JP3302813B2 - Steel sheet coated with inorganic / organic fusion, inorganic / organic fusion coating, method for producing them, and coating liquid for inorganic / organic fusion coating formation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a weather-resistant and heat-resistant steel sheet having excellent workability and a high hardness coating, a coating,
The present invention relates to a production method and a coating solution for forming a film .

[0002]

2. Description of the Related Art Steel sheets are generally used after being painted. The purpose of the coating is to protect the base steel plate and at the same time to increase its durability and to beautify it. Painted steel sheets are used in large structures such as buildings, ships, bridges, etc., as well as various machines, automobiles, furniture, small electrical appliances, and daily necessities.

[0003] The coating of these steel plates is generally called post-coating and is performed after processing and assembly. However,
In recent years, particularly in the field of home electric appliances and the like, a method of processing and assembling a prepainted steel sheet that has already been coated has been shifting to a method in which the steel sheet is already processed. Pre-coated steel sheets are required to have workability in addition to the conventional functions such as corrosion protection. In order to satisfy the above function, an organic polymer such as a polyester resin is used as a coating material.

On the other hand, as a coating excellent in heat resistance, corrosion resistance and the like, there is an enamel in which a steel plate is coated with glass. The enamel is manufactured by post-coating in which a steel plate is processed into a desired shape and then coated with glass.

[0005]

The pre-coated steel sheet can be omitted from the processing / assembly line because the coating process can be omitted. Therefore, the pre-coated steel sheet can be pre-coated even in fields such as high hardness, high weather resistance, high heat resistance, etc. which currently rely on post coating. It has come to be required. However, since the conventional precoated steel sheet is basically coated with an organic polymer, there are limitations on surface hardness, weather resistance, heat resistance, and the like. On the other hand, a method of coating glass or ceramics to improve the surface hardness and heat resistance of the steel sheet can be considered, but the workability is impaired and the steel sheet cannot be used as a precoated steel sheet. For example, enamel cannot be processed, and if it is bent or the like, the coated glass is easily peeled off. Accordingly, the present invention has been made to solve the above-mentioned problems, and has excellent weatherability and heat-resistant steel sheet coated with excellent workability and high hardness, coating film, and the like.
It is an object of the present invention to provide a method for producing a film and a coating solution for forming a film .

[0006]

Means for Solving the Problems Inorganic-organic fusion of the present invention
The steel sheet covering the body is an MOM bond (M is metal, half metal
Skeleton of the inorganic polymer comprising -O-Si
(R) ₂ -O- group (R is an alkyl group)
It is a steel sheet coated with an organic fusion material. -Si (R) ₂ - in
M which is not bonded to an organic component and an alkyl group
The ratio of the organic components is 8.0 to 8.0 in terms of the molar ratio of organic components / inorganic components.
0.1, the film thickness should be 0.5-50 μm
Is preferred. Further, the inorganic-organic fusion coating of the present invention,
Inorganic consisting of MOM bond (M is a metal or metalloid atom)
The skeleton of the polymer is represented by an —O—Si (R) ₂ —O— group (R is
This is an inorganic / organic fusion coating substituted with an alkyl group. −
Bonding of an organic component which is Si (R) _2- with an alkyl group;
The ratio of the inorganic component that is not M is the ratio of the organic component / the inorganic component.
The molar ratio is 8.0 to 0.1, and the film thickness is 0.5 to 5
Preferably, it is 0 μm. Inorganic and organic fusion of the present invention
The body-coated steel sheet is made of alkoxide or alkoxy.
Derivative or hydrolyzed alkoxide or alkoxide
Dialkyl dialkoxysilane is added to the cooxide derivative.
After applying the hydrolyzed solution to the steel sheet,
It is manufactured by heat treatment at 00 ° C. At this time, it becomes an organic component
Dialkyl dialkoxysilane and alcohol as inorganic component
The ratio to the oxide and alkoxide derivatives is determined by the ratio of organic components / none
The molar ratio of the organic components is preferably in the range of 8.0 to 0.1. Ma
In addition, the inorganic / organic fusion coating film of the present invention also includes an alkoxide.
Or alkoxide derivatives or hydrolyzed alcohol
Dialkyl dialcohols for side or alkoxide derivatives
After adding the xysilane and applying the hydrolyzed solution,
It is manufactured by heat treatment at 00 to 600 ° C. At this time,
Dialkyldialkoxysilane (A) and inorganic component
Of alkoxide and alkoxide derivative (B)
In this case, the molar ratio of A / B is preferably in the range of 8.0 to 0.1.
No. The coating liquid for forming an inorganic / organic fusion coating film of the present invention comprises:
Lucoxide, alkoxide derivative or hydrolyzed
Dialkyl dialkals for alkoxides and alkoxide derivatives
It is a solution that has been hydrolyzed by adding coxysilane.
Dialkyldialkoxysilane (A) and inorganic component
Of alkoxide and alkoxide derivative (B)
In the case, the molar ratio of A / B is in the range of 8.0 to 0.1.

