JP2003119386A - Inorganic polymer composition, method for producing the same, inorganic coating using the same and coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic polymer composition useful for forming a film having excellent weather resistance and scarcely causing cracks occurred in the case of a conventional inorganic film, a method for producing the composition, an inorganic coating agent using the same and a coated product obtained by coating an article such as a vehicle, a wall, a household appliance and a mechanical part with the coating agent. SOLUTION: This inorganic polymer composition is obtained by reacting at least one kind of compound (component a) selected from the group of an organosilane represented by general formula (1), a hydrolyzate of the organosilane and a condensate of the organosilane with a linear polysiloxane condensate represented by general formula (2) and/or a cyclic polysiloxane represented by general formula (3) (component b). The method for producing the inorganic polymer composition comprises reacting the component a with the component b in the presence of a catalyst in a solvent. The inorganic coating agent consists essentially of the inorganic polymer composition. The coated product is obtained by coating the article such as the vehicle, wall, household appliance and mechanical part with the inorganic coating agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inorganic polymer composition, a method for producing the same, an inorganic coating agent using the same,
And related to painted products. More specifically, cracks that occur in the case of conventional inorganic films are unlikely to occur, and an inorganic polymer composition useful for forming a film having excellent weather resistance, a method for producing the same, an inorganic coating agent using the same, And a coated product obtained by coating the inorganic coating agent on an article such as a vehicle, a wall, a home electric appliance, and a machine part.

[0002]

2. Description of the Related Art Conventionally, products such as metals, inorganic materials, plastics, and wood have been subjected to surface coating such as coating with an organic material paint for the purpose of protecting them, imparting design characteristics, imparting functionality, etc. An organic material coating film is often formed on the surface. However, when the organic material coating film is exposed to rainwater or ultraviolet rays for a long time, hydrolysis and oxidative deterioration gradually progress,
It is easy to cause deterioration of coating aesthetics such as reduction of coating thickness, choking, gloss reduction, peeling, etc. In addition, when coating metal products and inorganic materials, reduction of coating thickness due to choking etc. ), Water is allowed to enter, rust is generated on the metal, and cracks are caused on the inorganic material in cold regions, so that the base material protecting function is deteriorated. In addition, the decrease in the coating thickness promotes the transmission of ultraviolet rays, causing delamination of the coating film, and in the coating of plastic products, the ultraviolet rays deteriorate the primer resin that exists for the purpose of adhering to the plastic, and the coating film and the substrate Is the cause of peeling.

Further, in recent years, there is a strong need for weather resistance for coating films of parts and members used outdoors for 20 years or more. Especially, as a coating material for outer walls and roof tiles,
The development of inorganic coating agents for applying coating films of inorganic materials has become active. For example, JP-A-7-39810
Japanese Patent Publication discloses a coating agent containing a silicon compound having four alkoxy groups in one molecule and a silicon compound having three alkoxy groups as main components. (Mainly a coating film of organopolysiloxane having a three-dimensional network structure) tends to change its physical properties in the course of time of use environment, become brittle and crack. The reason for this is that the inorganic film made from these raw materials has a fairly high crosslink density and the film itself is brittle, and in addition, the unreacted residual alkoxysilyl groups react during the durability process, increasing internal stress. I think that it is for doing. In addition, when such a coating agent is applied on an inorganic material base material whose volume changes by absorbing water like cement or a base material whose volume changes by heat such as soft plastic, the volume change of the base material However, there is a problem that the elongation of the coating film cannot be followed and cracks occur. In the present specification, the case where the substance constituting the main component of the coating agent mainly contains an element other than carbon in the main skeleton, for example, silicon such as siloxane bond is referred to as an inorganic coating agent. The case of containing a carbon element is called an organic coating agent.

As a countermeasure for such a problem, further development of an inorganic / organic hybrid material type coating agent has been studied. For example, (1) a method of blending an organic substance with an inorganic coating to improve brittleness,
(2) There is a method of reacting an organic polymer having a functional group that reacts with an alkoxysilyl group or a hydroxyl group with a silicon compound having 3 to 4 alkoxy groups. However, the degree of weather resistance and the degree of brittleness are determined by the ratio of the organic material component and the inorganic material component used, and they remain in a trade-off relationship, and the conflicting properties have not yet been improved.

As another countermeasure, a brittle inorganic material film having a thickness of several μm or less is formed to make it difficult to break or to separate even if it breaks, as a paint film containing pigment or an inorganic clear film. Membranes have been developed. However, with enamel coating containing a pigment, a thickness of several μm cannot cover the underlying color, resulting in uneven mottled colors or subtle color changes depending on the product. Also, when an inorganic clear film is applied on the order of several μm instead of a pigment system, even if an ultraviolet absorber is put in the clear, the film is too thin with a thickness of several μm, so that sufficient ultraviolet light is not generated between the clear layers. There is a problem that the coating film under the clear film cannot be absorbed due to photodegradation, and peeling occurs between the clear film and the coating film underneath.

[0006]

The object of the present invention is to:
In view of the above problems, cracks that occur in the case of a conventional inorganic film is less likely to occur, and an inorganic polymer composition useful for forming a film having excellent weather resistance, a method for producing the same, an inorganic coating using the same It is intended to provide an agent and a coated article obtained by coating the agent on an article such as a vehicle, a wall, an electric home appliance, and a machine part.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have obtained the following findings. That is, the resin skeleton of the coating film formed by the inorganic coating using silicon atoms consists of a siloxane bond in which silicon and oxygen are bonded, and this siloxane bond is a structure in which molecular rotation can occur with a small amount of energy. The constituent materials are so-called flexible. But,
The reason why the inorganic film composed of siloxane bond in the prior art exhibits a brittle property is that the cross-link density of the film becomes too high and the molecular rotation of the siloxane bond is significantly restricted.
A general cross-linked coating film has a three-dimensional network structure, and since this physical property largely depends on the network density and the thermal mobility (molecular rotation of chains) of the components that make up the network, elasticity is improved. In order to obtain an existing inorganic film, it is important to lower the crosslink density and reduce the restriction of molecular rotation. That is, 3
It has been found that it is necessary to connect the dimensionally cross-linked inorganic gel units with a coil-shaped (thread-like) siloxane bond chain to form a finished film. FIG. 1 schematically shows such a form, and the gel unit 2 is firmly and elastically bonded through the coil-shaped siloxane bonding chain 1.

To obtain such an inorganic film, as a polymer raw material, an organosilane compound represented by R ¹ _n Si (OR ² ) _{4-n in} which n is 0 and / or 1 and n is 2 It was found that there are the following two types of synthetic methods using the above-mentioned ones. (I) A method for obtaining an inorganic polymer composition by mixing R ¹ _n Si (OR ² ) _4-n in which n is 0 to 1 and n is 2 and reacting with polysiloxanes . _{^{(Ii) R 1 n Si (}} OR 2) 4-n (R 1) n n a 0-1
A method for obtaining an inorganic polymer composition by reacting polysiloxanes with those obtained by the method.

