JPS599666B2 - fiber treatment agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION 5 The present invention relates to a textile stripping agent comprising an improved water- and oil-repellent polymer.

There are many polymers that have been developed for the purpose of imparting water and oil repellency to textile products.

Such polymers generally contain pendant perfluoroalkyl groups having three or more carbon atoms, which provide the desired repellency. The perfluoroalkyl group is attached by various linking groups to the polymerized vinyl group that is the polymer chain repeat unit forming the main or backbone polymer chain. Methods for making such polymers either in aqueous emulsion systems or in solvent systems are also well known in the art. One of the problems with prior art polymer systems is providing stable, easy-to-handle aqueous dispersions of such fluorine-containing polymers. Another problem is obtaining the maximum efficiency of the intended use of such fluorine-containing polymers, i.e. reducing the adhesion of the polymer to the outer surface of the fibers of the treated textile products, which requires its beneficial effects. That's true. U.S. Patent No. 3,645,990 discloses that methyl acrylate or ethyl acrylate and the structure RfCH2
A unit derived from a monomer of CH2O2CC(CH3)=CH2 (wherein Rf is a perfluoroalkyl group having about 4 to 14 carbon atoms) and optionally a small amount of C
H2=CRCONHCH2OH, CH2=CRCO2C
Contains units derived from monomers selected from H2CH2OH and mixtures thereof (wherein R is H or CH3), has water and oil repellency, and has dry stain resistance with fluorinated disclosed emulsion polymers.

This polymer provides oil repellency and good dry stain resistance (DJysOil) to textile materials when air dried rather than heat cured.
It is an object of the present invention to provide improved water- and oil-repellent polymers that form stable aqueous dispersions.

Another object of the present invention is to provide improved polymers with water and oil repellency and dry stain resistance that form stable aqueous dispersions. Yet another object is to provide such dispersions useful in the treatment of textile products. Yet another object is to provide such aqueous dispersions that are stable in the presence of other textile treatment agents. Yet another objective is to prepare such aqueous dispersions that are stable even in the presence of textiles containing residues of textile treatment agents applied during previous textile treatments. C(
CH3) COOCH* is to be provided.

In summary, the present invention provides, on a weight basis, the following (a) and (b):
) is 100%, (a) formula RfCH2
CH2O2CC(R)=CH2 (in the formula, Rf is carbon number 4
-14 perfluoroalkyl groups, R is hydrogen or methyl) monomer; (b) non-vinyl fluorine-free vinyl; 1-80% of polymer chain repeat units derived from monomers; and (c) 0.1-4% based on the total amount of (a) and (b) of the formula CH2=C
(R)-Z-YeXO (wherein R is hydrogen or methyl, z is a bonding group that activates vinyl polymerization, and Y4
is an onium ion group and XO is a water-solubilizing anion).

The above definition of polymer excludes the presence of mixed repeating units derived from a mixture of monomers at position 2 from (a), (b) or @) that all meet the definition of that monomer. It's not something you do.

Also, other polymer chain repeating units, i.e.
Nor does it exclude the presence of units derived from monomers that are outside the scope of the above definition of monomer. For example, useful polymers within the above definition include, in addition to each of the repeating units listed above, the formula CH2=C(R)CONHCH2OH
, CH2=C(R)COOCH21) H2 and CH2
=C(R)COOCH2CH(R)0H (wherein R is hydrogen or methyl) is a polymer chain repeating unit derived from one or more monomers selected from the monomers (wherein R is hydrogen or methyl).
Mention may be made of those containing up to 8%, based on the total weight of a) and (b).

Preferred monomers of the invention include those in which R in the monomer defined in (a) is methyl; no fluorine atoms or only fluorine atoms bonded directly to the double-bonded carbon of the vinyl group. is a Cl-Cl8 alkyl ester of methacrylic acid; the monomer defined in (c) has the formula [CH2=C(CH3)COO(CH2)NY'']EX
Q and H(0H)CH2r]1x0 (where n is 2-6
, Y is (-NRlR2R3]4, and R1, R2 and R3 are each a C1-C4 alkyl group, provided that R1,
Any two of R2 and R3 may be alkylene having 4 to 5 carbon atoms or 1(CH2)2-0-(CH2)2-, and Y5 is Y or a pyridinium group)
monomers selected from the monomers; furthermore, polymer chain repeat units derived from one or more of the three monomers mentioned immediately above as optional components are present in an amount of up to 8%. There are some.

The polymers included in the present invention include (1) and (3) by weight.
) is 100 parts, formula (g) RfCH2
70-95 parts of units derived from the monomer CH2O2CC(CH3)=CH2 (wherein Rf is perfluoroalkyl having 4 to 14 carbon atoms), (Ii) 5 units derived from methyl or ethyl acrylate -30 copies, and (1)
and (9) in an amount of O-1 part per 100 parts of CH2-
CRCONHCH2OH,. CH2=CRCO2CH2
CH2OH and mixtures thereof (wherein R is H or C
Contains units derived from one or more monomers selected from H3), based on the total weight of the monomers, 0.0
0.1-1.0 per 100 parts of (1) and (4) combined in the polymer prepared in the presence of 4-1.0% chain transfer agent.
The formula for the amount of parts ψ CH2=CRCO2CH2CHOHCH2NRl(R2
)(R3)XC) (where m is H or CH3,
Rl. Also included are polymers improved by further containing units derived from monomers in which R2 and R3 are each C1-C4 alkyl and X is chlorine or bromine.

