JPH04296336A - Surface-treating agent - Google Patents

Abstract

PURPOSE:To obtain a surface-treating agent having excellent adhesivity to organic materials and exhibiting excellent water and oil repellency, antifouling property, non-tackiness, lubricity, etc., by using an organic silicon compound having fluoroalkyl group as an active component. CONSTITUTION:The objective surface-treating agent contains, as an active compound, an organic silicon compound having fluoroalkyl group and expressed by formula V [Y is group of formula VI, formula VII or formula VIII (m1 is integer of 1-10; m2 is integer of 0-9)] (or its hydrolyzate, hydrolytic condensate or their mixture) obtained by polymerizing (A) a difluoroalkanoyl peroxide of formula I [RF is group of formula II or formula III (X is H, F or Cl; n1 is integer of l-10; n2 is integer of 0-8)] and (B) an organic silicon compound having vinyl group and expressed by formula IV (R is 1-10C alkyl, alkoxy or alkylcarbonyloxy group; m3 is integer of 1-10) preferably at a molar ratio of 1:(1-10) at -20 to +150 deg.C in a halogenated aliphatic solvent (e.g. 1,1,2- trichlorotrifluoroethane).

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 base materials such as metals, glass, inorganic materials such as cement, various plastics, and organic 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-based compounds do not have sufficient adhesion to the substrate, and furthermore, they have the disadvantage of reduced water and oil repellency. At present, surface treatment agents are not yet known.

[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 organosilicon compound represented by the following general formula 2 (hereinafter referred to as organosilicon compound 1), a hydrolyzate thereof, a hydrolyzed condensate thereof Provided is a surface treatment agent containing as an active ingredient an ingredient selected from the group consisting of: and a mixture thereof.

[0007]

[Case 2]

The present invention will be explained in more detail below.

The surface treatment agent of the present invention is characterized in that the active ingredient is a component selected from the group consisting of a specific organosilicon compound, its hydrolyzate, its hydrolyzed condensate, and a mixture thereof.

The specific organosilicon compound used as an active ingredient in the surface treatment agent of the present invention is organosilicon compound 1 represented by the general formula 2 above. In the organosilicon compound 1, if R is an alkyl group, alkoxy group, or alkylcarbonyloxy group having 11 or more carbon atoms, if m1 exceeds 10 or m2 exceeds 9, it is difficult to manufacture; If n2 exceeds 10 or n2 exceeds 8, the solubility in a solvent decreases, and therefore, it cannot be used.

In addition, in the organosilicon compound 1, the applicable RF, namely -(CF2)n1X or the following general formula 3 is specifically enumerated: F3C-,F(CF
2) 2-, F(CF2)3-, F(CF2)4-, F(
CF2)5-, F(CF2)6-, F(CF2)7-,
F(CF2)8-, F(CF2)9-, F(CF2)1
0-, HCF2-, H(CF2)2-, H(CF2)3
-, H(CF2)4-, H(CF2)5-, H(CF2
)6-, H(CF2)7-, H(CF2)8-, H(C
F2)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 formula 4, chemical formula 5,
These are chemical formula 6, chemical formula 7, chemical formula 8, chemical formula 9, chemical formula 10, chemical formula 11, and chemical compound 12.

0012

[Chemical formula 3]

[0013]

[C4]

[0014]

[C5]

[0015]

[C6]

[0016]

[C7]

[0017]

[Chemical formula 8]

[0018]

[Chemical formula 9]

[0019]

[Chemical formula 10]

[0020]

[Chemical formula 11]

[0021]

[Chemical formula 12]

Specific examples of the organosilicon compound 1 include the following structural formulas 13, 14, 15, and 1.
6, 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 35, Chemical 36, Chemical 37, Chemical 38, Chemical 39, Chemical 40, Chemical 4
1, 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 60, Chemical 61, Chemical 62, Chemical 63, Chemical 64, Chemical 65, Chemical 6
6, Chemical 67, Chemical 68, Chemical 69, Chemical 70, Chemical 71, Chemical 72
, 73, 74, 75, 76, 77, 78,
Preferably, compounds 79, 80, 81, 82, 83, 84, etc. can be mentioned (however, in the above structural formula, m1 represents an integer of 1 to 10, and m2 represents an integer of 0 to 9. )
.

