JPH0480217A - Fluorine-containing water and oil repellent - Google Patents

Abstract

PURPOSE:To prepare the title repellent exhibiting excellent water- and oil- repellent properties without adversely affecting handle and comprising an aq. dispersion contg. a copolymer consisting of structural units derived from specified compds. and a polymn. initiator by using a specific compd. as the initiator. CONSTITUTION:A water and oil repellent comprising an aq. dispersion contg. a copolymer consisting of structural units derived from a polymerizable polyfluoroalkyl compd. (e.g. a perfluoroalkylethyl acrylate). stearyl (meth) acrylate, and a compd. copolymerizable with the polyfluoroalkyl compd. (e.g. N-methylolacrylamide) and a polymn. initiator is prepared by using a compd. which contains no Cl ion in the form of a hydrochloride and is dispersible in water [e.g. azobis(dimethyleneisobutyramidine)] as the initiator.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an improved water and oil repellent,
More specifically, it is a compound consisting of a copolymer containing as a constituent unit a polymerizable compound containing a polyfluoroalkyl group, stearyl acrylate or stearyl methacrylate, and a compound copolymerizable with this polyfluoroalkyl group-containing compound. , relates to a water and oil repellent having higher water and oil repellency than conventional ones.

[Prior Art] Conventionally, as a water-dispersible fluorine-based water and oil repellent, a polyfluoroalkyl group-containing polymerizable compound, vinyl chloride or vinylidene chloride, and this polyfluoroalkyl group-containing compound copolymerizable have been used. It is known that copolymerized compounds are very useful for water and oil repellency. However, fabrics treated with a water-dispersed water-repellent agent containing vinyl chloride or vinylidene chloride as a copolymerized component have a hard texture due to the physical properties of the film-forming components, vinyl precipitate and vinylidene chloride themselves. It had drawbacks.

To solve this problem, as a water-dispersible fluorine-based water and oil repellent, a polymerizable compound containing a polyfluoroalkyl group can be copolymerized with stearyl acrylate or stearyl methacrylate and this compound containing a polyfluoroalkyl group. A product copolymerized with a compound has been developed. It has been discovered that this water and oil repellent exhibits good water and oil repellency without impairing texture. However, these copolymer compositions were inferior in initial water repellency and washing durability compared to water-dispersible fluorine-based water and oil repellents containing vinyl chloride as a copolymer component.

[Problems to be Solved by the Invention] It is an object of the present invention to improve water and oil repellency in a water-dispersible fluorine-based water and oil repellent containing stearyl acrylate or stearyl methacrylate as a copolymerization component, which was present in the prior art. The aim is to improve the washing durability of

[Means for Solving the Problems] The present inventor copolymerized a polyfluoroalkyl group-containing polymerizable compound with stearyl acrylate or stearyl methacrylate and a compound copolymerizable with the polyfluoroalkyl group-containing compound. As a result of various studies and examinations aimed at developing even higher water repellency f8G without impairing the excellent texture of the water-dispersed fluorine-based water and oil repellent obtained from stearyl acrylate or stearyl. In water-dispersible fluorine-based water and oil repellents containing methacrylate as a copolymerization component, a polymerization initiator that does not contain chlorine ions in the form of hydrochloride and is water-dispersible is used as a polymerization initiator during copolymerization. The present invention was achieved by discovering that a water and oil repellent obtained by using a water and oil repellent exhibits good water and oil repellency.

That is, the present invention uses hydrochloric acid as a polymerization initiator when copolymerizing a polyfluoroalkyl group-containing polymerizable compound with stearyl acrylate or stearyl methacrylate and a compound copolymerizable with the polyfluoroalkyl group-containing compound. By using a water-dispersible polymerization initiator that does not contain chloride ions in the form of salt, the polymerization terminals of the copolymer composition are made nonionic, reducing its affinity for water and creating a pleasant texture. The present invention also provides a fluorine-based water and oil repellent that imparts high water and oil repellency.