The above polymers can be produced by a known aqueous emulsion polymerization method. The resulting aqueous dispersions of polymers have outstanding storage stability. It exhibits high efficiency when applied to textiles and similar substrates. In addition, dyed fabrics treated with this polymer also suffer from flaking (
Cmck) It was found that the firmness was improved. The polymer also provides improved stain removal properties for synthetic fibers such as polyester, polyamide and polyester/polyamide blends. Formula RfCH2CH2O2CC(R)=C
Monomers of H2 are well known in the art.

This can be prepared by esterifying the appropriate alcohol RfCH2CH2OH with acrylic or methacrylic acid. Methacrylic esters are more preferred than acrylic esters. The perfluoroalkyl group Rf may be linear or branched, but is preferably linear. Monomer RfCH2CH2O2CC(R)=CH2 is one type of perfluoroalkyl group (e.g. perfluorooctyl)
or a mixture of two or more types of perfluoroalkyl groups. Alcohol R
Since fCH2CH2OH is commercially available as a mixture of 4-14 carbon atoms, consisting primarily of 6 and 8 carbon atoms, monomers prepared from such alcohol mixtures are preferred. The most preferred monomers in the above formula are those in which R is methyl and Rf is CF3CF2(CF2)m- (wherein m is 4,
6, 8, 10 and 12 perfluoroalkyl groups in a weight ratio of approximately 35/30/18/8/3). The molecular weight of such a monomer is 552. The molecular weight of the corresponding acrylate monomer is 508. Another monomer used in the preparation of the above polymers is a non-vinyl fluorine-free vinyl monomer.

The term “non-vinyl fluorine-free” used here means
This means that the fluorine atoms that can be contained in this vinyl monomer are limited to those that are directly bonded to the double-bonded carbon atoms of the vinyl group. In this sense, therefore, vinyl fluoride and vinylidene fluoride are included among the vinyl monomers listed below. This is because in these two types of vinyl monomers, the fluorine atoms are both directly bonded to double-bonded carbon atoms. 0 vinyl used here refers to vinyl group -CH=CH2 and vinylidene group -CR4
Monomers containing =CH2 (R4 is a substituent such as lower alkyl, eg, methyl, methyl, or halogen) are intended to be included. Both monovinyl compounds and conjugated dienes can be used in the present invention. Non-conjugated dienes in which each vinyl group is separately polymerized are not included here since such monomers cause undesirable cross-linking of the polymer chains. For reasons discussed below, the nature of the vinyl monomer selected must be taken into account in determining the polymerization method to be used. Non-vinyl fluorine-free polymerizable monovinyl compounds that can be used in the present invention include C1-Cl8 alkyl esters of acrylic acid and methacrylic acid, vinyl esters of fatty acids, styrene, alkylstyrenes,
There are vinyl halides, vinylidene halides, allyl esters, and vinyl alkyl ketones.

Representative examples of specific compounds useful in the invention include methyl, ethyl, propyl, butyl, isoamyl, 2-ethylhexyl, octyl, dosyl, lauryl, cetyl, octadecyl esters of acrylic and methacrylic acids; vinyl acetate, propionic acid Vinyl, vinyl fluoride, vinyl laurate, vinyl stearate; styrene, α-methylstyrene, p-methylstyrene; vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride; allyl heptanoate, acetic acid allyl, allyl furylate,
Allyl caproate; vinyl methyl ketone, vinyl ethyl ketone; 1, 3-butadiene, 2-chloro-1, 3
-butadiene, 2,3-dichloro-1,3-butadiene and isoprene. Preferred vinyl monomers are alkyl acrylates and methacrylates, especially methyl, ethyl, butyl and 2-ethylhexyl methacrylate. Another monomer used in the preparation of the above polymer is an ionic monomer of the formula CH2=C(R)-Z-YeXΘ, where R is hydrogen or methyl and z is a vinyl polymer. (Y(f) is an onium ion group, and XΘ is a water-solubilizing group).

z may be any bonding group, but representative examples include -C-NH(C
H2)n-, -0-C-(CH2)n-, -0-(CH
2) n- and -S-(CH2)n- (wherein n is an integer)
There is. In all cases, including the above specific examples, the carbonyl group, ether oxygen atom, or sulfur sulfur atom of z is directly bonded to the vinyl group of the monomer. z can also be a divalent aromatic group (e.g. 1,4-phenylene) or a divalent aralkyl group (e.g. ROCH,) n-,
However, it may be n (mixing integer). In such cases, the aromatic group is bonded directly to the vinyl group of the monomer. Although all of the above specific examples of linking groups contain an unsubstituted polymethylene moiety -(CH2)n-, it will be understood that other groups may also be present. For example, polymethylene moieties containing non-reactive substituents, ie, substituents that do not participate in the polymerization reaction (eg, hydrocarbon side chains or hydroxy groups), may be present in the linking group. The above onium ionic group Y
e may be any known type of onium ion that is not sensitive to pH changes.