[0023]

[Chemical formula 13]

[0024]

[Chemical formula 14]

[0025]

[Chemical formula 15]

[0026]

[Chemical formula 16]

[0027]

[Chemical formula 17]

[0028]

[Chemical formula 18]

[0029]

[Chemical formula 19]

[0030]

[C20]

[0031]

[C21]

[0032]

[C22]

[0033]

[C23]

[0034]

[C24]

[0035]

[C25]

[0036]

[C26]

[0037]

[C27]

[0038]

[C28]

[0039]

[C29]

[0040]

[C30]

[0041]

[Chemical formula 31]

[0042]

[C32]

[0043]

[Chemical formula 33]

[0044]

[C34]

[0045]

[C35]

[0046]

[C36]

[0047]

[C37]

[0048]

[C38]

[0049]

[C39]

[0050]

[C40]

[0051]

[C41]

[0052]

[C42]

[0053]

[C43]

[0054]

[C44]

[0055]

[C45]

[0056]

[C46]

[0057]

[C47]

[0058]

[C48]

[0059]

[C49]

[0060]

[C50]

[0061]

[C51]

[0062]

[C52]

[0063]

[C53]

[0064]

[C54]

[0065]

[C55]

[0066]

[C56]

[0067]

[C57]

[0068]

[C58]

[0069]

[C59]

[0070]

[C60]

[0071]

[C61]

[0072]

[C62]

[0073]

[C63]

[0074]

[C64]

[0075]

[C65]

[0076]

[C66]

[0077]

[C67]

[0078]

[C68]

[0079]

[C69]

[0080]

[C70]

[0081]

[C71]

[0082]

[C72]

[0083]

[C73]

[0084]

[C74]

[0085]

[C75]

[0086]

[C76]

[0087]

[C77]

[0088]

[C78]

[0089]

[C79]

[0090]

[C80]

[0091]

[Chemical formula 81]

[0092]

[C82]

[0093]

[Chemical formula 83]

[0094]

[Chemical formula 84]

To prepare the organosilicon compound 1,
It can be obtained by reacting a difluoroalkanoyl peroxide represented by the following general formula 85 with a vinyl group-containing organosilicon compound represented by the following general formula 86.

[0096]

[Chemical formula 85]

[0097]

[C86]

The molar ratio of the difluoroalkanoyl peroxide to the vinyl group-containing organosilicon compound is preferably in the range of 1:1.0 to 10.0, particularly preferably 1:1.2 to 5.0. The range is 0. The charging molar ratio of the vinyl group-containing organosilicon compound is less than 1.0 or 1.
If it exceeds 0, it is not preferable because it is difficult to obtain the desired fluoroalkyl group-containing organosilicon compound. At this time, the reaction can be carried out at normal pressure, and the reaction temperature is preferably in the range of -20 to +150°C, particularly preferably in the range of 0 to 100°C. A compound in which Y is represented by the following general formula 87 can be obtained, while the reaction temperature is preferably -
After reacting in the range of 20 to +150°C until the raw peroxide completely disappears, preferably 100 to 300°C
Y in the general formula 2 is treated by heat treatment in the range of
is -CH=CH(CH2)m1-, -CH2CH=C
A compound of H(CH2)m2- can be obtained simultaneously as a mixture. Furthermore, the reaction time is 30 minutes to 20 minutes.
It can be carried out for a range of hours, and industrially it is desirable to set it as a range of 3 to 10 hours.

