JPH09302257A - Composite composed of fine inorganic particle and organic polymer, production thereof, and film-forming composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain fine composite particles usable as an additive and having an excellent dispersion stability and a particularly high affinity for an organic matrix by fixing a specified organic polymer on the surfaces of fine inorganic particles. SOLUTION: Fine composite particles comprising fine inorganic particles having an organic polymer containing a perfluoroalkyl group and/or a silicone group fixed on the surfaces thereof are obtained through a step wherein at least one organic polymer containing at least one polysiloxane group per molecule, which has at least one Si-OR<1> group (wherein R<1> is H, an alkyl group or an acyl group) in the polysiloxane group, and a perfluoroalkyl group and/or a silicone group is hydrolyzed and condensed alone or together with a hydrolyzable metal compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic polymer composite inorganic fine particle useful as an additive to various paints, molding materials, etc., a method for producing the same, various paints, surface treatment agents, coating agents, adhesives, and tackifiers. The present invention relates to a film forming composition useful as an agent, a sealing agent, and the like.

[0002]

2. Description of the Related Art Conventionally, in order to produce additives such as various paints and molding materials, inorganic fine particles have been surface-modified by various methods using organic polymers, etc., and the affinity between the inorganic fine particles and the organic medium has been improved. Is being improved. However, the dispersibility and stability of the additive thus obtained are not sufficient, and the manufacturing process thereof is complicated,
Not in practical use.

[0003]

The present inventors have developed special composite fine particles in which an organic polymer is fixed on the surface of inorganic fine particles (Japanese Patent Laid-Open No. 178335/1995). It has excellent dispersibility and stability and can be easily manufactured. When this is added to a paint or the like and used, physical properties of the coating excellent in weather resistance, stain resistance, chemical resistance, adhesiveness, surface hardness and the like can be obtained. But,
Since the composite fine particles are distributed almost uniformly over the entire coating and are not selectively concentrated on the coating surface, it is necessary to add a large amount of the composite fine particles in order to improve the physical properties of the coating surface.

Therefore, the problem to be solved by the present invention is that it is useful as an additive for various paints, molding materials and the like, and the physical properties of the coating can be particularly enhanced by using a small amount thereof, and it can be applied to various organic solvents and polymers. To form a film with excellent dispersion stability and organic polymer composite inorganic fine particles that have a particularly good affinity for the organic matrix and excellent weather resistance, stain resistance, chemical resistance, adhesion, surface hardness, etc. And a film forming composition capable of performing the above.

Another problem to be solved by the present invention is to produce organic polymer composite inorganic fine particles having the above-mentioned characteristics simply and efficiently.

[0006]

The organic polymer composite inorganic fine particles according to the present invention are composite fine particles in which an organic polymer is fixed on the surface of the inorganic fine particles, and the organic polymer is a perfluoroalkyl group and / or silicone. Including a group. In the method for producing inorganic fine particles of an organic polymer composite according to the present invention, at least one polysiloxane group is bonded per molecule, and at least one Si—OR ¹ group (R ¹ is a hydrogen atom or at least one optionally selected group selected from an alkyl group and an acyl group, and when there are plural R ¹ 's in one molecule, the plural R ^1's may be the same as each other. , Which may be different) and comprises a perfluoroalkyl group and / or a silicone group.
The step of hydrolyzing and condensing the seed organic polymer (P) with (P) alone or with the hydrolyzable metal compound (G) is included.

In the method for producing organic polymer composite inorganic fine particles according to the present invention, at least one polysiloxane group is bonded per molecule, and at least one Si-OR ^{1 is} contained in the polysiloxane group. Group (R ¹ is at least one group which may be substituted and is selected from a hydrogen atom, an alkyl group and an acyl group, and when there are plural R ¹ 's in one molecule, the plural R ^1's are the same as each other; At least one organic polymer (P) having a functional group capable of introducing a perfluoroalkyl group and / or a silicone group.
(P) alone or a hydrolyzable metal compound (G)
And a compound containing a group that reacts with the functional group, a perfluoroalkyl group and / or a silicone group, and a hydrolysis / condensation product of the organic polymer (P) obtained in the step And a step of reacting with each other.

The film-forming composition according to the present invention contains the organic polymer composite inorganic fine particles of the present invention.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Organic Polymer Composite Inorganic Fine Particles The inorganic fine particles constituting the organic polymer composite inorganic fine particles of the present invention are not particularly limited as long as they are fine particles of an inorganic substance composed of any element, and are preferably used as an inorganic substance. What is used is an inorganic oxide. Inorganic oxides are defined as various oxygen-containing metal compounds in which a metal element mainly forms a three-dimensional network through a bond with an oxygen atom. As the metal element constituting the inorganic oxide, for example, an element selected from Groups II to VI of the Periodic Table of the Elements is preferable, and an element selected from Group III to V of the Periodic Table of the Elements is more preferable. Among them, an element selected from Si, Al, Ti, and Zr is particularly preferable, and silica fine particles in which the metal element forming the inorganic oxide is Si is most preferable as the inorganic fine particles. Further, the inorganic oxide may contain an organic group or a hydroxyl group, or various groups derived from the metal compound (G) as a raw material described below may remain, or a part of the organic polymer may be included. . The organic group is at least one selected from the group consisting of an optionally substituted alkyl group having 20 or less carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group. The inorganic oxide is one kind or two or more kinds.

The shape of the inorganic fine particles made of such an inorganic material may be any particle shape such as spherical, needle-like, plate-like, scale-like, and crushed, and is not particularly limited. The content of the inorganic substance in the organic polymer composite inorganic fine particles is not particularly limited, when the organic polymer composite inorganic fine particles are added to various resins, the hardness of the inorganic material, the characteristics such as heat resistance, In order to exhibit more effectively, it is advantageous to increase the content of the inorganic substance in the organic polymer-composite inorganic fine particles as much as possible, and the content of the inorganic substance is 50 to 99.5% by weight of the organic polymer-composite inorganic fine particle. preferable.

When the organic polymer-composite inorganic fine particles are used for various paints and molding materials, the dispersibility of the organic polymer-composite inorganic fine particles and the dispersion between the fine particles and the organic medium are considered. It contributes to the improvement of affinity, and also acts as a binder when the organic polymer composite inorganic fine particles are used in the film forming composition.

The organic polymer contains perfluoroalkyl groups and / or silicone groups, ie at least one of perfluoroalkyl groups and silicone groups. Specific examples of the perfluoroalkyl group are not particularly limited, but include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group. , A perfluorododecyl group, a perfluorotetradecyl group and the like. The perfluoroalkyl group may be only one kind or may be a combination of two or more kinds appropriately. Above all, it is preferable that the perfluoroalkyl group is at least one of a perfluoromethyl group and a perfluoroethyl group, because the introduction into the organic polymer is easy. In addition, a part of the fluorine atoms in the perfluoroalkyl group may be substituted with another atom such as a chlorine atom within a range that does not impair the effects of the present invention.

Specific examples of the silicone group include, but are not limited to, a dimethyl silicone group, a diphenyl silicone group, a methylphenyl silicone group, a diethyl silicone group and a methylethyl silicone group.
Only one silicone group may be used, or two or more silicone groups may be appropriately combined. Among them, the silicone group is
At least one of a dimethyl silicone group and a diphenyl silicone group is preferable because it can be easily introduced into an organic polymer.

The molecular weights of the perfluoroalkyl group and the silicone group are not particularly limited, but are preferably 50,000 or less because they can be easily introduced into the organic polymer, and more preferably 10,000 or less. preferable. Organic polymers contain perfluoroalkyl groups and / or silicone groups, which are linked by chemical bonds to the backbone of the organic polymer. The bond form between the main chain of the organic polymer and these groups is not particularly limited, but in addition to those in which these groups and the main chain of the organic polymer are directly bonded, an ester group (-COO
-) Or an ether group (-O-) or the like may be used for bonding.