In this respect, it must not be an acid salt of a tertiary amine group.
A preferred example of Ye is quaternary ammonium ion [-NR
lR2R3]e. (Wherein R1, R2 and R3 are each a lower alkyl group having 1 to 4 carbon atoms.) Other useful ammonium ions include R1, . Any two of R2 and R3 taken together are an alkylene group having 4-5 carbon atoms or 1(CH2)2-0-(CH2)2-
It is what forms the. The former is an ammonium salt based on N-alkylpyrrolidone-O''' or N-alkylpiperidi, and the latter is an ammonium salt based on N-alkylmorpholine-N'6.

In some cases, Y4 may be a pyridinium ion. Particularly preferred ionic monomers include:

In the latter, Y' is as defined above; in the former; Y' is [-NRlR2R3] or a pyridinium ion group as defined above; n is 2-6.

Particularly preferred ionic monomers are.

Another preferred monomer is.

Many of the ionic monomers that can be used in the present invention are known in the art. CH2-C(R)-Z-Y4XOf)
When Z is -C(CH2), this monomer has the formula C
H2=C(R)-C (AI2 ends) can be prepared by reacting a halogen vinyl haloalkyl ketone with a tertiary amine or pyridine.

When Z is -C-0-(CH2)n- or -C-NH(CH2)n-, the monomer is a tertiary amino group of the formula HO(CH2)n-NRlR2, 7
:, or a diamine of formula H2N(CH2)NN with acrylic acid or methacrylic acid or their derivatives, and then react the resulting ester or amide with di(
(lower alkyl) sulfates or lower alkyl halides to form ammonium salts.

z is -0-C1(CH2)n-, {-(CH2). −
or -S1(CH2)n-, this monomer can be prepared by reacting the corresponding halo fatty acid vinyl ester, vinyl haloalkyl ether or vinyl haloalkyl sulfide with a tertiary amine or pyridine. It can be prepared by It can be prepared by reacting with sulfuric acid, a particularly preferred monomer mentioned above.

Another preferred monomer, mentioned above, is a commercially available product.

The type of anion X in the ionic monomer is generally determined by the method of synthesizing the onium salt.

Usually XΘ is a halogen ion, especially a chlorine, bromine or iodine ion, or an alkyl sulfate ion,
-SO3〇. However, it is known that quaternary ammonium salts can also be prepared by reaction of tertiary amines with alkyl esters of benzene or toluenesulfonic acid. In such cases, XΘ is the anion of benzenesulfonic acid or toluenesulfonate. Anion Xe&A Like all of the above anions, it is water soluble. Anions that tend to reduce water solubility should be avoided. As mentioned above, certain of the above polymers may optionally (but preferably)
, in an amount up to 8% based on the total amount of (a) and (b) of the polymer definition above, of the formula CH2=C(R)CONHCH2
It may contain a polymer chain repeating unit derived from one or more monomers of OH, , and CH2=C(R)COOCH2CH(R)0H (where m is hydrogen or methyl).

Although these monomers can be used alone, it is often preferred to use monomer mixtures, especially mixtures of the first and third monomers mentioned above. A preferred optional monomer is N-methylolacrylamide (CH2=
CHCONHCH2OH), glycidyl methacrylate and 2-hydroxyethyl methacrylate (CH2=C
(CH3)COOCH2CH2OH, both of which are commercially available.

Preferred concentrations of optional monomers include monomers (a) and (b).
and the most preferred polymer contains 2% each of N-methylolacrylamide and 2-hydroxyethyl methacrylate. Generally, the above polymers can be prepared by any of a number of methods known as emulsion polymerization of vinyl compounds.

The polymerization process can be carried out in a reaction vessel equipped with a stirrer and external means for heating or cooling the raw materials. Each monomer to be polymerized is emulsified in an aqueous surfactant solution to a predetermined emulsion concentration of about 5-50%. The temperature is usually raised to 40-70 DEG C. and the polymerization is carried out in the presence of added catalyst. Suitable catalysts are any of the well known catalysts for initiating the polymerization of ethylenically unsaturated compounds. These well-known catalysts include 2 ・2'
-Azodiisobutyramidine dihydrochloride, 2/2'
-Azodiisobutyronitrile and 2-2'-azobis(
2,4-dimethyl-4-methoxyvaleronitrile). The concentration of polymerization catalyst is usually 0.1-2%, based on the total amount of monomers undergoing polymerization. The surfactant used to stabilize the emulsion during its preparation and polymerization process may be one or more emulsifiers, cationic or nonionic. Cationic surfactants that can be used include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethyl There are ammonium chloride and N-[2-(diethylamino)ethyl]oleamide hydrochloride. Nonionic surfactants that can be used include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, C.
There are condensation products with 2-C,6 alkanethiols or Cl2-Cl8 alkylamines. Further, when it is necessary to control the molecular weight as described below, a suitable chain transfer agent, such as an alkanethiol having 4 to 12 carbon atoms, may be present during the polymerization. Ingredient (a). (b) and (c) An important feature of the preparation of the above mentioned polymers by VC is that one of the monomers used is ionic in nature and acts as a surfactant. It is to show.

