JPH0474468B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a water/oil repellent agent for solid materials,
Specifically, the present invention relates to a water/oil repellent agent for solid materials that can impart durable water and oil repellency to various solid materials. [Prior Art] It has been known to treat solid materials such as textile products and leather products with a treatment agent containing a fluorocarbon hydrocarbon having perfluoroalkyl as a main component in order to impart oil repellency. It is also known to treat these solid materials with a treatment agent based on a certain type of organopolysiloxane in order to impart water repellency. Furthermore, it is known to treat solid materials using a combination of organic compounds containing perfluoroalkyl groups and organopolysiloxanes containing reactive groups such as hydroxy, epoxy, amino or carboxy groups (particularly (See Publication No. 58-1232, Special Publication No. 47071/1983). [Problems to be Solved by the Invention] However, when solid materials, especially textile products, are treated only with a treatment agent containing fluorinated hydrocarbons as a main component, the unique texture and softness inherent to the textile products may be affected. The disadvantage was that the sex was impaired. Furthermore, treatment with organopolysiloxane has the disadvantage that oil repellency cannot be imparted to solid materials. Furthermore, even when using a combination of an organic compound containing a perfluoroalkyl group and an organopolysiloxane containing a reactive group, the expected oil repellency is generally not obtained or the oil repellency is not durable. However, it has the disadvantage that it cannot simultaneously impart durable water repellency and oil repellency. The present invention aims to solve the above-mentioned drawbacks of the prior art, and aims to provide a novel water and oil repellent for solid materials that can impart durable water and oil repellency to solid materials. It provides an imparting agent. [Means for Solving the Problems] The above objectives are (A) monovalent organic groups containing an amino group bonded to at least one silicon atom and alkenyl bonded to at least one silicon atom in one molecule; Initiate radical polymerization of an organopolysiloxane having a group and (B) an organic fluorine compound having a group represented by the formula CH ₂ =CR- (in the formula, R is a hydrogen atom or an alkyl group) and a perfluoroalkyl group in one molecule. This can be achieved by using a water/oil repellent agent for solid materials whose main ingredient is a product copolymerized in the presence of an agent. To explain this, component (A) is an organopolymer having in one molecule an amino group-containing monovalent organic group bonded to at least one silicon atom and an alkenyl group bonded to at least one silicon atom. It is siloxane. A typical example of the amino group ^- containing monovalent organic group bonded to the silicon atom of this component is a group represented by the general formula ^-R1- ( _NHCH2CH2 )a- _CHR2 . In the above formula, R ¹ is a divalent hydrocarbon group, which includes -CH ₂ -, -(CH ₂ ) ₂
−, −(CH ₂ ) ₃ −, −CH ₂ CH(CH ₃ )CH ₂ −, −
Examples include alkylene groups such as (CH ₂ ) ₄ - and alkylenearylene groups such as -(CH ₂ ) ₂ -C ₆ H ₄ -. R ² is a hydrogen atom or an alkyl group, and the alkyl group is a methyl group,
Examples include ethyl group, propyl group, and hexyl group. a is an integer from 0 to 10. Other groups bonded to the silicon atom include monovalent hydrocarbon groups, alkoxy groups, and hydroxyl groups, and monovalent hydrocarbons include alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl groups. , unsubstituted monovalent hydrocarbon groups such as aralkyl groups such as , 2-phenylethyl group, 2-phenylpropyl group, aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, or hydrogen atoms of these groups An example is a group in which is partially substituted with a halogen atom such as a chlorine atom or a fluorine atom. Alkoxy groups include methoxy group, ethoxy group, isopropoxy group,
