JPH0240108B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silicone-based treatment agent, and in particular, it is an object of the present invention to provide a treatment agent that can impart excellent properties to various products, particularly water repellency and water repellency with excellent durability. . Another object of the present invention is to provide a processing agent that can exhibit its properties under low-temperature processing conditions and can also impart properties such as antifouling properties and mold release properties. . It has been known to treat various products and materials, including textile products, with organic compounds containing perfluoroalkyl groups, such as perfluoroalkyl acrylate polymers, to impart water and oil repellency to them. . However, there is a problem in that textile products and the like treated with conventional organic compounds become hard, and the unique texture that the textile products originally have is lost. On the other hand, treatment with a certain type of organopolysiloxane is effective in imparting water repellency.
Moreover, it is also known that this method can simultaneously impart a unique soft texture to textile products. However, treatment with organopolysiloxane has the disadvantage that oil repellency cannot be imparted. Therefore, attempts have been made to use organic compounds containing perfluoroalkyl groups and organopolysiloxanes together in order to impart water repellency and oil repellency at the same time.
In general, the oil repellency is significantly impaired and the expected remarkable effect cannot be obtained at present. That is, at present, no processing agent is known that can impart excellent water and oil repellency to various products. The present invention relates to a new silicone-based treatment agent which eliminates the disadvantages of the prior art as described above, and which has (A) the general formula (In the formula, R ¹ is a perfluoroalkyl group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ³ is a divalent organic group, and Y is a hydroxyl group or 5 to 95 mol% of an organosilane containing a perfluoroalkyl group represented by a hydrolyzable atom or group (x is 0, 1 or 2), (B) general formula R ² _y -Si-Y _4-y ... ...(ii) (wherein R ² and Y are the same as above, y is 0,
1, 2 or 3) and (C) general formula (In the formula, R ² and Y are the same as above, A is a monovalent organic group having at least one nitrogen atom, w
is 1 or 2, and z is 0, 1 or 2) whose main component is a partially cohydrolyzed condensate of a mixture consisting of 5 to 95 mol% of an organosilane having a nitrogen atom-containing monovalent organic group It is. Various products including textile products treated with the treatment agent of the present invention having the above-mentioned structure can be imparted with water repellency and oil repellency due to the perfluoroalkyl group in the condensate. At the same time, the siloxane skeleton can impart a soft texture unique to silicone, making it possible to obtain extremely good treated products. Moreover, at the same time, a good antifouling effect can be obtained, and thus a treated product having a function of preventing the adhesion of dirt can be obtained.Furthermore, the treatment agent of the present invention undergoes a condensation reaction on the treated surface by heating or moisture in the air. Because it forms a film on the surface of the treated object, it can simultaneously impart both water repellency and oil repellency under lower temperature treatment conditions than conventional organic compounds containing perfluoroalkyl groups. can. Furthermore, the film treated with the treatment agent of the present invention is
