formed as they are or by mixing them with another coating resin, the aggregation of the particles is remarkable, the average particle size is large, and the particle size distribution is wide, It has been found that the obtained coating film has a problem that white turbidity and cracks occur and a transparent and glossy coating film cannot be obtained.

Further, the conventional example of hydrolyzing and condensing a hydrolyzable organometallic compound in a reaction liquid such as water and alcohol to obtain inorganic fine particles is intended to control the particle size distribution or the shape of the particles. For the purpose of modifying the generated inorganic fine particles, a bond is formed between the organic polymer and the inorganic fine particles during the hydrolysis / condensation reaction, and the inorganic fine particles are surface-modified with the organic polymer while being generated. Inorganic fine particles are not known.

In the conventional method for binding an acrylic polyol resin and an inorganic organosol using a binder,
The resin has poor storage stability and tends to gel. Also, a side reaction product obtained by crosslinking between acrylic polyol resins,
There is a high possibility that a side reaction product obtained by cross-linking between the inorganic organosols is obtained, and it is difficult to react selectively and efficiently only between the acrylic polyol resin and the inorganic organosol targeted by the binder. Moreover, the film-forming composition containing the inorganic organosol surface-modified with the acrylic polyol resin thus obtained has low physical properties such as weather resistance, adhesion and flexibility, and still has satisfactory physical properties. There wasn't.

Therefore, the present invention has the above-mentioned minute average particle diameter, narrow particle diameter distribution, excellent dispersion stability in various organic solvents and polymers, and particularly good in organic matrix. Inorganic fine particles surface-modified with an organic polymer having a high affinity, that is, organic polymer composite inorganic fine particles, a method for producing the same, and a dispersion containing the organic polymer composite inorganic fine particles useful as an additive for various paints, molding materials, etc. An object of the present invention is to provide a film forming composition containing a body and organic polymer composite inorganic fine particles which are excellent in weather resistance, stain resistance, chemical resistance, adhesion, surface hardness and the like.

[0012]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors succeeded in synthesizing the following organic polymer composite inorganic fine particles for the first time and completed the present invention. Came to do. That is, the organic polymer composite inorganic fine particles in the present invention is a composite fine particle in which an organic polymer is fixed on the surface of the inorganic fine particles,
The organic polymer composite inorganic fine particles have an average particle diameter of 5 to 200 nm and a variation coefficient of particle diameter of 50% or less.

The inorganic fine particles used in the present invention are not particularly limited as long as they are fine particles of an inorganic substance composed of an arbitrary element, and an inorganic oxide is preferably used as the inorganic substance. The inorganic oxide is defined as various oxygen-containing metal compounds in which a metal element mainly forms a three-dimensional network through a bond with an oxygen atom. Examples of the metal element forming the inorganic oxide include, for example, the periodic table of elements II to VI.
An element selected from the group is preferable, and the periodic table of elements III to V is used.
More preferred is an element selected from the group. Among them, S
An element selected from i, Al, Ti, and Zr is particularly preferable, and silica fine particles in which the metal element forming the inorganic oxide is Si is most preferable as the inorganic fine particles. Also,
The inorganic oxide may contain an organic group or a hydroxyl group, or various groups derived from the metal compound (G) as a raw material to be described later may remain, or a part of the organic polymer may be included. The organic group is at least one selected from the group consisting of an optionally substituted alkyl group having 20 or less carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group. The inorganic oxides may be used alone or in combination of two or more.

The shape of the inorganic fine particles made of such an inorganic substance may be any particle shape such as spherical, needle-like, plate-like, scale-like, and crushed, and is not particularly limited. Organic polymer of the organic polymer composite inorganic fine particles in the present invention, when used in various paints and molding materials, the dispersibility of the fine particles,
It contributes to the improvement of the affinity between the fine particles and the organic medium, and also acts as a binder when used as a film-forming composition.

The molecular weight, shape, composition of the organic polymer
The presence or absence of a functional group is not particularly limited, and any organic polymer can be used. With respect to the shape of the organic polymer, any shape such as a linear shape, a branched shape, and a crosslinked structure can be used. Further, specific examples of the resin forming the organic polymer include (meth)
Acrylic resins, polystyrene, polyvinyl acetate, polyolefins such as polyethylene and polypropylene, polyesters such as polyvinyl chloride, polyvinylidene chloride and polyethylene terephthalate, and their copolymers and functional groups such as amino groups, epoxy groups, hydroxyl groups and carboxyl groups. Examples thereof include resins partially modified with a group. Among them, the organic polymer contains an organic polymer containing a (meth) acrylic unit such as a (meth) acrylic resin, a (meth) acrylic-styrene resin, a (meth) acrylic-polyester resin, and the like, and forms a film. The organic polymer composite inorganic fine particles having the function can be used as a suitable one for the film forming composition described later.

As the organic polymer, any organic polymer can be used as described above, but in particular, it is composed of an organic chain and a polysiloxane group, and at least one polysiloxane group is bonded per molecule. And an organic chain contained in the below-mentioned organic polymer (P) having a structure containing at least one Si—OR ¹ group in the polysiloxane group is preferable.

The organic polymer-composite inorganic fine particles in the present invention are composite fine particles in which an organic polymer is fixed on the surface of the inorganic fine particles. Here, fixing does not mean mere adhesion and adhesion, and This means that the organic polymer is not detected in the washing liquid obtained by washing the organic polymer composite inorganic fine particles with an arbitrary solvent, which strongly suggests that a chemical bond is formed between the organic polymer and the inorganic fine particles. is doing.

The organic polymer composite inorganic fine particles may contain an organic polymer in the fine particles. This makes it possible to impart appropriate softness and toughness to the inorganic material that is the core of the organic polymer composite inorganic fine particles. The presence or absence of an organic polymer in the organic polymer-composite inorganic fine particles is determined by, for example, 500 to 70
This can be confirmed by comparing the measured value of the specific surface area of the fine particles after heating at 0 ° C. to thermally decompose the organic polymer with the theoretical value of the specific surface area calculated from the diameter of the fine particles. That is, when an organic polymer is included in the organic polymer composite inorganic fine particles, the organic polymer is thermally decomposed by heating, and a large number of pores are generated in the fine particles. The surface area becomes a value considerably larger than the theoretical value of the specific surface area calculated from the diameter of the fine particles.

The average particle diameter of the organic polymer composite inorganic fine particles is 5 to 200 nm, preferably 5 to 100 nm. The average particle diameter of the organic polymer composite inorganic fine particles is 5n
When it is less than m, the surface energy of the organic polymer-composite inorganic fine particles becomes high, so that aggregation or the like easily occurs. The average particle size of the organic polymer composite inorganic fine particles is 200
If it exceeds nm, the physical properties such as transparency of the coating film are deteriorated when it is used for paints and the like.

The coefficient of variation of the particle diameter of the organic polymer composite inorganic fine particles is 50% or less, preferably 30% or less.
When the particle size distribution of the organic polymer composite inorganic fine particles is wide, that is, when the coefficient of variation of the particle size exceeds 50%, when used as a filler such as a plastic film, the film surface is not smooth and the unevenness is severe. Not preferable.

The content of the alkoxy groups in the organic polymer-composite inorganic fine particles of the present invention is preferably 0.01 to 50 mmol per 1 g of the organic polymer-composite inorganic fine particles. The alkoxy group referred to here is an R ⁴ O group bonded to a metal element forming the fine particle skeleton. Here, R ⁴ is an optionally substituted alkyl group, and R ⁴ O in the fine particles is
The groups may be the same or different. Specific examples of R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl and the like.

The above-mentioned alkoxy group has a function of complementarily improving the affinity with the organic medium and the dispersibility in the organic medium when the organic polymer composite inorganic fine particles are used as various paints and molding materials. There is. The content of the inorganic substance in the organic polymer composite inorganic fine particles of the present invention is not particularly limited, but when the fine particles are added to various resins, the hardness of the inorganic substance, properties such as heat resistance, In order to exert the effect more effectively, it is advantageous to increase the content of the inorganic substance in the fine particles as much as possible.
It is preferably 99.5% by weight.

The content of the organic polymer in the organic polymer-composite inorganic fine particles of the present invention is not particularly limited, but it is 0.5 to 5 of the organic polymer-composite inorganic fine particles.
0% by weight is preferred. The organic polymer composite inorganic fine particles of the present invention can be produced by any method. The method for producing the organic polymer composite inorganic fine particles of the present invention, which will be described in detail below, is an example thereof, and is not limited to the method described below.

The present invention also includes at least one molecule per molecule.
Also has one polysiloxane group bonded, and
At least one Si-OR in the polysiloxane group¹ Basis
(R ¹ Is a hydrogen atom, an alkyl group, or an acyl group.
At least one group which may be substituted
R¹ When there are multiple R in one molecule, multiple R¹ Are each other
May be the same or different. ) Having
Organic polymer (P) can be hydrolyzed (P) alone or
A special feature is that it is hydrolyzed and condensed with the metal compound (G).
Providing a method for producing organic polymer composite inorganic fine particles
To do.

The organic polymer (P) used in the method for producing organic polymer-composite inorganic fine particles of the present invention can be hydrolyzed and condensed alone to produce organic polymer-composite inorganic fine particles. It is also possible to co-hydrolyze and condense the metal compound (G) and the organic polymer (P) described below together to produce organic polymer composite inorganic fine particles. The organic polymer (P) is composed of an organic chain and a polysiloxane group, and 1
At least one polysiloxane group is bonded per molecule, and at least 1 is present in the polysiloxane group.
Has a structure containing ^one Si—OR ¹ group. In the organic polymer (P), the structure of the organic chain is not particularly limited. In addition, the polysiloxane group and the organic chain in the organic polymer (P) are chemically bonded via a Si—C bond, a Si—O—C bond, or the like for the reason that the organic polymer (P) is easily available. It is preferable that the polysiloxane group and the organic chain have a Si—C bond because the bond site is excellent in hydrolysis resistance and it is desirable that it is less likely to undergo an unfavorable reaction such as an exchange reaction at the bond site. More preferably, it is chemically bonded via.

The structure of the organic polymer (P) is not particularly limited as long as it can be dissolved in an organic solvent and / or water described later, and for example, a polymer in which a polysiloxane group is grafted to an organic chain, a polysiloxane A plurality of linear or branched organic chains having a siloxane group bonded to one or both ends of the organic chain or a polysiloxane group as a core (the plural organic chains may be the same or different. And the like) may be mentioned. Here, the organic chain in the organic polymer (P),
It is a portion other than the polysiloxane group. The main chain in the organic chain is mainly composed of carbon, the carbon atoms participating in the main chain bond occupy 50 to 100 mol%, and the balance is N,
Those composed of elements such as O, S, Si and P are easily obtained, which is preferable. Specific examples of the resin constituting the organic chain include (meth) acrylic resins, polystyrene, polyvinyl acetate, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyesters such as polyethylene terephthalate, and the like. Examples thereof include copolymers and partially modified resins. Among these, a resin that essentially contains a (meth) acrylic unit is preferable from the viewpoint of the film-forming ability of the film-forming composition of the present invention.

The R ¹ O group in the Si-OR ¹ group is a functional group capable of being hydrolyzed and / or condensed, and there is at least one R ¹ O group per molecule of the organic polymer (P), and an average of 5 or more. Preferably, 20 or more are more preferable. As the number of R ¹ O groups increases, the number of reaction sites for hydrolysis / condensation increases, and fine particles forming a stronger skeleton can be obtained. Here, R ¹ is a hydrogen atom or at least one group which may be substituted and is selected from an alkyl group and an acyl group. The carbon number of the alkyl group and the acyl group is not particularly limited, but an alkyl group and an acyl group having 1 to 5 carbon atoms are preferable because the hydrolysis rate of the R ¹ O group is high. Specific examples of the alkyl group having 1 to 5 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, and a pentyl group. Can be mentioned. Carbon number 1
Specific examples of the acyl group of to 5 include acyl groups such as acetyl group and propionyl group. As the substituted alkyl group or acyl group, for example, one or more hydrogen atoms of the above alkyl group or acyl group is, for example, an alkoxy group such as a methoxy group or an ethoxy group; an acetyl group or a propionyl group. Acyl groups such as chlorine;
Examples thereof include groups substituted with halogen such as bromine.
When plural R ^1's are present in one molecule, the plural R ^1's may be the same or different from each other. R ¹ is preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a methyl group, because the hydrolysis / condensation rate of the R ¹ O group is further increased.

Si-, in which the R ¹ O group is bonded to a Si atom
A polysiloxane group having one or more OR ¹ groups means that two or more Si atoms have a polysiloxane bond (Si-O-Si).
A group formed by linearly or branchedly connecting by a bond. The number of Si atoms contained in this polysiloxane group is
Although not particularly limited, the number of R ¹ O groups described above can be large, and the average number of polysiloxane groups is preferably 4 or more, more preferably 11 or more. Specific examples of such a polysiloxane group include, for example, a polymethylmethoxysiloxane group, a polyethylmethoxysiloxane group, a polymethylethoxysiloxane group, a polyethylethoxysiloxane group, a polyphenylmethoxysiloxane group, and a polyphenylethoxysiloxane group. Etc.

