JPH0434084A - Treatment of cloth and treated cloth - Google Patents

Abstract

PURPOSE:To obtain cloth having excellent durability and water and oil repellency, by treating cloth with an aqueous dispersion comprising a fluorine-containing copolymer having a unit of polymerized fluoroolefin and a unit of polymerized macromonomer with a hydrophilic site. CONSTITUTION:A fluoroolefin, preferably 2-4C fluoroolefin such as tetrafluoroolefin is copolymerized with a macromonomer with a hydrophilic site such as a polyether shown by formula I or formula II (1 is 1-10; m is 1-4; n is 2-20; X is H or lower alkyl) to give a fluorine-containing copolymer having 30-70mol% unit of polymerized fluoroolefin and 0.3-20mol% unit of polymerized macromonomer with a hydrophilic site. Cloth is provided with an aqueous dispersion of the copolymer to give cloth having excellent handle, improved durability and excellent water and oil repellency.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fabric treated with a fluororesin.

[Prior Art] Fabrics treated with a fluororesin containing fluoroacrylate for the purpose of imparting water and oil repellency have been known.

Conventionally, copolymer latex containing perfluoroalkyl groups for the purpose of imparting water and oil repellency (Japanese Patent Publication No. 5
0-3438 JP 55-9619), perfluoroalkyl group-containing urethane compounds (USP 33
98182), or a mixture of the above compound and silicone (
Japanese Patent Publication No. 5g-1232) is known. However, the above compositions cannot satisfy all the demands that are becoming more sophisticated year by year.

In particular, the durability for washing and dry cleaning is insufficient.
In order to overcome this drawback, the combination of melamine resin and polyisocyanate is widely used, but although durability is improved, there is a problem that the texture becomes stiff.

[Problems to be solved by the invention] In conventional fluororesin-treated fabrics, the adhesion of the fluororesin to the fabric is weak, and the strength of the polymer itself is weak.
There is a problem that the durability is insufficient and the water and oil repellency decreases due to scratches, washing, etc. Furthermore, since the weather resistance is poor, there is a problem that the durability is extremely short.

The fluorine-containing copolymer in the present invention is based on a fluoroolefin (based on a fluorine-containing copolymer whose essential constituents are a polymerized unit and a polymerized unit based on a macromonomer having a hydrophilic site. As the fluoroolefins, fluoroolefins having about 2 to 4 carbon atoms, such as tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, and pentafluoropropylene, are preferably employed. Rhoolefins are preferred.

In the present invention, it is important that the fluorine-containing copolymer has a polymerized unit based on a macromonomer having a hydrophilic moiety. Not only can the mechanical and chemical stability of the aqueous dispersion be improved, but also the film-forming properties can be improved.Especially for fluorine-containing copolymers having functional groups such as hydroxyl groups, Also, extremely excellent aqueous dispersion stability is achieved.

In the present invention, the hydrophilic site of a macromonomer having a hydrophilic site refers to a site having a hydrophilic group, a site having a hydrophilic bond, and a site consisting of a combination thereof. This hydrophilic group may be ionic, nonionic, amphoteric, or a combination thereof, but in the case where the above hydrophilic site consists only of a site having an ionic hydrophilic group, It is preferable to combine with a moiety having a nonionic or amphoteric hydrophilic group, or a moiety having a hydrophilic bond. Macromonomer refers to a low molecular weight polymer or oligomer that has a radically polymerizable unsaturated group at one end.In other words, it is a compound that has a radically polymerizable unsaturated group at one end and has at least two repeating units. .

Although it varies depending on the type of repeating unit, those having 100 or less repeating units are usually preferably employed from the viewpoint of polymerizability, durability, etc.