The content of the perfluoroalkyl group and / or the silicone group in the organic polymer is not particularly limited, but for example, when the organic polymer composite inorganic fine particles are used in a film-forming composition such as a coating composition described later, In order to improve the coating physical properties such as weather resistance, stain resistance and surface strength, etc., by exerting the effect that the organic polymer composite inorganic fine particles are densely present in the vicinity of the coating surface, without deteriorating other physical properties of the coating. Is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, of the perfluoroalkyl group and / or the silicone group with respect to the organic polymer.
% By weight. The molecular weight, shape, composition, etc. of the organic polymer are not particularly limited, and any organic polymer having a perfluoroalkyl group and / or a silicone group can be used. Regarding the shape of the organic polymer, any shape such as a linear, branched, or crosslinked structure can be used. In addition, specific examples of the resin that constitutes the organic polymer are not particularly limited, and examples thereof include (meth) acrylic resin, polystyrene, polyvinyl acetate, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, and polyethylene. Examples thereof include polyesters such as terephthalate and copolymers thereof, and resins partially modified with functional groups such as amino groups, epoxy groups, hydroxyl groups and carboxyl groups. Among them, organic polymers are (meta)
Acrylic resin, (meth) acrylic-styrene resin,
An organic polymer containing a (meth) acrylic unit such as (meth) acrylic-polyester resin is an essential component, and
The organic polymer composite inorganic fine particles capable of forming a film can be used as a suitable one for a film forming composition described later.

Regarding the organic polymer, as described above,
Although any organic polymer having a perfluoroalkyl group and / or a silicone group can be used,
In particular, a structure composed of an organic chain and a polysiloxane group, to which at least one polysiloxane group is bonded per molecule, and containing at least one Si—OR ¹ group in the polysiloxane group, An organic chain that is contained in the below-mentioned organic polymer (P) is preferable.

The content of the organic polymer in the organic polymer composite inorganic fine particles is not particularly limited, but it is 0.5 to 50% by weight of the organic polymer composite inorganic fine particles.
Is preferred. The organic polymer-composite inorganic fine particles are composite fine particles in which an organic polymer is fixed on the surface of the inorganic fine particles. Here, fixing does not mean mere adhesion and adhesion, but the organic polymer-composite inorganic fine particles are This means that the organic polymer is not detected in the washing liquid washed with any solvent, which strongly suggests that a chemical bond is formed between the organic polymer and the inorganic fine particles.

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

The average particle diameter of the organic polymer-composite inorganic fine particles is not particularly limited, but is preferably 5 nm or more, for example, in order to prevent the surface energy of the organic polymer-composite inorganic fine particles from increasing and aggregation and the like to easily occur. Further, when the organic polymer composite inorganic fine particles are used for a coating material or the like, the thickness is preferably 200 nm or less, more preferably 100 nm or less so that the physical properties such as transparency of the coating film are not deteriorated.

The particle diameter variation coefficient, which is an index of the particle size distribution of the organic polymer composite inorganic fine particles, is not particularly limited. For example, when the organic polymer composite inorganic fine particles are used as a filler such as a plastic film, a film is obtained. In order to prevent the surface from becoming smooth and the irregularities becoming severe, 50% or less is preferable, and 30% or less is more preferable. At least 1 in the organic polymer composite inorganic fine particles
One or more kinds of alkoxy groups may be contained, and the content thereof is not particularly limited. The alkoxy group referred to here is R ⁴ O bonded to the metal element forming the fine particle skeleton.
Represents a group. Here, R ⁴ is an optionally substituted alkyl group, and the R ⁴ O groups in the fine particles may be the same or different. Specific examples of R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. Such an alkoxy group has a function of complementarily improving the affinity with the organic medium and the dispersibility in the organic medium when the organic polymer composite inorganic fine particles are used as various paints and molding materials. In order to exert such an action, the alkoxy group in the organic polymer composite inorganic fine particles is preferably 0.01 to 50 mmol per 1 g of the organic polymer composite inorganic fine particles. Method for Producing Organic Polymer Composite Inorganic Fine Particles The organic polymer composite inorganic fine particles of the present invention can be produced by any method. As a method for producing the organic polymer-composite inorganic fine particles of the present invention, it is preferable to apply the production method A described in detail below, because the organic polymer-composite inorganic fine particles can be produced easily and efficiently.

In the production method A, at least one polysiloxane group is bonded per molecule, and at least one Si-OR ¹ group (R ¹ is a hydrogen atom or an alkyl group is contained in the polysiloxane group. group, selected from acyl groups, 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 may be different. And at least one organic polymer (P) having
It is a method including a step of condensing.

Organic polymer (P) used in production method A
Can be independently hydrolyzed and condensed to produce organic polymer composite inorganic fine particles. Further, it is also possible to produce organic polymer composite inorganic fine particles by co-hydrolyzing / condensing the metal compound (G) and the organic polymer (P) described later together. The organic polymer (P) contains an organic chain and a polysiloxane group, and has at least one polysiloxane group bonded to each molecule, and at least one Si—OR ¹ group in the polysiloxane group. Has a structure containing.

The organic polymer (P) further contains at least one of the following groups and: Perfluoroalkyl group and / or silicone group. A functional group capable of introducing a perfluoroalkyl group and / or a silicone group.

Specific examples of the above include the groups explained in the above-mentioned organic polymer composite inorganic fine particles. Also,
Specific examples of the above include functional groups such as hydroxyl group, carboxyl group, amino group, epoxy group, mercapto group, oxazoline group and aldehyde group. When the organic polymer (P) does not contain, but contains only,
The production method A needs to further include a step of converting the functional group to introduce a perfluoroalkyl group and / or a silicone group, as described later. On the other hand, when the organic polymer (P) contains both and, the production method A may further include a step of converting the functional group to introduce a perfluoroalkyl group and / or a silicone group. Good, but not necessary.

In the organic polymer (P), the structure of the organic chain is not particularly limited. In addition, the polysiloxane group and the organic chain in the organic polymer (P) are chemically bonded via a Si—C bond, a Si—O—C bond, or the like for the reason that the organic polymer (P) is easily available. It is preferable that the polysiloxane group and the organic chain have a Si—C bond because the bond site is excellent in hydrolysis resistance and it is desirable that it is less likely to undergo an unfavorable reaction such as an exchange reaction at the bond site. More preferably, it is chemically bonded via.

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

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

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

In addition, all S in the polysiloxane group
The i atom is preferably bonded only to the R ¹ O group in addition to the bond with the organic chain and the polysiloxane bond (Si—O—Si bond). In such a case, the ionicity of the Si atom is further increased, and as a result, the rate of hydrolysis / condensation of the R ¹ O group is further increased, and the number of reaction points in the organic polymer (P) is increased, resulting in a stronger skeleton. Fine particles having are obtained. Specific examples of such a polysiloxane group include a polydimethoxysiloxane group, a polydiethoxysiloxane group, a polydiisopropoxysiloxane group, and a poly-n-butoxysiloxane group.

The molecular weight of the organic polymer (P) is not particularly limited, but for example, in order to reliably dissolve it in the organic solvent described later, the number average molecular weight is preferably 200,000 or less, preferably 50,000 or less. Is more preferable. The organic polymer (P) can be produced by a conventionally known method. As described above, the organic polymer (P) contains at least the polysiloxane group and the above-mentioned perfluoroalkyl group and / or silicone group and a functional group capable of introducing the perfluoroalkyl group and / or silicone group. Includes one and.

As a method of introducing the polysiloxane group into the organic polymer (P), for example, the following (1) to
Although the method of (4) is mentioned, it is not limited to these methods. (1) After radical (co) polymerizing a radically polymerizable monomer in the presence of a silane coupling agent having a double bond group or a mercapto group, the resulting (co) polymer and a silane compound (H ) And / or its derivative (s) and co-hydrolysis / condensation.

(2) Co-hydrolysis obtained by co-hydrolyzing and condensing a silane coupling agent having a double bond group or a mercapto group and a silane compound (H) and / or its derivative described later. A method of radically (co) polymerizing a radically polymerizable monomer in the presence of a condensate (hereinafter abbreviated as polymerizable polysiloxane). (3) After reacting a silane coupling agent having a reactive group such as a double bond group, an amino group, an epoxy group, and a mercapto group with a polymer having a group capable of reacting with the reactive group A method of co-hydrolyzing / condensing the obtained polymer with the silane compound (H) and / or its derivative described below.

