JPH04370187A - Surface treating agent - Google Patents

Abstract

PURPOSE:To obtain a surface treating agent, containing a specific fluoroalkyl group-containing silicone-based compound as an active component and excellent in water and oil repellency, substrate adhesion, low surface adhesion and surface lubricity, etc. CONSTITUTION:The objective surface treating agent containing a component selected from fluoroalkyl group-containing silicone compounds expressed by formula I [R is 1-10C alkyl, alkoxy or alkylcarbonyloxy; RF is (CF3)n1 X or formula II (X is H, F or Cl; n1 is an integer of 1-10; n2 is an integer of 0-8) ; x, y and z are integers of 0-3; m is 1, 2 or 3; (x+y+z) is 1, 2 or 3; (x+y+z+m) is 4; a, b and c are integer of 0-5 and (a+b+c) is an integer of 1-6] and/or their hydrolyzates (condensates) as an active component.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluoroalkyl group-containing silicone surface treatment agent.

0002

BACKGROUND OF THE INVENTION Organic compounds containing fluoroalkyl groups have attracted attention as compounds that exhibit useful properties such as light resistance, water and oil repellency, and physiological activity.

Conventionally, surface treatment agents that form a film on the surface of a substrate to impart properties such as protection, cosmetic properties, water and oil repellency, insulation, mold releasability, and stain resistance include: Fluororesins having fluoroalkyl groups, such as fluoroacrylate polymers, are often used. However, the fluororesin has problems such as poor adhesion to inorganic materials such as metals, glass, and cement, various plastics, and organic materials such as base materials.

On the other hand, in order to improve the adhesion, fluoroalkyl group-containing silicone compounds have been proposed in JP-A-59-140280 and other publications. However, the aforementioned silicone compounds have not yet achieved sufficient adhesion, and furthermore, they have the disadvantage of decreasing water and oil repellency.Therefore, surface treatment agents with excellent water and oil repellency and adhesion development is desired.

[0005]

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

[0006]

[Means for Solving the Problems] According to the present invention, a fluoroalkyl group-containing silicon compound represented by the following general formula 2 (hereinafter referred to as silicon compound 1), a hydrolyzate thereof, a hydrolysis condensate thereof, and Provided is a surface treatment agent whose active ingredient is a component selected from the group consisting of a mixture of the following.

[0007]

[Case 2]

The present invention will be explained in more detail below.

One of the active ingredients in the surface treatment agent of the present invention
The fluoroalkyl group-containing silicon compound used as one is silicon compound 1 represented by the general formula 2 above. In the silicon compound 1, the number of carbon atoms in R is 11
In the above cases, production is difficult, and when n1 exceeds 10 or when n2 exceeds 8, the solubility in solvents decreases, so that they cannot be used.

In addition, in the silicon compound 1, to specifically enumerate the applicable RF, namely -(CF2)n1X or the following general formula 3, F3C-,F(CF2
)2-, F(CF2)3-, F(CF2)4-, F(C
F2)5-, F(CF2)6-, F(CF2)7-, F
(CF2)8-, F(CF2)9-, F(CF2)10
-, HCF2-, H(CF2)2-, H(CF2)3-
, H(CF2)4-, H(CF2)5-, H(CF2)
6-, H(CF2)7-, H(CF2)8-, H(CF
2) 9-,H(CF2)10-,ClCF2-,Cl(
CF2)2-, Cl(CF2)3-, Cl(CF2)4
-, Cl(CF2)5-, Cl(CF2)6-, Cl(
CF2)7-, Cl(CF2)8-, Cl(CF2)9
-, Cl(CF2)10-, the following chemical formulas 4, 5, 6, 7, 8, 9, 10, 11, and 12.

[0011]

[Chemical formula 3]

0012

[C4]

[0013]

[C5]

[0014]

[C6]

[0015]

[C7]

[0016]

[Chemical formula 8]

[0017]

[Chemical formula 9]

[0018]

[Chemical formula 10]

[0019]

[Chemical formula 11]

[0020]

[Chemical formula 12]

Specific examples of the silicon compound 1 include the following structural formulas 13, 14, 15, and 16.
, Chemical 17, Chemical 18, Chemical 19, Chemical 20, Chemical 21, Chemical 22,
Chemical 23, Chemical 24, Chemical 25, Chemical 26, Chemical 27, Chemical 28, Chemical 29, Chemical 30, Chemical 31, Chemical 32, Chemical 33, Chemical 34, Chemical 3
5, Chemical 36, Chemical 37, Chemical 38, Chemical 39, Chemical 40, Chemical 41
, Chemical 42, Chemical 43, Chemical 44, Chemical 45, Chemical 46, Chemical 47,
Chemical 48, Chemical 49, Chemical 50, Chemical 51, Chemical 52, Chemical 53, Chemical 54, Chemical 55, Chemical 56, Chemical 57, Chemical 58, Chemical 59, Chemical 6
0 etc. can be preferably mentioned.

