JPH0711108B2 - Softening agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a softening agent in which a specific silicone resin, an emulsifier and an antistatic agent are allowed to coexist, and more specifically, a specific functional group. A silicone resin containing a bond, a specific emulsifier, and a specific antistatic agent are stably dispersed in an aqueous medium at a specific ratio, and the treated fiber has a durable slimy feel, flexibility and processability. The present invention relates to an industrially advantageous fabric softening agent that can be applied simultaneously.

(B) Conventional technology It is well known that knitted and woven fabrics made of animal fibers such as wool, cashmere, and angora rabbit hair have an excellent texture based on a unique slimy feel, and in recent years synthetic fibers such as acrylic fibers. Attempts have been actively made to impart a texture peculiar to animal hair fibers.

For example, JP-B-44-26436 discloses a mixed treating agent of a silicone resin and an epoxy resin as a treating agent for an acrylic fiber product, but the final product has a rough texture due to adhesive curing between fibers and a silicone. Since the epoxy resin hinders the slimy feeling imparted by the resin, the commercial value of the final product is greatly reduced. On the other hand, in Japanese Patent Publication No. 51-2556 relating to the present applicant, a specific silicone resin is referred to as polyoxyethylene (hereinafter referred to as PO
Abbreviated as E) (n ') A swelling gel-like acrylic fiber obtained by mixing with an emulsifier selected from the group of alkylphenyl phosphates, adding water with stirring to form a weakly acidic emulsion, and wet spinning. A technical means was proposed in which the emulsion was adhered to and then immediately dried, and then a spinning oil agent was further applied. By adopting such a technical means, it is possible to give the acrylic fiber or its product a slimy feeling, flexibility and shrink-proof property that are very similar to animal hair fiber products, but in such means, two-step treatment by two baths of silicone treatment and spinning oil agent addition Is essential, and it is not always said to be an industrially preferable method, and further improvement has been desired.

(C) Problems to be Solved by the Invention Under such circumstances, the present inventors have made a treating agent capable of simultaneously satisfying the feeling and processability by coexisting an antistatic agent in a silicone emulsion bath. We have added various studies to provide However, when an antistatic agent is added to the silicone emulsion, the stability of the emulsion is significantly impaired and the treatment agent cannot be attached uniformly, so that continuous operability such as yarn breakage and winding in the subsequent step is significantly impaired. Further, when a stable emulsion is obtained, it is not possible to obtain a fiber having a satisfactory texture and processing, and in any case, it is extremely difficult to satisfy the texture and the spinning property at the same time. It turned out.

Here, as a result of diligent research by the present inventors on a treating agent capable of imparting durable slimy texture and processability at the same time by a one-step treatment which has been considered to be an unsolvable problem, a specific silicone resin was obtained. The present inventors have found that the intended softening agent can be obtained only by selecting one of the three, the emulsifier and the antistatic agent, and coexisting the three in a specific ratio.

That is, an object of the present invention is to provide a softening agent capable of imparting durable slimy feel and processability such as spinnability at the same time by a one-step treatment.

Another object of the present invention is that it is excellent in bath stability and can be applied to the fibers to be treated with good operability and evenness. Further, yarn breakage, winding, etc. during subsequent raw cotton production or processing such as spinning etc. It is an object of the present invention to provide a softening agent having excellent continuous operability that does not cause the above problems.

A different object of the present invention is to provide a versatile softening agent which can be applied to fibers in a desired raw cotton production process such as immediately after spinning prevention and after heat treatment, and can be applied to fibers of various brands. It is to be.

Further different objects of the present invention will be apparent from the following description.

