JPS5854073A - Anti-stain finish treating agent of thermoplastic synthetic 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 improves productivity and improves quality in 6-1 by attaching a raw fiber oil containing a fluorine compound to synthetic fibers. , while giving off a vague effect, it has abrasion resistance r nj+ for products after slightly dyed.
i Concerning the stain-resistant finish treatment agent for thermoplastic synthetic wire XJI that provides significantly improved washability and durable water and oil repellency, so-called stain resistance.4 Fabrics, especially fabrics containing synthetic fibers, have strong lipophilic properties. In the past, various improvement methods have been devised to prevent stains and corrosion. As an example of Ji et al., 1) surface coating with a hydrophilic polymer or grafting with a hydrophilic monomer,
Method of making stains easier to remove by washing 2) Method of making the single fibers and fibers that make up the fabric into a hollow irregular cross-sectional shape and making stains less noticeable by light splitting 3) Adding a substance with low surface free energy to the fiber surface There are methods such as lowering the surface free energy of i1 human fibers and improving their water and oil repellency to actively make them less likely to get dirty, but generally methods 1) and 2) are Compared to 3), the effect of imparting stain resistance is small.

On the other hand, in concept 3), a fluorine compound is used as a substance to be attached to the fibers in order to lower the surface free energy of the fibers. This fluorine-based compound has a low intermolecular force, so the surface free ability A~
It is small and can be attached to the surface of other substances, making it water repellent.

4) It is a well-known oilseed that exhibits oil repellency and mold release properties. Currently, among fluorine compounds, a fluorocarbon resin based on Di (di) has been developed as a material that can be expected to create a surface with the lowest surface free energy and have good antifouling properties, and is used in carpets and waterproof clothing. It has come to be widely used mainly in the rear 11 engineering field for industrial applications that require heavy water pressure.

By the way, if the above-mentioned surface treatment process can be carried out in the yarn spinning-crimping process using the thermal energy especially during crimping setting, and it is possible to impart good antifouling performance with a durability of 11 tons,
This will greatly contribute to reducing the total energy cost required for product production in an environment where the cost of crude oil is increasing due to rising prices of crude oil. However, most of the processing of such fluorine compounds into fibers is currently in the field of post-processing. This means that even if a post-processing agent containing a fluorocarbon resin compound, which has antifouling properties, is used at the yarn stage, it will have no lubricating ability (and productivity in the spinning, drawing, and crimping steps). This is due to the fact that they cannot be compatible with each other.77.In other words, when the post-processing agent and an oil having lubricating ability are used together, the oil component becomes J, which causes the resin coating of the post-processing agent to become thinner, which reduces the film strength. It is impossible to obtain durable antifouling performance.In the past, during the heat centrifugation process, the resin component adheres and accumulates on the hot roller (7 bubbles of gum), causing fuzz,
Process problems such as wrapping may occur.

However, in order to solve the above problem in the spinning process, it is also possible to use a well water low molecular weight compound that also contains a perfluoroalkyl group according to US Pat. j.

-5-- 4192754.4193880.41905=15
However, the fluorine compounds described in these specifications have poor emulsion stability and cause some precipitation when processed into fibers as an aqueous emulsion. (sufficient performance of expensive fluorine compounds)
I haven't reached 11 by the time I make it b.

The inventors of the present invention attempted to arrive at the 4F invention as a result of diligent efforts to solve such problems.

That is, the present invention is represented by the following general formula 4] fluorinated metal, (wherein, , Y is an alkylene, cycloalkylene or fullkyleneoxy group, containing 2 to 6-20 carbon atoms, and having a small number (both containing 2 carbon atoms) in the main chain. 2 is oxygen, or in the draft, When 2 is oxygen, p is 2, and when Z is purple, p is 2. R, R' are H or C2 to C1, hydrocarbon group, aryl group, or Z
B kl is a ralkyl group, a hydroxyfurkyl group,
-ell, R″CHOH or -C几R″CI(OCH,
R''CllOH, where R'l:l', water or methyl group, or B is -CO2C1((OH) 1.Q
Or -C)LCH(OH)CT is also 0CJLCH(O
ii) C1(,Q, where Q is a halogen atom, hydroxyl-X
'y is a nitrile group.

t is 0 or JT, r and q are integers of at least 1, and the sum of r + q
) m and Y are linear monobranched or cyclic. In addition, the substituents in the above general formula may be the same or different. This is a stain-resistant finishing treatment agent for thermoplastic synthetic fibers, which is characterized by containing a small amount of (31% Ja).

Furthermore, in order to obtain the desired stain-resistant effect by adhering the stain-resistant finishing agent to the cultivated fibers, the finishing agent itself must exhibit sufficient water and oil repellency, and at the same time, It is important that it is emulsified into fine emulsion particles and uniformly adheres to the fibers.

From the viewpoint of stiffness, one finishing agent is a group that exhibits water and oil repellency in each molecule and intermolecular cohesive force.

