JP2001348430A - Stainproof coating film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stainproof coating film exhibiting excellent stainproofness and being excellent in durability and the easiness of slip of water drops and a method for producing the same. SOLUTION: Provided is a stainproof coating film prepared by laying a water slip stainproof layer containing a polydimethylsiloxane containing hydrolyzable silyl groups and/or a hydrolyzate thereof on an adhesive layer containing an adhesive component comprising a hydrolyzate of RaSiXb and a hydrolyzate of a silicon compound having an amino and a hydrolyzable silyl group in the molecule. The respective layers are formed by coating the surface of a substrate with an adhesive layer treating fluid and a water slip stainproof layer treatment fluid in turn and drying them.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling coating film and a method for producing the same, and more particularly, to an antifouling coating film having excellent slipperiness of water droplets adhering to a substrate surface, for example, a vehicle. The present invention relates to an antifouling coating film and a method for manufacturing the same, in which water droplets generated on an exterior of a vehicle, an aircraft, and the like easily slide down and are not easily contaminated by floating dust such as dust and exhaust gas.

[0002]

2. Description of the Related Art Conventionally, dust and floating dust such as automobile exhaust gas adhere to surfaces such as exteriors of vehicles and aircrafts and exterior walls of buildings used outdoors. Traces of water running when it rains can be soiled and impair the aesthetic appearance. In order to reduce this contamination, various surface treatment methods have been conventionally proposed. As a surface treatment of antifouling properties, generally, a hydrophilic surface from which adhered dirt such as airborne dust is easily removed by rain is excellent, and is often used for the appearance of buildings and the like.
However, the exterior surface of vehicles and the like is not a definitive antifouling treatment surface because a hydrophobic surface that repels water is preferred.

For example, Japanese Patent Application Laid-Open No. 5-70761 discloses a hydrophobic treatment method using a fluorine-based compound to make it difficult to adhere dirt. However, this method has a problem that the adhesion of dirt cannot be completely prevented, and the adhered dirt is hard to be removed by water, so that the dirt is easily stained. In addition, there is also a problem that the raindrops hardly fall down, so they remain on the surface, and the stains become uneven and conspicuous.

Further, Japanese Patent Application Laid-Open Nos. 11-80667, 11-92714, and 7-252472 disclose the following.
In order to solve such problems of the fluorine-based compound, Japanese Patent Application Laid-Open No. 8-283662 discloses a method of using a silicone-based compound having good water falling properties. However, these methods do not have sufficient water-sliding properties, and small water droplets remain on the coating film, so that satisfactory antifouling properties cannot be obtained. Further, in the case of using silicone oil, not only the silicone oil gradually elutes and the performance is lowered, but also the stained silicone oil adheres to the soil, and on the contrary, the oil tends to be easily soiled.

Further, Japanese Patent Application Laid-Open Nos. 11-293199 and 11-293184 propose a resin film in which a silicone compound is bonded to a resin coating film.
In such a hybrid configuration, the water slipping property was poor and sufficient antifouling property could not be obtained.

Further, Japanese Patent Application Laid-Open Nos. 10-225658 and 11-114488 propose antifouling surface treatment methods using a photocatalyst. In these methods, however, the surface is hydrophilic. Therefore, it cannot be used for applications where a hydrophobic surface is preferred.

Further, Japanese Patent Application Laid-Open No. H11-256134,
JP-A-10-147730 and JP-A-10-15
Japanese Patent No. 2626 proposes a method of maintaining the hydrophobicity of the surface and utilizing the antifouling property of the photocatalyst. In this method, although the repellency of water droplets is low, the water droplets have low sliding properties. Since the state is still adhered, there is a problem that light irradiation is required and it takes time to remove the adhered dirt.

[0008]

However, in the above-mentioned prior art, no satisfactory antifouling property can be obtained while maintaining hydrophobicity on the resin coating film. There was a problem that it was insufficient as a method for preventing dirt due to rain streaks.

The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object to realize excellent antifouling property, and also have excellent durability and water drop sliding property. And a method for producing the same.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the above-mentioned problems have been solved by laminating an adhesive layer containing a predetermined compound and an anti-slippery layer. And found that the present invention was completed.

That is, the antifouling coating film of the present invention is formed by laminating a water-repellent antifouling layer on an adhesive layer, and is coated on the substrate surface. The following chemical formula

[0012] _R a SiX _b ...

(Wherein R is a monovalent hydrocarbon group, X is a hydrolyzable group, a and b are integers and 0 ≦ a ≦ 2, b = 4-a
And a primer component consisting of a hydrolysis product of a silicon compound having an amino group and a hydrolyzable silyl group in the same molecule. The above-mentioned anti-slip antifouling layer comprises an antifouling component comprising a polydimethylsiloxane having a hydrolyzable silyl group and / or a hydrolysis product thereof.

The preferred form of the antifouling coating film of the present invention is
The adhesive layer is obtained by laminating an adhesive layer containing the adhesive component on a primer layer containing the primer component.

Further, another preferred embodiment of the antifouling coating film of the present invention comprises 30 to 95% of the above adhesive component, 5 to 50% of the above primer component, and 0 to 60% of the resin binder component.
Characterized by the following ratio.

Further, the method for producing an antifouling coating film of the present invention is a method for producing the above antifouling coating film, comprising: a treatment liquid for an adhesive layer in which the above-mentioned adhesive component and primer component are dissolved; It is characterized in that the anti-fouling component treatment liquid in which the anti-fouling component is dissolved is sequentially applied to the substrate surface and dried to form the above-mentioned adhesive layer and water-repellent antifouling layer.

[0017]

In the antifouling coating film of the present invention, a predetermined antifouling component is added to an adhesive component corresponding to the surface of the substrate and an adhesive layer containing a primer component that forms a siloxane bond with the water-slip antifouling layer. The contained anti-slip layer was laminated. Therefore, the antifouling coating film is excellent in slipperiness of water droplets, is hardly stained by dust and exhaust gas, and has high durability.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The antifouling coating film of the present invention will be described below in detail. In addition, in this specification, "%"
Unless otherwise specified, mass percentages are indicated. As described above, the antifouling coating film of the present invention is formed by laminating a water-repellent antifouling layer on an adhesive layer, and is characterized by being coated on a substrate surface.