0099

[Chemical formula 87]

To prepare the organosilicon compound 1,
It can be obtained in a one-step reaction by reacting the difluoroalkanoyl peroxide with the vinyl group-containing organosilicon compound under the various reaction conditions, but the handling and reaction of the difluoroalkanoyl peroxide may be more difficult. It is preferable to use a solvent for smooth operation. 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, and 1,1,2-trichlorotrifluoroethane is particularly preferred from an industrial standpoint. 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 hydrolysis condensate of organosilicon compound 1, which can be used as an active ingredient in the surface treatment agent of the present invention, include the organosilicon compound 1.
can be obtained by dissolving it in a mixed solvent of a fluorinated chlorinated hydrocarbon and an alkyl alcohol containing water, or an alkyl alcohol solvent or an alcohol solvent containing water, and subjecting it to hydrolysis or hydrolytic condensation. , especially hydrolytic condensation,
It can be obtained preferably at room temperature to 200°C for 5 to 24 hours. The fluorinated chlorinated hydrocarbon is 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. Further, the mixing ratio of the mixed solvent is not particularly limited as long as it can dissolve the organosilicon compound 1, and the water content may be in the range of 1 to 30% by weight based on the mixed solvent or solvent. It is preferable to do so.

In order to use the surface treatment agent of the present invention, it is preferable to dilute the active ingredient in the solvent and use it as a solution.In this case, even if only the organosilicon compound 1 is used as the active ingredient, its A part or all of it can be used as a hydrolyzate and a hydrolysis condensate. Further, the concentration of the active ingredient in the solution is preferably in the range of 0.005% by weight to 20% by weight. The concentration is 0.005
If it is less than 20% by weight, the film thickness of the surface treatment agent will be thin and the water and oil repellency will decrease, and if it exceeds 20% by weight, the film thickness will become thicker but the water and oil repellency will not improve and the surface uniformity will decrease. However, this is not preferable because it tends to peel off easily.

[0104] As a treatment method when using the surface treatment agent of the present invention, known coating methods such as brush coating, spray method, roll coating method, spin coating method, dip coating method, etc. are 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 adjust to

[0105]

[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 agents for floors, wall tiles, glass, stone, wood, plaster, wallpaper, exterior wall materials, bath wall materials, etc., surface treatment agents for painted or unpainted metals such as appliances and automobile bodies, etc. , surface treatment agents that have good adhesion to iron, stainless steel, duralumin, etc., and plastics such as polyester resins, urethane resins, ABS resins, vinyl chloride resins, epoxy resins, and phenol resins for the purpose of contributing to low adhesion to surfaces. surface treatment agents to facilitate mold release, surface treatment agents to prevent icing on airplanes, surface treatment agents to prevent baking in frying pans, and even magnetic tape, floppy disks, hard disks, etc. It can be widely used as a solid lubricant for the surface of magnetic materials such as disks, etc., and is useful as a surface treatment agent that imparts water and oil repellency, antifouling properties, non-stick properties, lubricity, etc.

[0106]

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.

[0107]

[Example 1] Allyltrimethylsilane 0.97g (6m
mol), diperfluoro-2-methyl-3-peroxide
1, containing 2.0 g (3 mmol) of oxahexanoyl;
1,2-trichlorotrifluoroethane solution 17.5g
was added, and the reaction was carried out at 30° C. for 5 hours under a nitrogen atmosphere. After the reaction was completed, the reaction solvent was removed, followed by distillation to obtain a compound represented by the following structural formula 88 in a yield of 70%.

[0108]

[Chemical formula 88]

Next, the obtained compound was dissolved in a 95% by weight aqueous ethanol solution whose pH was adjusted to 5.0 by adding acetic acid to prepare a 1% by weight solution. Next, three stainless steel plates (SUS304) and a glass plate were added to the obtained solution.
After dipping for a minute, it was dried at 100° C. for 15 minutes, and the contact angles with respect to water and dodecane were measured. The results are shown in Table 1.

[0110] 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 poured into the resulting cup, and the molded product obtained with the mixture was released from the mold. A metal hook was erected in the injected mixture as a handle for 12 minutes.
It was heated and cured at 0°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.

[0111]

[Example 2] Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl, diperfluoro-2,5 peroxide
The reaction was carried out 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 89 was obtained in a yield of 63%.

[0112]

[Chemical formula 89]

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

[0114]

[Example 3] Diperfluoro-2-methyl-3-peroxide
The reaction was carried out in the same manner as in Example 1 except that oxahexanoyl was replaced with diperfluorobutyryl peroxide, and a compound represented by the following structural formula 90 was obtained in a yield of 79%.