However, in the method (i), the raw material unit price is high, the molecular weight of the polysiloxane is large, and the molecular weight of the homopolymer in which the polysiloxanes have reacted with each other becomes too large, resulting in compatibility with the homopolymer of the organosilane compound. It was found that the uniform reaction between the organosilane compound and the polysiloxane did not occur easily, and the polysiloxane raw material itself was unstable, and the condensation reaction occurred over time during the raw material storage.

On the other hand, in the method (ii), the raw material unit price is low and the catalyst decomposes the polysiloxane to reduce the molecular weight. Even if some condensation occurs at that time, a high molecular weight polysiloxane condensation It is difficult to form a product, and the compatibility of the organosilane compound with the homopolymer is unlikely to decrease, and a uniform reaction product is easily obtained. Further, polysiloxane having no hydroxyl group terminal is stable, and the condensation reaction does not occur with time during storage of the raw material. Although the polymer obtained from this method has an organic component directly bonded to elemental silicon, it also contains the organic component in the film obtained in the main chain of the polymer, but the organic group introduced from this material is , It was found that the membrane was not introduced into the network skeleton but was introduced into the side chain, and the cross-linking structure of the network was not broken and the membrane was not destroyed even if the organic part was oxidatively deteriorated by ultraviolet rays.

Therefore, the present inventors have made the above (ii)
The film from the inorganic polymer composition obtained by the method of
A highly elastic inorganic film is obtained by having an inorganic skeleton with high elasticity, and a coating agent containing the inorganic polymer composition as a main component provides a coating film with crack resistance and weather resistance. It was found that the above object can be ensured by combining the polymer with a dipolar protic solvent, and the present invention has been completed.

That is, the first aspect of the present invention is as follows:
It is an inorganic polymer composition obtained by reacting a component with a component b. Component a: General formula (1) R ¹ _n Si (OR ² ) _4-n (1) (In the formula, R ¹ is an organic group having 1 to 30 carbon atoms, and R ² is 1 carbon atom.
To 6 alkyl groups, C1 to C6 acyl groups or phenyl groups, and n is an integer of 0 to 1. However, R ¹ ,
R ² may be the same or different. )
One or two or more compounds b component selected from organosilane represented by: and a hydrolyzate or condensate thereof: general formula (2)

[0013]

[Chemical 4] (Wherein, R ³ to R ⁸ is an organic group having 1 to 8 carbon atoms may each be the same or different. However, R ³ ~
One of R ⁴ or one of R ^{6 to} R ⁸ may be a hydroxyl group or a hydrolyzable group. Further, m is an integer of 2 or more. ) One or more linear polysiloxane condensates represented by), and / or the general formula (3)

[0014]

[Chemical 5] (In the formula, R ^{9 to} R ¹⁰ are organic groups having 1 to 8 carbon atoms and may be the same or different. N is 2
It is an integer above the above. ) 1 type (s) or 2 or more types of cyclic polysiloxane represented by these.

In the second aspect of the present invention, the above-mentioned molar ratio of the component a and the component b is calculated and the basic structure (unit) of the component b is represented by the following general formula (4). When considered as a component, the inorganic polymer composition according to the first invention is characterized in that a component: b component = 1: 0.2 to 30.

[0016]

[Chemical 6] Furthermore, a third invention of the present invention is the inorganic polymer composition according to the first or second invention, characterized in that the a component and the b component are reacted in a solvent in the presence of a catalyst. It is a manufacturing method.

The fourth invention of the present invention is the production of the inorganic polymer composition according to the third invention, characterized in that the catalyst is any one of an acid catalyst, a basic catalyst and a metal catalyst. Is the way. As the above metal catalyst,
Metal alcoholate, a chelate compound obtained from the metal alcoholate and β-diketones and / or β-diketoesters, a hydrolyzate obtained by reacting the chelate compound with water, organotin, or organotin Chelate compounds and the like obtained from β-diketones and / or β-diketoesters are preferable.

On the other hand, a fifth invention of the present invention is an inorganic coating agent containing the inorganic polymer composition according to the first or second invention as a main component.

Further, the sixth invention of the present invention further comprises at least one compound selected from a coupling agent, an ultraviolet absorber, a light stabilizer and titanium oxide. The inorganic coating agent described in 1.

The seventh invention of the present invention is the inorganic coating agent according to claim 5 or 6, which comprises 0.5 to 10 parts of a dipolar proton solution.

Further, an eighth invention of the present invention is a coated article obtained by coating the inorganic coating agent according to the seventh invention.

A ninth aspect of the present invention is a coated article,
The coated product according to the eighth invention, which is a plastic molded product, a siding board, an outer wall, a pre-coated metal, or a home electric appliance. The coated surface of the above coated article is a PP bumper / PP primer surface, a PP bumper / PP primer / base coat surface, a PP bumper / PP modified acrylic resin base coat surface, an inorganic material / sealer / base coat surface, a plated steel plate / rust-preventive primer. /
Base coated surface, steel plate / electrodeposition coating / intermediate coating / base coated surface, hard plastic / primer / base coated surface, or plated steel sheet / rust preventive primer / base coated surface. The base coat may contain a coupling agent, or may contain a blend of a condensation product having a siloxane bond and an acrylic resin, a polyester resin, a polyether resin or a polyurethane resin.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The polymer composition according to the present invention has the above-mentioned a
It is an inorganic polymer composition obtained by reacting a component with a component b.

In the method for producing an inorganic polymer composition according to the present invention, the a component and the b component are reacted in a solvent in the presence of a catalyst.

Further, the inorganic coating agent according to the present invention is mainly composed of an inorganic polymer composition obtained by reacting the a component and the b component.

The inorganic coating agent according to the present invention contains an inorganic polymer composition containing a dipolar proton solution as a main component.

Further, the coated article according to the present invention is obtained by coating the coated surface of various articles with the inorganic coating agent according to the present invention.

The organosiloxane represented by the general formula (1), the organosiloxane hydrolyzate, and the condensate of the organosiloxane, which are the component a used in the present invention, will be described below.