In addition, all S in the polysiloxane group
i atom is a bond with an organic chain and a polysiloxane bond
R other than (Si-O-Si bond)¹ Bond only with O group
Is preferred. In such a case, the Si atom
As a result, R ¹ O group hydrolysis / condensation
As the speed becomes faster, the reaction in the organic polymer (P)
The response point is increased, and fine particles with a stronger skeleton are obtained.
It Specific examples of such polysiloxane groups
And, for example, polydimethoxysiloxane groups, polydieto
Xysiloxane group, polydiisopropoxysiloxane
Group, a poly-n-butoxysiloxane group, and the like.

The molecular weight of the organic polymer (P) is not particularly limited, but the number average molecular weight is preferably 200,000 or less, more preferably 50,000 or less. If the molecular weight is high, it may not be dissolved in the organic solvent described later, which is not preferable. The organic polymer (P) can be produced by a conventionally known method. For example, the following (1)-
Although the method of (4) is mentioned, it is not limited to these methods.

(1) Obtained (co) after radical (co) polymerization of a radical-polymerizable monomer in the presence of a silane coupling agent having a double bond group or a mercapto group.
A method of co-hydrolyzing and condensing a polymer and a silane compound (H) and / or its derivative described below. (2) A silane coupling agent having a double bond group or a mercapto group and a silane compound (H) and / or
Alternatively, after the co-hydrolysis / condensation of the derivative thereof, the radical-polymerizable monomer is converted into a radical (co) in the presence of the obtained co-hydrolysis / condensation product (hereinafter abbreviated as “polymerizable polysiloxane”).
How to polymerize.

(3) A silane coupling agent having a reactive group such as a double bond group, an amino group, an epoxy group and a mercapto group was reacted with a polymer having a group capable of reacting with the reactive group. Then, a method of co-hydrolyzing / condensing the obtained polymer with the silane compound (H) and / or its derivative described below. (4) After co-hydrolyzing / condensing a silane coupling agent having a reactive group such as a double bond group, an amino group, an epoxy group and a mercapto group, and a silane compound (H) and / or a derivative thereof described below. A method of reacting the polymer obtained by co-hydrolysis / condensation having the obtained reactive group with a polymer having a group capable of reacting with the reactive group.

Among the above, the method (2) is preferable because the organic polymer (P) can be obtained more easily. The hydrolyzable metal compound (G) can be three-dimensionally formed by hydrolysis and further condensation. Specific examples of such a metal compound (G) include metal halides, metal nitrates, metal sulfates, metal ammonium salts, organic metal compounds, alkoxy metal compounds, and derivatives of these metal compounds. To be The metal compound (G) can be used alone or in combination of two or more.

As the metal compound (G), the metal elements constituting the metal compound (G) are groups III and IV of the periodic table of the elements.
At least 1 selected from the group consisting of elements of Group V and Group V
Those which are the metallic elements of the species are preferred. Above all, a metal compound in which the metal element constituting the metal compound (G) is composed of at least one metal element selected from the group consisting of Si, Al, Ti and Zr is more preferable. Also,
If the hydrolysis rate of the metal compound (G) is equal to the hydrolysis rate of the R ¹ O group of the polysiloxane group in the organic polymer (P), the co-hydrolysis / condensation reaction can be easily controlled. Si is most preferable as the metal element constituting the metal compound (G).

Specific examples of such a metal compound (G) include boric acid, ammonium borate, boron tribromide, boron trichloride, methylboron dichloride, trimethyl borate,
Triethyl borate, triisopropyl borate, tributyl borate, methyl boric acid, dimethyl methyl borate, aluminum hydroxide, aluminum chloride, aluminum nitrate, aluminum sulfate, ammonium aluminum sulfate, aluminum trimethoxide, aluminum triethoxide, aluminum triiso Propoxide, aluminum tributoxide, dimethyl aluminum methoxide, isopropyl aluminum dichloride, ethyl ethoxy aluminum chloride, silicon tetrachloride, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethylethoxysilane, phenyltrihydroxysilane, trimethylhydroxysilane, dimethyl Dihydroxysilane, methyltriacetoxysilane, dimethyldiacetate Sisilane, trimethylacetoxysilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-
(2-Aminoethylaminopropyl) trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylsilane, diethoxymethylsilane, diethoxy-3-
Glycidoxypropylmethylsilane, 3-chloropropyldimethoxymethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, dimethoxydiethoxysilane, germanium tetrachloride, methylgermanium trichloride, dimethylgermanium dichloride , Trimethylgermanium chloride, methylgermanium triacetate, dimethylgermanium diacetate, trimethylgermanium acetate, germanium tetramethoxide, germanium tetraethoxide,
Methyl germanium triethoxide, dimethyl germanium dimethoxide, trimethyl germanium methoxide, stannous chloride, stannic chloride, methyl tin trichloride, dimethyl tin dichloride, trimethyl tin chloride, dibutyl tin diacetate, tributyl tin hydride, trimethyl tin Formate, trimethyltin acetate, triethyltin hydroxide, dimethyltin dimethoxide, trimethyltin methoxide, dimethyltin diethoxide, dibutyltin dibutoxide, phosphorous acid, phosphoric acid, phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride, monoammonium phosphate , Diammonium phosphate, triammonium phosphate, methyl phosphite dichloride, phenyl phosphite dichloride, dimethyl phosphite chloride, methyl phosphite dichloride, methyl phosphite Acid, methyl phosphoric acid, trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, triphenyl phosphite, methyl methyl phosphite, diethyl phenyl phosphite, dimethyl ethyl phosphite, Ethyl diphenyl phosphite, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dimethyl methyl phosphate, diethyl ethyl phosphate, ethyl dimethyl phosphate, methyl diethyl phosphate, titanium tetrachloride, titanyl sulfate, methyl trichloro titanium,
Dimethyldichlorotitanium, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetra (2-ethylhexyloxy)
Titanium, diethoxydibutoxytitanium, isopropoxytitanium trioctarate, diisopropoxytitanium diacrylate, tributoxytitanium stearate, zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium lactate, tetramethoxyzirconium, tetraethoxyzirconium, Examples thereof include tetraisopropoxy zirconium and tetrabutoxy zirconium.

As the metal compound (G), a derivative of the above metal compound can be used. The derivative of the metal compound means, for example, a part of a hydrolyzable group such as halogen, NO ₃ , SO ₄ , alkoxy group, and acyloxy group as a dicarboxylic acid group, an oxycarboxylic acid group, a β-diketone group, and a β-diketone group.
A metal compound substituted with a group capable of forming a chelate compound such as a ketoester group, a β-diester group, an alkanolamine group, or a partial hydrolysis and / or condensation of the metal compound and / or the chelate-substituted metal compound. The resulting oligomers and polymers are the same.

Examples of the above chelate-substituted compound include diisopropoxytitanium diacetylacetonate,
Examples thereof include oxytitanium diacetylacetonate, dibutoxytitanium bistriethanolaminate, dihydroxytitanium dilactate, zirconium acetylacetonate, acetylacetone zirconium butoxide, triethanolamine zirconium butoxide, and aluminum acetylacetonate. Among them, the metal compound (G) has the following general formula (R ² O) _m MR ³ _nm (wherein M is Si, Al, Ti and Zr.
At least one metal element selected from the group consisting of
R ² is a hydrogen atom or at least one group that may be substituted selected from an alkyl group and an acyl group, and R ³ is selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, which may be substituted. At least one group, n is a valence of the metal element M, m is an integer of 1 to n, R ²
And / or when there are a plurality of R ^{3 s} in one molecule, a plurality of R ^{2 s} and / or R ^{3 s} may be the same as each other,
May be different. It is preferable to use at least one selected from the compounds shown in (4) and their derivatives.

Specific examples of R ² include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group and tertiary group.
Examples thereof include a butyl group and a pentyl group. Further, examples of the acyl group include an acetyl group and a propionyl group. R ² is preferably a hydrogen atom, a methyl group or an ethyl group,
Most preferred is the methyl group. This is the hydrolysis of R ² O groups
This is because the condensation rate becomes higher.

Specific examples of R ³ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group and tertiary group.
Examples thereof include a butyl group and a pentyl group. Examples of the cycloalkyl group include a cyclohexyl group and the like. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and the like. Examples of the aralkyl group include groups such as benzyl group. An optionally substituted alkyl group, cycloalkyl group,
The aryl group and the aralkyl group are, for example, one or more hydrogen atoms contained in the above alkyl group, cycloalkyl group, aryl group and aralkyl group, for example, an alkoxy group such as a methoxy group and an ethoxy group, an amino group and a nitro group. A group, an epoxy group, a group substituted with a functional group such as halogen are shown.

Specific examples of the metal compound (G) represented by the general formula include methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylacetoxysilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisoproxysilane, Tetrabutoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, dimethoxydiethoxysilane, aluminum trimethoxide Aluminum triethoxide, aluminum triisopropoxide,
Aluminum tributoxide, dimethylaluminum methoxide, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetra (2-ethylhexyloxy) titanium, diexcitodibutoxytitanium, isoproxytitanium trioctarate, di Examples thereof include isopropoxy titanium diacrylate, tributoxy titanium stearate, zirconium acetate, tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, and tetrabutoxy zirconium. Specific examples of the derivative of the metal compound (G) represented by the general formula include diisopropoxytitanium diacetylacetonate,
Examples thereof include oxytitanium diacetylacetonate, dibutoxytitanium bistriethanolaminate, dihydroxytitanium dilactide, zirconium acetylacetonate, acetylacetone zirconium butoxide, triethanolamine zirconium butoxide, and aluminum acetylacetonate.

Furthermore, the silane compound (H) in which M is Si in the general formula and the compound thereof are easily available industrially and contain no halogen or the like which adversely affects the physical properties of the production apparatus and the final product. It is more preferable to use at least one selected from derivatives. Specific examples of the silane compound (H) include methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylacetoxysilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and methyltrimethoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, dimethoxydiethoxysilane and the like. Further, specific examples of the derivative of the silane compound (H) include the hydrolysis / condensation products of the silane compound (H).

Among the silane compounds (H), alkoxysilane
The orchid compound is particularly preferable because it is easily available as a raw material. Well
Moreover, the silane compound (H) and its derivative are
R² ) _Four And its derivatives, the rate of hydrolysis and condensation
Organic polymer composite that forms a stronger and stronger skeleton
It is preferable in that inorganic fine particles can be obtained. Yes in the present invention
Organic polymer composite inorganic fine particles
Hydrolysis / condensation by itself or with the above metal compound (G)
Manufactured. The method of hydrolysis / condensation is not particularly limited.
However, in the solution, it can be easily reacted.
It is preferable to carry out. The solution referred to here is an organic compound described later.
A solution containing a solvent and / or water, wherein the solution
The composition of is not particularly limited.

Specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, ethylene acetate. Esters of glycol monoethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; tetrahydrofuran, dioxane, Ethers such as ethyl ether and di-n-butyl ether; methanol, ethanol, isopropyl alcohol, n-butanol, ethylene group Alcohols such as coal, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether; halogenated carbonization of methylene chloride, chloroform, etc. Examples thereof include hydrogens, and at least one kind or two or more kinds of these organic solvents may be used. Above all, it is preferable to essentially use water-soluble alcohols, ketones, and ethers.

The hydrolysis / condensation of the organic polymer (P) alone or the organic polymer (P) and the metal compound (G) can be carried out without a catalyst, but one or more of an acidic catalyst or a basic catalyst can be used. Can be used. Specific examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as acetic acid, propionic acid, oxalic acid and p-toluenesulfonic acid; acidic ion exchange resins and the like. Specific examples of the basic catalyst include, for example, ammonia; organic amine compounds such as triethylamine and tripropylamine; sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, and hydroxylation. Examples thereof include alkali metal compounds such as sodium and potassium hydroxide; basic ion exchange resins and the like. When a basic catalyst is used rather than an acidic catalyst, an inorganic component obtained by hydrolysis / condensation forms a stronger skeleton, which is preferable.

The raw material composition at the time of hydrolysis / condensation is not particularly limited, but is based on the total amount of the raw material composition consisting of the organic polymer (P), the metal compound (G), the organic solvent, the catalyst and water. The amount of organic polymer (P) is 0.1
-80% by weight is preferable, and 0.5-30% by weight is more preferable. The amount of the metal compound (G) is preferably 0 to 80% by weight, more preferably 0 to 50% by weight. The amount of the organic solvent is preferably 0 to 99.9% by weight, and 20 to 99% by weight.
Is more preferable. The amount of the catalyst is preferably 0 to 20% by weight, more preferably 0 to 10% by weight.

The amount of water used for the hydrolysis / condensation is not particularly limited as long as the organic polymer (P) alone or the amount of the organic polymer (P) and the metal compound (G) is formed into particles by hydrolysis / condensation. However, in order to carry out the hydrolysis / condensation more sufficiently and to strengthen the skeleton of the particles, the larger the amount of water used, the better. Specifically, the molar ratio of water to the hydrolyzable group that hydrolyzes and condenses is 0.1
Or more, preferably 0.5 or more, more preferably 1
By carrying out hydrolysis / condensation under the above conditions, organic polymer composite inorganic fine particles can be obtained.