The polymerization initiator used in the present invention is a water-dispersible polymerization initiator that does not contain chlorine ions in the form of hydrochloride,
For example, the following azo-based initiators are exemplified.

CH.

CH3-C-N=N-CONH.

N CH3 HOCH2-C-N N CH3 C-CH20H N As exemplified here, the water and oil repellent composition of the present invention does not contain chlorine ions in the form of hydrochloride and also contains a water-dispersible polymerization initiator. stearyl acrylate or stearyl methacrylate and a compound copolymerizable with the polyfluoroalkyl group-containing compound in an aqueous medium,
It can be obtained by emulsion polymerization using a surfactant and, if necessary, a water-soluble organic solvent as a dispersion aid. Although the polymerization temperature can be selected depending on the initiator, 40°C to 80°C is usually suitable.

Preferred examples of the polymerizable compound containing a polyfluoroalkyl group include (meth)acrylic acid esters containing a polyfluoroalkyl group such as (where R1 is H or CHl); Two or more species or compounds with different carbon numbers
It is also possible to use more than one species in combination.

The above-mentioned Rf is a linear or branched polyfluoroalkyl group having 3 to 21 carbon atoms, preferably 4 to 16 carbon atoms, and usually a perfluoroalkyl group is selected at the terminal end. , those containing a hydrogen atom or chlorine atom at the end, or a group containing oxypolyfluoroalkylene can also be used.

Compounds that can be copolymerized with a polymerizable compound containing a polyfluoroalkyl group, such as an acrylic ester or a methacrylic ester containing a polyfluoroalkyl group, include the following compounds having radically reactive unsaturated bonds. , CH2=CR, C00R2 CH2=CR, C00(CH2CH20) pH (P is 1
~12) (Here, R1 is Hl or CH3, R, is Hl
or methacrylic acid and acrylic acid or their esters such as C4H2□1 and q is 1 to 23, preferably 1 to 6), or CH2=CR,C0 as shown in the following formula.
NHCH20HCH2=CR,C0N)Ic)120C
, H9CH2=CHCI CH2=CCl
2CH2=CH20COCH3CH2=CH2CH20
HCHCOOC-H+7CH2=CR+C0N(CH3
)2CHCOOC, Hl.

(Here, R1 is Hl or CH,) (meth)acrylic acid amide derivatives such as vinyl chloride, halogen-containing vinyl monomers such as vinylidene chloride, ethylene, vinyl alkyl ether, vinyl acetate, maleic anhydride, and maleic acid dialkyl ester , styrene, a-methylstyrene, p-methylstyrene, acrylonitrile, butadiene, isoprene, chlorobrene,
Methyl vinyl ketone and the like are preferred.

Furthermore, it is also possible to use two or more of these copolymerizable compounds in addition to stearyl acrylate or stearyl methacrylate. By copolymerizing these polymerizable compounds that do not contain polyfluoroalkyl groups, in addition to water and oil repellency and stain resistance, dry cleaning resistance, washing resistance, solubility, hardness, texture, etc. Various properties can be improved.

The copolymerization ratio of the polyfluoroalkyl group-containing polymerizable compound to 100 parts by weight of the copolymer is 20 to 80 parts by weight.
Parts by weight are appropriate.

Various types of surfactants such as nonionic, anionic, cationic, and amphoteric surfactants can be used as the dispersant for making the composition water-dispersible, and these may be used in combination as appropriate. Specifically, polyoxyethylene monooleyl ether, polyoxyethylene monoalkyl ether, polyoxyethylene mono(alkylphenyl) ether, polyoxyethylene monooleyl ester, polyoxyethylene monoalkyl carboxylic acid ester, sorbitan ester, sucrose. Nonionic surfactants such as esters, cationic surfactants such as tertiary amine acetates and quaternary ammonium salts, alkylsulfonic acids and their salts, alkylbenzenesulfonic acids and their salts, alkylcarboxylic acids and their salts, Preferred are anionic surfactants such as sodium alkoxypolyoxyethylene sulfonate, and amphoteric surfactants such as betaine type or phosphate ester type such as choline and ethanolamine.

