JPH0480282A - Fluorine-containing water/oil repellent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an improved water and oil repellent,
More specifically, a compound consisting of a copolymer containing as a constituent unit a polymerizable compound containing a polyfluoroalkyl group, vinyl chloride or vinylidene chloride, and a compound copolymerizable with this polyfluoroalkyl group-containing compound, The present invention relates to a water and oil repellent that has high water and oil repellency and washing durability, and shows extremely little change over time in the product.

[Prior Art] Conventionally, fluorine-based water and oil repellents have been produced by copolymerizing a polyfluoroalkyl group-containing polymerizable compound with vinyl chloride or vinylidene chloride and a compound copolymerizable with the fluoroalkyl group-containing compound. It is known that the treated materials are very useful for water and oil repellency. However, these copolymer compositions have a problem in that their water and oil repellency decreases when washed or dry cleaned. Furthermore, since the emulsion itself is hydrophobic, it has had the problem of insufficient stability in various aspects such as mechanical stability.

In order to compensate for these drawbacks, the base fabric and the resin used have adsorption properties, can be cross-linked by heat, and promote the insolubilization of the fluorine film after treatment, and are soluble in water, which improves the stability of the emulsion produced after polymerization. Effective N-methylol acrylamide has been used as an essential copolymer component of fluorinated water and oil repellents and as a constituent unit of water and oil repellent compositions. However, N-methylolacrylamide gradually causes a crosslinking reaction during storage, resulting in a decrease in the stability of the latex.
There are storage problems such as morphological changes such as precipitation of solid content in the solvent and a decrease in performance, which requires appropriate measures.

[Problems to be Solved by the Invention] It is an object of the present invention to solve the problems of practical applications such as laundry and dry cleaning in fluorine-based water and oil repellents containing vinyl chloride or vinylidene chloride as a copolymer component, which were present in the prior art. To provide a water and oil repellent agent which is excellent in durability and has excellent storage stability without problems such as change in form or deterioration of performance of the water and oil repellent agent due to changes over time during storage.

[Means for Solving the Problems] The present inventor added vinyl chloride or vinylidene chloride to a polyfluoroalkyl group-containing polymerizable compound and a compound copolymerizable with the polyfluoroalkyl group-containing compound in a specific ratio. A fluorine-based water and oil repellent obtained by copolymerization! As a result of repeated research and consideration, we have conducted various research and studies with the aim of providing a water and oil repellent that has excellent durability during washing and dry cleaning, and has excellent storage stability without sacrificing its performance. In fluorine-based water and oil repellents containing vinylidene as a copolymerization component, water and oil repellents containing a nitrogen-containing copolymerizable compound and a hydroxyl group-containing copolymerizable compound as copolymerization components have high water repellency. The present invention has been achieved by discovering that water and oil repellency with excellent oil repellency and washing durability and good storage stability can be exhibited.

That is, the present invention provides a method for copolymerizing a polyfluoroalkyl group-containing polymerizable compound with vinyl chloride or vinylidene chloride and a compound copolymerizable with the polyfluoroalkyl group-containing compound. As copolymerizable compounds, both a nitrogen-containing copolymerizable compound and a hydroxyl group-containing copolymerizable compound are essential components, and the initial stage can be made without using the conventionally used N-methylolacrylamide. It exhibits good water and oil repellency even after washing or dry cleaning without interfering with the water and oil repellency of the product, and also eliminates storage stability problems such as morphological changes and performance deterioration during storage. The company supplies water and oil repellents.

Polyfluoroalkyl group-containing polymerizable compounds include: CH2=CCOOCH2CH2Rf R, CH3 CH2=CCOOCHCH2Rf R,C,H.

CH2=CC00CH2CH2NCORfRI
CH3 CH2=CC00CH2CH2NSO2RfR,CH,
R, C2H5 CH2=CCOOCH2CH2NCORf CH2
=CC00CH2C)12NSO2RfR,C,R5R
,C,,H.

CH2=CC00CH2CH2NCORf CH2
=CC00CH2CH2NSO□RfR, CH2Cl
CH3 CH2=CC00CHCH20(:H2CH2N5O2
Preferred examples include (meth)acrylic acid esters containing a polyfluoroalkyl group such as Rf (where R1 is H or CH), and two or more of these or compounds with different carbon numbers can be used as
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 one whose terminal end is usually a perfluoroalkyl group is selected. , 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. , CH2=CR, C00R2 CH co=CRICOO(CH, CH, O), H (P is 1
~12) CH2=CR, C00CH2CH-CH.

＼ 1 (Here, R3 is Hl or CH, R2 is Hl or C
In QH2a*l, q is 1 to 23, preferably 1 to 6
) such as methacrylic acid and acrylic acid or their esters, and CH2=CR,C0 as shown in the following formula.
NHCH20HCH2=CR, C0NHCH20C4H
9CH+1=CHCI CH2=CCl2
CH2=CH20COCH, CH2=CH2CH20H
CHCOOCsH=t CH2=C
R4COO(CH3)2cHcOQcsH,.

(Here, R, is Hl or CH3) (meth)acrylic acid amide derivatives such as vinyl chloride, halogen-containing vinyl salts such as vinylidene chloride, ethylene, vinyl alkyl ether, vinyl acetate, maleic anhydride, and maleic acid. Dialkyl esters, styrene, a-methylstyrene, p-methylstyrene, acrylonitrile, butadiene, isoprene, chlorobrene, methyl vinyl ketone, and the like are preferred.