The component a is an organosiloxane represented by the following general formula (1), a hydrolyzate of the organosiloxane,
It is a condensate of the organosiloxane. R ¹ _n Si (OR ² ) _4-n (1)

In the general formula (1), R ¹ has 1 to 30 carbon atoms.
It is a stable hydrophobic group that is resistant to hydrolysis and is stable. As the organic group, carbon number such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, pentyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and eicosyl group. 1-30 alkyl groups, halogenated alkyl groups such as fluorinated, chlorinated and brominated alkyl groups (for example, 3-chloropropyl group, 6-chloropropyl group, 6-chlorohexyl group, and 6,6,6) 6-trifluorohexyl group, etc.), aromatic substituted alkyl group such as halogen-substituted benzyl group (eg, benzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, etc.), aryl group (eg, phenyl group, tolyl group) , Mesityl group, naphthyl group, etc.), organic group containing vinyl group or epoxy group, organic group containing amino group, thiol And an organic group containing a group.

In the general formula (1), R ² has 1 carbon atom.
6 alkyl group, an acyl group or a phenyl group having 1 to 6 carbon atoms, OR ² is a hydrolyzable functional group,
C1-C1 such as methoxy, ethoxy, and propoxy groups
6 alkoxy groups can be mentioned. In addition, OR ² is chlorine,
It may be a halogen such as bromine, an amino group, a hydroxyl group, or a carboxyl group.

Further, in the general formula (1), n is 0 or 1.

Specific compounds of the organosilane represented by the general formula (1) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, methyl-tri-n-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyl-
Tri-n-propoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyl-tri-
n-propoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, n-
Hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltripropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, dodecyl Trimethoxysilane, dodecyltriethoxysilane, dodecyltripropoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, tetradecyltripropoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, hexadecyltripropoxysilane, Octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltripropoxysilane, Cosyldecyltrimethoxysilane, eicosyltriethoxysilane, eicosyltripropoxysilane, 6-chlorohexyltrimethoxysilane, 6,6,6-trifluorohexyltrimethoxysilane; benzyltrimethoxysilane, 4-chlorobenzyltri Methoxysilane, 4-bromobenzyltri-n
-Propoxysilane; dodecyltrichlorosilane, dodecyltribromosilane, phenyltrimethoxysilane,
Phenyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxysilane), β- (3,4epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-
Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-phenyl-γ-aminopropyltrimethoxysilane , Γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like. These organosilane compounds are
They may be used alone or in combination of two or more.

The hydrolyzate of the organosilane represented by the general formula (1) is a hydrolyzate of the above various organosilanes. Further, the organosilane condensate represented by the general formula (1) is preferably a condensate of n = 0 tetraalkoxysilane or a condensate of n = 1 alkyltrialkoxysilane, or a mixture thereof. The average degree of condensation of the condensate is preferably 10 or less, more preferably 6 or less. If the average degree of condensation exceeds 10, gelation tends to occur during synthesis. These hydrolyzates or condensates of organosilane compounds may be used alone or in combination of two or more.

The component b used in the present invention is a linear polysiloxane condensate or a cyclic polysiloxane. This will be described below. The component b linear polysiloxane condensate used in the present invention is represented by the following general formula (2).

[0037]

[Chemical 7]

In the general formula (2), R ^{3 to} R ⁸ have 1 to 8 carbon atoms.
Are organic groups, and may be the same or different. As the organic group, an alkyl group having 1 to 8 carbon atoms,
Examples thereof include a phenyl group, a substituted alkyl group and a substituted phenyl group. Further, one of R ^{3 to} R ⁴ or one of R ^{6 to} R ⁸ may be a hydroxyl group or a hydrolyzable group.

In the general formula (2), m is an integer of 1 or more.

Examples of the linear polysiloxane condensate represented by the general formula (2) include commercially available silicone oils (silicone oils), such as dimethyldimethoxysilane, dimethyldiethoxysilane, dibutyldimethoxysilane and diisobutyl. Dimethoxysilane, dimethyldiethoxysilane, dibutyldiethoxysilane, diisobutyldiethoxysilane, dimethyldipropoxysilane, dibutyldipropoxysilane, diisobutyldipropoxysilane and other diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane , Methylphenyldimethoxysilane, ethylphenyldimethoxysilane, propylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyldiethoxysilane, Ropylphenyldiethoxysilane, methylphenyldipropoxysilane, ethylphenyldipropoxysilane, propylphenyldipropoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ -Methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane and the like are obtained by polymerization.

The linear polysiloxane condensate used in the present invention is a silicone oil obtained by modifying the above polysiloxane, such as (R ¹¹ ) _{3 on the} above polysiloxane.
SiOR ¹² (in the formula, R ¹¹ is an organic group having 1 to 30 carbon atoms, R ¹² is an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or a phenyl group) is reacted. The organic group-terminated silicone oil obtained in this way may be used.

As the organic group-terminated silicone oil,
Octamethylpolysiloxane (KF96A-1cs: manufactured by Shin-Etsu Chemical Co., Ltd.), decamethyltetrasiloxane (KF9
6A-1.5cs: manufactured by Shin-Etsu Chemical Co., Ltd.) or KF96
A (2-5000) cs: Shin-Etsu Chemical Co., Ltd. methyl polysiloxane KF96H (6000-1 million) cs: Shin-Etsu Chemical Co., Ltd. high polymerization degree methyl polysiloxane, KF5
0KF53KF54, KF56: Methylphenyl silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. and the like.

Further, a modified silicone oil obtained by partially modifying a pure silicone oil may be used, for example, amino-modified silicone oil: KF-8010, X-22-1.
61A, X22-161B, X-22-1660B-
3, KF-8008, KF-8012, KF-393,
KF-859, KF-860, KF-861, KF-8
67, KF-869, KF-880, KF-8002,
KF-8004, KF-8005, KF-858, KF
-864, KF-865, KF-868, KF-800
3 (all manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified silicone oil: KF105, X22-163A, X2
2-163B, X-22-153C (all manufactured by Shin-Etsu Chemical Co., Ltd.), KF-1001, KF-101, X-2
2-2000, X-22-169AS, X-22-16
9B, KF-102, etc., carboxyl-modified silicone oil: X-22-162C, X-22-3701E, X
-22-3710 (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc.
Carbinol-modified silicone oil: X-22-160
AS, KF-6001, KF-6002, KF-600
3, X-22-4015 (all manufactured by Shin-Etsu Chemical Co., Ltd.), methacryl-modified silicone oil: X-22-
164A, X-22-164B, X-22-164C,
X-22-2404 (all manufactured by Shin-Etsu Chemical Co., Ltd.)
Etc., mercapto-modified silicone oil: X-22-16
7B, KF-2001, KF-2004 (all manufactured by Shin-Etsu Chemical Co., Ltd.), phenol-modified silicone oil: X-22-1821 (Shin-Etsu Chemical Co., Ltd.), one-end hydroxyl group-modified silicone oil: X-22-170DX ,
X-22-176DX, X-22-176F (all manufactured by Shin-Etsu Chemical Co., Ltd.), one-terminal epoxy group-modified silicone oil: X-22-173DX (manufactured by Shin-Etsu Chemical Co., Ltd.), one-terminal vinyl group-modified silicone, etc. Oil: X-2
2-174DX, X-24-8201, X-22-24
26 (all manufactured by Shin-Etsu Chemical Co., Ltd.), amino group, alkoxy group-terminated silicone oil: KF-857, KF-
862, KF-8001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy group, polyether group-terminated silicone oil: X-22-3667, X-22-4741 (all manufactured by Shin-Etsu Chemical Co., Ltd.), amino group, etc. , Polyether group-terminated silicone oil: X-22-3908A, X
-22-3939A (all manufactured by Shin-Etsu Chemical Co., Ltd.)
Etc., polyether modified silicone oil: KF-35
1, KF-352, KF-353, KF-354L, K
F-355A, KF-615A, KF-945, KF-
618, KF-6011, KF-6015, KF-60
04, X-22-4252, X-22-4272, X-
22-6266 (all manufactured by Shin-Etsu Chemical Co., Ltd.), methyl styryl-modified silicone oil: KF-410 (Shin-Etsu Chemical Co., Ltd.), alkyl-modified silicone oil: K, etc.
F-412, KF-413, KF-414 (all manufactured by Shin-Etsu Chemical Co., Ltd.), higher fatty acid ester-modified silicone oil: KF-910, X-22-715 (more,
Hydrophilic special modified silicone oil: X-22-904, KF-905, KF-70
0 (all manufactured by Shin-Etsu Chemical Co., Ltd.), higher fatty acid-containing silicone oil: KF-3935 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The cyclic polysiloxane of the component b used in the present invention is represented by the following general formula (3).

