JPH0156113B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyfluoroalkyl group-containing water and oil repellent, and more specifically, a vinyl polymer or copolymer containing a structural unit obtained by addition polymerization of a specific vinyl monomer containing a densified polyfluoroalkyl group. The present invention relates to a novel high-performance water and oil repellent consisting of: 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. According to the research of the present inventors, in the above-mentioned polyfluoroalkyl group-containing water and oil repellent, when the polyfluoroalkyl group is highly densified so that it is blocked, it is found that when the polyfluoroalkyl group is densified, compared to conventional random copolymers, etc. The surface of the substrate to be treated, such as fibers, can be efficiently covered with polyfluoroalkyl groups,
Therefore, it has been discovered that high water and oil repellency can be imparted even with low concentration treatment. In addition, by adopting a highly densified polyfluoroalkyl group, even if strong adsorption groups (such as -N=C=O groups) are introduced into fibers, high water and oil repellency can be maintained, resulting in high durability. It is also possible to add gender. According to the research conducted by the present inventors, telomers synthesized by a telomerization reaction using perfluoroalkyl group-containing acrylates as taxogens and thioglycolic acids as telogens are those in which perfluoroalkyl groups are blocked. -CO ₂ H, -CH ₂ OH, -
Since it has an active group such as CH ₂ NH ₂ , it has been found that various polymerizable organic groups can be introduced using this active group. The inventors have also discovered that the resulting vinyl monomer can be easily polymerized or copolymerized with other vinyl monomers to provide a high-performance water and oil repellent. Thus, the present invention has been completed based on the above findings, and has the following formula:

[Formula] [However, in the formula Z is

[Formula] (where, R' represents a hydrogen atom or a methyl group, A is a bifunctional organic group, and q represents 0 or 1), R is a hydrogen atom or a methyl group, Rf represents a carbon number of 3 to 20 Contains a polyfluoroalkyl group represented by the following polyfluoroalkyl group, Q is -O-R ¹ -, R ¹ is a bifunctional alkylene group having 1 to 10 carbon atoms, and n is an integer of 2 to 50. A polyfluoroalkyl group-containing water and oil repellent agent comprising a vinyl polymer containing a constitutional unit obtained by addition polymerization of a vinyl monomer, wherein the polyfluoroalkyl group-containing vinyl in all the monomers for forming the vinyl polymer Water and oil repellent containing polyfluoroalkyl groups, in which the proportion of monomers is at least 25% by weight. This is a new offering. The water and oil repellent of the present invention has high density polyfluoroalkyl groups, so it can exhibit high water and oil repellency at a low concentration. Furthermore, even when copolymerizing durability-improving components or hydrophilic group-containing components to impart durability and dirt removal performance, the polyfluoroalkyl groups are already densified at the monomer stage. Therefore, various additional properties can be effectively imparted without impairing high water and oil repellency. In the present invention, it is important to employ a structural unit obtained by addition polymerization of a specific blocked polyfluoroalkyl group-containing vinyl monomer.
That is, the specific polyfluoroalkyl group-containing vinyl monomer in the present invention is represented by the above general formula, and R _f is preferably a perfluoroalkyl group, particularly a perfluoroalkyl group having 6 to 14 carbon atoms. Preferably, it is a group. Of course, as R _f

[Formula] H (CF ₂ ) ₁₀ --, CF ₂ Cl(CF ₂ ) ₁₀ --, or a group containing an ether bond can be exemplified, but as water and oil repellents, perfluoroalkyl-terminated Those containing groups are more desirable. R may be either a hydrogen atom or a methyl group, and n is an integer of 2 to 50, but preferably n is an integer of 5 to 30, and the larger n is, the better the durability such as water repellency is. It is something to do. Q is a difunctional organic group, usually -O-(R ¹ ) _p - (wherein R ¹ is a divalent alkylene group having 1 to 10 carbon atoms, preferably 2 to 4 carbon atoms). , p is 0 or 1, preferably p is 1
) is selected. Of course, Q is -SO ₂ N (R ² ) - (R ¹ ) _p -O- (however,
R ² is a hydrogen atom or lower alkyl group), -CON
(R ² )—(R ¹ ) _p —O—, etc. may be used. As mentioned above, the specific polyfluoroalkyl group-containing vinyl monomer has a polymerizable organic group represented by Z, where Z is an organic group containing a vinyl group. In general, Z is a monomer with high density polyfluoroalkyl groups as long as the polymer contains vinyl groups necessary to form a copolymer.

