JPH0465113B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a water/oil repellent agent and a water/oil repellent composition containing a copolymer of acrylic acid ester or methacrylic acid ester having a fluoroaliphatic group as an active ingredient. <Prior Art> Conventionally, copolymers containing 25 to 75% by weight of acrylic esters or methacrylic esters having fluoroaliphatic groups have been used as water and oil repellents for various purposes. In addition, as a water and oil repellent composition that can be easily used at home, an aerosol composition is known in which the copolymer is dissolved in an organic solvent and a propellant is added (Japanese Patent Application Laid-Open No. 1983-1989-1).
79186 and Japanese Unexamined Patent Publication No. 104978/1983). The aerosol water- and oil-repellent composition can be easily applied to the object to be treated, and can then exhibit water- and oil-repellent effects simply by air-drying. However, there may be problems such as whitening or dusting caused by uneven spraying, or a decrease in water and oil repellency due to a decrease in the volatility of the organic solvent when treated in a low-temperature atmosphere. Conventionally, 1,1,1-trichloroethane has been commonly used as a solvent. This has the drawbacks of low volatility and a bad odor characteristic of chlorine.
Therefore, it may be possible to replace this with trichlorotrifluoroethane. However, it has been found that when trichlorotrifluoroethane is used as an active ingredient in conventional water and oil repellents, the whitening or dusting phenomenon is not solved, but rather becomes more severe. <Objective of the Invention> The object of the present invention is to improve the whitening phenomenon and the dusting phenomenon, and to improve the water and oil repellency when processing in a low temperature atmosphere, based on the premise that trichlorotrifluoroethane is used as the organic solvent. An object of the present invention is to provide a water- and oil-repellent agent and a water- and oil-repellent composition. <Structure of the Invention> The present inventors have discovered that 1, which is conventionally commonly used as a solvent,
When highly volatile trichlorotrifluoroethane (D) is used instead of 1,1-trichloroethane, (A) more than 80% by weight of an acrylic ester or methacrylic ester having a fluoroaliphatic group; (B) A copolymer consisting of 2% by weight or more and less than 20% by weight of ethylhexyl acrylate or ethylhexyl methacrylate and (C) 0 to 10% by weight of ethylene or other copolymerizable substituted ethylene is used as the active ingredient of the water and oil repellent. It has been found that the above problem can be solved by The acrylic ester or methacrylic ester (A) having a fluoroaliphatic group typically has the formula: Rf−(CH ₂ ) nOCOCR ³ = CH ₂ (2) [Wherein, Rf is a perfluoroalkyl group or perfluoroalkenyl group having 3 to 21 carbon atoms, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is an alkylene group having 1 to 10 carbon atoms, R ³ represents hydrogen or a methyl group, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10. ] Compounds represented by these can be mentioned. Furthermore, as specific examples, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₁ 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 ) ₆ (CH ₂ ) ₂ OCOC(CH ₃ )=CH ₂ CF(CF ₃ ) ₂ (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH=CH ₂ CF (CF ₃ ) ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOCH=OH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ OCOCH=
CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOC (CH ₃ )
＝CH ₂ CF (CF ₃ ) ₂ (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH＝
CH ₂ CF (CF ₃ ) ₂ (CF ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) OCOC
(CH ₃ ) = CH ₂ CClF ₂ (CF ₂ ) ₁₀ CH ₂ OCOC (CH ₃ ) = CH ₂ H (CF ₂ ) CH ₂ OCOCH = CH ₂ CF (CF ₃ ) (CClF ₂ ) (CF ₂ ) ₇ CONHCOOCH =
Examples include CH ₂ and the like. A methacrylic ester compound corresponding to the above acrylic ester compound and an acrylic ester compound corresponding to the above methacrylic ester compound can also be used. Monomer (A) is contained in the copolymer in an amount of 80% by weight or more. At this time, good water and oil repellency for synthetic fibers can be obtained, but cannot be obtained when the amount is less than 80% by weight. Ethylhexyl acrylate or ethylhexyl methacrylate (B) is usually 2-ethylhexyl acrylate or 2-ethylhexyl methacrylate, [In the formula, R is a methyl group or hydrogen. ] It is a compound shown by. Monomer (B) is contained in the copolymer in an amount of 2 to 20% by weight, preferably 2 to 10% by weight. If the amount is less than 2% by weight, the whitening phenomenon or dusting phenomenon will not be improved. If the amount is more than 20% by weight, the monomer (A) will be less than 80% by weight, and good water and oil repellency cannot be obtained. There are various other copolymerizable substituted ethylenes (C), but examples include (1) acrylic acid and methacrylic acid, and their methyl, ethyl, butyl, isobutyl, t-butyl, propyl, hexyl, Decyl, lauryl, stearyl, isobornyl, β-hydroxyethyl, glycidyl ester, phenyl, benzyl,