[0045]

[Chemical 8]

In the general formula (3), R ^{9 to} R ¹⁰ have 1 carbon atom.
To 8 organic groups, which may be the same or different. Examples of the organic group include an alkyl group having 1 to 8 carbon atoms, a phenyl group, a substituted alkyl group, a substituted phenyl group and the like.

In the general formula (3), n is an integer of 2 or more.

Examples of the cyclic polysiloxane represented by the general formula (3) include octaalkylcyclotetrasiloxane, decaalkylcyclopentasiloxane, octaphenylcyclosiloxane, decaphenylcyclopentasiloxane, tetraalkylcyclodisiloxane and tetra. Examples thereof include phenylcyclodisiloxane, heptaalkylcyclotrisiloxane, and heptaphenylcyclotrisiloxane.

As the component b, a linear polysiloxane condensate represented by the general formula (2) and a cyclic polysiloxane represented by the general formula (3) may be mixed and used.

The weight average molecular weight of the component b polysiloxane is preferably 500 to 500,000, more preferably 1,000 to 200,000. Weight average molecular weight is 50
If it is less than 0, the effect of lowering the crosslink density is weak, and the film is easily cracked. On the other hand, if it exceeds 500000, the compatibility in the reaction system becomes low, and there is a problem that the a component and the b component do not react well.

Next, the production of the inorganic polymer composition according to the present invention will be described. The inorganic polymer composition according to the present invention can be produced by using a hydrophilic solvent, water,
Add a catalyst at 40-100 ° C, preferably 60-80
React at ℃. The reaction time is 0.2 to 50 hours, preferably 0.5 to 8 hours.

The molar ratio of water to the organosilane represented by the general formula (1) is preferably 1: 0.1-4, more preferably 0.5-3.5. Water molar ratio is 0.1
If it is less than the above range, the reaction of the polymer does not proceed sufficiently and the intended product cannot be obtained. On the other hand, if it exceeds 4, the reaction proceeds too much and gelation occurs during the synthesis.

When the basic structure (unit) of the polysiloxane of the component b is considered to be represented by the following general formula (4), the ratio of the component a to the component b is calculated as follows:

[0054]

[Chemical 9]

The molar ratio is as follows: a component: b component = 1: 0.2
30 is preferred. When the substrate to be coated has a large dimensional change and is soft, the range of a component: b component = 1: 2 to 30 is preferable. Further, when the dimensional change of the substrate to be coated is small and the hardness is high, the range of a component: b component = 1: 0.2 to 2 is preferable.

The dipolar protic solvent used here is N
-Methyl-2-pyrrolidone, 1-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, dioxane, dimethylformamide, dimethylacetamide, 2-ethyl-
4-methylimidazole and the like.

Examples of the hydrophilic solvent include methanol, ethanol, propanol, isopropanol, n.
Alcohols such as butanol and isobutanol; ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether,
Examples thereof include ethylene glycol derivatives such as ethylene glycol tertiary butyl ether and ethylene glycol monoethyl ether acetate; propylene glycol derivatives such as propylene glycol monomethyl ether and propylene glycol monomethyl ether propionate; and other diethylene glycol derivatives and diacetone alcohol. These can use 1 type (s) or 2 or more types. The hydrophilic solvent may be mixed with a water-insoluble or insoluble solvent such as ethyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene and xylene.

The catalyst is not particularly limited, and any of an acid catalyst, a basic catalyst and a metal catalyst can be used.

Of these catalysts, examples of acid catalysts include hydrochloric acid and carboxylic acids (eg, acetic acid, chloroacetic acid,
Citric acid, formic acid, propionic acid, oxalic acid, maleic acid, etc.), paratoluenesulfonic acid, ammonium salts thereof, phosphonium salts, phosphoric acid esters (eg, monooctyl phosphate, monopropyl phosphate, monolauryl phosphate, etc.), phosphoric acid monoester , Phosphate diesters (eg, dioctyl phosphate, dipropyl phosphate, dilauryl phosphate, etc.),
Examples thereof include phosphorous acid esters, phosphoric acid esters of unsaturated group-containing alcohols, chelate compounds of these acids, and the like.

Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, metaphenylenediamine, ethanolamine, triethylamine, γ-aminopropyl. Triethoxyamine, γ- (2
-Aminoethyl) -aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyldimethoxysilane, γ-anilinopropylmethyltrimethoxysilane Amino compounds and the like.

As the metal catalyst, (i) a metal alcoholate, (ii) a chelate compound in which a metal alcoholate and a chelate-forming compound form a coordinate bond, and (iii) a chelate compound obtained by reacting the chelate compound with water are obtained. Partial hydrolysates, (iv) organotin compounds, and (v) chelate compounds in which an organotin compound and a chelate-forming compound form a coordinate bond.

As the above-mentioned (i) metal alcoholate,
General formula Ti (OR ") ₄ , Al (OR") ₃ [wherein R "
Is an alkyl group having 2 to 5 carbon atoms (for example, ethyl group, normal propyl group, isopropyl group, normal butyl group, secondary butyl group, tertiary butyl group, normal pentyl group). ] A compound represented by, for example, tetraisopropoxy titanium, tetranormal butoxy titanium, tetrakis (2-ethylhexyloxy) titanium tetrastearyloxy titanium, triethoxyaluminum, triisopropoxyaluminum mono-secondary butoxydipropoxyaluminum,
Tri-secondary butoxy aluminum and the like can be mentioned.