The operation method of hydrolysis / condensation is not particularly limited, but specific examples include, for example, the case where the organic polymer (P) or a solution thereof is used and the metal compound (G) is also used. , The metal compound (G) or a solution thereof is added to a solution containing water, and the reaction temperature is 0 to 1
At 00 ° C, preferably in the range of 0 to 70 ° C for 5 minutes to 1
It is performed by stirring for 00 hours. At this time, the organic polymer (P) or a solution thereof, the metal compound (G) or a solution thereof are mixed or separately, collectively,
The reaction can be performed by any addition method such as division or continuous addition. Alternatively, the solution containing water may be added in the reverse order to the organic polymer (P) or the solution thereof or the metal compound (G) or the solution thereof. Further, in the hydrolysis / condensation, one kind or two or more kinds of the above catalysts can be used. The method of using the catalyst is not particularly limited, but water, an organic solvent, an organic polymer (P),
It can be used by mixing with the metal compound (G). After completion of the reaction, by-products and catalysts produced by hydrolysis / condensation may be removed by filtration, distillation, etc., and the method for isolating the obtained organic polymer-composite inorganic fine particles from the reaction mixture should be a conventional method. And can be isolated and purified by, for example, distilling off the solvent, centrifugation, reprecipitation, ultrafiltration and the like.

The hydrolysis / condensation method is not particularly limited as described above, but is narrower (sharp).
The following method is more preferable in that the organic polymer composite inorganic fine particles having a particle size distribution can be produced. That is, the following raw material liquid (A) and raw material liquid (B) are separately and simultaneously supplied into the reaction vessel to perform hydrolysis / condensation, whereby the organic polymer composite inorganic fine particles are more preferably produced.

Raw material liquid (A): Liquid containing organic polymer (P) or organic polymer (P) and hydrolyzable metal compound (G) Raw material liquid (B): Liquid containing water as an essential component It is also preferable to separately and simultaneously supply the following raw material liquid (C) into the reaction vessel together with the raw material liquid (A) and the raw material liquid (B).

Raw Material Liquid (C): Liquid Containing Hydrolyzable Metal Compound (G) Further, the raw material liquid (A) contains at least one hydrolyzable metal compound (G). The above-mentioned hydrolysis / condensation is also preferable. Hydrolysis in this way
When the condensation is performed, the precipitation process of the organic polymer-composite inorganic fine particles due to hydrolysis / condensation can be more easily controlled, and the organic polymer-composite inorganic fine particles having a sharper particle size distribution can be obtained.

Individual supply of the raw material liquids (A) to (C) into the reaction vessel means that the raw material liquids are not mixed with each other before they are fed into the reaction vessel. Is to be supplied. Further, the raw material liquid (A) to the raw material liquid (C)
The simultaneous supply of the raw material liquid (A) and the raw material liquid (C) to the raw material liquid (B) at an arbitrary time t defined by the following formula: X _a , X _c Is preferably 0.1 to 10, and more preferably 0.3 to 3.
In particular, it is preferably supplied at 0.5 to 2.

[0052] (In the formula, A represents the total amount of the raw material liquid (A), B represents the total amount of the raw material liquid (B), and C represents the total amount of the raw material liquid (C). Further, a was already supplied at an arbitrary time t. Amount of raw material liquid (A),
b indicates the amount of the raw material liquid (B) already supplied at an arbitrary time t, and c indicates the amount of the raw material liquid (C) already supplied at the arbitrary time t. The present invention also provides a dispersion of the organic polymer-composite inorganic fine particles, the dispersion of the organic polymer-composite inorganic fine particles dispersed in various solvents obtained by the manufacturing method, and a film-forming composition containing the organic polymer-composite inorganic fine particles. Is provided.

The organic polymer composite inorganic fine particle dispersion in the present invention contains the above organic polymer composite inorganic fine particles. The organic polymer-composite inorganic fine particle dispersion in the present invention contains the organic polymer-composite inorganic fine particles obtained by the production method of the present invention. That is, the organic polymer composite inorganic fine particle dispersion in the present invention is obtained, for example, by dispersing the organic polymer composite inorganic fine particle of the present invention in an arbitrary solution, and obtained by the method for producing the organic polymer composite inorganic fine particle of the present invention. Reaction mixture, the solvent in the reaction mixture was replaced with another solvent while distilled under heating, the solvent in the reaction mixture was distilled off, centrifugation, reprecipitation, ultrafiltration, etc. organic polymer composite inorganic fine particles After being isolated, it is dispersed in a dispersion medium or the like, which is a dispersion in which various dispersion media are dispersed.

The organic polymer-composite inorganic fine particle dispersion of the present invention has no coarse particles, agglomerates, and precipitates, and has the property of not causing precipitation or gelation for a long period of time. The dispersion state of the organic polymer composite inorganic oxide fine particles in the dispersion can be confirmed by light scattering type particle size distribution measurement or the like. Unlike dispersions obtained by conventional methods,
The organic polymer composite inorganic fine particle dispersion of the present invention does not aggregate the organic polymer composite inorganic fine particles in the dispersion,
It is a dispersion that maintains a sharp particle size distribution.

The dispersion medium of the organic polymer-composite inorganic fine particle dispersion of the present invention is not particularly limited in its composition and the like, but an organic solvent or water in which an organic chain in the organic polymer-composite inorganic fine particle is dissolved is preferable. Among the organic solvents described in the above production method, the organic polymer composite inorganic fine particles are dispersed in at least one organic solvent selected from the group consisting of esters, alcohols, ketones and aromatic hydrocarbons and / or water. Since the dispersion has good storage stability for a long period of time and good dispersion stability in various organic media, it can be used for various purposes.

The concentration of the organic polymer-composite inorganic fine particles in the organic polymer-composite inorganic fine particle dispersion of the present invention is not particularly limited, but is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight. is there. When the concentration of the organic polymer-composite inorganic fine particles in the organic polymer-composite inorganic fine particle dispersion is high, the viscosity of the dispersion becomes high and it becomes difficult to use for various purposes.

Next, the film-forming composition according to the present invention contains the organic polymer composite inorganic fine particles of the present invention. The film-forming composition according to the present invention contains the organic polymer composite inorganic fine particles obtained by the production method of the present invention. The organic polymer that constitutes the organic polymer composite inorganic fine particles in the film-forming composition of the present invention is not particularly limited, but among them, a (meth) acrylic resin and a (meth) acrylic-styrene resin that have film-forming ability. , (Meth) acrylic-polyester resins are preferred.

Since the film-forming composition of the present invention essentially contains the organic polymer composite inorganic fine particles as compared with the conventional film-forming composition, the physical properties of the film are improved as compared with the conventional products.
For example, a film-forming composition obtained by adding the organic polymer composite inorganic fine particles of the present invention to a general coating resin or the like has a surface hardness,
It gives a coating film with good coating physical properties such as heat resistance, abrasion resistance and stain resistance.

The organic polymer composite inorganic fine particles obtained in the present invention have a structure in which the organic polymer is fixed on the surface of the inorganic fine particles, and the organic polymer acts as a binder, so that it can be directly applied to various base materials described later. A film can be formed even when applied alone, and the film-forming composition containing the organic polymer-composite inorganic fine particles can provide a transparent and good film.

The film-forming composition of the present invention is not particularly limited in its amount and the presence or absence of other components such as coating resin as long as it contains organic polymer composite inorganic fine particles as an essential component. However, in the coating film after applying the film forming composition, if the organic polymer has a crosslinked structure,
It is preferable because physical properties of the coating such as solvent resistance, heat resistance and surface hardness are improved.

Examples of the film-forming composition in which the organic polymer has a crosslinked structure in the film finally obtained after the film-forming composition is applied include the following. (1) Organic polymer (P) having a functional group (X), the organic polymer composite inorganic fine particles having a functional group (X) obtained by the above-mentioned method, and a function capable of reacting with the functional group (X) A film-forming composition comprising a compound or resin having two or more groups (Y). (2) Organic polymer (P) having a functional group (X), the organic polymer composite inorganic fine particles having a functional group (X) obtained by the above-mentioned method, and a function capable of reacting with the functional group (X) A film-forming composition comprising organic polymer composite inorganic fine particles having a functional group (Y) obtained by the above-mentioned method using an organic polymer (P) having a group (Y). (3) Organic polymer (P) having a functional group (X), the organic polymer composite inorganic fine particles having a functional group (X) obtained by the above-mentioned method, and a function capable of reacting with the functional group (X) Using a compound or resin having two or more groups (Y) and an organic polymer (P) having a functional group (W) that reacts with the functional group (X), the functional group (W A film forming composition comprising organic polymer composite inorganic fine particles having (4) A film forming composition as described in (1) to (3) above, which further contains a compound and / or a resin having two or more functional groups (X).

Here, as the functional group (X), for example,
Examples thereof include a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a mercapto group, an oxazoline group and an aldehyde group. Examples of the functional group (Y) and the functional group (W) that react with these functional groups (X) include isocyanate. Group, epoxy group, hydroxyl group, mercapto group, amino group, unsaturated group,
Examples thereof include a carboxyl group.

Further, each of the functional group (X), the functional group (Y) and the functional group (W) in the organic polymer composite inorganic fine particles having the functional group (X), the functional group (Y) and the functional group (W), respectively. The number of is not particularly limited, but if it is too small, the number of cross-linking points tends to decrease, and the physical properties of the coating such as solvent resistance, heat resistance and surface hardness tend to deteriorate. Among them, organic polymer composite inorganic fine particles having a hydroxyl group as the functional group (X), a compound having two or more functional groups (Y) capable of reacting with the hydroxyl group, and /
Alternatively, a film-forming composition containing, as a resin, at least one compound (J) selected from a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin,
It is preferable because it has good storage stability and can give a coating film having good coating physical properties such as stain resistance, flexibility, weather resistance, and storage stability, and the obtained coating film has gloss. The film-forming composition containing the organic polymer composite inorganic fine particles having a hydroxyl group in the organic polymer and at least one compound (J) selected from a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin is also the same as above. Is preferred.

Examples of the polyfunctional isocyanate compound include aliphatic, alicyclic, aromatic and other polyfunctional isocyanate compounds and modified compounds thereof. Specific examples of the polyfunctional isocyanate compound include, for example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2,4-
Trimer such as trimethylhexylmethane diisocyanate, methylcyclohexane diisocyanate, biuret body of 1,6-hexamethylene diisocyanate, isocyanurate body, etc .; polyfunctional isocyanates thereof and propanediol, hexanediol, polyethylene glycol, trimethylolpropane, etc. Compounds in which two or more isocyanate groups formed by the reaction with the polyhydric alcohol remain; these polyfunctional isocyanate compounds are alcohols such as ethanol and hexanol, compounds having a phenolic hydroxyl group such as phenol and cresol, and aceto Blocked polyfunctional isocyanate compounds blocked with blocking agents such as oximes, oximes such as methylethylketoxime, ε-caprolactam, γ-caprolactam, etc. The thing etc. can be mentioned. These polyfunctional isocyanate compounds may be used either individually or in combination of two or more. Among them, a non-yellowing polyfunctional isocyanate compound having no isocyanate group directly bonded to an aromatic ring is preferable in order to prevent undesired yellowing of the coating.

Examples of the melamine compound include:
Examples thereof include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, isobutyl ether type melamine, n-butyl ether type melamine and butylated benzoguanamine. Specific examples of the aminoplast resin include an alkyl etherified melamine resin, a urea resin, a benzoguanamine resin, and the like, and these aminoplast resins may be used alone or as a mixture or co-condensate of two or more kinds.

Here, the alkyl etherified melamine resin is obtained by converting aminotriazine into methylol, and alkyl etherified with cyclohexanol or an alkanol having 1 to 6 carbon atoms. Butyl etherified melamine resin and methyl etherified melamine resin. Resin and methylbutyl mixed melamine resin are typical ones. Also,
Sulfonic acid-based catalysts to accelerate curing, for example,
Paratoluene sulfonic acid and its amine salt can be used.

When the film-forming composition of the present invention contains a polyol (Q) having two or more hydroxyl groups in one molecule, the resulting film has strength, flexibility and solvent resistance. It is more preferable because the physical properties are improved.

The polyol (Q) containing two or more hydroxyl groups in one molecule is not particularly limited as long as it is soluble in the above-mentioned organic solvent, but it is not limited to the organic polymer in the organic polymer composite inorganic fine particles. It is preferable that they are compatible, because the gloss or transparency of the coating is improved. Therefore, those having the same composition as the organic polymer are most preferable.

As the polyol (Q), for example, a polyol obtained by polymerizing a monomer component containing a hydroxyl group-containing unsaturated monomer described later, a polyester polyol obtained under the condition of excess hydroxyl groups, and the like can be mentioned. . These may use 1 type (s) or 2 or more types. Examples of the hydroxyl group-containing unsaturated monomer include (a) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, allyl alcohol, homoallyl alcohol. Hydroxyl group-containing unsaturated monomers such as cinnamic alcohol, crotonyl alcohol, (b) For example, ethylene glycol, ethylene oxide, propylene glycol, propylene oxide, butylene glycol, butylene oxide, 1,4-bis (hydroxymethyl) cyclohexane , Phenyl glycidyl ether,
Dihydric alcohols or epoxy compounds such as glycidyl decanoate and Praxel FM-1 (manufactured by Daicel Chemical Industries, Ltd.) and, for example, acrylic acid, methacrylic acid,
Examples thereof include a hydroxyl group-containing unsaturated monomer obtained by a reaction with an unsaturated carboxylic acid such as maleic acid, fumaric acid, crotonic acid, and itaconic acid. At least one selected from these hydroxyl group-containing unsaturated monomers can be polymerized to produce a polyol.