It is necessary that a group that provides adsorption power is attached to the mother nucleus. In this regard, in the present invention, l) the fluorine compound is adsorbed onto the fiber surface earlier than the oil component used in combination due to the presence of -COOB U) 13 groups therein, resulting in synthetic M! An antifouling film is formed at the position closest to the fiber polymer, and the oil agent is distributed on the uppermost part of the fiber surface, so it still functions as an oil agent.

For example, it maintains the productivity of various processes such as spinning, stretching, crimping, and tact, and is also effective in preventing troubles such as gumming up of the fluorine component on the heated p-craper. The preferred structure of the B group is -CHC(M)C or -CH(OH)Cl0CI(ac)I(OH)C
Le C! It is.

2) Furthermore, the Bellful Jp alkyl group in the molecule lowers the surface free energy, making it excellent. CM Demonstrates water and oil repellency, so-called stain resistance. It is preferred that the backbone of the formula contain at least 6 carbon atoms and at least 4 perfluorinated carbon atoms in the group.

3) Also, 21! of the sulfonamide structure in the fluorine compound molecule!・The emulsion dispersibility varies considerably depending on the person, and emulsion is stable, with almost no precipitation occurring in the 1-in circulation vacuum and in the emulsion tank.
Where! It is now possible to make liquid I, ensuring uniform durability I'1
1. (+1 i, ・The formation of the filtration antifouling film becomes easier.

4) Further = (Co(')R')t is the sulfone 7
Compared to a group having a mido structure, the molecular weight is lower, but it has the effect of lowering the molecular ratio of the finishing agent and improving the emulsifying power-dispersing properties.

The chain length of R' is C1 to C24, preferably C1 to C24.
It is C8. If it exceeds C14 (1, intermolecular cohesive force
9- decreases, the strength of the antifouling film is low, and the antifouling durability is poor, which is not preferable.

The stain-resistant finishing agent of the present invention can be applied by any known method applied to synthetic organic polymer fibers, yarns, or yarn products, such as spraying, dipping, or There is a contact method, and the most preferred embodiment is a method in which it is applied as a finishing agent to melt-spun undrawn yarn.

In the present invention, the fluorine compound is used in conjunction with the oil agent, which has lubricity, antistatic property, convergence property, and properties on the heater in order to maintain the productivity of various processes such as spinning, drawing, crimping, and tufting. For each process, such as heat resistance that can withstand thermal decomposition of the oil agent (it must satisfy various required characteristics), as the optimal oil agent, the smoothing agent component is an ester type with excellent heat resistance. Smoothing agents are preferred, such as - basic acid esters,
The main ingredient is a single component of an ester smoothing agent such as dibasic acid esters, polybasic acid esters, glycol esters, polyhydric alcohol esters, and aromatic carboxylic acid esters, or a composite component thereof. However, mineral oil, polypropylene glycol, polyisobutylene, polypuran or polyether may also be included. Such smoothing agents are alkyl phosphates, alkyl sulfonates, alkyl sulfosuccinate-toyoalkyl sulfates and/or their fullylene oxide adducts, which also serve as nonionic emulsifiers and antistatic properties, or alkali gold of higher fatty acids.
lj, ammonium salt, cationic surfactant, or amphoteric surfactant, etc., and the emulsion stability and thread-forming T8. of the finishing agent containing the fluorine compound. If the post-IAI process is satisfied, there are no particular restrictions on the oil.

By treating yarns and/or yarn products with the stain-resistant finishing agent composition of the present invention, not only water/oil repellency and stain resistance are imparted, but also the subsequent steps such as stretching, stain-repellent treatment, etc. In the yarn manufacturing process of bulk texture treatment and bulk, especially bulky carpet yarn or texture yarn, it is possible to impart lubricity, antistatic property, and cohesiveness to the yarn.This invention The target synthetic fibers include polyamide, polyester, and other synthetic fibers, and their shape includes continuous strands constituting filaments or discontinuous strands such as staples.Also, yarn products may be used, such as clothing fabrics, chair fabrics, This is used to punch holes in fabrics used for interior decoration, textile carpets, and similar purposes.

Next, the present invention will be explained by examples.

Example (2) Preparation of spinning finishing oils 1 to (2) The fluorine compound used in this example is a mixture of benzybuenonetetracarboxylic acid esters having the following structure.

2n+1 However, n=-CH, CII(O)I) ("H, C/n=
8 (average value) 13- For convenience, the present mixture of benzophenone tetracarboxylic acid esters is hereinafter referred to as fluorine compound composition CAI.

As shown in Table-1, the above fluorine compound composition [A] is mixed with an emulsifier and an anion (undiluted solution mixture-1),
A mixture of coconut oil as a smoothing agent component and an emulsifier (undiluted solution mixture-2) was heated to 80°C and poured into 80°C warm water in the order of undiluted solution mixture-2 and undiluted solution mixture-1 under stirring to emulsify. After dispersion and uniform stirring, the mixture was cooled to 35°C.

The spinning finishing oils 1 to ■ obtained as shown in ε have a concentration of 20
Both heavy and heavy molecules are translucent and stable emulsions.

