JPH0532953A - Surface-treating agent - Google Patents

Abstract

PURPOSE:To obtain the subject treating agent having the properties of both fluoroalkyl compound and silicon compound and exhibiting excellent water and oil repellency, surface lubricity, etc., by using a component selected from an organofluorosilicone compound, its hydrolyzed product, etc., as an active component. CONSTITUTION:The objective treating agent contains an active component selected from the compound of formula I [R1 and R2 are 1-10C alkyl, alkoxy or alkylcarbonyloxy; RF is (CF2)n1 X (n1 is 1-10; X is H, F or Cl) or group of formula II (n2 is 0-8); m1 is 1-10; m2 is 1-5 (e.g. the compound of formula III, formula IV, etc.), its hydrolyzate, its hydrolytic condensation product and their mixture. The compound of formula I can be produced by reacting a compound of formula V with a compound of formula VI.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an organofluorosilicone type surface treatment agent.

[0002]

2. Description of the Related Art A compound containing a fluoroalkyl group in an organic compound has been attracting attention as a compound having useful properties such as light resistance, water and oil repellency, and physiological activity.

Conventionally, as a surface treatment agent for forming a film on the surface of a base material to impart properties such as protection of the base material, cosmetic properties, water and oil repellency, insulation properties, releasability and antifouling property, A fluororesin having a fluoroalkyl group such as a fluoroacrylate polymer is often used. However, the fluororesin has a problem that it has poor adhesion to inorganic materials such as metal, glass and cement, and various organic materials such as plastics and base materials.

On the other hand, in order to improve the adhesion, JP-A-59-140280 and the like propose a fluoroalkyl group-containing silicone compound. However, the silicone-based compound has a drawback that sufficient adhesion is not yet obtained, and further the water and oil repellency is deteriorated. Therefore, a surface treatment that is excellent in water and oil repellency and adhesion at the same time. The development of agents is desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a surface treating agent which is excellent in adhesion to inorganic materials and organic materials and is also excellent in water and oil repellency.

[0006]

According to the present invention, an organofluorosilicon compound represented by the following general formula (2) (hereinafter referred to as organosilicon compound 1), its hydrolyzate, its hydrolyzed condensate, and Provided is a surface treatment agent containing an active ingredient selected from the group consisting of these mixtures.

[0007]

[Chemical 2]

The present invention will be described in more detail below.

One of the active ingredients in the surface treatment agent of the present invention
The organofluorosilicon compound used as one is the organosilicon compound 1 represented by the general formula 2. In the organosilicon compound 1, when R ₁ or R _{2 has} a carbon number of 11 or more, m ₁ exceeds 10, or m ₂ exceeds 5, production is difficult, and n ₁
When it exceeds 10 or when n ₂ exceeds 8, it cannot be used because the solubility in a solvent decreases.

In the organosilicon compound 1, the applicable RF, namely,-(CF ₂ ) n ₁ X or the following general formula 3 is specifically listed. F ₃ C--, F (CF ₂ ) _{2
-, F (CF 2) 3} -, F (CF 2) 4 -, F (CF 2)
_{5 -, F (CF 2)} 6 -, F (CF 2) 7 -, F (CF 2) 8
_{-, F (CF 2) 9} -, F (CF 2) 10 -, HCF 2 -, H
_{(CF 2) 2 -, H} (CF 2) 3 -, H (CF 2) 4 -, H
(CF ₂ ) ₅ −, H (CF ₂ ) ₆ −, H (CF ₂ ) ₇ −, H
(CF ₂ ) ₈ −, H (CF ₂ ) ₉ −, H (CF ₂ ) ₁₀ −, C
_{lCF 2 -, Cl (CF 2} ) 2 -, Cl (CF 2) 3 -, C
l (CF ₂ ) ₄ −, Cl (CF ₂ ) ₅ −, Cl (CF ₂ ).
_{6 -, Cl (CF 2)} 7 -, Cl (CF 2) 8 -, Cl (C
F ₂ ) ₉ −, Cl (CF ₂ ) ₁₀ −, the following chemical formulas 4, 5, 5, 6, 7, 8, 9 and 10, 11 and 12
Is.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[0013]

[Chemical 5]

[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

[Chemical 8]

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical formula 12]

Specific examples of the organosilicon compound 1 include those represented by the following structural formulas 13, 14, and 15.
6, chemical formula 17, chemical formula 18, chemical formula 19, chemical formula 20, chemical formula 21, chemical formula 2
2, chemical formula 23, chemical formula 24, chemical formula 25, chemical formula 26, chemical formula 27, chemical formula 28
And the like (provided that m in the above structural formula is
₁ represents an integer of ₁ to 10 and m ₂ represents an integer of 1 to 5). The average molecular weight of the organosilicon compound 1 is 50.
It is preferably in the range of 0 to 10,000.

