JP3157141B2 - Organic polymer composite inorganic fine particles, dispersion containing the fine particles, and composition for film formation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to various coatings, useful organic polymer composite inorganic fine particles as an additive to molding materials, the dispersed dispersion and the fine particles of the organic polymer composite inorganic fine particles in a variety of dispersant Various paints contained,
The present invention relates to a film-forming composition useful as a surface treatment agent, a coating agent, an adhesive, a pressure-sensitive adhesive, a sealing agent, and the like.

[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, concealing property, heat resistance, surface hardness and rust prevention. It has been put to practical use. However, its performance is not sufficient, and in order to solve this problem, the surface modification of inorganic fine particles using an organic polymer or the like is performed by various methods, and the affinity between the inorganic fine particles and the organic medium has been improved. ing.

For example, JP-A-3-271114 describes fine particles obtained by treating silica fine particles having a particle diameter of 5 to 300 nm with a silyl etherified polymer. Also found that the particle size obtained by the gas phase method was several tens n.
After the introduction of a polymerizable functional group and a polymerization initiating group on the surface of 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 obtain silica particles grafted with an organic polymer. ("Surface" Vol. 28, No. 4, 286-29
8, p. 1990).

Further, JP-A-5-115772 discloses that a polymerizable functional group is introduced into the surface of silica fine particles having a particle diameter of several tens of nm obtained by a gas phase method, and then emulsion polymerization is carried out. Describes fine particles having an average particle diameter of 100 nm or less, which are grafted with a polymer. On the other hand,
Japanese Patent Publication No. -180921 discloses that the particle diameter is 10 to 5000 n.
A method is described in which a m-colloidal silica surface is previously treated with a coupling agent and then surface-treated with an acid group-containing polymer to obtain silica fine particles surface-modified with a polymer. Yoshinaga et al. Have reported an example of silica fine particles whose surface is modified with an organic polymer by treating monodispersed silica fine particles with an alkoxysilyl group-containing polymer ("Journal of the Textile Society", Vol. 49, No. 3). , 130th to 136th
1993).

[0005] Apart from these, there are many known methods for producing inorganic fine particles as a base material. Hydrolyzable organic metal compounds are hydrolyzed and condensed in a reaction solution such as water and alcohol. There is a typical way to do this. For example, Japanese Patent Publication No. 1-59974 discloses that by hydrolyzing an organic silicon compound such as a hydrolyzable alkoxysilane without substantially changing the concentrations of water and ammonia in a reaction solution, an A method for obtaining silica fine particles having a good monodispersity in particle diameter is described. JP-A-63-77940 discloses that a mixed solution of an organic solvent such as methyltrialkoxysilane is used as an upper layer, and an aqueous solution of ammonia or an amine and / or a mixed solution of ammonia or an amine and an organic solvent is used as a lower layer. A method of hydrolyzing and condensing methyltrialkoxysilane and the like at these interfaces to obtain a polymethylsilsesquioxane powder having a substantially true spherical shape and a particle size distribution in a range of ± 30% of an average particle size. ing. Furthermore, Japanese Patent Publication No. 5-4325 discloses that the average particle size is 0.05 to 20.
μm, the standard deviation of 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. Have been.

Acrylic polyols and polyester polyols, which are resin components contained in conventional film-forming compositions, are excellent in weather resistance, workability, etc., but the film-forming compositions containing these are applied. The surface hardness of the later coating is low,
There was a disadvantage that it was easily damaged. Therefore, various paints containing various inorganic fine particles for the purpose of improving the above-mentioned drawbacks, and for the purpose of imparting properties such as strength, flame retardancy, concealing property, heat resistance and rust resistance of the film-forming composition. And the like.

However, its performance is not sufficient.
For example, the dispersibility of the inorganic fine particles is poor, or the adhesiveness between the inorganic fine particles and the resin used for the film-forming composition is not sufficient, and a minute gap is formed at the interface between the two, and water permeates into this space. For this reason, there is a problem that the weather resistance of the coating is significantly reduced. In order to solve such problems, 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. Improvement of the affinity between the medium and the inorganic fine particles has been measured. For example, there is a film-forming composition containing inorganic fine particles that have been surface-treated with an acid group-containing polymer or an alkoxysilyl group-containing polymer after the inorganic fine particles have been surface-treated with a coupling agent in advance. In addition, Japanese Unexamined Patent Publication No.
No. 173882 discloses an acrylic polyol resin, 2
An acrylic resin-based coating composition containing a binder such as an isocyanate compound having at least two functional groups, an inorganic organosol, and a solvent is mentioned. It is described that use of this composition improves weather resistance.

[0008]

SUMMARY OF THE INVENTION The present inventors have carried out additional tests for the methods described in the above-mentioned publications or documents, and
After a detailed study, after the inorganic fine particles are surface-treated with a coupling agent in advance, and then surface-treated with an acid group-containing polymer, or when surface-treated with an alkoxysilyl group-containing polymer, if the particles are not subjected to a drying treatment, The drying step is essential because the polymer and the inorganic fine particles do not combine,
It has been found that when such a drying treatment is performed, aggregation of the inorganic fine particles and crosslinking between the fine particles by the polymer occur, and the particle size distribution of the fine particles becomes wider than before the surface treatment. In particular,
When inorganic fine particles having an average particle diameter of 200 nm or less were used, the aggregation was remarkable, and it was revealed that the average particle diameter of the finally obtained fine particles after surface treatment was larger than 200 nm. When the thus-obtained surface-treated fine particles are used as is or mixed with another coating resin to form a film, the aggregation of the particles is remarkable, the average particle diameter is large, and the particle diameter distribution is wide, It was found that the resulting coating film had a problem that cloudiness and cracks were generated, and a transparent and glossy coating film could not be obtained.

Further, the conventional example of hydrolyzing and condensing a hydrolyzable organometallic compound in a reaction solution such as water and alcohol to obtain inorganic fine particles is intended to control the particle size distribution or the shape of the particles. During the hydrolysis / condensation reaction, a bond is formed between the organic polymer and the inorganic fine particles for the purpose of modifying the generated inorganic fine particles, and the surface is modified with the organic polymer while the inorganic fine particles are being generated. No inorganic fine particles are known.

In a conventional method of bonding an acrylic polyol resin and an inorganic organosol using a binder,
Resin has poor storage stability and tends to gel. Also, by-products crosslinked between acrylic polyol resins,
There is a high possibility that a side reaction product in which the inorganic organosol is crosslinked is obtained, and it is difficult for the binder to react selectively and efficiently only between the intended acrylic polyol resin and the inorganic organosol. Moreover, the film-forming composition containing an inorganic organosol surface-modified with the acrylic polyol resin obtained in this manner has low physical properties such as weather resistance, adhesion and flexibility, and still has satisfactory physical properties. Did not.

Therefore, the present invention has a fine average particle size as described above, a narrow particle size distribution, excellent dispersion stability for various organic solvents and polymers, and particularly good for an organic matrix. Do surface-modified inorganic particles with an organic polymer having an affinity, i.e., a dispersion containing the organic polymer composite inorganic fine particles, the seed coating material, the useful organic polymer composite inorganic fine particles as an additive, such as a molding material, weather It is an object of the present invention to provide a film-forming composition containing organic polymer composite inorganic fine particles having excellent properties, stain resistance, chemical resistance, adhesion, and surface hardness.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, succeeded in synthesizing the following organic polymer composite inorganic fine particles for the first time, and completed the present invention. I came to. That is, the organic polymer composite inorganic fine particles according to the present invention include Si, Al, Ti
Of oxides of metal elements selected from Zr and Zr
With inclusion of the organic polymer in the child, the surface organic polymer of said fine particles is fixed by chemical bonding,
Before SL organic polymer comprises a (meth) acrylic units, with average particle diameter of 5 to 200 nm, and the variation coefficient of the particle diameter of the organic polymer composite inorganic fine particles is 50% or less.
The organic polymer composite inorganic fine particle dispersion according to the present invention,
It contains the organic polymer composite inorganic fine particles. The film-forming composition according to the present invention contains the organic polymer composite inorganic fine particles.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION [Organic polymer composite inorganic fine particles] The inorganic fine particles used in the present invention include Si, Al, Ti and
Fine particles made of an oxide of a metal element selected from Zn
Ri, silica fine metal element is Si is most preferred as the inorganic fine particles. The oxide of this metal element
Element is mainly a three-dimensional network through bonds with oxygen atoms.
It constitutes Further, in the oxide of the metal element , an organic group or a hydroxyl group is contained, or various groups derived from a metal compound (G) as a raw material to be described later remain, or a part of the organic polymer is included. You may.
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 oxide of the metal element is only one kind or two or more kinds.

The shape of the inorganic fine particles composed of such an oxide of a metal element may be any shape such as a sphere, a needle, a plate, a scale, and a crushed shape, and is not particularly limited. The organic polymer of the organic polymer composite inorganic fine particles in the present invention,
When used in various paints and molding materials, it contributes to improving the dispersibility of the fine particles and the affinity between the fine particles and an organic medium, and acts as a binder when used as a film-forming composition. Is what you do.

The molecular weight, shape and composition of the organic polymer,
The presence or absence of the functional group is not particularly limited, and any organic polymer can be used. Regarding the shape of the organic polymer, any shape such as a linear, branched, or crosslinked structure can be used. Specific examples of the resin constituting the organic polymer include, for example, (meth)
Acrylic resin, (meth) acryl-styrene resin,
(Meth) acrylic-polyester resin
Those having a krill unit as an essential component are exemplified. This
The organic polymer composite inorganic fine particles in which the organic polymer further has a film forming ability can be used as a suitable material for a film-forming composition described later.

[0016] For the organic polymer, especially, is composed of an organic chain and a polysiloxane group, at least one polysiloxane group per molecule binds, and,
At least one Si-OR in the polysiloxane group;
Organic polymer (P) described below having a structure containing ^one group
Are preferred.