Examples of macromonomers having a hydrophilic site include (1) CH,=CH0(CHI), [0(CH21,
1nOX (1 is 1 to 101m is 1 to 4, n is an integer of 2 to 20, X is H or a lower alkyl group) (2) C
H2=CHCH-0(CHz)+[0(CHz)-]+
10X (1, m, n, X are the same as those in formula (1)) (l is 1 to 10, m is 2 to 20, n is 0 to 20
, X is H or a lower alkyl group, and the oxyethylene units and oxypropylene units may be arranged in either block or random form) is similar to
Examples include polyethers having a radically polymerizable unsaturated group at one end, such as (oxyethylene units and oxypropylene units may be arranged in either a block or random arrangement). Among these, those having a vinyl ether type structure at one end are preferably employed because they have excellent copolymerizability with fluoroolefins. In particular, polyether chain portions consisting of oxyethylene units or oxyethylene units and oxypropylene units are preferred because they have excellent hydrophilicity. Further, unless it has at least two oxyethylene units, various properties such as stability cannot be achieved. Furthermore, if the number of oxyalkylene units is too large, the hydrophilicity and weather resistance of the coating film will deteriorate, which is not preferable. Such a macromonomer having a hydrophilic moiety can be produced by a method such as polymerizing a vinyl ether or allyl ether having a hydroxyl group with formaldehyde or a diol, or ring-opening polymerizing an alkylene oxide or a compound having a raftone ring. be.

In addition, as a macromonomer having a hydrophilic site, a macromonomer having a chain formed by radical polymerization of a hydrophilic ethylenically unsaturated monomer and having a radically polymerizable unsaturated group such as vinyl ether or allyl ether at the end may be used. good. Such macromonomers can be produced by the method described by Yamano et al. in Polym, Bull, Fi, 335 (1981). That is, a polymer having a condensable functional group is produced by radical polymerizing an ethylenically unsaturated monomer having a hydrophilic group in the presence of an initiator having a condensable functional group and a chain transfer agent, and then Examples include a method in which a compound such as glycidyl vinyl ether or glycidyl allyl ether is reacted with the functional group of this polymer to introduce a radically polymerizable unsaturated group at the terminal end.

Ethylenically unsaturated monomers used in the production of this macromonomer include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, 2-methoxyethyl acrylate, 2-
Methoxyethyl methacrylate, diacetone acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, acrylic ester of polyhydric alcohol and methacrylic ester of polyhydric alcohol, and vinylpyrrolidone and so on. In addition, copolymerizable monomers include acrylamide and its derivatives, methacrylamide and its derivatives, N
-Methyloacrylamide derivative, ethyl calpitol acrylate, methyl triglycol acrylate, 2-
Examples include hydroxyethyl acryloyl phosphate and butoxyethyl acrylate.

In addition, 4.4°-azobis-4-cyanovaleric acid, 2
,2°! Examples include -azobis-2-amidinopropane hydrochloride, potassium peroxide, ammonium peroxide, azobisisobutyronitrile, and benzoyl peroxide.

The fluorine-containing copolymer of the present invention may contain a polymerized unit containing a hydroxyl group in addition to the above two types of units. However, stability is not compromised. Further, when the fluorine-containing copolymer has a hydroxyl group, there is an advantage that a treated layer having extremely excellent water resistance and solvent resistance can be obtained by using a curing agent in combination.

Further, the polymerized unit containing a hydroxyl group can be formed by copolymerizing a hydroxyl group-containing monomer or by subjecting a polymer to a polymer reaction to form a unit containing a hydroxyl group. Here, hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether, hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether, hydroxyethyl acrylate,
Examples include hydroxyalkyl esters, hydroxyalkyl vinyl esters, and hydroxyalkylaryl esters of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate. In addition, as a method for forming a unit containing a hydroxyl group by polymerizing a polymer, a method is to copolymerize a vinyl ester that can be hydrolyzed after polymerization, and then hydrolyze it to form a hydroxyl group. Examples include.

In addition to the above units, the fluorine-containing copolymer in the present invention also includes:
Units based on monomers copolymerizable with these may be included.