Further, ethyl acrylate and acrylic acid n-
Propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, methacrylic acid Ethylhexyl, glycidyl methacrylate, styrene, vinyltoluene, 1-methylstyrene, acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, allyl acetate, diallyl adipate, diallyl itaconic acid, diethyl maleate, Vinyl chloride, vinylidene chloride, acrylamide, N
-Methylol acrylamide, N-butoxymethyl acrylamide, diacetone acrylamide, at least one or more ethylenically unsaturated monomers selected from ethylene, propylene, isoprene and the above (a) and (b)
A polyol can also be produced by polymerizing with a hydroxyl group-containing unsaturated monomer selected from

The molecular weight of the polyol obtained by polymerizing the monomer component containing the hydroxyl group-containing unsaturated monomer is 1,00.
0 to 500,000, preferably 5,000 to
It is 100,000. The hydroxyl value is 5 to 30.
It is 0, and preferably 10 to 200. The polyester polyol obtained under the condition of excess hydroxyl group is, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-
Butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, 2,2,4
-Trimethyl-1,3-pentanediol, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, cyclohexanediol, hydrogenated bisphenol A, bis (hydroxymethyl) cyclohexane, hydroquinone bis (hydroxyethyl ether), tris (hydroxyethyl) With polyhydric alcohols such as isocyanurate and xylylene glycol, for example,
Maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, azelaic acid, trimetic acid, terephthalic acid, phthalic acid, isophthalic acid and other polybasic acids, the number of hydroxyl groups in the polyhydric alcohol is the polybasic acid It can be produced by reacting under conditions in which the number of carboxyl groups is larger than that of

The molecular weight of the polyester polyol obtained under the above-mentioned excess of hydroxyl groups is 500 to 300,000, preferably 2,000 to 100,000.
The hydroxyl value is 5 to 300, preferably 1
It is 0 to 200. The polyol (Q) may be added in any amount to the film-forming composition, but the weight ratio of polyol (Q) / organic polymer composite inorganic fine particles in the film-forming composition is 0. / 100 to 99/1, preferably 30/70 to 95/5. Polyol (Q)
When the ratio is 30% or more, the flexibility of the coating is high, and when the ratio of the organic polymer composite inorganic fine particles is 5% or more, the surface hardness and the stain resistance of the coating are excellent.

As the polyol (Q), the above polyester polyol is preferably used. An acrylic polyol, which is a polyol obtained by polymerizing a monomer component containing the hydroxyl group-containing unsaturated monomer and having a (meth) acryl unit or the like, is also preferably used. As the polyol (Q), either a polyester polyol or an acrylic polyol may be used, or both may be used, depending on the application.

The number of hydroxyl groups in the polyol (Q) is 1
It is not particularly limited as long as it is 2 or more per molecule, but if the hydroxyl value in the solid content is 10 or less, the number of crosslinking points decreases,
The physical properties of the coating such as solvent resistance, water resistance, heat resistance and surface hardness tend to deteriorate. The film-forming composition of the present invention may be prepared by dispersing organic polymer composite inorganic fine particles in various organic solvents and / or water, and there is no particular limitation on the type and composition of the dispersion medium used, An organic solvent and / or water in which the organic chains in the organic polymer composite inorganic fine particles are dissolved are preferable. As such an organic solvent, for example, when the organic polymer composite inorganic fine particles contained in the film-forming composition of the present invention are produced by hydrolyzing / condensing the organic polymer (P) alone or with the metal compound (G). The above-mentioned organic solvent used for can be mentioned. The amount of the organic solvent and / or water used is not particularly limited and can be used in an appropriate amount. It may also be a mixture of other components such as various coating resins.

Further, one or more additives may be mixed in the film-forming composition. The additive used in the film-forming composition is not particularly limited, and examples thereof include various leveling agents generally used for paints, pigment dispersants, ultraviolet absorbers, antioxidants, viscosity modifiers, and light stability. Agents, metal deactivators, peroxide decomposers, fillers, reinforcing agents, plasticizers, lubricants, anticorrosives, rust preventives, emulsifiers, template decolorizers, carbon black, fluorescent brighteners, organic protective agents Examples include flame retardants, inorganic flame retardants, anti-dripping agents, melt flow modifiers, and antistatic agents. The above suitable additives are described in Canadian Patent No. 1,19.
No. 0,038.

A pigment can be added to the film-forming composition of the present invention, and the kind of the pigment to be added is not limited, and examples thereof include yellow lead, molybdate orange, dark blue, cadmium pigment, titanium white, Examples thereof include composite oxide pigments, inorganic pigments such as transparent iron oxide, cyclic higher pigments, soluble azo pigments, copper phthalocyanine pigments, dyed pigments, and organic pigments such as pigment intermediates.

When the film-forming composition of the present invention contains at least one compound (J) selected from a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin, a curing catalyst for promoting the crosslinking reaction. Is preferably used. An acidic or basic curing catalyst can be used as the curing catalyst. Specific examples of the acidic curing catalyst include organic sulfonic acids such as toluene sulfonic acid, methane sulfonic acid and dodecylbenzene sulfonic acid. Specific examples of the basic curing catalyst include amine catalysts such as triethylamine, methylimidazole, acridine, and hexadecyltrimethylammonium stearate; organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and stanna octoate. Can be mentioned. At least one kind or two or more kinds of these curing catalysts may be used, and a co-catalyst may be used in combination if necessary.

The film-forming composition of the present invention is an inorganic material such as aluminum, stainless steel, galvanized iron, tin plate, steel plate, concrete, mortar, slate and glass, or an organic material such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate and paper. The coating can be formed on any substrate or film. Also, dip,
It can be applied by a conventional method such as spraying, brush coating, roll coating, spin coating or bar coating.

The coating film obtained from the film-forming composition of the present invention is optionally baked and dried. For example, the coating film is formed by heating at a temperature in the range of room temperature to 300 ° C. for 0.2 minutes or more, and this coating film is a transparent and glossy excellent coating film.

[0080]

In the organic polymer-composite inorganic fine particles of the present invention, the organic polymer is fixed to the inorganic fine particles, and the organic polymer is not detected in the washing liquid in which the organic polymer-composite inorganic fine particles are washed with an arbitrary solvent. This strongly suggests that the fixing of the organic polymer is not merely adhesion or adhesion, but a chemical bond is generated between the inorganic fine particles and the organic polymer. Further, the organic polymer composite inorganic fine particles of the present invention have a good affinity for the organic matrix because the organic polymer is fixed on the surface of the inorganic fine particles.

In the conventional surface treatment of inorganic fine particles,
Since the drying step is essential, aggregation and cross-linking of the inorganic fine particles occur during drying, the particle size of the inorganic fine particles is increased, and the particle size distribution thereof is widened, whereas in the production method of the present invention, it is uniform. Since the reaction can be performed and the production rate of the composite inorganic fine particles does not vary greatly, the particle size distribution is narrow.

In the conventional surface treatment of inorganic fine particles with a coupling agent or the like, the number of reactive groups capable of reacting with the inorganic fine particles per one molecule of the coupling agent is very small, which is a typical coupling agent. Even a silane coupling agent usually has only a maximum of three reactive groups per molecule. On the other hand, all Si atoms in the polysiloxane group of the organic polymer (P) used in the present invention are bonded only to an alkoxy group, etc., except that they are bonded to the organic chain and also to a polysiloxane bond. In this case, the number of the reactive groups is larger than that of the conventional one. In the manufacturing process of the organic polymer composite inorganic fine particles, such an organic polymer reacts almost quantitatively even if it is reacted in a solution, because of the large number of the reactive groups, whereby the complicated drying step is prevented. It is not necessary and the organic polymer can be effectively used.

The organic polymer-composite inorganic fine particle dispersion of the present invention comprises organic polymer-composite inorganic fine particles fixed on the surface of the inorganic fine particles with an organic polymer and has excellent compatibility with the dispersion medium. Therefore, even after a lapse of time after preparation, no aggregation of particles, increase in viscosity, etc. are observed, and good stability over time is obtained. The film-forming composition of the present invention is a transparent and glossy coating film because the organic polymer composite inorganic fine particles contained in the composition have a fine average particle size and a narrow particle size distribution. Is obtained. Further, by fixing the organic polymer on the surface of the inorganic fine particles, it has a good affinity for an organic matrix such as a resin for coating material contained in the film-forming composition, and the organic polymer serves as a binder. Since it can act, even if it is applied to various base materials as it is, the resulting coating film does not have cloudiness and cracks, and has excellent weather resistance.

Since the film-forming composition of the present invention essentially contains the organic polymer composite inorganic fine particles as compared with the conventional film-forming composition, the physical properties of the film are improved as compared with the conventional product.
For example, a film-forming composition obtained by adding the organic polymer composite inorganic fine particles of the present invention to a general coating resin or the like has a surface hardness,
It gives a coating film with good coating physical properties such as heat resistance, abrasion resistance and stain resistance.

The organic polymer forming the organic polymer composite inorganic fine particles contained in the film-forming composition of the present invention contains a hydroxyl group, and the film-forming composition further contains a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin. When at least one compound (J) selected from the above is included, a crosslinked structure is formed, and the film-forming composition has flexibility,
It has good film properties such as weather resistance and hardness.
Further, the organic polymer composite inorganic fine particles contained in the film-forming composition of the present invention show good compatibility, and compared with general film-forming compositions, stain resistance, flexibility, weather resistance, Excellent film properties such as hardness. When the film-forming composition further contains the polyol (Q), the film has a stronger crosslinked structure, and thus the physical properties of the film are further improved.

[0086]

EXAMPLES Specific examples of the present invention will be shown below, but the present invention is not limited to the following examples. Polymerizable polysiloxane and organic polymer (P) used in the following examples were synthesized by the following Production Examples 1 to 14.

-Production Example 1- (Synthesis of Polymerizable Polysiloxane (S-1)) 144.5 g of tetramethoxysilane and γ-methacryloxypropyl were placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube. Trimethoxysilane 23.6 g, water 19
g, 30.0 g of methanol, and 5.0 g of Amberlyst 15 (cation exchange resin manufactured by Rohm and Haas Japan Co.) were added, and the mixture was stirred at 65 ° C. for 2 hours to be reacted. After cooling the reaction mixture to room temperature, a distillation column instead of the cooling pipe, a cooling pipe connected to this, and an outlet are provided,
The temperature was raised to 80 ° C. under normal pressure over 2 hours, and the temperature was kept at the same temperature until methanol stopped flowing out. In addition, 200
At a temperature of 90 ° C. at a pressure of mmHg, the same temperature was maintained until methanol did not flow out, and the reaction was further advanced. After cooling to room temperature again, Amberlyst 15 was filtered off to obtain a polymerizable polysiloxane (S-1) having a number average molecular weight of 1800.

-Production Example 2- (Synthesis of Polymerizable Polysiloxane (S-2)) In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube, 129.3 g of methyltrimethoxysilane and γ-methacryloxy were prepared. Propyltrimethoxysilane 23.4 g, water 1
8.8g, methanol 30.0g, 35% hydrochloric acid 1.0g
Was charged and reacted at 65 ° C. for 1 hour with stirring. After cooling the reaction mixture to room temperature, a distillation column was provided instead of the cooling tube, a cooling tube and an outlet connected to the distillation column were installed, and the temperature was adjusted to 80
The temperature was raised to 0 ° C. over 2 hours, and the temperature was kept at the same temperature until methanol stopped flowing out. Furthermore, at a pressure of 200 mmHg and a temperature of 90 ° C., the same temperature was maintained until methanol did not flow out to further advance the reaction. After further adding 2.0 g of triethylamine to form a white precipitate, 2
Under a pressure of 00 mmHg, the temperature inside the flask was raised to 90 ° C., and triethylamine was distilled off. After cooling to room temperature again, the precipitate was filtered off to obtain a polymerizable polysiloxane (S-2) having a number average molecular weight of 3000.

-Production Example 3- (Synthesis of Polymerizable Polysiloxane (S-3)) In Production Example 1, except that 14.1 g of vinyltrimethoxysilane was used instead of γ-methacryloxypropyltrimethoxysilane. In the same manner as in Production Example 1, a polymerizable polysiloxane (S-3) having a number average molecular weight of 1500 was obtained.

-Production Example 4- (Synthesis of Polymerizable Polysiloxane (S-4)) 86.7 g of tetraacetoxysilane and γ-methacryloxypropyl were placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube. Trimethoxysilane 8.1 g, water 6.5
g, 18 g of methanol and 3 g of Amberlyst 15 were added, and the mixture was stirred at 65 ° C. for 2 hours for reaction. After cooling the reaction mixture to room temperature, a distillation column was replaced with a cooling tube, a cooling tube and an outlet connected to the distillation column were installed, and the temperature was raised to 80 ° C. under normal pressure over 2 hours until methanol did not flow out. It was kept at the same temperature. Furthermore, 90 at pressure of 200 mmHg
The temperature was kept at the same temperature until methanol and acetic acid stopped flowing out, and the reaction was further advanced. After cooling to room temperature again, Amberlyst 15 was filtered off, and the polymerizable polysiloxane having a number average molecular weight of 2,000 (S-
4) was obtained.