As a result, the amount of surfactant required during polymerization is
No other way! The amount is small compared to what is needed.
Based on the combined weight of monomers (a) and (b), usually about 1-
4% of a suitable surfactant is required. A preferred surfactant has the formula [R5N(CH3)3]1zθ (where R5
is a long chain group with about 12-20 carbon atoms, and zθ is water-soluble 1
It is a quaternary salt of a chemical group, generally a rogen ion. The most preferred surfactant is dodecyltrimethylammonium chloride. The most useful polymers in this invention have been found to have viscosity average molecular weights in the range of 10,000-100,000.

Methods for measuring viscosity average molecular weight are well known. For example, F. W. Written by Billmeyer [TextbOOkO
fPOlymerSeience”, International
iOnalPubllshersll962, P79-85. Depending on the purity and nature of the respective monomers used (even traces of impurities can sometimes affect the molecular weight), it may be necessary to add chain transfer agents during the polymerization. Any monomer CH2=C(R)CO
NHCH2OH,. CH2-C(R)COOCH bar presentation H2 or CH2=C(R)COOCH2CH(R)0
It has also been found that when H is present, careful control of molecular weight is desirable. Such monomers are highly susceptible to cross-linking between polymer chains. In order to overcome the defects caused by this crosslinking, it is preferable to reduce the molecular weight of the polymer chain appropriately. Therefore,
For optimal results, the amount of chain transfer agent added is directly proportional to the amount of any monomer added. For the reasons stated above, the molecular weights of apparently identical monomer combinations can vary over a wide range, so a simple rule for determining the amount of chain transfer agent to be added for a given amount of any component used is: cannot be determined. To obtain optimal results, it is necessary to repeat the tests using the actual monomers and the actual amounts used. Ionic monomer CH2=C(R)-Z-YC
f) It has also been found that a certain degree of care must be taken when mixing XQ into the polymer during polymerization to ensure that mixing occurs.

This ionic monomer is water-soluble, whereas monomer R
fCH, CH2O2CC(R)=CH, is not.
Therefore, it is possible that each monomer is polymerized separately in the same aqueous polymerization system. If the non-vinyl fluorine-containing vinyl monomer has some water solubility (as is the case, for example, with lower alkyl acrylates and methacrylates or lower fatty acid vinyl esters), the vinyl monomer It tends to facilitate incorporation of repeating units of ionic monomers into perfluoroalkyl-containing polymers. However, if the vinyl monomer is essentially water-insoluble (as is the case, for example, with higher alkyl acrylates and methacrylates or long-chain fatty acid vinyl esters with 12 or more carbon atoms), the ionic monomer It becomes necessary to take measures to facilitate the incorporation of repeating units into the perfluoroalkyl-containing polymer. A convenient method for performing such lysis is
This involves adding a water-soluble organic solvent such as acetone, methanol, or ethanol. The polymer is obtained as an aqueous dispersion.

Although it is possible to isolate the polymer as a solid if desired, e.g. by filtration, centrifugation or evaporation of the liquid fraction, for most applications the aqueous dispersion should be at least water- and oil-repellent. It can be used directly for application to the textile or substrate to be coated. The polymer may be applied to the textile or substrate alone or in admixture with non-fluorinated polymers, which are well known diluents. Generally, such non-fluorinated polymers are prepared from the monomers described above as vinyl monomers that do not contain non-vinylic fluorine atoms. When such non-fluorinated diluent polymers are used, the ionic monomers CH2=C(R)-Z, as defined above, are identical to the water and oil repellent polymers described above. -Y4xO polymer chain repeat unit 100 polymer chain repeat units of other monomers
It should be present in a weight ratio of 0.1-4 parts per part. The amount of the diluent polymer is up to about 80% by weight of the total O weight of the water/oil repellent polymer and the diluent polymer (i.e.,
(up to 400% by weight of the water/oil repellent polymer). The preferred amount of diluent polymer is about 16-2/3% of the total weight of the polymer (20% by weight based on the weight of the water and oil repellent polymer). The polymers mentioned above are generally used in aqueous dispersion by spraying, dipping, padding or other well known methods onto textile fabrics.

After excess liquid has been removed, e.g. with a squeegee roll, the treated fabric is dried and then subjected to e.g.
5-193°C for at least 40 seconds, typically 60-18°C
It is cured by heating for 0 seconds. This curing increases oil repellency and durability. The polymers of the present invention can also be applied at any time with other adjuvants, such as textile resins, water repellents and other additives applicable to textiles. but,
If the highest stain resistance is to be obtained, the application of additives that reduce dry stain resistance should be avoided at any time. On the other hand, the highest water repellency and durability are obtained in the presence of textile resins, especially those based on melamine-formaldehyde. The above-mentioned polymer of the present invention can be used in textile products for various purposes. For example, it can be applied to automotive seat upholstery, especially those with nylon tricot surfaces where prevention of dry stains is a particularly important issue. Another important use of this polymer is in knitted and woven polyester or polyester/cotton blend lanewear. When preparing aqueous dispersion padbaths of the above polymers for textile applications, it is common to add surfactants (generally non-ionic surfactants) as bath stabilizers. . Bath stabilizers are used particularly when both anionic and cationic surfactants enter the bath along with other ingredients. Bath stabilizers appear to ameliorate the undesirable effects caused by the interaction of the two ionic surfactants. Surfactants as stabilizers can be selected from the commonly available types, such as ethoxylated fatty acids, ethoxylated phenols, ethoxylated amides, ethoxylated amines, ethoxylated fatty alcohols and fatty amines. A preferred nonionic surfactant is Cl2-Cl
Ethylene oxide addition products of 6-alkyl alcohols, such as Cl3H2,O(C2H4O)8H. This surface active agent is not intended to replace conventional emulsion polymerized surfactants, but rather assists in dispersion retention. This is usually added when preparing the pad bath. Optionally, salts such as alkali metal sulfates and low molecular weight alkyl amine hydrochlorides may also be included in the textile treatment bath as adjuvants to aid in the deposition of polymeric or other substances onto the textile substrate. In addition, the use of surfactants and salts can enhance the changes that occur in the textile product during the drying and optional curing steps of the process.