[Formula] (where R' represents a hydrogen atom or a methyl group, A is a difunctional organic group, and q is 0 or 1) is preferable. Also, Z is

【formula】

[Formula] etc. may be used. Such a specific polyfluoroalkyl group-containing vinyl monomer can be obtained by various methods or routes, but can usually be synthesized by a process including the following telomerization reaction. That is, A telomerization reaction can be employed. The Y of the resulting telomer is changed to Z. for example,
If thioglycol HSCH ₂ CH ₂ OH is a telogen, IR _f SCH ₂ CH ₂ OH (However, IR _f is

A blocked R _f group-containing telomer is obtained, and the IR _f SCH ₂ CH ₂ OH contains a halide of acrylic acids CH ₂ =CR'COX (however, By reacting (X is a halogen atom, R' is a hydrogen atom or a methyl group),

[Formula] can be synthesized. In the telomerization reaction, thioglycolic acid HSCH ₂ CO ₂ H was used instead of thioglycol.
, we get IR _f SCH ₂ COOH, and the IR _f
By reacting SCH ₂ COOH with 2-hydroxyethyl acrylate, IR _f
SCH ₂ COOCH ₂ —CH ₂ OCOCH=CH ₂ and the like can also be synthesized. In the telomerization reaction, Y is -
Thioglycol, thioglycolic acid, aminothioethanol, etc. corresponding to CH ₂ OH, -COOH, -CH ₂ NH ₂ can be employed as telogens, and IR _f SCH ₂ CH ₂ OH, IR _f respectively.
General formulas such as SCH ₂ COOH, IR _f SCH ₂ CH ₂ NH ₂
The telomer IR _f SCH ₂ Y is obtained. Furthermore, the applicable
Y in IR _f SCH ₂ Y is changed to a vinyl group-containing polymerizable organic group Z and used as the specific vinyl monomer of the present invention. As mentioned above, Z can be of various types, but depending on availability etc.