The organic polymer-composite inorganic fine particles of the present invention are characterized in that an organic polymer is formed on the surface of the inorganic fine particles by chemical bonding.
Although the composite fine particles are fixed, here, fixing does not mean mere adhesion and adhesion, and the organic polymer is contained in a washing liquid obtained by washing the organic polymer composite inorganic fine particles with an arbitrary solvent. it means that it is not detected
You.

The organic polymer composite inorganic fine particles contain an organic polymer in the fine particles . This makes it possible to impart appropriate softness and toughness to the inorganic substance as the core of the organic polymer composite inorganic fine particles. The presence or absence of the organic polymer in the organic polymer composite inorganic fine particles can be determined, for example, by measuring the specific surface area of the fine particles after heating the organic polymer composite inorganic fine particles at 500 to 700 ° C. and thermally decomposing the organic polymer, and the diameter of the fine particles. Can be confirmed by comparing with the theoretical value of the specific surface area calculated from.
That is, when the 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 is a value considerably larger than the theoretical value of the specific surface area calculated from the diameter of the fine particles.

The average particle size of the organic polymer composite inorganic fine particles is 5 to 200 nm, preferably 5 to 100 nm. Average particle diameter of organic polymer composite inorganic fine particles is 5n
If 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 diameter of the organic polymer composite inorganic fine particles is 200
If it exceeds nm, physical properties such as transparency of the coating film are deteriorated when used for a paint or 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.
If the particle size distribution of the organic polymer composite inorganic fine particles is wide, that is, if the coefficient of variation of the particle size exceeds 50%, when used as a filler for plastic films and the like, the film surface is not smooth and the unevenness is severe. Not preferred.

The content of the alkoxy group 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. Here, the alkoxy group refers to an R ⁴ O group bonded to a metal element forming the skeleton of the inorganic fine particles. Here, R ⁴ is an alkyl group which may be substituted, and R ⁴ in the fine particles
^{The 4} O 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 supplementarily 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 coating materials 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 exhibit the effect more effectively, it is advantageous to increase the content of the inorganic substance in the fine particles as much as possible.
-99.5% by weight is preferred.

The content of the organic polymer in the organic polymer composite inorganic fine particles of the present invention is not particularly limited.
0% by weight is preferred. The organic polymer composite inorganic fine particles of the present invention can be produced by any method. Method for producing organic polymer composite inorganic fine you described below is an example, not limited to the method described below.

Another organic polymer composite inorganic fine particle of the present invention
At least one polysiloxane group is bonded per molecule and wherein the polysiloxane at least one Si-OR ¹ group in the radical (R ¹ is a hydrogen atom or an alkyl group, selected from an acyl group is, substituted is also good at least one group, when R ¹ are a plurality in one molecule, a plurality of R ¹ may be the same as each other or different.) the organic polymer having a ( P) to (P)
Obtained singly or features and to that Manufacturing method that hydrolysable metal compound with (G) to hydrolysis and condensation
Organic polymer composite inorganic fine particles.

Organic polymer (P) used in the above production method
Can be independently hydrolyzed and condensed to produce organic polymer composite inorganic fine particles. The metal compound (G) and the organic polymer (P) described below can be co-hydrolyzed and condensed together to produce organic polymer composite inorganic fine particles. The organic polymer (P) is composed of an organic chain and a polysiloxane group, and has at least one polysiloxane group bonded per molecule, and at least one Si-OR ^{1 in the} polysiloxane group. It has a structure containing a group. In the organic polymer (P), the structure of the organic chain is not particularly limited. In addition, for reasons such as the availability of the organic polymer (P), the polysiloxane group in the organic polymer (P) and the organic chain are chemically bonded via a Si-C bond, a Si-OC bond, or the like. It is preferable that the polysiloxane group and the organic chain form a Si-C bond because, in particular, the bonding site is excellent in hydrolysis resistance and it is desirable that the bonding site is not easily subjected to an undesired reaction such as an exchange reaction at the bonding site. It is further preferred that the chemical bond is formed through

The structure of the organic polymer (P) is not particularly limited as long as it is soluble in an organic solvent and / or water described later. For example, a polymer in which a polysiloxane group is grafted to an organic chain, A polymer having a siloxane group bonded to one or both ends of an organic chain or a plurality of linear or branched organic chains having a polysiloxane group as a core (the plurality of organic chains may be the same or different. Good) bonded thereto. Here, the organic chain means, in the organic polymer (P),
It is a part other than the polysiloxane group. The main chain in the organic chain is mainly composed of carbon, and carbon atoms participating in the main chain bond occupy 50 to 100 mol%, and the remainder is N,
It is preferable because a material composed of elements such as O, S, Si, and P can be easily obtained. Specific examples of the resin constituting the organic chain include, for example, (meth) acrylic resin, polystyrene, polyvinyl acetate, polyolefin such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyester such as polyethylene terephthalate, and polyesters thereof. Copolymers and partially modified resins are exemplified. Among them, from the viewpoint of the ability to form a film in the film-forming composition of the present invention, a resin essentially containing a (meth) acrylic unit is preferable.

The R ¹ O group in the Si—OR ¹ group is a functional group which can be hydrolyzed and / or condensed. At least one R ¹ O group is present per molecule of the organic polymer (P). Preferably, there are 20 or more. As the number of R ¹ O groups increases, the number of reaction sites for hydrolysis and condensation increases, and fine particles that form a stronger skeleton can be obtained. Here, R ¹ is a hydrogen atom or at least one group which may be substituted and selected from an alkyl group and an acyl group. The number of carbon atoms in the alkyl group and the acyl group is not particularly limited, but an alkyl group or an acyl group having 1 to 5 carbon atoms is 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, for example, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, and pentyl group. No. Carbon number 1
Specific examples of the acyl groups (1) to (5) include acyl groups such as an acetyl group and a propionyl group. Examples of the substituted alkyl group and acyl group include, for example, one or more hydrogen atoms of the above-mentioned alkyl group and acyl group, for example, an alkoxy group such as a methoxy group and an ethoxy group; an acetyl group and a propionyl group Acyl groups such as chlorine;
And groups substituted with halogen such as bromine.
When a plurality of R ¹ are present in one molecule, the plurality of R ¹ may be the same or different. R ¹ is preferably a hydrogen atom, a methyl group, or an ethyl group, and most preferably a methyl group, because the rate of hydrolysis and condensation 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 at least one OR ¹ group means that two or more Si atoms have a polysiloxane bond (Si—O—Si
A group linked by a bond) in a linear or branched manner. The number of Si atoms in the polysiloxane group is
In particular but not limited, in that it can contain a large amount of R ¹ O group described above, the average per polysiloxane group, preferably 4 or more, more preferably 11 or more. Specific examples of such a polysiloxane group include a polymethylmethoxysiloxane group, a polyethylmethoxysiloxane group, a polymethylethoxysiloxane group, a polyethylethoxysiloxane group, a polyphenylmethoxysiloxane group, and a polyphenylethoxysiloxane group. And the like.

Further, all S in the polysiloxane group
The i atom is a bond with an organic chain and a polysiloxane bond.
(Si-O-Si bond) other than R¹ Only with the O group
Is preferred. In such a case, the Si atom ion
Properties, and as a result, R ¹ Hydrolysis and condensation of O group
As the speed becomes faster, the reaction in the organic polymer (P) becomes
As a result, the fine particles with a stronger skeleton can be obtained.
You. Specific examples of such polysiloxane groups
And, for example, a polydimethoxysiloxane group, a polydiet
Xysiloxane group, polydiisopropoxysiloxane
Group, 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 an organic solvent described below, which is not preferable. The organic polymer (P) can be produced by a conventionally known method. For example, (1) to
Although the method of (4) is mentioned, it is not limited to these methods.

(1) Radical (co) polymerization of a radically polymerizable monomer in the presence of a silane coupling agent having a double bond group or a mercapto group, followed by (co) polymerization
A method of co-hydrolyzing and condensing a polymer with a silane compound (H) described later and / or a derivative thereof. (2) a silane coupling agent having a double bond group or a mercapto group and a silane compound (H) and / or
Alternatively, after co-hydrolyzing and condensing a derivative thereof, a radical polymerizable monomer is radically (co)
How to polymerize.

(3) A silane coupling agent having a reactive group such as a double bond group, an amino group, an epoxy group, or a mercapto group is reacted with a polymer having a group that reacts with the reactive group. Thereafter, a method of co-hydrolyzing and condensing the obtained polymer with a silane compound (H) and / or a derivative thereof described below. (4) After co-hydrolysis / condensation of a silane coupling agent having a reactive group such as a double bond group, an amino group, an epoxy group, a mercapto group and a silane compound (H) and / or a derivative thereof described below. And reacting a polymer obtained by co-hydrolysis / condensation having the 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 form a three-dimensional network by hydrolysis and further condensation. Specific examples of such a metal compound (G) include, for example, metal halides, metal nitrates, metal sulfates, metal ammonium salts, organometallic compounds, alkoxymetal compounds, and derivatives of these metal compounds. Can be The metal compound (G) can be used alone or in combination of two or more.

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

Specific examples of such a metal compound (G) include boric acid, ammonium borate, boron tribromide, boron trichloride, methyl boron dichloride, trimethyl borate,
Triethyl borate, Triisopropyl borate, Tributyl borate, Methyl boric acid, Dimethyl methyl borate, Aluminum hydroxide, Aluminum chloride, Aluminum nitrate, Aluminum sulfate, Aluminum ammonium 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,
Methylgermanium triethoxide, dimethylgermanium dimethoxide, trimethylgermanium methoxide, stannous chloride, stannic chloride, methyltin trichloride, dimethyltin dichloride, trimethyltin chloride, dibutyltin diacetate, tributyltin hydride, trimethyltin Formate, trimethyltin acetate, triethyltin hydroxide, dimethyltin dimethoxide, trimethyltin methoxide, dimethyltin diethoxide, dibutyltin dibutoxide, phosphorous acid, phosphoric acid, phosphorous trichloride, phosphorus oxychloride, phosphorus pentachloride, monoammonium phosphate , Diammonium phosphate, triammonium phosphate, methyl phosphite dichloride, phenyl phosphite dichloride, dimethyl phosphite chloride, methyl phosphate dichloride, methyl phosphite Acid, methylphosphoric acid, trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, triphenyl phosphite, diethyl methyl phosphite, diethyl phenyl phosphite, dimethyl ethyl phosphite, Ethyl diphenyl phosphite, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dimethyl methyl phosphate, diethyl ethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, titanium tetrachloride, titanyl sulfate, methyl trichlorotitanium,
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, Tetraisopropoxy zirconium, tetrabutoxy zirconium and the like can be mentioned.