The purpose of this is to obtain the optimum effect with the minimum amount of treatment agent. A typical "sud bath" for applying the above polymers is 0.025 - 1 % based on the weight of the dry fabric
．． Adjustments are made such that 0%, preferably about 0.2%, of the polymer is deposited on the fabric.

Assuming a wet pick-up (Wetpiclcup) by the fabric backing of 100% (relative to the weight of the backing), the concentration of the pad bath will be 0.025-1.0%. Lower impregnation rates require higher concentrations.

Applying chemical treatment agents to textile products and their physical effects. Beauty/
In industrial operations that change chemical properties, it is desirable for economic reasons to carry out such treatments in as few steps as possible.

Ideally, all drugs should be applied at the same time.
Examples of such treatment agents include Permanet Press or anti-wrinkle treatments, water and oil repellents, anti-dry stain agents,
Hand Improver Over
, and stain remover (SOil release agent)
t). Some or all of these may have an effect on each other that precludes simultaneous application of the some mixture using the butt bath method. moreover,
Chemicals used during fiber processing and weaving, spinning, knitting, or scouring enter the adjuvant application bath as residue on the fabric, further complicating the composition of the bath. It has been found that many aqueous dispersion products that work very well alone in baths can coagulate or otherwise become undesirable when other processing chemicals are present. The water- and oil-repellent polymers of the present invention described above largely overcome this problem. This polymer exhibits remarkable tolerance to a wide range of chemicals in the application bath by remaining well dispersed during the textile application process. In particular, there is a high tolerance for the presence of inorganic salts of polyvalent anions (eg, tetrasodium pyrophosphate) in aqueous baths and other chemicals that may be present as residues from spinning, weaving, knitting, dyeing or scouring processes. The following examples are intended to illustrate the invention.

Parts refer to parts by weight unless otherwise specified.
Example 1 Deionized water was heated for about 1 hour while bubbling nitrogen gas.
It was refluxed for an hour and then cooled to 70°C.

This treatment removed dissolved oxygen and carbon dioxide from the water. In a high shear mixer (0sterizer), 97.4 parts of deionized water, 7.4 parts of dimethyldodecylamine,
3.7 parts of dimethylhexadecylamine, 9.0 parts of glacial acetic acid, and the formula C2F5(CF2)NC2H4O2CC(CH
3) = CH2 (where n is 4, 6, 8, 10 and 12,
A mixture of fluorinated monomers (average molecular weight 522) whose relative proportions are 35:30:18:8:3 17
5.6 parts were added.

The mixture was stirred vigorously for 10 minutes, then 58.8 parts of water was added and mixing continued for an additional minute. The resulting homogeneous emulsion was divided into two parts (A and B) each consisting of 152.0 parts.
). A has CH, =C(CH,)CO2CH2
0.8 parts of CH(0H)CH2N-(CH,)3C1e was added, and 0.4 parts of the same was added to B. Both were then purged with nitrogen for 1 hour, and A and B were each
-Hydroxyethyl methacrylate 0.19%, 42%
0.39 parts of N-methylolacrylamide aqueous solution and t
0.24 part of dodecylme, captan was added. A and B were each added to 150 parts of nitrogen-purged deionized water in a reaction flask and the contents were heated to 65°C. To each content was added 4.2 parts of methyl acrylate and 0.2 parts of azobis(isobutyramidine) dihydrochloride as a solution dissolved in 10 parts of water. The two contents were held at approximately 70° C. for 4 hours with gentle agitation. This 4
Approximately 30 minutes before the time was up, 10.7 parts of a 15% solution of dimethylhexadecylamine acetate was added to each content.
The resulting preparations each contained approximately 23-23.5% solids. Both were uniform and stable dispersions. The stability of this polymer dispersion must ultimately satisfy industrial use tests.

However, stability testing can be carried out in the laboratory by centrifuging the sample and evaluating the amount of coagulum separated and removed from the dispersion by the centrifugation action.