(D) Means for Solving the Problems The softening agent according to the present invention for achieving such an object has a general formula: —RNHR′NH ₂ (where R and R ′ are carbon atoms of 1 to 1).
6 alkylene group) and an organopolysiloxane (A) containing primary and secondary amino groups bound thereto, POE (l) alkylphenyl ether or POE having an acid value of 14 to 60.
(M) sec-alkyl ether (where l and m represent the degree of polymerization of polyoxyethylene and have a value of 5 to 20; the alkyl group has 8 to 12 sec-alkyl group has 9 to 17 carbon atoms) ) Partial phosphoric acid ester (B) and the degree of phosphorylation
POE (n) alkyl ether with an acid value of 0.5 or more and 14 or less (where n is the degree of polymerization of polyoxyethylene and is 3 to
30), the alkyl group has 8 to 18 carbon atoms), and the neutral or complete phosphoric acid ester neutralization salt (C) has 0.1 to 5 parts of B and 0.1% of C per 1 part by weight of A. It is stably dispersed in an aqueous medium at a ratio of up to 4.0 parts.

Hereinafter, the present invention will be described in detail.

First, the organopolysiloxane (A) according to the present invention is
Formula -RNHR'NH ₂ (where, R, R 'is an alkylene group having 1 to 6 carbon atoms) a silicone resin containing bond as an essential functional group a primary and secondary amino groups represented by, Only by employing a silicone resin containing such a specific functional group as a bond, a stable emulsion can be prepared, and at the same time, a durable slimy feel and processability can be imparted to the treated fiber. The bond content of the amino group is 0.1 to 2.0 mmol / g, more preferably 0.2.
The use of a silicone resin having a concentration of ~ 1.0 mmol / g is desirable because the object of the present invention can be achieved more effectively, and the molecular weight is 10 from the viewpoint of viscosity and workability.
Silicone resin of less than 0,000 is recommended.

Next, PO adopted as an essential emulsifier in the present invention
E (l) alkyl phenyl ether or POE (m) sec-
In the partial phosphoric acid ester (B) of alkyl ether (wherein l and m are the polymerization degrees of polyoxyethylene), 1 is 5 to 2
0, more preferably 6-10, m is 5-20, more preferably 7-10, and the alkyl group has 8-12 carbon atoms, se
By using a c-alkyl group having a carbon number of 9 to 17 and an acid value of 14 to 60, preferably 25 to 45, in combination with the above specific silicone resin (A), It is desirable because the feeling, spinning property, bath stability and the like can be further improved. Examples of such emulsifiers include octyl phenyl ether of POE (7), POE (8) octyl phenyl ether, POE (9) octyl phenyl ether, POE (7) nonyl phenyl ether, POE
(8) nonyl phenyl ether, POE (9) nonyl phenyl ether, POE (10) dodecyl phenyl ether,
Union Carbide Co. TERGITOL 13-S, 15-S, 45
Partial phosphoric acid esters such as -S may be mentioned.

In the present invention, the neutral or complete phosphate ester neutralization salt (C) of POE (n) alkyl ether coexisted in the treating agent as an essential antistatic agent has n of 3 to 30, more preferably 5 to 20. And the alkyl group has 8 to 18 carbon atoms,
More preferably 12 to 16, the degree of phosphorylation (molar ratio of the phosphoric acid ester neutralization salt to the total amount of the antistatic agent) is 0.5 or more, more preferably 0.6 to 0.9, and the acid value It is desirable to adopt the following 14 or less because the object of the present invention can be achieved more effectively. Such antistatic agents include complete or partial phosphoric acid such as POE (5) octyl ether, POE (5) dodecyl ether, POE (10) cetyl ether, POE (15) cetyl ether and POE (20) stearyl ether. Examples of the neutralizing salt of phosphoric acid ester include, but are not limited to, potassium salts,
It is desirable to employ a strongly basic salt such as sodium salt.

Further, the mixing ratio of the components A to C is 0.1 to 0.5 parts by weight of the emulsifier (B) per 1 part by weight of the silicone resin (A),
Preferably 0.2 to 0.4 parts, and the antistatic agent (C) is 0.1 to 4.0.
Part, preferably 0.2 to 2.0 parts, more preferably 0.3 to 1.0
It is necessary to adjust the mixing ratio to be within the range of parts, and when the mixing ratio is out of the range recommended in the present invention, a stable emulsion cannot be prepared, and the treated fiber has durability. A certain slimy texture or good workability cannot be imparted.