-Production Example 5- (Synthesis of Organic Polymer (P-1)) 200 g of toluene as an organic solvent was placed in a 1 liter flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube and an N ₂ gas inlet. Put in, introduce N ₂ gas, and while stirring, keep the temperature inside the flask at 1
Heated to 10 ° C. Then, a solution prepared by mixing 20 g of the polymerizable polysiloxane (S-1) obtained in Production Example 1, 90 g of methyl methacrylate, 90 g of butyl acrylate, and 6 g of 2,2′-azobisisobutyronitrile was added from a dropping port for 2 hours. Was dropped. After the dropwise addition, stirring was continued for 1 hour at the same temperature, and then 1,1′-bis (t-butylperoxy)-
0.4 g of 3,3,5-trimethylcyclohexane was added to 30
The polymer was added twice every minute and was further heated for 2 hours for copolymerization to give an organic polymer having a number average molecular weight of 12,000 (P-
A solution in which 1) was dissolved in toluene was obtained. Table 3 shows the number average molecular weight and the solid content of the obtained organic polymer (P-1).

-Production Examples 6 to 14- (Synthesis of Organic Polymers (P-2 to P-10)) In the same manner as in Production Example 5 except that the composition shown in Table 1 was changed, the organic polymer (P-2 To P-10) was obtained by dissolving it in an organic solvent. Obtained organic polymer (P-2 to P-10)
Table 3 shows the number average molecular weight and solid content of the above.

[0093]

[Table 1] -Production Examples 15 to 18- (Synthesis of Organic Polymers (P-11 to P-14)) The organic polymers (P-11 to P-) were prepared in the same manner as in Production Example 5 except that the compositions shown in Table 2 were changed. A solution in which 14) was dissolved in an organic solvent was obtained. Obtained organic polymer (P-11 to P-
Table 3 shows the number average molecular weight and solid content of 14).

[0094]

[Table 2] The number average molecular weights of the polymerizable polysiloxane and the organic polymer (P) obtained in Production Examples 1 to 18 were analyzed by the following method. [Number average molecular weight] The polystyrene-reduced number average molecular weight of the polymerizable polysiloxane and the organic polymer (P) was measured by gel permeation chromatography (GPC) under the following conditions.

(Preparation of Sample) Using tetrahydrofuran as a solvent, 0.05 g of the polymerizable polysiloxane or the organic polymer (P) was dissolved in 1 g of tetrahydrofuran to prepare a sample. (Device) High-speed GPC device HLC-8 manufactured by Tosoh Corporation
020 was used.

(Column) G3000 manufactured by Tosoh Corporation
H, G2000H and GMH _XL were used. (Standard polystyrene) TSK standard polystyrene manufactured by Tosoh Corporation was used. (Measurement conditions) The measurement temperature was 35 ° C and the flow rate was 1 ml / min.

[0097]

[Table 3] -Example 1- (Synthesis of organic polymer composite inorganic fine particle dispersion (Z-1)) In a 500 ml four-necked flask equipped with a stirrer, two dropping ports (dripping port a and dropping port b), and a thermometer,
Put 200 g of butyl acetate and 50 g of methanol,
The internal temperature was adjusted to 20 ° C. Then, while stirring the inside of the flask, a mixed solution (raw material solution A) of 20 g of the butyl acetate solution of the organic polymer (P-1) obtained in Production Example 5, 30 g of tetramethoxysilane, and 20 g of butyl acetate was added from the dropping port a to 25
A mixed solution (raw material solution B) of 20% aqueous ammonia 20 g and methanol 20 g was added dropwise from the dropping port B over 1 hour. After the dropping, stirring was continued for 2 hours at the same temperature to obtain an organic polymer composite inorganic fine particle dispersion (Z-1). Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 6.

Further, the obtained organic polymer composite inorganic fine particle dispersion (Z-1) was treated with a pressure of 150 mmHg for 120
The specific surface area of the fine particles obtained by heating and drying at 3 ° C. for 3 hours was measured with Autosorb 6 (manufactured by Yuasa Ionics Co., Ltd., gas adsorption amount measuring device) and found to be 4.8 m ² / g.
Furthermore, the specific surface area after the fine particles were heated at 600 ° C. for 2 hours to thermally decompose the organic polymer was 227.6 m ² / g.

Example 2- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-2)) 500 ml four-necked machine equipped with stirrer, two dropping ports (dripping port a and dropping port b), and thermometer In a flask,
Put 200 g of butyl acetate and 50 g of methanol,
The internal temperature was adjusted to 20 ° C. Then, while stirring the inside of the flask, a solution of the organic polymer obtained in Production Example 5 in butyl acetate 4
A mixed solution of 0 g and 40 g of butyl acetate (raw material solution A) was dropped from the dropping port a, and a mixed solution of 5 g of 25% ammonia water and 5 g of methanol (raw material solution B) was dropped from the dropping port b over 1 hour. After the dropping, stirring was continued at the same temperature for 2 hours to obtain an organic polymer composite inorganic fine particle dispersion (Z-2). Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging Table 6 for stability
Shown in.

-Examples 3 to 15- (Organic polymer composite inorganic fine particle dispersion (Z-3 to Z-1)
Synthesis of 5)) The kinds of the organic solvent, the organic polymer (P), the metal compound (G), and the amounts of the organic solvent, aqueous ammonia, and the metal compound (G) are variously changed as shown in Tables 4 and 5. Except for this, in the same manner as in Example 1, organic polymer composite inorganic fine particle dispersions (Z-3 to Z-15) were obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Tables 6 and 7.

[0101]

[Table 4]

[0102]

[Table 5] -Comparative Example 1-A toluene solution of an organic polymer (P'-1) (in the same manner as in Production Example 5 except that γ-methacryloxypropyltrimethoxysilane was used in place of the polymerizable polysiloxane (S-1). Solid content 49%) was obtained. Production Example 5
A dispersion was obtained in the same manner as in Example 2 except that the toluene solution of the organic polymer (P′-1) was used in place of the toluene solution of the organic polymer (P-1) obtained in 1. The dispersion was heavily aggregated, and the particles rapidly precipitated after the stirring was stopped.

Example 16- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-16)) 500 ml equipped with a stirrer, three dropping ports (dripping port a, dropping port b and dropping port c) and a thermometer 200 g of butyl acetate and 50 g of methanol were placed in the four-necked flask described in (1) to adjust the internal temperature to 20 ° C. Then, while stirring the inside of the flask, a mixed solution of 20 g of a butyl acetate solution of the organic polymer obtained in Production Example 5 and 20 g of butyl acetate (raw material solution A) was added from a dropping port a to a mixed solution of 20 g of 25% ammonia water and 20 g of methanol. 30 g of tetramethoxysilane (raw material liquid C) was dropped from the dropping opening B over 1 hour. After dropping, continue stirring at the same temperature for 2 hours,
An organic polymer composite inorganic fine particle dispersion (Z-16) was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

-Example 17- (Synthesis of Organic Polymer-Complex Inorganic Fine Particle Dispersion (Z-17)) In the same manner as in Example 1 except that the reaction temperature was 50 ° C, the organic-polymer complex inorganic fine particle dispersion ( Z-1
7) was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

Example 18- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-18)) In a 500 ml four-necked flask equipped with a stirrer, a dropping port and a thermometer, 200 g of butyl acetate and 70 parts of methanol were added.
g, and 20 g of 25% aqueous ammonia were put thereinto, and the internal temperature was adjusted to 20 ° C. Then, while stirring the inside of the flask,
20 g of a butyl acetate solution of the organic polymer (P-1) obtained in Production Example 5, 30 g of tetramethoxysilane, and butyl acetate 2
0 g of the mixed solution was dropped from the dropping port over 1 hour. After the dropping, stirring was continued for 2 hours at the same temperature to obtain an organic polymer composite inorganic fine particle dispersion (Z-18). Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

-Example 19- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-19)) In a 500 ml four-necked flask equipped with a stirrer, a dropping port and a thermometer, 150 g of ethyl cellosolve, and in Production Example 5. 50 g of a toluene solution of the obtained organic polymer (P-1) and 50 g of tetramethoxysilane were put in advance, and the internal temperature was 20 ° C.
Adjusted to. Then, a mixed solution of 16 g of 25% aqueous ammonia and 30 g of ethyl cellosolve was added dropwise from the dropping port over 15 minutes while stirring the inside of the flask. After the dropping, stirring was continued at the same temperature for 2 hours to obtain an organic polymer composite inorganic fine particle dispersion (Z-19). Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

Example 20 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-20)) In a 500 ml four-necked flask equipped with a stirrer and a thermometer, 150 g of isopropyl alcohol and the organic compound obtained in Production Example 13 were used. 30 g of an isopropyl alcohol solution of the polymer (P-9), 10 g of titanium tetrachloride, 50 g of distilled water, and 10 g of urea were added, the internal temperature was gradually raised, and the inside of the flask was heated and maintained at 80 ° C. for 1 hour while stirring. Then, NH ₄ Cl produced as a by-product was removed by ultrafiltration to obtain an organic polymer composite inorganic fine particle dispersion (Z-20). Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

Example 21 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-21)) Stirrer, Two Drop Ports (Drop Port A and Drop Port B), Four Ports of 500 ml equipped with a thermometer In a flask,
Put 150g of ethyl cellosolve and keep the internal temperature at 20 ℃.
Adjusted to. Then, while stirring the inside of the flask, a toluene solution 50 of the organic polymer (P-3) obtained in Production Example 7 was obtained.
g, 10 g of zirconium butoxide, and 10 g of ethyl cellosolve (raw material liquid A) from a dropping port a, and a mixture of 20 g of 25% ammonia water and 50 g of ethyl cellosolve (raw material liquid B) from the dropping port b over 1 hour. Dropped.
After the dropping, stirring was continued at the same temperature for 2 hours to obtain an organic polymer composite inorganic fine particle dispersion (Z-21). Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

-Example 22- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-22)) Organic compound was prepared in the same manner as in Example 21 except that zirconium butoxide in Example 21 was replaced with aluminum isopropoxide. Polymer composite inorganic fine particle dispersion (Z-
22) was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

Example 23 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-23)) Tetramethoxysilane (150.0 g) was added to a 300 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube.
γ-glycidoxypropyltrimethoxysilane 23.3
g, 19.5 g of water, 30.0 g of methanol, 15 and 5.0 g of Amberlyst were added, and the mixture was stirred at 65 ° C. for 2 hours to cause a reaction. After cooling the reaction mixture to room temperature, a distillation column was replaced with a cooling tube, a cooling tube and an outlet connected to the distillation column were installed, and the temperature was 65 ° C. under a pressure of 200 mmHg and the same temperature was maintained until methanol stopped flowing out. The pressure was maintained and the pressure was further reduced to 50 mmHg to further advance the reaction. After cooling to room temperature again, Amberlyst 15 was filtered off to obtain a reactive polysiloxane (S-5) having a number average molecular weight of 1600.

Next, in a 300 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube, 5 g of reactive polysiloxane (S-5) and a COOH group-containing polyester resin (manufactured by Toyobo Co., Ltd., "Byron-200") were used. , Number average molecular weight 16,000, carboxyl group 0.02-0.0
6 mmol / g, hydroxyl group 0.1 to 0.15 mm
40 g (containing sol / g), 160 g of ethyl acetate and 0.5 g of triethylamine were added and heated at 60 ° C. for 5 hours to obtain a solution (solid content 21.9%) in which the organic polymer (P-11) was dissolved in ethyl acetate. It was The number average molecular weight of the obtained organic polymer was 18,000.

Then, 120 g of ethyl acetate was placed in a 500 ml four-necked flask equipped with a stirrer, a dropping port and a thermometer.
30 g of methanol and 10 g of 25% ammonia water were added and the internal temperature was adjusted to 20 ° C. Then, a mixed solution of 70 g of an ethyl acetate solution of the organic polymer (P-11) and 15 g of tetramethoxysilane was added dropwise from the dropping port over 2 hours while stirring the inside of the flask. After the dropping, stirring was continued at the same temperature for 1 hour to obtain an organic polymer composite inorganic fine particle dispersion (Z-23). Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

-Example 24- (Synthesis of organic polymer composite inorganic fine particle dispersion (Z-24)) Example 7
400 g of the organic polymer-composite inorganic fine particle dispersion (Z-7) obtained in the above was added, and the temperature inside the flask was adjusted to 1 under a pressure of 110 mmHg.
The temperature was raised to 00 ° C., ammonia, methanol, and butyl acetate were distilled off until the solid content concentration became 30%, and a dispersion (Z-
24) was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

Example 25- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-25)) In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a distillation column connected to an outlet, Example 4
400 g of the organic polymer-composite inorganic fine particle dispersion (Z-4) obtained in the above was put, and the temperature inside the flask was set to 1 under the pressure of 110 mmHg.
The temperature was raised to 00 ° C., ammonia, methanol, and ethyl cellosolve were distilled off until the solid content concentration reached 30%, to obtain a dispersion (Z-25) in which organic polymer-composite inorganic fine particles were dispersed in ethyl cellosolve. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

Example 26 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-26)) In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a distillation column connected to an outlet, Example 1
2. Organic polymer composite inorganic fine particle dispersion (Z-1
2) Add 350 g and 100 g of toluene, raise the temperature inside the flask to 100 ° C. under a pressure of 110 mmHg, and add ammonia, methanol, acetone, and toluene to a solid concentration of 3
It was distilled off until it reached 0% to obtain a dispersion (Z-26) in which organic polymer composite inorganic fine particles were dispersed in toluene. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

Example 27 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-27)) In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a distillation column connected to an outlet, Example 1
2. Organic polymer composite inorganic fine particle dispersion (Z-1
2) 250 g and 100 g of methyl isobutyl ketone were added, the temperature inside the flask was raised to 100 ° C. under a pressure of 110 mmHg, and ammonia, methanol, acetone, and methyl isobutyl ketone were distilled off until the solid content concentration became 30%, A dispersion (Z-27) in which the organic polymer composite inorganic fine particles were dispersed in methyl isobutyl ketone was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 7.