[0007] The inorganic / organic fused material is a material which is fused at the atomic / molecular level by polymerizing a metal or metalloid by chemical bonding to an organic substance comprising carbon, hydrogen, oxygen, nitrogen and the like. . In addition, the inorganic polymer is MO-
A polymer polymerized with an M bond as a skeleton;
The bond represents an inorganic component. And -O-Si
The alkyl group (R) in (R) 2-O-group, _{e.g., -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9,
Is representative of the organic components -C ₆ H ₅ and the like.

[0008]

In the present invention, the steel sheet coated with the fused inorganic / organic composite has the M-
-O-Si is added to the skeleton of the inorganic polymer composed of OM bonds.
Since (R) 2-O- group is introduced, it is more processable than glass and ceramics, and has higher hardness than organic polymers.
Can exhibit high heat resistance. That is, if only the inorganic component is used, the bond is three-dimensionally developed to form a strong structure, and the workability is impaired. However, part of the inorganic skeleton is -O-Si
When the (R) 2-O- group is introduced, this terminal is free without bonding to another metal, and a part of the three-dimensional network of the inorganic skeleton is broken, so that the processability is enhanced. Furthermore, since the basic bond is an MOM inorganic bond, the organic bond C
Heat resistance, hardness, etc. are higher than those of -C.

This inorganic-organic fusion is 0.5 to 50 μm
It is preferred to coat with a thickness of 0.5μ coating thickness
If it is less than m, sufficient heat resistance and corrosion resistance cannot be obtained. On the other hand, when the thickness exceeds 50 μm, cracks and the like occur during the heat treatment in the coating process.

[0010] The steel sheet coated with an inorganic / organic fusion body of the present invention is manufactured as follows. That is, a solution obtained by adding a dialkyldialkoxysilane to an alkoxide or an alkoxide derivative or a hydrolyzed alkoxide or an alkoxide derivative and applying the solution to the steel plate is applied to a steel plate, and then heat-treated at 100 to 600 ° C.

The ratio of the alkoxide or alkoxide derivative as the inorganic component and the dialkyldialkoxysilane as the organic component is 8.0 to 8.0 in terms of the molar ratio of the organic component / inorganic component.
It is preferred to be in the range of 0.1. If it is less than 0.1, the workability is impaired, so that the coating peels off or cracks during processing. On the other hand, when it exceeds 8.0, there is no problem in workability, but the surface hardness and heat resistance are significantly reduced.

The ratio of organic component / inorganic component can be calculated, for example, from the absorption peak of Si—C bond and C—H bond and the absorption peak of MO bond in the infrared absorption spectrum. In addition, analysis methods such as NMR and XPS, and thermal analysis methods for thermally decomposing organic components can be used.