(4) Co-hydrolysis of a silane coupling agent having a reactive group such as a double bond group, an amino group, an epoxy group and a mercapto group, and a silane compound (H) and / or its derivative described later. A method of reacting the polymer obtained by co-hydrolysis / condensation having the above-mentioned reactive group after condensation with a polymer having a group capable of reacting with the above-mentioned reactive group.

Among the above, the method (2) is preferable because the reaction can be carried out more easily. Further, the above-mentioned perfluoroalkyl group and / or silicone group,
As a method of introducing at least one kind of group selected from functional groups capable of introducing a perfluoroalkyl group and / or a silicone group into the organic polymer (P), for example, the above-mentioned organic polymer (P) At least one selected from the above-mentioned perfluoroalkyl group and / or silicone group and a functional group capable of introducing a perfluoroalkyl group and / or silicone group as a copolymerization component in the production of The method can be performed by using a polymerizable monomer containing a group of, but is not limited to this method.

The hydrolyzable metal compound (G) can be three-dimensionally formed by hydrolysis and further condensation. Specific examples of such metal compound (G) include metal halides, metal nitrates, metal sulfates, metal ammonium salts, organometal compounds, alkoxy metal compounds, and derivatives of these metal compounds. To be The metal compound (G) can be used alone or in combination of two or more.

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

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

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

Examples of the above chelate-substituted compound include diisopropoxytitanium diacetylacetonate,
Examples thereof include oxytitanium diacetylacetonate, dibutoxytitanium bistriethanolaminate, dihydroxytitanium dilactate, zirconium acetylacetonate, acetylacetone zirconium butoxide, triethanolamine zirconium butoxide, and aluminum acetylacetonate.

Among them, the metal compound (G) 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, and R ³ is selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, which may be substituted. At least one group, n is a valence of the metal element M, m is an integer of 1 to n, R ²
And / or when there are a plurality of R ^{3 s} in one molecule, a plurality of R ^{2 s} and / or R ^{3 s} may be the same as each other,
May be different. It is preferable to use at least one selected from the compounds shown in (4) and their derivatives.

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

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

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

Further, since it is industrially available and does not contain halogen etc., which adversely affects the physical properties of the production equipment and the final product, the silane compound (H) in which M is Si in the general formula and its It is more preferable to use at least one selected from derivatives. Specific examples of the silane compound (H) include methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylacetoxysilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and methyltrimethoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, dimethoxymethylphenylsilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, dimethoxydiethoxysilane and the like. Further, specific examples of the derivative of the silane compound (H) include a hydrolysis / condensate of the silane compound (H).

Of the silane compounds (H), the alkoxysilane compounds are particularly preferable because they are easily available as raw materials. Further, the silane compound (H) and its derivative are
R ² ) ₄ and its derivatives are preferable in that the hydrolysis / condensation rate is fast and the organic polymer composite inorganic fine particles having a stronger skeleton are obtained. In the manufacturing method A,
The organic polymer composite inorganic fine particles are produced by hydrolyzing and condensing the organic polymer (P) alone or with the above metal compound (G). The method of hydrolysis / condensation is not particularly limited, but it is preferably carried out in a solution because the reaction can be easily carried out. The solution here is a solution containing an organic solvent and / or water described below, and the composition thereof is not particularly limited.

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

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

The raw material composition at the time of hydrolysis / condensation is not particularly limited. The amount of organic polymer (P) is 0.1
-80% by weight is preferable, and 0.5-30% by weight is more preferable. The amount of the metal compound (G) is preferably 0 to 80% by weight, more preferably 0 to 50% by weight. The amount of the organic solvent is preferably 0 to 99.9% by weight, and 20 to 99% by weight.
Is more 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 hydrolysis / condensation is not particularly limited as long as the organic polymer (P) alone or the amount of the organic polymer (P) and the metal compound (G) formed into particles by hydrolysis / condensation. However, in order to carry out hydrolysis / condensation more sufficiently and to strengthen the skeleton of the particles, the larger the amount of water used, the better. Specifically, the molar ratio of water to the hydrolyzable group that hydrolyzes and condenses is 0.1
Or more, preferably 0.5 or more, more preferably 1
By carrying out hydrolysis / condensation under the above conditions, organic polymer composite inorganic fine particles can be obtained.

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

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

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

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

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

X _a = (a / A) / (b / B) X _c = (c / C) / (b / B) (where A is the total amount of the raw material liquid (A) and B is the raw material liquid ( B represents the total amount of the raw material liquid (C), C represents the total amount of the raw material liquid (C), and a represents 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 the arbitrary time t, and c indicates the amount of the raw material liquid (C) already supplied at the arbitrary time t. ) In the case where the organic polymer (P) contains a functional group capable of introducing the above-mentioned perfluoroalkyl group and / or silicone group, the production method A includes a group that reacts with this functional group and a perfluoroalkyl group. And / or a silicone group-containing compound is reacted with the hydrolysis / condensation product of the organic polymer (P) obtained in the hydrolysis / condensation step of the production method A to give a perfluoroalkyl group and / or a silicone group. By further including the step of introducing, a perfluoroalkyl group and / or a silicone group can be introduced into the obtained organic polymer composite inorganic fine particles.

The group which reacts with the functional group varies depending on the kind of the functional group. Specific examples thereof include, for example, when the functional group is a hydroxyl group, an oxazoline group, a carboxyl group and an epoxy group; When it is a carboxyl group, it is an oxazoline group, hydroxyl group, epoxy group and mercapto group; when the functional group is an epoxy group, it is an oxazoline group, carboxyl group, hydroxyl group, amino group and mercapto group; In some cases, an oxazoline group, an epoxy group, and a vinyl group; when the functional group is a vinyl group, an amino group; when the functional group is an oxazoline group, an epoxy group, a carboxyl group, a hydroxyl group, an amino group, and Mercapto group; when the functional group is a mercapto group, an oxazoline group, an epoxy group, a carboxyl group And an epoxy group and. Organic polymer composite inorganic fine particle dispersion The organic polymer composite inorganic fine particle dispersion contains the organic polymer composite inorganic fine particle of the present invention. Further, the organic polymer-composite inorganic fine particle dispersion may contain the organic polymer-composite inorganic fine particle obtained by the method for producing an organic polymer-composite inorganic fine particle of the present invention. That is, the organic polymer composite inorganic fine particle dispersion is, for example, one obtained by dispersing the organic polymer composite inorganic fine particle of the present invention in an arbitrary solution, the reaction mixture obtained by the method for producing the organic polymer composite inorganic fine particle of the present invention, After replacing the solvent in the reaction mixture with another solvent while heating under distillation, after distilling off the solvent in the reaction mixture, centrifugation, reprecipitation, ultrafiltration, etc. after isolation of the organic polymer composite inorganic fine particles And a dispersion medium dispersed in various dispersion media.

The organic polymer-combined inorganic fine particle dispersion has no coarse particles, agglomerates, and precipitates, and has the property of not causing precipitation or gelation for a long period of time. The dispersion state of the organic polymer composite inorganic 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 is a dispersion in which the organic polymer-composite inorganic fine particles in the dispersion do not aggregate and maintain a sharp particle size distribution.

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

The concentration of the organic polymer composite inorganic fine particles in the organic polymer composite inorganic fine particle dispersion is not particularly limited, but is preferably 0.5 to 70% by weight, and more preferably 1 to 50% by weight. When the concentration of the organic polymer-composite inorganic fine particle dispersion in the organic polymer-composite inorganic fine particle dispersion is high, the viscosity of the dispersion becomes high and it becomes difficult to use it for various applications. Film-forming composition The film-forming composition of the present invention contains organic polymer composite inorganic fine particles. The film forming composition may contain the composite inorganic fine particles obtained by the method for producing the organic polymer composite inorganic fine particles described above, or the organic polymer composite inorganic fine particle dispersion.