Example 28- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-28)) Example 1
Organic polymer composite inorganic fine particle dispersion (Z-1
4) Add 250 g and 100 g of water, raise the flask internal temperature to 100 ° C. under a pressure of 150 mmHg, and add ammonia,
Methanol and isopropyl alcohol have a solid content of 3
The organic polymer-composite inorganic fine particles were dispersed in water to obtain a dispersion (Z-28). Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle diameter and variation coefficient of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging Table 7 for stability
Shown in.

The organic polymer composite inorganic fine particle dispersions (Z-1 to Z-28) obtained in Examples 1 to 28 and the supernatants obtained when the respective dispersions were centrifuged were G
When analyzed by PC, no organic polymer was detected.
Further, the organic polymer composite inorganic fine particle dispersion (Z-1
.About.Z-28), each organic polymer-composite inorganic fine particle as a precipitate after centrifugation was washed with THF or water, and the washing was analyzed by GPC, but no organic polymer was detected. The above results indicate that the organic polymer is not simply attached to the inorganic fine particles but is firmly fixed.

Regarding the organic polymer-composite inorganic fine particle dispersions obtained in the above respective examples, the concentration of the organic polymer-composite inorganic fine particles in the obtained dispersion, the content of the inorganic substance in the organic polymer-composite inorganic fine particles, the organic polymer-composite inorganic fine particles The average particle diameter and coefficient of variation, the alkoxy group content in the organic polymer composite inorganic fine particles, and the stability over time were analyzed and evaluated by the following methods.

[Organic Polymer Composite Inorganic Fine Particle Concentration] The organic polymer composite inorganic fine particle dispersion was dried at 130 ° C. for 24 hours under a pressure of 100 mmHg, and calculated from the following formula. (Here, D: Weight of organic polymer-composite inorganic fine particles after drying (g) W: Weight of organic polymer-composite inorganic fine particle dispersion before drying (g)) [Inorganic content in organic polymer-composite inorganic fine particles] Organic The polymer composite inorganic fine particle dispersion was dried at 130 ° C. for 24 hours under a pressure of 100 mmHg, and elemental analysis was performed to determine the ash content as the inorganic substance content in the organic polymer composite inorganic fine particle.

[Average Particle Size and Coefficient of Variation] The average particle size and the coefficient of variation were measured at 23 ° C. by the dynamic light scattering measurement method using the following device. The measured average particle diameter is a volume average particle diameter. (Apparatus) Submicron particle size analyzer (NICOMP MODEL 370 manufactured by Nozaki Sangyo Co., Ltd.) (Measurement sample) Organic polymer composite inorganic fine particle concentration is 0.1
To 2.0% by weight of tetrahydrofuran dispersed in an organic polymer composite inorganic fine particle (if the organic polymer in the organic polymer composite inorganic fine particle is insoluble in tetrahydrofuran, a dispersion prepared by dispersing in an organic polymer-soluble solvent) ).

(Variation coefficient) The coefficient of variation is obtained by the following equation. [Alkoxy group content in organic polymer composite inorganic fine particles] 100 mm of organic polymer composite inorganic fine particle dispersion
5g dried at 130 ° C for 24 hours under Hg pressure
Was dispersed in a mixture of 50 g of acetone and 50 g of a 2N-NaOH aqueous solution, and the mixture was stirred at room temperature for 24 hours. Then, the alcohol in the liquid was quantified with a gas chromatograph to calculate the alkoxy group content of the organic polymer composite inorganic fine particles.

[Stability over time] The obtained dispersion was sealed in a Gardner viscosity tube and stored at 50 ° C. After one month, no aggregation of particles, sedimentation, or increase in viscosity was observed.

[0124]

[Table 6]

[0125]

[Table 7] -Comparative Example 2- (Radical Graft Polymerization from Colloidal Silica Surface)
In a 500 ml flask equipped with a stirrer, a thermometer, and a cooling tube, colloidal silica (Japan Aerosil Co., Ltd. “Aer
osil200 ", average particle size 12 nm (catalog value) 0.2 g, γ-glycidoxypropyltrimethoxysilane 5 g and butyl acetate 300 g were added, and the mixture was refluxed at 120 ° C. for 10 hours. Thereafter, 5.5 g of 4,4′azobis (4-cyanovaleric acid) and 0.1 g of triethylamine were added, and the mixture was heated with stirring at 40 ° C. for 3 hours to introduce an azo group on the surface of the colloidal silica. Next, an N ₂ gas inlet was provided in the flask, 100 g of methyl methacrylate was added,
N ₂ gas was introduced, the temperature was raised to 70 ° C. with stirring, the temperature was maintained at the same temperature for 6 hours, and heating was further performed at 100 ° C. for 1 hour to carry out polymerization. Many agglomerates were observed in the obtained reaction liquid slurry. When the supernatant was collected and the particle size distribution was examined, the particles in the obtained dispersion had an average particle size of 380.
nm, the coefficient of variation was 275%, and the particle size distribution was very wide. No alkoxy group was found in the fine particles.

Comparative Example 3- (Treatment of colloidal silica with silyletherified polymer) A polyol obtained by dehydration reaction of 1,10-decanediol was placed in a 200 ml flask equipped with a stirrer, a thermometer, and a cooling tube. 7 g, diethoxydimethylsilane 15 g and tetrahydrofuran (THF) 135 g
Was added and the mixture was refluxed at 65 ° C. for 15 hours. Then, a silyl etherified polymer was obtained by vacuum drying at 150 ° C. and 100 mmHg. The number average molecular weight of this polymer is 7,000
And the ash content was 26.2%. Next, in a 200 ml flask equipped with a stirrer, a thermometer, and a cooling tube, colloidal silica (average particle size: 37
nm, coefficient of variation: 53%) of 1,2-dimethoxyethane dispersion (SiO ₂ 30% containing) 2 g, the silyl ether polymers 1g and 1,2-dimethoxyethane 13
0 g was refluxed at 80 ° C. for 10 hours. After reprecipitating the obtained reaction solution with methanol, the precipitate was examined by elemental analysis.
The ash content in the precipitate was almost the same (26.0%) as that in the raw material silyl etherified polymer. In addition, when the reaction solution was analyzed by GPC, the number average molecular weight was 7,000.
Only the polymer of 0 was detected, and it was confirmed that the silyl etherified polymer did not bind to the colloidal silica by heating in the liquid phase as described above. The reaction solution was vacuum dried at 150 ° C. and 100 mmHg and then redispersed in THF, but some precipitate was observed. When the supernatant was collected and the particle size distribution was examined, the particles in the obtained dispersion were
The average particle size was 92 nm, the coefficient of variation was 128%, and the particle size distribution was very wide. No alkoxy group was found in the fine particles.

Comparative Example 4- (Treatment of Colloidal Silica with Coupling Agent and Acid Group-Containing Polymer) In a 200 ml flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube and a N ₂ gas inlet,
Add 80 g of isopropyl alcohol (IPA), add N ₂
Gas was introduced and the temperature inside the flask was heated to 80 ° C. with stirring. Then, a solution obtained by mixing 56 g of acrylic acid, 24 g of methyl acrylate and 0.4 g of 2,2′-azobisisobutyronitrile was added dropwise from the dropping port over 1 hour. After dropping, the mixture was continuously stirred at the same temperature for 2 hours to carry out copolymerization to obtain an IPA solution of an acrylic acid / methyl acrylate copolymer having a number average molecular weight of 8,000. Next, in a 500 ml flask equipped with a stirrer, 133 g of an ethylene glycol dispersion (containing 30% SiO ₂ ) of colloidal silica (average particle size: 35 nm, variation coefficient: 58%),
Ethylene glycol (267 g), γ-glycidoxypropyltrimethoxysilane (0.4 g) and water (0.4 g) were added, and the mixture was stirred at room temperature for 2 hours to obtain a coupling agent-treated colloidal silica slurry (A). To this slurry (A), 1 g of the above IPA solution of acrylic acid / methyl acrylate copolymer was added and stirred at room temperature for 1 hour to obtain a slurry (B). After reprecipitating the obtained slurry (B) with hexane, the precipitate was examined by elemental analysis, but no ash was found in the precipitate. Moreover, when the slurry (B) was analyzed by GPC, only a polymer having a number average molecular weight of 8,000 was detected, and it was confirmed that the acrylic acid / methyl acrylate copolymer did not bind to the colloidal silica by the above method. Slurry (B) at 150 ℃ 1
The particles were vacuum dried at 00 mmHg, but when the obtained particles were mixed with ethylene glycol or IPA, they were hardly redispersed, and most of the particles were aggregates, and only a dispersion which was a precipitate was obtained. Further, no alkoxy group was found in these fine particles.

Comparative Example 5 (Treatment of Colloidal Silica with Polymer Silane Coupling Agent) Stirrer, Droplet, Thermometer, Cooling Tube and N ₂
80 g of butyl acetate was placed in a 200 ml flask equipped with a gas inlet, N ₂ gas was introduced, and the temperature inside the flask was heated to 120 ° C. with stirring. Then, a solution prepared by mixing 80 g of methyl methacrylate, 5 g of 3-mercaptopropionic acid and 0.8 g of 2,2′-azobisisobutyronitrile was added dropwise from the dropping port over 1 hour. After the dropping, the mixture was continuously stirred at the same temperature for 2 hours for polymerization to obtain a polymer having an acid group at the terminal. To this, 10.5 g of γ-aminopropyltriethoxysilane and 50 mg of N, N′-dicyclohexylcarbodiimide were added and stirred at 100 ° C. for 1 hour to obtain a polymer silane coupling agent. The number average molecular weight of this polymer silane coupling agent is 9,
000 and the ash content was 3.0%. Then stirrer,
In a 1 liter flask equipped with a thermometer and condenser,
500 g of 2-dimethoxyethane, 2 g of an ethanol dispersion (containing 30% of SiO ₂ ) of colloidal silica (average particle diameter: 40 nm, coefficient of variation: 48%), 2 g of the above polymer silane coupling agent solution and 1 g of 5% ammonia water.
Was added and the mixture was heated with stirring at 60 ° C. for 2 hours. After reprecipitating the obtained reaction liquid with hexane, the precipitate was examined by elemental analysis, and the ash content in this precipitate was the same as that in the raw material polymer silane coupling agent. Further, when the reaction solution was analyzed by GPC, only a polymer having a number average molecular weight of 9,000 was detected, and it was confirmed that the polymer silane coupling agent did not bind to the colloidal silica by the above method. This reaction liquid is 100 mmHg at 150 ° C.
After vacuum drying, it was redispersed in butyl acetate, but some precipitate was observed. When the supernatant was collected and the particle size distribution was examined, the particles in the obtained dispersion had an average particle size of 25.
The particle size distribution was very wide with 0 nm and a coefficient of variation of 78%. In the fine particles, the methoxy group is 0.06 mmo.
1 / g was observed.

-Comparative Example 6- (Treatment of Colloidal Silica with Organic Polymer (P))
In a 300 ml flask equipped with a stirrer, a thermometer, and a cooling tube, 160 g of ethyl cellosolve, 50 g of a methanol dispersion of colloidal silica (average particle size: 31 nm, coefficient of variation: 60%) (containing 30% SiO ₂ ), Production Example 5 The organic polymer (P-1 number average molecular weight 12,000
20 g of toluene solution of 0, ash content 5.8%) and 1 g of 5% ammonia water were added, and the mixture was heated with stirring at 60 ° C. for 2 hours.
After reprecipitating the obtained reaction solution with hexane, the precipitate was examined by elemental analysis. The ash content in this precipitate was almost the same as that in the raw material organic polymer (P-1) (5.7%). Met. Further, when the reaction solution was analyzed by GPC, a polymer having a number average molecular weight of 12,000 was detected, and it was confirmed that the organic polymer (P-1) did not bind to the colloidal silica by the above method. The reaction solution is heated at 150 ° C.
After mmHg was vacuum dried, it was redispersed in toluene, but some precipitate was observed. When the supernatant was sampled and the particle size distribution was examined, the particles in the obtained dispersion had an average particle size of 143 nm and a coefficient of variation of 113%, showing a very wide particle size distribution. A methoxy group of 0.06 mmol / g was found in these fine particles.

