JPS5818474A - Anti-stain finishing 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 provides an anti-stain finishing treatment agent, more specifically, a fiber oil agent containing a connecting compound, by adhering it to synthetic fibers.
Abrasion resistant for improving productivity and quality in spinning, drawing, and post-processing processes.

This invention relates to a stain-resistant finishing agent for heat-warmable synthetic fibers that imparts durable water and oil repellency, so-called stain resistance, with markedly improved washing resistance.

Since fabrics, especially fabrics containing synthetic fibers, have strong lipophilic properties and are easily stained, various countermeasures have been taken in the past. Examples of these methods include 1) surface coating of hydrophilic polymers or grafting of hydrophilic monomers to make stains easier to remove by washing; and 2) methods of making the single fibers constituting the fabric have a hollow, irregular cross-sectional shape to absorb light. Method of making dirt less noticeable through diffused reflection 3) A method of actively making dirt less likely to stick by attaching substances with low surface free energy to the fiber surface to lower the surface free energy of the fiber and improve water and oil repellency. etc., but in general, compared to method 1) and method 3),
The effect of imparting stain resistance is small.

On the other hand, in concept 3), a linked compound is used as a substance to be attached to the surface of the fiber in order to lower the surface free energy. It is a well-known fact that linked compounds have low intermolecular forces and therefore have low surface free energy, and that they can impart water repellency, oil repellency, and mold release properties by attaching them to the surface of other substances. be. Currently,
Among the linked compounds, linked resin made from perfluorofurkyl compound was developed as a material that creates a surface with the lowest surface free energy and can be expected to have good antifouling properties.
carpet.

It has come to be widely used mainly in the post-processing field for waterproof clothing and industrial materials that require water pressure resistance.

By the way, if the above-mentioned surface treatment process could be applied at the spinning-crimping stage, especially by utilizing the thermal energy during crimping setting, to provide durable antifouling performance, the cost would increase due to the rising price of crude oil. This will greatly contribute to reducing the total energy cost for producing products in this environment.

However, at present, most of the processing of such linked compounds into fibers is in the field of post-processing.

This is because even if a post-processing agent containing a continuous resin compound having an antifouling effect is applied at the yarn stage, it has no lubricating ability and is not compatible with productivity in the spinning, elongating, and crimping processes. That is, if the post-processing agent and an oil having lubricating ability are used together, the resin coating of the post-processing agent will be plasticized by the oil component and the film strength will temporarily deteriorate, making it impossible to obtain durable antifouling performance. Furthermore, during the heat setting process, the resin component adheres and accumulates (gum-up) on 1-2, resulting in fluff.

Process problems such as wrapping occur.

However, in order to solve the above-mentioned problems in the spinning process, the use of a linked low molecular weight compound containing a perfluorofuryl group is disclosed in US Pat. No. 4,134,839, 4192,754.
No. 9388G and No. 4190545, and these have achieved some degree of effectiveness. However, the linked compounds described in these specifications have poor emulsion stability, and some precipitation occurs when processed into fibers as an aqueous emulsion, making it difficult to fully demonstrate the performance of the expensive linked compounds. Not yet reached.

The present inventors have arrived at the present invention as a result of intensive studies to solve such problems.

That is, the present invention relates to a linked compound represented by the following general formula, (1) (wherein, , Y is an alkylene, cycloalkylene, or alkyleneoxy group consisting of 2 to 20 carbon atoms and containing at least 2 carbon atoms in the main chain. 2 is oxygen or nitrogen, and when 2 is oxygen p is 1. When Z is nitrogen, p is 2. R and R' are H or a C+ -C+a hydrocarbon group, a 7-aryl group, a 7-ralkyl group, or a hydroxyfurkyl group. B is -CHI R 'CHOH or -CH snow f
cyioc-R'caou, where R' is hydrogen or a methyl group, or B is -CH5CH(OH)CHsQ, where Q is a halogen atom, a hydroxyl group, or a nitrile group,
Furthermore, B is -C
((OH)CHs Q (Q is the same as above)
. t is 0.1 or 2, r and q are integers of at least 1, and the sum of r + q + t is 4.

X (CF)m and Y are a linear bibranched chain or a cyclic substance.

This stain-resistant finishing agent for thermoplastic synthetic fibers is characterized by containing at least 3 weights or more of substituents of the above general formula (same or different).

