JPS6342954B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to water and oil repellents. More specifically, the present invention relates to a water and oil repellent made of a polymer having a perfluoroalkyl ether group in its side chain. Water and oil repellents made of polymers having perfluoroalkyl groups in their side chains have been known for a long time. For example, in Japanese Patent Publication No. 49-35348, diacetone acrylamide is added to a polymerizable monomer containing a fluoroalkyl group. A water and oil repellent made of a copolymer obtained by copolymerizing a compound or its -CH ₂ OR derivative and, if necessary, vinyl chloride, has also been disclosed in Japanese Patent Publication No. 1973-
No. 9416 discloses that a methacrylic ester having a perfluoroalkyl group at the end of the ester group is
A water and oil repellent agent comprising a copolymer of ethylhexyl methacrylate, a (meth)acrylic acid ester having a hydroxyl group in the ester group, and N-methylolacrylamide is described. These copolymers having perfluoroalkyl groups in their side chains have the specificity of perfluoroalkyl groups, that is, they lack affinity with substances that do not have perfluoroalkyl groups, and they have extremely low surface tension. It is used in water and oil repellents as a copolymer that has improved other required physical properties by copolymerizing it with other comonomers. For example, in the case of the copolymer described in Japanese Patent Publication No. 47-9416, perfluoroalkyl group-containing methacrylic ester provides water and oil repellency, 2-ethylhexyl methacrylate provides water repellency and flexibility, and hydroxyl group provides water and oil repellency. The (meth)acrylic acid ester and N-methylolacrylamide contained in the copolymer are copolymerized in order to impart adhesion to fibers and the like to the copolymer. Generally, water and oil repellents are used as treatment agents for fibers, etc., but homopolymers with perfluoroalkyl groups in their side chains are crystalline because the perfluoroalkyl groups are rigid and long chains. ,
When such a crystalline polymer is applied to fibers, etc., the fibers become stiff and their texture is impaired. In addition, since it is a crystalline polymer, if it is applied to colored fabrics, the dried water and oil repellent film will not become transparent and the color of the fabric will be damaged.
In practice, it is never used in the form of a homopolymer. In order to avoid these drawbacks that occur when a homopolymer having a perfluoroalkyl group in the side chain is used for a water and oil repellent, copolymerization with other comonomers as described in the above-mentioned patent publications is necessary. However, even if the modification is successful, the proportion of perfluoroalkyl group-containing monomer components in the copolymer decreases, resulting in In many cases, water and oil repellency, which is the most desired property, is impaired, and to date, there have been almost no water and oil repellents that can satisfy both water and oil repellency and other physical properties at the same time. This is the reality. The present inventor has conducted various studies in search of a polymer that does not take the form of a copolymer that impairs water and oil repellency, but also reduces the rigidity and crystallinity seen in homopolymers. Even if a polymer having a (perfluoroalkylene glycol) group in its side chain is a homopolymer, it does not impair the texture or color when applied to fabrics, etc., and also exhibits sufficient water and oil repellency. I discovered that. Also,
This polymer can be in the form of a copolymer within a range that does not impair its water and oil repellency, and in this case, the washing resistance will be even better. Therefore, an object of the present invention is to provide a water and oil repellent made of a homopolymer or a copolymer that exhibits sufficient water and oil repellency without impairing the texture or color when applied to fabric or the like. It is said that Such water and oil repellents are used in the form of homopolymers or copolymers, respectively. Consists of a polymer with poly(perfluoropropylene glycol) groups in the side chains. And, as a polymer having a poly(perfluoropropylene glycol) group in the side chain, the general formula is (Here, R is a divalent organic bonding group,
R' is a hydrogen atom or a methyl group, n is 0 or an integer, generally an integer of 50 or less, and m is an integer, generally an integer of 1 to 10). Consolidation is used. Examples of such vinyl compounds include:

[Formula] When the group is R _f , CH ₂ = CR'-COOCH ₂ -R _f CH ₂ = CR'-OCO-R _f CH ₂ = CR'-CH ₂ OCO-R _f CH ₂ = CR' ―CH ₂ OCH ₂ ―R _f CH ₂ ＝CR′―CONR″CO―R _f CH ₂ ＝CR′―COOCH ₂ CH ₂ NR″CO―R _f CH ₂ ＝CR′―COOCH ₂ CH(OH)CH ₂ OCO―R _f CH ₂ = CR′―COOCH ₂ CH(OH)CH ₂ OCH ₂ ―
R _f CH ₂ =CR′―CONR″CH ₂ OCO―R _f CH ₂ =CR′―COOCH ₂ CH ₂ OCO―R _f (Here, R'' is a hydrogen atom or a lower alkyl group.) These various vinyl compounds can be synthesized by using perfluoropropylene oxide alone or by using CF ₃ Using COF, COF ₂ , etc. as a reaction initiator, the acid fluoride of poly(perfluoropropylene glycol) obtained by polymerization is treated with the corresponding carboxylic acid, carboxylic acid ester, alcohol, N-substituted acid amide, etc. acrylic halide with these converted compounds,
This is carried out by condensation or addition reactions with hydroxyalkyl acrylate, glycidyl acrylate, or their corresponding methacrylic acid derivatives, and further by transesterification with vinyl acetate or the like. Alternatively, the acid fluoride itself can be subjected to a condensation reaction with a hydroxyl group-containing compound or a metal salt thereof. For the polymerization of vinyl compounds, general radical polymerization techniques can be applied as is. That is, in the case of emulsion polymerization, for example, octadecyldimethylamine hydrochloride or the like is used as an emulsifier, and azobisisobutyramidine hydrochloride or the like is used as a polymerization initiator. In the case of solution polymerization, aromatic compounds, ketones, The polymerization reaction is carried out using alcohol, halogenated hydrocarbon, etc. as a polymerization solvent, and azobisisobutyronitrile, peroxide, etc. as a polymerization initiator. These vinyl compounds can be used as water and oil repellents by themselves in the form of homopolymers having desired properties, but they can also be used as water and oil repellents in the form of copolymers with other vinyl compounds. Various other vinyl compounds that can be used as comonomers include the following. (1) Vinyl compounds having a hydrocarbon group having 4 or more carbon atoms, such as butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, etc.; halogen-containing vinyl compounds, such as vinyl chloride, Vinylidene chloride, 2-
Chlorethyl vinyl ether, vinyl bromide, vinyl fluoride, vinylidene fluoride, etc.; diene compounds, such as chloroprene, isoprene, butadiene, etc.: These vinyl compounds or diene compounds are about 99% by weight or less, preferably about 90% by weight or less It is more preferably used in a proportion of about 75% by weight or less, and contributes to improving the flexibility of the polymer and the solubility in halogenated solvents. (2) Vinyl compounds having active groups such as hydroxyl group, amide group, amino group, carboxyl group, phosphoric acid group, sulfonic acid group, etc., such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylolacrylamide, acrylamide , methacrylamide, 4
-Aminostyrene, acrylic acid, methacrylic acid, maleic acid, 2-acryloyloxyethyl acid phosphate, 4-sulfonylstyrene, etc.: These vinyl compounds are contained in an amount of about 0.01 to 10% by weight, preferably about 0.05 to 5% by weight. %, more preferably from about 0.1 to 2% by weight, and the presence of active groups in the vinyl compound increases the polymeric fiber,
Strengthens adhesion to paper, leather, etc. (3) Vinyl compounds having a lower perfluoroalkyl group, such as 2,2,2-trifluoroethyl acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl acrylate, etc.: These vinyl compounds is about 10-90% by weight,
Preferably about 20-80% by weight, more preferably about
Used in proportions of 30 to 60% by weight, they further slightly improve the water and oil repellency and flexibility, respectively, of the polymer. Water and oil repellents are prepared in the form of diluted aqueous solutions of polymers synthesized in an aqueous medium by emulsion polymerization or suspension polymerization, or by bulk polymerization. Alternatively, when the solution polymerization method is used, it is carried out in the form of a diluted solution of the organic solvent. Water and oil repellent treatment uses the water and oil repellent prepared in this way to treat various fibers such as cotton, wool, silk, polyester, polyamide, and regenerated cellulose, or woven fabrics made from blends thereof, pulp products, leather, etc. This is done on the workpiece. Next, the present invention will be described with reference to examples. Reference example 1 By the method described in Japanese Patent Publication No. 40-10061,
The following reaction was performed. The acid fluoride was hydrolyzed in the absence of a catalyst and converted to the corresponding carboxylic acid. This carboxylic acid was esterified by reaction with ethanol in the presence of a para-toluenesulfonic acid catalyst and converted to the corresponding carboxylic acid ethyl ester. This carboxylic acid ethyl ester was converted to the corresponding alcohol by reduction with lithium aluminum hydride in tetrahydrofuran solvent. The carboxylic acid ester was also converted to the corresponding N-substituted acid amide by reacting with hydroxyethylmethylamine in the absence of a catalyst. Reference example 2 Alcohol obtained in reference example 1 (n=1) 100
g (0.207 mol) and add 0.1 g of hydroquinone,
27g of acrylic acid chloride in this mixture
(0.298 mol) was added dropwise. After reacting at 70° C. for 4 hours, 20 ml (0.210 mol) of pyridine was added dropwise and the reaction was continued for an additional hour. After the reaction is complete, reduce the reaction solution to 10%
Wash with aqueous _NaHCO3 solution and separate the organic phase.
This phase is dehydrated and then distilled, with a boiling point of 55-70℃/0.1mmH.
61 g of fraction (yield 74.4%) was obtained. Based on the results of NMR spectrum, infrared absorption spectrum measurements, and elemental analysis of this fraction, this fraction is considered to be a compound represented by the following formula. F-NMR (CF ₃ COOH external standard; same below): 6-8ppm (CF ₃ , CF ₂ ) 55ppm (CF ₃ CF ₂ CF ₂ O) 69.5ppm (CF) H-NMR (TMS internal standard; same below) ; 5.5-6.5ppm (acrylic group) Infrared absorption spectrum: 1740cm ^-1 (ester group) Elemental analysis: Calculated values C: 26.87%, H: 0.93%, F: 60.26% Actual values C: 26.31%, H: 0.81% , F: 60.01% Reference Example 3 Acid fluoride obtained in Reference Example 1 (n=1) 100
g (0.210 mol), add 0.1 g of hydroquinone and 20 g of sodium fluoride, and add 25 g (0.216 mol) of 2-hydroxyethyl acrylate to this mixture.
drip. After reacting at 60-70° C. for 6 hours, the reaction mixture is filtered, and after washing the filtrate with 10% aqueous NaHCO ₃ solution, the organic phase is separated. This phase was dehydrated and then distilled to obtain 89 g (75% yield) of a fraction with a boiling point of 58-70°C/0.1 mmHg. Based on the results of NMR spectrum, infrared absorption spectrum, and elemental analysis of this fraction, this fraction is considered to be a compound represented by the following formula. F-NMR: Same as Reference Example 2 H-NMR: Same as Reference Example 2 Infrared absorption spectrum: 1780 cm ^-1 (Ester group