As the metal compound (G), a derivative of the above metal compound can be used. Derivatives of metal compounds include, for example, a part of a hydrolyzable group such as halogen, NO ₃ , SO ₄ , an alkoxy group, an acyloxy group, or the like, a dicarboxylic acid group, an oxycarboxylic acid group, a β-diketone group, β
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 the metal compound and / or the chelate-substituted metal compound is partially hydrolyzed and / or condensed; The resulting oligomers and polymers.

The above-mentioned chelate-substituted compounds include, for example, diisopropoxytitanium diacetylacetonate,
Oxytitanium diacetylacetonate, dibutoxytitanium bistriethanolaminate, dihydroxytitanium dilactate, zirconium acetylacetonate, acetylacetone zirconium butoxide, triethanolamine zirconium butoxide, aluminum acetylacetonate, and the like.

In particular, the metal compound (G) is represented by 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 which may be substituted selected from an alkyl group and an acyl group; R ³ is 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, and R ²
And / or when R ³ is plural in one molecule, plural R ² and / or R ³ may be the same as each other;
May be different. ) Is preferably used.

Here, as specific examples of R ² , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group and a tertiary butyl group.
And a butyl group and a pentyl group. 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,
Methyl groups are most preferred. This is due to the hydrolysis of the R ² O group.
This is because the condensation rate is further increased.

As specific examples of R ³ , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group and a tertiary butyl group.
And 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, and a xylyl group. Examples of the aralkyl group include a group such as a benzyl group. An alkyl group which may be substituted, a cycloalkyl group,
The aryl group and the aralkyl group refer to one or more hydrogen atoms of the alkyl group, the cycloalkyl group, the aryl group, and the 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 substituted with a functional group such as a group, an epoxy group, or a halogen.

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, diethoxytobutoxytitanium, isoproxytitanium trioctarate, diprotitanium Examples include isopropoxytitanium diacrylate, tributoxytitanium stearate, zirconium acetate, tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, and tetrabutoxyzirconium. Specific examples of the derivative of the metal compound (G) represented by the general formula include diisopropoxytitanium diacetylacetonate,
Oxytitanium diacetylacetonate, dibutoxytitanium bistriethanolaminate, dihydroxytitanium dilactide, zirconium acetylacetonate, acetylacetone zirconium butoxide, triethanolamine zirconium butoxide, aluminum acetylacetonate, and the like.

Further, the silane compound (H) in which M is Si in the general formula and its silane compound (H) because it is easily available industrially and does not contain a halogen or the like which adversely affects various 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, methyltrimethoxysilane Phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, dimethoxydiethoxysilane, and the like. Further, specific examples of the derivative of the silane compound (H) include a hydrolysis / condensate of the silane compound (H).

Of the silane compounds (H),
A run compound is particularly preferable because it is easily available as a raw material. Ma
In addition, the silane compound (H) and its derivative are Si (O
R^Two ) _Four And its derivatives, hydrolysis and condensation speed
Organic polymer composite with faster and stronger skeleton
This is preferable in that inorganic fine particles can be obtained. In the present invention
Polymer composite inorganic fine particles consist of a single organic polymer (P).
Hydrolysis / condensation with Germany or the above metal compound (G)
Manufactured. The method of hydrolysis and condensation is particularly limited.
However, because the reaction can be performed easily,
It is preferred to do so. The solution referred to here is an organic
A solution containing a solvent and / or water, wherein the solution
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 and ethylene acetate. Ester such as 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 glycol; 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, and propylene glycol monobutyl ether; and halogenated carbonization such as methylene chloride and chloroform. Hydrogens, etc., and at least one or two or more of these organic solvents may be used. Among them, it is preferable to use alcohols, ketones, and ethers that are soluble in water as essential components.

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 may be used. Can be used. Specific examples of the acidic catalyst include, for example, 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; and acidic ion exchange resins. 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 hydroxide. Alkali metal compounds such as sodium and potassium hydroxide; and basic ion exchange resins. As for the type of catalyst, it is preferable to use a basic catalyst rather than an acidic catalyst, since an inorganic component obtained by hydrolysis / condensation forms a stronger skeleton.

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 comprising the organic polymer (P), the metal compound (G), the organic solvent, the catalyst and water. The amount of the organic polymer (P) is 0.1
It is preferably from 80 to 80% by weight, more preferably from 0.5 to 30% by weight. The amount of the metal compound (G) is preferably from 0 to 80% by weight, more preferably from 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 preferred. 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 amount is such that the organic polymer (P) alone or the organic polymer (P) and the metal compound (G) form particles by hydrolysis / condensation. However, in order to perform hydrolysis / condensation more sufficiently and to make the skeleton of the particles stronger, the larger the amount of water used, the better. Specifically, the molar ratio of water to the hydrolyzable group to be hydrolyzed and condensed is 0.1
Or more, preferably 0.5 or more, more preferably 1
By conducting hydrolysis and condensation under the above conditions, organic polymer composite inorganic fine particles can be obtained.

The method of hydrolysis / condensation is not particularly limited, but specific examples include the case where the organic polymer (P) or a solution thereof is used and the metal compound (G) is also used. , A metal compound (G) or a solution thereof is added to a solution containing water, and the reaction temperature is 0 to 1
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 the solution thereof, the metal compound (G) or the solution thereof are mixed or separately, collectively,
The reaction can be carried out by any addition method such as division, continuation and the like. The addition may be reversed, and the solution containing water may be added to the organic polymer (P) or its solution or the metal compound (G) or its solution. In the hydrolysis / condensation, one or more of the above-mentioned 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 as a mixture with the metal compound (G). After completion of the reaction, by-products and catalysts generated by hydrolysis and condensation may be removed by filtration, distillation, or the like.The method of isolating the obtained organic polymer composite inorganic fine particles from the reaction mixture may be a conventional method. For example, it can be isolated and purified by distilling off the solvent, centrifugation, reprecipitation, ultrafiltration and the like.

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

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 supply the following raw material liquid (C) individually and simultaneously with the raw material liquid (A) and the raw material liquid (B) into the reaction vessel.

Raw material liquid (C): Liquid containing a hydrolyzable metal compound (G) Also, at least one hydrolyzable metal compound (G) is contained in the raw material liquid (A). It is also preferable to carry out the above-mentioned hydrolysis and condensation. Hydrolysis in this way
When the condensation is performed, the precipitation process of the organic polymer composite inorganic fine particles accompanying the hydrolysis / condensation can be more easily controlled, and the organic polymer composite inorganic fine particles having a sharper particle size distribution can be obtained.

The individual supply of the raw material liquids (A) to (C) into the reaction vessel means that the raw material liquids are not mixed before each raw material liquid is supplied to the reaction vessel. Supply is to take place. Also, the raw material liquid (A) to the raw material liquid (C)
Simultaneous supply into the reaction vessel means the supply ratio X _a , X _c 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: But preferably 0.1 to 10, more preferably 0.3 to 3
In particular, it is preferably supplied at 0.5 to 2.

A / Ac / C X _a = ───── X _c = ───── b / B b / B (where A is the total amount of the raw material liquid (A), and B is the raw material liquid ( B) indicates the total amount of the raw material liquid (C), and a indicates the amount of the raw material liquid (A) already supplied at an arbitrary time t.
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 an arbitrary time t. )

[0054] that written [Organic polymer composite inorganic fine particle dispersion The present invention organic polymer composite inorganic fine particle dispersion,
It contains the above-mentioned organic polymer composite inorganic fine particles of the present invention . Organic polymer composite inorganic fine particle dispersion of the present invention, for example, that the organic polymer composite inorganic fine particles of the present invention described above is dispersed in any solution, the reaction mixture obtained by the production method of the organic polymer composite inorganic fine particles ,
The solvent in the reaction mixture was replaced with another solvent while being distilled under heating, the solvent in the reaction mixture was distilled off, and the organic polymer composite inorganic fine particles were isolated by centrifugation, reprecipitation, ultrafiltration, or the like. Later, those dispersed in a dispersion medium, etc.
It is a dispersion dispersed in various dispersion media.

The organic polymer composite inorganic fine particle dispersion of the present invention is free from coarse particles, agglomerates, and precipitates, and has the property of not producing precipitates or gelling over 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 the dispersion obtained by the conventional method, the organic polymer composite inorganic fine particle dispersion of the present invention is a dispersion that maintains a sharp particle size distribution without agglomeration of the organic polymer composite inorganic fine particles in the dispersion. .

The dispersion medium of the organic polymer composite inorganic fine particle dispersion of the present invention is not particularly limited in the composition and the like, but is preferably an organic solvent or water in which the organic chains in the organic polymer composite inorganic fine particles are dissolved. Among the organic solvents described in the above manufacturing 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. The dispersion has good long-term storage stability and good dispersion stability in various organic media, and thus can be used for various applications.

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 increases, and the dispersion becomes difficult to use for various applications.

[ Composition for Film Formation ] The composition for film formation according to the present invention contains the organic polymer composite inorganic fine particles of the present invention . The organic polymer constituting the organic polymer composite inorganic fine particles in the film-forming composition of the present invention is not particularly limited.
Styrene resins and (meth) acryl-polyester resins are preferred.