[0022]

[Chemical formula 13]

[0023]

[Chemical formula 14]

[0024]

[Chemical formula 15]

[0025]

[Chemical formula 16]

[0026]

[Chemical formula 17]

[0027]

[Chemical formula 18]

[0028]

[Chemical formula 19]

[0029]

[C20]

[0030]

[C21]

[0031]

[C22]

[0032]

[C23]

[0033]

[C24]

[0034]

[C25]

[0035]

[C26]

[0036]

[C27]

[0037]

[C28]

[0038]

[C29]

[0039]

[C30]

[0040]

[Chemical formula 31]

[0041]

[C32]

[0042]

[Chemical formula 33]

[0043]

[C34]

[0044]

[C35]

[0045]

[C36]

[0046]

[C37]

[0047]

[C38]

[0048]

[C39]

[0049]

[C40]

[0050]

[C41]

[0051]

[C42]

[0052]

[C43]

[0053]

[C44]

[0054]

[C45]

[0055]

[C46]

[0056]

[C47]

[0057]

[C48]

[0058]

[C49]

[0059]

[C50]

[0060]

[C51]

[0061]

[C52]

[0062]

[C53]

[0063]

[C54]

[0064]

[C55]

[0065]

[C56]

[0066]

[C57]

[0067]

[C58]

[0068]

[C59]

[0069]

[C60]

The silicon compound 1 can be easily prepared by reacting difluoroalkanoyl peroxide represented by the following general formula 61 with a vinyl group-containing organosilicon compound represented by the following general formula 62. Can be done.

[0071]

[C61]

[0072]

[C62]

The difluoroalkanoyl peroxide represented by the general formula 61 includes the RF (fluoroalkyl group) specifically listed in the silicon compound 1.
Specifically, for example, peroxide diperfluoro-2-methyl-3-
Oxahexanoyl, diperfluoro-2,5-peroxide
Dimethyl-3,6-dioxanonanoyl, diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide, diperfluorobutyryl peroxide,
Preferred examples include diperfluoroheptanoyl peroxide. Further, in the general formula 61, when n1 exceeds 10 or when n2 exceeds 8, the solubility in the solvent decreases.

In the phenyl group-containing organosilicon compound represented by the general formula 62, when R is an alkyl group, alkoxy group, or alkylcarbonyloxy group having 11 or more carbon atoms, it is difficult to manufacture. Specifically, the phenyl group-containing organosilicon compound includes, for example,
Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetyloxysilane, phenyltrimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiacetyloxysilane, diphenyldimethylsilane, triphenylmethoxysilane, triphenylethoxysilane, triphenyl Preferred examples include acetyloxysilane.

[0075] When the difluoroalkanoyl peroxide and the vinyl group-containing organosilicon compound are reacted, the molar ratio of the difluoroalkanoyl peroxide and the vinyl group-containing organosilicon compound is preferably 1:1.0. ~10.0, particularly preferably 1
: It is desirable to set it as the range of 1.2-5.0. If the charged molar ratio of the vinyl group-containing organosilicon compound is less than 1.0, a large amount of decomposed products of the difluoroalkanoyl peroxide will be generated, making it difficult to isolate the desired fluoroalkyl group-containing organosilicon compound. Moreover, if it exceeds 10, the yield will decrease, which is not preferable. In addition, the reaction can be carried out at normal pressure, and the reaction temperature is -20 to
It is preferably in the range of +150°C, particularly preferably in the range of 0 to 100°C. When the reaction temperature is less 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. Furthermore, the reaction time can be carried out in the range of 30 minutes to 20 hours, and industrially it is preferably in the range of 3 to 10 hours.