More specifically, in order to obtain the desired stain-resistant effect by adhering an anti-stain finishing agent to fibers, the finishing agent itself must exhibit sufficient water and oil repellency and at the same time must be emulsified into fine emulsion particles. It is important to adhere uniformly to the fibers.

From this point of view, the finishing agent should be a single molecule group that exhibits water and oil repellency and intermolecular cohesion.

It is necessary that a group that provides adsorption power is bonded to the mother nucleus. In this regard, in the present invention, 1) due to the presence of the B group of 1000B in the linked compound, the antifouling agent is adsorbed to the fiber hm before the oil component used in combination and is located at the position closest to the synthetic fiber polymer. It forms a film and the oil agent is distributed in the top layer of the fiber surface, so it performs the same function as a conventional oil agent.

For example, it maintains productivity in various processes such as spinning, drawing, crimping, and tufting, and furthermore, it is effective in preventing troubles caused by the heating of p-siler and gum amplifier of connected components. The preferred structure of group B is -CHz CH(OH)C CI or -CH! CM(OH)CH鵞OCH寞('H(OH)
CHs C1.

2) Furthermore, the perfluoroalkyl group in the molecule that minimizes surface free energy exhibits excellent water and oil repellency, so-called antifouling properties.

3) In addition, the introduction of a sulfonamide structure into the linked compound molecules significantly improves emulsion dispersibility, creating a stable emulsion treatment solution with almost no precipitation during emulsion circulation, in pipes, and in emulsion tanks. This makes it easier to form a uniform and durable antifouling film.

In addition, 2 in the above general formula (I) is preferably oxygen from the viewpoint of ease of synthesis, and also provides a good balance between the adsorption effect on fibers, the antifouling effect due to water repellency and oil repellency, and the effect of improving emulsification and dispersibility. , in order to maximize the performance, q, r are q-r=
2 is preferable. In addition, if the number of formulas is large, it will disturb the arrangement of the linked compound differences and have a negative effect on the antifouling property, so it is better to have a smaller number of constituent carbons.
．． A propyl group is preferred because of its ease of formation.

4) Also, the hydrocarbon group in the form of -(Cot ic/),
Although its function is lower than the group containing -coon or 8QN, -(COs R') itself may lower the molecular specific gravity of the finishing agent and facilitate emulsification and dispersion.

The stain-resistant finishing agent of the present invention can be applied using known methods for applying synthetic organic polymers to fibers, yarns, or yarn products, such as spraying, dipping, or p-coating on fibers, yarns, or yarn products. 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 oil agent to be used in conjunction with the chain compound has lubricating properties, antistatic properties, convergence properties, and heater properties in order to maintain productivity in various processes such as spinning, drawing, crimping, and tufting. It must be heat resistant and able to withstand the thermal decomposition of oils.It must satisfy various required characteristics in each process. As the optimal lubricant component, an ester-based smoothing agent with excellent heat resistance is preferable. For example, a single component of an ester smoothing agent such as basic acid esters, dibasic acid esters, polybasic acid esters, glycol esters, polyhydric alcohol esters, and aromatic carboxylic acid esters, or a composite component thereof. The main component is mineral oil, polypropylene glycol, polyisobutylene, polypuran, or polyether. Such smoothing agents include furkyl phosphate and alkyl sulfonate, which also serve as nonionic emulsifiers and antistatic properties.

Furkylsulfosuccinate, alkyl sulfate and/or their furkylene oxide adducts, or alkali metal salts of higher fatty acids.

If it is used in combination with ammonium salts, cationic surfactants, or amphoteric surfactants, etc., and satisfies the emulsion stability of the finishing agent containing the linked compound, as well as the silk spinning process and post-processing process, there are no restrictions on oil agents under 4IiVC. .

Water repellency can be achieved by treating yarn and/or yarn products with the stain-resistant finishing agent composition of the present invention.

Not only is oil repellency and stain resistance imparted, but the yarn is also protected during subsequent processes such as ivy stretching, steam jet texturing and yarn manufacturing for bulky yarns, especially bulky carpet yarns or textured and treated clothing fabrics. It can provide lubricity, antistatic properties, and focusing properties. The synthetic fibers targeted by the present invention are polyamide, polyester, and other synthetic fibers, and their shapes include continuous strands constituting filaments or discontinuous strands such as staples.

It may also be a series of products, including textiles used for similar purposes, such as clothing, chair coverings, interior decoration, textiles, and carpets.

Next, the present invention will be explained by examples.

