JPS6410556B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water and oil repellent with excellent durability,
More specifically, the present invention relates to a water and oil repellent made of a copolymer containing a polymerizable compound containing a polyfluoroalkyl group and a specific functional compound as a constituent unit. Conventionally, polymers of polyfluoroalkyl group-containing polymerizable compounds such as perfluoroalkyl group-containing acrylates or methacrylates, or these together with alkyl acrylates, maleic anhydride, vinyl chloride, chloroprene, butadiene, styrene, methyl vinyl, etc. Water and oil repellents made of copolymers with other polymerizable compounds such as ketones are known and are widely used commercially, primarily for textile treatment. Therefore, the durability of such water and oil repellents against washing and friction is -NHCH ₂ OH, -
COOCH ₂ CH ₂ OH, or

[Formula] Group-containing monomers have been copolymerized with polyfluoroalkyl group-containing monomers, and improvements have been made by crosslinking or adsorption to fibers, but conventional methods have not always yielded sufficiently satisfactory results. According to the research of the present inventor, the -N=C=O group is effective in improving the durability of water and oil repellents containing polyfluoroalkyl groups, but monomers having such functional groups are generally difficult to obtain. Furthermore, since the --N=C=O group is extremely active, it is extremely difficult to handle water and oil repellents containing this group. for example,-
Monomers containing N=C=O groups cannot be polymerized in aqueous media and cannot provide water and oil repellents in the form of aqueous dispersions. Furthermore, during storage and transportation, the activity is lost due to the action of moisture. As a result, the durability improvement effect is reduced before use. The inventor is

[Formula] Focusing on the fact that group-containing compounds can change into highly reactive -N=C=O groups at appropriate temperatures, and are stable against water at room temperature, It has been discovered that a functional compound containing a polyfluoroalkyl group can be advantageously used as a durability-improving component of a water and oil repellent containing a polyfluoroalkyl group. That is,

[Formula] When a polymerizable compound containing such groups is copolymerized with a polyfluoroalkyl group-containing monomer, polymerization is possible in an aqueous medium, resulting in a versatile water and oil repellent in the form of an aqueous dispersion. It has been found that excellent durability can be achieved by heat-treating fibers treated with the obtained water- and oil-repellent at 100°C or higher. Furthermore, copolymers containing such functional compounds are stable at room temperature and are very advantageous in terms of handling. Thus, the present invention has been completed based on the above findings, and it provides a polymerizable compound containing a polyfluoroalkyl group and a compound that is stable in water at room temperature.
The present invention provides a new highly durable water and oil repellent made of a copolymer containing as a structural unit a polymerizable compound having a group that can change to -N=C=O at a temperature of 100°C or higher. be. The water and oil repellent of the present invention not only has the above-mentioned advantages in terms of handling and general use, but also can exhibit superior durability compared to the case where conventional durability-improving components are used. In addition, the initial water and oil repellency immediately after treatment is also very excellent. Furthermore, various advantages such as improved abrasion resistance and dry soil resistance are recognized. In the present invention, as the polyfluoroalkyl group-containing polymerizable compound, various compounds can be exemplified without particular limitation, such as conventionally known or well-known compounds. For example, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH=CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ OCOC(CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ OCOC (CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ OCOCH=
CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₄ OCOCH=CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOC (CH ₃ )
= CH ₂ , CF ₃ (CF ₂ ) ₆ COOCH = CH ₂ , Examples include unsaturated esters represented by acrylates or methacrylates containing a perfluoroalkyl group having 3 to 20 carbon atoms. In addition, the polyfluoroalkyl group-containing polymerizable compound in the present invention includes: Although polymerizable compounds such as H(CF ₂ ) ₁₀ CH ₂ OCOCH=CH ₂ and CF ₂ Cl(CF ₂ ) ₁₀ CH ₂ OCOC(CH ₃ )=CH ₂ can also be mentioned, the above-mentioned compounds are usually used. Those containing a terminal perfluoroalkyl group are more desirable. In the present invention, as the polymerizable functional compound, a monomer having a group that is stable in water at room temperature and convertible to -N=C=O group at a temperature of 100° C. or higher is employed. For example, the amimid group

[Formula] Containing monomer is suitable, specifically CH ₂ = C (CH ₃ ) CON--N
( _CH3 ) _{2 CH2CH} (OH) _CH3 , _CH2 =C( _CH3 )
CON―N (C ₆ H ₅ ) ₂ CH ₂ CH (OH) CH ₃ , CH ₂ =C
Examples include (CH ₃ ) CON-N (CH ₃ ) ₃ . That is, the general formula