Here, the preparation method of such a softening agent is not particularly limited as long as the above components A to C can coexist in the above ratio, but for example, the emulsifier (B) is dissolved in an aqueous medium under stirring. After that, the silicone resin (A) and then the antistatic agent (C) are added and mixed in a predetermined amount, whereby it can be advantageously prepared. In addition, as an aqueous medium,
Industrially, water alone is preferred, but a mixed solvent of water and a water-miscible organic solvent (for example, alcohols, ketones, etc.) can be used as long as a desired emulsion can be produced. Also, in handling viscosity, emulsifying property, etc.
It is desirable that the total amount of the components A to C is 50% or less, preferably 30% or less based on the total weight of the treating agent at a temperature of 35 ° C, more preferably 35 to 60 ° C.

It should be noted that there is no limitation with respect to the type of fibers to be treated to which the softening agent according to the present invention is applied, but it is applied to acidic group-containing fibers such as basic dye-dyeable acrylic fibers and polyester fibers. In that case, the amino group bonded to the silicone resin is desirable because it can form a strong ionic bond with the acidic group present in the fiber to be treated and the durability of the feeling can be remarkably improved.

The weight for adhering the softening agent according to the present invention to the fiber to be treated should be appropriately determined in consideration of the desired texture, the type of the fiber to be treated, etc., but with respect to the dry weight of the fiber to be treated. The silicone resin (A) in the treatment agent is approximately 0.05
It is desirable to adhere in the range of up to 2.0%.

(E) Effect of the Invention By applying the softening agent according to the present invention in which the above-mentioned specific silicone resin, emulsifier and antistatic agent are stably dispersed in a horizontal medium in a specific ratio, a small amount of adhesion and It is a remarkable effect of the present invention that the fiber to be treated can be imparted with a durable slippery feel as well as processability such as spinnability by only one treatment step.

Further, the softening agent having excellent bath stability according to the present invention can be applied to the fiber to be treated with good operability and uniformly, and also in each step such as subsequent raw cotton production or spinning, yarn breakage or winding It is a characteristic advantage of the present invention that the texture of the fiber to be treated can be remarkably improved without causing troubles such as the above.

The appearance of the present invention relating to a softening agent capable of simultaneously satisfying such a durable slimy feel and processability in a single bath treatment is an animal hair-like slimy wind while maintaining the advantages of the treated fiber. It will make a great contribution in the field of giving a match.

(F) Examples In order to facilitate understanding of the present invention, representative examples will be described below, but the gist of the present invention is not limited to the description of these examples. All parts and percentages are by weight unless otherwise specified. In addition, the stress reduction rate during dynamic friction tan α foil after slipping and spinnability shown in the examples are measured by the following methods.

(1) Stress reduction rate during dynamic friction tan α The stress reduction rate during dynamic friction tan α is obtained by magnifying and measuring the dynamic friction force between sample cloths using the cloth friction tester shown in FIG. 1 (A). More specifically, referring to FIG. 1 (B) together, the sample cloth 1 in a humidity controlled atmosphere of 22 ° C. and 65% relative humidity is used.
Is placed on the sample table 2, one end is fixed by the sample retainer 3 and a load 4 of 30 g is applied to the other end to maintain a tension state, and an effective contact area of 450 g of which a compressive load 5 is applied. 3 cm
³ (2 cm x 1.5 cm) slider 6 is placed, sample piece 7 is fixed on the lower surface of the slider 6 and sample table 2 is moved at a constant rate of 12 mm / min to reduce the frictional force generated between sample cloths. It is detected by the resistance wire strain gauge 8 connected to 6, and is recorded in the recorder 9. In the measurement, when the dynamic frictional force shows a steady state, the recorder is zero-shifted, and then the detection sensitivity is magnified 5 to 10 times as shown by points F and G to magnify and measure a minute change in the dynamic frictional force.
The stress reduction rate tan α during dynamic friction means the slope of the stress-reduced portion where slippage occurs between the sample cloths in the enlarged measurement diagram, and can be displayed as the stress reduction rate per 1 mm displacement of the sample cloth. It is an average value of tan αi of 20 pieces and 5 repeated measurements for one set of 100 pieces in total. When tan α is 25 g / mm or less, it has a good animal hair-like slimy feel.