Example 29 The organic polymer composite inorganic fine particle dispersion (Z-24) obtained in Example 24 was coated on a glass substrate with a bar coater. After drying at room temperature for 30 minutes and at 60 ° C. for 40 minutes, a transparent and glossy good coating film was obtained. -Example 30- 3 g of an isocyanate curing agent "Sumijour N-3500" manufactured by Sumitomo Chemical Co., Ltd. was added to 100 g of the organic polymer composite inorganic fine particle dispersion (Z-24) obtained in Example 24, and after mixing, glass. The substrate was coated with a bar coater. After drying at room temperature for 30 minutes and at 80 ° C. for 60 minutes, a transparent and glossy good coating film was obtained.

Example 31 To 100 g of the organic polymer composite inorganic fine particle dispersion (Z-24) obtained in Example 24 was added 8 g of a curing agent "Super Beckamine J820-60" manufactured by Dainippon Ink and Chemicals, Inc. After mixing, a glass substrate was coated with a bar coater. After drying at room temperature for 30 minutes and at 150 ° C. for 30 minutes, a transparent and glossy good coating film was obtained.

Example 32 100 g of the organic polymer composite inorganic fine particle dispersion (Z-24) obtained in Example 24 and 2060, 80 g of acrylic resin Arotane manufactured by Nippon Shokubai Co., Ltd. were mixed to obtain a resin mixture. . The resin mixture was stored in a closed container at 50 ° C. for 1 month, but no aggregation or thickening was observed. To this resin mixture, 14 g of an isocyanate curing agent "Sumijour N-3500" manufactured by Sumitomo Chemical Co., Ltd. was added, mixed, and then coated on a glass substrate with a bar coater. After drying at room temperature for 30 minutes and then at 80 ° C. for 60 minutes, a transparent and glossy good coating film was obtained.

-Example 33- 100 g of the organic polymer composite inorganic fine particle dispersion (Z-24) obtained in Example 24 and 80 g of the alkyd resin "Alloplatz 0B-110" manufactured by Nippon Shokubai Co., Ltd. were mixed to form a resin mixture. Obtained. This resin mixture is placed in a closed container at 50 ° C. for 1 hour.
After storing for a month, no aggregation or thickening was observed. To this resin mixture, 15 g of a curing agent "Super Beckamine J820-60" manufactured by Dainippon Ink and Chemicals, Inc. was added,
After mixing, the glass substrate was coated with a bar coater. After drying at room temperature for 30 minutes and at 150 ° C. for 30 minutes, a transparent and glossy good coating film was obtained.

-Comparative Example 7- 50 g of methanol-silica dispersion manufactured by Nissan Chemical Industries, Ltd. and Arotane 2060, 8 which is an acrylic resin manufactured by Nippon Shokubai Co., Ltd.
0 g was mixed to obtain a resin mixture. The resin mixture was stored at room temperature in a closed container, but aggregation occurred about 3 hours after mixing. An isocyanate curing agent "Sumijour N-" manufactured by Sumitomo Chemical Co., Ltd. was added to the resin mixture before aggregation occurred.
3500 "14g was added and mixed, and then coated on a glass substrate with a bar coater, then at room temperature for 30 minutes, and then at 80 ° C.
After drying for 60 minutes, the resulting coating film became cloudy due to agglomeration of particles and the surface smoothness of the coating film was poor.

Comparative Example 8 50 g of a butyl acetate dispersion of colloidal silica (particle concentration 30%) surface-treated with the polymer silane coupling agent obtained in Comparative Example 5 and Arotan 2060, an acrylic resin manufactured by Nippon Shokubai Co., Ltd. , 80g and Sumitomo Chemical Co., Ltd. isocyanate curing agent "SUMIDUR N-3500" 1
4 g was mixed to obtain a resin mixture. After coating the resin mixture on a glass substrate with a bar coater, at room temperature for 30 minutes,
Then, it was dried at 80 ° C. for 60 minutes, but the obtained coating film became cloudy due to agglomeration of particles, and the smoothness of the coating film surface was inferior.

-Examples 34 to 37- (Organic polymer composite inorganic fine particle dispersion (Z-29 to Z-
Synthesis of 32)) Except that the kinds of the organic solvent, the organic polymer (P), the metal compound (G), and the amounts of the organic solvent, aqueous ammonia, and the metal compound (G) are changed as shown in Table 8. In the same manner as in Example 1, organic polymer composite inorganic fine particle dispersions (Z-29 to Z-32) were obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle size and coefficient of variation of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 9.

[0137]

[Table 8] -Example 38- (Synthesis of organic polymer composite inorganic fine particle dispersion (Z-33)) 250 g of butyl acetate and 90 g of methanol were placed in a 500 ml four-necked flask equipped with a stirrer, a dropping port, and a thermometer.
g and 25 g of 25% ammonia water were put thereinto, and the internal temperature was adjusted to 20 ° C. Then, while stirring the inside of the flask,
A mixed solution of 4 g of a butyl acetate solution of the organic polymer (P-1) obtained in Production Example 5 and 40 g of tetramethoxysilane was added dropwise from the dropping port over 1 hour. After the dropping, stirring was continued at the same temperature for 2 hours to obtain an organic polymer composite inorganic fine particle dispersion (Z-
33) was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle size and coefficient of variation of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 9.

Example 39 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-34)) In a 500 ml four-necked flask equipped with a stirrer, two dropping ports (dripping ports a and b), and a thermometer. , 120 g of butyl acetate and 30 g of methanol are added beforehand, and the internal temperature is adjusted to 20
The temperature was adjusted to ° C. Then, while stirring the inside of the flask, 50 g of a toluene solution of the organic polymer (P-13) obtained in Production Example 17, 10 g of zirconium butoxide, and 1 butyl acetate.
0 g of the mixed solution (solution A) was dropped from the dropping port a, and a mixture of 20 g of 25% aqueous ammonia and 50 g of methanol (solution B) was dropped from the dropping port b over 1 hour. After the dropping, stirring was continued for 2 hours at the same temperature to obtain an organic polymer composite inorganic fine particle dispersion (Z-39). Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle size and coefficient of variation of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 9.

-Example 40- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-35)) In the same manner as in Example 39 except that zirconium butoxide in Example 39 was replaced with aluminum isopropoxide. Polymer composite inorganic fine particle dispersion (Z-
35) was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle size and coefficient of variation of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 9.

Example 41 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-36)) An organic compound was prepared in the same manner as in Example 39 except that zirconium butoxide in Example 39 was replaced with titanium isopropoxide. Polymer composite inorganic fine particle dispersion (Z-36)
Got Organic polymer composite inorganic fine particle concentration of the obtained dispersion, the inorganic substance content in the organic polymer composite inorganic fine particle,
Table 9 shows the average particle size and coefficient of variation of the organic polymer-composite inorganic fine particles, the content of alkoxy groups in the organic polymer-composite inorganic fine particles, and the stability over time.

Example 42- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-37)) In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a distillation column connected to an outlet, Example 1
400 g of the organic polymer-composite inorganic fine particle dispersion (Z-1) obtained in the above was put, and the temperature inside the flask was set to 1 under a pressure of 110 mmHg.
The temperature was raised to 00 ° C., ammonia, methanol, water and butyl acetate were distilled off until the solid content concentration became 30%, and the organic polymer composite inorganic fine particle dispersion (Z- 37) was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle size and coefficient of variation of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 10.

-Examples 43 to 44- (Organic polymer composite inorganic fine particle dispersion (Z-38 to Z-
Synthesis of 39)) In Example 42, instead of the organic polymer composite inorganic fine particle dispersion (Z-1) obtained in Example 1,
Organic polymer composite inorganic fine particle dispersion obtained in Example 2 (Z
-2), except that the same as Example 42,
An organic polymer composite inorganic fine particle dispersion (Z-38) in which organic polymer composite inorganic fine particles were dispersed in butyl acetate was obtained.
Similarly, in Example 42, in place of the organic polymer composite inorganic fine particle dispersion (Z-1) obtained in Example 1, the organic polymer composite inorganic fine particle dispersion (Z-2 obtained in Example 34.
Except for using 9), an organic polymer composite inorganic fine particle dispersion (Z-39) in which organic polymer composite inorganic fine particles were dispersed in butyl acetate was obtained in the same manner as in Example 42. Organic polymer composite inorganic fine particle concentration of each dispersion obtained, the inorganic content in the organic polymer composite inorganic fine particles,
Table 10 shows the average particle diameter and coefficient of variation of the organic polymer-composite inorganic fine particles, the content of alkoxy groups in the organic polymer-composite inorganic fine particles, and the stability over time.

Example 45- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-40)) In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a distillation column connected to an outlet, Example 3
Organic polymer composite inorganic fine particle dispersion (Z-3
0) Add 250g and 100g of butyl acetate, 110mmHg
Under pressure, the temperature inside the flask is raised to 100 ° C., ammonia, methanol, ethyl acetate, water, and butyl acetate are distilled off until the solid content concentration becomes 30%, and the organic polymer composite inorganic fine particles are dispersed in butyl acetate. An organic polymer composite inorganic fine particle dispersion (Z-40) was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle size and coefficient of variation of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 10.

Example 46 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-41)) In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a distillation column connected to an outlet, Example 3
Organic polymer composite inorganic fine particle dispersion (Z-3
1) Add 250g and 100g butyl acetate, 110mmHg
Under pressure, the temperature inside the flask was raised to 100 ° C., ammonia, methanol, butanol, water, and butyl acetate were distilled off until the solid content concentration became 30%, and the organic polymer composite inorganic fine particles were dispersed in butyl acetate. An organic polymer composite inorganic fine particle dispersion (Z-41) was obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle size and coefficient of variation of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 10.

Example 47 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-42)) In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a distillation column connected to an outlet, Example 3
Organic polymer composite inorganic fine particle dispersion (Z-3
2) Add 250 g and 100 g of water, raise the temperature inside the flask to 100 ° C. under a pressure of 150 mmHg, and add ammonia,
Methanol, isopropyl alcohol, and water were distilled off until the solid content concentration became 30% to obtain an organic polymer-composite inorganic fine particle dispersion (Z-42) in which the organic polymer-composite inorganic fine particles were dispersed in water. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle size and coefficient of variation of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 10.

-Examples 48 to 51- (Organic polymer composite inorganic fine particle dispersion (Z-43 to Z-
Synthesis of 46)) In place of the organic polymer composite inorganic fine particle dispersion (Z-7) obtained in Example 7 in Example 24, the organic polymer composite inorganic fine particle dispersion (Z) obtained in Examples 38 to 41 was used. -33 to Z-36) except that
In the same manner as in Example 24, organic polymer composite inorganic fine particle dispersions (Z-43 to Z-46) in which organic polymer composite inorganic fine particles were dispersed in butyl acetate were obtained. Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic substance content in the organic polymer composite inorganic fine particle, average particle size and coefficient of variation of the organic polymer composite inorganic fine particle, alkoxy group content in the organic polymer composite inorganic fine particle, aging The stability is shown in Table 10.

The organic polymer composite inorganic fine particle dispersions (Z-29 to Z-46) obtained in Examples 34 to 51 and the supernatants obtained when the respective dispersions were subjected to a centrifuge were analyzed by GPC. When analyzed, no organic polymer was detected. Further, the organic polymer composite inorganic fine particle dispersion (Z
-29 to Z-46), each organic polymer-composite inorganic fine particle as a precipitate after centrifugation was washed with THF or water, and the washing was analyzed by GPC, but no organic polymer was detected. The above results indicate that the organic polymer is not simply attached to the inorganic fine particles but is firmly fixed.

Regarding the organic polymer-composite inorganic fine particle dispersions obtained in each of the above Examples 34 to 51, the organic polymer-composite inorganic fine particle concentration of the obtained dispersion, the inorganic substance content in the organic polymer-composite inorganic fine particle, the organic polymer The average particle size and coefficient of variation of the composite inorganic fine particles, the content of the alkoxy groups in the organic polymer composite inorganic fine particles, and the stability over time were analyzed and evaluated by the same methods as in Examples 1-28.

[0149]

[Table 9]

[0150]

[Table 10] -Examples 52 to 64 and Comparative Examples 9 to 14-Dispersions and resins were mixed with the resin compositions shown in Tables 11 and 12 to obtain resin mixtures. These resin mixtures were stored in a closed container at 50 ° C. for 1 month, and their appearance and storage stability were examined. The results are shown in Tables 11 and 12. Titanium oxide (Taipaque CR-95, manufactured by Ishihara Sangyo Co., Ltd.) was added to the resin mixture so as to have a nonvolatile pigment concentration of 40% by weight, and well dispersed by a sand mill. Polyfunctional isocyanate (Sumijour N-3200, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added to each of the obtained dispersion liquids (hereinafter, referred to as I-1 liquid) to obtain hydroxyl groups in the I-1 liquid. An II-1 solution was prepared by weighing an amount such that the equivalent ratio of the isocyanate groups in the polyfunctional isocyanate was 1: 1.
This I-1 solution and II-1 solution were mixed to obtain a coating composition.
The coating composition obtained was applied to a 0.8 mm mild steel plate to give a film thickness of 30 μ.
After coating for 1 hour at room temperature, it was dried forcibly at 80 ° C. for 2 hours to prepare test pieces for various performance tests. The performance of the coating film was evaluated by the performance test method described below. Table 1 shows the evaluation results
1 and Table 12.