As the chelate compound (ii) in which the metal alcoholate and the chelate-forming compound form a coordinate bond, the above-mentioned various metal alcoholates and, for example, the general formula R ¹ COCH ² COR ² [wherein R ¹ is carbon An alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a secondary butyl group, a tertiary butyl group); and R 2 is an alkyl group having 1 to 5 carbon atoms (for example, , Methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, secondary butyl group, tertiary butyl group),
An alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, normal propoxy group, isopropoxy group,
One or more β-diketones and / or β-ketoesters (hereinafter, simply referred to as “β-diketones and / or β-diketoesters”) represented by normal butoxy group, secondary butoxy group, tertiary butoxy group) The above-mentioned metal alcoholate and β-diketones and / or β-ketoesters obtained by reacting with the above-mentioned) form a coordination bond.
The chelate compound is preferable from the viewpoint of storage stability of the polymer obtained by the reaction. Examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, normal butyl acetoacetate, secondary butyl acetoacetate, tert-butyl acetoacetate, and 2,4 hexanedione. , 4 heptanedione, 3,5 heptanedione 2,4 octanedione, 2,4 nonanedione, 5-methylhexanedione and the like can be mentioned, with ethyl acetoacetate and acetylacetone being particularly preferable. The β-diketones and / or β-diketoesters are preferably used in a proportion of 0.8 to 2.5 mol, particularly preferably 1 to 1.5 mol, relative to 1 mol of the metal alcoholate. .

The partial hydrolyzate (iii) obtained by reacting a chelate compound in which a metal alcoholate and a chelate-forming compound form a coordination bond with water is a metal hydrolyzate and a β-diketone. And / or β-ketoesters are partial hydrolysates obtained by reacting a chelate compound having a coordinate bond with water with water. This water is used in a ratio of preferably 0.8 to 3 mol, more preferably 1 to 2 mol, based on 1 mol of the chelate compound. The chelate compound is preferable from the viewpoint of storage stability of the polymer obtained by the reaction. The ratio of the chelating chelate compound (ii) in which the metal alcoholate and β-diketones and / or β-ketoesters form a coordinate bond to the component b is preferably 1 mol of silicon atom in the component b. 0.001-1 mol,
More preferably, it is 0.01 to 0.5 mol. If this ratio is less than 0.001 mol, the storage stability of the obtained polymer will be reduced, and if it exceeds 1 mol, the formation of the polymer will be insufficient.

As the above-mentioned (iv) organotin compound,
For example, (C_FourH₉)₂Sn (OCOC₁₁H_{twenty three}), (C_FourH
₉) Sn (OCOCH = CHCOOCH₃)₂, (C
_FourH₉)₂Sn (OCOCH = CHCOOC_FourH₉)₂, (C
₈H₁₇)₂Sn (OCOC₁₁H_{twenty three})₂, (C₈H₁₇)₂Sn
(OCOCH = CHCOOC₈H₁₇)₂, Sn (OCOC
₈H₁₂)₂, (C_FourH₉)₂Sn (SCH₂COOC
₈H₁₇)₂, (C₈H₁₇)₂Sn (SCH₂COO), (C₈
H₁₇)₂Sn (SCH₂COOCH₂OCOCH₂S),
(C ₈H₁₇)₂Sn (SCH₂COOCH₂CH₂CH₂CH
₂OCOCH₂S), (C₈H_{1 7})₂Sn (SCH₂COO
C₈H₁₇)₂, (C₈H₁₇)₂Sn (SCH₂COOC1₂H
_{twenty five})₂,

[0066]

[Chemical 10] Etc.

The above-mentioned (v) chelate compound in which organotin and a chelate-forming compound form a coordinate bond include
A chelating chelate compound in which the organotin compound and the β-diketones and / or β-ketoesters form a coordinate bond is mentioned. The β-diketones and / or β-ketoesters are preferably used in a proportion of 0.8 to 2.5 mol, particularly preferably 1 to 1.5 mol, per mol of the organic tin.

The inorganic coating agent according to the present invention will be described.

The weight average molecular weight of the inorganic polymer contained in the inorganic polymer composition as the main component is 1000 to 100.
0000 is preferable, and more preferably 1500 to 50
It is 0000. The weight average molecular weight of the inorganic polymer is 10
If it is less than 00, the curing shrinkage during film formation by the coating becomes large and cracks occur. On the other hand, when it exceeds 500000, the coating workability is deteriorated and the appearance is deteriorated.

Further, in order to reduce the shrinkability of the inorganic coating agent during curing and impart hardness to the coating film, a part of the component a may be replaced with colloidal silica during the production of the above inorganic polymer. The ratio is preferably colloidal silica / a component = 0.001 to 1.5, more preferably 0.01 to 1. If this value is less than 0.001, the effect of preventing cracks and imparting hardness is low, and if it exceeds 1.5, the physical properties become brittle.

Further, the inorganic coating agent may be mixed with an ultraviolet absorber and a light stabilizer. When these are contained, it can be used as a clear coating having weather resistance. A pigment or a light stabilizer may be mixed. When these are contained, they can be used as an enamel paint. A glittering agent, an anti-sagging agent or an anti-settling agent, a leveling agent, and an antifoaming agent may be contained.

Further, in the inorganic polymer composition as the main component, if a large amount of the silicone oil component used in the reaction between the component a and the component b is present, the adhesiveness to the organic film is lowered, which is not preferable. . A coupling agent may be contained in order to improve the adhesion. Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and the like.

As the silane coupling agent, known and general coupling agents can be used. For example, vinyltrichlorosilane vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, β- (3,4epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycine Sidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxy Propyltriethoxysilane N-
β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-
Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Phenyl-γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ
-Mercaptopropyltrimethoxysilane and the like.

As the titanium coupling agent, known general coupling agents can be used. For example, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate tetraisopropyl bis (dioctyl phosphate) titanate,
Tetraoctyl bis (ditridecyl phosphite) titanate Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate isopropyl Tri (N-aminoethyl-
Aminoethyl) titanate and the like.

The above coupling agent may be added to the lower layer coating agent of the inorganic coating agent of the present invention, or may be contained in both the inorganic coating agent of the present invention and the lower layer coating agent. . The amount contained is 0.01 to 50% by weight based on the resin solid content.
Is preferable, and more preferably 0.1 to 20% by weight. If the content is less than 0.01% by weight, there is no effect of improving the adhesiveness, and if it exceeds 50% by weight, the physical properties of the inorganic coating agent become brittle and the desired performance cannot be obtained.