Since the film-forming composition of the present invention essentially contains organic polymer composite inorganic fine particles as compared with the conventional film-forming composition, the film properties are improved as compared with 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,
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. Even if applied alone, a film can be formed, and the film-forming composition containing the organic polymer composite inorganic fine particles can provide a transparent and glossy favorable film.

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

After coating the film-forming composition, in the film finally obtained, examples of the film-forming composition having an organic polymer having a crosslinked structure include the following. (1) Using an organic polymer (P) having a functional group (X), an organic polymer composite inorganic fine particle having a functional group (X) obtained by the above-described method, and a function that reacts with the functional group (X) A film-forming composition comprising a compound or a resin having two or more groups (Y). (2) An organic polymer (P) having a functional group (X), an organic polymer composite inorganic fine particle having a functional group (X) obtained by the above-described method, and a functional group that reacts with the functional group (X). A film-forming composition comprising an organic polymer composite inorganic fine particle having a functional group (Y) obtained by the method described above using an organic polymer (P) having a group (Y). (3) Using the organic polymer (P) having the functional group (X), the organic polymer composite inorganic fine particles having the functional group (X) obtained by the above-described method, and the function 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), a functional group (W A) a film-forming composition comprising organic polymer composite inorganic fine particles having (4) The film-forming composition according to (1) to (3), further containing a compound and / or a resin having two or more functional groups (X).

Here, as the functional group (X), for example,
Examples 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 the functional group (X) include isocyanate Group, epoxy group, hydroxyl group, mercapto group, amino group, unsaturated group,
And 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). The number is not particularly limited, but if it is too small, the number of cross-linking points decreases, and the coating properties such as solvent resistance, heat resistance, and surface hardness tend to decrease. Among them, an organic polymer composite inorganic fine particle having a hydroxyl group as a functional group (X), a compound having two or more functional groups (Y) that react with the hydroxyl group, and / or
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 provide a coating film having good coating physical properties such as stain resistance, flexibility, weather resistance, storage stability, and the like, and the obtained coating film is glossy. A film-forming composition containing an organic polymer composite inorganic fine particle containing a hydroxyl group in an 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 described 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-
Trimethylhexylmethane diisocyanate, methylcyclohexane diisocyanate, trimers such as biuret and isocyanurate of 1,6-hexamethylene diisocyanate; these polyfunctional isocyanates and propanediol, hexanediol, polyethylene glycol, trimethylolpropane, etc. A compound in which two or more isocyanate groups generated by the reaction of the above with a 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 acetoacetates. Blocked polyfunctional isocyanate compounds blocked with blocking agents such as oximes such as oximes and methyl ethyl ketoxime, and lactams such as ε-caprolactam and γ-caprolactam. Objects and the like. One of these polyfunctional isocyanate compounds or a mixture of two or more thereof can be used. 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.

The melamine compound includes, for example,
Examples thereof include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, isobutyl ether melamine, n-butyl ether 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. These aminoplast resins can be used alone or as a mixture or cocondensate of two or more.

Here, the alkyl etherified melamine resin is obtained by methylolating an aminotriazine and alkyl etherifying it with cyclohexanol or an alkanol having 1 to 6 carbon atoms. Resin and melamine resin mixed with methylbutyl are typical. Also,
Sulfonic acid-based catalysts for accelerating curing, for example,
Paratoluenesulfonic acid and its amine salt can be used.

[0068] film-forming composition of the present invention, in its composition,
It is more preferable to include a polyol (Q) containing two or more hydroxyl groups in one molecule because the resulting film has improved film properties such as strength, flexibility, and solvent resistance. 1
The polyol (Q) containing two or more hydroxyl groups in the molecule is not particularly limited as long as it is soluble in the above-mentioned organic solvent, but it has compatibility with the organic polymer in the organic polymer composite inorganic fine particles. It is preferable to use such a material because the gloss or transparency of the film is improved. Therefore,
Those having the same composition as the organic polymer are most preferred.

Examples of the polyol (Q) include a polyol obtained by polymerizing a monomer component containing a hydroxyl group-containing unsaturated monomer described later, and a polyester polyol obtained under an excessive hydroxyl group condition. . These may be used alone or in combination of two or more. 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 silicon alcohol, crotonyl alcohol, etc .; , Phenylglycidyl ether,
A dihydric alcohol or an epoxy compound such as glycidyl decanoate or Praxel FM-1 (manufactured by Daicel Chemical Industries, Ltd.), 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. A polyol can be produced by polymerizing at least one or more selected from these hydroxyl-containing unsaturated monomers.

Ethyl acrylate, n-acrylic acid
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 itaconate, diethyl maleate, Vinyl chloride, vinylidene chloride, acrylamide, N
-At least one ethylenically unsaturated monomer selected from methylol acrylamide, N-butoxymethyl acrylamide, diacetone acrylamide, ethylene, propylene, isoprene and the like, and the above (a) and (b)
And a hydroxyl group-containing unsaturated monomer selected from the above to produce a polyol.

The polyol obtained by polymerizing the monomer component containing the hydroxyl group-containing unsaturated monomer has a molecular weight of 1,000.
0 to 500,000, preferably 5,000 to
100,000. The hydroxyl value is 5-30.
0, preferably 10 to 200. Polyester polyols obtained under the condition of excess hydroxyl groups include, 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) Polyhydric alcohols such as isocyanurate and xylylene glycol;
Maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, azelaic acid, trimetic acid, terephthalic acid, phthalic acid, polybasic acids such as isophthalic acid, and the number of hydroxyl groups in the polyhydric alcohol is the polybasic acid The reaction can be carried out under conditions that are larger than the number of carboxyl groups.

The molecular weight of the polyester polyol obtained under the condition of an excess of hydroxyl groups is from 500 to 300,000, preferably from 2,000 to 100,000.
Further, its hydroxyl value is 5-300, preferably 1
0 to 200. The amount of the polyol (Q) to be added to the film-forming composition may be any amount, and the weight ratio of the 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 stain resistance of the coating are excellent.

As the polyol (Q), the above-mentioned polyester polyols are preferably used. Further, an acrylic polyol obtained by polymerizing a monomer component containing the hydroxyl group-containing unsaturated monomer and having a (meth) acrylic unit or the like is also preferably used. As the polyol (Q), either one of the polyester polyol and the 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
There is no particular limitation 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,
Film properties such as solvent resistance, water resistance, heat resistance, and surface hardness tend to decrease. The film-forming composition of the present invention may be obtained 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 preferred. 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 hydrolysis and condensation with the organic polymer (P) alone or the metal compound (G), The organic solvents described above can be used. The amount of the organic solvent and / or water used is not particularly limited, and can be appropriately used. Further, it may be a mixture of other components such as various paint resins.

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

[0076] For film forming composition of the present invention, the pigment can be added, there is no limitation on the kind of pigment to be added, for example, chrome yellow, molybdate orange, iron blue, cadmium pigments, titanium Organic pigments such as inorganic pigments such as white, composite oxide pigments, and transparent iron oxide, cyclic high-grade pigments, soluble azo pigments, copper phthalocyanine pigments, dye pigments, and pigment intermediates can be exemplified.

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 accelerating the crosslinking reaction It is preferable to further use As the curing catalyst, an acidic or basic curing catalyst can be used. Specific examples of the acidic curing catalyst include organic sulfonic acids such as toluenesulfonic acid, methanesulfonic acid, and dodecylbenzenesulfonic acid. Specific examples of the basic curing catalyst include amine catalysts such as triethylamine, methylimidazole, acridine, and hexadecyltrimethylammonium stearate; and organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and stannasoctoate. 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 as needed.

The film-forming composition of the present invention may be, for example, an inorganic material such as aluminum, stainless steel, galvanized iron, tinplate, steel plate, concrete, mortar, slate or glass, or an organic material such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate or paper. A film can be formed on a substrate or film of the above. Also immersion,
It can be applied by a conventional method such as spraying, brush coating, roll coating, spin coating, bar coating and the like.

The coating obtained from the film-forming composition of the present invention is subjected to baking and drying, if necessary . In the example <br/>, is intended to form a coating film by heating or 0.2 minutes at temperatures ranging from room temperature to 300 ° C., this coating is a coating film excellent in transparency and gloss.

[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 obtained by washing the organic polymer composite inorganic fine particles with an arbitrary solvent. This strongly suggests that the fixation of the organic polymer is not a mere adhesion or adhesion, but that a chemical bond is formed 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,
For the drying process is essential, aggregation of inorganic fine particles, the crosslinking occurs during drying, the particle size of the inorganic fine particles is increased, whereas widens also the particle size distribution, in the above manufacturing method, uniform reaction Can be performed, and since the generation speed 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 molecule of the coupling agent is extremely small, and is a typical coupling agent. Even silane coupling agents usually have only up to three of the above reactive groups per molecule. On the other hand, except that all the Si atoms in the polysiloxane group of the organic polymer (P) used in the present invention are bonded to an organic chain and are also bonded to a polysiloxane, they are bonded only to an alkoxy group or the like. In this case, the number of the reactive groups is larger than that of the conventional one. In the production process of the organic polymer composite inorganic fine particles, even if such an organic polymer is reacted in a solution, it reacts almost quantitatively because of the large number of the reactive groups, whereby a complicated drying process is performed. It is not necessary, and the organic polymer can be used effectively.

The organic polymer composite inorganic fine particle dispersion of the present invention is obtained by fixing the organic polymer composite inorganic fine particles on the surface of the inorganic fine particles with an organic polymer, and has excellent compatibility with a dispersion medium. Therefore, even after a lapse of time after the preparation, no aggregation of particles, no increase in viscosity, and the like are observed, and the composition has good temporal stability. The film-forming composition of the present invention is a transparent and glossy coating film, since 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, since the organic polymer is fixed on the surface of the inorganic fine particles, the organic polymer has a good affinity for an organic matrix such as a resin for paint 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 substrates as it is, the resulting film does not cause white turbidity and cracks, and is a film excellent in weather resistance.