The above-mentioned adhesive layer contains an adhesive component and a primer component. Here, the adhesive component has the following chemical formula

[0020] _R a SiX _b ...

(Wherein R is a monovalent hydrocarbon group, X is a hydrolyzable group, a and b are integers and 0 ≦ a ≦ 2, b = 4-a
Is shown)). Such an adhesive component has a strong siloxane bond (≡Si—O—Si) between the adhesive layer and the anti-slip layer through a silanol group (≡SiOH) formed on the surface of the adhesive layer.
≡) can be formed.

Examples of the hydrolyzable group X of the adhesive component R _a SiX _b include an alkoxyl group, a hydroxyl group, a chlorine atom or an isocyanate group, and a combination thereof arbitrarily. Such a hydrolyzable group X
In the case of, more silanol groups can be formed on the surface of the adhesive layer.

The primer component includes an amino group and a hydrolyzable silyl group (@ Si-X: "X" is an alkoxyl group, a hydroxyl group, a chlorine atom and an isocyanate group).
In the same molecule. The adhesion between the antifouling coating film and the substrate surface (such as a resin coating film) is improved by such a primer component. Also,
When the adhesive layer is only the adhesive component, it becomes difficult to coat the entire surface of the base material with the adhesive layer with good adhesion.

In other words, in the primer component, the amino group has good compatibility with a general resin coating film, so that when a resin coating film or the like is used as a substrate, it is easily localized on the surface side. In addition, the adhesive layer and the substrate surface can be firmly adhered. On the other hand, the hydrolyzable silyl group and the silanol group generated by hydrolysis of the hydrolyzable silyl group tend to be localized on the surface side of the adhesive layer (the side on which the anti-slippery layer is laminated). And the adhesion between the adhesive layer and the anti-slip layer can be improved. For this reason, it is more preferable that the adhesive layer has a configuration in which an adhesive layer containing the adhesive component is laminated on a primer layer containing the primer component.

Further, the silicon compound of the primer component
As, for example, H₂N (CH₂)₂NH (CH₂)
₃Si (OC₂H₅)₃, H₂N (CH₂)₂NH (C
H₂)₃Si (OCH₃)₃, H₂N (CH₂)₂NH
(CH₂)₃Si (CH₃) (OCH₃)₂, H₂N
(CH₂)₃Si (OC₂H₅)₃, H₂N (CH₂)
₂N (CH₂CHCH₂) (CH₂)₃Si (OC
H₃)₃, H₂N (CH₂) ₂NHCH₂C₆H₄(C
H₂)₂Si (OCH₃)₃, H₂NCH₂CH₂N
[(CH₂)₃Si (OCH₃)₃]₂, H₂N (CH
₂CH₂NH)₂(CH ₂)₃Si (OCH₃)₃, H
₂N (CH₂CH₂NH)₃(CH₂)₃Si (OCH
₃)₃Or H₂NC₆H₄NH (CH₂)₃Si (O
CH₃)₃And compounds obtained by arbitrarily combining them.
be able to. When these are used, they must be
Adhesion can be further improved.

The adhesive layer contains the adhesive component in an amount of 30 to 9
It is preferable to contain 5% of the above primer component at a ratio of 5 to 50%. When the content of the adhesive component is less than the above range or when the content of the primer component is more than the above range, the above-mentioned siloxane bond may be insufficient, and the adhesion to the water-slip resistant soil layer may be reduced. . On the other hand, when the content of the adhesive component is larger than the above range or the content of the primer component is smaller than the above range, adhesion to the substrate surface is reduced, and a durable antifouling coating film is obtained. May not be obtained.

The adhesive layer preferably contains a resin binder component at a ratio of 0 to 60%. In this case, the adhesion between the adhesive layer and the surface of the base material can be increased, and the durability of the antifouling coating film can be further improved. Further, the resin binder component is desirably one that can be mixed with a dilute solution of the adhesive component and the primer component at the time of forming the adhesive layer. For example, a silicone resin, an epoxy resin, an acrylic resin, a urethane resin, or the like It can be appropriately selected and used according to the material type of the surface.

Further, the adhesive layer may contain silica (SiO ₂ ) at a ratio of 30% or less. In particular, SiO ₂
Is preferably fine particles, and its content can be adjusted by including it in the adhesive layer treatment liquid described below. Such S
iO ₂ particles has silanol groups on the particle surface to form a siloxane bond between R _a SiX _b as well as slipping flood smudge layer described above. When the content of the SiO ₂ fine particles is 3
If it exceeds 0%, the adhesive layer becomes brittle and the abrasion resistance may decrease. Further, the SiO ₂ fine particles are not particularly limited, but, for example, generally commercially available colloidal silica can be used. Further, when high gloss is required on the surface of the coating film, it is desirable that the particle size of the SiO ₂ fine particles is 7 to 50 nm. If it is less than 7 nm, it is easy to aggregate and practically difficult to synthesize, and if it exceeds 50 nm, visible light may be scattered on the surface of the coating film, resulting in poor gloss.

Further, the adhesive layer has a ratio of 5% or less.
With titania (TiO₂) May be contained. In this case
Is effective because it can improve the abrasion resistance of the antifouling coating film.
You. However, if the content exceeds 5%, due to the photocatalytic effect,
Decomposes substrate surface, adhesive layer or anti-slip antifouling layer and promotes deterioration
Sometimes. The above TiO₂Content of TiO
₂Fine particles or TiO₂Precursors and the like are appropriately selected and used,
It can be adjusted by including it in the adhesive layer treatment liquid described later. What
Contact, the above TiO₂As the precursor, TiO₂Alcoqui
Sid and its hydrolysis products can be used
You.