Due to the functional groups of the condensate, it exhibits excellent resistance to washing, cleaning, and various deterioration effects, and is extremely durable. The treatment agent according to the present invention is suitable for clothing products made from natural fibers such as cotton, wool, silk, and hemp, synthetic fibers such as polyester and nylon, semi-synthetic fibers such as acetate, blended fibers such as cotton-polyester, etc. Adding water repellency and oil repellency to various textile products for materials, providing stain resistance to equipment and buildings where stains are a problem regardless of whether they are water-based or oil-based, and having adhesive properties such as urethane and epoxy. It can be widely applied to various purposes, including the purpose of imparting mold releasability to a mold when molding a synthetic resin material. The silicone-based treatment agent of the present invention will be explained in detail below. First, the perfluoroalkyl group-containing organosilane (A) used in the present invention has the general formula (i) described above.
The perfluoroalkyl group having 1 to 20 carbon atoms represented by R ¹ in the formula is, for example, -CF ₃ , -C ₄ F ₉ , -C ₈ F ₁₇ , -C _{10 F21} ,
-C ₁₂ F ₂₅ and the like, and this perfluoroalkyl group may be either linear or branched. In addition, R ² is a hydrogen atom or a carbon atom number of 1 to 20
represents a monovalent hydrocarbon group, including methyl group,
Alkyl groups such as ethyl group, propyl group, 1-propyl group, butyl group, tert-butyl group, octyl group, dodecyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group, aralkyl group such as 2-phenylethyl group, phenyl group unsubstituted monovalent hydrocarbon groups such as aryl groups, tolyl groups, naphthyl groups, xylyl groups, etc., or groups in which the hydrogen atoms of these groups are partially substituted with halogen atoms such as chlorine atoms or fluorine atoms. etc. can be given. Furthermore, R ³ represents a divalent organic group, which includes (-
CH ₂ )— ₂ , (—CH ₂ )— ₃ , −CONH (—CH ₂ )— ₃ , (—CH
₂
)— ₂ S(—CH ₂ )— ₂ , −SO ₂ NH(—CH ₂ )— ₃ , −O(—C
_H2
)-- ₂ , etc. Hydrolyzable atoms or groups represented by Y include halogen atoms (Cl, Br, etc.), alkoxy groups (methoxy groups,
(ethoxy group, etc.), acyloxy group (acetoxy group, etc.), aminoxy group, amide group, alkenyloxy group, etc. Specific examples of the perfluoroalkyl group-containing organosilane (A) represented by the above general formula (i) include those shown below. CF ₃ (-CH ₂ )- ₂ SiCl ₃ , C ₇ F ₁₅ CONH(-CH ₂ )- ₃ Si(-OC ₂ H ₅ ) ₃ , Furthermore, the organosilane (B) used in the present invention is represented by the above-mentioned general formula (ii).
R ² and Y each have the same meaning as above. Examples of such organosilane (B) include those shown below. ( _CH3 ) _2SiCl2 , _CH3Si ( _{-OCH3 ) 3} , _HSi ( _-OC2H5 ) ₃ , Furthermore, the organosilane (C) having a nitrogen atom-containing monovalent organic group used in the present invention is represented by the above-mentioned general formula (iii), in which R ² and Y have the same meaning as above. and A is a monovalent organic group having at least one nitrogen atom, including (-CH ₂ )- ₃ NH ₂ , (-CH ₂ )- ₃ NH(-CH ₂ )- ₂ NH ₂ , etc. can be given. Examples of the organosilane (C) represented by the general formula (iii) include the following compounds. _{H2N ( -CH2} ) _-3Si ( _-OC2H5 ) ₃ , The main component in the present invention is formed by partially cohydrolyzing and condensing a mixture of the three organosilanes (A) to (C) described above, and the mixing ratio of each component is determined by the general formula (i). 5 to 95 mol% of silane (A) represented by
It is necessary to set the silane (B) represented by the general formula (ii) to 0 to 90 mol% and the silane (C) represented by the general formula (iii) to be 5 to 95 mol%. The silane (A) represented by the general formula (i) improves oil repellency as the mixing ratio increases, but on the other hand, the texture of the treated material becomes hard and the unique soft texture of the treated material is impaired, so it is not preferable. is considered to be 20 to 50 mol% of the total. In addition, silane (B) represented by general formula (ii) is 90 mol%