The organic polymer constituting the organic polymer composite inorganic fine particles contained in the film-forming composition is not particularly limited, but among them, a (meth) acrylic resin having a film-forming ability and a (meth) acrylic-styrene. Resin, (meta)
Acrylic-polyester resins are preferred. The film-forming composition of the present invention essentially contains the organic polymer-composite inorganic fine particles of the present invention as compared with the conventional composition, and thus the physical properties of the film are improved as compared with the conventional product. For example, in a film-forming composition in which the organic polymer composite inorganic fine particles of the present invention are added to a general coating resin or the like, surface hardness, adhesion, weather resistance, chemical resistance, heat resistance, abrasion resistance, stain resistance It gives a coating film with good physical properties. Further, even when the amount of the organic polymer composite inorganic fine particles used is smaller, the composite inorganic fine particles become dense in the vicinity of the surface of the coating film to be obtained.
High coating physical properties such as surface hardness, weather resistance, abrasion resistance and stain resistance.

The organic polymer composite inorganic fine particles of the present invention are
It has a structure in which an organic polymer is fixed on the surface of the inorganic fine particles, and by the organic polymer acting as a binder, it is possible to form a coating by itself alone on various base materials described below, The film-forming composition containing the organic polymer composite inorganic fine particles can provide a transparent and good coating film.

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

As the film-forming composition in which the organic polymer has a crosslinked structure in the film finally obtained after applying the film-forming composition, for example, the following may be mentioned. (1) 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 reacts with the functional group (X). A film-forming composition comprising a compound or resin having two or more functional groups (Y). (2) The organic polymer composite inorganic fine particles having the functional group (X) obtained by the above-mentioned method using the organic polymer (P) having the functional group (X) reacts with the functional group (X). Organic polymer (P) having functional group (Y)
To obtain the functional group (Y) obtained by the method described above.
A film-forming composition comprising: an organic polymer composite inorganic fine particle having: (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 reacts with the functional group (X). A functional group (W) capable of reacting with a compound or resin having two or more functional groups (Y) and the functional group (X).
A film-forming composition comprising: an organic polymer (P) having the formula (1) and an organic polymer composite inorganic fine particle having a functional group (W) obtained by the method described above. (4) A film forming composition as described in (1) to (3) above, which further contains a compound and / or a resin having two or more functional groups (X).

Here, examples of the functional group (X) include a hydroxyl group, a carboxyl group, an amino group, an epoxy group,
Examples thereof include 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 an isocyanate group, an epoxy group, a hydroxyl group, a mercapto group and an amino group. Group, unsaturated group, carboxyl group and the like.

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

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, 1, Biuret body of 6-hexamethylene diisocyanate, isocyanurate body and the like 3
Polymers; these polyfunctional isocyanates and propanediol, hexanediol, polyethylene glycol,
Compounds in which two or more isocyanate groups produced by the reaction with a polyhydric alcohol such as trimethylolpropane remain; Compounds having, oximes such as acetoxime and methylethylketoxime,
Examples thereof include blocked polyfunctional isocyanate compounds blocked with a blocking agent such as lactams such as ε-caprolactam and γ-caprolactam. These polyfunctional isocyanate compounds may be used either individually or in combination of two or more. Among them, a non-yellowing polyfunctional isocyanate compound having no isocyanate group directly bonded to an aromatic ring is preferable in order to prevent undesired yellowing of the coating.

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

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

When the film-forming composition further contains a polyol (Q) containing two or more hydroxyl groups in one molecule, the resulting film has physical properties such as strength, flexibility and solvent resistance. It is more preferable because it improves. 2 in one molecule
The polyol (Q) containing one or more hydroxyl groups is not particularly limited as long as it is soluble in the above-mentioned organic solvent, but is not limited as long as it is compatible with the organic polymer in the organic polymer composite inorganic fine particles. It is preferable because the gloss or transparency of the coating is improved. Therefore, those having the same composition as the organic polymer are most preferable.

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

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

The molecular weight of the polyol obtained by polymerizing a monomer component containing a hydroxyl group-containing unsaturated monomer is 1,000 to
500,000, preferably 5,000 to 10
It is 0000. The hydroxyl value is 5 to 300, preferably 10 to 200. The polyester polyol obtained under the condition of excess hydroxyl group is, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, Hexamethylene glycol, decamethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, cyclohexanediol, hydrogenated bisphenol A, bis (hydroxymethyl) cyclohexane, Polyhydric alcohols such as hydroquinone bis (hydroxyethyl ether), tris (hydroxyethyl) isosinurate, xylylene glycol, and maleic acid, Mar acid, succinic acid, adipic acid, sebacic acid, azelaic acid, trimellitic acid, terephthalic acid, phthalic acid,
It can be produced by reacting a polybasic acid such as isophthalic acid under the condition that the number of hydroxyl groups in the polyhydric alcohol is larger than the number of carboxyl groups in the polybasic acid.

The molecular weight of the polyester polyol obtained under the condition of excess hydroxyl group is 500 to 300,000,
It is preferably 2,000 to 100,000. The hydroxyl value is 5 to 300, preferably 10
~ 200. The polyol (Q) may be added in any amount to the film-forming composition, but the weight ratio of polyol (Q) / organic polymer composite inorganic fine particles in the film-forming composition is 0. / 100 to 99/1, preferably 30/70 to 95/5. When the proportion of the polyol (Q) is 30% or more, the flexibility of the coating is high, and when the proportion 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 polyester polyol is preferably used. An acrylic polyol, which is a polyol obtained by polymerizing a monomer component containing the hydroxyl group-containing unsaturated monomer and having a (meth) acrylic unit or the like, is also preferably used. As the polyol (Q), either a polyester polyol or an acrylic polyol may be used, or both may be used, depending on the application.

The number of hydroxyl groups in the polyol (Q) is 1
It is not particularly limited as long as it is 2 or more per molecule, but if the hydroxyl value in the solid content is 10 or less, the number of crosslinking points decreases,
The physical properties of the coating such as solvent resistance, water resistance, heat resistance and surface hardness tend to deteriorate. The film-forming composition of the present invention may be one in which organic polymer composite inorganic fine particles are dispersed in various organic solvents and / or water, and the kind and composition of the dispersion medium used are not particularly limited, An organic solvent and / or water in which the organic chains in the organic polymer composite inorganic fine particles are dissolved are preferable. Examples of such an organic solvent include the above-mentioned organic solvents used in the production method A. The amount of the organic solvent and / or water used is not particularly limited and can be used in an appropriate amount. It may also be a mixture of other components such as various coating resins.

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

A pigment can be added to the film-forming composition as needed, and the type of the pigment to be added is not limited. For example, yellow lead, molybdate orange, navy blue, cadmium pigment, titanium white Examples thereof include complex oxide pigments, inorganic pigments such as transparent iron oxide, cyclic high-grade pigments, soluble azo pigments, copper phthalocyanine pigments, dyed pigments, and organic pigments such as pigment intermediates.

When the film-forming composition contains at least one compound (J) selected from the group consisting of polyfunctional isocyanate compounds, melamine compounds and aminoplast resins, to accelerate the crosslinking reaction. It is preferable to additionally use a curing catalyst. An acidic or basic curing catalyst can be used as the curing catalyst. Specific examples of the acidic curing catalyst include organic sulfonic acids such as toluene sulfonic acid, methane sulfonic acid and dodecylbenzene sulfonic acid. Specific examples of the basic curing catalyst include amine catalysts such as triethylamine, methylimidazole, acridine, and hexadecyltrimethylammonium stearate; organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and stannas octoate. Can be mentioned. At least one kind or two or more kinds of these curing catalysts may be used, and a co-catalyst may be used in combination if necessary.

The film-forming composition is, for example, an inorganic material such as aluminum, stainless steel, galvanized iron, tin plate, steel plate, concrete, mortar, slate, or glass, or a substrate of organic material such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate, or paper. A coating can be formed on the film. Further, it can be applied by a conventional method such as dipping, spraying, brush coating, roll coating, spin coating, bar coating and the like.