The slip resistant antifouling layer laminated on the above-mentioned adhesive layer is
An antifouling component comprising a polydimethylsiloxane having a hydrolyzable silyl group and / or a hydrolysis product thereof is contained. At this time, the adhesive layer and the anti-slip layer are bonded via a siloxane bond formed by condensation of the hydrolyzable silyl group with a silanol group present on the surface of the adhesive layer. Thereby, the lubricating antifouling layer and the adhesive layer are firmly adhered to each other, and the durability of the antifouling coating film is improved. Further, as the hydrolyzable silyl group, for example, an alkoxysilyl group,
Examples thereof include a hydroxysilyl group, a chlorosilyl group, and an isocyanatesilyl group.

Further, the polydimethylsiloxane of the antifouling component has the following chemical formula:

[0032]

Embedded image

Wherein A is a fluoroalkyl group having 1 to 8 carbon atoms or a monovalent hydrocarbon group, B is a divalent hydrocarbon group, and D is a monovalent hydrocarbon having 1 to 4 carbon atoms. The group, X is at least one selected from the group consisting of an alkoxyl group, a hydroxyl group, a chlorine atom and an isocyanate group;
c and d are integers and represent 5 ≦ c ≦ 70 and 0 ≦ d ≦ 2)
It is preferable to have a structure represented by In this case, it is possible to obtain a film having extremely high water drop sliding property and excellent antifouling property. Although the cause of this effect is not always clear at the present time, it can be inferred that the orientation and easiness of movement of the polydimethylsiloxane molecule have an influence.

When the repetition number c of dimethylsiloxane in the above chemical formula is less than 5, the sliding property of water droplets tends to be insufficient, and when it is more than 70, the viscosity becomes high and handling becomes difficult, and the pot life of the processing solution becomes poor. Is sometimes not preferable because it may be shorter. Further, the hydrocarbon group B in the above chemical formula may contain an oxygen atom (O) or a nitrogen atom (N).

Here, as the base material for coating the antifouling coating film, an inorganic or organic material having a functional group (such as a hydroxyl group, an amino group, a thiol group, a carboxyl group and an acetate group) on the surface is used. For example, resin, glass, and the like can be used. Further, the substrate surface can be pre-treated before the surface treatment, for example, acid treatment with diluted hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid, etc., alkali treatment with sodium hydroxide aqueous solution, or plasma irradiation, corona irradiation, The adhesion between the substrate surface and the adhesive layer can be improved by treatment such as electron beam irradiation. In addition, specifically, it is preferable to perform such a treatment on a resin coating film such as a steel plate coating for automobiles.

Next, a method for producing the antifouling coating film of the present invention will be described. The antifouling coating film of the present invention is prepared by applying and drying an adhesive layer treatment liquid in which the adhesive component and the primer component are dissolved, and a slippery antifouling layer treatment liquid in which the antifouling component is dissolved, to the substrate surface in order. To form the above-mentioned adhesive layer and anti-slip soiling layer.

Here, an example of a method of forming the adhesive layer will be described. First, the adhesive component and the primer component are dissolved in an organic solvent to prepare an adhesive layer treatment liquid. At this time, (such as R _a SiX _b) water and acid were added adhesive ingredient material and primers ingredient material (silica compound) preferably the hydrolyzing. In addition, such a hydrolysis treatment can be performed for each component or can be performed after dissolution. Also,
It is desirable to adjust the concentration of the treatment solution for the adhesive layer so that the adhesive component and the primer component are included in the adhesive layer at a suitable content ratio after application and drying, and it is preferable to dilute the solution to an appropriate concentration according to the application method. it can. Further, by containing silica fine particles in the adhesive layer treatment liquid, the amount of silica in the adhesive layer can be adjusted to the above-mentioned desired content. Furthermore,
The adhesive layer treatment liquid contains titania fine particles, and / or a titania precursor (a titanium alkoxide compound and a hydrolysis product thereof or any combination thereof),
By adjusting the amount of titania in the adhesive layer to the desired amount described above, the abrasion resistance of the film can be improved. The organic solvent may be any solvent as long as it can dissolve each component. For example, alcohols, ketones, esters, ethers, hydrocarbons, aromatics, amines, and the like can be used as appropriate, and one kind can be used alone. They can be used alone or in combination of two or more.

Next, after adjusting the treatment liquid for the adhesive layer, the treatment liquid is applied to the surface of the substrate. At this time, as a coating method, dipping and pulling method (dipping method), spray method,
A general coating method such as a flow coating method, a spin coating method, a roll coating method, or a method using a blade coater, a bar coater, or the like can be appropriately employed. Alternatively, the treatment solution for the adhesive layer may be absorbed by a cotton cloth or a sponge, and used to apply the solution to the surface of the base material.

Further, after the application of the adhesive layer treatment liquid, the applied portion is dried to accelerate the polycondensation reaction between the adhesive component and the primer component, thereby forming an adhesive layer. At this time, the drying can be performed at room temperature (room temperature) or by appropriately heating. If the polycondensation reaction is insufficient, the adhesion to the substrate surface may be insufficient, or the silanol groups required to form a siloxane bond with the water-slip resistant soil layer may not be sufficient. On the other hand, if the reaction time is too long or the temperature is too high, the polycondensation reaction proceeds too much, and silanol groups formed on the surface form siloxane bonds, and do not adhere sufficiently to the anti-slippery layer. There is. For this reason, it is good to dry in a suitable temperature range and within a suitable time, and it is particularly preferable that the drying temperature is 20 to 170 ° C. If the temperature is lower than 20 ° C., the above-mentioned polycondensation reaction is not promoted, and the durability of the antifouling coating film tends to deteriorate. On the other hand, if the temperature exceeds 170 ° C., the resin coating on the surface of the base material tends to undergo thermal decomposition.

On the other hand, in the method for forming the anti-slip layer, first, an organic solvent (eg, alcohols, ketones, esters, ethers, hydrocarbons, aromatics, Amine-based liquid) to make the anti-slip anti-fouling layer treatment liquid. At this time, it is preferable to add water and an acid to hydrolyze the antifouling component material (eg, polydimethylsiloxane). Such hydrolysis treatment can be performed before or after dissolution. In addition, the anti-fouling layer treatment liquid includes
A metal oxide or a precursor thereof, or a silica compound having a fluoroalkyl group can be added together with the antifouling component. In this case, durability can be improved. However, if the addition amount is too large, the composition ratio of the antifouling component in the slippery antifouling layer is reduced, and the antifouling performance is also easily reduced. Therefore, the above addition amount is desirably 60% or less. In addition, it is desirable to adjust the concentration of the treatment liquid so that the antifouling component and the like are contained in the slippery antifouling layer at a suitable content ratio after coating and drying, and to a suitable concentration depending on the coating method. Can be.