The presence of a water-soluble organic solvent improves the fractional properties of the polymerizable compound containing a polyfluoroalkyl group, and improves the copolymerizability with other copolymerizable polymers. Suitable foaming agents for this purpose include water-tolerant
8 solvents can be used without particular limitation, but ketones such as acetone, methyl ethyl ketone,
Ethylene glycol, ethylene glycol derivatives such as polyethylene glycol, alkyl ethers of ethylene glycol derivatives such as polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol monobutyl ether, propylene glycol derivatives such as propylene glycol, dipropylene glycol, polypropylene glycol, Preferred examples include boethers such as cyclodextrin and dextrin, and esters such as methyl acetate and ethyl acetate. The amount of these organic solvents added is usually selected from the range of 2 to 300 parts by weight, preferably 5 to 120 parts by weight, per 100 parts of the polymer of the present invention.

When the water and oil repellent of the present invention is made into a water dispersion type, the solid content concentration of the polymer of the present invention is not particularly determined, but is usually adjusted to 2 to 60 wt%, preferably 5 to 50 wt%. , during processing, add water to a concentration of 0.2 to 1
It is used diluted to about 6 wt%. Such emulsion-type water and oil repellents have advantages over organic solvent-type ones, such as a higher flash point of the stock solution and the ability to increase the solid content concentration, and they also have advantages during processing. It has various advantages such as being able to minimize pollution of the working environment.

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 to be treated. For example, a method may be adopted in which the coating material is adhered to the surface of the object to be treated using a known coating method such as dip coating, and then dried. Further, if necessary, curing may be performed by applying a suitable crosslinking agent. Furthermore, it is of course possible to add and use other water and oil repellents, insect repellents, flame retardants, antistatic agents, dye fixing agents, anti-wrinkle agents, etc. to the water and oil repellent of the present invention.

Articles that can be treated with the water and oil repellent of the present invention are not particularly limited and include various examples as long as they are textile products.

For example, natural fibers of animal and plant origin such as cotton, hemp, wool, and silk; various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; glass fibers; Examples include inorganic fibers such as asbestos fibers, and mixed fibers and fabrics thereof.

[Function] In the present invention, a water-dispersible fluorine-based water and oil repellent containing stearyl acrylate or stearyl methacrylate as a copolymerization component contains chlorine ions in the form of hydrochloride as an initiator during polymerization. However, it is not clear why the use of a water-dispersible polymerization initiator allows for higher water and oil repellency than before. Generally, a polymerization initiator is incorporated into a copolymer as a polymerization terminal during the polymerization process, but it is generally thought that this initiator terminal does not have a great effect on the physical properties of the copolymer. However, in water and oil repellents, unlike the bulk case, the film after treatment forms an extremely thin film on the order of angstroms, so the initiator terminal in the copolymer is thick ( There is a very high possibility that the contact angle is highly dependent on the surface condition of the film, which is on the order of just a few tens of angstroms. Considering the influence of the polymerization end on the film from the above perspective, when using a conventional initiator, the polymerization end is an amidine hydrochloride, which is highly hydrophilic and has a high relationship with the entire film. (Since the delta resolution is different, it is thought that the higher-order structure of the film is likely to be disturbed.

It does not contain chlorine ions in the form of hydrochloride, which was shown in the invention of Rikiki.
Furthermore, when a water-dispersible polymerization initiator is used, the polymerization terminals are relatively hydrophobic, and it is expected that the higher-order structure of the film will be less likely to be disturbed. This difference may be manifested as a difference in the film-forming process during treatment, that is, a difference in initial water and oil repellency. In addition, in terms of washing durability, with conventional water and oil repellents using hydrophilic initiators, the hydrophilic end tends to be solubilized and partially eluted in water, so the membrane structure of the water and oil repellent film is made thicker. (However, in the water and oil repellent of the present invention, which does not have a hydrophilic end at the copolymerization end, such adverse effects are removed,
It is expected that this will result in high washing durability. It goes without saying that this explanation does not limit the invention in any way.