Since the film-forming composition of the present invention essentially contains organic polymer composite inorganic fine particles as compared with the conventional film-forming composition, the film properties are improved as compared with 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,
Gives a coating film with good coating physical properties such as heat resistance, abrasion resistance and stain resistance.

The organic polymer constituting 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 group consisting of the compound (J) is contained, a crosslinked structure is formed, and the film-forming composition has flexibility,
It has good coating 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, compared with general film-forming compositions, stain resistance, flexibility, weather resistance, Excellent film properties such as hardness. When the polyol (Q) is further contained in the composition for film formation, a stronger crosslinked structure is obtained, so that the properties of the film are further improved.

[0086]

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

Production Example 1 (Synthesis of Polymerizable Polysiloxane (S-1)) In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser, 144.5 g of tetramethoxysilane and γ-methacryloxypropyl were added. 23.6 g of trimethoxysilane, water 19
g, 30.0 g of methanol and 5.0 g of Amberlyst 15 (a cation exchange resin manufactured by Rohm and Haas Japan) were stirred and reacted at 65 ° C. for 2 hours. After cooling the reaction mixture to room temperature, a distillation column was provided in place of the cooling tube, and a cooling tube and an outlet connected to the distillation column were provided.
The temperature was raised to 80 ° C. over 2 hours under normal pressure, and maintained at the same temperature until no more methanol flowed out. In addition, 200
The reaction was further maintained at a temperature of 90 ° C. under a pressure of mmHg until no more methanol flowed out. After cooling to room temperature again, Amberlyst 15 was separated by filtration 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 condenser, 129.3 g of methyltrimethoxysilane and γ-methacryloxy were placed. Propyltrimethoxysilane 23.4 g, water 1
8.8 g, methanol 30.0 g, 35% hydrochloric acid 1.0 g
And stirred at 65 ° C. for 1 hour to cause a reaction. After the reaction mixture was cooled to room temperature, a distillation column was provided in place of the cooling tube, a cooling tube connected to the distillation column, and an outlet were provided.
The temperature was raised to 2 ° C. over 2 hours, and maintained at the same temperature until no more methanol flowed out. Further, the temperature was maintained at a temperature of 90 ° C. under a pressure of 200 mmHg until methanol no longer flowed out, and the reaction was further advanced. Further, 2.0 g of triethylamine was added to form a white precipitate.
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 separated by filtration 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)) In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser, 86.7 g of tetraacetoxysilane and γ-methacryloxypropyl were added. 8.1 g of trimethoxysilane, 6.5 of water
g, 18 g of methanol, and 3 g of Amberlyst 15, and the mixture was stirred and reacted at 65 ° C. for 2 hours. After the reaction mixture was cooled to room temperature, a distillation column was provided in place of the cooling tube, a cooling tube connected to the distillation column and an outlet were provided, and the temperature was raised to 80 ° C. over 2 hours under normal pressure until methanol did not flow out. It was kept at the same temperature. Further, at a pressure of 200 mmHg, 90
At a temperature of ° C., the temperature was maintained until no more methanol and acetic acid flowed out, and the reaction was allowed to proceed further. After cooling again to room temperature, Amberlyst 15 was filtered off and a polymerizable polysiloxane having a number average molecular weight of 2,000 (S-
4) was obtained.

Production Example 5- (Synthesis of Organic Polymer (P-1)) In a 1-liter flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube, and a N ₂ gas inlet, 200 g of toluene as an organic solvent was added. placed, N ₂ gas was introduced, the internal temperature of the flask while stirring for 1
Heated to 10 ° C. Then, a solution obtained 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 dropped from the dropping port for 2 hours. And dropped. After the 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 is added to 30
The polymer was added twice every minute and further heated for 2 hours to carry out copolymerization.
A solution of 1) 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)) Organic polymers (P-2 To P-10) was dissolved in an organic solvent. Obtained organic polymer (P-2 to P-10)
Table 3 shows the number average molecular weight and solid content of

[0093]

[Table 1]

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

[0095]

[Table 2]

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

(Preparation of Sample) Using tetrahydrofuran as a solvent, 0.05 g of polymerizable polysiloxane or organic polymer (P) was dissolved in 1 g of tetrahydrofuran to prepare a sample. (Equipment) High-speed GPC equipment 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) Measurement was performed at a measurement temperature of 35 ° C. and a flow rate of 1 ml / min.

[0099]

[Table 3]

Example 1 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-1)) A 500-ml four-port equipped with a stirrer, two drop ports (drop port A and drop port B), and a thermometer In the 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 mixed solution (raw material liquid 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 through the dropping port A through 25 drops.
A mixed solution of 20% aqueous ammonia (20 g) and methanol (20 g) (raw material liquid B) was dropped from the dropping port (2) over 1 hour. After dropping, stirring was continued for 2 hours at the same temperature to obtain an organic polymer composite inorganic fine particle dispersion (Z-1). The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 6 shows the stability.

Further, the obtained organic polymer composite inorganic fine particle dispersion (Z-1) was treated under a pressure of 150 mmHg under a pressure of 120 mmHg.
The specific surface area of the fine particles obtained by heating and drying at 3 ° C. for 3 hours was 4.8 m ² / g as measured by Autosorb 6 (gas adsorption amount measuring device, manufactured by Yuasa Ionics Co., Ltd.).
The specific surface area after heating the fine particles 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)) A 500-ml four-port equipped with a stirrer, two drop ports (drop port A and drop port B), and a thermometer In the 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 butyl acetate solution 4 of the organic polymer obtained in Production Example 5 was obtained.
A mixed solution of 0 g and 40 g of butyl acetate (raw material liquid A) was dropped from a dropping port A over 1 hour from a dropping port of a mixed liquid of 5 g of 25% aqueous ammonia and 5 g of methanol (raw material liquid B). After dropping, stirring was continued at the same temperature for 2 hours to obtain an organic polymer composite inorganic fine particle dispersion (Z-2). The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 6 shows stability
Shown in

-Examples 3 to 15- (Organic polymer composite inorganic fine particle dispersion (Z-3 to Z-1)
5) Synthesis) The types of the organic solvent, the organic polymer (P) and 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 the above, an organic polymer composite inorganic fine particle dispersion (Z-3 to Z-15) was obtained in the same manner as in Example 1. The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, The stability is shown in Tables 6 and 7.

[0104]

[Table 4]

[0105]

[Table 5]

Comparative Example 1 An organic polymer (P′-1) was prepared in the same manner as in Production Example 5 except that γ-methacryloxypropyltrimethoxysilane was used instead of the polymerizable polysiloxane (S-1). A toluene solution (49% solids) was obtained. Production Example 5
A dispersion was obtained in the same manner as in Example 2 except that a toluene solution of the organic polymer (P′-1) was used instead of the toluene solution of the organic polymer (P-1) obtained in the above, but was obtained. The dispersion was highly agglomerated, and the particles precipitated immediately after 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 (dropping port A, dropping port B and dropping port C), and a thermometer Was charged with 200 g of butyl acetate and 50 g of methanol, and the internal temperature was adjusted to 20 ° C. Then, a mixture 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 liquid A) was added through a dropping port A while stirring the inside of the flask. 30 g of tetramethoxysilane (raw material liquid C) was dropped from the dropping port c over 1 hour from the dropping port c. After dropping, continue stirring at the same temperature for 2 hours,
An organic polymer composite inorganic fine particle dispersion (Z-16) was obtained. The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

-Example 17- (Synthesis of organic polymer composite inorganic fine particle dispersion (Z-17)) An organic polymer composite inorganic fine particle dispersion (Synthesis of organic polymer composite inorganic fine particle dispersion (Z-17)) Z-1
7) was obtained. The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

Example 18 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-18)) 200 g of butyl acetate and 70 g of methanol were placed in a 500 ml four-necked flask equipped with a stirrer, a dropping port and a thermometer.
g and 20 g of 25% ammonia water, 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 dropping, stirring was continued at the same temperature for 2 hours to obtain an organic polymer composite inorganic fine particle dispersion (Z-18). The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

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 was prepared. 50 g of a toluene solution of the obtained organic polymer (P-1) and 50 g of tetramethoxysilane were put therein, and the internal temperature was 20 ° C.
Was adjusted. Then, a mixture 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 dropping, stirring was continued at the same temperature for 2 hours to obtain an organic polymer composite inorganic fine particle dispersion (Z-19). The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

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 was prepared. 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 flask was heated and maintained at 80 ° C. for 1 hour while stirring. Next, by-product NH ₄ Cl was removed by ultrafiltration to obtain an organic polymer composite inorganic fine particle dispersion (Z-20). The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

Example 21 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-21)) A 500-ml four-hole equipped with a stirrer, two dropping ports (dropping port A and dropping port B), and a thermometer In the flask,
Put 150 g of ethyl cellosolve and keep the internal temperature at 20 ° C.
Was adjusted. Then, while stirring the inside of the flask, a toluene solution 50 of the organic polymer (P-3) obtained in Production Example 7 was prepared.
g, 10 g of zirconium butoxide and 10 g of ethyl cellosolve (raw material liquid A) from a dropping port A, and a mixed solution of 25 g of 25% aqueous ammonia and 50 g of ethyl cellosolve (raw material liquid B) from a dropping port over 1 hour. It was 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). The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

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

Example 23 Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-23) 150.0 g of tetramethoxysilane was placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser.
γ-glycidoxypropyltrimethoxysilane 23.3
g, water 19.5 g, methanol 30.0 g, Amberlyst 15, and 5.0 g, and the mixture was stirred at 65 ° C. for 2 hours to be reacted. After the reaction mixture was cooled to room temperature, a distillation column was provided in place of the cooling tube, a cooling tube connected to the distillation column, and an outlet were provided. The pressure was reduced to 50 mmHg and the reaction was allowed to proceed further. After cooling again to room temperature, Amberlyst 15 was filtered off to obtain a reactive polysiloxane (S-5) having a number average molecular weight of 1600.