An example is a methethoxy group. As an alkenyl group bonded to a silicon atom,
Examples include vinyl group, allyl group, butenyl group, and propenyl group, with vinyl group and allyl group being preferred. Other groups bonded to the silicon atom include monovalent hydrocarbon groups, alkoxy groups, and hydroxyl groups, and the monovalent hydrocarbon groups and alkoxy groups are as described above. In this component, the proportion of organosiloxane units having an amino group-containing monovalent organic group bonded to a silicon atom is such that at least one amino group-containing monovalent hydrocarbon group is present in one molecule. There is no particular restriction, and it varies depending on the purpose and use, but from the viewpoint of imparting durability, among all organosiloxane units,
It is preferably 0.5 to 50 mol%, more preferably 1 to 30 mol%. Further, the proportion of organosiloxane units having an alkenyl group bonded to a silicon atom is not particularly limited as long as at least one alkenyl group is present in one molecule, and varies depending on the purpose and use. From the viewpoint of efficiently exhibiting oil repellency, it is preferably 1 to 70 mol%, more preferably 2 to 50 mol% of the total organosiloxane units. This component may be composed only of these siloxane units, or may contain other organosiloxane units. Among other organosiloxane units, groups bonded to silicon atoms include monovalent hydrocarbon groups, alkoxy groups, and hydroxyl groups. The monovalent hydrocarbon group and alkoxy group are as described above. The proportion of organosiloxane units is 95
It is preferably less than mol%, more preferably 20 to 90 mol%. The molecular structure of the organopolysiloxane of this component may be linear, branched, cyclic, or network-like, and the viscosity and molecular weight are not particularly limited. Specific examples of this ingredient include: is exemplified. Component (B) used in the present invention is an organic fluorine compound containing a group represented by the formula CH ₂ =CR- (wherein R is a hydrogen atom or an alkyl group) and a perfluoroalkyl group in one molecule. be. In the above formula, R is a hydrogen atom or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. _{Perfluoroalkyl} groups include _{-CF3 , -C2F5} , _{-C3F7 , -C4F7 , -C8F17} , -
Examples include C ₁₀ F ₂₁ , -C ₁₂ F ₂₅ and -C ₂₀ F ₂₁ , and from the viewpoint of imparting oil repellency, perfluoroalkyl groups having 3 or more carbon atoms are preferred. Specific examples of _{this component} include _{CH2 = CHC6F13} , _{CH2 = CHC8F17 , CH2} = _CHCOOCH2C4F9 , _CH2 =CHCOO _{- C2H4} - _C8F17 , CH ₂ = CHCOO−C ₂ H ₄ −C ₈ F ₁₇ , CH ₂ = C(CH ₃ )C ₂ H ₄ −C ₈ F ₁₇ , CH ₂ = CHCOO−C ₃ H ₆ −C ₈ F ₁₇ , CH ₂ = CHCOO−C ₁ H ₂₂ −C ₈ F _{17 An} example _{is CH2 = CHCH2OCOC10H20N} ( _{CH3 ) SO2C8F17} . The water/oil repellent agent for solid materials of the present invention can be obtained by copolymerizing components (A) and (B) in the presence of a radical polymerization initiator. The ratio of copolymerization of component (A) and component (B) is not particularly limited, but as the ratio of component (A) increases,
The copolymer product becomes softer and more viscous, imparting more flexibility to the solid material, and as the proportion of component (B) increases, the copolymer product becomes harder and more flexible to the solid material. It is preferable to add 95 parts by weight of component (B) to 5 to 80 parts by weight of component (A) because it imparts more oil repellency to the
~20 parts by weight. The radical polymerization initiator may be any polymerization catalyst conventionally used for radical polymerization of vinyl resins, such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, and di-t-butyl. Peroxide, 2.5