The coating film obtained from the film-forming composition is optionally baked and dried. For example, room temperature to 3
The coating film is formed by heating at a temperature in the range of 00 ° C. for 0.2 minutes or more, and the coating film is a transparent and glossy excellent coating film. The film-forming composition of the present invention utilizes the above-mentioned solvent resistance, stain resistance, flexibility, weather resistance, heat resistance, good film properties such as storage stability, for automobiles, ships, vehicles, It can be applied to the surface of various base materials such as metal materials such as building materials, electrical appliances, industrial machines, beverage cans, buildings, structures, inorganic materials, organic materials such as plastics, and surface protection and cosmetics of various base materials. Etc. to form a useful film. Action In the organic polymer-composite inorganic fine particles of the present invention, the organic polymer is fixed to the inorganic fine particles, and the organic polymer is not detected in the washing liquid in which the organic polymer-composite inorganic fine particles are washed with an arbitrary solvent. Further, the organic polymer composite inorganic fine particles have a good affinity for the organic matrix because the organic polymer is fixed on the surface of the inorganic fine particles.

In the conventional surface treatment of inorganic fine particles,
Since the drying step is indispensable, aggregation and cross-linking of the inorganic fine particles occur at the time of drying, the particle size of the inorganic fine particles increases, and the particle size distribution of the inorganic fine particles also broadens. In the production method (1), the reaction can be carried out uniformly, and since the production rate of the composite inorganic fine particles does not greatly vary, the particle size distribution thereof becomes narrow.

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

Since the organic polymer composite inorganic fine particles contain a perfluoroalkyl group and / or a silicone group in the organic polymer which constitutes them, for example, when added to a general paint resin or the like, they are clustered in the vicinity of the surface of the coating film. Since they are lined up in a line, the physical properties of the coating such as weather resistance, stain resistance, abrasion resistance and surface hardness can be improved with a smaller addition amount.

In the film-forming composition of the present invention, the organic polymer composite inorganic fine particles contained in the composition have a thickness of 5 to 200 nm.
Has a very small average particle size, and the coefficient of variation of the particle size is 5
When the particle size distribution is 0% or less and the particle size distribution is narrow, a transparent and glossy coating film can be formed. Further, since the organic polymer is fixed on the surface of the inorganic fine particles, it has a good affinity for the organic matrix such as the resin for coating material contained in the film forming composition, and the organic polymer serves as a binder. Since it can act, even if it is directly applied to various base materials, the resulting coating film does not have cloudiness or cracks and has excellent weather resistance.

Since the film-forming composition essentially contains the organic polymer composite inorganic fine particles of the present invention as compared with the conventional film-forming composition, the physical properties of the film are improved as compared with the conventional products.
For example, a film-forming composition obtained by adding the organic polymer composite inorganic fine particles of the present invention to a general coating resin or the like has a surface hardness,
It gives a coating having good coating physical properties such as adhesion, weather resistance, chemical resistance, heat resistance, abrasion resistance, and stain resistance. Since the organic polymer composite inorganic fine particles added to the film-forming composition contain a perfluoroalkyl group and / or a silicone group in the organic polymer forming the composition, they are densely arranged in a line near the surface of the coating film. Therefore, the physical properties of the coating such as weather resistance, stain resistance, wear resistance and surface hardness are improved with a smaller amount added.

[0086]

EXAMPLES Specific examples of the present invention will be shown below together with comparative examples, but the present invention is not limited to the following examples. In the examples,% means% by weight and part means part by weight unless otherwise specified. Polymerizable polysiloxane and organic polymer (P) used in the following examples were prepared as in Production Examples 1 to 10 below.
Was synthesized by.

-Production Example 1- (Synthesis of Polymerizable Polysiloxane (S-1)) 144.5 parts of tetramethoxysilane and γ-methacryloxy were placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube. Propyltrimethoxysilane 23.6 parts, water 19
Parts, 30.0 parts of methanol, and 5.0 parts of Amberlyst 15 (cation exchange resin manufactured by Rohm and Haas Japan Co.) were added, and the mixture was stirred at 65 ° C. for 2 hours to react. 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
At a temperature of 90 ° C. at a pressure of mmHg, the same temperature was maintained until methanol did not flow out, and the reaction was further advanced. After cooling to room temperature again, Amberlyst 15 was separated by filtration to obtain a polymerizable polysiloxane (S-1) having a number average molecular weight of 1800.

-Production Example 2- (Synthesis of Organic Polymer (P-1)) 200 parts of toluene as an organic solvent was placed in a 1 liter flask equipped with a stirrer, a dropping port, a thermometer, a cooling pipe and an N ₂ gas inlet. , N ₂ gas was introduced, and the temperature inside the flask was adjusted to 1 with stirring.
Heated to 10 ° C. Then, 20 parts of the polymerizable polysiloxane (S-1) obtained in Production Example 1, 80 parts of cyclohexyl methacrylate, and 2-ethylhexyl acrylate 1
0 parts, styrene 54 parts, butyl acrylate 10 parts, 2
A solution obtained by mixing 20 parts of hydroxyethyl methacrylate, 6 parts of methacryloxy-terminated polydimethylsiloxane, and 6 parts of 2,2′-azobisisobutyronitrile was added dropwise from a dropping port over 2 hours. After the dropwise addition, stirring was continued for 1 hour at the same temperature, and then 1,1'-bis (t-butylperoxy)
-3,3,5-trimethylcyclohexane 0.4 parts to 3
Add twice every 0 minutes and heat for 2 hours for copolymerization to obtain an organic polymer having a number average molecular weight of 12,000 (P
A solution in which -1) was dissolved in toluene was obtained. Table 2 shows the number average molecular weight and solid content of the obtained organic polymer (P-1).
Shown in

-Production Examples 3 to 10- (Synthesis of Organic Polymers (P-2 to P-9)) In the same manner as in Production Example 2 except that the composition shown in Table 1 was changed, the organic polymer (P-2 ~ P-9) was dissolved in toluene to obtain a solution. Table 2 shows the number average molecular weight and solid content of the obtained organic polymers (P-2 to P-9).

[0090]

[Table 1] S-1: Polymerizable polysiloxane obtained in Production Example 1 AIBN: 2,2′-azobisisobutyronitrile BPTC: 1,1′-bis (t-butylperoxy) -3,3,5- Trimethylcyclohexane CHMA: Cyclohexyl methacrylate 2-EHA: 2-Ethylhexyl acrylate St: Styrene MMA: Methyl methacrylate BA: Butyl acrylate HEMA: 2-Hydroxyethyl methacrylate MAA: Methacrylic acid AEMA: Aminoethyl methacrylate GMA: Glycidyl methacrylate PDMSMA: Methacryloxy one end. Polydimethylsiloxane PFMMA: Perfluoromethylmethacrylate Incidentally, the polymerizable polysiloxane obtained in Production Examples 1 to 10 and the number average molecule of the organic polymer (P). The amount was analyzed by the following method. [Number Average Molecular Weight] The polystyrene-reduced number average molecular weight of the polymerizable polysiloxane and the organic polymer (P) was measured by gel permeation chromatography (GPC) under the following conditions.

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

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

[0093]

[Table 2] -Example A1- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-1)) In a 500 ml four-necked flask equipped with a stirrer, two dropping ports (dripping port a and dropping port b), and a thermometer,
Put 200 parts of butyl acetate and 50 parts of methanol,
The internal temperature was adjusted to 20 ° C. Then, while stirring the inside of the flask, a mixed solution (solution A) of 12 parts of a toluene solution of the organic polymer (P-1) obtained in Production Example 2, 30 parts of tetramethoxysilane, and 20 parts of butyl acetate was added from a dropping port a. A mixed solution (solution B) of 20 parts of 25% aqueous ammonia and 20 parts of methanol was dropped from the dropping port B over 1 hour. After dripping,
Stirring was continued for 2 hours at the same temperature. Then, under a pressure of 110 mmHg, the temperature inside the flask was raised to 100 ° C., and ammonia, methanol, toluene, and butyl acetate were distilled off until the solid content concentration became 30%. Dispersed in (Z-1)
I got Table 3 shows the average particle diameter and coefficient of variation of the obtained organic polymer-composite inorganic fine particles, the content of alkoxy groups in the organic polymer-composite inorganic fine particles, and the stability over time.