[Water repellency test]

A drop of water was dropped onto the treated cotton cloth, and the condition was observed after 5 minutes.

[Table] [Oil repellency test] Drop one drop of the test liquid (mixed liquid at a specific ratio shown in the table below) onto the treated cotton cloth and observe the condition after 5 minutes have elapsed. If the dropped test solution is retained on the cloth, test with a test solution with higher n-heptane content, and conversely, if it is not retained on the cloth, test with a test solution with higher n-heptane content. do. Then, using the test liquid that can be retained on the cloth at its limit, the oil repellency is evaluated based on the oil repellency evaluation shown in the table below. In the oil repellency evaluation, the case where 100% Nudyol is retained is 50, and the case where 100% Nudyol is not retained is 0.

【table】

[Rigidity test]

The bending resistance is measured based on the JIS L-1096B method, and then the flexibility is calculated according to the following formula. The closer the softness value is to 1, the closer it is to untreated cloth, and the smaller the value, the harder it is. Softness=bending resistance of untreated fabric/bending resistance of treated fabric The results obtained are shown in Table 1 below. Table 1 Test Item Test Results Water repellency 100 Oil repellency 150 Washing resistance (water repellency) 90 〃 (Oil repellency) 130 Softness 0.99 Texture Good Example 2 In Example 1, 25 parts out of 100 parts of compound ' Substitution was made with 2-ethylhexyl acrylate. Example 3 In Example 1, the same amount of compound ', which was obtained in the same manner as in Reference Example 5 and represented by the following formula, was used in place of compound '. Example 4 In Example 1, the same amount of Compound ', which was obtained in the same manner as in Reference Example 4 and represented by the following formula, was used in place of Compound '. Example 5 In Example 1, the same amount of Compound ', which was obtained in the same manner as in Reference Example 6 and represented by the following formula, was used in place of Compound '. Example 6 In Example 1, the same amount of Compound ', which was obtained in the same manner as in Reference Example 3 and represented by the following formula, was used in place of Compound '. Comparative Example 1 In Example 1, the same amount of Compound X represented by the following formula was used in place of Compound '. Many precipitates were observed during the polymerization reaction. CH ₂ =CHCOOCH ₂ CH ₂ C ₈ F ₁₇ [Compound X] Comparative Example 2 In Example 2, the same amount of Compound X was used instead of Compound'. The water-based latex obtained in Examples 2 to 6 and Comparative Examples 1 to 2 above was subjected to a water repellency test, an oil repellency test, a washability test, and a stiffness test on cotton cloth soaked therein in the same manner as in Example 1. I did it. The results obtained are shown in Table 2 below.

【table】

Table: Examples 7 to 10 in which agents were desorbed from fabrics In example 2, the same amounts of various compounds' with different average values of n were used. For each of the obtained aqueous latexes,
A water repellency test, an oil repellency test, a washability test, and a stiffness test of the cotton cloth soaked therein were conducted in the same manner as in Example 1. The results obtained are as follows:
Shown in the table.

【table】

Claims (1)

[Claims] 1. The hydroxyl group-containing vinyl compound is 0.05 to 5
A water- and oil-repellent agent comprising an aqueous latex of a polymer of a vinyl compound represented by the following general formula, which is copolymerized in a weight percent. R: divalent organic group R': hydrogen atom or methyl group n: 0 or an integer m: an integer.