These include compounds represented by the formula: R ¹ in the formula is a hydrogen atom or a lower alkyl group, preferably a hydrogen atom or a methyl group. R ² and R ³ are a hydrogen atom, an alkyl group, or an aryl group, preferably a lower alkyl group. R ⁴ is an alkyl group or a hydroxyalkyl group, preferably a methyl group, 2
-Those having 1 to 3 carbon atoms such as hydroxypropyl group. In addition, as a specific functional compound, ―CONH
-A-NHCO- group-containing monomers are exemplified, specifically, those having the general formula CH ₂ =C(R ¹ )COO(CH ₂ CH ₂ O) _o
These include compounds represented by CONH-A-NHCOB. R ¹ in the formula is a hydrogen atom or a lower alkyl group, preferably a hydrogen atom or a methyl group. A is a divalent alkylene group or a phenylene group, preferably a divalent alkylene group or a phenylene group having 2 to 6 carbon atoms. B is an oxyalkyl group, an oxyphenyl group, or -CH
(COOR ⁵ ) ₂ groups, and R ⁵ is a lower alkyl group. A preferred example of B is -OC ₆ H ₅ . Also n
is an integer of 0 or 150. Specific compounds include: For example, The durability of water and oil repellents can be improved by using small amounts of functional compounds such as those mentioned above.
In the present invention, in particular, by employing the monomer containing an aminimide group, it is possible to achieve not only simple washability but also advantages such as improved abrasion resistance and dry soil resistance. In the present invention, the polyfluoroalkyl group-containing polymerizable compound has the general formula CH ₂ =C
(R ¹ )COO(R) _n Rf (However, Rf in the formula has 3 carbon atoms.
~20 linear or branched polyfluoroalkyl groups, R ¹ is a hydrogen atom or a methyl group, R is 1 to 10
The use of acrylates or methacrylates represented by straight-chain or branched divalent alkylene groups having 5 carbon atoms, where m is 0 or 1, respectively, is suitable for wide-ranging commercial applications and performance. This can be said to be particularly advantageous. In addition, Rf has a carbon number of 6 to 12
m is a perfluoroalkyl group, and R is an alkylene group having 2 to 4 carbon atoms.
It is particularly desirable that the value is 1. In addition to the above-mentioned polyfluoroalkyl group-containing polymerizable compound and specific functional compound, the copolymer in the present invention further includes ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, acrylamide, methacrylamide, Styrene, α-methylstyrene, p-methylstyrene, alkyl esters of acrylic or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ethers, halogenated alkyl vinyl ethers, vinyl alkyl ketones, cyclohexyl acrylate or methacrylate, maleic anhydride,
Butadiene, isoprene, chloroprene, hydrophilic monomers, such as those with the general formula CH ₂ =C(R')COO-(
AIK―O―) _x R″ (AIK is a C ₂ to C ₆ alkylene group,
x is an integer of 1 to 50, and R' and R'' are hydrogen atoms or methyl groups). It is also possible to polymerize.By appropriately selecting and copolymerizing these polymerizable compounds, in addition to water and oil repellency and durability, dry soil resistance, abrasion resistance, and selective solubility can be achieved. , flexibility, tactility, etc. In the copolymer of the present invention, the copolymerization ratio of the polyfluoroalkyl group-containing polymerizable compound is at least 25% by weight, preferably at least 25% by weight. 40% by weight
In particular, about 50 to 80% by weight is appropriate. Further, the copolymerization ratio of the specific functional compound may be small, usually about 1 to 10% by weight, particularly about 2 to 5% by weight. Other monomers can be employed at appropriate copolymerization ratios depending on the purpose. In order to obtain the copolymer of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected, including bulk polymerization,
Any of various polymerization methods such as liquid polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization can be employed. For example, a method may be employed in which a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant or the like and copolymerized with stirring. As a polymerization initiation source, various polymerization initiators such as organic peroxides, azo compounds, persulfates, and further ionizing radiation such as γ-rays can be employed. Furthermore, as a surfactant, almost all of the various anionic, cationic, or nonionic emulsifiers can be used. Therefore, the raw material polymerizable compound may be dissolved in a suitable organic solvent and subjected to solution polymerization by the action of a polymerization initiation source (peroxide, azo compound, ionizing radiation, etc. soluble in the organic solvent used). I can do it. Suitable solvents for solution polymerization include trichlorotrifluoroethane, tetrachlorodifluoroethane, methylchloroform, and the like. Aerosol type, organic solvent type, or latex type water and oil repellents can be directly produced by solution polymerization or emulsion polymerization. The water- and oil-repellent agent made of the copolymer of the present invention thus obtained is prepared in any form such as an emulsion, a solvent solution, or an aerosol according to a conventional method. for example,