-Examples A2 to A5- (Organic polymer composite inorganic fine particle dispersion (Z-2 to Z-
Synthesis of 5)) In Example A1, the organic polymer (P-
The organic polymer composite inorganic fine particles were dispersed in butyl acetate in the same manner as in Example A1 except that the organic polymers (P-2 to P-5) obtained in Production Examples 3 to 6 were used instead of 1). Dispersions (Z-2 to Z-5) were obtained. Table 3 shows the average particle diameter and coefficient of variation of the obtained organic polymer-composite inorganic fine particles, the content of alkoxy groups in the organic polymer-composite inorganic fine particles, and the stability over time.

Example A6 (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-6)) 500 ml four-necked machine equipped with stirrer, two dropping ports (driving port a and dropping port b), and thermometer In a flask,
Put 200 parts of butyl acetate and 50 parts of methanol,
The internal temperature was adjusted to 20 ° C. Then, while stirring the inside of the flask, a mixed solution (solution A) of 20 parts of a toluene solution of the organic polymer (P-6) obtained in Production Example 7, 30 parts of tetramethoxysilane, and 20 parts of butyl acetate was added from a dropping port a. A mixed solution (solution B) of 20 parts of 25% aqueous ammonia and 20 parts of methanol was dropped from the dropping port B over 1 hour. After dripping,
Stirring was continued for 2 hours at the same temperature. Then, under a pressure of 110 mmHg, the temperature inside the flask was raised to 100 ° C., and ammonia, methanol, toluene, and butyl acetate were distilled off until the solid content concentration became 30%. Then, after adding 0.2 parts of epoxy-terminated polydimethylsiloxane, 1 under normal pressure
By stirring at 00 ° C. for 1 hour, a dispersion (Z-6) in which organic polymer composite inorganic fine particles were dispersed in butyl acetate was obtained. Table 3 shows the average particle diameter and coefficient of variation of the obtained organic polymer-composite inorganic fine particles, the content of alkoxy groups in the organic polymer-composite inorganic fine particles, and the stability over time.

-Example A7- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-7)) A 500 ml four-necked machine equipped with a stirrer, two dropping ports (dripping port a and dropping port b), and a thermometer. In a flask,
Put 200 parts of butyl acetate and 50 parts of methanol,
The internal temperature was adjusted to 20 ° C. Then, while stirring the inside of the flask, a mixed solution (solution A) of 20 parts of a toluene solution of the organic polymer (P-8) obtained in Production Example 9, 30 parts of tetramethoxysilane, and 20 parts of butyl acetate was added from a dropping port a. A mixed solution (solution B) of 20 parts of 25% aqueous ammonia and 20 parts of methanol was dropped from the dropping port B over 1 hour. After dripping,
Stirring was continued for 2 hours at the same temperature. Then, under a pressure of 110 mmHg, the temperature inside the flask was raised to 100 ° C., and ammonia, methanol, toluene, and butyl acetate were distilled off until the solid content concentration became 30%. Then, after adding 0.2 parts of epoxy-terminated polydimethylsiloxane, 1 under normal pressure
By stirring at 00 ° C. for 1 hour, a dispersion (Z-7) in which organic polymer composite inorganic fine particles were dispersed in butyl acetate was obtained. Table 3 shows the average particle diameter and coefficient of variation of the obtained organic polymer-composite inorganic fine particles, the content of alkoxy groups in the organic polymer-composite inorganic fine particles, and the stability over time.

Example A8- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-8)) Stirrer, Two Droplets (Droplet A and Droplet B), 500 ml Four Ports Equipped with Thermometer In a flask,
Put 200 parts of butyl acetate and 50 parts of methanol,
The internal temperature was adjusted to 20 ° C. Then, while stirring the inside of the flask, a mixed solution (solution A) of 20 parts of a toluene solution of the organic polymer (P-8) obtained in Production Example 9, 30 parts of tetramethoxysilane, and 20 parts of butyl acetate was added from a dropping port a. A mixed solution (solution B) of 20 parts of 25% aqueous ammonia and 20 parts of methanol was dropped from the dropping port B over 1 hour. After dripping,
Stirring was continued for 2 hours at the same temperature. Then, under a pressure of 110 mmHg, the temperature inside the flask was raised to 100 ° C., and ammonia, methanol, toluene, and butyl acetate were distilled off until the solid content concentration became 30%. Then, 0.2 part of vinyl-terminated polydimethylsiloxane was added, and then 10
By stirring at 0 ° C. for 1 hour, a dispersion (Z-8) in which organic polymer composite inorganic fine particles were dispersed in butyl acetate was obtained. Table 3 shows the average particle diameter and coefficient of variation of the obtained organic polymer-composite inorganic fine particles, the content of alkoxy groups in the organic polymer-composite inorganic fine particles, and the stability over time.

Example A9- (Synthesis of Organic Polymer Composite Inorganic Fine Particle Dispersion (Z-9)) A 500 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube was charged with the organic compound obtained in Production Example 10. Polymer (P
300 parts by weight of a toluene solution of -9) and 15 parts by weight of perfluorodecanoic acid were added, and the mixture was refluxed for 2 hours to obtain a toluene solution of the organic polymer (P-9 ').

Then, 200 parts of butyl acetate and 50 parts of methanol were placed in a 500 ml four-necked flask equipped with a stirrer, two dropping ports (driving port a and dropping port b), and a thermometer, and the internal temperature was adjusted. The temperature was adjusted to 20 ° C. Then, the organic polymer (P-
9 ') 20 parts toluene solution, tetramethoxysilane 3
A mixed solution of 0 parts and 20 parts of butyl acetate (solution A) was dropped from a dropping port a, and a mixed solution of 20 parts of 25% ammonia water and 20 parts of methanol (solution B) was dropped from a dropping port b over 1 hour. After dropping, stirring was continued at the same temperature for 2 hours. Then 1
Under a pressure of 10 mmHg, the temperature inside the flask was raised to 100 ° C., and ammonia, methanol, toluene and butyl acetate were distilled off until the solid content concentration became 30%. Then, 0.2 part of epoxy-terminated polydimethylsiloxane was added, and the mixture was stirred at 100 ° C. under normal pressure for 1 hour to obtain a dispersion (Z-9) in which organic polymer composite inorganic fine particles were dispersed in butyl acetate. . Table 3 shows the average particle diameter and coefficient of variation of the obtained organic polymer-composite inorganic fine particles, the content of alkoxy groups in the organic polymer-composite inorganic fine particles, and the stability over time.

-Comparative Example A1- (Comparative Organic Polymer Composite Inorganic Fine Particle Dispersion (Z'-
Synthesis of 1)) In Example A1, the organic polymer (P-
Instead of 1), the organic polymer (P-
A comparative dispersion (Z′-1) in which organic polymer composite inorganic fine particles were dispersed in butyl acetate was obtained in the same manner as in Example A1 except that 7) was used. Table 3 shows the average particle diameter and coefficient of variation of the obtained organic polymer-composite inorganic fine particles, the content of alkoxy groups in the organic polymer-composite inorganic fine particles, and the stability over time. Organic polymer composite inorganic fine particle dispersions (Z-1 to Z-9) obtained in Examples A1 to A9, and comparative organic polymer composite inorganic fine particle dispersions (Z'-1) obtained in Comparative Example A1. , And the supernatant obtained when each dispersion was centrifuged was analyzed by GPC, but no organic polymer was detected. In addition, the organic polymer-composite inorganic fine particle dispersions (Z-1 to Z-9) and (Z'-1), which are precipitates after centrifugation, are washed with THF or water, The washings were analyzed by GPC and 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 dispersions obtained in the above Examples and Comparative Example A1, the average particle diameter and coefficient of variation of the organic polymer-composite inorganic fine particle, the alkoxy group content in the organic polymer-composite inorganic fine particle, The stability over time was analyzed and evaluated by the following method. [Average Particle Size and Coefficient of Variation] The average particle size and the coefficient of variation were measured at 23 ° C. by the dynamic light scattering measurement method using the following device. The measured average particle diameter is a volume average particle diameter.

