JPH0480218A - Aqueous water and oil repellent dispersion - Google Patents

Abstract

PURPOSE:To prepare the title repellent excellent in storage stability by specifying the concn. of unreacted vinyl or vinylidene chloride in the repellent which contains a copolymer obtd. by copolymerizing vinyl or vinylidene chloride with specific compds. CONSTITUTION:In a water and oil repellent contg. a copolymer obtd. by copolymerizing vinyl or vinylidene chloride, a polymerizable polyfluoroalkyl compd. (e.g. a perfluoroalkylethyl acrylate), and a compd. copolymerizable with the polyfluoroalkyl compd. (e.g. dioctyl maleate, N,N-dimethylacrylamide), the concn. of unreacted vinyl or vinylidene chloride is regulated to 10ppm or lower.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an improved water and oil repellent,
More specifically, the present invention relates to a water and oil repellent that has high water and oil repellency and washing durability, and shows very little change in the product over time.

[Prior Art] Conventionally, as a fluorine-based water and oil repellent, a polyfluoroalkyl group-containing polymerizable compound is copolymerized with vinyl chloride or vinylidene chloride and a compound copolymerizable with the polyfluoroalkyl group-containing compound. It is known that polymerized products are very useful for water and oil repellency. However, these copolymers have the drawback of poor emulsion stability and long-term storage stability.

[Problems to be Solved by the Invention] It is an object of the present invention to provide water-dispersible fluorine-based water and oil repellents that contain vinyl chloride or vinylidene chloride as a copolymerization component, which the prior art has, in laundry, dry cleaning, etc. It has storage stability that does not impede the practical durability of the product.It does not have the problems of conventional products, such as changes in the form of the water and oil repellent and deterioration of performance due to changes over time during storage. An object of the present invention is to provide an excellent water and oil repellent.

[Means for Solving the Problems] The present inventor copolymerized a polyfluoroalkyl group-containing polymerizable compound with vinyl chloride or vinylidene chloride and a compound copolymerizable with the polyfluoroalkyl group-containing compound. With the aim of providing a water- and oil-repellent with excellent storage stability without impairing the excellent performance of the resulting water-dispersible fluorine-based water- and oil-repellent and its durability against washing and dry cleaning, we have developed various As a result of repeated research and consideration, we found that in water-dispersible fluorine-based water and oil repellents containing vinyl chloride or vinylidene chloride as copolymerization components, vinyl chloride and vinylidene chloride remaining in the emulsion as unreacted monomers after polymerization. The present invention was based on the discovery that this significantly inhibits storage stability.

That is, the present invention involves copolymerizing a polyfluoroalkyl group-containing polymerizable compound with vinyl chloride or vinylidene chloride and a compound copolymerizable with the polyfluoroalkyl group-containing compound, and then impregnating the copolymerizable compound into an emulsion. By removing unreacted vinyl chloride and vinylidene chloride from the emulsion using methods such as vacuum distillation, and suppressing the residual concentration of unreacted vinyl chloride and vinylidene chloride in the emulsion to below 1 Oppm, morphological changes during storage can be prevented. The objective is to provide an excellent water and oil repellent that eliminates storage stability problems such as deterioration in performance and performance.

The fluoroalkyl group-containing polymerizable compound such as the perfluoroalkyl group-containing acrylic ester or methacrylate ester used in the present invention includes a polyfluoroalkyl group such as (where R+ is H or CH). Preferred examples include (meth)acrylic acid esters, and two or more of these, or two or more 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.

Examples of compounds that can be copolymerized with polymerizable compounds containing polyfluoroalkyl groups, such as acrylic esters or methacrylic esters containing polyfluoroalkyl groups, include the following compounds with radically reactive unsaturated bonds. and CH,=CR,C0OR.