In order to improve the adhesion of the inorganic coating agent according to the present invention to the lower layer, a coating agent containing an organic-inorganic hybrid polymer as a main component can be used in the lower layer. Such organic-inorganic hybrid polymers include cold blends or hot blends of organic polymers such as acrylic resins, polyester resins, polyether resins, polyurethane resins and inorganic polymers of silicon condensates.

Further, in order to secure the adhesiveness with the lower layer of the inorganic coating agent, an organic group may be introduced into the side chain of the inorganic polymer contained in the inorganic polymer composition as the main component. That is, a compound having a hydroxyl group and the general formula (1)
A method of reacting an organosilane represented by and introducing an organic group into the side chain of the inorganic polymer can be used. The compound having a hydroxyl group may be a compound having one hydroxyl group in one molecule or a compound having one secondary hydroxyl group in one molecule and a secondary hydroxyl group.

Examples of the UV absorbers include benzotriazole UV absorbers such as TINUVIN 900, TINUVIN 384, and TINUVIN P (all manufactured by Ciba Geigy), and anilide anilide UV absorbers such as Sandbar 3206 (manufactured by Sand). It can be preferably used. As the light stabilizer, for example, hindered amine light stabilizers such as Tinuvin 292 (manufactured by Ciba Geigy) and Sandbar 3058 (manufactured by Sand) can be preferably used.

Examples of the pigments and brighteners include titanium oxide, carbon black, red iron oxide, lead chromate, lead oxide chromium molybdate, cobalt aluminate, azo pigments, phthalocyanine pigments, anthraquinone pigments, and precipitated barium calcium carbonate sulfate. , Talc, kaolin, silica, mica and aluminum can be preferably used.

Further, the inorganic coating agent of the present invention comprises
An anti-sagging agent or an anti-settling agent, a leveling agent, a dispersant, an antifoaming agent and the like can be mixed and used. As the anti-sagging agent or the anti-settling agent, for example, bentonite, castor oil wax, amide wax, microgel and the like can be preferably used. Examples of the leveling agent include KF
69, KP321, KP301 (all manufactured by Shin-Etsu Chemical Co., Ltd.)
Such silicone type, Modaflow (manufactured by Mitsubishi Monsanto), BYK358, BYK301 (manufactured by Big Chemie Japan) and the like can be preferably used. Examples of the dispersant include Anti-Terra P and Disperbyk.
-101 (all manufactured by Big Chemie Japan) and the like can be preferably used. Examples of the defoaming agent include BYK
-O (manufactured by Big Chemie Japan) and the like can be preferably used.

The inorganic coating agent of the present invention can be used, for example, for coating automobiles, walls, machine parts, home electric appliances and the like.

As a coating on a plastic material of an automobile, a primer such as a PP primer is coated on a plastic bumper base material in a plastic coating process for bumper or the like, and after wet-on-on-wet or after drying. It is preferable that the enamel-based main paint is applied and dried. Further, in the case of a clear type, it is preferable to apply wet-on-on-wet after coating with a primer and apply organic enamel coating after drying, and then apply and dry the main coating after wet-on-on-wet or after drying. Alternatively, it is preferable that a colored coating material containing a resin that adheres well to the base material is directly applied to the plastic, and the present coating material is applied after wet-on-on-wet or after drying.

When coating a steel plate such as an automobile outer panel, the plated steel plate is treated with a chemical conversion treatment agent such as zinc phosphate, and then publicly known electrodeposition coating / drying mainly using an epoxy material is performed to obtain a polyester resin. After applying / drying the main paint of the main body, apply this enamel paint and dry it.
It is preferable that the clear coating is applied and dried after wet-on-wet or after the acrylic resin-based base coat (enamel) is applied. It can also be used favorably for general precoat painting on home appliances.

The coating on the plated steel plate or the like is carried out by applying a rust-preventive primer mainly composed of an epoxy resin or a polyester resin after the chemical conversion treatment and then performing a wet-on-wet or a drying process followed by drying the enamel coating. The base coat (enamel) of the main body is applied and dried, then the clear coating is applied and dried to obtain a coated steel plate.
This is processed later.

For the coating of ceramic outer walls, etc., the inorganic base material is subjected to sealer coating / drying, and the main enamel coating is dried, or after the sealer coating, base coat (enamel) coating is carried out, and then wet-on-wet and dry Clear coating can be performed.

When used as an adhesive and jointing agent for outer walls of tiles, the inorganic coating agent of the present invention is applied directly onto a metal plate or a ceramic plate, or on a metal plate or a ceramic plate. After applying and drying an organic sealer, the inorganic coating agent of the present invention is applied and tiles are applied and dried.

The paints other than the main paint in the above-mentioned paint system may be water-based paints, solvent-based paints, powder paints, and UV-curable paints. The film thickness of the inorganic coating agent of the present invention is 0.1 to
5000 μm, preferably 1-100 for coating
μm. Also, for tile adhesion, preferably 50 to
It is 1000 μm.

[0088]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In Examples and Comparative Examples, unless otherwise specified,
All "parts" and "%" are based on weight.

Examples 1 to 33 (1) Production of Inorganic Polymer Composition Methyltrimethoxysilane: 136.2 was charged in a four-necked flask equipped with a reflux condenser, a stirrer, a thermometer and a dropping funnel.
5 parts, water: 27.03 parts, hydrochloric acid: 10 parts, ethoxyethyl acetate: 60 parts, xylene: 60 parts were added ((i) component), the temperature was raised to 80 ° C., and the mixture was stirred. After that, KF96-
A mixed solution ((ii) component) of 20cs: 222.51 parts and isopropanol: 30 parts was added dropwise over 1 hour, and 4
Refluxing was continued for an hour to obtain an inorganic polymer composition (P-1). Further, the inorganic polymer compositions (P-2) to (P-1) were used in the same manner as above except that the organosilane, polysiloxane, solvent, catalyst and the like shown in Tables 1 and 2 were used.
1), (P-13) to (P-21), (P-23) to
(P-24) was obtained.

Further, ethylene glycol was added to a four-necked flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel.
7.2 parts and 4-methylhexahydrophthalic anhydride: 16.
Charge 8 parts, react at 100 ° C. for 1 hour, then 16
The temperature was raised to 0 ° C., and AOEX-24: 19.8 parts (prepared component (iii)) was reacted for 2 hours. Thereafter, the temperature was lowered to 80 ° C., and methyltrimethoxysilane: 136.2
5 parts, water: 27.03 parts, hydrochloric acid: 10 parts, ethoxyethyl acetate: 60 parts, xylene: 60 parts ((i) component) were added and reacted at 80 ° C. for 0.5 hours. After that, KF96
-20 cs: 222.51 parts and isopropanol: 30
Part of the mixed solution ((ii) component) was added dropwise over 1 hour,
Refluxing was continued for 4 hours to obtain a polymer composition (P-12). Further, a polymer composition (P-22) was obtained in the same manner as above except that the chemicals and the like were changed as shown in Table 2.