(Device) Submicron particle size analyzer (NICOMP MODEL 3 manufactured by Nozaki Sangyo Co., Ltd.)
70) (Measurement sample) Organic polymer composite inorganic fine particle concentration is 0.1
To 2.0% by weight of tetrahydrofuran dispersed in an organic polymer composite inorganic fine particle (if the organic polymer in the organic polymer composite inorganic fine particle is insoluble in tetrahydrofuran, a dispersion prepared by dispersing in an organic polymer-soluble solvent) ).

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

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

[0105]

[Table 3] -Example A10- 400 parts of butyl acetate was charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen gas introduction tube, and the temperature was raised to 110 ° C. While blowing nitrogen gas therein, 100 parts of organic polymer composite inorganic fine particle dispersion (Z-1), 10 parts of 2-isopropenyl-2-oxazoline, 90 parts of styrene, 60 parts of t-butyl methacrylate, 10 parts of 2-ethylhexyl acrylate.
Part, 60 parts of 2-hydroxyethyl methacrylate, and 4 parts of 2,2′-azobisisobutyronitrile were added dropwise from a dropping funnel over 4 hours, and a further 9 parts were added.
After holding at 5 ° C. for 3 hours, it was cooled to room temperature to obtain a resin solution (Z-10) in which organic polymer composite inorganic fine particles were dispersed in a resin. The solid content concentration and viscosity of this resin solution are shown in Table 4.

-Example A11- 400 parts of butyl acetate and an organic polymer-composite inorganic fine particle dispersion (Z
-1) 100 parts was charged and the temperature was raised to 100 ° C. While blowing nitrogen gas therein, 70 parts of cyclohexyl methacrylate, 70 parts of styrene, 20 parts of t-butyl methacrylate, 10 parts of 2-ethylhexyl acrylate,
2-hydroxyethyl methacrylate 60 parts and 2,
A mixture of 4 parts of 2'-azobisisobutyronitrile was added dropwise from a dropping funnel over 4 hours, and the mixture was further heated to 95 ° C.
After being held for 3 hours, the mixture was cooled to room temperature to obtain a resin solution (Z-11) in which the organic polymer composite inorganic fine particles were dispersed in the resin. The solid content concentration and viscosity of this resin solution are shown in Table 4.

-Examples A12 to A13- In Example A11, Table 4 shows the amount of the organic polymer composite inorganic fine particle dispersion (Z-1) used and the composition (type and amount) of the polymerizable monomer. Example A11 except that
By repeating the same operation as above, the resin solution (Z-12) in which the organic polymer composite inorganic fine particles are dispersed in the resin
(Z-13) was obtained. Table 4 shows the solid content concentration and viscosity of these resin solutions.

Comparative Example A2-In Example A11, the organic polymer-composite inorganic fine particle dispersion (Z-1) was not used at all, and the composition (type and amount of use) of the polymerizable monomer is shown in Table 4. A resin solution for comparison (Z′-2) was obtained by repeating the same operations as in Example A11 except for the above. Table 4 shows the solid content concentration and viscosity of these resin solutions.

[0109]

[Table 4] -Comparative Example B1-A resin mixture was obtained by mixing the organic polymer composite inorganic fine particle dispersion and the resin with the resin composition shown in Table 5. The resin mixture was stored in a closed container at 50 ° C. for 1 month, and its appearance and storage stability were examined. The results are shown in Table 5. Titanium oxide (Taipec CR-95, Ishihara Sangyo Co., Ltd.)
Was prepared so as to have a nonvolatile pigment concentration of 40% by weight and well dispersed by a sand mill. A polyfunctional isocyanate (Sumijour N-3200, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added to the obtained dispersion liquid (hereinafter, referred to as I-1 liquid) to obtain a hydroxyl group and a polyfunctional compound in the I-1 liquid. The equivalent ratio with the isocyanate group in the isocyanate is 1:
An amount of 1.1 was weighed to obtain a liquid II-1. This I
-1 liquid and II-1 liquid were mixed to obtain a coating composition. The obtained coating composition was coated on a polyethylene film with a film thickness of 30 μ, allowed to stand at room temperature for 1 hour, and then forcedly dried at 80 ° C. for 2 hours. FIG. 2 is a transmission electron microscope (TEM) photograph of the air interface portion of the coating film in the cross section of the coating film. FIG.
From this, it is confirmed that the fine particles of this comparative example are spread almost uniformly over the entire cross section of the coating film, and are not dense at the interface with air.

The above coating composition obtained by mixing the liquids I-1 and II-1 was coated on a 0.8 mm mild steel plate with a film thickness of 30 μ, left at room temperature for 1 hour, and then at 80 ° C. for 2 hours. Forcibly dried to prepare test pieces for various performance tests. The performance of the coating film was evaluated by the performance test method described below. The evaluation results are summarized in Table 5. -Example B1-A resin mixture was obtained by mixing the organic polymer composite inorganic fine particle dispersion and the resin with the resin composition shown in Table 5. The resin mixture was stored in a closed container at 50 ° C. for 1 month, and its appearance and storage stability were examined. The results are shown in Table 5. Titanium oxide (Taipec CR-95, Ishihara Sangyo Co., Ltd.)
Was prepared so as to have a nonvolatile pigment concentration of 40% by weight and well dispersed by a sand mill. A polyfunctional isocyanate (Sumijour N-3200, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added to the obtained dispersion liquid (hereinafter, referred to as I-1 liquid) to obtain a hydroxyl group and a polyfunctional compound in the I-1 liquid. The equivalent ratio with the isocyanate group in the isocyanate is 1:
An amount of 1.1 was weighed to obtain a liquid II-1. This I
-1 liquid and II-1 liquid were mixed to obtain a coating composition. The obtained coating composition was coated on a polyethylene film with a film thickness of 30 μ, allowed to stand at room temperature for 1 hour, and then forcedly dried at 80 ° C. for 2 hours. FIG. 1 is a transmission electron microscope (TEM) photograph of a portion of the cross section of the coating film at the air interface of the coating film. FIG.
From this, it is confirmed that the organic polymer composite inorganic fine particles are concentrated on the coating film surface. In addition, the amount of the inorganic fine particles added in this example is 1/4 of the amount in Comparative example B1.
Despite this, the amount of inorganic fine particles on the surface of the coating film was found to be almost the same when visually evaluated by comparing FIGS. 1 and 2.

The above coating composition obtained by mixing the liquids I-1 and II-1 was coated on a 0.8 mm mild steel plate with a film thickness of 30 μ, left at room temperature for 1 hour, and then at 80 ° C. for 2 hours. Forcibly dried to prepare test pieces for various performance tests. The performance of the coating film was evaluated by the performance test method described below. The evaluation results are summarized in Table 5. -Examples B2-B8 and Comparative Examples B2-B3-A resin mixture was obtained by mixing the organic polymer-composite inorganic fine particle dispersion and the resin with the resin compositions shown in Table 5. Table 5 shows the results of examining the appearance and storage stability of these resin mixtures stored in a closed container at 50 ° C. for 1 month. Titanium oxide (Taipaque CR-95, manufactured by Ishihara Sangyo Co., Ltd.) was added to the resin mixture so that the non-volatile pigment concentration was 40% by weight, and well dispersed by a sand mill. Polyfunctional isocyanate (Sumijour N-3200, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added to each of the obtained dispersion liquids (hereinafter, referred to as I-1 liquid) to obtain hydroxyl groups in the I-1 liquid. An II-1 solution was prepared by weighing an amount such that the equivalent ratio to the isocyanate group in the polyfunctional isocyanate was 1: 1.1. This I-1 solution and II-1 solution were mixed to obtain a coating composition. This coating composition was applied to a 0.8 mm mild steel plate to give a film thickness of 30.
It was coated with μ, left at room temperature for 1 hour, and then forcedly 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. The evaluation results are summarized in Table 5.