The silicon compound 1 can be prepared in one step by reacting the difluoroalkanoyl peroxide with the vinyl group-containing organosilicon compound under the various reaction conditions described above. It is preferable to use a solvent in order to more smoothly handle and react the difluoroalkanoyl peroxide. The solvent is particularly preferably a halogenated aliphatic solvent, and specific examples include methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, and 1,2-dibromohexane. 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 etc. can be used,
Particularly from an industrial standpoint, 1,1,2-trichlorotrifluoroethane is preferably mentioned. When the solvent is used, the concentration of the difluoroalkanoyl peroxide in the entire solution is preferably in the range of 0.5 to 30% by weight.

The reaction product obtained by the above reaction can be purified by known methods such as distillation and column chromatography.

Further, the hydrolyzate and hydrolyzed condensate of silicon compound 1, which can be used as an active ingredient in the surface treatment agent of the present invention, include the silicon compound 1,
It is a compound obtained by dissolving in a mixed solvent of a fluorinated chlorinated hydrocarbon containing water and an alkyl alcohol, or an alkyl alcohol solvent or an alcohol solvent containing water, and subjecting it to hydrolysis or hydrolytic condensation. . As the fluorinated chlorinated hydrocarbon, 1,1,2-trichlorotrifluoroethane, 1,2-difluorotetrachloroethane, benzotrifluoride, etc. can be preferably used, and as the alkyl alcohol, ethanol , isopropanol, butanol, etc. can be preferably used. The mixing ratio of the mixed solvent is not particularly limited as long as it can dissolve the silicon compound 1, and the water content is in the range of 1 to 30% by weight based on the mixed solvent or solvent. is preferable. That is, in order to use the surface treatment agent of the present invention, it is preferable to dilute the active ingredient in the solvent. In this case, even if only the silicon compound 1 is used as the active ingredient, a part or all of it may be used. It can be a hydrolyzate and a hydrolysis condensate.

[0079] The concentration of the active ingredient in the solution is 0.00
It is preferably in the range of 5% 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 decreases, and when it exceeds 20% by weight, the film thickness becomes thick but the water and oil repellency does not improve. This is not preferable because it reduces the uniformity of the surface and makes it easy to peel off.

[0080] As a treatment method when using the surface treatment agent of the present invention, known coating methods such as brush coating, spraying, roll coating, spin coating, and dip coating can be used. be able to. Further, the treatment temperature can be carried out at room temperature, but the temperature conditions can also be set to arbitrary conditions for the purpose of adjusting the film formation rate. Furthermore, the film thickness of the surface treatment agent is preferably in the range of several angstroms to several tens of microns, and any film thickness can be determined depending on the concentration, treatment temperature, rotation speed in spin coating, pulling speed in dip coating, etc. It is possible to prepare

[0081]

[Effects of the Invention] Since the surface treatment agent of the present invention has the characteristics of both a fluoroalkyl group and a silicon compound, it has excellent water and oil repellency, adhesion to substrates, low surface adhesion, surface lubricity, etc. . Therefore, textiles, clothing, furniture, hangings, rugs, paper bags, cardboard containers, trunks, handbags, shoes, jackets, raincoats, tents, carpets, wood and asbestos wall coverings, bricks, concrete, Surface treatment of flooring, wall tiles, glass, stone, wood, plaster, wallpaper, exterior wall materials, wall materials such as bath wall materials, surface treatment agents for various resins, medical materials, optical materials such as plastic lenses, etc. Surface treatment agents for painted or unpainted metals such as appliances and car bodies, surface treatment agents with excellent adhesion to iron, stainless steel, duralumin, etc., polyester resins, urethane resins, ABS resins, vinyl chloride resins , surface treatment agents that contribute to low adhesion on the surface of plastics such as epoxy resins and phenol resins to facilitate mold release, surface treatment agents that have an anti-icing effect on airplanes, etc.
It can be widely used as a surface treatment agent that prevents frying from burning, as well as a surface solid lubricant for magnetic tape, floppy disks, hard disks, etc., and has water and oil repellency, stain resistance, It is useful as a surface treatment agent that imparts non-stick properties, lubricity, etc. Furthermore, since the surface treatment agent of the present invention can be used at room temperature, it is possible to work easily.

[0082]

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

[0083]

[Example 1] Phenyltrimethoxysilane (2.97g
, 15 mmol), diperfluorobutyryl peroxide (
4.26 g, 6.7 mmol) of 1,1,2-trichlorotrifluoroethane solution was added thereto, and the reaction was carried out at 30° C. for 5 hours under a nitrogen atmosphere. After the reaction is complete,
The reaction solvent was removed, and then distillation was performed to obtain a fluoroalkyl group-containing silicon compound (mixture of meta and para forms) represented by the following structural formula 63 with a yield of 65%.