(2) Soiling property after boil The test cotton is subjected to a free boil treatment for 60 minutes under the following conditions, and a sensory evaluation is performed after dehydration and drying. However, the organoleptic evaluation of sliminess indicates that ◯ is good, Δ is slightly good, and x is poor.

Boil processing conditions (3) Spinnability When the raw cotton under test was used in a normal worsted spinning process, card operability, roller winding with a gil, roller winding with a spinning machine, yarn breakage and other operability were evaluated.

As a general evaluation excluding special notes, ○ indicates good, Δ indicates slightly good, and × indicates bad.

Example 1 3 parts of a partial phosphoric acid ester of POE (9) nonylphenyl ether having an acid value of 33 (emulsifier a) was dissolved in 80 parts of water at 30 ° C., and then three kinds of silicones shown in Table 1 were stirred. Add 11 parts of each resin, then POE with phosphorylation degree 0.7 and acid value 8
(15) Three types of treating agents (a to c) were prepared by adding and mixing 6 parts of potassium phosphate partial salt of cetyl ether (antistatic agent). Table 1 also shows the evaluation results of the bath stability of the treatment agent.

A spinning dope obtained by dissolving a polymer obtained by polymerizing 90% acrylonitrile, 9.8% methyl acrylate and 0.2% sodium methallylsulfonate in an aqueous solution of soda rhodan, is wet-spun in a coagulation bath, washed with water and stretched according to a conventional method. A fiber tow obtained by heat treatment was prepared.

After dipping the fiber tow in the treatment agents (a to c) diluted so that the silicone resin concentration becomes 0.5%, squeeze so that the amount of the emulsion adhered becomes 70% of the dry weight of the fiber, and then 125 After drying for 15 minutes under hot air at ℃, 76mm to 1
Test fibers (1 to 3) were prepared by cutting unequal lengths in a range of 30 mm. The results of evaluation of the sliminess and spinnability of this fiber are also shown in Table 1.

As is clear from the results shown in Table 1, it is understood that the treating agent using the silicone resin containing the functional group bond according to the present invention satisfies both bath stability, post-boil sliminess and spinnability. .

On the other hand, the treatment agents (b and c) showed good post-boil sliminess when the antistatic agent was not mixed, but the present one-bath treatment system was not preferable because the post-boil sliminess was poor.

Example 2 Five kinds of treatment agents (d to d) were prepared in the same manner as in Example 1 No.a except that the emulsifier and the antistatic agent were changed as shown in Table 2 below.
h) was prepared, and the bath stability of these treatment agents and the post-boil sliminess and spinnability of the test fibers (4 to 8) prepared in the same manner as in Example 1 were evaluated.

The results are shown in Table 2.

From Table 2, it is clearly understood that the softening agent of the present invention comprehensively satisfies bath stability, post-boil sliminess and spinnability.

On the other hand, when an emulsifier (b) whose acid value does not satisfy the present invention is used (treatment agent e) and when an antistatic agent (-) outside the range of the present invention is used (treatment agents f to h). ) Was not able to satisfy both sliminess and spinnability.

Example 3 In the treating agent (a) described in Example 1, the ratio of the silicone resin (A), the emulsifier (B), and the antistatic agent (C) was set to the third.
6 kinds of treatment agents (i to n) by changing as shown in the table
Was produced.