[Formula] is preferable. A is a difunctional organic group. Specifically, Z is
CH ₂ = CHCOOCH ₂ -, CH ₂ = C (CH ₃ )
COOCH ₂ -, CH ₂ = CHCOO (CH ₂ CH ₂ O) _n CO -,
Examples include CH ₂ =C(CH ₃ )COO(CH ₂ CH ₂ O) _n CO—(m is an integer of 1 to 50). The water and oil repellent of the present invention is composed of a vinyl polymer containing a structural unit obtained by addition polymerization of the above-mentioned specific polyfluoroalkyl group-containing vinyl monomer, but it is usually composed of the above-mentioned IR _f group-containing vinyl monomer and various other vinyl monomers. An embodiment consisting of a copolymer with is preferred. Of course, it may be a homopolymer of a vinyl monomer containing an IR _f group, but a copolymer form is desirable from the standpoint of other additional performance or wide-ranging commercial application. Other vinyl monomers to be copolymerized with the IR _f group-containing vinyl monomer include:
A wide range of examples may be given without particular limitation. For example, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, α-methylstyrene, p-methylstyrene, alkyl esters of acrylic acid or methacrylic acid, benzyl One or more vinyl monomers such as acrylates or methacrylates, vinyl alkyl ethers, halogenated alkyl vinyl ethers, vinyl alkyl ketones, cyclohexyl acrylates or methacrylates, maleic anhydride, butadiene, isoprene, and chlorobrene are combined with IR _f group-containing vinyl monomers. Can be copolymerized. By selecting and copolymerizing these appropriate monomers, various properties such as water and oil repellency, durability, dry soil resistance, abrasion resistance, selective solubility, flexibility, and texture can be achieved. This can be improved. For example, by copolymerizing N-methylol acrylamide, etc., to improve durability, by copolymerizing a hydrophilic monomer, such as an alkylene oxide adduct of a polymerizable carboxylic acid, to improve stain removability.
Antistatic properties can be improved by copolymerizing monomers containing anionic groups. In the polymer of the present invention, the content of the IR _f group-containing vinyl monomer is suitably at least 25% by weight, preferably at least 40% by weight, particularly about 50 to 80% by weight. In addition, the content of durability-improving components such as N-methylol acrylamide may be contained in a small amount, usually about 0.5 to 5% by weight, and other vinyl monomers can be used at appropriate copolymerization ratios depending on the purpose. It is. In order to obtain the polymer or copolymer of the present invention,
Various polymerization reaction methods and conditions can be selected arbitrarily,
Any of various polymerization methods such as bulk polymerization, 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 polymerized is emulsified in water in the presence of a surfactant and polymerized while 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. By solution polymerization method or emulsion polymerization method, aerosol type,
Organic solvent type or latex type water and oil repellents can be directly produced. The water- and oil-repellent agent made of the polymer 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 can be prepared directly by emulsion polymerization, or a solvent solution type can be prepared directly by solution polymerization. In addition, for solvent solution type polymers, polymers obtained by other polymerization methods such as bulk polymerization method or emulsion polymerization method can be used in acetone, methyl ethyl ketone, diethyl ether, etc.
It may also be prepared by dissolving it in one or a mixture of two or more suitable organic solvents such as dioxane, methylchloroform, trichloroethylene, tetrachloroethylene, and salt fluorinated saturated hydrocarbons such as tetrachlorodifluoroethane, trichlorotrifluoroethane. obtain. For the aerosol type, prepare a solution type solvent solution as described above, add a propellant such as dichlorodifluoromethane, monofluorotrichloromethane, or dichlorotetrafluoroethane, and fill it into a suitable container. Good. 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 also 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] 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,
Make the treated cloth 1kg with ballast cloth, put it in an electric washing machine, and add 60g of detergent (Super Zabu: brand name).
After treatment at 50°C for 10 minutes in a bath volume of 35, rinse and air dry. After repeating this operation a predetermined number of times, water and oil repellency is measured to determine durability. Example 1 The IR _f group-containing vinyl monomer used in this example was synthesized as follows. R _f CH ₂ CH ₂ OCOCH=CH ₂ (R _f is C ₈ F ₁₇ /
It is a mixture of C ₁₀ F ₂₁ /C ₁₂ F ₂₅ = 3/2/1, and R _f
CH ₂ CH ₂ -OCOCH=CH ₂ is hereinafter referred to as FA) 568
g (1.0 mol), thioglycol 2.1 g (0.03 mol),
500ml acetone, azobisisobutyronitrile
2.20 g was placed in a 1.5 glass four-necked flask equipped with a Dimroth thermometer, a mercury thermometer, and a polytetrafluoroethylene crescent-shaped stirrer, stirred under a nitrogen stream, and after about 1 hour, boiled. Prepare and react at 60°C for 2 hours while stirring. Then, 2.1g of thioglycol was added and after stirring for 2 hours,
Furthermore, 2.2 g of thioglycol was added and reacted for 16 hours. That is, the total amount of thioglycol was 6.4 g (0.1 mol), and the reaction was carried out for 20 hours. Analysis by gas chromatography showed that the conversion rate of FA was 98.5%. After the reaction is complete, hydroquinone
Added 0.5g, plus acrylic acid chloride 9.05
g (0.1 mol) was added dropwise over 6 hours, and then
Allowed time to react. The conversion rate of acrylic acid chloride was 98.3%. The resulting reaction mixture was placed in a beaker (No. 2), ion-exchanged water (No. 1) was added, and the mixture was washed with water while thoroughly stirring. Next, vacuum dry
Excess acetone and unreacted substances were removed. can get
The molecular weight of the IR _f group-containing vinyl monomer is 5800, (n is 10 on average). Hereinafter, this compound will be referred to as BFA. 73g of the above BFA, 25g of butyl methacrylate,
2 g of N-methylol acrylamide, 100 g of trichlorotrifluoroethane, 100 g of acetone, and 0.5 g of azobisisobutyronitrile were placed in a 500 ml glass container equipped with a Dimroth thermometer, a mercury thermometer, and a polytetrafluoroethylene crescent blade stirrer. Place it in a four-necked flask and heat it for about 1 hour under a nitrogen stream.
After stirring for an hour, the polymerization reaction was carried out at 60° C. for 15 hours with slow stirring. The resulting polymer solution was diluted with acetone to a polymer concentration of 0.1% by weight. Soak a nylon taffeta cloth in this diluted solution for 10 minutes, shake off the solution thoroughly, then dry at room temperature for 1 hour.
Curing was performed at 170°C for 1 minute. The water repellency and oil repellency of the resulting cloth were measured and found to be 100 and 6, respectively. The water repellency and oil repellency after washing five times were ⁹⁰⁺ and ⁵⁺ , respectively. Examples 2 to 4 and Comparative Examples 1 to 2 In the same manner as in Example 1, water repellency, oil repellency, and durability were measured using copolymers having the copolymer composition shown in Table 3 below. The results are summarized in Table 3. In addition, the case where an equal amount of FA is used instead of BFA is also shown in Table 3 below as Comparative Examples 1 and 2.