[0115]

[C90]

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

[0117]

[Example 4] Diperfluoro-2-methyl-3-peroxide
The reaction was carried out in the same manner as in Example 1 except that oxahexanoyl was replaced with diperfluoroheptanoyl peroxide, and a compound represented by the following structural formula 91 was obtained in a yield of 71%.

[0118]

[Chemical formula 91]

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

[0120]

[Example 5] The reaction was carried out in the same manner as in Example 1 except that allyltrimethoxysilane was replaced with allyltriethoxysilane, and the compound represented by the following structural formula 92 was produced in a yield of 68.
Obtained in %.

[0121]

[C92]

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

[0123]

[Example 6] Allyltrimethoxysilane was replaced with allyltriethoxysilane, and diperfluoro-2-methyl-3-oxahexanoyl peroxide was replaced with diperfluoro-2,5-dimethyl-3,6-dimethyl peroxide. The reaction was carried out in the same manner as in Example 1 except that oxanonanoyl was used, and a compound represented by the following structural formula 93 was obtained in a yield of 66%.

[0124]

[C93]

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

[0126]

[Example 7] Same as Example 1 except that allyltrimethoxysilane was replaced with allyltriethoxysilane and diperfluoro-2-methyl-3-oxahexanoyl peroxide was replaced with diperfluorobutyryl peroxide. A compound represented by the following structural formula 94 was obtained in a yield of 77%.

[0127]

[C94]

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

[0129]

[Example 8] Same as Example 1 except that allyltrimethoxysilane was replaced with allyltriethoxysilane and diperfluoro-2-methyl-3-oxahexanoyl peroxide was replaced with diperfluorooctanoyl peroxide. The compound represented by the following structural formula 95 was obtained in a yield of 77.
Obtained in %.

[0130]

[C95]

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

[0132]

[Example 9] Allyltrimethylsilane 0.97g (6m
mol), diperfluoro-2-methyl-3-peroxide
1, containing 2.0 g (3 mmol) of oxahexanoyl;
1,2-trichlorotrifluoroethane solution 17.5g
was added, and the reaction was carried out at 30° C. for 5 hours under a nitrogen atmosphere. After the reaction was completed, the reaction solvent was removed, and then heat treatment was performed at 180° C. for 5 hours to obtain a mixture of compounds represented by the following structural formulas 96 and 97 in a yield of 76%.

[0133]

[C96]

[0134]

[C97]

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

[0136]

[Example 10] Diperfluoro-2-methyl-3 peroxide
-oxahexanoyl, diperfluoro-2 peroxide,
The reaction was carried out in the same manner as in Example 9 except that 5-dimethyl-3,6-dioxanonanoyl was used, and the following structural formula 98 was obtained.
, a mixture of compounds represented by Chemical Formula 99 was obtained in a yield of 74%.

[0137]

[C98]

[0138]

[C99]

[0139]

[Example 11] Diperfluoro-2-methyl-3 peroxide
The reaction was carried out in the same manner as in Example 9 except that -oxahexanoyl was replaced with diperfluorobutyryl peroxide, and a mixture of compounds represented by the following structural formulas 100 and 101 was obtained in a yield of 90%.

[0140]

[Chemical formula 100]

[0141]

[Chemical formula 101]

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

[0143]

[Example 12] Diperfluoro-2-methyl-3 peroxide
- The reaction was carried out in the same manner as in Example 9, except that oxahexanoyl was replaced with diperfluoroheptanoyl peroxide,
A mixture of compounds represented by the following structural formulas 102 and 103 was obtained in a yield of 78%.

[0144]

[Chemical formula 102]

[0145]

[Chemical formula 103]

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

[0147]

[Example 13] The reaction was carried out in the same manner as in Example 9 except that allyltrimethoxysilane was replaced with allyltriethoxysilane, and a mixture of compounds represented by the following structural formulas 104 and 105 was prepared in a yield of 95%. Obtained.

[0148]

[Chemical formula 104]

[0149]

[Chemical formula 105]

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

[0151]

[Comparative Example] Evaluations were made in the same manner as in Example 1 for untreated stainless steel plates and glass plates. The results are shown in Tables 1 and 2.

[0152]

[Table 1]

[0153]

[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 release properties.

Claims (1)

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