[Examples] 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 were expressed using the following scale. In other words, the water repellency is JIS L
-1092 water repellency number (see Table 1 below) by spray method, 78 bending The test solution shown in Table 2 below was applied to two places on the test cloth several millimeters in diameter (approximately 4 mm in diameter).
mm) and determined by the state of penetration after 30 seconds (AA
TCCT M 118-1966).

Table 1 Note that the water repellency number and oil repellency number marked with a + mark indicate slightly better performance.

Example 1 Perfluoroalkylethyl acrylate (hereinafter referred to as FA) [CaF, C
H2CH20COCH=CH2 120 g, stearyl acrylate 76 g, N-methylol acrylamide 4 g, polyoxyethylene lauryl ether 10
g, stearyltrimethylammonium chloride 2
g, acetone 120 g, water 350 g, azobis (dimethylene isobutyramidine) Wako Kasei products VA061
> 2 g was added, and the mixture was replaced with nitrogen for about 20 minutes while stirring, and then the temperature was raised to 60°C to start polymerization. 6
After stirring at 0°C for 15 hours, it was cooled to a solid concentration of 3.
A 1% emulsion was obtained. The conversion rate of the copolymerization reaction by gas chromatography is 99.0 to 99.8% (relative to a polymerizable compound containing a perfluoroalkyl group)
Met. Moreover, the yield of stable emulsion based on all reacted monomers was 95 to 99%.

Examples 2 to 6, Comparative Examples 1 to 4 Emulsion polymerization was carried out in the same manner as in Example 1 by changing the monomer and emulsifier polymerization initiator. The monomers, emulsifiers, and polymerization initiators used are shown in Tables 3 and 4.

Water and oil repellency tests were conducted using the latex obtained by the above method with a solid content of 12% by weight as a stock solution. The latex stock solution was diluted with water, and the water and oil repellency performance was measured using a ratio of the stock solution to water of 15%.

The test was conducted on nylon taffeta cloth, and the water and oil repellent treatment was performed as follows. That is, as described above (immerse the test cloth in the diluted latex treatment solution for 30 seconds, squeeze the cloth between two rubber rollers, and apply wet pickup for 30 seconds.
It was set to 0%. Next, dry at 110°C for 90 seconds, and then dry for 1
Heat treatment was performed at 70°C for 60 seconds. The initial water and oil repellency was measured for the treated cloth obtained in this way. Also, in the washing durability test, 1000 g of the treated cloth obtained in this way was
40℃ water containing liquid detergent (beads, part name) 33ρ
Stir for 25 minutes in a
This was done by rinsing for minutes (45 minutes per wash) and drying. A household electric washing machine was used for the washing process. Durability evaluation was shown by the water and oil repellency values after the treated fabric was air-dried after four washes. The results of the initial water and oil repellency test and the results of the water and oil repellency after the washing durability test are shown in Table 5.

Table 5 [Effects of the Invention] The present invention provides a fluorine-based water-dispersed water and oil repellent containing stearyl acrylate or stearyl methacrylate as a copolymerization component, by polymerizing using a polymerization initiator that does not contain chlorine ions. It has become possible to provide an excellent water- and oil-repellent shaver that can achieve high water and oil repellency without detracting from the conventional texture.

Claims (1)

[Scope of Claims] 1. A copolymer containing as a constituent unit a polymerizable compound containing a polyfluoroalkyl group, stearyl acrylate or stearyl methacrylate, and a compound copolymerizable with this polyfluoroalkyl group-containing compound; In a water-dispersible fluorine-based water and oil repellent containing a polymerization initiator, the polymerization initiator does not contain chlorine ions in the form of hydrochloride,
A fluorine-based water and oil repellent characterized by being water-dispersible. 2. The fluorine-based water and oil repellent according to claim 1, wherein the water-dispersible polymerization initiator that does not contain chloride ions in the form of hydrochloride is an azo polymerization initiator. 3. The azo polymerization initiator is N,N'-azobis[2-(
3. The fluorine-based water and oil repellent according to claim 2, which is 2-imidazolin-2-yl)propane.