4-cyanophenyl esters, RO
(CH ₂ CH ₂ O) mH (where R is an alekyl group, m
is an integer greater than or equal to 1. ), (2) acetic acid,
Vinyl esters of fatty acids such as propionic acid, caprylic acid, lauric acid, and stearic acid, (3) styrenic compounds such as styrene, α-methylstyrene, and p-methylstyrene, (5) allyl heptanoate, allyl caprylate, Aliphatic allyl esters such as allyl caproate, (6) vinyl alkyl ketones such as vinyl methyl ketone and vinyl ethyl ketone, (7) N
- Acrylamides such as methylacrylamide and H-methylolmethacrylamide; (8) dienes such as 2,3-dichloro-1,3-butadiene and isoprene; and (9) alkylene glycols such as ethylene dimethacrylate; These include acrylic acid or methacrylic acid esters of polyalkylene glycol. Monomer (C) is contained in the copolymer in an amount of 0 to 10% by weight. Ethylene or other copolymerizable substituted ethylene (C)
Among them, the preferred one is the formula: [In the formula, R is a methyl group or hydrogen. ] Glycidyl acrylate or glycidyl methacrylate. The copolymerized terpolymer also provides good water and oil repellency to natural fibers. It is also possible to use this in combination with ethylene or other copolymerizable substituted ethylenes. Glycidyl acrylate or glycidyl methacrylate is preferably contained in the copolymer in an amount of 2 to 10% by weight, more preferably 2 to 8% by weight. When the amount is less than 2% by weight, good water and oil repellency against natural fibers cannot be obtained. Ten
If the amount is more than 1% by weight, the whitening phenomenon or dusting phenomenon will not be improved. To produce the water and oil repellent of the present invention, the monomer
(A), monomer (B) and, if necessary, monomer (C) may be polymerized by a known method applicable to the polymerization of vinyl compounds. The polymerization is carried out in a vessel equipped with a stirrer and means for external heating or cooling. The method of polymerization reaction can be arbitrarily selected, including bulk polymerization,
Any of solution polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, etc. can be used. The polymerization is preferably carried out by solution polymerization using a solvent.
The resulting solution is typically used to directly prepare the compositions of the invention by simply adding other ingredients. In solution polymerization, trichlorotrifluoroethane is preferably used alone as a solvent. In addition, other solvents with low boiling points other than trichlorotrifluoroethane, such as acetone and tetrachlorodifluoroethane (1,1,2,2-tetrachloro-1,2-difluoroethane), may be added to the total weight of trichlorotrifluoroethane. It is also possible to add up to 50% by weight and use it in combination with trichlorotrifluoroethane. Solution polymerization can be performed, for example, as follows. Add the monomer mixture to the solvent, make the monomer concentration 5-50% by weight, and adjust the temperature of the monomer solution to 40-150%.
℃ and the polymerization is carried out in the presence of a catalyst. The catalyst is
Can be any of the known agents for initiating solution polymerization of vinylically unsaturated compounds, typically
Peroxides and azo compounds that are soluble in solvents are used. Such peroxides include acyl peroxides such as benzoyl peroxide and lauroyl peroxide, organic peresters such as t-butyl perbenzoate, and dialkyl peroxides such as di-t-butyl peroxide. is azobis (isobutyronitrile),
Examples include azobis(2,4-dimethylvaleronitrile). The amount of catalyst is usually 0.1-2% based on the monomer weight. If the catalyst alone or other conditions are insufficient to control the molecular weight, a small amount of a chain transfer agent such as an alkane ( _C1 - _C12 ) thiol may be added. The copolymer preferably has a molecular weight of 1,000 to 50,000. When the molecular weight is lower than 1,000, water and oil repellency decreases, and when it is higher than 50,000, whitening and flaking phenomena occur. The molecular weight of the copolymer is particularly preferably from 5,000 to 30,000. In the water and oil repellent composition of the present invention, the solvent trichlorotrifluoroethane (D) usually contains 1,
1,2-trichloro-1,2,2-trifluoroethane. The amount is preferably such that the copolymer accounts for 0.2 to 2.0% by weight based on the total weight of the copolymer and solvent. The propellant (E) is preferably a fluoroalkane or chlorofluoroalkane having 1 or 2 carbon atoms, LPG gas or carbon dioxide gas. Representative examples of fluoroalkane or chlorofluoroalkane having 1 or 2 carbon atoms include dichlorodifluoromethane, trichlorotrifluoromethane, chlorodifluoromethane, chlorodifluoroethane,
Examples include dichlorotrifluoroethane, tetrafluoroethane, and mixtures of two or more thereof, with dichlorodifluoromethane being preferred. The amount of propellant (E) is based on the total weight of copolymer and solvent.