Hereinafter, it is preferably 40 to 70 mol%. This is because if the mixing ratio is too high, the effect of imparting oil repellency to the object to be treated will be impaired. This is a necessary component for imparting a soft texture to the treated object. Furthermore, the silane (C) represented by the general formula (iii) is 5 to 95
It is necessary to use it in a proportion of mol %, preferably 5 to 30 mol %. The larger the mixing ratio, the better the durability of the properties of the treated object and the properties themselves are greatly improved, but on the other hand, the treated object becomes discolored and the partially co-hydrolyzed condensate changes over time. When partially cohydrolyzing and condensing the above three components, an appropriate amount of water is added to the mixture, and as a hydrolytic condensation catalyst, an acidic catalyst such as hydrochloric acid, sulfuric acid, acid clay, trifluoroacetic acid, potassium hydroxide,
After partial cohydrolytic condensation in the presence of an alkaline catalyst such as sodium hydroxide, the catalyst used may be neutralized and removed, and by doing so, the condensate which is the main component of the present invention can be obtained. As the neutralizing agent, propylene oxide, sodium carbonate, sodium hydrogen carbonate, ethylene chlorohydrin, a small amount of trimethylchlorosilane, etc. can be used. The above three components are not limited to only one type each, and two or more types may be used in combination, which is optional. Further, although the main component of the present invention is obtained by partially cohydrolyzing and condensing the three components described above (copolymer), each component may be added alone to the copolymer. . The treatment agent of the present invention is mainly composed of a partial cohydrolyzed condensate consisting of the three components described above, but it also contains various additives that have conventionally been added to similar treatment agents of this type. Other agents such as water repellents, oil repellents, antistatic agents, dye stabilizers, anti-wrinkle agents, etc. may be added to the composition as long as they do not impede the object of the present invention. When actually using the treatment agent of the present invention, it is common to dilute it appropriately with an organic solvent such as methyl isobutyl ketone, methyl ethyl ketone, acetone, trichloroethane, trichloroethylene, perchloroethylene, or chlorofluorocarbon. It may be used as an emulsion using a suitable surfactant. Next, the present invention will be explained based on examples. Preparation of Partial Cohydrolyzed Condensate Condensate 1 In a flask with an internal _volume of 200 ml equipped with a stirrer, thermometer, reflux condenser and dropping funnel, _C8F17 ( _-CH2 ) _-2S ( _-CH2 )― ₂ Si(−OCH ₃ ) ₃ 20.0
g, _CH3 -Si( _-OCH3 ) ₃ 7.2g and acetone 50
After adding 0.2 g of 30% HCl dropwise with stirring, 4.8 g of H ₂ N(-CH ₂ )- ₂ NH(-CH ₂ )- ₃ Si(-OCH ₃ ) ₃ was added.
was dripped. The temperature was gradually raised in a N ₂ stream, and the reaction was continued for 2 hours under refluxing acetone to complete the cohydrolysis. After cooling, the reaction solution was neutralized using propylene oxide, and the solution was evaporated to obtain a product. Condensate 2 In the same flask ₍ hereinafter simply abbreviated as flask) used to prepare the above condensate 1, _C8F17 ( _-CH2 ) _-2S ( _-CH2 ) _-2Si ( _-OCH3 ). ₃ 20.0
g, _CH3Si ( _-OCH3 ) ₃ 7.2g and acetone 50g
was charged, and 0.2 g of 30% HCl was added dropwise while stirring. Then 5.3 g was added dropwise, and the following treatment was carried out in the same manner as in the preparation of condensate 1 above. Condensate 3 In a flask, add C ₇ F ₁₅ CONH(-CH ₂ )- ₃ Si(-
Add 20.0 g of OC ₂ H ₅ ) ₃ , 9.6 g of CH ₃ Si(-OC ₂ H ₅ ) ₃ and 50 g of acetone and reduce to 30% while stirring.
0.2 g of HCl was added dropwise. Then