The alkoxide used in the present invention is not particularly restricted but includes, for example, methoxide, ethoxide, propoxide, butoxide and the like. Further, the alkoxide derivative refers to a part of the alkoxy group as β-diketone, β-diketone,
It is substituted with ketoester, alkanolamine, alkylalkanolamine, organic acid and the like. Therefore, the metals and metalloids constituting the inorganic component in the present invention are limited to those capable of forming an alkoxide. For example, Si, Al, Ti, Zr, Ta, Nb,
Y, Co, etc.

In the present invention, the term "hydrolysis of alkoxides and alkoxide derivatives" means to add up to 10 moles of water to alkoxides and alkoxide derivatives for hydrolysis. At this time, an inorganic acid, an organic acid or both of them may be used as a catalyst. The water to be added is
It may be diluted with an organic solvent such as alcohol. If water is used in an amount of 10 mol times or more, gelation occurs immediately, which is not preferable.

The dialkyl dialkoxy silane used in the present invention includes, for example, dimethyl dimethoxy silane,
Dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane , Dipropyldibutoxysilane,
Examples include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, and the like.

In the hydrolysis of the present invention, 0.5 to 10.0 moles of water is added to the unhydrolyzed alkoxy group. At this time, an inorganic acid, an organic acid or both of them may be used as a catalyst. The water to be added may be diluted with an organic solvent such as alcohol. If the amount of water is less than 0.5 mole times, the degree of polymerization is low, and it cannot be applied because it volatilizes during heat treatment. On the other hand, if it exceeds 10.0 mole ratio, it will gel immediately and cannot be applied.

In the partial hydrolysis and hydrolysis, an organic solvent capable of uniformly dispersing and dissolving the dialkyl dialkoxysilane and alkoxide is used. For example, various alcohols such as methanol, ethanol, propanol and butanol, acetone, toluene, xylene and the like.

After the hydrolysis, the solvent and the alcohol produced by the hydrolysis may be distilled off under normal pressure or reduced pressure for application.

The steel sheet used in the present invention is not particularly limited, and examples thereof include stainless steel sheets, steel sheets for various platings such as aluminum and zinc, and steel sheets provided with these plating methods.

The coating on the steel sheet is performed by a spray coating method, a dip coating method, a spray coating method, a roll coating method, a spin coating method or the like.

The heat treatment after the coating is performed at 100 to 600 ° C. When the temperature is lower than 100 ° C., the solvent or the like does not sufficiently evaporate, and hardness and heat resistance cannot be obtained. When the temperature exceeds 600 ° C., the solvent or the like evaporates rapidly, and pinholes and cracks occur in the coating.

[0022]

The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to only these examples.

Under the conditions shown in Tables 1 and 2, a steel sheet was coated with an inorganic / organic fusion product and heat-treated. The workability, surface hardness, corrosion resistance and heat resistance of the produced inorganic / organic fusion coated steel sheet were evaluated. Table 3 summarizes these results. Workability was evaluated based on the limit of cracks in the coating film after bending at JIS G 3312180 °. The surface hardness was evaluated by a pencil hardness test method. As for the corrosion resistance, the degree of rust generation after 240 hours of the salt spray test was evaluated based on the following criteria: ○: no rust, Δ: slight rust, ×: significant rust. Further, the corrosion resistance after the 90-degree bending was also examined by a salt spray test. The heat resistance was determined by heating at 200 ° C. to 600 ° C. for 48 hours and then examining a temperature at which rust does not occur in a salt spray test.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

In Examples, the workability was good (0 to 1T), the surface hardness was high (3 to 6H), and the corrosion resistance and the corrosion resistance after processing were good. Heat resistance showed 450-600 degreeC. On the other hand, in the comparative example, one having all the characteristics was not obtained. For example, no. In No. 15, the hardness and heat resistance were high because the inorganic component was too large, but the processability was very poor.
No. No. 16 had insufficient hardness and corrosion resistance because of too much organic component. No. In No. 17, the applied sol did not solidify because the heat treatment temperature was too low. No. 1
In No. 8, since the heat treatment temperature was too high, cracks and pinholes occurred in the coating, and the corrosion resistance was poor. No. No. 19 was insufficient in hardness and corrosion resistance because of its thin film thickness. N
o. Sample No. 20 was inferior in workability because the film thickness was too thick, and was poor in corrosion resistance due to cracks generated during heat treatment.