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

Next, 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 put therein, and the internal temperature was adjusted to 20 ° C. Then, a mixture 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 dropping, stirring was continued at the same temperature for 1 hour to obtain an organic polymer composite inorganic fine particle dispersion (Z-23). The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

-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., and ammonia, methanol, and butyl acetate were distilled off until the solid content concentration became 30%, and a dispersion (Z-
24) was obtained. The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

Example 25 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-25)) A 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a distillation column connected to an outlet was prepared. Example 4
400 g of the organic polymer composite inorganic fine particle dispersion (Z-4) 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., and ammonia, methanol, and ethyl cellosolve were distilled off until the solid content concentration became 30%, to obtain a dispersion (Z-25) in which organic polymer composite inorganic fine particles were dispersed in ethyl cellosolve. The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

Example 26 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-26)) A 500 ml four-necked flask equipped with a stirrer, a thermometer, a condenser, and a distillation column to which an outlet was connected was prepared. Example 1
Organic polymer composite inorganic fine particle dispersion (Z-1)
2) 350 g and 100 g of toluene were added, and the temperature inside the flask was raised to 100 ° C. under a pressure of 110 mmHg, and ammonia, methanol, acetone, and toluene were added at a solid concentration of 3%.
Evaporation was carried out until the concentration became 0% to obtain a dispersion (Z-26) in which organic polymer composite inorganic fine particles were dispersed in toluene. The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

-Example 27- (Synthesis of organic polymer composite inorganic fine particle dispersion (Z-27)) Example 1
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. The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 7 shows the stability.

-Example 28- (Synthesis of organic polymer composite inorganic fine particle dispersion (Z-28)) Example 1
4 and the organic polymer composite inorganic fine particle dispersion (Z-1)
4) 250 g and 100 g of water were added, and the temperature in the flask was increased to 100 ° C. under a pressure of 150 mmHg, and ammonia,
Methanol and isopropyl alcohol with solid concentration of 3
Evaporation was performed until the concentration became 0%, to obtain a dispersion (Z-28) in which organic polymer composite inorganic fine particles were dispersed in water. The concentration of the organic polymer composite inorganic fine particles of the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particles, the average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, 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 supernatant obtained when each of the dispersions was centrifuged were separated into G
When analyzed by PC, no organic polymer was detected.
Further, the organic polymer composite inorganic fine particle dispersion (Z-1)
ＺZ-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.

With respect to the organic polymer composite inorganic fine particle dispersion obtained in each of the above examples, the concentration of the organic polymer composite inorganic fine particle in the obtained dispersion, the content of the inorganic substance in the organic polymer composite inorganic fine particle, the organic polymer composite inorganic fine particle 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.

[Concentration of Organic Polymer Composite Inorganic Fine Particles] The organic polymer composite inorganic fine particle dispersion was dried at 130 ° C. for 24 hours under a pressure of 100 mmHg, and determined by the following equation. (Here, D: weight of organic polymer composite inorganic fine particles after drying (g) W: weight of organic polymer composite inorganic fine particles dispersion before drying (g)) [Inorganic content in organic polymer composite inorganic fine particles] Organic Elemental analysis was performed on the polymer composite inorganic fine particle dispersion dried at 130 ° C. for 24 hours under a pressure of 100 mmHg, and the ash content was taken as the inorganic content in the organic polymer composite inorganic fine particles.

[Average Particle Size and Coefficient of Variation] Dynamic light scattering was measured at 23 ° C. using the following apparatus. 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
Organic polymer composite inorganic fine particle dispersion dispersed in about 2.0% by weight of tetrahydrofuran (in the case where the organic polymer in the organic polymer composite inorganic fine particle is not soluble in tetrahydrofuran, a dispersion dispersed in a solvent in which the organic polymer is dissolved) ).

(Variation coefficient) The variation coefficient is obtained by the following equation. [Alkoxy group content in organic polymer composite inorganic fine particles] Organic polymer composite inorganic fine particle dispersion was 100 mm
5 g 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 aqueous solution of NaOH, and the mixture was stirred at room temperature for 24 hours. Thereafter, the alcohol in the liquid was quantified using a gas chromatograph, and the alkoxy group content of the organic polymer composite inorganic fine particles was calculated.

[Temperature stability] The obtained dispersion was sealed in a Gardner viscosity tube and stored at 50 ° C. One month later, those in which no aggregation, sedimentation, or increase in viscosity of the particles were observed were evaluated as ○.

[0128]

[Table 6]

[0129]

[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 (Nippon Aerosil Co., Ltd. "Aer
Osil 200 ", 0.2 g of an average particle diameter of 12 nm (catalog value), 5 g of γ-glycidoxypropyltrimethoxysilane and 300 g of butyl acetate 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 and stirred 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, and 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 for 6 hours, and the mixture was heated at 100 ° C. for 1 hour to perform 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. Also, no alkoxy group was found in the fine particles.

Comparative Example 3 (Treatment of Colloidal Silica with Silyl Etherified Polymer) A polyol obtained by a dehydration reaction of 1,10-decanediol in a 200 ml flask equipped with a stirrer, a thermometer, and a condenser. 7 g, 15 g of diethoxydimethylsilane and 135 g of tetrahydrofuran (THF)
Was added and refluxed at 65 ° C. for 15 hours. Thereafter, 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, colloidal silica (average particle diameter: 37) obtained by solvent replacement was placed in a 200 ml flask equipped with a stirrer, thermometer, and cooling tube.
2 g of 1,2-dimethoxyethane dispersion (containing 30% of SiO ₂ ), 1 g of the above silyl etherified polymer 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 the value in the starting silyl etherified polymer. When the reaction solution was analyzed by GPC, the number average molecular weight was found to be 7000
Only polymer No. 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. This reaction solution was vacuum-dried at 150 ° C. and 100 mmHg, and then redispersed in THF, but a slight precipitate was observed. When the supernatant was collected and the particle size distribution was examined, the particles in the resulting dispersion were:
The average particle size was 92 nm, the coefficient of variation was 128%, and the particle size distribution was very wide. Also, no alkoxy group was found in the fine particles.

Comparative Example 4 (Treatment with Colloidal Silica Coupling Agent and Acid-Group-Containing Polymer) A 200 ml flask equipped with a stirrer, a dropping port, a thermometer, a cooling pipe, and an N ₂ gas inlet was placed in a 200-mL flask.
Add 80 g of isopropyl alcohol (IPA) and add N ₂
Gas was introduced, and the flask was heated to 80 ° C. while stirring. Next, a solution obtained by mixing 56 g of acrylic acid, 24 g of methyl acrylate and 0.4 g of 2,2′-azobisisobutyronitrile was dropped from the dropping port over 1 hour. After the dropwise addition, copolymerization was carried out with stirring at the same temperature for 2 hours to obtain an IPA solution of an acrylic acid / methyl acrylate copolymer having a number average molecular weight of 8,000. Next, 133 g of an ethylene glycol dispersion (containing 30% of SiO ₂ ) of colloidal silica (average particle diameter: 35 nm, coefficient of variation: 58%) was placed in a 500 ml flask equipped with a stirrer.
267 g of ethylene glycol, 0.4 g of γ-glycidoxypropyltrimethoxysilane and 0.4 g of water were added, and the mixture was stirred at room temperature for 2 hours to obtain a colloidal silica slurry (A) which had been subjected to a coupling agent treatment. To the slurry (A) was added 1 g of the IPA solution of the acrylic acid / methyl acrylate copolymer, and the mixture was stirred at room temperature for 1 hour to obtain a slurry (B). After re-precipitating the obtained slurry (B) with hexane, the precipitate was examined by elemental analysis, but no ash was found in the precipitate. Further, 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 colloidal silica in the above method. Slurry (B) at 150 ° C for 1
After vacuum drying at 00 mmHg, when the obtained particles were mixed with ethylene glycol or IPA, they were hardly redispersed, and almost only particles were obtained as dispersions that were aggregates and precipitates. Also, no alkoxy group was found in the 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 flask was heated to 120 ° C. while stirring. Next, a mixed solution of 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 dropping, polymerization was continued with stirring at the same temperature for 2 hours to obtain a polymer having a terminal acid group. 10.5 g of γ-aminopropyltriethoxysilane and 50 mg of N, N′-dicyclohexylcarbodiimide were added thereto, followed by stirring 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%. Next, a stirrer,
In a 1 liter flask equipped with a thermometer and a condenser,
2-dimethoxyethane 500 g, colloidal silica (average particle diameter: 40 nm, coefficient of variation: 48%) of ethanol dispersion (SiO ₂ 30% containing) 2g, the polymer silane coupling agent solution 2g and 5% aqueous ammonia 1g
Was added and heated and stirred at 60 ° C. for 2 hours. After the obtained reaction solution was reprecipitated with hexane, the precipitate was examined by elemental analysis. The ash content in the precipitate was the same as that in the raw material polymer silane coupling agent. 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 in the above method. This reaction solution is heated at 150 ° C to 100 mmHg.
After vacuum drying, the precipitate was redispersed in butyl acetate, but a slight 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 diameter of 25%.
0 nm, the coefficient of variation was 78%, and the particle size distribution was very wide. In the fine particles, a methoxy group contained 0.06 mmol
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 condenser, 160 g of ethyl cellosolve, 50 g of a methanol dispersion of colloidal silica (average particle diameter: 31 nm, variation coefficient: 60%) (containing 30% of SiO ₂ ), Production Example 5 (P-1 number average molecular weight of 12,000)
20 g of a toluene solution of 0, ash content: 5.8%) and 1 g of 5% aqueous ammonia were added, and the mixture was heated and stirred at 60 ° C for 2 hours.
After the obtained reaction solution was reprecipitated with hexane, the precipitate was examined by elemental analysis. The ash content in the precipitate was almost the same as the value in the raw material organic polymer (P-1) (5.7%). Met. 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 in the above method. The reaction solution is heated at 150 ° C. for 100
After vacuum drying at mmHg, the precipitate was redispersed in toluene, but a slight 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 143 nm, a coefficient of variation of 113%, and a very wide particle size distribution. A methoxy group was found in the fine particles at 0.06 mmol / g.

