JPS60199973A - Easily dyeable anti-staining fiber - 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 The present invention relates to stain-resistant fibers that can be easily dyed.

Textile products, especially sportswear, raincoats, and tent fabrics.

Water repellent, oil repellent, and liquid stain resistant for carpets, etc.

As a method of imparting antifouling properties such as dry stain resistance, a method of treating the surface with a fluorine-containing compound is generally employed. As for how to handle it.

Traditionally, the focus has been on post-processing the product.

There are drawbacks such as complicating the process, lowering operability, and leading to cost savings. For this reason, in recent years, yarns have been treated with fluorine-containing compounds at the yarn manufacturing stage for weaving.

The method of dyeing after knitting is gradually becoming popular. However, in this method, due to the water repellency of the fluorine-containing compound, the affinity between the fiber and the dyeing solution is poor, resulting in problems such as decreased dyeing properties and the occurrence of staining spots. Wetting agent.

Even with the addition of leveling agents, etc., the results were not satisfactory.
The reality is that there are restrictions on its commercialization.

The present inventors conducted various studies to solve the above problems, and first proposed a fiber whose surface was coated with a film containing a fluorine-based antifouling agent and a fluorine-based wetting agent. It turns out that problems can easily occur. In other words, even though most of the wetting agent had fallen off from the dyed cloth and only the antifouling agent remained attached, once it was moistened with water, it was dried (air-dried) without applying heat. In some cases, it is difficult to develop water- and oil-repellent effects, or in other words, it lacks natural recovery (usually requires dry heat treatment at 100°C or higher).
. The cause of this phenomenon is unknown, but in Jitsukawa, it is necessary to apply heat every time it is washed, leading to a narrower range of uses as a product.

Therefore, the present inventors conducted further studies in order to obtain stain-resistant fibers with excellent natural recovery properties while maintaining good dyeability.As a result, it was found that the stain-proofing agent and wetting agent were present in separate films. I know it's effective.

The invention has been completed.

In other words, the present invention provides an easily dyeable stain-proofing product characterized in that a film containing a fluorine-based antifouling agent is formed on the surface of the fiber, and a film containing a fluorine-based wetting agent is further formed on the outside of the film. The main focus is fiber.

The fibers used in the present invention include polyethylene terephthalate, polybutylene terephthalate, etc., polyesters containing these as main components, nylon 6, nylon 66, etc., polyamides containing these as main components, polyethylene, polypropylene, etc., and polyolefins containing these as main components. Fibers from melt-spun polymers as well as wet spinning.

There are fibers produced by dry spinning or emulsion spinning.

Next, in the present invention, what is the fluorine-based antifouling agent?

Generally, it refers to fluorine compounds used as water repellents and LA oil agents, and the following are typical examples.

(al) A polymer obtained by homopolymerizing or copolymerizing fluorine-containing monomers represented by the following general formulas (1) to (3), or a polymer obtained by copolymerizing these seven monomers and other monomers not containing fluorine atoms.

I Cl1ll = CC00Rf (11Clb+ =
CCOOR* Not SRf (2) (where R1 is a hydrogen atom or a methyl group, and Rt is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group, an arylene group, or an aralkylene group.

R3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
Cycloalkyl group, aryl group or aralkyl group, R
f represents a fluoroalkyl group having 7 to 30 carbon atoms in which some or all of the hydrogen atoms on the carbon atoms are substituted with fluorine atoms. Also.

Some or all of the hydrogen atoms on the carbon atoms of R2 and 'R3 may be substituted with fluorine or chlorine atoms. ) (bl A fluorine-containing urethane compound represented by the following general formula (4).

Rf 0CONII R4N11COORf (41(
R4 is a divalent organic group having 2 to 20 carbon atoms.

0, SO++, Coo-+-CON(R3)
.

It may also include combinations such as. Rs and Rf represent the groups described above. ) (C1 A fluorine-containing polyester having a repeating unit represented by the following general formula (5).

Rf 00CR4COOR5(5) (Rs is a trivalent hydrocarbon group having 2 to 10 carbon atoms.

Re and Rf represent the groups described above. ) In addition, the term fluorine-based wetting agent refers to a fluorine-containing surfactant having a hydrophilic group.1 Typical examples include those represented by the following general formulas (a) to (g). .

Rf COOM (a) Rf 50s M (b) 3 Rf Sow N -R203(h M (c)3! Rf CoooN's -(C1lz Cl1a O) n
tl (d)haR3Ra Rf S(h N (C1h CIl* 0) n
If (g) (M is a hydrogen atom, an alkali metal atom, or an ammonium group;
3 represents the already mentioned group. ) In the present invention, the amount of the fluorine-based antifouling agent that forms the film is 0.05 to 2% by weight, preferably 0.05 to 2% by weight based on the uh fiber.
．． 1 to 1.5% by weight, and the amount of the fluorinated wetting agent to be 0.5 to 30% by weight, preferably 1 to 25% by weight of the amount of the fluorinated antifouling agent, for good dyeability and stain resistance. It is desirable from the point of view of expressing gender.

The fiber of the present invention can be manufactured by applying a known method. That is, this is a method in which treatment with a fluorine-based antifouling agent and treatment with a fluorine-based wetting agent are sequentially performed in any step after spinning. It is particularly preferable to apply appropriate amounts of a liquid containing an antifouling agent and a liquid containing a wetting agent to the spun undrawn fiber yarn in sequence.

This is a method in which the stretching of the yarn and the heat fixation treatment of the fluorinated antifouling agent are carried out simultaneously or separately.In addition to the effect of directly obtaining antifouling fibers in the fiber forming process, it also has the effect of forming a film of the fluorinated antifouling agent. Another advantage is that it has excellent adhesion to fibers.