Next, after adjusting the above-mentioned anti-slip antifouling layer treatment liquid,
This treatment liquid is applied to the surface of the adhesive layer. At this time, the same application method as in the case of the adhesive layer treatment liquid can be used as the application method.

Further, after application of the anti-slip anti-fouling layer treatment liquid, the applied portion is dried to form an anti-slip anti-fouling layer. In other words, an antifouling coating film is obtained. At this time, the drying can be performed at room temperature (room temperature) or by appropriately heating. However, drying after application is preferably performed at 20 to 170 ° C. If the temperature is lower than 20 ° C., the siloxane bond between the adhesive layer and the adhesive layer cannot be sufficiently formed, so that the adhesiveness becomes insufficient and the durability of the antifouling coating film tends to deteriorate. If the temperature is higher than 170 ° C., the surface of the base material (such as a resin coating film) tends to be thermally degraded. In addition, when the anti-slip layer is excessively applied after the drying treatment, the excess can be wiped off if necessary. In addition, if unreacted antifouling components are present, the gloss of the surface may be reduced, or floating dust may adhere to the surface, causing contamination.

As described above, the antifouling coating film of the present invention has such a property that it is hardly stained even by floating dust such as dust and exhaust gas. Specifically, the antifouling coating film, which is an example of the present invention, has a high water repellency having a contact angle of about 100 °, unlike a hydrophobic surface treatment material using a fluorine compound, and has a mass of 5 to 5. Extremely small water droplets, such as 10 mg, show excellent water droplet sliding properties that can fall down by their own weight due to the inclination of the application surface. As a result, even if it rains, black rain streaks are less likely to occur, and antifouling properties not available in conventional hydrophobic coating films are obtained. In addition, the antifouling coating film has a configuration in which the respective component layers are firmly bonded to each other, so that the antifouling coating film has excellent durability and has a performance that can withstand long-time use.

[0044]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

In the following Examples and Comparative Examples, antifouling coating films having a two-layer structure (Constitution 1) and antifouling coating films having a three-layer structure (Constitution 2) were manufactured separately. , Contamination test and durability test. Tables 1 to 3 show the raw material compositions and evaluation results of the coating films of Structure 1 and Structure 2, respectively.

[Contamination test method] As a contaminant, JSTM J7602-T-1992 according to Building Material Testing Center Standard
25 g channel black, 25 g test dust (12 types), 675 g yellow ocher, 225 g test dust (8 types), and 50 test dust (3 types)
g was uniformly blended. The test was performed according to the following procedure.

(1) 0.2 g / cm of contaminants on the coating film
² and the contaminants were spread with a brush as uniformly as possible over the entire surface.

(2) The coated plates obtained in the examples and comparative examples were set upright to remove the contaminants that fall naturally.

(3) 60 mW / cm by super UV
Light irradiation was performed for 6 hours at ² .

(4) Using a washing bottle, apply 5
The adhering contaminants were washed away by allowing the water to flow for seconds.

(5) The coated plate was allowed to stand and left standing to dry the water.

(6) The state of contamination on the surface of the coated film plate was visually evaluated and evaluated according to the following criteria. ○: a level at which almost no dirt is felt Δ: a level at which dirt is slightly recognized ×: a level at which dirt is remarkably adhered

(7) The above operations (1) to (6) were repeated five times.

[Durability test] The surface of the coating film was dried with a dry cotton cloth.
It was wiped by sliding it 0 times and its wear resistance was visually inspected.

1. Antifouling coating film of constitution 1

(Example 1) The outermost surface is made of clear coat
2 coat 1 bake type acrylic melamine resin
For automobiles baked at 140 ° C for 30 minutes
Was prepared as a substrate. Isopropyl alcohol
(IPA), Si (OC₂H₅)₄[Formula A1] and
H ₂N (CH₂)₃Si (OC₂H₅)₃[Formula B1]
When the weight ratio is 70:30, the solid concentration becomes 2%.
And mixed with stirring. Also, diluted 100 times with water
The total amount of the compound A1 and the compound B1 is set to 100
50 parts by weight, and stirred for 2 hours.
A coating solution was used. CH₃− (Si (CH₃)₂)₄₀Si
(CH₃)₂-C₃H₆-OCH₂CH (OH) CH₂
-NHC₃H₆Si (OCH₃)₃Hydrolysis represented by
Polydimethylsiloxane having a reactive silyl group [C1]
Was added to IPA so as to have a solid content of 5%.
Nitric acid diluted with water 100 times
20 parts by weight based on 100 parts of
The stirred solution was used as a second layer coating solution.

The coating solution for the first layer was applied to the coating film of an automobile prepared as a base material by flowing coating, and then the solvent was evaporated by air drying, followed by heat treatment at 130 ° C. for 1 hour. After the coating film was cooled to room temperature, the second layer was formed on the first layer.
The layer coating solution was soaked in cotton cloth and applied by hand coating. The solvent was evaporated at room temperature and further heat treated at 60 ° C. for 2 hours. After cooling to room temperature, the excess second layer component was wiped off with a cotton cloth impregnated with IPA to obtain an antifouling coating film.