-Examples B9-B15 and Comparative Example B4-
B7- An organic polymer composite inorganic fine particle dispersion and a resin were mixed with the resin composition shown in Table 6 to obtain a resin mixture. Table 5 shows the results of examining the appearance and storage stability of these resin mixtures stored in a closed container at 50 ° C. for 1 month. Titanium oxide (Taipaque CR-95, manufactured by Ishihara Sangyo Co., Ltd.) was added to the resin mixture so as to have a nonvolatile pigment concentration of 50% by weight, and well dispersed by a sand mill. A polyfunctional isocyanate (Desmodur BL-3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added to the obtained dispersion liquid (hereinafter, referred to as I-2 liquid), with a hydroxyl group in the I-2 liquid and polyfunctional. An equivalent ratio of the isocyanate groups in the isocyanate is 1: 1.1, and dibutyltin dilaurate as a curing catalyst is added to the resin in an amount of 1000 P.
PM was weighed to give a liquid II-2. This I-2 liquid and II-2
The liquids were mixed to obtain a coating composition. This coating composition was
It was coated on a 3 mm mild steel plate with a film thickness of 15 μ, left to stand at room temperature for 1 hour, and then forcedly dried at 240 ° C. for 1 minute to prepare test pieces for various performance tests. The performance of the coating film was evaluated by the performance test method described below. The evaluation results are summarized in Table 6. Coating film performance test method : The resin mixtures obtained in the above Examples and Comparative Examples were evaluated for appearance and storage stability after storage at 50 ° C for 1 month by the following methods. Also, the drying property of the coating film, solvent resistance, pencil hardness, stain resistance, weather resistance,
Adhesion and bendability were analyzed and evaluated by the following methods.

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

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

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

⊚: No adhesion ○: Almost no adhesion Δ: Some adhesion X: Adhesion [Stain resistance B] Coating film facing south in Suita City, Osaka Prefecture 3
After 1 year of exposure at 0 °, the paint film was examined for dirt. ⊚: Color difference within 5 ○: Color difference 5 to 10 Δ: Color difference 10
[Staining resistance C] At room temperature of 20 ° C, a line was drawn on the coated surface with magic ink red (oil-based ink), and after 1 hour, wiped off with gauze soaked with n-butanol. Then
The appearance of the red mark of the magic ink after being wiped off was visually evaluated.

◯: No traces Δ: Some traces are observed ×: Complete traces are observed [Weather resistance] The state of the coating film after 3000 hours was examined with a sunshine weather meter. ◎: Excellent ○: Good △: Normal
X: Poor [Adhesion] A cross-cut test of JIS K5400 6.15 was performed.

⊚: No peeling ○: Slight peeling at the intersection of cuts Δ: Peeling area 5 to 35% ×: Peeling area 35%
[Bending Property] The coating film was examined for peeling and peeling by a bending tester specified in JIS K5400 6.16. (Mandrel diameter 2 mm) ◎: Excellent ○: Good △: Normal
×: defective

[0119]

[Table 5]

[0120]

[Table 6] Arotane 2060: Acrylic resin manufactured by Nippon Shokubai Co., Ltd., non-volatile content: 60.0%, hydroxyl value (in varnish): 48.0 UD S-2817: Acrylic resin manufactured by Nippon Shokubai Co., Ltd., non-volatile content: 60.0%, hydroxyl value (In varnish): 48.0

[0121]

The organic polymer composite inorganic fine particles of the present invention are composite fine particles in which an organic polymer is fixed on the surface of the inorganic fine particles, and the organic polymer contains a perfluoroalkyl group and / or a silicone group. It is useful as an additive for various paints, molding materials, etc., and can be used to improve the physical properties of the coating with a small amount. It has excellent dispersion stability in various organic solvents and polymers, and is particularly good in organic matrices. Can have an affinity.

Since the organic polymer composite inorganic fine particles have the organic polymer fixed on the surface of the inorganic fine particles, for example, when the organic polymer is used as a film-forming composition by adding it to a coating resin, etc. It has a good affinity for the organic matrix, the coating obtained by applying it to various substrates has a glossy and desirable appearance, and it does not cause cracks and has excellent adhesion and weather resistance. Can have sex. In particular, since the organic polymer contains a perfluoroalkyl group and / or a silicone group, for example, when it is used as a film-forming composition by adding it to a coating resin or the like, the organic polymer-composite inorganic fine particles may be present in the vicinity of the coating film surface. Since they are present in close proximity, with a smaller addition amount, weather resistance,
The physical properties of the coating such as stain resistance, abrasion resistance and surface hardness can be remarkably improved.

The method for producing organic-polymer composite inorganic fine particles of the present invention can easily and efficiently produce the organic-polymer composite inorganic fine particles having the above physical properties. Since the film-forming composition of the present invention essentially contains the organic polymer composite inorganic fine particles of the present invention as compared with the conventional composition, the physical properties of the coating film are improved as compared with the conventional product. For example, a film-forming composition obtained by adding the organic polymer composite inorganic fine particles of the present invention to a general coating resin or the like has surface hardness, adhesion, weather resistance,
It gives a coating film with good physical properties such as chemical resistance, heat resistance, abrasion resistance and stain resistance. Further, since the organic polymer constituting the organic polymer composite inorganic fine particles contains a perfluoroalkyl group and / or a silicone group, the fine particles are densely present in the vicinity of the coating film surface. Therefore, the film forming composition of the present invention Can form a coating film in which the physical properties of the coating such as weather resistance, stain resistance, abrasion resistance and surface hardness are remarkably improved, even if the amount of the organic polymer composite inorganic fine particles added is small.

When the organic polymer has a crosslinked structure in the coating film after coating the film-forming composition, the physical properties of the coating film such as solvent resistance, heat resistance and surface hardness are further improved. The organic polymer forming the organic polymer composite inorganic fine particles contained in the film-forming composition further contains a hydroxyl group, and the film-forming composition is selected from the group consisting of a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin. When at least one compound (J) is further contained, a crosslinked structure is formed, and good film properties such as solvent resistance, stain resistance, flexibility, weather resistance, heat resistance, and storage stability are provided. Like In addition, when the film-forming composition further contains the polyol (Q), a stronger crosslinked structure is obtained,
The physical properties of the coating are further improved.

[Brief description of drawings]

FIG. 1 is a transmission electron micrograph of a cross section of an air interface portion of a coating film of Example B1.

FIG. 2 is a transmission electron microscope photograph of a cross section of an air interface portion of a coating film of Comparative Example B1.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08K 9/04 KCP C08K 9/04 KCP (72) Inventor Masaya Yoshida 5-8 Nishimitabicho, Suita City, Osaka Prefecture Nippon Shokubai Co., Ltd.

Claims (6)

[Claims] 1. A composite fine particle in which an organic polymer is fixed on the surface of the inorganic fine particle, wherein the organic polymer contains a perfluoroalkyl group and / or a silicone group. 2. At least one polysiloxane group is bonded per molecule, and at least one Si—OR ¹ group (R ¹ is a hydrogen atom, an alkyl group or an acyl group) is contained in the polysiloxane group. Is at least one group which may be substituted and is selected from the group, and when plural R ^1's are present in one molecule, the plurality of R ^1's may be the same or different from each other. And an organic polymer composite including a step of hydrolyzing and condensing at least one organic polymer (P) containing a perfluoroalkyl group and / or a silicone group (P) alone or with a hydrolyzable metal compound (G). Method for producing inorganic fine particles. 3. At least one polysiloxane group is bonded per molecule, and at least one Si—OR ¹ group (R ¹ is a hydrogen atom or an alkyl group, an acyl group) is contained in the polysiloxane group. Is at least one group which may be substituted and is selected from the group, and when plural R ^1's are present in one molecule, the plurality of R ^1's may be the same or different from each other. And at least one organic polymer (P) containing a functional group capable of introducing a perfluoroalkyl group and / or a silicone group,
(P) a step of hydrolyzing / condensing alone or with a hydrolyzable metal compound (G); a compound containing a group that reacts with the functional group, and a perfluoroalkyl group and / or a silicone group; And a step of reacting with the hydrolysis / condensation product of the organic polymer (P) obtained in the above step. 4. A film-forming composition comprising the organic polymer composite inorganic fine particles according to claim 1. 5. The film formation according to claim 4, further comprising at least one compound selected from the group consisting of a polyfunctional isocyanate compound, a melamine compound and an aminoplast resin, and the organic polymer further containing a hydroxyl group. Composition. 6. The film-forming composition according to claim 4, further comprising a polyol having two or more hydroxyl groups in one molecule.