CH2=CRICOO(CH2CH20), H(P is 1
~12) CH2CH2 \ 1 (Here, R1 is Hl or CH3, R, is Hl or C
methacrylic acid and acrylic acid or their esters such as
NHCH20HCH2=CRICONHCH20C4H
9CH2"CHCl CHz"CC1zC
H,=CH20COCH! CH2=CH2C
(Meth)acrylic acid amide derivatives such as H20H (where R1 is Hl or CH3), halogen-containing vinyl monomers such as vinyl chloride and vinylidene chloride, ethylene, vinyl alkyl ether, vinyl acetate, maleic anhydride and dialkyl maleate. Ester, styrene, a-methylstyrene, p-methylstyrene, acrylonitrile, butadiene, isobrene, chloroprene, methylvinyl ketone and the like are preferred.

Among these, vinyl chloride or vinylidene chloride is particularly required as an essential component. Further, in the present invention, N-methylolacrylamide can be used for the purpose of improving washing and try-cleaning durability and preventing performance deterioration during storage. Also, for the same purpose, N-
Instead of methylol acrylamide, it is also possible to use both a nitrogen-containing copolymerizable compound and a hydroxyl group-containing copolymerizable compound as essential components, which are more effective in imparting stability.

The copolymerization ratio of vinyl chloride or vinylidene chloride to 100 parts by weight of the copolymer is 20 to 80 parts by weight! section is appropriate.

As the nitrogen-containing copolymerizable compound, C)12=
cR, cON(CH,), CH2CH2 group-containing (C2H,)2CH.

CH*=CRICONCxH-N(CHs)x (here, R1 is H5 or CH), etc. can be cited as suitable examples, and it is possible to use these in combination.

As a copolymerizable compound containing a hydroxyl group, CH2=CR4COOCH2CH20HCH2''CR4
C00CHxCHCHzH CH,=CR,C00CH2CH2CH,0)lCH,
=CR4C00 (C, H40), H (P is 1 to 12)C
H,=CR4C00(C,H,O),H(P is 1-12
)CH,=CR4C00(C,H,O),H(P is 1~
12) (herein, R4 is Hl or CH) etc., and these can be used in combination.

Furthermore, as a copolymerizable compound, in addition to vinyl chloride or vinylidene chloride and N-methylolacrylamide or a nitrogen-containing copolymerizable compound and a hydroxyl group-containing copolymerizable compound, one kind of the above-mentioned copolymerizable compound is used. It is also possible to use the above in combination. By copolymerizing these polymerizable compounds that do not contain polyfluoroalkyl groups, in addition to water and oil repellency, stain resistance, washing durability, and dry cleaning durability, we can improve solubility, hardness, texture, etc. Various properties can be improved.

In order to obtain a copolymer of a polymerizable compound containing a fluoroalkyl group, such as an acrylic acid ester or a methacrylic acid ester containing a perfluoroalkyl group, and a copolymerizable compound other than this polymerizable compound, bulk polymerization is necessary. Various polymerization methods such as , solution polymerization, suspension polymerization, and emulsion polymerization can be employed. Moreover, various polymerization initiation methods such as polymerization using an initiator, radiation polymerization, and photopolymerization can be employed as the polymerization initiation method. The water and oil repellent in the present invention can be used in the form of an organic solution or organic dispersion, but in consideration of application to dyeing processes and the impact on the processing work environment, it is preferable to use it in the form of a water dispersion. It is preferable that Therefore, it is preferable to use a water-soluble organic solvent as a dispersion aid and carry out emulsion polymerization in water in the presence of a surfactant.

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 dispersibility of the polymerizable compound containing a polyfluoroalkyl group, and improves the copolymerizability with other copolymerizable polymers. Suitable solvents for this purpose are not particularly limited as long as they are water-soluble solvents that are soluble in polymerized vine compounds containing polyfluoroalkyl groups (although acetone, methyl ethyl ketone, etc. can be used). Ketones such as ethylene glycol, ethylene glycol derivatives such as polyethylene glycol, alkyl ethers of ethylene glycol derivatives such as polyethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol monobutyl ether, propylene glycol, dipropylene glycol,
Preferred examples include propylene glycol derivatives such as polypropylene glycol, polyethers 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.