As a result of performing a stain test on this coating film,
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

(Example 2: lower limit of preferred addition amount of compound A1)
Si (OC ₂ H ₅ ) ₄ [formula A1] and H ₂ N (CH ₂ ) ₃
Ratio of Si (OC ₂ H ₅ ) ₃ [formula B1] and colloidal silica (Snowtex IPA-ST-S: Nissan Chemical Industries, Ltd.) in a weight ratio of 35:40:10 (colloidal silica is converted to SiO ₂ ). And diluted 2-fold with IPA. To this diluent, nitric acid diluted with water 100-fold was added in an amount of 50 parts by weight based on the total amount of the solid contents of the above-mentioned compound A1, compound B1 and colloidal silica as 100. It was hydrolyzed. Further, an acrylic resin / melamine resin clear paint (Bellcoat No. 6000 Clear: Nippon Oil & Fats Co., Ltd.) is mixed and stirred as a resin binder so that the resin binder component is 10% of the total solid content, and the first layer is applied. Liquid. The same coating liquid as in Example 1 was used as the second layer coating liquid. The same operation as in Example 1 was repeated, except that the first layer coating solution was applied by a barcode method, to obtain an antifouling coating film.

As a result of performing a stain test on this coating film,
After repeated washing, some stains were seen after the fourth time, but there was no remarkable attachment of stains, and the condition was almost clean. The results of the durability test were also good.

(Example 3: upper limit of the amount of compound A1 is preferably added)
The same operation as in Example 1 was repeated, except that the weight ratio of the compound A1 and the compound B1 was 95: 5, to obtain an antifouling coating film.

As a result of performing a contamination test on this coating film,
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

(Example 4: Lower limit of preferred addition amount of compound B1)
The same operation as in Example 1 was repeated, except that the ratio of the compound A1 to the compound B1 was 93: 7 by weight, to obtain an antifouling coating film.

As a result of performing a stain test on this coating film,
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

Example 5: The upper limit of the amount of compound B1 is preferably added.
The same operation as in Example 1 was repeated, except that the ratio of the compound A1 to the compound B1 was 53:47 by weight, to obtain an antifouling coating film.

As a result of performing a stain test on this coating film,
After repeated washing, some stains were seen after the fourth time, but there was no remarkable attachment of stains, and the condition was almost clean. The results of the durability test were also good.

(Example 6: Suitable amount of resin binder added)
Upper limit) CH₃Si (OCH₃)₃[Formula A6] and H₂
N (CH₂)₂NH (CH₂) ₃Si (OCH₃)
₃[Formula B6] was mixed at a weight ratio of 37: 5.
And diluted 2-fold with IPA. Add 100
The nitric acid diluted twice with water is added to the total of the above chemical A6 and chemical B6.
Add 50 parts by weight based on 100, stir for 2 hours, and add
The hydrolyzable silyl group was hydrolyzed. Also, resin vine
Silicone resin (XS66-B0735:
GE Toshiba Silicone Co., Ltd.)
The mixture was mixed and stirred to be 8% to obtain a first layer coating liquid. C
₄H₉− (Si (CH₃)₂O)₃₀Si (CH₃)₂
-C₂H₄-Si (OCH₃)₃Hydrolysable represented by
Polydimethylsiloxane having a silyl group [C6]
Add the solid component concentration to IPA to 5%, and add 1
The nitric acid diluted with water 100 times was added to the above-mentioned compound B6 in an amount of 100.
And then stirred for 2 hours.
A layer coating solution was prepared.

The coating solution for the first layer was applied to a coating film of an automobile prepared as a base material by a bar code method, the solvent was evaporated by air drying, and a heat treatment was performed at 130 ° C. for 1 hour. After this coating film was cooled to room temperature, the coating solution for the second layer was soaked in a cotton cloth and applied on the formed first layer. The solvent was evaporated at room temperature and further heat treated at 60 ° C. for 2 hours. After cooling to room temperature, the excess second layer component was wiped off with a cotton cloth impregnated with IPA to obtain an antifouling coating film.

The coating film was subjected to a contamination test.
When the washing was repeated, stains were found a little after the third time, but there was no remarkable attachment of stains, and the condition was almost clean. The results of the durability test were also good.

(Example 7: Upper limit of the preferable addition amount of SiO ₂ ) A6 and B6 and colloidal silica (Snowtex IPA-ST-S: Nissan Chemical Industry Co., Ltd.) in a weight ratio of 65:10:25. (Colloidal silica was converted to SiO ₂ ), and the mixture was diluted with IPA to a solid component concentration of 3%. To this diluent, add nitric acid diluted 100 times with water to
The mixture was stirred for 2 hours, and the hydrolyzable silyl group was hydrolyzed to obtain a first layer coating solution. As the second layer coating solution, the same one as in Example 6 was used.
Other than these, the same operation as in Example 1 was repeated to obtain an antifouling coating film.

As a result of performing a stain test on this coating film,
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. In addition, as a result of the durability test, the surface was good without any scratches.

Example 8: Addition of TiO ₂ fine particles
6 and Compound B6 were mixed at a weight ratio of 90: 8, and diluted 20-fold with IPA. Add 10
50 parts by weight of nitric acid diluted with water 0 times with respect to the total of the above compound A6 and compound B6 as 100 was added, and the mixture was stirred for 2 hours,
The hydrolyzable silyl group was hydrolyzed. In addition, TiO ₂
5% of fine particles (ST-21: Ishihara Sangyo Co., Ltd.) in IPA
Concentration TiO ₂ dispersion solution obtained by dispersing in a, TiO ₂ to the total amount 98 of the reduction A6 and of B6 was added to a 2 by weight, and a first layer coating liquid was mixed and stirred .
As the second layer coating solution, the same one as in Example 6 was used. Other than these, the same operation as in Example 1 was repeated to obtain an antifouling coating film.

As a result of performing a contamination test on this coating film,
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

(Example 9: TiO ₂ is preferably added in an upper limit amount) Compound A6, compound B6 and Ti (OC ₃ H ₇ ) ₄ are in a weight ratio of 90: 5: 5, and the solid component concentration is 5%. And mixed with IPA to obtain a coating solution for the first layer. As the second layer coating solution, the same one as in Example 6 was used.
Other than these, the same operation as in Example 1 was repeated to obtain an antifouling coating film.

As a result of performing a stain test on this coating film,
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

(Example 10: The number of repeating dimethylsiloxane n in Chemical Formula C is 3) CH ₃ — (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ —
Polydimethylcyclohexane having a hydrolyzable silyl group represented by C ₂ H ₄ —Si (OCH ₃ ) ₃ [C1
0] to IPA so that the solid component concentration becomes 5%,
Further, 20 parts by weight of nitric acid diluted 100 times with water was added when the amount of polydimethylcyclohexane was 100, and the mixture was stirred for 2 hours to obtain a second layer coating solution. Except for this, the same operation as in Example 1 was repeated to obtain an antifouling coating film.