Example 29 The organic polymer composite inorganic fine particle dispersion (Z-24) obtained in Example 24 was applied on a glass substrate with a bar coater. After drying at room temperature for 30 minutes and at 60 ° C. for 40 minutes, a clear and glossy good coating film was obtained. Example 30 To 100 g of the organic polymer composite inorganic fine particle dispersion (Z-24) obtained in Example 24, 3 g of an isocyanate curing agent “Sumidur N-3500” manufactured by Sumitomo Chemical Co., Ltd. was added, mixed, and then mixed with 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, 8 g of a curing agent "Super Beckamine J820-60" manufactured by Dainippon Ink and Chemicals, Inc. is added. After mixing, the mixture was applied to a glass substrate with a bar coater. After drying at room temperature for 30 minutes and at 150 ° C. for 30 minutes, a clear 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 80 g of Arotan 2060, an acrylic resin manufactured by Nippon Shokubai Co., Ltd., were mixed to obtain a resin mixture. . This resin mixture was stored in a closed container at 50 ° C. for one month, but no aggregation or thickening was observed. 14 g of an isocyanate curing agent “Sumidur N-3500” manufactured by Sumitomo Chemical Co., Ltd. was added to the resin mixture, mixed, and then applied to a glass substrate with a bar coater. Drying was performed at room temperature for 30 minutes and then at 80 ° C. for 60 minutes to obtain a transparent and glossy good coating film.

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

Comparative Example 7 50 g of a methanol silica dispersion manufactured by Nissan Chemical Industries, Ltd. and Arotan 2060, 8 of an acrylic resin manufactured by Nippon Shokubai Co., Ltd.
0 g was mixed to obtain a resin mixture. This resin mixture was stored at room temperature in a closed container, but aggregation occurred about 3 hours after mixing. Before aggregation occurs, the resin mixture is mixed with an isocyanate curing agent "Sumidur N-" manufactured by Sumitomo Chemical Co., Ltd.
After adding and mixing 14 g of “3500”, the mixture was applied to a glass substrate with a bar coater, and then at room temperature for 30 minutes.
For 60 minutes, the obtained coating film became cloudy due to aggregation of particles, and the surface of the coating film was inferior in smoothness.

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

-Examples 34 to 37-(Organic polymer composite inorganic fine particle dispersions (Z-29 to Z-
32) Synthesis) The procedure was carried out except that the types of the organic solvent, the organic polymer (P) and the metal compound (G) and the amounts of the organic solvent, aqueous ammonia and the metal compound (G) were variously 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. 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 average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 9 shows the stability.

[0142]

[Table 8]

Example 38 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-33)) In a 500 ml four-necked flask equipped with a stirrer, a dropping port, and a thermometer, 250 g of butyl acetate and 90 parts of methanol were placed.
g and 25 g of 25% aqueous ammonia, 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 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-
33) was obtained. 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 average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 9 shows the stability.

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 (dropping ports A and B), and a thermometer. , 120 g of butyl acetate, and 30 g of methanol.
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 g of butyl acetate
A mixed solution of 0 g (solution A) was dropped from a dropping port A over 1 hour from a dropping port B of a mixed solution of 20 g of 25% aqueous ammonia and 50 g of methanol (solution B). After dropping, stirring was continued at the same temperature for 2 hours to obtain an organic polymer composite inorganic fine particle dispersion (Z-39). 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 average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 9 shows the stability.

-Example 40-(Synthesis of organic polymer composite inorganic fine particle dispersion (Z-35)) An organic compound was prepared in the same manner as in Example 39 except that zirconium butoxide of Example 39 was replaced with aluminum isopropoxide. Polymer composite inorganic fine particle dispersion (Z-
35) was obtained. 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 average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 9 shows the stability.

-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)
I got Organic polymer composite inorganic fine particle concentration of the obtained dispersion, inorganic content in the organic polymer composite inorganic fine particles,
Table 9 shows the average particle size and the variation coefficient of the organic polymer composite inorganic fine particles, the content of the alkoxy group 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)) A 500 ml four-necked flask equipped with a stirrer, a thermometer, a condenser, and a distillation column connected to an outlet was prepared. Example 1
400 g of the organic polymer composite inorganic fine particle dispersion (Z-1) 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., and 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. 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 average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 10 shows the stability.

-Examples 43 to 44- (Organic polymer composite inorganic fine particle dispersions (Z-38 to Z-
39) In Example 42, instead of the organic polymer composite inorganic fine particle dispersion (Z-1) obtained in Example 1,
The organic polymer composite inorganic fine particle dispersion obtained in Example 2 (Z
Except for using -2), in the same manner as in Example 42,
An organic polymer composite inorganic fine particle dispersion (Z-38) in which the organic polymer composite inorganic fine particles were dispersed in butyl acetate was obtained.
Similarly, in Example 42, the organic polymer composite inorganic fine particle dispersion (Z-2) obtained in Example 34 was replaced with the organic polymer composite inorganic fine particle dispersion (Z-2) obtained in Example 1.
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, inorganic content in the organic polymer composite inorganic fine particles,
Table 10 shows the average particle size and the variation coefficient of the organic polymer composite inorganic fine particles, the alkoxy group content 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)) A 500 ml four-necked flask equipped with a stirrer, a thermometer, a condenser, and a distillation column connected to an outlet was prepared. Example 3
The organic polymer composite inorganic fine particle dispersion (Z-3) obtained in
0) Add 250 g and 100 g of butyl acetate, and add 110 mmHg
The pressure inside the flask was raised to 100 ° C., and ammonia, methanol, ethyl acetate, water and butyl acetate were distilled off until the solid concentration became 30%, and the organic polymer composite inorganic fine particles were dispersed in butyl acetate. Thus, an organic polymer composite inorganic fine particle dispersion (Z-40) was obtained. 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 average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 10 shows the stability.

Example 46 Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-41) A 500 ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a distillation column connected to an outlet was prepared. Example 3
6 and the organic polymer composite inorganic fine particle dispersion (Z-3)
1) Put 250g and butyl acetate 100g, 110mmHg
The pressure inside the flask was raised to 100 ° C., and 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. 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 average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 10 shows the stability.

Example 47 Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-42) A 500 ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a distillation column connected to an outlet was prepared. Example 3
7, the organic polymer composite inorganic fine particle dispersion (Z-3)
2) 250 g and 100 g of water were added, and the temperature in the flask was increased to 100 ° C. under a pressure of 150 mmHg, and 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 organic polymer composite inorganic fine particles were dispersed in water. 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 average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 10 shows the stability.

-Examples 48 to 51-(Organic polymer composite inorganic fine particle dispersions (Z-43 to Z-
46) Synthesis) The organic polymer composite inorganic fine particle dispersions (Z-7) obtained in Examples 38 to 41 are replaced with the organic polymer composite inorganic fine particle dispersions (Z-7) obtained in Example 7 in Example 24. -33 to Z-36),
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. 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 average particle diameter and the coefficient of variation of the organic polymer composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, Table 10 shows the stability.

The organic polymer composite inorganic fine particle dispersions (Z-29 to Z-46) obtained in Examples 34 to 51 and the supernatant obtained when each of the dispersions was centrifuged were subjected to GPC. Analysis revealed no organic polymer. Further, the organic polymer composite inorganic fine particle dispersion (Z
Each of the organic polymer composite inorganic fine particles as precipitates after centrifugation of -29 to Z-46) 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.

For the organic polymer composite inorganic fine particle dispersions obtained in the above Examples 34 to 51, 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 The average particle diameter and the coefficient of variation of the composite inorganic fine particles, the alkoxy group content in the organic polymer composite inorganic fine particles, and the stability over time were analyzed and evaluated in the same manner as in Examples 1 to 28.

[0155]

[Table 9]

[0156]

[Table 10]

Examples 52 to 64 and Comparative Examples 9 to 14
-A resin mixture was obtained by mixing the dispersion and the resin with the resin compositions shown in Tables 11 and 12. These resin mixtures were stored in a closed container at 50 ° C. for one month, and the appearance and storage stability were examined. The results are shown in Tables 11 and 12. Titanium oxide (Taipec CR-95, manufactured by Ishihara Sangyo Co., Ltd.) was mixed with the resin mixture so that the concentration of the nonvolatile component pigment became 40% by weight, and the mixture was well dispersed with a sand mill. For each of the obtained dispersions (hereinafter referred to as liquid I-1), a polyfunctional isocyanate (Sumidur N-3200, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added to the hydroxyl group in liquid I-1. An amount equivalent to an isocyanate group equivalent ratio of 1: 1 in the polyfunctional isocyanate was weighed to obtain a liquid II-1.
This I-1 solution and II-1 solution were mixed to obtain a coating composition.
The obtained coating composition was coated on a 0.8 mm mild steel sheet with a thickness of 30 μm.
And left for 1 hour at room temperature, then forcibly dried 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.

[0158]

[Table 11]

[0159]

[Table 12]

Example 65 and Comparative Examples 15 to 16 A resin mixture was obtained by mixing a dispersion and a resin with the resin compositions shown in Table 13. These resin mixtures were placed in a closed
It was stored at 0 ° C. for one month and its appearance and storage stability were examined. The results are shown in Table 13. Titanium oxide (Taipec CR-95, manufactured by Ishihara Sangyo Co., Ltd.) was blended with the resin mixture so that the concentration of the nonvolatile component pigment became 50% by weight, and the mixture was well dispersed with a sand mill. The obtained dispersion liquid (hereinafter, referred to as liquid I-2)
To polyfunctional isocyanates (Desmodur BL-3175, Sumitomo Bayer Urethane Co., Ltd.)
Was weighed so that the equivalent ratio of the hydroxyl group in the liquid I-2 to the isocyanate group in the polyfunctional isocyanate was 1: 1. Further, dibutyltin dilaurate was used as a curing catalyst at 1000 ppm based on the resin mixture. In addition, II
-2 liquid. The coating liquid composition was obtained by mixing the liquids I-2 and II-2. The obtained coating composition was applied on a 0.8 mm mild steel sheet at a film thickness of 15 μm, and left at room temperature for 1 hour.
C. for 1 hour to prepare test pieces for various performance tests. The performance of the coating film was evaluated by the performance test method described below. Table 13 shows the evaluation results.