-(peroxybenzoate)hexyne-3,
1,3-bis(t-butylperoxyisopropyl)benzene, lauryl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di(t
Organic peroxide catalysts such as -butylperoxy)hexane-3,2.5-dimethyl-2,5-di(t-butylperoxy)hexane, azobis-isobutyronitrile, dimethylazodiisobutyrate, etc. Examples include azo compound-based catalysts and redox-based catalysts. The polymerization reaction involves acetone, methyl isobutyl ketone, methyl ethyl ketone, trichloroethylene,
In the presence of organic solvents such as perchlorethylene, trifluoroethane, trichlorotrifluoroethane, toluene, or emulsifiers such as higher alcohol polyoxyalkylene adducts, higher fatty acid polyoxyalkylene phenol polyoxyalkylene adducts, and water. The polymerization can be carried out by solution polymerization, suspension polymerization, emulsion polymerization, etc. in a homogeneous or heterogeneous system. The polymerization temperature is approximately 30
~100°C, and the polymerization time may be approximately 1 to 30 hours. In order to impart water and oil repellency to a solid material using the water/oil repellent imparting agent for solid materials according to the present invention, spraying, roll coating, brushing,
This is done by methods such as immersion. The amount of adhesion varies depending on the solid material and is not particularly limited, but it is generally 0.01 to 10.0% by weight based on the solid material. Then, durable water and oil repellency can be imparted to the solid material by leaving it at room temperature, blowing hot air, heat treatment, etc. The water/oil repellent agent for solid materials of the present invention may further contain water repellents, oil repellents, antistatic agents, dye stabilizers, anti-wrinkle agents, etc., as long as they do not impede the purpose of the present invention. You may. Solid materials to which the treatment agent of the present invention can be applied include various fibers and their knitted fabrics, paper, natural or synthetic leather, cellophane, sheet-like materials such as plastic film, foam-like materials such as synthetic resin foam, synthetic Examples include resin molded products, natural or synthetic rubber molded products, metal molded products, glass molded products, and powdered materials such as inorganic powder or synthetic resin powder. The aforementioned fibers include hair, alpeca, mohair, angora, wool, silk, linen, cotton,
Examples include natural fibers such as asbestos, recycled fibers such as rayon and acetate, synthetic fibers such as polyester, polyamide, vinylon, polyacrylonitrile, polyethylene, polypropylene, and spandex, glass fibers, carbon fibers, and silicone carbide fibers. Examples of shapes include staples, filaments, tows, tops, and threads, and examples of knitted fabrics include knitted fabrics, woven fabrics, nonwoven fabrics, resin-treated fabrics, and sewn products thereof. [Function] In the copolymer, the organopolysiloxane unit derived from component (A) imparts water repellency, flexibility and durability to the solid material, and the organopolysiloxane unit derived from component (B) imparts water repellency, flexibility and durability to the solid material. unit of water repellency for solid materials,
It imparts oil repellency, and the organopolysiloxane units derived from component (A) and the organic fluorine compound units derived from component (B) combine to provide durable water repellency, oil repellency, and flexibility to solid materials. Indicates the effect that is imparted at the same time. [Example] Next, the present invention will be explained with reference to an example. Example 1 11.1 g of cyclic methylvinylsiloxane tetramer, 80.3 g of cyclic dimethylsiloxane tetramer, Formula Amino group-containing organopolysiloxane represented by
5.2 g and 5.4 g of dimethylpolysiloxane end-blocked with trimethylsilyl groups at both ends and having a viscosity of 10 centistokes at 25°C, and 0.015 g of potassium hydroxide as a medium.
