JPS6356912B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel water and oil repellent having high water repellency, which is made of a specific copolymer containing a perfluoroalkyl group. Traditionally, perfluoroalkyl groups (hereinafter referred to as
Water and oil repellents made of various copolymers containing PFA groups (sometimes abbreviated as PFA groups) are well known. Various other monomers have been proposed to be copolymerized with the PFA group-containing polymerizable compound. For example, JP-A-55-9619, JP-A-55-29501, JP-A-55-45756.
JP-A-2006-100003 describes a water and oil repellent comprising a polymerizable compound containing a PFA group and a copolymer containing stearyl acrylate and stearyl methacrylate as constituent units. When such stearyl acrylates are used, water repellency is improved without impairing oil repellency, and solubility in organic solvents is also improved. According to studies conducted by the present inventors, it has been found that although the use of stearyl acrylates has the effect of improving water repellency, the water repellency is still insufficient when treating polyamide and polyester fibers. Based on the recognition of this problem, the present inventor has conducted various studies and examinations, and has determined that in order to improve water repellency, the hydrophilic portion should be

It has been found that it is important to protect the group [Formula]. the result,
It has been found that it is extremely effective to copolymerize a branched higher alkyl acrylate such as isostearyl methacrylate with a polymerizable compound containing a PFA group. The present invention thus provides polymerizable compounds containing perfluoroalkyl groups and compounds of the general formula CH ₂ =
CR ¹ COOR (in the formula, R ¹ is a hydrogen atom or a methyl group, R
The present invention provides a new water and oil repellent agent comprising a copolymer containing as a constitutional unit an acrylate (branched higher alkyl group having 8 to 40 carbon atoms). The water and oil repellent of the present invention has very excellent water and oil repellency, and can impart sufficiently high water and oil repellency even at low concentrations, for example, in fiber treatment. In the present invention, it is important to copolymerize a specific branched higher alkyl acrylate of the general formula CH ₂ =CR ¹ COOR with a polymerizable compound containing a PFA group (hereinafter abbreviated as a PFA compound).
Specific acrylates include acrylates in which R ¹ is a hydrogen atom and methacrylates in which R ¹ is a methyl group. And R has 8 to 40 carbon atoms
It is a higher alkyl group with a branched structure. In particular, R is preferably C ₁₈ H ₃₇ having 18 carbon atoms and having a branched structure. By adopting a branched structure of R, the hydrophilic moiety becomes more concentrated than a linear alkyl group.

[Formula] The effect of protecting groups is increased, and film-forming properties are improved, so it provides high water and oil repellency. It goes without saying that this explanation helps in understanding the present invention and does not limit the present invention in any way. The branched structure of R in specific acrylates can be varied in various ways, and examples include secondary and tertiary structures. For example, as R