[0091]

[Table 1]

[0092]

[Table 2]

The explanatory symbols of the samples used in Tables 1 and 2 are as follows. * 1 MS-51: Condensation product of tetraethoxysilane (average tetramer) made by Tama Chemical Co., Ltd. * 2 Aluminum catalyst: ethyl acetate aluminum isopropylate * 3 Tin catalyst: dibutyltin dilaurate * 4 KF96-20cs: polydimethylsiloxane
Molecular weight 3000 Shin-Etsu Chemical Co., Ltd. * 5 KF6001: Carbinol modified polydimethylsiloxane Shin-Etsu Chemical * 6 KF905: Hydrophilic special modified polydimethylsiloxane Shin-Etsu Chemical * 7 X-21-5841: Silanol-terminated polydimethylsiloxane Shin-Etsu Chemical Industrial * 8 KF50-100cs: Polymethylphenylsiloxane Shin-Etsu Chemical Co., Ltd. * 9 KF96-2cs: Polydimethylsiloxane molecular weight about 500 Shin-Etsu Chemical Co., Ltd. * 10 KF96-5000cs: Polydimethylsiloxane molecular weight about 2000 Shin-Etsu Chemical Co., Ltd. * 11 AOEX-24: Monoepoxy compound manufactured by Daicel Chemical Industries * 12 KF994: Octamethylcyclotetrasiloxane manufactured by Shin-Etsu Chemical Co., Ltd. * 13 KF995: Decamethylcyclipentasiloxane manufactured by Shin-Etsu Chemical Co., Ltd. * 4 NKC-ST: organo-silica sol: Nissan Chemical Industries, Ltd.

(2) Preparation of Inorganic Coating Agent Inorganic polymer composition (P-1): 100 parts, tin catalyst:
0.48 parts, tinuvin 384: 1.4 parts, tinuvin 29
2: 0.7 parts and BYK080: 0.1 parts were weighed and stirred to obtain an inorganic coating agent (A1), which was adjusted to 17 seconds for Ford cup with ethoxyethyl diacetate and used for the next coating. Similarly, as shown in Tables 3 and 4, inorganic coating agents (A2) to (A28) were obtained and used for coating evaluation. In addition, the inorganic polymer composition (P-24) at 60 ℃
The solvent was removed under reduced pressure with to obtain a solid content of 94%, and the additives shown in Table 4 were added to obtain an inorganic coating agent (A29). This was used as it was as a coating liquid.

[0095]

[Table 3]

[0096]

[Table 4]

The additives used in Tables 3 and 4 are as follows. * 15 TINUVIN 384: Benzotriazole UV absorber manufactured by Ciba Geigy * 16 TINUVIN 292: Hindered amine manufactured by Ciba Geigy * 17 KBM403: Silane coupling agent manufactured by Shin-Etsu Chemical * 18 KBM603: Silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. * 19 KBM303: Silane Coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. * 20 BYK080: surface modifier manufactured by BYK Japan Japan Solvent A: N-methyl-2-pyrrolidone solvent B: dimethylacetamide

(3) Coating Inorganic coating agent solution (A1)
Test plate (painting specifications 1 to 3) for which (A28) is described below
Coating with air spray to a film thickness of 25 μm
It was dried at 50 ° C. for 30 minutes. The appearance, weather resistance, warm water resistance, adhesion, gasoline resistance, impact resistance, and storage stability of the obtained test plate were measured. The results are shown in Table 5. In addition, in Example 33, the test plate (tile specification 4) described below was evaluated by applying 600 μm of the solution of A29 and drying at 90 ° C. for 60 minutes.

Adjustment coating specification 1 of test plate (for steel plate and hard plastic): 50 μm of Rethane intermediate coating E (manufactured by Kansai Paint) on an electrodeposition plate of zinc phosphate treated steel plate
It was applied and baked at 140 ° C. for 30 minutes. Then the letter 60
After applying 00 (manufactured by Kansai Paint Co., Ltd.) to 30 μm, 140 ° C 30
A baking test plate 1 was obtained. Coating specification 2 (soft plastic): polypropylene is wiped with toluene, and then PRIMAC No.
Apply 1500 primer (made by NOF CORPORATION), 120 ℃
And dried for 10 minutes. After that, the primac No. 3000
A top coat (manufactured by NOF CORPORATION) was applied and dried at 120 ° C for 30 minutes to obtain a test plate. Coating specification 3 (for outer wall): Apply 10 μm of AQUA SK sealer (made by Kanae paint) on wood chip cement board, and
After drying at 0 ° C. for 10 minutes, V-Celan # 600 top coat (manufactured by Dainippon Paint Co., Ltd.) was applied and dried at 100 ° C. for 10 minutes to obtain a test plate. Tile specification 4 (for attaching tiles): A piece of wood cement board was wiped with a cloth to remove dust and effluent on the surface to obtain a test board.

Comparative Example 1 Tetraethoxysilane: 208 parts, water: 27 parts, hydrochloric acid: 10 parts, in a four-necked flask equipped with a thermometer and a reflux device.
Isopropanol: 60 parts was charged, and stirring was continued at 70 ° C. for 30 minutes to obtain an inorganic polymer composition (b-1). Then, (b-1): 100 parts, tin catalyst: 0.7 part, tinuvin 384: 1.8 parts, and tinuvin 292: 0.9 parts were mixed and stirred to obtain an inorganic coating agent (C1). Ford cup no. 4 was adjusted to 17 seconds and used in the next coating test. A test plate was coated with the obtained inorganic coating agent in the same manner as in the example. The results are shown in Table 5.

Comparative Example 2 In a four-necked flask equipped with a thermometer and a reflux device, 100 parts of xylene was charged, the temperature was raised to 140 ° C., and the mixture was stirred. Butyl methacrylate: 40 parts, methyl methacrylate: 10 parts, butyl acrylate: 5 parts, γ-methacryloxypropyltrimethoxysilane: 5 parts, perbutyl O: 0.5 part A monomer mixture is charged into the dropping funnel and added dropwise over 2 hours. Then, after the dropping was completed, the reaction was continued for another 2 hours. Then, the temperature was lowered to 80 ° C., and methyltrimethoxysilane: 60 parts, isopropanol: 10 parts,
Water: 5 parts and acetic acid: 2 parts were charged and the reaction was continued for 1 hour to obtain an organic-inorganic hybrid polymer (b-2). And (b-2): 100 parts, tin: 0.7 parts, tinuvin 3
84: 1.8 parts and tinuvin 292: 0.9 parts were mixed and stirred to obtain an inorganic coating agent (C2). It was diluted to 4 for 17 seconds to prepare the next coating solution. A test plate was coated with the obtained inorganic coating agent in the same manner as in the example. The results are shown in Table 5.