500 with stirrer, reflux condenser and thermometer
The mixture was poured into a CC four-necked flask and reacted at 130°C for 10 hours. After the reaction, neutralize the catalyst with 0.016g of acetic acid,
After distilling off low volatile components at 130℃ and 20mmHg, the average composition formula An organopolysiloxane shown by was synthesized. Next, 6.0 g of this organopolysiloxane and 20.0 g of an organic fluorine compound represented by the formula CH ₂ =CHCOO(CH ₂ ) ₂ (CF ₂ ) ₈ F were mixed with 69.8 g of methyl isobutyl ketone as a solvent and 1.1.1- Pour 150 g of trichloroethane into a 500 c.c. four-necked flask equipped with a stirrer, reflux condenser, and thermometer, and heat to 75°C. Add 0.15 g of azobisisobutyronitrile and heat at the same temperature for 2 Water/oil repellent agent A for solid materials of the present invention was synthesized by copolymerizing with holding for a certain period of time. Obtained processing agent A
was a transparent and stable dispersion with a solids content of 10.6% by weight. After removing the solvent, the obtained water/oil repellent agent A for solid materials was analyzed using a Shibai absorption spectrophotometer and an infrared absorption spectrophotometer, and no vinyl groups were detected, indicating that it was a copolymer. This was confirmed. In addition, 1 g of water/oil repellent agent A for solid materials was placed in an aluminum dish, the solvent was evaporated at room temperature, and then heated to 150°C.
When the aluminum plate was heated for 3 minutes, a flexible and transparent film-like substance was observed that adhered closely to the aluminum plate. Next, a treatment bath was prepared by diluting water/oil repellent agent A for solid materials with methyl ethyl ketone so that the solid content was 0.5% by weight, and 65% of polyester fibers with a size of 30 x 30 cm were added to this bath. Three pieces of Burberry fabric made of a 35% cotton blend were soaked for 10 seconds and adjusted using a roller to achieve a squeezing rate of 100%. After drying these three cloths at room temperature, they were heat-treated at 150° C. for 3 minutes. One of the three treated fabrics was washed for 15 minutes using a 0.3% by weight aqueous solution of synthetic detergent manufactured by Lion Corporation (trade name: New White), then washed with water for 10 minutes and dried to be washed with water. In addition, another piece of treated cloth was stirred in perchlorethylene (bath ratio 1:50) for 15 minutes to dry clean. A flexibility test, a texture test, a water repellency test, and an oil repellency test were conducted on each of the obtained fabrics as follows. *Flexibility test: JIS L1096, general textile testing method,
The extrusion length (mm) was measured by the cantilever method. *Texture test: Evaluation was performed on the following three levels based on the feel of the product. 〇…It is extremely flexible and has good elasticity at the waist and rebound. △…Flexibility, waist, and rebound elasticity are insufficient. ×: Rough and hard, with poor waist and rebound elasticity. *Water repellency: According to JIS L1092 (1977). *Oil repellency: One drop of liquid paraffin was dropped on a cloth, and the time (seconds) it took for the drop to disappear after being diffused onto the cloth was measured. In addition, as Comparative Example 1, 10.0 g of the organopolysiloxane synthesized in Example 1 was mixed with 28.5 g of methyl isobutyl ketone and 1.1.1-trichloroethane.
A treatment bath having a solid content of 0.5% by weight was prepared by dissolving 61.5 g of the same material and 1910 g of methyl ethyl ketone, and the same Burberry fabric as in Example 1 was immersed therein, and heat treatment, washing treatment, and various tests were conducted in the same manner. In addition, as Comparative Example 2, only an organic fluorine compound was polymerized in the same manner as in Example 1 except that no organopolysiloxane was added, and after the reaction, methyl ethyl ketone was added to make the solid content 0.5% by weight.
A treatment bath was prepared by diluting the solution. Burberry fabric was treated in exactly the same manner as in Example 1, and subjected to heat treatment, washing treatment, and various tests. Further, as Comparative Example 3, Comparative Example 1 and Comparative Example 2
A mixed solution of equal weight was prepared and applied to Burberry fabric in exactly the same manner as in Example 1, followed by heat treatment and various tests. Note that the untreated fabric was also subjected to washing treatment and various tests in the same manner. As shown in Table 1, the results show that the treatment agent of the present invention can impart water repellency, oil repellency, and flexibility at the same time, and its effects remain almost unchanged even after washing with water or dry cleaning, and are highly durable. was.