As mentioned above, an aqueous emulsion is made by emulsion polymerization,
Solvent solution forms can also be prepared directly by solution polymerization. In addition, solvent solution type copolymers are obtained by other polymerization methods such as bulk polymerization and emulsion polymerization.
In one or a mixture of two or more suitable organic solvents such as acetone, methyl ethyl ketone, diethyl ether, dioxane, methyl chloroform, trichloroethylene, tetrachloroethylene, and chlorinated saturated hydrocarbons such as tetrachlorodifluoroethane, trichlorotrifluoroethane. It can also be prepared by dissolving it in In addition, for the aerosol type, prepare a solution type solvent solution as described above,
Furthermore, a propellant such as dichlorodifluoromethane, monofluorotrichloromethane, or dichlorotetrafluoroethane may be added thereto, and the mixture may be filled into a suitable container. The water and oil repellent of the present invention can be applied to the article to be treated by any method depending on the type of the article and the preparation form (solvent solution type, aerosol type, etc.). For example, in the case of an aqueous emulsion or a solvent solution type, a method may be employed in which the coating is applied to the surface of the object to be treated and dried by a known coating method such as dip coating. Further, if necessary, curing may be performed by applying a suitable crosslinking agent. In addition, with an aerosol type water and oil repellent, it is sufficient to simply spray it onto the object to be treated.
It dries immediately and exhibits sufficient water and oil repellency. Furthermore, the water and oil repellent of the present invention may be mixed with other polymer blenders, such as other water and oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents, etc. Of course, it is also possible to add appropriate additives and use them together. In order to treat textiles, etc. with the water and oil repellent of the present invention, after application by the various means described above, the object to be treated is heated at a temperature of 100°C or higher, preferably at a temperature of about 120 to 170°C for 10 seconds to Heat treatment is carried out for 60 minutes, preferably for about 1 to 20 minutes, in order to improve durability. By such heat treatment, the specific group of the functional compound is converted into a highly active -N=C=O group, and it also reacts with various base materials and adheres closely to the water- and oil-repellent base agent. Therefore, the present invention is particularly preferably applied to objects to be treated that contain functional groups, such as active hydrogen groups, which can react with -N=C=O groups. There are various examples of articles that can be treated with the water and oil repellent of the present invention without particular limitation. Examples include textiles, glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, nitrogen products, plastics, painted surfaces and plasters. The fiber fabrics include natural fibers of animal and plant origin such as cotton, linen, wool, and silk, various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, and rayon and acetate. Examples include semi-synthetic fibers, glass fibers, inorganic fibers such as asbestos fibers, and woven fabrics of mixed fibers thereof. The water and oil repellent of the present invention is used as an antifouling agent due to its high water and oil repellency and durability, and can be used for carpets, reception sets, curtains, wallpaper, etc.
Interior products such as car interior parts, outdoor tents,
It can also be applied to buildings, etc., and is applied to the surfaces of articles made of the various materials mentioned above. Of course, it can be suitably used for textile fabrics. Next, examples of the present invention will be described in more detail, but it goes without saying that this description does not limit the present invention. The water repellency and oil repellency shown in the following examples are shown using the following scale. That is, water repellency is expressed by the water repellency number (see Table 1 below) determined by the JISL-1005 spray method, and oil repellency is expressed by applying the test solution shown in Table 2 below to two locations on the sample cloth. Place several drops (approximately 4 mm in diameter) and judge by the penetration state after 30 seconds (AATCC-
TM118―1966).