Comparative Examples 3 to 5 In comparison with Examples A18 to A20 shown in Table 4, the inorganic coating agents (C2) to (C5) obtained by the compounding composition excluding the solvent A from each were used and compared with the Examples. The test plate was coated in the same manner. The results are shown in Table 5.

[Table 5]

The test methods in Table 5 are as follows. (1) Weather resistance: Sunshine weather meter JIS
8000 using K 5400 (1990) 9.8.1
After exposure for 60 hours, the coating film has a 60 ° specular gloss value of JISK 54
00 (1990) 7.6 Specular glossiness was measured, and abnormality of the coating film was visually judged or compared with glossiness before unexposed.
After the test, those having a gloss retention of 85% or more were evaluated as ◯, those having a gloss retention of 60% or more as Δ, and those less than that were evaluated as x. (2) Impact resistance: JIS K 5400 (1990)
8.3.2 Using DuPont's method, the test piece was sandwiched between shot dies having a radius of 6.35 mm, and a 500 g weight was dropped from a height of 40 cm to visually determine the damage to the coating film. After the test, those having no abnormality in the coating film were evaluated as ◯, and those having cracks were evaluated as x. (3) Adhesion: JIS K 5400 (1979) 6.
In accordance with No. 15, a cellophane tape test was performed.
After the test, those that were not peeled at all were evaluated as ◯, and those that peeled less than 5% were evaluated as Δ, and those above were evaluated as x. (4) Gasoline resistance: A part of the coating molded product was immersed in regular gasoline (Nippon Petroleum Silver Gasoline manufactured by Nippon Oil Co., Ltd.) at 20 ° C., taken out and visually evaluated for swelling property. A sample that was significantly swollen was rated as X, a sample that was slightly swollen was rated as Δ, and a sample that was barely swollen was rated as O. (5) Warm water resistance: A part of the coated molded product was immersed in warm water of 50 ° C. for 10 days and taken out, and then the adhesiveness and the presence or absence of blisters were evaluated. The case where peeling or blistering occurred was evaluated as x, the case where there is little blistering is evaluated as Δ, and the case where neither blistering nor peeling occurs is evaluated as o. (6) Storage stability: A gelled state was observed by immersing the solution in a poly container in a constant temperature water bath at 20 ° C. The case where there was no gel for 1 month or more was evaluated as ○, the case where gelled within 2 weeks to 1 month was evaluated as Δ, and the case where gelled within 2 weeks was evaluated as ×.
In addition, even if the result of this test is inferior in stability, it can be used as the second liquid. (7) Appearance: Immediately after curing, the presence or absence of cracks due to curing shrinkage was confirmed. Those with cracks are marked with X, and those without cracks are marked with ○.
It was evaluated.

As is clear from Table 5, the film obtained by the inorganic coating agent according to the present invention is excellent in weather resistance, impact resistance and adhesion.

[0105]

EFFECTS OF THE INVENTION According to the present invention, an inorganic polymer composition useful for forming a film which is less likely to crack in the case of a conventional inorganic film and has excellent weather resistance, a method for producing the same, and It is possible to provide an inorganic coating agent using, and a coated article obtained by coating the same with articles such as vehicles, walls, home appliances, and machine parts.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a film formed by connecting three-dimensionally crosslinked inorganic gel units with a coil-shaped (thread-like) siloxane bond chain.

[Explanation of symbols]

1 Coil-like (thread-like) siloxane bond chain 2 Three-dimensional cross-linked inorganic gel unit

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Akiyoshi Osaka             3-1-1 Tsushimachu, Okayama City, Okayama Prefecture Okayama University             Faculty of Engineering (72) Inventor Satoshi Hayakawa             3-1-1 Tsushimachu, Okayama City, Okayama Prefecture Okayama University             Faculty of Engineering (72) Inventor Kanji Tsuru             3-1-1 Tsushimachu, Okayama City, Okayama Prefecture Okayama University             Faculty of Engineering F-term (reference) 4J002 CP031 EC077 EX036 EZ017                       GH00                 4J038 DL031 HA216 KA08 KA12                       MA14 PB05 PB07 PB09 PC01                       PC02 PC06 PC08

Claims (9)

[Claims] 1. An inorganic polymer composition obtained by reacting the following components a and b. Component a: General formula (1) R ¹ _n Si (OR ² ) _4-n (1) (In the formula, R ¹ is an organic group having 1 to 30 carbon atoms, and R ² is 1 carbon atom.
To 6 alkyl groups, C1 to C6 acyl groups or phenyl groups, and n is an integer of 0 to 1. However, R ¹ ,
R ² may be the same or different. )
One or more compounds b component selected from organosilane represented by: and a hydrolyzate or condensate thereof: a general formula (2): (Wherein, R ³ to R ⁸ is an organic group having 1 to 8 carbon atoms may each be the same or different. However, R ³ ~
One of R ⁴ or one of R ^{6 to} R ⁸ may be a hydroxyl group or a hydrolyzable group. Further, m is an integer of 1 or more. ) One or more linear polysiloxane condensates represented by the formula (1) and / or the general formula (3) (In the formula, R 9 to R 10 are organic groups having 1 to 8 carbon atoms and may be the same or different. N is 2
It is an integer above the above. ) 1 type (s) or 2 or more types of cyclic polysiloxane represented by these. 2. When the molar ratio of the a component and the b component is calculated and the basic structure (unit) of the b component is considered to be represented by the following general formula (4), the a component: b Ingredient =
The inorganic polymer composition according to claim 1, wherein the inorganic polymer composition is 1: 0.2 to 30. : General formula (4) 3. The method for producing an inorganic polymer composition according to claim 1, wherein the a component and the b component are reacted in a solvent in the presence of a catalyst. 4. The catalyst is any one of an acid catalyst, a basic catalyst and a metal catalyst.
A method for producing the inorganic polymer composition according to the item 1. 5. An inorganic coating agent containing the inorganic polymer composition according to claim 1 or 2 as a main component. 6. The inorganic coating agent according to claim 5, further comprising at least one compound selected from a coupling agent, an ultraviolet absorber, a light stabilizer and titanium oxide. 7. The inorganic polymer composition according to claim 5 or 6, which comprises 0.5 to 10 parts of a dipolar proton solution. 8. A coated article obtained by coating the inorganic coating agent according to claim 7. 9. The coated product according to claim 8, wherein the coated product is a plastic molded product, a siding board, an outer wall, a pre-coated metal, or a home electric appliance.