Among these, vinyl chloride or vinylidene chloride is particularly required as an essential component. In addition, in the present invention, in order to improve washing and try-cleaning durability and prevent performance deterioration during storage, and to solve problems such as change in form and performance deterioration during storage, nitrogen-containing Both a copolymerizable compound and a copolymerizable compound containing a hydroxyl group are required as essential components.

As the nitrogen-containing copolymerizable compound, C)12=
cR,C0N(CH3)2 CH,=CR4C0
0H(C2H5)2Cl(.

CHz:CR+C0NCJ4N(CHs)z (here R
1 is preferably Hl or CH, etc., and these can be used in combination.

Copolymerizable compounds containing hydroxyl groups include CH,=CR,C00CH,CH,0HCH1=CR,
C00CH, CHCH.

H CH2=CR, C00CH2CH2CH20HCH,=
CR4C00 (C2H40), H (P is 1 to 12) CH
2=CR4COO(C,H,0) pH (P is 1-12)
CH2=CR4COO (CJ40) pH (P is 1-12
) (where R4 is Hl or CO), etc., and it is possible to use these in combination.

Furthermore, as a copolymerizable compound, in addition to vinyl chloride or vinylidene chloride, a nitrogen-containing copolymerizable compound, and a hydroxyl group-containing copolymerizable compound, it is also possible to use one or more of the above-mentioned copolymerizable compounds in combination. It is. 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.

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.
A copolymer of a polymerizable compound containing a polyfluoroalkyl group such as an acrylic ester or a methacrylate ester containing a perfluoroalkyl group in an appropriate weight part and a copolymerizable compound other than this polymerizable compound. In order to obtain this, various polymerization methods such as bulk polymerization, 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 monoalkylcarboxylic acid ester, monorubitan ester, and Nonionic surfactants such as sugar 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 , 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, but examples include acetone and methyl ethyl ketone. Ketones such as 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, dipropylene glycol, polypropylene glycol, etc. Suitable examples include propylene glycol derivatives, 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, ? Water-soluble initiators such as azo amine compounds such as “CHx-C-N”N-CONH2N, cyclic amine compounds, amino compounds containing phenyl groups, hydrochlorides of nitrile compounds, and potassium persulfate. Suitable examples include water-soluble peroxide-based initiators. Although the polymerization temperature can be selected depending on the initiator, 40°C to 80°C is usually suitable.

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 have a higher solid content concentration. 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 as long as they are textile products (to name a few).

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.

[Examples] Next, Examples of the present invention will be described 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 JIS L
-1092 is expressed by the water repellency number (see Table 1 below) determined by the spray method.
) and determined by the state of penetration after 30 seconds (AATC
C-TM 118-1966). In addition, the durability test method was carried out as follows↓In other words, in the washing durability test, 1100g of the treated test cloth was mixed with 66g of liquid detergent (
The beads were stirred for 25 minutes in 33 L of water at 40'C containing (trade name), rinsed for 20 minutes at a water flow rate of 601/hour (each washing time was 45 minutes), and dried.

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-softened after 5 dry cleaning treatments and 4 washing treatments.

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

Example 1 Perfluoroalkylethyl acrylate (hereinafter referred to as FA) [C,F,? C
H2CH20COCH=CH2] 120g, dioctyl maleate 36g, NN-dimethylacrylamide 4g, hydroxyethyl acrylate 4g, polyoxyethylene lauryl ether log, stearyltrimethylammonium chloride 2g, acetone 1
20g, water 350g, azobis(dibutylamidine) 2
Add 1 g of hydrochloride (Wako Kasei Co., Ltd. V-50) and replace with nitrogen for about 20 minutes while stirring to obtain vinyl chloride 76.
After adding g, the temperature is 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 the copolymerization reaction by gas chromatography was 99.0 to 998% (based on the fluoroalkyl group-containing polymerizable compound). 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 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 melamine resin as a combined resin.
was added to prepare a treatment liquid, and the water and oil repellency was measured. The test was conducted on nylon taffeta cloth, and the water and oil repellent treatment was performed 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 thus obtained treated cloth are summarized in Table 5 below, together with the water and oil repellency after the durability test.

No. table *1 Leave it in a constant tank at 50℃ for 6 months, Visually observe John's condition.

Subsequent Emul [Effect of the Invention] The present invention provides a fluorine-based water and oil repellent containing vinyl chloride or vinylidene chloride as a copolymerization component, in which nitrogen is substituted for N-methylolacrylamide as a copolymerization component other than vinyl chloride or vinylidene chloride. To provide a water and oil repellent having excellent storage stability while maintaining conventional high durability by polymerizing a copolymerizable compound containing a hydroxyl group and a copolymerizable compound containing a hydroxyl group. became possible.

Claims (1)

[Claims] 1. Consisting of a copolymer containing as a constituent unit a polymerizable compound containing a polyfluoroalkyl group, vinyl chloride or vinylidene chloride, and a compound copolymerizable with this polyfluoroalkyl group-containing compound. A fluorine-based water and oil repellent, characterized in that a nitrogen-containing copolymerizable compound and a hydroxyl group-containing copolymerizable compound are used as the copolymerizable compound. 2. The fluorine-based water and oil repellent according to claim 1, wherein the nitrogen-containing copolymerizable compound is NN-dimethylacrylamide or NN-dimethylmethacrylamide. 3. The fluorine-based water and oil repellent according to claim 1, wherein the copolymerizable compound containing a hydroxyl group is hydroxyethyl acrylate or hydroxyethyl methacrylate.