EXAMPLE The connecting compound used in this example is a mixture of pimelic acid esters having the lower B-p structure.

CI ■ Ma (a) (b) However, B = CHs CH (0H) CH yi Cjn-
8 (average value) For convenience, the present mixture of pipellitic acid esters is hereinafter referred to as fluorine compound composition CA).

As shown in @-1, the above linked compound composition (A) is mixed with an emulsifier and an anion (II stock 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.
2 was added to water at 80°C under stirring, and then stock solution mixture-1
was added and emulsified and dispersed, and after uniform stirring, the mixture was cooled to 35°C (For spinning finishing oil-V, only the stock solution mixture = 2 was emulsified)
.

The spinning finishing oils I to V obtained in this way have a concentration of 20
Both are translucent and stable emulsions by weight.

The above-mentioned spinning finishing oils (1) to (V) were applied to the undrawn polyamide (Nine 6) yarn during the spinning process in such an amount that approximately 1.0 weight of oil was applied to the yarn.

Next, stretch the thread approximately 3 times and use a stylinometer.
A bulky yarn was produced by processing at a temperature of 40 to 180°C.

There were no problems with the crimped form, physical properties, tufting properties, and dyeability of the bulky yarn even when the continuous strand compound of the present invention was used.

The evaluation results of the antifouling performance of the polyamide twill prepared in this example are shown in *-2.

From the table above, polyamide fabrics to which the treatment agent of the present invention is applied (spinning finishing oils I to ■) have excellent water repellency, oil repellency, and durability, while spinning finishing oils with a low content of fluorine compounds It can be seen that in the case of (Comparative Example), the antifouling performance is lowered, and in particular, the durability is extremely lowered.

The measurement conditions employed in the above evaluation are as follows.

l) Use a 20 volume aqueous solution of water-repellent isopropyl alcohol. The time (seconds) it takes for the water droplet to disappear after a drop is placed on the sample.
Measure. However, in the case after Fumi:Iξ, the measurement is performed after vacuuming.

2) According to II Oil-based AATCC118-1972. A drop of the reagent shown in Table 3 is gently dropped onto the horizontally spread surface of the sample, and the state of penetration is judged after 3 minutes. However, if it has been cleaned, it should be cleaned after vacuuming.

3) Paste the sample in the 7-micomi test corridor and conduct a fumi-comi test with your shoes on.
See the effects of dirt.

The number of days of Fumi Fumi is 28 days. Vacuum once a day.

4) Artificial dirt by rotary contamination machine. Rotate for 1 hour under a load of 3 kp and 20 rpm.

The contaminant is black soil containing 8% water. Spray at o, lp 7 seconds.

5) Staining rate After applying the vacuum cleaner to the sample after the fumikomi or artificial staining test, the reflectance is determined to lit using a digital color difference meter, and the staining rate is calculated using the following formula.

Here, R0 is the reflectance of the sample before Fumikomi Rs - after Fumikomi 〃 〃

Claims (1)

[Claims] A fluorine compound (I) represented by the following general formula (I) (wherein, X is fluorine or a perfluoroalkoxy group containing 1 to 6 carbon atoms, m is the arithmetic mean An integer from 2 to 20, Y is alkylene. Dichloroflukylene or fullkyleneoxy group from 2 to 20
It consists of 11 carbon atoms and contains 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 C1-014 hydrocarbon group, a 7-aryl group, a 7-ralkyl group, or a hydroxyfurkyl group. The 38th seal is -CHtR'CHO1!
or -〇IbR'CHOCHsR'CHOH, where λ' is hydrogen or a methyl group, or B is -CH* CH(
OR) CM mushroom q, where Q is a halogen atom. Hydrogen group or nitrile group, further B is -CH*CH(on
)c OC&CH(OR)C1ll嘗Q. (Q
is the same as above). t is o, i, or 2, r and q are integers of at least 1, and the sum of r + q + t is 4. X(CF戈)m and Y are straight chains. Branched or cyclic. In addition, the substituents in the above general formula may be the same or different. 1. A stain-resistant finishing agent for thermoplastic synthetic fibers, characterized in that it contains at least 3 parts by weight of: (2) The stain-resistant finishing agent according to claim 1, wherein 2 in general formula (I) is oxygen, and the substituent R on the nitrogen atom is a propyl group. (3) q, r and t of general formula (I) are q w r
= 2. The stain-resistant finishing agent according to claim 2, which is 1-0;