Example 66 and Comparative Example 17 A resin mixture was obtained by mixing a dispersion and a resin with the resin compositions shown in Table 13. These resin mixtures were placed in a closed
It was stored at 0 ° C. for one month and its appearance and storage stability were examined. The results are shown in Table 13. Titanium oxide (R-8)
20, manufactured by Ishihara Sangyo Co., Ltd.) so that the concentration of the non-volatile component pigment is 50% by weight, and well dispersed by a sand mill.
A dispersion (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 obtain II-3 liquid. The coating liquid composition was obtained by mixing the liquids I-3 and II-3. The obtained coating composition was coated on a 0.8 mm mild steel sheet with a film thickness of 1
After coating at 5μ, left at room temperature for 1 hour, and forcedly dried at 170 ° C for 16 minutes, test pieces for various performance tests were prepared. The performance of the coating film was evaluated by the performance test method described below. Table 13 shows the evaluation results.

Example 67 and Comparative Example 18 A resin mixture was obtained by mixing a dispersion and a resin with the resin compositions shown in Table 13. These resin mixtures were placed in a closed
It was stored at 0 ° C. for one month and its appearance and storage stability were examined. The results are shown in Table 13. Titanium oxide (Taipec CR-95, manufactured by Ishihara Sangyo Co., Ltd.) was blended with the resin mixture so that the concentration of the non-volatile pigment was 50% by weight, and the mixture was dispersed well by a sand mill to obtain a dispersion (hereinafter referred to as I-3 liquid). .).
Further, the resin and the curing agent were mixed in the amounts shown in Table 13 to obtain II-
There were three liquids. The coating liquid composition was obtained by mixing the liquids I-3 and II-3. The obtained coating composition was applied on a 0.8 mm mild steel sheet at a thickness of 15 μm, left at room temperature for 1 hour, and then left at 150 ° C.
For 20 minutes to prepare test pieces for various performance tests. The performance of the coating film was evaluated by the performance test method described below. Table 13 shows the evaluation results.

[0163]

[Table 13]

Examples 68-70 and Comparative Examples 19-2
2- A resin mixture was obtained by mixing the dispersion and the resin with the resin composition shown in Table 14. These resin mixtures were placed in a closed
It was stored at 0 ° C. for one month, and its appearance and storage stability were examined. The results are shown in Table 14. After adding and mixing a curing agent and a catalyst with the composition shown in Table 14, the resin mixture was applied on a 0.8 mm untreated dull steel plate at a thickness of 30 μm, and left at room temperature for 1 hour.
The film was forcibly dried at 60 ° C. for 20 minutes, and the performance of the coating film was evaluated by the performance test method described later. Table 14 shows the evaluation results.

[0165]

[Table 14]

Example 71 and Comparative Examples 23 to 24 A resin mixture was obtained by mixing a dispersion and a resin with the resin compositions shown in Table 15. These resin mixtures were placed in a closed
It was stored at 0 ° C. for one month, and its appearance and storage stability were examined. The results are shown in Table 15. A curing agent and a catalyst were added to the resin mixture in the composition shown in Table 15 and mixed.
The coated film was applied on a 0-treated steel sheet at a film thickness of 5 to 10 μm, left at room temperature for 1 hour, and dried at 200 ° C. for 10 minutes, and the performance of the coating film was evaluated by a performance test method described later. Table 15 shows the evaluation results.
Shown in

[0167]

[Table 15]

The appearance and storage stability of the resin mixtures obtained in the above Examples and Comparative Examples after storage at 50 ° C. for one month were evaluated by the following methods. In addition, drying properties of the coating film, solvent resistance, pencil hardness, stain resistance, weather resistance, adhesion,
The bendability and corrosion resistance 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 Δ: Acceptable X: Not Acceptable [Storage Stability] The stability in storage after storage at 50 ° C. for one month was observed. ：: stable ○: slightly thickened △: thickened ×: large amount of condensate [drying property] evaluated by touch after forced drying.

◎: No change 少 し: Slight trace X: Strong trace [solvent resistance] Surface state after rubbing 50 times with absorbent cotton impregnated with methyl ethyl ketone. ：: No change ：: Glossiness ×: Dissolved and disappeared coating film [Pencil hardness] A pencil scratch test according to JIS K5400 6.14 was performed, and evaluation based on scratches was performed.

[Stain Resistance] A 0.05% aqueous solution of carbon was applied to the coating film 30 times with a brush, and the coating film was forcibly dried at 80 ° C. for 1 hour and then washed 30 times with a brush while washing with water. The degree of adhesion of dirt was examined. ：: No adhesion ：: Almost no adhesion や: Slight adhesion X: Adhesion [Weather resistance] The state of the coating film after 3000 hours was examined with a sunshine weather meter.

A: Excellent B: Good B: Normal C: Poor [Adhesion] A cross-cut test according to JIS K5400 6.15 was performed. ◎: No peeling ○: Slight peeling at the intersection of cuts △: Peeling area 5 to 35% ×: Peeling area 35% or more [Bendability] Peeling and peeling of the coating film by a bending tester specified in JIS K5400 6.16. Examined. (Diameter of mandrel: 2 mm) 優秀: excellent ：: good 普通: normal ×: poor [Corrosion resistance] In the salt spray test, the time during which the width of the blister at the cross cut portion was 2 mm or less at maximum was measured.

[0173]

The organic polymer composite inorganic fine particles of the present invention have an average particle diameter of 5 to 200 nm and a coefficient of variation of the particle diameter of 50.
% Or less, has a fine average particle size, narrow particle size distribution, and has been used in coatings and molding materials for its dispersion stability and compatibility with organic matrices. It is particularly superior as compared to. In the method of manufacturing the organic <br/> machine polymer composite inorganic fine particles, a specific organic polymer (P) alone or a hydrolyzable metal compound together with (G) that hydrolysis and condensation, by a very simple method In addition, the organic polymer can be fixed on the surface of the inorganic fine particles, and it is not always necessary to incorporate a complicated drying step as in the related art into the manufacturing method.

The organic polymer composite inorganic fine particles and the dispersion obtained by dispersing the organic polymer composite inorganic fine particles in water or an organic solvent according to the present invention are useful as additives for various paints and molding materials. And its dispersion 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 coatings because the organic polymer is fixed on the surface of the inorganic fine particles, The coating obtained by coating the material has a glossy and favorable appearance, has no cracks, and has excellent adhesion and weather resistance.

Since the film-forming composition of the present invention essentially contains organic polymer composite inorganic fine particles as compared with the conventional film-forming composition, the film properties are improved as compared with 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, heat resistance,
Gives a film with good film properties such as abrasion resistance and stain resistance.
Furthermore, a hydroxyl group is contained in the organic polymer constituting the organic polymer composite inorganic fine particles contained in the film-forming composition, and at least one selected from a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin in the film-forming composition. When one kind of the compound (J) is contained, a crosslinked structure is formed, and the film-forming composition has a good film having solvent resistance, stain resistance, flexibility, weather resistance, heat resistance, storage stability and the like. It has physical properties. When the polyol (Q) is further contained in the composition for film formation, a stronger crosslinked structure is obtained, so that the properties of the film are further improved.

This film-forming composition can be used for automobiles, ships, vehicles, etc. by utilizing the above-mentioned good film properties such as solvent resistance, stain resistance, flexibility, weather resistance, heat resistance and storage stability. , Building materials,
It can be applied on the surface of various base materials such as metal materials such as electrical appliances, industrial machines, beverage cans, buildings and structures, organic materials such as inorganic materials and plastics, and for surface protection and cosmetics of various base materials. Form a useful coating.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C09C 3/12 C09C 3/12 C09D 7/12 C09D 7/12 (72) Inventor Tadahiro Yoneda No. 5 Nishimitabicho, Suita-shi, Osaka No. 8 Nippon Shokubai Central Research Laboratory Co., Ltd. (72) Masaya Yoshida, Inventor 5-8 Nishiburi-cho, Suita-shi, Osaka Pref. Japan Co., Ltd. No. 5-8, Nishiomibori-cho, Japan Catalyst Functional Resins Research Dept. (56) References JP-A-5-115772 (JP, A) JP-A-5-287213 (JP, A) JP-A-6-228457 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09C 1/00-3/12 C09D 7/12

Claims (6)

(57) [Claims] 1. A material selected from Si, Al, Ti and Zr
Organic polymer wrapped in fine particles of metal oxide
As well as containing, organic polymers to the surface of the fine particles is fixed by chemical bonding, prior Symbol organic polymer comprises a (meth) acrylic units, average particle diameter of flat 5~200nm
And organic polymer composite inorganic fine particles having a particle diameter variation coefficient of 50% or less. Wherein said skeletal 0.01~50mmol / g containing an alkoxy group attached to the metal element which forms fine particles, organic polymer composite inorganic particles of claim 1. 3. An organic polymer composite inorganic fine particle dispersion comprising the organic polymer composite inorganic fine particle according to claim 1 or 2 . 4. A film-forming composition comprising the organic polymer composite inorganic fine particles according to claim 1 or 2 . 5. A organic polymer composite inorganic fine particles according to claim 1 or 2 containing a hydroxyl group in the organic polymer, the polyfunctional isocyanate compound, at least one compound selected from melamine compounds and aminoplast resins (J) containing, film-forming composition of claim 4. 6. A polyol containing two or more hydroxyl groups in one molecule containing (Q), film-forming composition according to claim 4 or 5.