As a result of performing a stain test on this coating film,
When the washing was repeated, a little dirt was seen from the second time onward, but there was no remarkable adhesion of dirt and the condition was almost clean. The results of the durability test were also good.

Example 11: The number of repeating dimethylsiloxanes in Chemical Formula C is 10 CH ₃ — (Si (CH ₃ ) ₂ O) ₁₀ Si (CH ₃ ) ₂
The same operation as in Example 10 was repeated except that polydimethylsiloxane having a hydrolyzable silyl group represented by —C ₂ H ₄ —Si (OCH ₃ ) ₃ [Formula C11] was used, and the antifouling property was evaluated. A coating was obtained.

As a result of performing a stain test on this coating film,
After repeated washing, some stains were seen after the fifth time, but there was no remarkable attachment of stains, and the condition was almost clean. The results of the durability test were also good.

(Example 12: The number of dimethylsiloxane repeats n in Chemical Formula C is 60) CH ₃ — (Si (CH ₃ ) ₂ O) ₆₀ Si (CH ₃ ) ₂
Polydimethylsiloxane having a hydrolyzable silyl group represented by —C ₂ H ₄ —Si (OCH ₃ ) ₃ [C12]
Was used to obtain an antifouling coating film.

As a result of performing a stain test on this coating film,
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

Example 13: The number of dimethylsiloxane repeats n of Chemical Formula C is 90. CH ₃ — (Si (CH ₃ ) ₂ O) ₉₀ Si (CH ₃ ) ₂
Polydimethylsiloxane having a hydrolyzable silyl group represented by —C ₂ H ₄ —Si (OCH ₃ ) ₃ [C13]
Was used to obtain an antifouling coating film. However, the wiping of the excess second layer component was cloudy on the surface if it was performed quickly,
The procedure was repeated four times while replacing the cotton cloth impregnated with IPA.

The coating film was subjected to a contamination test.
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

(Example 14: Drying temperature: 10 ° C.) The same operation as in Example 1 except that the coating and drying steps of the first layer and the second layer were performed in a thermostatic chamber adjusted to 10 ° C. Was repeated to obtain an antifouling coating film.

As a result of performing a contamination test on this coating film,
When the washing was repeated, dirt adhered slightly to the surface, and the antifouling property was slightly lower than that of Example 1. The result of the durability test was good.

(Example 15: drying temperature is 190 ° C.)
The same operation as in Example 1 was repeated, except that the coating and drying steps of the layer and the second layer were performed at 190 ° C. for 20 minutes, to obtain an antifouling coating film. In addition, the obtained coating film was slightly thermally decomposed, and had lost its gloss in appearance.

As a result of performing a stain test on this coating film,
When the washing was repeated, dirt adhered slightly to the surface, and the antifouling property was slightly lower than that of Example 1. The result of the durability test was good.

(Comparative Example 1: No compound A) H ₂ N (CH ₂ )
₃ Si (OC ₂ H ₅ ) ₃ [formula B1] is diluted twice, and an acrylic resin / melamine resin-based clear paint (Bellcoat No. 6000 Clear: Nippon Oil & Fats Co., Ltd.) is used as a resin binder. The resin binder component was mixed and stirred at a weight ratio of 50:50 to obtain a first layer coating solution. The same coating liquid as in Example 1 was used as the second layer coating liquid.
A coating film was obtained by repeating the same operation as in Example 1 except that the first layer coating solution was applied by a barcode method.

As a result of performing a stain test on this coating film,
After the third washing, the adhesion of dirt was remarkable, and it was not a stain-resistant coating film. The result of the durability test was good.

(Comparative Example 2: No chemical compound B) Si (OC
₂ H _{5) 4} [of A1] and nitric acid diluted 100-fold with water, by weight 100: so that 50, were mixed to a solid concentration of 3% IPA, stirred for 2 hours This was the first layer coating solution. Except for this, the same operation as in Example 1 was repeated to obtain a coating film.

As a result of performing a stain test on this coating film,
After the third washing, the adhesion of dirt was remarkable, and it was not a stain-resistant coating film. The result of the durability test was good.

(Comparative Example 3: The second layer is a fluorine compound) C
_{8 F 17 C 2 H 4 Si} (OCH 3) 3 [ of C] and nitric acid diluted 100-fold with water, by weight 100: so that 50, so that the solid content concentration in IPA is 3% The same operation as in Example 1 was repeated, except that the mixture was stirred for 2 hours to obtain a coating liquid for the second layer, thereby obtaining a coating film.

As a result of performing a stain test on this coating film, the adhesion of stain was remarkable, and it could not be said that the coating film was an antifouling coating film.
The result of the durability test was good.

(Comparative Example 4: Silicone in which the second layer does not contain hydrolyzable silyl)

[0095]

Embedded image

The same operation as in Example 1 was repeated, except that the polydimethylsiloxane compound [C] represented by Thus, a coating film was obtained.

As a result of performing a stain test on this coating film, adhesion of stains was remarkable, and it could not be said that the coating film was an antifouling coating film.
The result of the durability test was good.

(Example 16: Compound A is less than the lower limit of the preferable addition amount and Compound B is higher than the upper limit of the preferable addition amount) The compound A1 and the compound B1 are mixed at a weight ratio of 20:55, and IPA is doubled. Diluted. To this diluted solution, nitric acid diluted 100 times with water was added by 50 parts by weight based on the total amount of solids of the above-mentioned compound A1 and compound B1 as 100, followed by stirring for 2 hours to hydrolyze the hydrolyzable silyl group. Was. Also, acrylic resin / melamine resin clear paint (Bellcoat N) is used as a resin binder.
o. 6000 Clear: Nippon Oil & Fats Co., Ltd.) was mixed and stirred so that the resin binder component was 25% of the total solid content to obtain a first layer coating solution. A coating film was obtained by repeating the same operation as in Example 1 except that the first layer coating solution was applied by a barcode method.