【table】

【table】

[Table] Water repellency No. and oil repellency are marked with a + mark.
Each shows slightly better performance. In addition, the durability test was conducted as follows. That is,
The treated cloth was made up to 1kg using ballast cloth, placed in an electric washing machine, and washed with 60g of detergent (Super Zabu: brand name).
Adjust the bath volume to 35, treat at 50°C for 10 minutes, then rinse and air dry. After repeating this operation a predetermined number of times, water and oil repellency is measured to determine durability. Examples 1 to 5 and Comparative Examples 1 to 3 Functional compounds used in this example CH ₂ =C
(CH ₃ ) CON―N (CH ₃ ) ₂ CH ₂ CH (OH) CH ₃
(DHA-3) is CH ₂ = C (CH ₃ )COOCH ₃ 100g
(1 mol), (CH ₃ ) ₂ N-NH ₂ 60g (1 mol),

[Formula] 58g (1 mol) and isopropanol 500ml were charged into a flask with an internal volume of 1,
After reacting at 60°C for 4 hours, isopropanol was removed and the product was recrystallized twice from ethyl acetate. RfCH ₂ CH ₂ OCOCH=CH ₂ (Rf
is C ₆ F ₁₃ /C ₈ F ₁₇ /C ₁₀ F ₂₁ /C ₁₂ F ₂₅ = 1/3/2/
1 (hereinafter referred to as FA), butyl methacrylate (BMA), vinyl chloride (VCl), tertiary butyl methacrylate (t-BMA), and DHA-3 in the composition shown in Table 3 below, and methyl chloroform.
After 200 g of azobisisobutyronitrile and 1 g of azobisisobutyronitrile were charged, the mixture was replaced with nitrogen for about 20 minutes, and then a copolymerization reaction was carried out at 70° C. for 15 hours with stirring. A resulting polymer solution containing a copolymer having the composition shown in Table 3 below was diluted with methyl chloroform to a polymer concentration of 0.1% by weight.
A nylon taffeta cloth was immersed in this diluted liquid for 10 seconds, the liquid was thoroughly shaken off, and the cloth was dried at room temperature for 1 hour and cured at 170°C for 1 minute, and the water and oil repellency of the resulting cloth was measured. In addition, for the durability test, water and oil repellency was measured after washing five times. The measurement results are shown in Table 3 below.
Table 3 below also shows the performance of a copolymer not containing DHA-3 and a copolymer containing other durability-enhancing components as comparative examples. In Table 3, HMDAA represents hydroxymethyl diacetone acrylamide and N-MAM represents N-methylol acrylamide.

【table】

[Table] Functional group compounds , _CH2 =CHCOO( _CH2CH2O ) _4H24.8g ( _0.1mol ), toluene diisocyanate 17.4g (0.1mol), phenol 9.4g (0.1mol), methyl isobutyl ketone 250ml in a 500ml internal volume scalpel. It was obtained by charging the mixture into a flask and reacting at 60°C for 4 hours. In a glass autoclave (inner volume 500 ml) equipped with a stirrer, FA 70 g Butyl methacrylate 28 g (A) 2 g Methyl chloroform 200 g Azobisisobutyronitrile
1 g was charged, and after purging with nitrogen for about 20 minutes, a copolymerization reaction was carried out at 70°C for 15 hours with stirring. As a result of treating the above polymer on nylon cloth in the same manner as above and evaluating its performance, the initial water repellency was
100, oil repellency 6, water repellency 90 after washing 5 times, and oil repellency 5.

Claims (1)

[Scope of Claims] 1. A polymerizable compound containing a polyfluoroalkyl group represented by the following general formula () and a compound represented by the following general formula () or () that is stable in water at room temperature and at a temperature of 100°C or higher. A water and oil repellent agent comprising a copolymer containing as a structural unit a polymerizable functional compound having a group that can be converted into a -N=C=O group. CH ₂ =C(R')COO(R) _n Rf...() (However, Rf in the formula is a linear or branched polyfluoroalkyl group having 3 to 20 carbon atoms, and R' is a hydrogen atom. or a methyl group, R is a linear or branched divalent alkylene group having 1 to 10 carbon atoms, and m is 0 or 1, respectively.) (However, R ¹ in the formula is a hydrogen atom or a lower alkyl group, R ² and R ³ are a hydrogen atom, an alkyl group, or an aryl group, and R ⁴ is an alkyl group or a hydroxyalkyl group.) CH ₂ =C(R ⁵ )COO(CH ₂ CH ₂ O) _o CONH―A―
NHCO-B...() (However, R ⁵ is a hydrogen atom or a lower alkyl group, A is a divalent alkylene group or phenylene group, B is an oxyalkyl group, oxyphenyl group, or -CH (COOR ⁶ ) ₂ groups, R ⁶ is a lower alkyl group, and n is 0 or an integer from 1 to 50.) 2 The copolymerization ratio of the polymerizable compound containing a polyfluoroalkyl group is at least 25% by weight. A water and oil repellent according to claim 1. 3. The water and oil repellent according to claim 1, wherein the copolymerization ratio of the functional compound is 1 to 20% by weight.