【formula】

[Formula] [(CH ₃ ) ₃ CCH ₂ CH ₂ ] ₂ CH (CH ₃ ) CH ₂ ―, (CH ₃ ) ₂ CH (CH ₂ ) ₃ CH (CH ₃ ) (CH ₂ ) ₂ CH
Specific examples include (CH ₃ )CH ₂ CH ₂ . In the present invention, various PFA 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 ) ₆ (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 4 to 20 carbon atoms. In addition, the PFA group-containing polymerizable compound in the present invention includes: Compounds that can be polymerized such as H(CF ₂ ) ₁₀ CH ₂ OCOCH=CH ₂ , CF ₂ Cl(CF ₂ ) ₁₀ CH ₂ OCOC(CH ₃ )=CH ₂ can also be mentioned, but usually the above-mentioned Those containing a terminal perfluoroalkyl group are more desirable. Therefore, as a PFA compound, the general formula CH ₂ =
CR ¹ COOR ² R _f (However, R _f in the formula is a perfluoroalkyl group represented by C _o F _2o+1 , R ¹ is a hydrogen atom or a methyl group, and R ² is represented by -C _n H _2n - A compound represented by alkylene group, n is a positive integer of 5 to 16, and m is a positive integer of 1 to 10 can be exemplified as a preferred specific example in the present invention. Particularly desirable PFA compounds are those in which n is a positive integer of 6 to 13 and m is a positive integer of 2 to 4. The water and oil repellent copolymer of the present invention preferably contains various crosslinkable monomers as structural units together with the PFA compound and specific acrylates. Such crosslinkable monomers include monomers having functional groups that can form covalent bonds with the object to be treated through addition or condensation reactions, or functional groups that can three-dimensionally cure the copolymer by the action of a curing catalyst. A wide range of monomers can be exemplified. For example, N-methylol acrylamide, N-methylol methacrylamide,
Glycidyl acrylate, glycidyl methacrylate, aziridinyl acrylate, aziridinyl methacrylate, diacetone acrylamide, diacetone methacrylamide, methylolated diacetone acrylamide, methylolated diacetone methacrylamide, ethylene diacrylate, ethylene dimethacrylate, hydroxyalkyl acrylate, Examples include hydroxyalkyl methacrylate. Suitable crosslinking monomers include:
Examples include N-methylolacrylamide and N-methylolmethacrylamide having the general formula CH ₂ =CR ¹ CONHCH ₂ OH (wherein R ¹ is a hydrogen atom or a methyl group). For the copolymer in the present invention, the copolymerization proportion of the PFA compound is at least 40% by weight, especially from 50% to 50% by weight.
Approximately 80% by weight is appropriate. In addition, the copolymerization ratio of specific acrylates is 5 to 40% by weight, especially 10 to 30% by weight.
Approximately % by weight is appropriate. Further, the copolymerization ratio of the crosslinkable monomer may be small, and usually about 1 to 10% by weight, particularly about 2 to 5% by weight is appropriate. If the amount of specific acrylates is too low, water repellency, oil repellency,
In particular, the water repellency decreases, and conversely, if the specific acrylates are too large, the oil repellency decreases, and high water and oil repellency cannot be achieved in either case. Furthermore, if the amount of the crosslinkable monomer is too large, the oil repellency will decrease, and if it is too small, problems such as a decrease in durability will occur. Of course, if the amount of the perfluoroalkyl group-containing monomer is too small, good water and oil repellency cannot be achieved. In addition to the PFA compound, specific acrylate, and crosslinkable monomer, the copolymer in the present invention further includes ethylene, vinyl chloride, vinylidene chloride, vinyl fluoride,
Acrylamide, methacrylamide, styrene,
α-methylstyrene, p-methylstyrene, lower alkyl ester of acrylic acid or methacrylic acid, benzyl acrylate or methacrylate,
One or more of various polymerizable compounds such as vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl acrylate or methacrylate, maleic anhydride, butadiene, isoprene, and chloroprene are used as constituent units of the copolymer. Copolymerization is also possible. By appropriately selecting and copolymerizing these polymerizable compounds, various properties such as durability, dry soil resistance, abrasion resistance, selective solubility, flexibility, and texture can be achieved in addition to water and oil repellency. can be appropriately improved. 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 solution 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). can. 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 can be obtained by using other polymerization methods such as bulk polymerization or 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. 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, ceramic 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 can be used for interior products such as carpets, reception sets, curtains, wallpaper, car interior products, outdoor tents, and buildings. It can also be applied to surfaces of articles made of various materials as 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 on the following scale. That is, water repellency is expressed by the water repellency No. (see Table 1 below) determined by the JIS L-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] Note that the water repellency No. and oil repellency marked with a + mark indicate slightly better performance. Reference Example 1 In this example, a typical method of emulsion polymerization for producing the copolymer of the present invention will be explained using a specific example of a binary copolymer of a PFA compound and isostearyl methacrylate. CH ₂ = in a glass reaction vessel (inner volume 500ml)
C(CH ₃ ) COOCH ₂ CH ₂ ―C _o F _2o+1 (n=6~12,
Average 8) 31.5g, isostearyl methacrylate
13.5g, deoxygenated pure water 250g, C _o H _2o+1 NH
(CH ₃ ) ₂・CH ₃ COO (n=8-16, average 13)
1.35 g, and C ₈ H ₁₇ C ₆ H ₅ (CH ₂ CH ₂ O) _o H (n=
3-30, average 20) Add 1.35g and mix with a stirrer for 10
Perform pre-emulsification for minutes. Next, this was transferred to a homogenizer (manufactured by Manton-Gaulin) and thoroughly emulsified and dispersed under a pressure of 500 kg/cm ² for 30 minutes. The product was placed in a glass autoclave (inner volume 500ml) and azobisisobutyramidine dihydrochloride 0.7
g was added thereto, and a copolymerization reaction was carried out at 60° C. for 15 hours while stirring under a nitrogen atmosphere. The obtained latex had a solid content concentration of 15.8%. Examples 1-10 and Comparative Examples 1-3 Nylon cloth is used as the test cloth. After diluting the water- and oil-repellent copolymer according to the present invention and the water- and oil-repellent agent other than the present invention with water to prepare an emulsion with a solid content concentration of 0.12%, each test cloth was immersed in the emulsion for 2 seconds. The cloth was soaked and squeezed between two rubber rollers to give a wet pick-up of 90%. Then 2 at 100℃
Water and oil repellent treatment was performed by drying for minutes and curing at 160°C for 40 seconds. The water and oil repellency of the thus obtained treated fabrics was compared. The results are shown in Table 3. In addition, in Table 3, FMA is CH ₂ = C (CH ₃ )
COOCH ₂ CH ₂ - (CF ₂ ) _o CF ₃ (n = 5 to 11, average 7), FA is CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) _o CF ₃ (n
= 5 to 11, average 7), StMA is CH ₂ = C (CH ₃ )
COOC ₁₈ H ₃₇ , EHMA is 2-ethylhexyl methacrylate, Octyl-MA is octyl methacrylate, EHA is 2-ethylhexyl acrylate,
DOM is dioctyl malate, N-MAM is N-
Each represents methylol acrylamide.

【table】

【table】

Claims (1)

[Claims] 1 General formula CH ₂ = CR ¹ COOR ² Rf (in the formula, Rf _is Co
Perfluoroalkyl group represented by F _2o+1 , R ¹
is a hydrogen atom or a methyl group, R ² is an alkylene group represented by -C _n H _2n -, n is a positive integer of 5 to 16, m is a positive integer of 1 to 10). Polymerizable compounds containing a fluoroalkyl group and acrylates of the general formula CH ₂ =CR ¹ COOR (wherein R ¹ is a hydrogen atom or a methyl group, and R is a branched higher alkyl group having 8 to 30 carbon atoms) A water and oil repellent made of a copolymer containing as a constituent unit.