As the initiator used for polymerization, it is preferable to use a water-soluble initiator among azo initiators and peroxide-based initiators.

for example, CH.

Water-soluble initiators such as azo amino compounds such as CHi-C-N”N-C0NHz N, cyclic amine compounds, amino compounds containing phenyl groups, hydrochlorides of nitrile compounds, and water-soluble initiators such as potassium persulfate. Preferred examples include peroxide-based initiators.The polymerization temperature can be selected depending on the initiator, but 40°C to 80°C is usually suitable.

After the polymerization reaction, the method for removing unreacted vinyl chloride and vinylidene chloride from the emulsion is not particularly limited (various existing methods can be used; for example, distillation under reduced pressure, heating under normal pressure, Examples include, but are not limited to, methods such as distillation by stirring, distillation by air or nitrogen stream under heating, steam bubbling, and methods using a packed column, spin coater, cylindrical volatilization device, etc. .

When the water and oil repellent of the present invention is made into a water-dispersed type, the solid content concentration of the polymer of the present invention is not particularly limited, but is usually 2 to 2.
The concentration is adjusted to 60 wt%, preferably 5 to 50 wt%, and during processing, it is reduced to 0.2 to 16 wt% with water.
Used in moderately diluted form. 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 in any desired manner 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, in the water-dispersible fluorine-based water and oil repellent composition containing vinyl chloride or vinylidene chloride as a copolymerization component, the concentration of unreacted vinyl chloride and vinylidene chloride in the emulsion is reduced to 10 ppm or less. This eliminates problems such as changes in the form of water and oil repellents and deterioration of performance due to changes over time during storage, which were problems with conventional products. However, the reason for this is not clear. However, in the aqueous dispersion, vinyl chloride and vinylidene chloride, which are the constituent components of the emulsion,
It is known that decomposition is promoted by chlorine ions dissolved in the system, and that the rate of decomposition is accelerated as the molecular weight of the vinyl chloride and vinylidene chloride moieties in the polymer decreases.

When unreacted vinyl chloride and vinylidene chloride are dissolved in the emulsion after polymerization, these unreacted monomers are first decomposed by the chlorine ions dissolved in the system, and new chlorine ions are supplied. It can be a source. This reaction increases the chloride ion concentration in the system, which accelerates the decomposition of the vinyl chloride and vinylidene chloride moieties in the polymer following the decomposition of the monomer, destroying the emulsion and reducing its long-term stability. Conceivable. Therefore, by distilling off unreacted monomers from the emulsion, the increase in the concentration of chlorine ions dissolved in the system is suppressed, and as a result, the decomposition of the polymer composition is suppressed.
This is thought to enable the long-term stability of the emulsion. It goes without saying that this explanation does not limit the invention in any way.

[Example] Next, an example of the present invention will be explained in more detail, but it goes without saying that this explanation 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 JISL-1
By the spray method of 092 (8 aqueous number (No. 1 below)
Oil repellency is measured by applying a few drops of the test solution shown in Table 2 below on the test cloth (approximately 4 mm in diameter).
It was determined by the state of penetration after 30 seconds (AATCC
-T M 11g-1966).

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

Example 1, Comparative Example 1 Perfluoroalkylethyl acrylate (hereinafter referred to as FA) [C,F,? C
I(2C820COC)l=cH2] 120g, dioctyl maleate 36g, NN-dimethylacnolamide 4g, hydroxyethyl acrylate 4g, polyoxyethylene lauryl ether 10g, stearyltrimethylammonium chloride 2g, acetone 120g
, 350 g of water, and 1 g of azobis(dibutylamidine) dihydrochloride <Wako Kasei V-50> were added, and while stirring,
After purging with nitrogen for 0 minutes and adding 76 g of vinyl chloride, the temperature was raised to 60°C to start polymerization. After stirring at 60° C. for 15 hours, the mixture was cooled to obtain an emulsion with a solid content concentration of 31%.