[Table] In Table 3, VCl stands for vinyl chloride, t-
BuMA is tertiary butyl methacrylate, HEA is 2-hydroxyethyl acrylate, N-MAM
respectively indicate N-methylol acrylamide. Example 5 In the same manner as in Example 1, (n is 20 on average) is synthesized (yield
96.3), 73g of this, 25g of butyl methacrylate,
Polymerization was carried out in the same manner as in Example 1 using 2 g of N-methylolacrylamide, 100 g of trichlorotrifluethane, 100 g of acetone, and 0.5 g of azobisisobutyronitrile. Using the produced polymer solution, we measured the water repellency and oil repellency, and the results showed that
It was 100.6. In addition, water repellency after washing 5 times,
The oil repellency was 100 and ⁵⁺ , respectively. Example 6 FA568g (1.0mol), thioglycolic acid 2.4g
(0.03 mol), 500 ml of acetone, and 2.20 g of azobisisobutyronitrile were placed in a four-neck glass flask with an internal volume of 3 equipped with a Dimroth thermometer, a mercury thermometer, and a polytetrafluoroethylene crescent-blade stirrer. , react at 60° C. for 2 hours with stirring under a nitrogen stream. So thioglycolic acid 2.4
After stirring for 2 hours, 3.2 g of thioglycolic acid was added and reacted for 16 hours. That is, the total amount of thioglycolic acid is 8.0 g (0.1 mol), and 20
This means a time reaction. As a result of analysis by gas chromatography, the addition rate of FA was 98.8%. After the reaction was completed, ion-exchanged water (1) was added and the mixture was washed with water while thoroughly stirring. Next, excess acetone,
Unreacted substances were removed. Put 550 g of this reaction product into the same four-necked flask as above, and add hydroquinone.
0.5g, 2-hydroxyethyl acrylate 13.9
(0.12 mol), 300 g of benzene, and 20 g of toluenesulfonic acid, and the mixture was reacted for 6 hours while water produced at 70° C. was azeotropically removed with benzene. 2
-Conversion rate of hydroxyethyl acrylate is 97.5
It was %. Furthermore, benzene is removed by distillation, and 1
of ion-exchanged water was added and washed with water. Next, unreacted substances were removed by vacuum drying. The molecular weight of the obtained IR _f group-containing vinyl monomer was 5900, (n is 10 on average). This compound is hereinafter referred to as B'FA. 73g of the above B'FA, butyl methacrylate 25
g, N-methylolacrylamide 2g, trichlorotrifluoroethane 100g, acetone 100g and azobisisobutyronitrile 0.5g using the above method, and using the copolymer, water repellency,
When the oil repellency was measured, it was 100 and 6, respectively. After 5 more washes, ⁹⁰⁺ and ^5+, respectively.
It was hot. The molecular weights of the polymers used in Examples and Comparative Examples were as follows. Number average molecular weight Example 1 Approximately 100,000 〃 2 〃 〃 3 〃 〃 4 〃 〃 5 〃 〃 6 〃 Comparative example 1 〃 〃 2 〃

Claims (1)

[Claims] 1 Formula [Formula] [However, Z in the formula is [Formula] (However, R' represents a hydrogen atom or a methyl group, A is a difunctional organic group, and q is 0 or 1), R is a hydrogen atom or a methyl group, Rf is a polyfluoroalkyl group having 3 to 20 carbon atoms, Q is -O-R ¹ -, R ¹ is a carbon number 1 to 10
A polyfluoroalkyl group-containing water repellent made of a vinyl polymer containing a constitutional unit obtained by addition polymerization of a polyfluoroalkyl group-containing vinyl monomer represented by 2 difunctional alkylene groups, n is an integer of 2 to 50. A polyfluoroalkyl group-containing water and oil repellent, which is an oil agent, and the proportion of the polyfluoroalkyl group-containing vinyl monomer in all the monomers used to form the vinyl polymer is at least 25% by weight. ] 2 The water and oil repellent according to page 1 of the claims, wherein Rf is a perfluoroalkyl group having 3 to 20 carbon atoms.