JPS6034730A - Polyperfluoroether emulsion - Google Patents

Abstract

PURPOSE:To obtain an additive capable of eliminating the end breakage in the manufacturing stage of raw thread and giving water- and oil-repellent properties by composing of oily polyperfluoroether, a compd. contg. perfluoroalkyl groups, a nonionic surfactant, a hydrophilic organic solvent, and water. CONSTITUTION:The emulsion consists of (a) oily polyperfluoroether expressed by the formula I (R and R' are the same or different perfluoroalkyl groups or an oxyperfluoroalkyl group, p, q, and r are positive integers and one or two thereof is 0, (b) a compd. expressed by thr formula II contg. perfluoroalkyl groups (Rf is a perfluoroaklyl group having >=4C or a perfluoroalkylene glycol group, R'' is a bivalent organic group, R''' is an H or a methyl atom, X is a hydroxyl, a carboxyl, and a sulfonic group, and the base thereof, an ammonium group, an amino group, etc., m is 0-4, and n is 0-50), (c) a nonionic surfactant, (d) a hydrophilic organic solvent, and (e) water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyperfluoroether emulsion. For more details, see Rainwater Oil Repellent β11. - Anthin'i1, which can be effectively added to emulsions, etc. γ "Bolivar Fluoroether Emulsionino K [1-1', ?).

In order to impart water and oil repellency to raw cotton, raw wool, etc., it is common practice to treat it with a water and oil repellent using a water and oil repellent. There were many cases of yarn breakage due to the heat generated during manufacturing. In order to avoid such drawbacks, it is possible to mix an oil component into the water and oil repellent, but the expanded hydrogen oil and silicone oil that are conventionally used for that purpose reduce the water and oil repellency. However, it had some problems.

As a result of various studies on additive components that do not cause yarn breakage during the raw yarn manufacturing process and sufficiently exhibit the performance of a water and oil repellent agent, the present inventors have developed a polyperfluoroether emulsion with a specific composition. It has been found that the method is stable and effective for such purposes.

Accordingly, the present invention relates to a polyperfluoroether emulsion, and this polyperfluoroether emulsion contains the following components.

(,) Oily polyperfluoroether Rf O3F 60 represented by the following general formula? 02F 40-1-7,000 or
2oiR' (where R and R' are the same or different perfluoroalkyl group or oxyperfluoroalkyl group, P% q and ril''j: positive a+
j2. : '* or monovalent ' or two of them may be 0) (1)) Perfluoroalkyl group-containing compound RfR"m +OOHR" OH2kX (here, Rf
is a perfluoroalkyl group or perfluoroalkylene gellicol group having 4 or more carbon atoms; R// is a divalent organic group; R″υ is a hydrogen atom or a methyl group;
X is a hydroxyl group, a carboxyl group 1. sulfonic group and 1,000) base, ammonium group, amino group or aminocarboxyl group, m is 0 to 4, and n is 0 to 50) (c) nonionic surfactant (d ) Hydrophilic organic solvent (e) Water Polyperfluor ether represented by the above general formula is:
It is an oily substance having a viscosity of about 10 centistokes (25°C) or higher, and is used, for example, in the fluorination of peroxy group-containing polyethers (Japanese Patent Publication No. 49-45719), in the fluorination of perfluoroalkylene oxide polymers (US Pat. 3,250,807-8) or the general formula % (where X is a fluorine atom or a trifluoromethyl group, and n is 0 or a positive integer) 1
It can also be obtained by treating a fluoride compound with fluorine gas and high fluorine (11).
(See No. 565). In addition, the polyperfluoroethers available are Garden D-3 (Monte Edison %b product), Fombl, in (Monte Edison product)
It is commercially available under trademarks such as , PFAZ-I size or -■ (Kluva product), and commercially available products such as Kagaru can also be used.

Further, examples of the perfluoroalkyl group-containing compound represented by the above general formula include the following.

onF 2 , +I OH20H20H(n'
6-12) o8ir,, (aH2)mon (m:
3-4) 0, F,, 0H20HOH20H OH a, F, 5oooon(na) Oa F, +7 S Os H(Na)OF OH
OH'0OOH (Na) 1722 o8r,, an2on2-(-oaH2oH,, MengOH
O,? ,,0-(3-OH2-fclOH20H2 temporary O
As the H nonionic surfactant, those commonly used can be used as they are. In addition, examples of hydrophilic solvents include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, isopropanol, and n-butanol, selon rubs such as methyl cellosolve and cellosolve acetate, diglyme, triglyme, and tetraglyme. , ethers such as dioxane and tetrahydrofuran, amides such as dimethylformamide and dimethylacetamide, and sulfur-containing compounds such as sulfolane and dimethylsulfoxide. These hydrophilic organic solvents serve to stabilize the emulsion by lowering the interfacial tension.