As a result of performing a stain test on this coating film, although a little dirt was attached, it was at a level usable as an antifouling coating film. The result of the durability test was good.

(Example 17: A is more than the upper limit of the preferred amount of compound A) The same operation as in Example 1 was repeated except that the ratio of compound A1 to compound B1 was 98: 2 by weight. A membrane was obtained.

As a result of conducting a stain test on this coating film, a little adhesion of dirt was observed, but it could be said that the coating film was an antifouling coating film. The result of the durability test was good.

(Example 18: Resin binder exceeds the upper limit)
CH₃Si (OCH₃)₃[Formula A6] and H₂N (CH
₂)₂NH (CH₂) ₃Si (OCH₃)₃[Formula B6]
Are mixed at a weight ratio of 30: 5, and IPA is mixed.
And diluted 2 times. Dilute the diluted solution 100 times with water
The total amount of the above-mentioned chemical A6 and chemical B6 was set to 100
Add 50 parts by weight of the mixture, stir for 2 hours, and
The hydroxyl group was hydrolyzed. In addition, as a resin binder,
Silicone resin (XS66-B0735: GE Toshiba series)
Corn Co., Ltd.) with a resin binder component of 6
The mixture was mixed and stirred so as to be 5% to obtain a first layer coating solution. Up
The same operation as in Example 1 was repeated except for the above operation,
I got

The coating film was subjected to a stain test. As a result, it was found that the film was slightly stained, but the antifouling property was recognized. Also,
The result of the durability test was good.

Example 19: SiO₂Fine particles are suitable
A6, B6 and colloidal silica (Suno
-Tex IPA-ST-S: Nissan Chemical Industries, Ltd.
And a weight ratio of 50:15:35 (colloidal silica is S
iO ₂(Conversion), and the solid content concentration is 3 by IPA.
%. Add 100-fold water to this diluent
The nitric acid diluted with
Add 50 parts by weight when the total of Rica is 100
For 1 hour to hydrolyze the hydrolyzable silyl group.
A coating solution was used. The second layer coating solution was the same as in Example 6.
Other than this, the same operation as in Example 1 was repeated,
A coating was obtained.

As a result of performing a stain test on this coating film,
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. However, as a result of the durability test, fine scratches were slightly generated on the surface of the film.

(Example 20: The amount of TiO ₂ added exceeds the upper limit)
Compound A6 and compound B6 were mixed at a weight ratio of 85: 7, and diluted 20-fold with IPA. In this diluent,
Nitric acid diluted 100-fold with water was added in an amount of 50 parts by weight, assuming that the total of the compound A6 and compound B6 was 100, followed by stirring for 2 hours to hydrolyze the hydrolyzable silyl group. Also, Ti
A TiO ₂ dispersion solution in which O ₂ fine particles (ST-21: Ishihara Sangyo Co., Ltd.) were dispersed in IPA at a concentration of 5% was converted into the above-mentioned compound A6.
TiO ₂ in a weight ratio of 8 to the total amount 92 of
And mixed and stirred to obtain a first layer coating solution. The same coating liquid as in Example 6 was used as the second layer coating liquid, and the same operation as in Example 1 was repeated except for this, to obtain a coating film.

As a result of performing a stain test on this coating film, a little stain was attached, but an antifouling coating film was recognized. Also,
The result of the durability test was good.

2. Antifouling coating film of constitution 2

Example 21 H ₂ N (CH ₂ ) ₃ Si
A mixture of (OC ₂ H ₅ ) ₃ [formula B1] and IPA with stirring at 3% was used as a first layer coating solution. In addition, Si
(NCO) [Formula A16] was mixed and stirred with ethyl acetate to a concentration of 1% to obtain a second layer coating solution. C ₄ H ₉ −
_{(Si (CH 3) 2 O} ) 30 Si (CH 3) 2 -C 2 H
₄ -Si _{(OCH 3)} using a polydimethylsiloxane [of C6] represented by _3, was formulated a third layer coating solution in the same manner as the second layer coating solution of Example 6.

The coating liquid for the first layer was applied to the coating film of an automobile prepared as a base material by flow coating, and then the solvent was evaporated by air drying, followed by heat treatment at 130 ° C. for 1 hour. After the coating film was cooled to room temperature, the second layer was formed on the first layer.
The layer coating solution was soaked in cotton cloth and applied by hand coating. This was left at room temperature for 4 hours, and then the third layer coating solution was soaked in cotton cloth and applied by hand. The coating film applied to the third layer was dried at 60 ° C. for 4 hours, and the excess second layer component was wiped off with a cotton cloth impregnated with IPA to obtain an antifouling coating film.

The coating film was subjected to a contamination test, and as a result, the
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

Example 22: TiO₂Addition) Si (OC
₂H₅)₄[Formula A1] and TiO₂Fine particles (ST-21:
(Ishihara Sangyo Co., Ltd.) dispersed in IPA at a concentration of 5%
iO₂A17 and TiO ₂Is 98:
2 and mixed with IPA at a solid concentration of 2% and stirred.
Was. In addition, nitric acid diluted 1002 with water was added to the compound A1.
At a ratio of 50 parts by weight to 100, and stirred for 1 hour.
This was used as a second layer coating solution. Other than this, Example 1
The same operation as in Example 4 was repeated to obtain an antifouling coating film.

The coating film was subjected to a contamination test.
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

Example 23: The upper limit of the amount of TiO ₂ added A1 and Ti (OC ₃ H ₇ ) ₄ were diluted to a weight ratio of 95: 5 to an IPA solid content concentration of 1% and stirred. A second layer coating solution was used. Except for this, the same operation as in Example 14 was repeated to obtain an antifouling coating film.

As a result of performing a stain test on this coating film,
Even after repeated washing, the surface dirt was not noticeable and was in a clean state. The results of the durability test were also good.