The fibers of the present invention can be used not only for antifouling purposes, but also for so-called breathable and moisture-permeable waterproof fabrics. (In this case, it is preferable to use yarn with a small single filament fineness.) It goes without saying that flame retardants, antistatic agents, softeners, etc. may also be introduced into the interior or surface of the fibers. especially, ! Jli
When a fluorine-based compound is also contained inside the fibers, the adhesion between the fibers and the antifouling agent is improved.

The present invention will be explained in more detail with reference to Examples below, and the performance of the fibers was evaluated by the following method.

Dyeing property (1) Wettability 2 Dye solution 1 is applied to the test cloth before dyeing at room temperature.
A drop (approximately 0.3 mjl) was placed gently, and the time (seconds) until the dye solution completely soaked in was measured.

(2) Dyeing grade: ordinary nylon 6 yarn (70d/24f) dyed cloth (weaved under the same conditions as in the example and dyed in the same bath as the test cloth) that has not been treated with a fluorine-based antifouling agent. As a standard, gray scale for discoloration (JIS-L-0804)
The dyed paper of grades 1 to 5 was judged based on the color difference between each color chart.

Stain resistance (11 Water repellency: Gently place one drop (approximately 0.3 mL) of the isopropyl alcohol/water mixture having the composition shown in Table 1 on the test cloth, and after 5 minutes, check the mixture composition that does not soak in. Achieved the highest level of water repellency.

Table 1 Example 1 The following antifouling and wetting agent solutions were prepared.

Antifouling agent liquid 2-perfluorooctylethyl acrylate [・701
A liquid prepared by dispersing 5 parts by weight of a copolymer consisting of 1%, tHt, 24ffi% of hinyl, 1 g of 2-chloroethyl vinyl ether triple ff, and 2% by weight of 2-hydroxyethyl acrylate in 95 parts by weight of a mineral oil-based oil solution.

i! ii lubricant liquid (C8Fl? C0NII C3Hs N' (C11
3) 3) A liquid in which 3 parts by weight of ClO is dispersed in 95 parts by weight of a mineral oil-based oil.

Then, 7% by weight of the antifouling agent solution was applied to the fibers of 24 filaments of 6 yarns of nylon running down from the melt spinneret. 1 part lubricant liquid per fiber
% by weight and was wound up at 1,000 m/min.

Next, this undrawn yarn was stretched at a stretching temperature of 90°C and a stretching ratio of 3.
The yarn was stretched twice for a stretching time of 0.1 seconds, and then heat-treated for 1 second in hot air at 150°C to obtain a drawn yarn of 70d/24f.

The drawn yarn is warp 110/2.54cm, weft 100/2.
Woven into taffeta with a density of 54 cm, Nylomine
Blue AG (ICI acid dye) 2% o, w,
f. Dyeing at 80°C for 15 minutes in a dye bath with a bath ratio of 1:100 and a pH of 4.0 at 105°C.

It was dried for 1 hour.

The antifouling performance (initial performance) of the obtained dyed fabric was measured, and the antifouling performance (natural recovery performance) of the dyed fabric that was submerged for 30 minutes and air-dried for 30 minutes was measured. The antifouling performance (forced recovery performance) of the samples treated with hot air at ℃ for 3 minutes was measured.

Example 2 The same operation as in Example 1 was carried out using the following antifouling agent liquid and wetting agent liquid.

Antifouling agent liquid 4. A liquid in which 5 parts by weight of 4'-bis(2-perfluorooctylethoxycarbonylaminodiphenylmethane) is dispersed in 95 parts by weight of a mineral oil-based oil solution.

ll 3 C8Fl? SO! N (CHt CHt O)a
A liquid in which 3 parts by weight of H3 is dispersed in 97 parts by weight of a mineral oil-based oil solution.

Comparative example 1 In Example 2, application of the wetting agent liquid was omitted.

Comparative Example 2 A solution in which 4 parts by weight of the antifouling agent and 1 part by weight of the wetting agent in Example 1 were dispersed in 95 parts by weight of a mineral oil-based oil solution was used as nylon 6.
The same operation as in Example 1 was carried out by adding 7% by weight to the undrawn yarn.

The above results are summarized in Table 1. (Wettability was measured before dyeing, and the reference example is an example of ordinary nylon 6 yarn without antifouling treatment.) Table 1 This table shows that the fibers of the present invention have dyeability and antifouling properties. It is clear that it has excellent stain resistance (natural recovery performance).

Patent Applicant: Unitika Co., Ltd. (Voluntary) May 150, 1980 1. Indication of the case: Japanese Patent Application No. 57095/1982 2. Name of the invention: Easily dyeable stain-resistant fiber 3. Amendments made Relationship with the patent case Patent applicant address 1-50 Higashihonmachi, Amagasaki City, Hyogo Prefecture Name (45
0) Ninijinka Co., Ltd. 541 Address 4-68 Kitakyutabe-cho, Higashi-ku, Osaka Name Name
UNIF-1 Co., Ltd. Patent Department Telephone: 06-281-52
58 (Dial-in) 4. Column 5, "Detailed Description of the Invention" of the specification subject to amendment, Contents of the amendment (11 Correct "original thread" in the bottom line of page 1 of the specification to "original thread".

(2) On page 3, line 11, "formed" is corrected to "formed."

(3) Formulas (E) and (F) on page 6 of the same are corrected as follows.

(4) Shows one unit on page 7, line 5. )” is a “group, R2 represents a hydrogen atom or an alkyl group having 1 to 1 o carbon atoms.”
” he corrected.

Claims (1)

[Claims] (1) Easily dyed and stain resistant, characterized by forming a film containing a fluorine-based antifouling agent on the back side of the fiber, and further forming a film containing a fluorine-based wetting agent on the outside of the film. fiber.