[0028]

The steel sheet coated with the inorganic / organic fusion of the present invention has higher workability than a steel sheet coated with glass or ceramics, and can exhibit higher hardness and higher heat resistance than a steel sheet coated with an organic polymer. Therefore, it cannot be used with conventional precoated steel sheets coated with an organic polymer, so that it can be used in, for example, fields that require high corrosion resistance and heat resistance that are post-coated. Furthermore, the inorganic-organic fusion coated steel sheet of the present invention has a higher hardness than conventional organic polymer-coated precoated steel sheets, so that it is hard to be damaged and easy to handle.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI B32B 15/08 B32B 15/08 G (56) References JP-A-48-103630 (JP, A) JP-A-54-130688 ( JP, A) JP-A-56-2871 (JP, A) JP-A-56-152762 (JP, A) JP-A-60-197773 (JP, A) JP-A-62-132575 (JP, A) (58) ) Surveyed field (Int.Cl. ⁷ , DB name) B05D 1/00-7/26 B32B 15/08

Claims (9)

(57) [Claims] 1. The skeleton of an inorganic polymer comprising MOM bonds (M is a metal or metalloid atom) is represented by --O--Si (R) ₂
-O- group (R is an alkyl group) steel plate coated with an inorganic or organic fusion substituted with. Wherein -Si inorganic or organic fusion (R) ₂ - with
M which is not bonded to an organic component and an alkyl group
The ratio of the organic component is 8.0 in terms of the molar ratio of the organic component / the inorganic component.
And the coating thickness is 0.5 to 50 μm.
The inorganic / organic fusion according to claim 1, which is coated.
Steel plate. 3. An MOM bond (M is a metal, a metalloid metal)
The skeleton of the inorganic polymer consisting of —O—Si (R) ₂
-O- (R is an alkyl group)
Inorganic / organic fusion coating. 4. -Si inorganic or organic fusion (R) ₂ - with
M which is not bonded to an organic component and an alkyl group
The ratio of the organic component is 8.0 in terms of the molar ratio of the organic component / the inorganic component.
And the coating thickness is 0.5 to 50 μm.
The inorganic / organic fusion coating film according to claim 2, characterized in that: 5. An alkoxide or an alkoxide derivative
Or hydrolyzed alkoxides and alkoxide derivatives
Dialkyl dialkoxysilane is added and the hydrolyzed solution
After applying the liquid to the steel plate, heat treatment at 100-600 ° C
Manufacture of steel sheet coated with inorganic / organic fusion
Construction method. 6. A dialkyl dialkoxysilane (A)
The ratio of the alkoxide and the alkoxide derivative (B) is represented by A
/ B in a molar ratio of 8.0 to 0.1.
A steel sheet coated with the inorganic / organic fusion product according to claim 5.
Manufacturing method. 7. An alkoxide or an alkoxide derivative
Or hydrolyzed alkoxides and alkoxide derivatives
Dialkyl dialkoxysilane is added and the hydrolyzed solution
Forming a coating film with a liquid and heat-treating at 100 to 600 ° C
A method for producing an inorganic / organic fusion coating film, characterized in that: 8. A dialkyl dialkoxysilane (A)
The ratio of the alkoxide and the alkoxide derivative (B) is represented by A
/ B in a molar ratio of 8.0 to 0.1.
8. A method for producing an inorganic / organic fusion coating film according to claim 7.
Law. 9. An alkoxide and an alkoxide derivative
Or hydrolyzed alkoxides and alkoxide derivatives
Dialkyl dialkoxysilane was added and hydrolyzed
A cloth liquid comprising a dialkyldialkoxysilane (A) and
When the ratio of the alkoxide and the alkoxide derivative (B) is A
/ B in a molar ratio of 8.0 to 0.1.
Coating solution for forming an inorganic / organic fusion film.