(Example 24: TiO ₂ added amount exceeds the upper limit)
Of A1 and TiO ₂ fine particles (ST-21: Ishihara Sangyo Kaisha (Co.)) TiO ₂ which is dispersed in a concentration of 10% in IPA
The dispersed solution, is of A1 and TiO ₂ so as to be 90:10 by weight, it was mixed and stirred in IPA at a solid concentration of 2%.
Nitric acid diluted 100-fold with water was added thereto, and 50 parts by weight of Compound A1 was added to 100 parts of the mixture, followed by stirring for 1 hour to obtain a second layer coating solution. Except for this, the same operation as in Example 1 was repeated to obtain a coating film.

As a result of performing a stain test on this coating film, adhesion of dirt was slightly recognized, but it was at a level that can be said to be an antifouling coating film. The result of the durability test was good.

[0118]

[Table 1]

[0119]

[Table 2]

[0120]

[Table 3]

Although the present invention has been described in detail with reference to preferred embodiments and comparative examples, the present invention is not limited to these embodiments, and various modifications can be made within the scope of the present invention. . For example, the substrate coated with the antifouling coating film of the present invention is not limited to a plate-like material such as a resin plate, and may be curved or have some irregularities. Further, the portion to which the antifouling coating film of the present invention is to be applied may be not only the so-called front surface but also the back surface or side surface.

[0122]

As described above, according to the present invention, an adhesive layer containing a predetermined compound and a water-repellent antifouling layer are provided, so that excellent antifouling properties are realized, and durability and water droplets are prevented. It is possible to provide an antifouling coating film excellent in slipperiness and a method for producing the same.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J035 CA052 CA152 CA162 CA212 HA01 LB01 LB07 4J038 DG011 DL051 DL081 HA166 HA446 NA05 PB03 PB07 PC04 PC08

Claims (14)

[Claims] Claims: 1. An anti-slip antifouling layer is laminated on an adhesive layer,
An antifouling coating film coated on the surface of a substrate, wherein the adhesive layer has the following chemical formula: R _a SiX _b (wherein R is a monovalent hydrocarbon group, X is a hydrolyzable group, a
And b are integers and 0 ≦ a ≦ 2, b = 4-a), an adhesive component comprising a hydrolysis product of a silicon compound, an amino group and a hydrolyzable silyl group in the same molecule. And a primer component comprising a hydrolysis product of a silicon compound having the same. The above-mentioned anti-slip antifouling layer comprises a polydimethylsiloxane having a hydrolyzable silyl group and / or an antifouling component comprising the hydrolysis product thereof. An antifouling coating film characterized in that: 2. The antifouling coating according to claim 1, wherein the adhesive layer is formed by laminating an adhesive layer containing the adhesive component on a primer layer containing the primer component. film. 3. The method according to claim 1, wherein X of R _a SiX _{b in} the above chemical formula is at least one selected from the group consisting of an alkoxyl group, a hydroxyl group, a chlorine atom and an isocyanate group. 2. The antifouling coating film according to 2. 4. The silicon compound of the primer component,
H₂N (CH₂)₂NH (CH₂)₃Si (OC
₂H₅)₃, H₂N (CH₂)₂NH (CH₂)₃Si
(OCH₃)₃, H₂N (CH₂)₂NH (CH₂)₃
Si (CH₃) (OCH₃)₂, H₂N (CH₂)₃S
i (OC₂H₅)₃, H₂N (CH₂)₂N (CH₂C
HCH₂) (CH₂)₃Si (OCH₃)₃, H₂N
(CH₂)₂NHCH₂C₆H₄(CH₂)₂Si (O
CH₃)₃, H₂NCH₂CH₂N [(CH₂)₃Si
(OCH₃)₃]₂, H₂N (CH₂CH₂NH)
₂(CH₂) ₃Si (OCH₃)₃, H₂N (CH₂C
H₂NH)₃(CH₂)₃Si (OCH₃)₃, And H
₂NC₆H₄NH (CH₂)₃Si (OCH₃)₃From
At least one compound selected from the group consisting of
The method according to any one of claims 1 to 3, wherein
Antifouling coating. 5. The adhesive layer, wherein the adhesive component is 30 to
The antifouling coating film according to any one of claims 1 to 4, comprising 95%, 5 to 50% of the primer component, and 0 to 60% of the resin binder component. 6. The antifouling coating film according to claim 1, wherein the adhesive layer contains silica in a proportion of 30% or less. 7. The antifouling coating film according to claim 1, wherein the adhesive layer contains titania at a ratio of 5% or less. 8. The polydimethylsiloxane of the antifouling component has the following chemical formula: (Where A is a fluoroalkyl group having 1 to 8 carbon atoms or a monovalent hydrocarbon group, B is a divalent hydrocarbon group, D is a monovalent hydrocarbon group having 1 to 4 carbon atoms, X Is at least one member selected from the group consisting of an alkoxyl group, a hydroxyl group, a chlorine atom and an isocyanate group, and c and d are integers and 5 ≦ c ≦ 70, and 0 ≦ d ≦ 2. The antifouling coating film according to any one of claims 1 to 7, comprising: 9. The method for producing an antifouling coating film according to any one of claims 1 to 8, wherein the adhesive component treatment solution is prepared by dissolving the adhesive component and the primer component. A method for producing an antifouling coating film, comprising sequentially applying and drying a treatment solution for a water-slip-repellent antifouling layer in which a fouling component is dissolved to form the adhesive layer and the water-repellent antifouling layer. 10. The method for producing an antifouling coating film according to claim 9, wherein the adhesive layer treatment liquid contains a hydrolysis product of the adhesive component and the primer component. 11. The method for producing an antifouling coating film according to claim 9, wherein the treatment liquid for the adhesive layer contains silica fine particles. 12. The method for producing an antifouling coating film according to claim 9, wherein the treatment liquid for the adhesive layer contains titania fine particles and / or a titania precursor. Method. 13. The antifouling coating according to any one of claims 9 to 12, wherein the anti-fouling layer treatment liquid contains a hydrolysis product of the antifouling component. Manufacturing method of membrane. 14. The antifouling method according to claim 9, wherein drying after applying the adhesive layer treatment liquid and the anti-slip antifouling layer treatment liquid is performed at 20 to 170 ° C. Method for producing a functional coating.