The conversion rate of copolymerization reaction by gas chromatography is 9
9.0 to 99.8% (based on the polymerizable compound containing perfluoroalkyl groups).

Moreover, the yield of stable emulsion based on all reacted monomers was 95 to 99%. Subsequently, the mixture was heated to 60° C. and bubbled with nitrogen gas for 5 hours while stirring to remove unreacted vinyl chloride. As a result of gas chromatogram analysis, approximately 11,000
Unreacted vinyl chloride, which was 1.5 ppm, was reduced to 6 ppm.

Example 1 was obtained by removing unreacted vinyl chloride by bubbling, and Comparative Example 1 was a polymer composition containing a high concentration of unreacted vinyl chloride before bubbling.

Examples 2 to 6, Comparative Examples 2 to 6 Emulsion polymerization was carried out in the same manner as in Example 1 by changing the monomer and emulsifier polymerization initiator.

Subsequently, the operation for removing unreacted sludge as shown in Example 1 was carried out. On the other hand, in Comparative Examples 2 to 6, polymerization was carried out using the same preparations and the same operations as in Examples 2 to 6, but the operation of removing unreacted monomers was not performed thereafter. The monomers, emulsifiers, and polymerization initiators used are shown in Tables 3 and 4.

Comparative Examples 7 to 11 In the same manner as in Example 1, monomers, ? Emulsion polymerization was carried out by changing the L-forming agent polymerization initiator. Next, Example 1
The unreacted monomer removal operation shown in 1 was carried out, but samples in which the remaining amount of unreacted vinyl chloride monomer was adjusted by shortening the removal operation time were obtained as Comparative Examples 7 to 11. Table 6 shows the vinyl chloride monomer ■ remaining in each comparative example.

Water and oil repellency tests were conducted using the latex obtained by the above method with a solid content concentration of 12% by weight as a stock solution. The latex stock solution was diluted with water, and the ratio of the stock solution to water was 1.5%. Sumitex Resin M-3 and Sumitex Accelerator ACX, which form a melamine resin, were added to this as a combined resin to prepare a treatment liquid, and the water and oil repellency was measured. The test was carried out on nylon taffeta cloth, and the water-repellent T8 oil treatment was carried out as follows. That is, the test cloth was immersed in the latex treatment solution diluted as described above for 30 seconds, and the cloth was squeezed between two rubber rollers to give a wet pickup of 30%. Next, dry at 110°C for 90 seconds, and then dry at 170°C.
Heat treatment was performed for 60 seconds. The results of measuring the water and oil repellency of the treated fabric thus obtained are summarized in Tables 5 and 6 below, together with the water and oil repellency after the durability test.

[Effects of the Invention] The present invention provides a fluorine-based moisture-repellent TG water and oil repellent containing vinyl chloride or vinylidene chloride as a copolymer component,
By removing unreacted vinyl chloride or vinylidene chloride from the emulsion after the polymerization reaction, it is possible to provide a water and oil repellent with excellent storage stability while maintaining the conventional high durability. became. In addition, improved storage stability has made it possible to supply high-concentration products, which previously had problems in terms of stability.

Claims (1)

[Claims] 1. A copolymer obtained by copolymerizing a polyfluoroalkyl group-containing polymerizable compound with vinyl chloride or vinylidene chloride and a compound copolymerizable with this polyfluoroalkyl group-containing compound. A water-dispersible water- and oil-repellent having an unreacted vinyl chloride monomer or vinylidene chloride monomer concentration of 10 ppm or less. 2. The water-dispersible water and oil repellent according to claim 1, wherein the copolymerization ratio of vinyl chloride or vinylidene chloride to 100 parts by weight of the copolymer is 20 to 80 parts by weight. 3. The water-dispersible water repellent according to claim 1, wherein the compound copolymerizable with the polyfluoroalkyl group-containing compound is a compound containing a hydroxyl group in its side chain or a compound containing a nitrogen atom in its side chain. Oil agent.