[0022]

[Chemical 13]

[0023]

[Chemical 14]

[0024]

[Chemical 15]

[0025]

[Chemical 16]

[0026]

[Chemical 17]

[0027]

[Chemical 18]

[0028]

[Chemical 19]

[0029]

[Chemical 20]

[0030]

[Chemical 21]

[0031]

[Chemical formula 22]

[0032]

[Chemical formula 23]

[0033]

[Chemical formula 24]

[0034]

[Chemical 25]

[0035]

[Chemical formula 26]

[0036]

[Chemical 27]

[0037]

[Chemical 28]

To prepare the organosilicon compound 1,
It can be easily obtained by reacting a difluoroalkanoyl peroxide represented by the following general formula 29 with a vinyl group-containing organosilicon compound represented by the following general formula 30.

[0039]

[Chemical 29]

[0040]

[Chemical 30]

As the difluoroalkanoyl peroxide represented by the general formula 29, the organic silicon compound 1
In the above, there may be mentioned compounds and the like in which RF (fluoroalkyl group) specifically listed is appropriately selected, and specific examples thereof include diperfluoro-2-methyl-peroxide.
3-oxahexanoyl, diperfluoro-2 peroxide,
5-Dimethyl-3,6-dioxanonanoyl, diperfluoro-2,5,8-trimethyl-3,6,9-peroxide
Preferable examples include trioxadodecanoyl, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide and the like. In the general formula 29, n
_{When 1} exceeds 10, or n ₂ exceeds 8, the solubility in a solvent decreases, and therefore it cannot be used.

Examples of the vinyl group-containing organosilicon compound represented by the general formula 30 include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldiacetyloxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, 3-methacryloxypropyltriacetyloxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltrimethylsilane, 3-methacryloxypropyltri-t-butoxysilane, Preferable examples include 3-methacryloxypropylethoxydiethylsilane and 3-methacryloxypropyldiethylmethylsilane.

When the difluoroalkanoyl peroxide and the vinyl group-containing organosilicon compound are reacted, the charging molar ratio of the difluoroalkanoyl peroxide and the vinyl group-containing organosilicon compound is preferably 1: 1.0. It is desirable to be in the range of from 10.0 to 10.0, and particularly preferably in the range of from 1: 1.2 to 5.0. When the charged molar ratio of the vinyl group-containing organosilicon compound is less than 1.0, a large amount of the decomposition product of the difluoroalkanoyl peroxide is generated, and it becomes difficult to isolate the target organofluorosilicone compound. Further, if it exceeds 10, the yield is lowered, which is not preferable. The reaction can be carried out at normal pressure, and the reaction temperature is -20 to +1.
It is preferably in the range of 50 ° C., particularly preferably 0 to
It is in the range of 100 ° C. When the reaction temperature is lower than -20 ° C, the reaction takes a long time, and when it exceeds + 150 ° C, the pressure during the reaction becomes high and the reaction operation becomes difficult, which is not preferable. Further, the reaction time may be in the range of 30 minutes to 20 hours, and industrially it is preferably in the range of 3 to 10 hours.

To prepare the organosilicon compound 1,
Under the various reaction conditions, by reacting the difluoroalkanoyl peroxide and the vinyl group-containing organosilicon compound, it can be obtained in a one-step reaction, the handling and reaction of the difluoroalkanoyl peroxide, more It is preferable to use a solvent for smooth operation. A halogenated aliphatic solvent is particularly preferable as the solvent, and specific examples thereof include methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, and 1,2-dibromohexa. Fluoropropane, 1,2-dibromotetrafluoroethane, 1,1
-Difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,
1,3-tetrachlorotetrafluoropropane, 1,
1,1-trichloropentafluoropropane, 1,1,
2-Trichlorotrifluoroethane or the like can be used, and industrially, 1,1,2-trichlorotrifluoroethane can be preferably mentioned. When the solvent is used, the concentration of the difluoroalkanoyl peroxide in the whole solution is preferably 0.5 to 30% by weight.

The reaction product obtained by the above reaction can be purified by a known method such as distillation or column chromatography.