Examples of such monomers include olefins such as ethylene and propylene, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether, vinyl esters such as butyl vinyl ester and octyl vinyl ester, styrene, and vinyl toluene. Examples include vinyl compounds such as aromatic vinyl compounds, allyl ethers such as ethyl allyl ether, allyl compounds such as butyl allyl ester, acryloyl compounds such as butyl acrylate, and methacryloyl compounds such as ethyl methacrylate. Ru. In particular, olefins, vinyl ethers, vinyl esters, allyl ethers, and allyl esters are preferably employed. Here, the olefins are preferably those having about 2 to 10 carbon atoms, and the vinyl ethers, vinyl esters, allyl ethers, and allyl esters are linear, branched, or aliphatic having about 2 to 15 carbon atoms. Those having a cyclic alkyl group are preferably employed. In such a monomer, a small amount (or a portion) of hydrogen bonded to carbon may be replaced with fluorine.

The fluorine-containing copolymer of the present invention contains 20 to 80 mol % of polymerized units based on fluoroolefins and 0.0 mol % of polymerized units based on macromonomers having a hydrophilic site.
The proportion is preferably 1 to 25 mol%. Based on fluoroolefins (too little polymerized units will not provide sufficient weather resistance, and too many units will result in extremely poor water dispersibility, which is not preferable; 30 to 70 mol% is particularly preferred. If the polymerized unit based on a macromonomer having a hydrophilic moiety is too small, the water dispersibility will be extremely poor, and if it is too large, the weather resistance and water resistance of the coating film will deteriorate, which is not preferable. In order to achieve a very good effect, this unit is 0.3~2
It is preferably contained in a proportion of 0 mol%. In addition, if polymerized units containing hydroxyl groups are included,
It is preferably 25 mol% or less. If the proportion of this unit is too large, water dispersibility will decrease, and when the coating film is cured, it may become hard and brittle, and water resistance may decrease due to the influence of residual hydroxyl groups. I don't like it because there is. In addition, if the polymerized unit based on the macromonomer having a hydrophilic moiety described above contains a hydroxyl group, the unit is based on the macromonomer having a hydrophilic moiety (polymerized unit and polymerized units containing hydroxyl groups are included in the calculation.Based on the above fluoroolefins (units other than polymerized units and polymerized units based on macromonomers with hydrophilic moieties are 0 to 7
The content of this unit is preferably 0 mol %; too much of this unit is not preferred because weather resistance deteriorates.

The aqueous dispersion in the present invention is one in which the above-mentioned fluorine-containing copolymer is dispersed in water. Furthermore, the aqueous dispersion of the present invention is
It exhibits excellent mechanical and chemical stability even in the absence of emulsifiers and hydrophilic organic solvents that are normally used in aqueous fluoropolymer dispersions. Of course, one or both of an emulsifier and a hydrophilic organic solvent may be added. However, emulsifiers reduce the water resistance of Treatment 1. It is preferable that no hydrophilic organic solvent is added because of solvent regulations. When using an emulsifier here, anionic, cationic, nonionic, amphoteric, nonionic-cationic, nonionic-anionic, or one having a reactive group can be used alone or in combination. .

The aqueous dispersion in the present invention can be produced by emulsion polymerization of a fluoroolefin, a macromonomer having a hydrophilic moiety, and, if necessary, other monomers in an aqueous medium. The initiation of emulsion polymerization is carried out by adding a polymerization initiator in the same manner as the initiation of ordinary emulsion polymerization. As such a polymerization initiator, an ordinary radical initiator can be used, but a water-soluble initiator is preferably employed, and specifically, a persulfate such as ammonium persulfate, hydrogen peroxide, or a combination of these and sodium bisulfite is used. , a redox initiator consisting of a combination with a reducing agent such as sodium thiosulfate,
In addition, inorganic initiators made by coexisting small amounts of iron, ferrous salts, silver sulfate, etc., or dibasic acid peroxides such as disuccinic acid peroxide and diglutaric acid peroxide,
Organic initiators such as azobisisobutyramidine hydrochloride and azobisbutyronitrile are exemplified. The amount of the polymerization initiator used can be changed as appropriate depending on the type, emulsion polymerization conditions, etc., but it is usually preferably about 0.00 to 0.5 parts by weight per 100 parts by weight of the monomer to be emulsion polymerized. Adopted. Further, these polymerization initiators may be added all at once, or may be added in portions as necessary.

