JP3381504B2 - Water / oil repellent treatment method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-repellent material for solid substrates.
The present invention relates to an oil repellent treatment method, and more particularly to improvement of a silane coupling treatment method.

[0002]

2. Description of the Related Art As a water / oil repellent treatment method for a solid substrate, a conventional method is to immerse the substrate in a solution of a trialkoxysilane compound and then heat-treat it (for example, JP-A-48-44181).
There is known a method of treating a solid substrate by immersing it in a solution of an alkyltrichlorosilane compound in an inert atmosphere (for example, JP-A-4-243934).

[0003]

However, in the conventional water / oil repellent treatment method, since the silane compound cannot be formed on the solid substrate with high density, the water / oil repellent property of the solid substrate is insufficient.

For example, on a plate for an electromagnetic cooker,
According to the method described in JP-A-48-44181, a silane compound having a fluoroalkyl group is formed, 1 ml of sugar / soy sauce (weight ratio 1: 1) is dropped, and heated at 250 ° C. for 5 minutes to stain. If you repeat the experiment of making a tissue and wiping it with a dry tissue 20 times, there is a problem that after about 10 times, the dirt sticks and cannot be removed.

Further, in the method described in JP-A-4-243934, since trichlorosilane is used for the water / oil repellent treatment, it cannot be treated in normal air, and it is necessary to treat it in dry air or an inert gas atmosphere. However, it is not suitable for mass production and has low industrial utility value. Also, with this method
The characteristic of the oil-repellent solid substrate is not always sufficient, and there is a problem that the stain cannot be removed after about 20 times with respect to the burn-in stain of sugar and soy sauce.

The water- and oil-repellent treatment method of the present invention aims to solve the above-mentioned problems and to obtain a water- and oil-repellent surface which can be treated in normal air and which is particularly excellent in durability. To do.

[0007]

The first water-repellent-oil repellent processing method of the problem-solving means for the invention, comprises a stable mono- or Axis Roroshi <br/> orchid compound and fluoroalkyl trialkoxysilane compound in air to the solution, a step of immersing the solid substrate having an active hydrogen on the surface, said submerged said solid substrate is dried to remove the solvent, and the heat treated pre SL solid substrate further trialkoxysilane compound The solid group
And a step of covalently attaching a plate.

[0008] In the present invention, it is preferable that a stable mono- or Axis Roroshiran compounds in air contains an alkyl or alkoxyl group.

A second water-repellent-oil repellent processing method of the present invention, A
A step of immersing a solid substrate having active hydrogen on the surface thereof in a solution containing a rukyiamine and a trialkoxy compound having a fluoroalkyl group;
The solid substrate is dried to remove the solvent, and a heat-treated the previous SL solid substrate further step of covalently attaching said trialkoxysilane compound with the solid substrate.

[0010]

[0011]

DETAILED DESCRIPTION OF THE INVENTION

(Embodiment 1) Water repellency in Embodiment 1 of the present invention
As shown in FIG. 1, the oil repellent treatment method is carried out by treating a solid substrate 1 having active hydrogen on the surface of glass, metal, metal oxide, ceramic, polymer, etc. with a tri-silane containing a mono- or ditrichlorosilane compound stable in air. It is immersed in a solution of an alkoxysilane compound, taken out of the solution, dried in air to remove the solvent, and subsequently heat treated. A silane compound having a fluoroalkyl group is conjugated to the surface of a solid substrate to form a high density. In the initial stages of drying and heat treatment of the solid substrate, the mono- or ditrichlorosilane compound reacts with the active hydrogen on the surface of the solid substrate, and the generated hydrogen chloride is used to react the alkoxysilane to silanol (shown below). Further, the reaction between silanol and active hydrogen on the surface of the solid substrate (see FIG. 1) is promoted, and a silane compound having a fluoroalkyl group is conjugated to the surface of the solid substrate to form a high density.

[0012]

[Chemical 1]

Examples of the solid substrate having active hydrogen on the surface which can be used in the present invention include glass materials such as lithium glass, soda glass, silica glass, borosilicate glass and lead glass, iron, aluminum, copper, Metal and metal oxide materials such as stainless steel and alumite, ceramic materials such as alumina, barium titanate, ferrite, silicon nitride and indium oxide, and polymer materials such as polyvinyl alcohol, polyimide and polyamide can be used.