[Formula] 5.4g was added dropwise. The same process was performed thereafter. Condensate 4 In a flask, add C ₈ F ₁₇ (-CH ₂ )- ₂ S(-CH ₂ )- ₂ Si(-
Add 20.0 g of OCH ₃ ) ₃ , 7.2 g of CH ₃ Si(-OCH ₃ ) ₃ and 50 g of acetone, and add 30% HCl0.2 while stirring.
g was added dropwise. Then

[Formula] 5.7g was added dropwise. The same process was performed thereafter. Condensate 5 In a flask, add C ₈ F ₁₇ (-CH ₂ )- ₂ Si(OCH ₃ ) ₃ 20.0
g, _CH3 -Si( _-OCH3 ) ₃ 8.0g and acetone 50
0.2 g of 30% HCl was added dropwise while stirring. Then

[Formula] 5.8g was added dropwise. The same process was performed thereafter. Condensate 6 In a flask, add C ₁₀ F ₂₁ (-CH ₂ )- ₂ S(-CH ₂ )- ₂ Si(
−
Add 20.0g of _OCH3 ) ₃ , 6.3g of CH3 _- Si( _-OCH3 ) ₃ and 50g of acetone and reduce to 30% with stirring.
0.2 g of HCl was added dropwise. Then, 4.1 _g of _H2N ( _-CH2 ) _-3Si ( _-CO2H5 ) ₃ was added dropwise.
The same process was performed thereafter. Condensate 7 In a flask, add C ₈ F ₁₇ (-CH ₂ )- ₂ S-CH ₂ -Si(-
Add 20.0 g of OCH ₃ ) ₃ , 6.5 g of HSi(-OCH ₃ ) ₃ and 50 g of acetone and add 0.2 g of 30% HCl while stirring.
was dripped. Then

[Formula] 5.3g was added dropwise. The same process was performed thereafter. Condensate 8 In a flask, add C ₈ F ₁₇ (-CH ₂ )- ₂ S(-CH ₂ )- ₂ Si

[Formula] 20.0 g, CH ₃ Si (-OCH ₃ ) ₃ 6.4 g and 50 g of methyl ethyl ketone were prepared, and 0.2 g of 30% HCl was added dropwise with stirring. Then _H2N ( _-CH2 ) _-2NH ( _-CH2 ) _-3Si ( _-OCH3 ) ₃ 4.2g
was dripped. The same process was performed thereafter. Preparation of treatment bath (1) Treatment baths (products of the present invention) 1 to 8 The condensates 1 to 8 prepared above were added to 1 wt.
A treatment bath was prepared by diluting and dissolving the mixture with 1,1,1-trichloroethane to give a concentration of 1,1,1-trichloroethane. (2) Treatment bath (control product) 9 _C8F17 ( _-CH2 ) _{-2S ( -CH2} ) _-2Si ( _-OCH3 ) ₃
A treatment bath was prepared by diluting and dissolving with 1,1,1 trichloroethane to a concentration of 1 wt%. (3) Treatment bath (control product) 10 1,1,1- so that perfluoroalkyl acrylate polymer is 0.8wt% and dimethyl silicone oil (1000cs) is 0.2wt%.
A treatment bath was prepared by diluting and dissolving with trichloroethane. (4) Treatment bath (control product) 11 1,1,1- so that perfluoroalkyl acrylate polymer was 0.5wt% and dimethyl silicone oil (1000cs) was 0.5wt%.
A treatment bath was prepared by diluting and dissolving with trichloroethane. Water repellency, oil repellency, texture test A polyester/cotton broadcloth (65/35) was immersed in the treatment bath prepared above, squeezed with a mangle, and then heated at 100°C for 2 minutes and at 170°C for 2 minutes. The treated broadcloth after heating was examined for water repellency, oil repellency, and texture, and the results are shown in the table below.

【table】

【table】

Claims (1)

[Claims] 1 (A) General formula (In the formula, R ¹ is a perfluoroalkyl group having 1 to 20 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ³ is a divalent organic group, and Y is a hydroxyl group or 5 to 95 mol % of an organosilane containing a perfluoroalkyl group represented by a hydrolyzable atom or group (x is 0, 1 or 2), (B) general formula R ² _y -Si-Y _4-y ( In the formula, R ² and Y are the same as above, y is 0,
1, 2 or 3) and (C) general formula (In the formula, R ² and Y are the same as above, A is a monovalent organic group having at least one nitrogen atom, w
is 1 or 2, and z is 0, 1 or 2), and z is 0, 1 or 2. system treatment agent.