Table 3 also shows the results of evaluating the bath stability of these treatment agents and the post-boil sliminess and spinnability of the test fibers (9) to (14) produced in the same manner as in Example 1.

As is clear from the results in Table 3, even if the specific (A) to (C) according to the present invention are selected, if the mixing ratios thereof deviate from the recommended range of the present invention, bath stability, No result was obtained that satisfied both sliminess and spinning property after boiling.

Example 4 In the treating agent (a) described in Example 1, the acid value of the emulsifier and the antistatic agent was changed as shown in Table 4 to prepare four types of treating agents (or).

Table 4 also shows the results of evaluating the bath stability of this treatment agent and the post-boil sliminess and spinnability of the test fibers (15 to 18) produced in the same manner as in Example 1.

As is clear from the results in Table 4, even if the specific emulsifier and antistatic agent of the present invention were selected, if their acid values were out of the recommended range of the present invention, bath stability and post-boil sliminess were obtained. However, the result that both the spinnability was satisfied was not obtained.

Example 5 Sample No. 1, 60% described in Example 1 and 40% highly shrinkable acrylic fiber having a latent shrinkability of 25% produced by a turbo stapler method by a conventional method were mixed and spun by a conventional method, 36
A count soybean yarn (meter count) was produced.

The blended yarn thus obtained is dyed, and at the same time bulkiness is imparted by expressing latent shrinkage ability, and further, two spun yarns are aligned and supplied to a 7G flat knitting machine, and knitted into a plain weave structure. It was stood and then stretched by 4% in the warp direction to give a Hoffman set.
(Knitted Fabric 1) Next, as a comparative example, a non-shrinkable acrylic resin to which only the cationic softener Sontes TA460-15 manufactured by Matsumoto Yushi Co., Ltd. was applied without performing the treatment recommended in the present invention was used as the sample No. 1 above. A knitted fabric having a plain weave structure was produced under the same conditions as above except that the knitted fabric was used instead of (Knitted Fabric 2) Table 5 shows the stress reduction rate during dynamic friction before and after washing of these knitted fabrics and the evaluation results of the sensory feeling. It can be seen that the knitted fabric using 60% of the fibers recommended in the present invention retains a good slimy feel even after washing.

Washing was carried out using a household electric washing machine at a bath temperature of 1: 200 for 10 minutes in a water temperature of 40 ° C containing 1 g / l of new beads, washed with water for 10 minutes, centrifugally dehydrated, and naturally dried on a flat plate.

[Brief description of drawings]

FIG. 1 (A) is an explanatory view of a cloth friction test apparatus used for measuring slimy feeling, and FIG. 1 (B) is a relationship between a friction resistance force recorded by the test apparatus and a sample cloth displacement amount. It is an orthogonal coordinate diagram which illustrates.

Claims (2)

[Claims] 1. A primary and _secondary compound represented by the general formula -RNHR'NH ₂ (wherein R and R'are alkylene groups having 1 to 6 carbon atoms).
Organopolysiloxane (A) having a bond with a primary amino group, polyoxyethylene (l) alkylphenyl ether or polyoxyethylene (m) se having an acid value of 14 to 60
Part of c-alkyl ether (wherein l and m represent the degree of polymerization of polyoxyethylene and have a value of 5 to 20; the alkyl group has 8 to 12 sec; the alkyl group has 9 to 17 carbon atoms) Phosphate ester (B) and polyoxyethylene (n) alkyl ether having a phosphorylation degree of 0.5 or more and an acid value of 14 or less (where n represents the degree of polymerization of polyoxyethylene and takes a value of 3 to 30, (Alkyl group has 8 to 18 carbon atoms) neutralized salt of complete or partial phosphate ester (C)
A softening agent which is stably dispersed in an aqueous medium at a ratio of 0.1 to 0.5 parts B and 0.1 to 4.0 parts C per 1 part by weight of A. 2. The bond content of amino groups in A is 0.1.
The softening agent according to claim 1, which is about 2.0 mmol / g.