The hydrolyzate and hydrolyzed condensate of the organosilicon compound 1 which can be used as an active ingredient in the surface treating agent of the present invention are the above-mentioned organosilicon compound 1
Is a compound obtained by dissolving in a mixed solvent of a fluorochlorohydrocarbon containing water and an alkyl alcohol, or an alkyl alcohol solvent containing water or an alcohol solvent, and hydrolyzing or hydrolyzing and condensing. is there. Examples of the fluorinated hydrocarbon include 1,1,2-trichlorotrifluoroethane, 1,2, -difluorotetrachloroethane,
Benzotrifluoride and the like can be preferably used, and as the alkyl alcohol, ethanol, isopropanol, butanol and the like can be preferably used. The mixing ratio of the mixed solvent is not particularly limited as long as it can dissolve the organosilicon compound 1, and the content of water is 1 to 30% by weight based on the mixed solvent or the solvent. Preferably.
That is, in order to use the surface treatment agent of the present invention, it is preferable to use the above-mentioned active ingredient after diluting it in the above-mentioned solvent. Can be a hydrolyzate and a hydrolyzed condensate.

The concentration of the active ingredient in the solution is 0.00
It is preferably in the range of 5% by weight to 20% by weight. When the concentration is less than 0.005% by weight, the film thickness of the surface treatment agent is thin and the water and oil repellency is lowered. When it exceeds 20% by weight, the film thickness is increased but the water and oil repellency is not improved. It is not preferable because the uniformity of the surface is deteriorated and peeling easily occurs.

As the treatment method when the surface treatment agent of the present invention is used, known coating methods such as brush coating, spray coating, roll coating, spin coating and dip coating are used. be able to. Further, the treatment temperature may be room temperature, but the temperature condition may be set to an arbitrary condition for the purpose of controlling the film formation rate. Furthermore, the film thickness of the surface treatment agent is preferably in the range of several Å to several tens of μ, and any film thickness can be selected depending on the concentration, the processing temperature, the rotation speed in the spin coat method, the pulling speed in the dip coat method, and the like. Can be prepared.

[0049]

Since the surface treating agent of the present invention has the properties of both a fluoroalkyl group and a silicon compound, it is excellent in water and oil repellency, adhesion to a substrate, low surface adhesion, surface lubricity and the like. .. Therefore, fabrics, clothing, furniture, drapes, rugs, paper bags, cardboard containers, trunks, handbags,
Shoes, jacket, raincoat, tent, carpet,
Wood and asbestos wall materials, bricks, concrete, floors, wall tiles, glass, stone, wood, plaster, wallpaper and exterior wall materials,
Surface treatment agent for bath wall materials, surface treatment agent for painted or unpainted metal such as appliances and car bodies, surface treatment agent with excellent adhesion to iron, stainless steel, duralumin, etc., polyester resin , Urethane resin, A
A surface treatment agent that imparts low adhesion to the surface to facilitate water and oil repellency and mold release of plastics such as BS resin, vinyl chloride resin, epoxy resin, phenol resin, polyimide resin, and cellophane resin, As a surface treatment agent that has an anti-icing effect on airplanes, a surface treatment agent that has a frying pan baking prevention effect, and as a surface solid lubricant for medical tapes, floppy disks, hard disks, etc. and medical materials, etc. It can be widely used and is useful as a surface treatment agent that imparts water and oil repellency, antifouling property, non-adhesiveness, lubricity and the like.

[0050]

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

[0051]

Example 1 2.5 g (10 mmol) of 3-methacryloxypropyltrimethoxysilane was added to 4.4 g (6.% of diperfluoro-2-methyl-3-oxahexanoyl peroxide).
50 g of a 1,1,2-trichlorotrifluoroethane solution containing 7 mmol) was added, and the reaction was carried out at 30 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solvent was removed, and then distillation was carried out to obtain a mixture of organofluorosilicone compounds having a yield of 3.0 g and m represented by the following structural formula 31, in the range of 1 to 10. The average molecular weight of the obtained mixture was 990.

[0052]

[Chemical 31]

Then, the obtained compound was dissolved in 95% by weight aqueous ethanol solution to prepare a 1% by weight solution. Then, a stainless plate (SUS304) and a glass plate were dipped in the obtained solution for 3 minutes and dried at 150 ° C. for 15 minutes, and the contact angle with water and dodecane was measured. The results are shown in Table 1.

A polyimide film (Ube Industries, Ltd., trade name "Upilex, 50S") and a cellulose diate film (Fuji Photo Film Co., Ltd., trade name "DE250") were added to the solution for 3 minutes. After dipping, it was dried at 120 ° C. for 1 hour, and the contact angle with water and dodecane was measured. The results are shown in Table 2.

Further, on the glass plate which has been subjected to the surface treatment,
After strongly sticking cellophane adhesive tape (trade name "Cellotape", manufactured by Nichiban Co., Ltd.), it was rapidly peeled in 90 ° direction, and the contact angle to water and dodecane was measured for the peeled portion, and the adhesion test was conducted. Was done. The results are shown in Table 3.
Shown in.