1ii4 of the emulsion ``A41'j'', about 1 to 80 N M parts of the river fluorony, 0.1 to 10 parts by weight of the perfluoroalkyl group-containing compound, 0.1 to 10 parts by weight of the nonionic surfactant This is carried out by mixing about 1 to 50 parts by weight of hydrophilic organic solution W and about 1 to 99 parts by weight of water using a colloid mill or the like.

The prepared emulsion exhibits very good stability due to the interaction between the perfluoroalkyl base compound and the hydrophilic organic solvent.

The polyperfluoroerthyl emulsion according to the present invention is effectively used by being added to water and oil repellents. Correspondingly, the water and oil repellent to which this emulsion is added is also generally preferably an aqueous emulsion. The polyperfluoroether emulsion contains about 0.1 to 500% by weight, preferably about 1 to 300% by weight of the polymer component in the water and oil repellent, of the polymer fluoroether contained therein. More preferably about 5~?00 city I+
It is used so that it becomes 111 times of 1%.

Water and oil repellent 7111 treatment using a water and oil repellent containing a polyperfluoroether emulsion is carried out by impregnating the washed fiber with the water and oil repellent and drying it. The dried fibers are worsted and/or spun. At this time, after impregnating the dry binding cord with polyperfluoroether emulsion,
F wool and/or straddle spinning 2 can also be performed.

By performing the water- and oil-repellent treatment in this manner, not only good water- and oil-repellency performance can be obtained, but also there is no occurrence of thread cutting edges due to heat generation during production of the raw thread. Moreover, by treating the yarn during spinning (carding, pre-spinning process), fabrics woven from this yarn, especially thick fabrics, can be treated to be water and oil repellent. It is superior in terms of wear resistance, durability, etc.

On the other hand, when a conventionally used silicone oil emulsion or the like is used in place of the polyperfluoroether emulsion, it does not show low values in terms of water and oil repellency, especially water repellency. Also, when the polyperfluoroether emulsion is used for combing and/or spinning,
During the production of single yarn, the yarn generates a lot of heat and turns into white smoke. Thread cutter'i''L
will occur.

Next, the present invention will be explained with reference to examples.

Example 1 Polyperfluoroether (viscosity 5
0 centistokes) 10 parts (weight, hereinafter 1, Jshi)
, perfluorooctylethyl alcohol 2t'dSs
Nonionic surfactant (Kao soap products Emulgen 95
0) 1 part, acetone 5 parts and water 82 parts in a food mill (between fig Q, l rrrm, rotation @ 4000 r
pm) for 3 minutes to form a homogeneous emulsion. The formed emulsion 1 was left at room temperature for a while, but the oil layer did not separate.

Examples 2 to 5 In Example 1, as polyperfluoroether,
1 in place of the one with a viscosity of 50 centistokes
00.250, 400 'i' take 500 centistokes is used. The emulsion formed showed excellent stability in all cases. Example 6
~9 In Example I, as the polyperfluoroether,
The following polyperfluoronidel from Alliance was used. All of the emulsion gradients formed showed similar stability.

(Example 6) OF,,0F20+0F20F20i
-70F.

(Example 7) (OF,), OI+'OF',,Omo0(OF',)201!゛2o-” (7op゛(c+r
+゛,).

(Example 8) Monte Edison product Fomb1. Lη
yu -iR+OBF 6ON O2F 40 part size OI
F,, 0-5R' viscosity 90 centistokes (38
C) (Example 9) Kleuber product PFA~z-"R-
f-02F'40K0F20R'Viscosity 100 centistokes (40°C) Examples 10-14 In Example 1, the same amount of ethanol, diglyme, dioxane, dimethylformamide or dimethyl sulfoxide was used instead of acetone. Ta. All emulsions formed showed similar stability.

Examples 15 to 18 In Example 1, the same amount of the following nonionic surfactant was used as the nonionic surfactant. All emulsions formed showed similar stability.

(Example 17) Kao Soap Product Emanon 3199 (Example 18) Polyethylene Oxytomo7 Carboxylate Example 19 In Actual ITp Example 1, the same amount of perfluorooctylethyl polyethylene oxide 08F was used instead of perfluorooctylethyl alcohol. ,,0H20H2 (-00H20H2iOH) was used. The emulsions formed showed similar stability.

Examples 20-23 In Example 1, 0.5 parts of each second half-fluoride instead of perfluorooctylethyl alcohol.

When an alkyl group-containing compound is used, the amount of nonionic surfactant used is changed to 25 parts.
g 0OF(0F3) 0OL)Ha (Example 21)
O2F+5OOONa (Example 22) 08F,,O
H,,0H200ONa (Example 23) 081i',
, 5o3Na formed emulsions showed all roundness and λ stability.

Example 24 Perfluorooctylethyl acrylate 50 "l"
u1. Cyclohexyl methacrylate 49 2-Hydroxyethyl acrylate 0.5 N-methylol acrylamide 0.5 γ setone 75 Nonionic surfactant (Emulgen 950) 7.5 Water 400 Copolymer emulsion prepared from each of the following components (
Solid content concentration 18%) Example 1
Add the specified iM of river fluoroether emulsion, mix it evenly, and dilute with water for 40 minutes.
It was diluted 4 times. A cotton cloth, a polyester cloth, a wool cloth, or a cotton (65)/polyester (35) blend cloth is dipped in this diluted solution, and the dipped cloth is heated to 80°C for 15 minutes, and then heated to 80°C for 17 minutes.
Heat treatment was performed at 0°C for 3 minutes, and the water-repellent and oil-retaining properties were determined to be I11! according to JISK-1006 and 3M method.
Water repellency was evaluated on a scale of 0 to 100, and oil repellency was evaluated on a scale of 0 to 150. The obtained results are shown in Table 1 below.

Table 1 Cotton cloth 90 90 9 (190 Polyester cloth 90 90 '10 90 Wool cloth 9
0" 1 (R11001, 110 blended fabric 90+100
100', 100 [Oil repellency] Cotton cloth 120 110 11 (111,0 Polyester 150 150 150 15+,) Wool cloth 14
0 140 140 130 Blended fabric 130 140
14 fl 14.0 Also, in the diluting solution, a thickness of 0.
51 glands, Nagado Z + O + Kaku octopus thread and absorbent cotton are soaked, and this water- and oil-repellent octopus thread is lengthwise 5
Q +IU1, packed with degreased R11 treated with water and oil in a box with width of 200mm, and applied a load of 11 (9G) to the entire top surface.
-J, it is installed horizontally at 1tl at exactly half the height of the absorbent cotton that indicates the height of li!Ii+, and the length is 1. One end of a 50 m octopus string was pulled to a length of 5Qs++ fJ, 1, and the pulling force when pulled and pulled out was measured five times as a frictional force. The results obtained are shown in Table 2 below.

Table 2 Polyperfluoro friction crab-chill emulsion C9) 10 parts by weight 150-170 20 parts by weight 140-155 100 parts by weight 130-145 200 parts by weight 100-135 Comparative example 1 In Example 24, polyperfluoroether emulsion Instead, use 5 parts by weight of silicone oil YA/John (oil content 30%) and mix the mixture with 4 parts of water.
Diluted 0 times. A water and oil repellency test was similarly conducted using this diluted solution, and the results are shown in Table 3.

Table 3 Water repellency Oil repellent cotton fabric 7090 Polyester fabric 50 110 Wool fabric 70 110 Blend fabric 50+100 Example 25 Pre-spun made from Australian merino fine wool (658i 0.259/”) io I (9)
100 parts by weight of the copolymer emulsion of Example 24 and 200%i of the polyperfluoroether emulsion
It was immersed in a 20Ky width of Li 2 mixture for 10 minutes to form soft hair.

This was put on a ring spinning machine (SO type manufactured by Osumi Iron Works) with a spindle rotation speed of 10,000 rpm and a feed rate of 7. ! j
rIJ: Single yarn was manufactured under the conditions of 25 layers and draft of 16, but there was no breakage of the single yarn during manufacturing.

Comparative Example 2 In Example z5, no polyperfluoroether emulsion was used. During single yarn milling, the yarn generated a lot of heat, and when exposed to white smoke, yarn breakage was often observed.

agent Patent Attorney Yoshi 1) Toshio

Claims (1)

[Claims] 1. Polyperfluoro knee containing the following components:
Chill emulsion. (,) Oily polyperfluoroether R-f-03F60 yen (-02F40 material + 011 = 20
R' (where R and R' are the same or different perfluoroalkyl groups or oxyperfluoroalkyl groups, pl q and r are positive integers, or one or two of them are O (L,) A perfluoroalkylnor-containing compound RfR//m-(-00HR111O)i2X represented by the following general formula (where Rf is a perfluoroalkyl group having 4 or more carbon atoms) ′ is a perfluoroalkylene glycol group, and l[
(/' is a divalent organic group, R/〃 is a hydrogen atom or a methyl group, X is a hydroxyl group, a carboxyl group, a sulfone group and their bases, an ammonium group,
is an ami7 group or an ami7 carboxyl group, and m is θ~
4, and n is 0 to 50) (C) Nonionic thread surfactant (d) Hydrophilic organic solvent (θ) Water 2, water and oil repellent added to the emulsion Claim 1 Polyperfluoroether emulsion as described. 3. The polyperfluoroether emulsion according to claim 2, which is added to a condensed oil repellent emulsion for fiber treatment.