[0151]

[Table 11]

[0152]

[Table 12] -Example 65 and comparative examples 15-16-The dispersion and resin were mixed by the resin composition shown in Table 13, and the resin mixture was obtained. Add these resin mixtures in a closed container for 5
The results were shown in Table 13 after storage at 0 ° C. for 1 month to examine the appearance and storage stability. Titanium oxide (Taipaque CR-95, manufactured by Ishihara Sangyo Co., Ltd.) was added to the resin mixture so as to have a nonvolatile pigment concentration of 50% by weight, and well dispersed by a sand mill. The obtained dispersion liquid (hereinafter, referred to as I-2 liquid).
In contrast, as a curing agent, a polyfunctional isocyanate (Desmodur BL-3175, Sumitomo Bayer Urethane Co., Ltd.)
Was prepared) and the equivalent ratio of the hydroxyl group in the liquid I-2 to the isocyanate group in the polyfunctional isocyanate was 1: 1 and dibutyltin dilaurate was used as a curing catalyst in an amount of 1000 ppm with respect to the resin mixture. Add II
-2 liquid. This I-2 solution and II-2 solution were mixed to obtain a coating composition. The obtained coating composition was coated on a 0.8 mm mild steel plate with a film thickness of 15 μ, and allowed to stand at room temperature for 1 hour.
Test pieces for various performance tests were prepared by forced drying at ℃ for 1 hour. The performance of the coating film was evaluated by the performance test method described below. The evaluation results are shown in Table 13.

-Example 66 and Comparative Example 17- Dispersions and resins were mixed with the resin compositions shown in Table 13 to obtain resin mixtures. Add these resin mixtures in a closed container for 5
The results were shown in Table 13 after storage at 0 ° C. for 1 month to examine the appearance and storage stability. Titanium oxide (R-8
20, Ishihara Sangyo Co., Ltd.) was mixed so that the non-volatile pigment concentration was 50% by weight, and well dispersed by a sand mill.
A dispersion liquid (hereinafter, referred to as liquid I-3) was obtained. Further, the resin and the curing agent were mixed in the amounts shown in Table 13 to prepare a liquid II-3. This I-3 solution and II-3 solution were mixed to obtain a coating composition. The coating composition obtained was applied to a 0.8 mm mild steel plate to give a film thickness of 1
The coating was applied at 5 μ, allowed to stand at room temperature for 1 hour, and then forcedly dried at 170 ° C. for 16 minutes to prepare test pieces for various performance tests. The performance of the coating film was evaluated by the performance test method described below. The evaluation results are shown in Table 13.

-Example 67 and Comparative Example 18- A resin mixture was obtained by mixing the dispersion and the resin with the resin composition shown in Table 13. Add these resin mixtures in a closed container for 5
The results were shown in Table 13 after storage at 0 ° C. for 1 month to examine the appearance and storage stability. Titanium oxide (Taipec CR-95, manufactured by Ishihara Sangyo Co., Ltd.) was added to the resin mixture so as to have a nonvolatile pigment concentration of 50% by weight, and well dispersed by a sand mill to prepare a dispersion liquid (hereinafter referred to as I-3 liquid) I got).
Further, the resin and the curing agent were mixed in the amounts shown in Table 13, and II-
It was 3 liquids. This I-3 solution and II-3 solution were mixed to obtain a coating composition. The obtained coating composition is coated on a 0.8 mm mild steel sheet with a film thickness of 15 μ, and left at room temperature for 1 hour, then at 150 ° C.
By force-drying for 20 minutes, test pieces for various performance tests were prepared. The performance of the coating film was evaluated by the performance test method described below. The evaluation results are shown in Table 13.

[0155]

[Table 13] -Examples 68-70 and Comparative Examples 19-22-The dispersion and resin were mixed with the resin composition shown in Table 14, and the resin mixture was obtained. Add these resin mixtures in a closed container for 5
It was stored at 0 ° C. for 1 month, and the appearance and storage stability were examined. The results are shown in Table 14. A curing agent and a catalyst having the composition shown in Table 14 were added to this resin mixture and mixed, and then coated on a 0.8 mm untreated dull steel sheet with a film thickness of 30 μ and left at room temperature for 1 hour.
After forced drying at 60 ° C. for 20 minutes, the performance of the coating film was evaluated by the performance test method described below. The evaluation results are shown in Table 14.

[0156]

[Table 14] -Example 71 and comparative examples 23-24-The dispersion and resin were mixed by the resin composition shown in Table 15, and the resin mixture was obtained. Add these resin mixtures in a closed container for 5
The appearance and storage stability were examined after storage at 0 ° C for 1 month. The results are shown in Table 15. A curing agent and a catalyst having the composition shown in Table 15 were added to and mixed with the resin mixture, and then Bonderite 310 was added.
It was applied on a 0-treated steel sheet with a film thickness of 5 to 10 μm, allowed to stand at room temperature for 1 hour, and then forcedly dried at 200 ° C. for 10 minutes, and the performance of the coating film was evaluated by the performance test method described below. Table 15 shows the evaluation results.
Shown in.

[0157]

[Table 15] The resin mixtures obtained in the above Examples and Comparative Examples were evaluated for appearance and storage stability after storage at 50 ° C. for 1 month by the following methods. Further, the dryness, solvent resistance, pencil hardness, stain resistance, weather resistance, adhesion, bendability, and corrosion resistance of the coating film were analyzed and evaluated by the following methods.

[Appearance] The state of the coating film (presence or absence of aggregates, surface irregularities, gloss) was visually evaluated. ◎: Excellent ○: Good △: Fair
X: not possible [Storage stability] The storage stability after storage for 1 month at 50 ° C was observed.

⊚: Stable ◯: Slightly thickened Δ: Thickened ×: A large amount of condensate was present [Drying property] Evaluation was performed by touching with fingers after forced drying. ⊚: No change ∘: Slightly marks X: Strong marks [Solvent resistance] Surface condition after rubbing 50 times with absorbent cotton soaked with methyl ethyl ketone.

◎: No change ○: Gloss
X: The coating film dissolves and disappears [Pencil hardness] A pencil scratching test of JIS K5400 6.14 was performed to evaluate the scratches. [Staining resistance] A 0.05% carbon aqueous solution is applied to the coating film 30 times with a brush, and after forcibly drying at 80 ° C. for 1 hour, dirt is attached to the coating film when washed 30 times with a brush while washing with water. The degree of

⊚: No adhesion ○: Almost no adhesion Δ: Some adhesion X: Adhesion [Weather resistance] The coating film state after 3000 hours was examined with a sunshine weather meter. ◎: Excellent ○: Good △: Normal
X: Poor [Adhesion] A cross-cut test of JIS K5400 6.15 was performed.

◎: No peeling ○: Slight peeling at the intersection of cuts △: Peeling area 5 to 35% ×: Peeling area 35%
[Bending Property] The coating film was examined for peeling and peeling by a bending tester specified in JIS K5400 6.16. (Axial diameter 2 mm) ◎: Excellent ○: Good △: Normal
X: Poor [Corrosion resistance] In the salt spray test, the time during which the maximum width of the blister piece at the cross cut portion was 2 mm or less was measured.

[0163]

The organic polymer composite inorganic fine particles of the present invention have an average particle size of 5 to 200 nm and a particle size variation coefficient of 50.
% Or less, having a fine average particle size, a narrow particle size distribution, and dispersion stability when used in paints and molding materials, and affinity with an organic matrix, which are conventionally used for the same purpose. Especially good compared to. The method for producing inorganic fine particles of an organic polymer composite according to the present invention is a very simple method of hydrolyzing and condensing a specific organic polymer (P) alone or with a hydrolyzable metal compound (G). The organic polymer can be fixed on the surface, and it is not always necessary to incorporate a complicated drying step as in the past into the manufacturing method.

The organic polymer-composite inorganic fine particles of the present invention and the dispersion comprising the organic polymer-composite inorganic fine particles dispersed in water or an organic solvent are useful as additives for various paints and molding materials. And the dispersion thereof can be used as it is as a film-forming composition. The organic polymer composite inorganic fine particles in the film-forming composition have a good affinity for an organic matrix such as a resin for paint because the organic polymer is fixed on the surface of the inorganic fine particles, and thus various groups can be used. The coating film obtained by coating the material has a glossy and desirable appearance, does not cause cracks, and has excellent adhesion and weather resistance.

Since the film-forming composition of the present invention essentially contains the organic polymer composite inorganic fine particles as compared with the conventional film-forming composition, the physical properties of the film are improved as compared with the conventional products. For example, a film-forming composition obtained by adding the organic polymer composite inorganic fine particles of the present invention to a general coating resin or the like has surface hardness, heat resistance,
It gives a coating film with good physical properties such as abrasion resistance and stain resistance.
Further, the organic polymer composite inorganic fine particles contained in the film-forming composition contains a hydroxyl group in the organic polymer, and the film-forming composition further contains at least a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin. When one compound (J) is contained, a crosslinked structure is formed, and the film-forming composition has a good film such as solvent resistance, stain resistance, flexibility, weather resistance, heat resistance, and storage stability. It has physical properties. When the film-forming composition further contains the polyol (Q), the film has a stronger crosslinked structure, and thus the physical properties of the film are further improved.

This film-forming composition utilizes the above-mentioned good coating physical properties such as solvent resistance, stain resistance, flexibility, weather resistance, heat resistance, and storage stability, and makes use of it in automobiles, ships and vehicles. , Building materials,
It can be applied to the surface of various base materials such as electrical materials, industrial machinery, beverage cans, buildings, structures, etc., metal materials, inorganic materials, organic materials such as plastics, etc. for surface protection and cosmetics of various base materials. Forms a useful coating.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C01B 33/159 C08J 5/18 9267-4F C08K 7/00 KCJ (72) Inventor Tadahiro Yoneda Osaka Prefecture 5-8 Nishiomitabicho, Suita-shi Central Research Institute of Nippon Shokubai Co., Ltd. (72) Inventor Masaya Yoshida 5-8 Nishimitabicho, Suita-shi, Osaka Pref. Japan Catalytic Functional Resins Research Department (72) Inventor Namura Ichiro 5-8 Nishimitabicho, Suita City, Osaka Prefecture, Japan Research Group for Catalytic Functional Resins

Claims (12)

[Claims] 1. A composite fine particle in which an organic polymer is fixed on the surface of an inorganic fine particle, having an average particle diameter of 5 to 20.
Organic polymer composite inorganic fine particles having a particle diameter variation coefficient of 0 nm and 50% or less. 2. An alkoxy group of 0.01 to 50 mmol
The organic polymer composite inorganic fine particles according to claim 1, wherein the organic polymer composite inorganic fine particles are contained in an amount of 1 / g. 3. At least one policy per molecule.
The polysiloxane having a roxane group bonded thereto
At least one Si-OR in the group¹ Group (R ¹ Is hydrogen
Selected from a child or an alkyl group or an acyl group,
R is at least one group which may be¹ Is one molecule
If there are multiple R's¹ Are the same as each other
Well, it may be different. ) -Containing organic polymer (P)
(P) alone or a hydrolyzable metal compound (G)
Organic polymer composite inorganic fine particles that hydrolyze and condense with
Child manufacturing method. 4. The metal compound (G) has the following general formula (R ² O) _m MR ³ _nm (wherein M is at least one selected from the group consisting of Si, Al, Ti and Zr). The metal element, R ² is a hydrogen atom or at least one group which may be substituted and is selected from an alkyl group and an acyl group, and R ³ is selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, At least one group which may be substituted, n is a valence of the metal element M, m is an integer of 1 to n, R ²
And / or when there are a plurality of R ^{3 s} in one molecule, a plurality of R ^{2 s} and / or R ^{3 s} may be the same as each other,
May be different. 4. The method for producing organic polymer composite inorganic fine particles according to claim 3, wherein the method is at least one selected from the compounds represented by the formula (4) and their derivatives. 5. The following raw material liquid (A) and raw material liquid (B) are separately and simultaneously supplied to a reaction vessel to carry out hydrolysis and
The method for producing organic polymer composite inorganic fine particles according to claim 3 or 4, wherein condensation is performed. Raw material liquid (A): Liquid containing organic polymer (P) or organic polymer (P) and hydrolyzable metal compound (G) Raw material liquid (B): Liquid containing water as an essential component 6. An organic polymer composite inorganic fine particle dispersion containing the organic polymer composite inorganic fine particle according to claim 1 or 2. 7. An organic polymer composite inorganic fine particle dispersion containing organic polymer composite inorganic fine particles obtained by the method according to claim 3. 8. A film-forming composition containing the organic polymer composite inorganic fine particles according to claim 1. 9. A film forming composition containing organic polymer composite inorganic fine particles obtained by the method according to claim 3. 10. The organic polymer composite inorganic fine particles according to claim 1 or 2, wherein the organic polymer contains a hydroxyl group.
The film-forming composition according to claim 8, containing at least one compound (J) selected from a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin. 11. An organic polymer (P) containing a hydroxyl group
And at least one compound (J) selected from a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin, and organic polymer composite inorganic fine particles obtained by the method according to any one of claims 3 to 5.
The film-forming composition according to claim 9, further comprising: 12. The film-forming composition according to claim 8, which contains a polyol (Q) having two or more hydroxyl groups in one molecule.