Furthermore, the surface-treated stainless plate, glass plate, polyimide film and cellulose diacetate film were treated with 1,1,2-trichlorotrifluoroethane (F-113), methyl ethyl ketone (ME).
K), ethyl acetate (AcOEt), acetone (AcM
After being immersed in e) for 24 hours, the contact angles with water and dodecane were measured. The results are shown in Table 4.

The resulting solution was applied to the inner surface of an aluminum cup and heated to 100 ° C. Then, a mixture of 10 g of "Coronet 4090" (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 1 g of methylenebisorthochloroaniline as a curing agent was poured into the obtained cup, and a hook was set as a handle for the molded product It was heat-cured at 120 ° C. for 1 hour. After the heating was completed, the hook was pulled and the releasability was evaluated. The results are shown in Table 5.

[0058]

Example 2 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl, diperfluoro-2,5 peroxide
-The reaction was performed in the same manner as in Example 1 except that dimethyl-3,6-dioxanonanoyl was used, and a compound represented by the following structural formula 32 in which m was in the range of 1 to 10 was obtained in a yield of 3.8.
Obtained in g. The average molecular weight of the obtained compound was 1460.

[0059]

[Chemical 32]

Then, about the obtained compound, Example 1
The same evaluation as was done. The results are shown in Table 1, Table 2, Table 3, and Table 4.
And shown in Table 5.

[0061]

Example 3 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl, diperfluoro-2 peroxide,
The reaction was performed in the same manner as in Example 1 except that 5,8-trimethyl-3,6,9-trioxadodecanoyl was used, and a compound represented by the following structural formula 33 in which m was in the range of 1 to 10 was obtained. Obtained in a yield of 4.2 g. The average molecular weight of the obtained compound was 1860.

[0062]

[Chemical 33]

Next, regarding the obtained compound, Example 1
The same evaluation as was done. The results are shown in Table 1, Table 2, Table 3, and Table 4.
And shown in Table 5.

[0064]

Example 4 Diperfluoro-2-methyl-3-peroxide
The reaction was performed in the same manner as in Example 1 except that oxahexanoyl was replaced with diperfluorobutyryl peroxide, and the yield of the compound represented by the following structural formula 34 in which m was in the range of 1 to 10 was 2.8 g. Obtained. The average molecular weight of the obtained compound was 796.

[0065]

[Chemical 34]

Then, about the obtained compound, Example 1
The same evaluation as was done. The results are shown in Table 1, Table 2, Table 3, and Table 4.
And shown in Table 5.

[0067]

Example 5 Diperfluoro-2-methyl-3-peroxide
The reaction was performed in the same manner as in Example 1 except that oxahexanoyl was replaced with diperfluoroheptanoyl peroxide, and the yield of the compound represented by the following structural formula 35 in which m was in the range of 1 to 10 was 4.0 g. Obtained. The average molecular weight of the obtained compound was 995.

[0068]

[Chemical 35]

Then, about the obtained compound, Example 1
The same evaluation as was done. The results are shown in Table 1, Table 2, Table 3, and Table 4.
And shown in Table 5.

[0070]

Comparative Example 1 The contact angle to water and dodecane was measured in the same manner as in Example 1 except that untreated stainless steel plate, glass plate, polyimide film and cellulose diacetate film were used. The results are shown in Tables 1 and 2.

[0071]

[Comparative Example 2] The polyimide film and the cellulose diacetate film used in Example 1 were converted to the following chemical formula 3
Silicon compound represented by 6 (Toshiba Silicon Co., Ltd.)
(Trade name: "TSL8257" manufactured by Mitsui Chemicals, Inc.) was subjected to a treatment for 3 minutes under a drying condition of 120 ° C. for 1 hour, and the contact angle to water and dodecane was measured. The results are shown in Table 2.

[0072]

[Chemical 36]

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

[Table 5]

From the results shown in Tables 1 and 2, it is understood that the base material whose surface is modified with the surface modifier of the present invention is excellent in water and oil repellency. Further, as is clear from the results shown in Tables 3 and 4, it is found that the adhesiveness to various substrates is excellent and the weather resistance to the solvent is also excellent. Further, as shown in Table 5, it can be seen that the low surface adhesion is also excellent.

Claims (1)

Claim: What is claimed is: 1. A component selected from the group consisting of an organofluorosilicone compound represented by the following general formula 1, a hydrolyzate thereof, a hydrolyzed condensate thereof and a mixture thereof. Surface treatment agent as an ingredient. [Chemical 1]