Further, a pH adjuster may be used for the purpose of increasing the pH of the emulsion. Such pI (adjusting agents include inorganic bases such as sodium carbonate, potassium carbonate, sodium 0-hydrogenphosphate, sodium thiosulfate, and sodium tetraborate, and organic bases such as triethylamine and triethanolamine. The amount of the regulator added is usually about 0.05 to 5 parts by weight, preferably about 0.1 to 1 part by weight, per 100 parts by weight of the emulsion polymerization medium.

In addition, the emulsion polymerization initiation temperature is appropriately selected depending on the type of polymerization initiator, but is usually 0 to 100°C,
In particular, a temperature of about 1O to 90°C is preferably employed. In addition, the reaction pressure can be selected as appropriate, but is usually 1 to 100
It is particularly desirable to adopt a range of 2 to 50 kg/cm.

In such a production method, additives such as monomers, solvents, and initiators may be added all at once and polymerized. For the purpose of improving various physical properties, before adding the polymerization initiator, it may be pre-emulsified using a stirrer such as a homogenizer, and then the initiator may be added dropwise to polymerize.
Monomers may be added in portions or continuously (
The composition of the monomers can then be different.

The method of treating the fabric with the above dispersion is not particularly limited, and examples thereof include general padding, spraying, exhaustion, coating, or a combination thereof. Further, antistatic agents, flame retardants, softeners, resins, etc., which are generally used for treating fabrics, can be used in combination.

[Example] The present invention will be specifically described below with reference to Examples.
The present invention is not limited in any way by such examples. Note that the numbers in the following examples indicate parts by weight unless otherwise specified.

Aqueous Dispersion Synthesis Example 1 In a 200 ml stainless steel autoclave with a stirrer (pressure resistance 50 kg 7 cm), 22.1 parts of ethyl vinyl ether and 1 part of hydroxybutyl vinyl ether were added.
5 parts, 4.5 parts of macromonomer A having a hydrophilic site,
66.1 parts of ion-exchanged water, 0.35 parts of perfluorooctanic acid ammonium salt, 0.3 parts of potassium carbonate
5 parts, 0.02 parts of sodium bisulfite, and 0.11 parts of ammonium persulfate, cooled with water, degassed by pressurizing nitrogen gas to 3.5 kg/go, and repeating this twice. After degassing to 10 mm Hg and removing dissolved air, chlorotrifluoroethylene was added to 38.
After charging 0 parts, the reaction was carried out at 30°C for 12 hours.

Synthesis Example 2 In the autoclave, 19.5 parts of cyclohexyl vinyl ether, 6.7 parts of ethyl vinyl ether, 5.7 parts of hydroxybutyl vinyl ether, 13.6 parts of macromonomer B having a hydrophilic moiety, 76.4 parts of ion-exchanged water, and 76.4 parts of ion-exchanged water were added. Fluorooctanoic acid ammonium salt 0
．． 44 parts of potassium carbonate, 0.44 parts of sodium hydrogen sulfite, and 0.14 parts of ammonium persulfate were treated in the same manner as in Example 1, and then 30.9 parts of tetrafluoroethylene was added thereto at 30°C. Synthesis Example 3 In the autoclave, 21.7 parts of cyclohexyl vinyl ether, 7.9 parts of ethyl vinyl ether, 6.4 parts of hydroxybutyl vinyl ether, 06.9 parts of a macromonomer having a hydrophilic site, and ions were placed in the autoclave. 82.9 parts of exchange water,
Barfle Kukunik Acid Ammonium Salt 0.
After charging 44 parts of potassium carbonate, 0.44 parts of potassium carbonate, 0.02 parts of sodium bisulfite, and 0.14 parts of ammonium persulfate and treating in the same manner as in Example 1, 40.0 parts of chlorotrifluoroethylene was charged, and the mixture was heated at 30°C. The reaction was carried out for 12 hours.