[0084]

[C63]

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

[0086] The obtained solution was also applied to the inner surface of an aluminum cup and heated to 100°C. Next, a mixture of 10 g of "Coronate 4090" (trade name, manufactured by Nippon Polyurethane Co., Ltd.) and 1 g of methylenebisorthochloroaniline as a hardening agent was injected into the resulting cup, and a hook was erected as a handle for the molded product. It was heated and cured at 120°C for 1 hour. After the heating was completed, the hook was pulled and the mold releasability was evaluated. The results are shown in Table 2.

[0087]

[Example 2] The reaction was carried out in the same manner as in Example 1 except that phenyltrimethoxysilane was replaced with diphenyldimethoxysilane, and a compound (mixture of meta and para forms) represented by the following structural formula 64 was obtained. The yield was 70%.

[0088]

[C64]

Next, regarding the obtained compound, Example 1
The same evaluation was conducted. The results are shown in Tables 1 and 2.

[0090]

[Example 3] The reaction was carried out in the same manner as in Example 1 except that diperfluorobutyryl peroxide was replaced with diperfluoro-2-methyl-3-oxadodecanoyl peroxide. A compound (mixture of meta and para forms) was obtained in a yield of 82%.

[0091]

[C65]

Next, regarding the obtained compound, Example 1
The same evaluation was conducted. The results are shown in Tables 1 and 2.

[0093]

[Example 4] The reaction was carried out in the same manner as in Example 1 except that diperfluorobutyryl peroxide was replaced with diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide. A compound represented by Chemical Formula 66 (a mixture of meta and para forms) was obtained in a yield of 88%.

[0094]

[C66]

Next, regarding the obtained compound, Example 1
The same evaluation was conducted. The results are shown in Tables 1 and 2.

[0096]

[Example 5] A reaction was carried out in the same manner as in Example 1 except that diperfluorobutyryl peroxide was replaced with diperfluoroheptanoyl peroxide. mixture) was obtained in a yield of 74%.

[0097]

[C67]

Next, regarding the obtained compound, Example 1
The same evaluation was conducted. The results are shown in Tables 1 and 2.

0099

[Example 6] The reaction was carried out in the same manner as in Example 1, except that diperfluorobutyryl peroxide was replaced with diperfluoro-2-methyl-3-oxanonanoyl peroxide and phenyltrimethoxysilane was replaced with diphenyldimethoxysilane. A compound represented by the following structural formula 68 (a mixture of meta and para forms) was obtained in a yield of 69%.

[0100]

[C68]

Next, regarding the obtained compound, Example 1
The same evaluation was conducted. The results are shown in Tables 1 and 2.

[0102]

[Example 7] Example except that diperfluorobutyryl peroxide was replaced with diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide, and phenyltrimethoxysilane was replaced with diphenyldimethoxysilane. The reaction was carried out in the same manner as in 1, and the compound represented by the following structural formula 69 (
A mixture of meta-form and para-form was obtained in a yield of 73%.

[0103]

[C69]

Next, regarding the obtained compound, Example 1
The same evaluation was conducted. The results are shown in Tables 1 and 2.

[0105]

[Example 8] The reaction was carried out in the same manner as in Example 1 except that diperfluorobutyryl peroxide was replaced with diperfluoroheptanoyl peroxide and phenyltrimethoxysilane was replaced with diphenyldimethoxysilane. Yield 79 of the indicated compound (mixture of meta and para forms)
Obtained in %.

[0106]

[C70]

Next, regarding the obtained compound, Example 1
The same evaluation was conducted. The results are shown in Tables 1 and 2.

[0108]

[Comparative Examples 1 and 2] Stainless steel plates and glass plates were treated in the same manner as in Example 1, except that phenyltrimethoxysilane (Comparative Example 1) and diphenyldimethoxysilane (Comparative Example 2) were used. I did it. The results are shown in Table 1 and Table 2.
Shown below.

[0109]

[Table 1]

[0110]

[Table 2]

From the results shown in Tables 1 and 2, it can be seen that the surface treatment agent of the present invention has excellent water and oil repellency and mold releasability.

Claims (1)

[Claims] 1. A surface treatment agent containing as an active ingredient a component selected from the group consisting of a fluoroalkyl group-containing silicone compound represented by the following general formula 1, a hydrolyzate thereof, a hydrolyzed condensate thereof, and a mixture thereof. . [Chemical formula 1]