When a mono- or ditrichlorosilane compound and a trichlorosilane compound which are unstable in air are added to a solution of a trialkoxysilane compound, the chlorosilane compound reacts with water in the air before reacting with the substrate. Hydrogen chloride is generated, the trialkoxysilane compound turns into silanol in the solution, and the polymerization further proceeds. Therefore, the pot life of the solution becomes extremely short, which is not suitable for mass production.

Of monochlorosilane compounds which are stable in air
For example, CH₃Si (OCH₃) ₂Cl, C₂H_FiveSi
(OCH₃)₂Cl, C₃H₇Si (OCH₃)₂Cl, C_Four
H₉Si (OCH₃)₂Cl, C_FiveH₁₁Si (OCH₃)₂C
l, C₆H₁₃Si (OCH₃)₂Cl, C₈H₁₇Si (OC
H₃)₂Cl, C_TenH_{twenty one}Si (OCH₃)₂Cl, C₁₂H_{2 Five}
Si (OCH₃)₂Cl, C₁₄H₂₉Si (OCH₃)₂C
l, C₁₆H₃₃Si (OCH₃)₂Cl, C₁₈H₃₇Si (O
CH₃)₂Cl, CH₃Si (OC₂H_Five)₂Cl, CF₃C₂
H_FourSi (OCH₃)₂Cl, C₂F_FiveC₂H_FourSi (OC
H₃)₂Cl, C₃F₇C₂H_FourSi (OCH₃)₂Cl, C_Four
F₉C₂H_FourSi (OCH₃)₂Cl, C₆F₁₃C₂H_FourSi
(OCH₃)₂Cl, C₈F₁₇C₂H_FourSi (OCH₃)₂C
l, Si (OCH ₃)₃Cl etc. can be raised.

Further, a dichlorosilane compound which is stable in air is used.
Examples of products include CH₃Si (OCH₃) Cl₂, C₂H_Five
Si (OCH₃) Cl₂, C₃H₇Si (OCH₃) Cl₂,
C_FourH₉Si (OCH₃) Cl₂, C₆H₁₃Si (OCH₃)
Cl₂, C₈H₁₇Si (OCH₃) Cl₂, C_TenH_{twenty one}Si
(OCH₃) Cl₂, C₁₂H_{twenty five}Si (OCH₃) Cl₂, C
₁₄H₂₉Si (OCH₃) Cl₂, C₁₆H₃₃Si (OC
H₃) Cl₂, C₁₈H₃₇Si (OCH₃) Cl₂, (CH₃
O)₂SiCl₂, (C₂H_FiveO)₂SiCl₂, (C₃H
₇O)₂SiCl₂, (C_FourH₉O)₂SiCl₂, (C₆H₁₃
O)₂SiCl₂, (C₈H₁₇O)₂SiCl₂, (C_TenH
_{twenty one}O)₂SiCl₂, (C₁₂H_{twenty five}O)₂SiCl₂, (C₁₄
H₂₉O)₂SiCl₂, (C₁₆H₃₃O)₂SiCl₂, (C
₁₈H₃₇O)₂SiCl₂, (CF₃O)₂SiCl₂, (C₂
F_FiveO)₂SiCl₂, (C₃F₇O)₂SiCl₂, (C_FourF
₉O)₂SiCl₂, (C₆F₁₃O)₂SiCl₂, (C₈F
₁₇O)₂SiCl₂And so on.

Examples of trialkoxysilane compounds include CF ₃ C ₂ H ₄ Si (OCH ₃ ) ₃ and C ₂ F ₅ C ₂ H ₄ Si.
(OCH ₃ ) ₃ , C ₃ F ₇ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₄ F ₉
C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₆ F ₁₃ C ₂ H ₄ Si (OC
_{H 3) 3, C 8 F} 17 C 2 H 4 Si (OCH 3) 3, CF 3 C 2 H 4
Si (OC ₂ H ₅ ) ₃ , C ₂ F ₅ C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ ,
_{C 3 F 7 C 2 H 4} Si (OCH 3) 3, C 4 F 9 C 2 H 4 Si (O
_{C 2 H 5) 3, C} 6 F 13 C 2 H 4 Si (OC 2 H 5) 3, C 8 F 17
C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ C ₆ H ₄ Si (OCH
₃ ) ₃ , etc. can be raised.

The concentration of the trialkoxysilane compound solution is preferably 0.1 to 10 wt%. When it is 0.1 wt% or less, the water / oil repellency of the treated substrate is insufficient. Also,
If it is 10 wt% or more, if it is formed on a glass substrate, it may become cloudy white and a transparent water / oil repellency treatment may not be possible.