It is preferably 0.05 to 2 times. In order to produce the water and oil repellent composition of the present invention, for example, a polymer obtained by solution polymerizing monomers (A), (B) and (C) in trichlorotrifluoroethane (D) is used. Trichlorotrifluoroethane (D) may be further added to the solution, and then the propellant (E) may be mixed. <Effects of the Invention> The advantages of the water and oil repellent of the present invention are as follows when an aerosol composition is prepared using trichlorotrifluoroethane as a solvent. Under all conditions, dusting and whitening of the fabric during spraying is significantly improved. Even when treated at low temperatures, it shows good water and oil repellency against synthetic fibers, especially good water repellency, and when glycidyl acrylate or glycidyl methacrylate is used as a component of the copolymer, it shows good repellency against natural fibers. The same is true. Further, the advantages of the water and oil repellent composition of the present invention are as follows. This is an aerosol composition that does not have the characteristic odor of chlorine. It is a safe, non-flammable aerosol composition. The water and oil repellent agent and water and oil repellent composition of the present invention include:
It has a wide range of uses, including use in high-quality clothing such as Japanese clothing, and use under adverse conditions such as winter mountains. <Example> Examples and comparative examples of the present invention are shown below. Example 1 12.7 g of CF ₃ (CF ₂ )nCH ₂ CH ₂ OCOCH=CH ₂ (average value of n=3.6) in a 4-necked 200 c.c. flask Add 61.1 g of trichlorotrifluoroethane, 23.5 g of tetrachlorodifluoroethane, and 9.4 g of acetone, attach a thermometer, glass tube, stirrer, and condenser, and blow in nitrogen gas while heating to 50°C to thoroughly fill the inside of the flask with nitrogen gas. Replaced with. Thereafter, 0.25 g of t-butyl peroxypivalate was added and polymerized for 2 hours at 50°C. As confirmed by gas chromatography, the polymerization rate of all monomers was 100%. Polymer concentration is 13.0% by weight as measured by evaporation to dryness method
It was hot. The average molecular weight of the polymer determined by vapor pressure osmometry was approximately 20,000. The polymer solution thus obtained was diluted with trichlorotrifluoroethane to adjust the polymer concentration.
The concentration was adjusted to 0.5% by weight, and 70g of the mixture was mixed with 30g of dichlorodifluoroethane to prepare an aerosol composition. Using this aerosol composition as a test specimen, tests were conducted on the degree of whitening (presence or absence of whitening) and water and oil repellency.
Tests for degree of whitening and water and oil repellency were conducted as follows. [Degree of whitening] An aerosol was sprayed at room temperature from a distance of 10 cm onto a black nylon cloth fixed vertically ^, and the presence or absence of whitening was visually evaluated. ○: No whitening. ×: Whitening occurs. [Water and oil repellency] The water repellency test method followed the spray method of JISL-1092. Water repellency test method is AATCC-TM-
118-1986 was followed. The ambient temperature was maintained at 5° C. during preparation of the sample cloth and water and oil repellency measurements. Test fabrics were prepared by spraying aerosol at a spray amount of 10 g/200 mm ² from a distance of 10 cm onto various fabrics fixed vertically, and water and oil repellency tests were conducted after 5 minutes. Evaluation criteria for water repellency and oil repellency are shown in Tables 1 and 2. Note that the + added to the right shoulder of the water repellency number indicates that the water repellency number has a value that is slightly better than the evaluation standard value.

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[Table] The test results are shown in Table 3. Examples 2 to 8 and Comparative Examples 1 to 10 In the same manner as in Example 1, polymerization was carried out using the compositions shown in Table 3, and aerosol compositions were prepared for Examples 2 to 8 and Comparative Examples 1 to 10, and tested. Served. The results are shown in Table 3.

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Claims (1)

[Scope of Claims] 1 (A) More than 80% by weight of acrylic ester or methacrylic ester having a fluoroaliphatic group, (B) 2% by weight or more and less than 20% by weight of ethylhexyl acrylate or ethylhexyl methacrylate, and (C ) A water and oil repellent composition containing as an active ingredient a copolymer consisting of 0 to 10% by weight of ethylene or other copolymerizable substituted ethylene. 2. The water and oil repellent composition according to claim 1, wherein the amount of ethylhexyl acrylate or ethylhexyl methacrylate (B) is 2 to 10% by weight. 3 Ethylene or other copolymerizable substituted ethylene
2. The water and oil repellent composition according to claim 1, wherein (C) is glycidyl acrylate or glycidyl methacrylate in an amount of 2 to 10% by weight. 4. The water and oil repellent composition according to claim 1, which comprises (D) trichlorotrifluoroethane and (E) a propellant. 5. The water and oil repellent composition according to claim 4, wherein the propellant (E) is a fluoroalkane or chlorofluoroalkane having 1 or 2 carbon atoms.