[Table] Example 2 Organopolysiloxane synthesized in Example 1
20g, polyoxyethylene nonylphenol ether (6 mole ethylene oxide adduct) 3.3g
and polyoxyethylene nonylphenol ether (ethylene oxide 12 mole adduct) 1.7 g
After uniformly mixing the mixture and 75 g of water, an emulsion was prepared using an emulsifying machine. Next, 23.0 g of an organic fluorine compound represented by the formula CH ₂ =CHCOO(CH ₂ ) ₂ (CF ₂ ) ₁₀ F and 30.0 g of acetone were mixed in four 500 c.c. tubes equipped with a stirrer, a reflux condenser, and a thermometer. The mixture was poured into a neck flask and uniformly dissolved. Add to this the emulsion 30.0 that was prepared earlier.
g and 16.8 g of water were added and heated to 62°C, and 0.2 g of ammonium persulfate was added, stirred at the same temperature for 3 hours and emulsion polymerized to obtain the water/oil repellent agent B for solid materials of the present invention. Prepared. The obtained water/oil repellent agent B for solid materials was diluted with water to a solid content of 0.5% by weight, and treated on a raincoat fabric so that the squeezing rate was 100%.
After air drying at room temperature, heat treatment and washing treatment were performed under the same conditions as in Example 1, and various tests were conducted in the same manner. As shown in Table 2, the results showed that durable water repellency, oil repellency, and flexibility could be imparted at the same time.

[Table] Example 3 Formula 30 g of an organopolysiloxane represented by the formula _CH2 =CH( _CF2 ) _6F , 70 g of an organic fluorine compound represented by the formula CH2=CH(CF2)6F, 180 g of methyl isobutyl ketone and 220 g of 1,1,1-trichloroethane were placed in a stirrer, a reflux condenser, and Pour azobisisobutyronitrile into a 1000 c.c. four-necked flask equipped with a thermometer and heat to 75°C.
g was added thereto, maintained at the same temperature for 2 hours, and copolymerized to synthesize water/oil repellent agent C for solid materials of the present invention. When the obtained water/oil repellent agent C for solid materials was analyzed using an ultraviolet absorption spectrophotometer and an infrared absorption spectrophotometer after removing the solvent, no vinyl groups were detected, indicating that it was a copolymer. was confirmed. In addition, 1 g of water/oil repellent agent C for solid materials was placed in an aluminum dish, and after volatilizing the solvent at room temperature,
When heat-treated at ℃ for 3 minutes, a flexible and transparent film-like substance was observed that adhered to the aluminum plate. Water/oil repellent agent C for solid materials has a solid content of 0.5
A treatment bath was prepared by diluting the bath with methyl ethyl ketone to give a weight percentage of 100% wool and cashmere skin men's wear fabric was treated with the bath at a squeezing rate of 100%. This was subjected to heat treatment and washing treatment under the same conditions as in Example 1, and various tests were conducted in the same manner. As shown in Table 3, durable water repellency, oil repellency and flexibility could be imparted at the same time.

[Table] [Effects of the invention] According to the water/oil repellent agent for solid materials of the present invention, the main ingredient is a copolymer of an organopolysiloxane having an amino group and an organic fluorine compound having a perfluoroalkyl group. Therefore, it is possible to simultaneously impart durable water repellency, oil repellency, and flexibility to a solid material. Therefore, it can be suitably used as a water repellent, oil repellent, antifouling agent, softener, mold release agent, polishing agent, etc. for various solid materials.

Claims (1)

[Scope of Claims] 1 (A) An organopolysiloxane having in one molecule an amino group-containing monovalent organic group bonded to at least one silicon atom and an alkenyl group bonded to at least one silicon atom, and (B) Copolymerizing an organic fluorine compound having a group represented by the formula CH ₂ =CR- (wherein R is a hydrogen atom or an alkyl group) and a perfluoroalkyl group in one molecule in the presence of a radical polymerization initiator. A water/oil repellent agent for solid materials whose main ingredient is a product obtained by