The mono- or ditrichlorosilane compound has a weight ratio of 0.
1 to 1.0 is desirable. If it is less than 0.1, the effect of adding the mono- or ditrichlorosilane compound cannot be obtained. Also,
Even if 1.0 or more is added, the reactivity of the trialkoxysilane compound is not different from the case where 1.0 is added.

As the solvent, alcohol solvents such as methanol and ethanol and perfluoroalkanes such as octadecafluorooctane are desirable.

After the solid substrate is taken out of the solution and dried to remove the solvent, the solid substrate is put in air for 5 to 30 times.
Just leave it for a minute. If it is 5 minutes or less, the solvent may not be removed, and if it is left for 30 minutes, the solvent is almost completely removed.

The condition for heat treatment of the solid substrate is 50 to 50.
Treatment at 200 ° C. for 10 to 60 minutes is desirable. When the heat treatment temperature is 50 ° C. or lower, the reaction may not proceed and the treated substrate may have insufficient water / oil repellency. 200 ° C
Even in the above cases, the trialkoxysilane compound may be vaporized before reacting with the substrate, and the water-repellent / oil-repellent property of the treated substrate may become insufficient. Processing time is 1
If it is 0 minutes or less, the reaction may not be completed and the water / oil repellency of the treated substrate may be insufficient. If treated for 60 minutes,
The reaction is almost complete and no further treatment is necessary.

(Embodiment 2) A water / oil repellent treatment method according to a second embodiment of the present invention is a method in which a solid substrate having active hydrogen on the surface of glass, metal, metal oxide, ceramic, polymer, etc. It is immersed in a solution of a trialkoxysilane compound containing an amine compound, taken out of the solution, dried in air to remove the solvent, and subsequently heat-treated to give an alkyl group or fluoroalkyl group on the surface of the substrate. A silane compound having a group is conjugated to form a high density. When drying the solvent in air,
Water in the air reacts with the organic amine compound to form hydroxyl ions. This hydroxide ion promotes the reaction of the alkoxyl group of the trialkoxysilane compound to become a silanol group, and as a result, a silane compound having an alkyl group or a fluoroalkyl group is formed at high density.

Organic amine compound used in the present embodiment
Examples of products include CH₃NH₂, C₂H_FiveNH₂, C₃H₇N
H₂, C_FourH₉NH₂, C_FiveH₁₁NH₂, C₆H₁₃NH₂, C₈
H₁₇NH, NH₂C₂H_FourNH₂, NH₂C₃H₆NH₂, NH
₂C_FourH₈NH₂, NH₂C₆H₁₂NH₂, (CH₃O)₃Si
C₃H₆NH₂, (C₂H_FiveO)₃SiC₃H₆NH₂, (CH ₃
O)₃SiC₃H₆NHC₂H_FourNH₂, (C₂H_FiveO)₃Si
C₃H₆NHC₂H_FourNH₂, (CH₃O)₂Si (CH₃) C
₃H₆NHC₂H_FourNH₂, (CH₃O)₃SiC₃H₆NHC₆
H_FiveAnd so on.

The concentration of the trialkoxysilane compound solution is preferably 0.1 to 10 wt%. If the content is 0.1 wt% or less, the water / oil repellency of the treated substrate is insufficient. Further, if it is 10 wt% or more, if it is formed on a glass substrate,
It may be cloudy white and transparent and may not be water and oil repellent. The amine compound is a trialkoxysilane compound 1
The weight ratio is preferably 0.1 to 1.0. Below 0.1,
The effect of adding the amine compound does not appear. Further, even if 1.0 or more is added, the reactivity of the trialkoxysilane compound is not different from the case where 1.0 is added.

As the solvent, alcohol solvents such as methanol and ethanol and perfluoroalkanes such as octadecafluorooctane are desirable.

After removing the solid substrate from the solution, it is dried to remove the solvent.
Just leave it for a minute. If it is 5 minutes or less, the solvent may not be removed, and if it is left for 30 minutes, the solvent is almost completely removed.

The conditions for heat treatment of the solid substrate are 50 to 50.
Treatment at 200 ° C. for 10 to 60 minutes is desirable. When the heat treatment temperature is 50 ° C. or lower, the reaction may not proceed and the treated substrate may have insufficient water / oil repellency. 200 ° C
Even in the above cases, the trialkoxysilane compound may be vaporized before reacting with the substrate, and the water-repellent / oil-repellent property of the treated substrate may become insufficient. Processing time is 1
If it is 0 minutes or less, the reaction may not be completed and the water / oil repellency of the treated substrate may be insufficient. If treated for 60 minutes,
The reaction is almost complete and no further treatment is necessary.