14- Table = 1 Composition of the stock solutions of spinning finishing oils 1 to ① Production of spinning finishing oil V-W The fluorine compound used singly in this example was An isomer mixture (fluorine compound composition [B]) with a structure in which 16+ is replaced with a pull group, and [
An isomer mixture with a structure in which one of the B groups in A) is replaced with an oleyl group (fluorine compound '4'a g + composition 15- fluorine compound composition CB), [C) is emulsified using the blending system shown in Table 2. This was done in the same manner as the mark.

The spinning finishing oil V~■ obtained in this way has a concentration of 20
The emulsion was stable in terms of weight percent, and the transparency of V and Vl was slightly better than that of the above-mentioned spinning finishing oil (2) containing the same amount of fluorine compound.

1. Evaluation of stain resistance performance The following describes how the spinning finishing oils described in I to ① above are applied in the conventional spinning-drawn bulk yarn manufacturing process to impart water repellency, oil repellency, and stain resistance.

The above-mentioned spinning finishing oils (1) to (2) were applied to the undrawn polyamide (Nipun-6) yarn in the spinning process in such a manner that about 1.0% by weight of oil was applied to the yarn.

Next, the thread is stretched approximately 3 times, and a steam jet is applied to stretch it to 14 times.
A bulky yarn was produced by treatment at a temperature of 0 to 180°C.

The crimp form, physical properties, tufting properties, and dyeability of the bulky yarn were all satisfactory (no problems were observed) even when the fluorine compound of the present invention was used.

Table 3 shows the evaluation results of the antifouling performance of the polyamide fabric prepared in this example.

In the case of the polyamide fabrics prepared according to the examples of the present invention, water repellency, oil repellency, and durability are all excellent.

In the case of the spinning finishing agent (Comparative Example) with a low content of fluorine compounds, the overall antifouling performance deteriorates, and the durability is particularly markedly lower than 1. In addition, in the case where R' in the fluorine compound of vl (comparative example) is a long chain (oleyl group), 161 has excellent emulsifying and dispersing properties, but the antifouling performance is insufficient. I understand.

In the above evaluation, an aqueous solution of 20 volumes of water-repellent isopropyl alcohol was used (the measurement conditions were as follows: 3°1). Add one drop to the top of the sample and measure the time (seconds) it takes for the water drop to disappear. However, in the case of dust removal, the measurement is performed after applying the OL1 vacuum cleaner.

2) Oil repellency AATCC+ Based on IB-1972. Gently drop one drop of the reagent shown in the table onto the horizontally spread surface of the sample.
Judgment is made based on the state of penetration after 3 minutes. However, if the area has been cleaned by fleas, measurements should be taken after vacuuming.

3) Stretch the sample in the Fumikomi test corridor and perform Fumikomi with your shoes on.
See the effects of dirt.

The number of days for Fumicomi is 28 days. Vacuum once a day.

4) Artificial dirt by rotary contamination machine. Rotate for 1 hour at 20 rpm with a load of 3 kg.

The contaminant is black soil containing water. Spread o and t as counterfeits.

5) Soil rate After applying the sample after the chiseling or artificial stain test to a vacuum cleaner, measure the reflectance with a digital color difference meter, and calculate the stain rate using the following formula.

Ro −Ra Contamination rate (row) = −111−−−−−−X 100O Here Too = 7 Reflectance Rs of sample before staining
-Fumi Fumi Ito No. 121-

Claims (2)

[Claims] (1) A fluorine compound represented by the following general formula (wherein, X is fluorine or a Verfluoropflukoxy group containing 1 to 6 carbon atoms, m is an integer of 2 to 20 as an arithmetic mean, and Y is alkylene. Cycloal Yalene or alkyleneoxy group from 2 to 20
carbon atoms and at least 2 carbon atoms in the main chain. 2 is oxygen or nitrogen; when 2 is oxygen, p is 1; when Z is nitrogen, p is 2. R and R' are H or a C3-CI4 hydrocarbon group, a 7-aryl group, an aralkyl group, or a human-xyfurkyl group. B is -CH,R"Cf(OH or -CH,R"CHOC)LR"CHOH, in which case R
rr is hydrogen or methyl group, or B bar C) I, C
J'1(OH)CH,Q or -(JLCI((OH)C
HtOCaCH(OH)CLQ, Q being a halogen atom, a hydroxyl group or a nitrile group. t is 0 or l, and r and q are integers of at least l'+1r+q+t
The total is 4. X (CFt )rn and Y are linear monobranched or cyclic. In addition, the ffi substituents in the above general formula are the same or different. 1.) A stain-resistant finishing agent for thermoplastic synthetic fibers, characterized in that it contains at least 3 times 1% or more of the following: (2) The fluorine compound is benzophenone tetracarboxylic acid ester and/or bis(diamide)/ester of benzophenone tetracarboxylic acid, and X(CF,)m
The main chain of the fluorine compound group of -8α-NR-Y is at least 6
and at least 4 Verfluorinated carbon atoms in the group.
Stain-resistant finishing agent as described in Section 1.