Synthesis Example 4 Ethyl vinyl ether 22.1 in the autoclave
1.5 parts of hydroxybutyl vinyl ether, 4.5 parts of macromonomer A having a hydrophilic moiety, 66.1 parts of ion-exchanged water, 0.35 parts of potassium carbonate, 0.02 parts of sodium bisulfite, 0.11 parts of ammonium persulfate. After the same treatment as in Example 1, 38.7 parts of chlorotrifluoroethylene was added and the reaction was carried out at 30°C for 12 hours. The obtained aqueous dispersion is designated as ■.

Synthesis Example: 22.5 ethyl vinyl ether in the autoclave.
1.5 parts of hydroxybutyl vinyl ether, 66.0 parts of ion-exchanged water, 8.0 parts of ethanol, 0.34 parts of perfluorooctanic acid ammonium salt, 0.23 parts of potassium carbonate, 0.01 parts of sodium bisulfite. , 0.11 part of ammonium persulfate was charged, and after the same treatment as in Example 1, 49.9 parts of chlorotrifluoroethylene was added.
9 parts were charged and the reaction was carried out at 30°C for 12 hours.

Examples 1 to 4 The aqueous dispersions obtained in Synthesis Examples 1 to 4 above were processed into fabrics by the following method, and their performance was evaluated.

The results are shown in the table.

・Processing condition test cloth Nylon taffeta Squeezing ratio 30% Dry 110℃ x 90 seconds Cure 170℃ x 60 seconds Processing liquid 5 parts by weight of water dispersion of Synthesis Examples 1 to 4
95 parts by weight Test method Water repellency Oil repellency Washing durability Texture [Comparative example] Aqueous dispersion synthesis example 5 Perfluoroalkylethyl acrylic JIS L-10 in a glass autoclave (11) equipped with a stirrer
92 AATCC-118 JIS L-0217, No. 103 Judgment rate based on texture of processed cloth (hereinafter referred to as FA) [C, F, ? C, H40CO
C) (=C811120g, stearyl acrylate
76g, N-methylolacrylamide 4g, polyoxyethylene cetyl alcohol 10g, acetone 120g
After adding 350 g of water and purging with nitrogen for about 20 minutes while stirring, the temperature was kept constant at 60° C., and 1 g of azobisisobutyramidine hydrochloride was added to initiate polymerization.

After heating and stirring at 60°C for 5 hours, it was cooled and the solid content concentration was 1.
An 8% latex was obtained.

Aqueous dispersion synthesis example 6 The amount of monomer charged was FAI 20g, vinylidene chloride 38
A stable latex was obtained in the same manner as in Synthesis Example 5, except that 38 g of benzyl methacrylate and 4 g of N-methylolacrylamide were used.

・Performance evaluation method Nylon taffeta was treated in the same manner as in the example except for the composition of the processing fluid and subjected to the test.

Processing fluid composition Dispersion liquid of Synthesis Examples 5 and 6 10 parts by weight water 90 parts by weight Evaluation results [Effect of the invention] The fabric according to the present invention is Excellent texture, and, repellent It has excellent durability such as water damage and oil resistance.

Claims (2)

[Claims] (1) A method for treating fabric using a treatment agent comprising an aqueous dispersion containing a fluorine-containing copolymer having polymerized units of a fluoroolefin and polymerized units of a macromonomer having a hydrophilic site. (2) A fabric treated with a treatment agent comprising an aqueous dispersion containing a fluoropolymer having polymerized units of a fluoroolefin and polymerized units of a macromonomer having a hydrophilic site.