In the test used here, Ntej-NatiOnalCl
lnicalCentrifuge, CLl34O3H
Using a mold, measure approximately 40 10WLI graduated test tubes.
This was done by rotating at 00 rpm for 15 minutes. Accurate measurement of the solids content of the dispersion (by drying) before and after the centrifugation treatment indicates the proportion of solids remaining in suspension in the dispersion. Suspensions A and B above showed a stability of 99.9% and 99.7%, respectively, in this test. Isolation of the polymer may be accomplished by mixing the dispersion with 10 times its volume of acetone to precipitate the solid polymer. This may then be isolated by P filtration. However, it is convenient to handle the dispersion as is, and its dilution with water produces a pad bath suitable for application to textiles. Samples taken from dispersions A and B were each applied to a sample of 100% polyester double knit fabric, which was dried, cured, and tested for water and oil repellency.

The pad bath consisted of 4% 23% dispersion (i.e. 0.92% water/oil repellent), 2% aqueous 10% alkylamine hydrochloride promoter and various amounts of Cl,H2,O (C2H,O).
8 surfactants. Soak the fabric sample and squeeze to achieve an impregnation rate of 60% (therefore, water repellent and
(containing 0.55% oil repellent), then horizontally dried at 121°C and cured at 160°C for 3 minutes. The treated fabric samples were then tested by the American Association of Textile, Chemical and Dyeing Technicians (AAT).
A water repellency test was conducted using Standard Test Method 22-1967 of CC). A rating of 100 means no water penetration or surface adhesion, a rating of 90 means slightly random adhesion or wetting, and lower values indicate greater wetting. . Oil repellency is A
It was measured according to a modified ATCC test method 118-1966. The test before modification is carried out by carefully placing a drop of one of the 68 test solutions onto a textile product placed on a flat horizontal surface. The properties of each test solution are shown below. After 30 seconds, visually observe whether it has penetrated or absorbed into the fabric.

Treated fabrics with a rating of 5 or higher are good to excellent. Items with an evaluation of 1 or more can be used for some purpose. For example, treated fabrics
If it repels solutions from to 6 but does not repel solutions from magic 7, its evaluation is 6. This AATCC oil repellency test was modified in this example to improve sensitivity.

That is, 0.2% by weight of blue dye 1.4 in each test solution.
-bis(2.4.6-triethylanilino)anthraquinone was added. The presence of dye makes it easier to see the penetration and absorption of oil into the fabric. Additionally, the test solution was left on the fabric surface for 3 minutes instead of the usual 30 seconds to check for penetration. The treated fabric samples were also tested for home wash waxiness.

The home washing test was carried out using a standard washing machine (KOnmOre6OO
The test was carried out using a detergent (Tide) 29 with a load of 4 pounds (1.8 kg). Hot the washing machine (
12 minute cycle) and warm water rinse (12 minutes). The total washing and rinsing time was 40 minutes. The spin-drying process used in the example was to spin-dry the spun dry fabric in a household dryer at a temperature of about 71°C.
It was hot. The treated fabric samples were also tested for dry cleaning fastness.

Dry cleaning test uses tetrachlorethylene 10
The samples were stirred for 120 minutes in tetrachlorethylene containing 1.5% of commercially available dry-cleaning detergent (R.R.Street CO. 886 detergent) per 0.0 g, leached with tetrachlorethylene, and removed from the drum. 66℃ inside
After drying for 3 minutes at room temperature, the fabric consists of pressing both sides of the fabric at about 149° C. for 15 seconds. The initial oil repellency should be at least 5 and the initial water repellency should be at least 80.

After washing or dry cleaning, the repellency usually decreases, but if the value is 2 or more for oil repellency and 70 or more for water repellency, it is significantly improved compared to untreated fabric foil.
The results of the water and oil repellency tests are shown in Table 1. Example 2 Another mixture was prepared according to the method of Example 1 using the following amounts of each ingredient.

The following was added to the above emulsified mixture.

This emulsion was treated with nitrogen purged deionized water for 30 minutes.
0 parts and heated to 65°C.

Next, the following was added. The total amount of the resulting dispersion (containing 24% solids) was 634.3 parts.

Its stability was 99.9% (only 0.1% loss of solids due to centrifugation). This dispersion has a solid content of 6
．． It was diluted with water to 58% and then divided into two parts, A and B. A was not denatured. B contains dispersion 10
0.572 parts of Cl3H2,O(C2H4
O) 8H was added. Samples A and B were applied to polyester double knit fabrics and tested for water and oil repellency.
The results of this test are listed in Table 2 below. Both A and B padding bath dispersions were stable for 24 hours, during which time nine pieces of fabric were padded.

Example 3 A suitable container was charged with 36.7 parts of water and a solution consisting of 5.13 parts of glacial acetic acid, 4.22 parts of dimethyldodecylamine and 2.11 parts of dimethyloctadecylamine.

The contents were stirred at 40-50°C to completely dissolve the amine salt. Next, 100.0 parts of the fluorinated monomer of Example 1 was added, and the entire contents were heated to about 50°C using a high shear mixer.
Homogenized with The apparatus was rinsed with another 51.8 parts of water, which was also added to the initial charge. 200 parts of water was placed in a separate container, and the mixture was refluxed for several hours while bubbling nitrogen to remove oxygen. The monomer mixture was also purged with nitrogen to remove oxygen. The following was then added to the monomer mixture: After mixing for a few minutes. This monomer mixture was added to the above nitrogen-purged water (65-70°C), and to this was added 0.135 parts of 2,2'-azobis(isobutyramidine) dihydrochloride dissolved in 1.7 parts of water. did.

The contents were polymerized for 3.5 hours at about 70°C, then a mixture of 2.11 parts dimethylhexadecylamine, 1.4 parts glacial acetic acid, and 9 parts water was added to further polymerize for 0.5 hours.
It lasted for hours. This was cooled to 30-35°C and the solids content was adjusted by adding water and mixing. This product was tested for water and oil repellency and for dispersion stability in processing baths.

This was applied to polyester double knit lanewear fabric dyed Aquagreen with 0.329% polymer solids and 0.029% C,3
It was applied from an aqueous treatment bath containing H2,O(C2H4O)8H and 0.23% 2-hydroxy-1-propylamine hydrochloride (as a 10% aqueous solution). The bath-soaked fabric samples were squeezed to 55% wet pick-up, then dried at 121°C and cured at 160°C for 3 minutes. The results of the water and oil repellency tests are shown in Table 3 below. The above treatment bath is 2-3
It showed satisfactory stability during the factory test operation which lasted for hours.

The treated fabric was tested for flaking (dye loss due to rubbing) and was comparable to untreated fabric. Examples 4-17 General Procedure I for Emulsion Polymerization Purge the Reactor A suitable reaction vessel equipped with an agitator, reflux condenser, thermometer, nitrogen inlet and addition funnel is charged with a predetermined amount of water (4).

The water is refluxed for 30 minutes at atmospheric pressure. During the reflux process, a gentle stream of nitrogen is introduced into the reaction vessel. Once the reflux purge is complete, the vessel is cooled to an internal temperature of 70'C while carefully increasing the nitrogen flow to prevent air being drawn back into the reaction vessel. Preparation of Monomer Dispersion Monomers that are relatively insoluble in water are dispersed into a stable emulsion of fine particles as follows.

A suitable commercially available high speed stirrer (e.g. 0sterize
Add water (B) and surfactant C) to a Waring Blender and stir the mixture gently to dissolve the surfactant. Then the composition is F(CF2CF2
) Add a mixture of relatively water-insoluble monomer (D), NCH2CH2O2CC(CH3)=CH2, and methacrylate comonomer D and run the 0sterizer at its highest speed for 10 minutes.

During this time the temperature of the mixture increases from 30-40°C (initially) to 70-380°C due to the heat generated by the mechanical stirring. Other suitable commercially available dispersion equipment, such as colloid mills or MantOn-Gaulin homogenizers, can also be used to prepare monomer dispersions to allow greater polymerization to occur. The resulting stable monomer emulsion is mixed with a predetermined amount of water D to adjust its concentration appropriately. Place the diluted emulsion in a dropping funnel and flush with nitrogen (below the surface) for 30 minutes. After purging the reaction vessel and sparging the monomer emulsion, place the monomer emulsion into the reaction vessel and bring the internal temperature to 6.
Adjust to 5°C. Next, the following ingredients are added. Relatively water-soluble hydrocarbon comonomer (G) Polymerizable ionic comonomer (self) Polymerizable comonomer having a reactive functional moiety in addition to a double bond (1) Suitable chain transfer agent (J) These additions are easy. Keep the temperature at 65°C for 30 minutes.

Next, the initiator (g) is added. 2-7 after 5-15 minutes
A temperature increase of 0.degree. C. is usually observed and after this temperature increase the mixture is held at 70.degree. C. for 4 hours to complete the polymerization.

Measure the true weight (1) of the obtained latex, and measure its nonvolatile (solid) content (b) (sample 1f7).
(measured by drying at 110°C for 4 hours). Data for Examples 4-17 are shown in Table 4. All parts are by weight except in column M. In all examples, the chain transfer agent used (J
) and initiator (8) are dodecylmercabutane and N
-N5-Azobisisobutyramidine [Tuna salt] The codes used in Table 4 are as follows. Pad baths were prepared by blending the predetermined amounts of the fluoropolymer from Examples 4-17 with other optional ingredients as shown in Table 5.

Wet impregnation rate of fabric (polyester double knit) 100
%, dry at 135°C, and dry at 17%.
Cured at 1°C. According to the method described above, first, 1.
After dry cleaning (DC) twice and washing five times, the repellency was measured. The data obtained are shown in Table 5. The symbols used in Table 5 are as follows. The present invention can be summarized as follows.

(1) By weight, (a) Formula RfCH2CH2O2CC(C
H3) 70-95 parts of polymer chain repeat units derived from a monomer having -CH2 (Rf is perfluoroalkyl having 14 carbon atoms); (b) polymer chain repeat units derived from methyl or ethyl acrylate; Unit 5-30
and (c) CH2=CRCONIiCH2OH
,, a polymer chain repeating unit derived from one or more monomers selected from CH2=CRCO2CH2CH2OH and mixtures thereof (R is H or CH3).
and (b) in the presence of 0.04-1.0% of a chain transfer agent based on the total weight of the monomers, , (a) and (b)
0.1-1.0 parts per 100 parts total of the formula (wherein R is H or CH3, R1, R2 and R3 are each C1-C4 alkyl, and X is C1 or Br
Fibrous fabric foil treated with a polymer having improved water and oil repellency and dry stain resistance characterized by containing polymer chain repeating units derived from the monomer of .

(2) Based on weight, the sum of (a) and (b) below is 100
%, (a) Formula RfCH2CH2O2CC (
R)=CH2 (wherein, Rf is a perfluoroalkyl group having 4 to 14 carbon atoms, and R is hydrogen or methyl)
Polymer chain repeat unit 20-
99%; (b) Polymer chain repeat unit 1 derived from a vinyl monomer that does not contain non-vinylic fluorine atoms
-80%; and (c) 0.1-4% based on the combined weight of (a) and (b) of the formula CH2=C(R)-Z-YlXO
(wherein R is hydrogen or methyl, z is a bonding group that activates vinyl polymerization, Ye is an onium ion group that is not sensitive to H changes, and Xe is a water-solubilizing anion). A textile fabric treated with a water- and oil-repellent polymer containing polymer chain repeat units derived from monomers.

(3) The textile fabric according to item (1) above, in which R in the polymer
f is C2F5(CF2)n-(n is 35:30:18:
4, 6, 8, 10 and 12 present in a relative ratio of 8:3
an integer).

(4) The fiber fabric according to item (1) above, in which R in the polymer is CH3 and the unit (b) is derived from methyl acrylate.

(5) The fiber fabric of item (1) above, in which R, , R2 and R3 in the polymer are each CH3, and X is C
What is l.

(6) The fiber fabric foil according to item (2) above, wherein Rf in the polymer is C2F5(CF2)n- (wherein, n is 35:3
4, 6, 8, 10 and 1 in relative proportions of 0:18:8:3
(an integer of 2).

(7) The fiber fabric according to item (2) above, in which R in the polymer is CH3, and the polymer chain repeating unit of (b) is derived from methyl acrylate.

(8) The fiber fabric of item (2) above, wherein the polymer chain repeating unit of (c) is CH2=(LeC(CH3)COOCH,CHOHCH,N(CH3)
3. Those derived from c1θ.

(9) A fiber fabric foil according to paragraph (2) above, wherein the polymer further comprises (d) 8% based on the total weight of (a) and (b).
of the formula CH2=C(R)CONHCH2OH,
CH2=C(R)COOCH2dH'CH2 and CH2
=C(R)COOCH2CH(R)0H (wherein R is hydrogen or methyl) Contains a polymer chain repeating unit derived from one or more monomers selected from the following monomers: Something that exists.

AO) The fibrous fabric of item (2) above, in which the polymer chain repeat unit of (a) is derived from a monomer of the formula in which R is methyl.

(auto) The fiber cloth according to item (2) above, wherein the polymer chain repeating unit of (b) has an alkyl group having 1 to 18 carbon atoms.
derived from alkyl methacrylate.

(auto) The fiber fabric foil of item (2) above, wherein the polymer chain repeating unit of (c) is [CH2=C(CH3)C
OO(CH,)NY press R1
, R2 and R3 can be taken together to form an alkylene group having 4-5 carbon atoms or 1(CH2)2-0-(
CH2)2-, and Y' is Y2 or a pyridinium ion group).

(Self) The above item (Section) Item 0 is a fiber fabric whose monomer is of the formula.

Claims (1)

[Claims] 1. On a weight basis, the sum of (a) and (b) below is 100%.
Assuming that, (a) formula RfCH_2CH_2O_2C
C(R)=CH_2 (in the formula, Rf is the number of carbon atoms 4-14
20-99% of polymer chain repeating units derived from the monomers (perfluoroalkyl group, R is hydrogen or methyl); (b) containing no fluorine atoms or containing vinyl groups; 1-80% of polymeric chain repeat units derived from vinyl monomers having only one fluorine atom directly bonded to a heavily bonded carbon atom; and (c) (
0.1-4% of formula C based on the total weight of a) and (b)
H_2=C(R)-Z-Y ＾ A fiber treatment agent consisting of a water- and oil-repellent polymer containing a polymer chain repeating unit derived from a monomer of the following: an ionic group and X^■ is a water-solubilizing anion. 2 Based on weight, the sum of (a) and (b) below is 100%
Assuming that, (a) formula RfCH_2CH_2O_2C
C(R)=CH_2 (in the formula, Rf is the number of carbon atoms 4-14
20-99% of polymer chain repeating units derived from the monomers (perfluoroalkyl group, R is hydrogen or methyl); (b) containing no fluorine atoms or double vinyl groups; 1-80% of polymeric chain repeat units derived from vinyl monomers having only one fluorine atom directly bonded to the bonded carbon atom; and (c) (a
0.1-4% of formula CH based on the total weight of ) and (b)
_2=C(R)-Z-Y^■ is an ionic group, and X^■ is a water-solubilizing anion). The polymer further comprises (d) an amount of up to 8% based on the total weight of (a) and (b) of the formula CH_2=C(R)CONHCH_
2OH, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and CH_
2=C(R)COOCH_2CH(R)OH (in the formula, R
1 or 2 selected from the monomers (hydrogen or methyl)
A fiber treatment agent containing polymer chain repeating units derived from more than one type of monomer.