(Examples) Next, specific examples of the present invention will be described.

Example 1 A 1 L beaker was charged with 1 L of methanol, 10 g of C ₈ F ₁₇ C ₂ H ₄ Si (OCH ₃ ) ₃ and C
After adding 1 g of H ₃ Si (OCH ₃ ) ₂ Cl and stirring well, a lithium glass (crystallized glass) substrate having a size of 5 cm × 5 cm × 0.3 mm is immersed. After 10 seconds, the glass substrate is taken out, air-dried in air for 10 minutes,
A sample was prepared by heat treatment for 20 minutes in an oven set to 150 ° C.

Example 2 CH ₃ Si (OC) of Example 1
A similar experiment was conducted by changing H ₃ ) ₂ Cl to (C ₄ H ₉ O) ₂ SiCl ₂ .

(Example 3) CH ₃ Si (OC) of Example 1
A similar experiment was conducted by changing H ₃ ) ₂ Cl to CH ₃ Si (OCH ₃ ) Cl ₂ .

Example 4 A 1 L beaker was charged with 1 L of methanol, 10 g of C ₈ F ₁₇ C ₂ H ₄ Si (OCH ₃ ) ₃ and C ₈
Add 1 g of H ₁₇ NH ₂ and stir well.
Immerse a m × 5 cm × 0.3 mm lithium glass (crystallized glass) substrate. After 10 seconds, the glass substrate was taken out, naturally dried in air for 10 minutes, and then heat-treated in an oven set at 150 ° C. for 20 minutes to prepare a sample.

(Example 5) A similar experiment was conducted by changing C ₈ H ₁₇ NH ₂ of Example 4 to (CH ₃ O) ₃ SiC ₃ H ₆ NH ₂ .

(Reference Example) CH ₃ Si in Example 1
A sample was prepared without adding (OCH ₃ ) ₂ Cl.

The contact angles of water and salad oil on the surfaces of the substrates prepared in Examples 1 to 5 and Reference Example were measured. Next, 1 ml of a mixture of sugar and soy sauce (weight ratio 1: 1) was dropped on the surface of the substrate and heated in an oven at 250 ° C. for 5 minutes,
Burnt dirt from sugar and soy sauce formed. Next, it was reciprocated 20 times with a force of ² kgw / cm ^{2 with} a dry tissue to remove scorched dirt. This experiment was repeated to examine how many cycles it was possible to wipe off the dirt. The results are shown in Table 1 below.

[0037]

[Table 1]

In the samples obtained by the present invention, the contact angle with water was 100 degrees or more. Moreover, the contact angle with respect to the salad oil showed a value of 60 degrees or more.
On the other hand, in the sample of Reference Example, the contact angle with water was 100 degrees or less, and the contact angle with salad oil was 60 degrees or less.

Further, the number of wipeable stains with sugar-soy sauce scorching was 5 times in the samples of the reference examples, but in the present invention, it was 50 times in the samples of all the examples.

[0040]

As described above, according to the present invention, it is advantageous that the surface of a solid substrate having active hydrogen on the surface can be made a surface having a large contact angle, water and oil repellency and excellent durability. The effect is obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a reaction of a trialkoxysilane with a substrate having active hydrogen using a hydrogen chloride catalyst.

[Explanation of symbols]

1 Solid substrate

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C23C 22/00-22/86

Claims (3)

(57) [Claims] And 1. A stable mono- or Axis Roroshi <br/> orchid compounds in air, in a solution containing a fluoroalkyl trialkoxysilane compound, immersing the solid substrate having an active hydrogen on the surface, A water-repellent / oil-repellent treatment method, which comprises: drying the immersed solid substrate to remove a solvent; and further heat-treating the solid substrate to covalently bond the trialkoxysilane compound to the solid substrate. 2. A water- repellant oil treatment method according to claim 1, stable mono- or Axis Roroshi <br/> run compound in air is characterized by containing an alkyl group or an alkoxyl group. 3. An alkylamine and a fluoroalkyl group
In a solution containing a trialkoxy compound having
A step of immersing the solid substrate having active hydrogen on the surface; drying the immersed solid substrate to remove the solvent; and further heat treating the solid substrate to covalently bond the trialkoxysilane compound to the solid substrate. A water / oil repellent treatment method including the step of: