JPS6245788A - Softening agent - 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 G) Industrial Application Field The present invention relates to a softening agent comprising a specific silicone resin, an emulsifier, and the king of antistatic agents. The contained silicone resin, specific emulsifier, and specific antistatic agent are stably dispersed in an aqueous medium in a specific ratio, giving the treated fiber a durable slimy texture, flexibility, and processability at the same time. The present invention relates to an industrially advantageous fiber softening agent.

P) Conventional technology It is well known that knitted fabrics made from animal hair fibers such as wool, cashmere, and angora rabbit hair have an excellent texture based on their unique sliminess. Attempts are being made to impart the texture unique to such animal hair fibers.

For example, Japanese Patent Publication No. 44-26436 discloses a mixed treatment agent of silico-7 resin and epoxy resin as a treatment agent for acrylic fiber products, but the texture of the final product becomes rough and hard due to the hardening of the adhesive between the fibers. Moreover, since the epoxy resin inhibits the slimy feeling imparted by the silicone resin, the commercial value of the final product is significantly reduced. on the other hand,
In Japanese Patent Publication No. 51-2556 filed by the present applicant,
A specific silicone resin and an emulsifier selected from the group of POE(n') alkylphenyl phosphates are mixed and stirred, and water is added to form a weakly acidic emulsion.
We have proposed a technical means in which the emulsion is applied to swollen gel-like acrylic fibers obtained by wet spinning, the emulsion is immediately dried, and then a spinning oil is further applied. By employing such technical means, it is possible to give acrylic fibers and their products a slimy feel, flexibility, and shrink-proofing properties that closely resemble those of animal hair fiber products. This method requires stage treatment and is not necessarily an industrially preferable method, and further improvements have been desired.

(/i Problems to be Solved by the Invention Under these circumstances, the present inventors have discovered that it is possible to simultaneously satisfy the texture and processability by coexisting an antistatic agent in the silicone emulsion bath. Various studies have been carried out to provide a treatment agent.However, when a charging agent is added to a silicone emulsion, the stability of the emulsion is significantly impaired and the treatment agent cannot be applied uniformly, making it difficult to apply the treatment agent in subsequent steps. If this is the case, it is not possible to obtain a fiber with satisfactory texture and processability, and in any case, there is inherent difficulty in simultaneously satisfying texture and spinnability. It turned out that there was.

Here, the present inventors have diligently researched a treatment agent that can simultaneously impart a durable slimy texture and workability through a single treatment, which was previously thought to be an unsolvable problem. The inventors have discovered that the desired softening agent can only be obtained by selecting a specific silicone resin, an emulsifier, and an antistatic agent, and coexisting these kings in a specific proportion, and have thus arrived at the present invention.

That is, an object of the present invention is to provide a softening agent that can simultaneously impart a durable slimy texture and processability such as spinnability through film treatment.

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

Another object of the present invention is to provide a versatile softening agent that can be applied to fibers in a desired raw cotton production process, such as immediately after spinning or after heat treatment, and can be applied to various brands of fibers. That's true.

Further objects of the invention will become apparent from the description below.

The softening agent according to the present invention for achieving the above object is represented by the general formula -RNHRNH2 (where R and R' are Alkyrev groups having 1 to 6 carbon atoms). organopolysiloxane (A) containing combined primary and secondary amino groups,
POE (d) alkylphenyl ether or POE (m) 5ec-7/l/-¥-/ with an acid value of 14 to 60
l/ether (m, 1% m is the degree of polymerization of polyoxyethylene):/acid ester CB), and POE (n) alkyl ether with a phosphorylation degree of 045 or higher (however,
The completely or partially neutralized salt (C) of phosphoric acid ester (n is the degree of polymerization of polyoxyethylene) contains 0.1 to 0.5 parts of B and 0.1 to 4.0 parts of C per 1 M part of AO. It is stably dispersed in an aqueous medium at a ratio of .

The present invention will be explained in detail below.

If, the organopolysiloxane (A) according to the present invention is
General formula -RNHR'NH2 (where R, R' has 1 carbon number
It is a silicone resin that has primary and secondary amino groups as essential functional groups bound to the alkylene group of ~6. The emulsion can be made into cloth, and the treated fibers can be given a durable slimy texture and processability. In addition, the bond content of such amino groups is Q, i ~2. Q m mo
l/g, more preferably 0.2 to 1. Ommol/
It is preferable to use a silicone resin having a molecular weight of ff1100, ff100, and ff100, from the viewpoint of viscosity, workability, etc.
000 or less silicone resin is recommended.

Next, as an essential emulsifier in the present invention, [select 7E
, POE(e) alkylphenyl ether or POE(
m) Partial phosphate ester of sec-alkyl ether (1.mid degree of polymerization of polyoxyethylene) (B)
1-j.

e is 5 to 20, more preferably 6 to 10, m is 5 to 20
, more preferably I to 7 to 10, and the alkyl group has 8 to 12 carbon atoms, and the sec -alkyl group has 9 carbon atoms.
~17 and an acid value of 1.4~60, preferably 25~45, together with the above specific silicone resin (A), the texture and spinning properties are improved. This is desirable because it can further improve properties such as properties and bath stability. Note that such emulsifiers include, for example, POE
(7) Octylphenyl ether, POEt8) Octylphenyl ether, POEt9) Octylphenyl ether, POE 17) Nonylphenyl ether, P
OE 18) Nonylphenyl ether, POEL91
Nonylphenyl ether, POE (10) dodecylphenyl ether, Ninio/Carpai)] TERGITO
Partial phosphoric acid esters such as L 13'-s and 15-8.45-8 can be mentioned.

Further, in the completely or partially neutralized phosphate salt (C) of POE(n) alkyl ether coexisting in the treatment agent as an essential antistatic agent in the present invention, n is 3 to 30, more preferably 5 to 20. and the number of carbon atoms in the alkyl group is 8
-18, more preferably 12-16, and the degree of phosphorylation (the ratio of sulfur to the total amount of the antistatic agent/acid ester neutralized salt) is 0.5 or more, more preferably 0. .6
~0.9 and an acid value of 14 or less is desirable because the object of the present invention can be achieved more effectively. In addition, such antistatic agents include:
P OE (51 octyl ether, P OE (5)
Dodecyl ether, POE (10) Cetyl ether, POE (15) Cetyl ether, POE (20
) Examples include completely or partially neutralized salts of phosphoric acid esters such as stearyl ether, and there are no limitations on the types of phosphoric acid ester intermediate salts, such as strong salts such as potassium salts and sodium salts. It is desirable to employ basic salts.

Furthermore, the mixing ratio of the above A and C components is 0.1 to 0.1 to 0.1 to 0.1 parts by weight of the emulsifier (B) per 1 part by weight of the silicone resin (A).
5 parts, preferably 0.2 to 0.4 parts, also an antistatic agent (C
) is 0.1 to 4.0 parts, preferably 0.2 to 2.0 parts,
More preferably, it is necessary to prepare the emulsion so that it is within the range of 0.3 to 1.0 parts; if the mixing ratio is outside the range recommended for the present invention, a stable emulsion cannot be produced. Furthermore, it is not possible to impart a durable slimy feel or good processability to the treated fibers.

In particular, it is preferable to set the silicone resin (A) and the emulsifier (B) as defined by the following relational expression, since the object of the present invention can be achieved more effectively.

38N≦X≦105N (However, the bond content (m mol/7) of amino groups in the silicone resin (A), and X indicates the acid value of the emulsifier (B).) The preparation method is not limited in any way as long as the A and C components can coexist in the above proportions, but for example, after dissolving the emulsifier (B) in an aqueous medium with stirring, the silicone resin (A ), and then adding and mixing a predetermined amount of the antistatic agent (C). In addition, as an aqueous medium,
Although industrial water alone is preferred, a mixed solvent of water and a water-miscible organic solvent (for example, alcohols, ketones, etc.) may also be used as long as the desired emulsion can be produced. Also, handling considerations such as viscosity and emulsifying properties.

Approximately 30-70'C, more preferably 35-60'C
It is desirable that the total amount of the h=c component be at a concentration of 50% or less, preferably 30% or less based on the total weight of the processing agent at a temperature of .

The type of fibers to be treated to which the softening agent of the present invention is applied is not limited in any way; This is desirable because the amino groups bonded and contained in the silicone resin form strong ionic bonds with the acidic groups present in the fibers to be treated, thereby significantly improving the durability of the texture.

The weight at which the softening treatment according to the present invention is applied to the fibers to be treated should be determined as appropriate considering the desired texture, type of fibers to be treated, etc., but the dry weight of the fibers to be treated It is desirable that the silicone resin (A) in the treatment nj be deposited in a range of approximately 0.05 to 2.0%.

Town Effects of the Invention By applying the softening agent according to the present invention, which is formed by stably dispersing the above-mentioned specific silicone resin, emulsifier, and antistatic agent in a specific proportion in an aqueous medium, a small amount of adhesion and a further improvement can be achieved. A noteworthy effect of the present invention is that it is possible to impart a durable slimy texture and processability such as spinnability to the treated fibers only through the treatment process.

In addition, the softening agent with excellent bath stability according to the present invention can be applied uniformly to the fibers to be treated with good operability, and in the subsequent raw cotton manufacturing process, yarn breakage and winding occur in each process such as spinning. A characteristic advantage of the present invention is that the feel of the treated fibers can be significantly improved without causing such troubles.

The advent of the present invention, which relates to a fabric softener that can simultaneously satisfy such a durable slimy texture and processability in a single bath treatment, has made it possible to create an animal hair-like slimy texture while taking advantage of the advantages of the treated fibers. This will make a major contribution to the field of providing information.

Examples In order to further facilitate understanding of the present invention, typical examples will be described below, but the gist of the present invention is not limited in any way by the description of these examples. In addition, unless otherwise specified, all parts and percentages are expressed on a weight basis. In addition, the stress reduction rate during friction friction, the slippage after the country foil, and the gravitation properties shown in the examples were measured by the following methods.

tll Stress reduction rate tanα during dynamic friction The stress reduction rate tanα during dynamic friction is determined by enlarging and measuring the kinetic friction force between the sample fabrics using the fabric friction test device shown in FIG. 1 (5). To explain in more detail using the first direction, 22'C
In a humidity-controlled atmosphere with a relative humidity of 65%, the sample cloth 1 is placed on the sample stage 2, one end is fixed with a sample holder 3, and the other end is
The effective contact area 3r is maintained in tension by applying a load 4 of 0y, and a compressive load 5 of 450y is applied thereto.
d (2clII x 1.5 (7)) is placed, the sample piece 7 is fixed on the bottom surface of the spheroid 6, and the sample stage 2 is set at 12 ax
The friction force generated between the sample cloths is detected by a resistance wire strain meter 8 connected to the Nufida 6, and recorded by a recorder 9. During measurement, the recorder was zero-shifted when the dynamic friction force showed a steady state, and then points F and G were
As shown in the figure, the detection sensitivity is expanded 5 to 10 times to measure minute changes in the dynamic friction force. Stress reduction rate ta during dynamic friction
nα means the slope of the stress reduction part where sliding occurs between the sample cloths in the enlarged measurement diagram, and can be expressed as the stress reduction rate per 1 g of the sample cloth position,
1. 20 pieces of the original sample and 5 repeated measurements, total 1
This is the average value of 00 tanαi.

In addition, tanα is 25! /! When it is below IN, it has a good slimy feeling like animal hair.

(2) Slimy injection after boiling The sample raw cotton was free-boiled for 60 minutes under the following conditions.
Sensory evaluation is performed after dehydration and drying.

However, in the sensory evaluation of sliminess, ○ indicates good, △ indicates slightly good, and × indicates poor.

Boil processing conditions (3) Spinability When spinning the sample raw cotton in a normal worsted spinning process, evaluate overall operability such as card passability, roller winding on the gill, roller winding on the spinning machine, yarn breakage, etc. I did it.

As for the overall evaluation excluding special notes, ◯ indicates good, △ indicates somewhat good; × indicates poor.

Example 1 After dissolving 3 parts of POE (9) partial phosphoric acid ester of nonylphenyl ether (emulsifier A) with an acid value of 33 in 80 parts of 30'C of water, the three types listed in Table 1 were dissolved under stirring. By adding 11 parts each of silicone resins, and then adding and mixing 6 parts of POE (15) cetyl ether partial phosphate potassium salt (antistatic agent ■) with a degree of phosphorylation of 0.7 and an acid value of 8. Table 1 also shows the evaluation results of the bath stability of the 0 treatment agents for which three types of treatment agents (a, c) were prepared.

Acrylonitrile 90%, methyl acrylate 9.8%
A spinning stock solution obtained by dissolving a polymer copolymerized with 0.2% sodium methalyl sulfonate in an aqueous solution of rhodan soda was wet-spun in a coagulation bath, washed with water, stretched, and heat-treated according to conventional methods. The resulting fiber tow was prepared.

The fiber tow is immersed in treatment agents (a-c) diluted to have a silicone dark fat concentration of 0.5%, and then squeezed so that the amount of emulsion applied is 70% of the dry weight of the fiber. , then after drying for 15 minutes under hot air at 125
76 [from 1301! Test fibers (1 to 3) were prepared by cutting the fibers into unequal lengths within the IM range. The results of evaluating the sliminess and spinnability of this fiber are also listed in Table 1.

Chapter 1 Table (Note) ○ indicates good, Δ indicates somewhat good, and × indicates poor.

(The same applies to the following Examples) As is clear from the results in Table 1, the treatment agent using the silicone resin containing a functional group according to the present invention has excellent bath stability, sliminess after peeling, The fact that they can be sexually satisfied together is understood.

On the other hand, treatment agents (b and C) showed good post-boiling sliminess when no antistatic agent was mixed, but the present one-bath treatment system had poor post-boiling sliminess and was not desirable. Ta.

Example 2 Five types of processing agents (dh) were prepared in the same manner as in Example I No. a, except that the emulsifier and antistatic agent were changed as shown in Table 2 below. The bath stability, and the slime property and spinnability after boiling of the test fibers (4 to 8) produced in the same manner as in Example 1 were evaluated.

The results are shown in Table 2.

Table 2 (Note 1) Emulsifier port: Same as emulsifier A except that the acid value is 10.

(Note 2) Antistatic agent ■: Cetylhonufate potassium salt (
Acid value: 2 (Note 2) Antistatic agent ■: POE (15) Partial phosphate ester of cetyl ether Triethanolamine salt (degree of phosphorylation 0.7, acid value 50) ■ Nidimethylstearyl betaine From Table 2 It is clearly understood that the softening agent of the present invention comprehensively satisfies bath stability, post-boiling sliminess, and spinnability.

On the other hand, when an emulsifier whose acid value does not satisfy the present invention (processing agent e) is used, and when an antistatic agent (■ to ■) outside the scope of the present invention is used (processing agent f, Regarding h), it was not possible to satisfy both the sliminess and spinnability.

Example 3 In the treatment Ml (a) described in Example 1, six types were prepared by changing the proportions of silicone resin (A), emulsifier (B), and antistatic agent (C) as shown in Table 3. Treatment agent'(
i-jn) was produced.

The bath stability of these treatment agents and the test fibers prepared using Palm-C similar to those in Example 1 and Table 3, 9) to 14). The results of evaluating the sliminess and spinnability after boiling are also listed in Table 3.

As is clear from the results in Table 3, even if specific (A) to (C) according to the present invention are selected, if their mixing ratio is outside the recommended range of the present invention, the bath No results were obtained that satisfied the stability, sliminess after boiling, and spinnability.

Example 4 In the treatment agent ta) described in Example 1, the acid values of the emulsifier and antistatic agent were changed as shown in Table 4 to prepare four volatile treatment agents (0 to r).

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

As is clear from the results in Table 4, even if specific emulsifiers and antistatic agents of the present invention are selected, if their acid values are outside the recommended range of the present invention, the bath stability and boiling No results were obtained that satisfied both wetness and spinnability.

Example 5 1.60% of the sample NIIL described in Example 1 and 40% of high shrinkage acrylic fibers having a latent shrinkage of 25% produced using a turbo stapler in a conventional manner were mixed and spun to obtain 36% Made from double thread (meter count).

The resulting blended yarn is introduced and dyed, and at the same time, the latent shrinkage ability is brought out to give it bulkiness, and the spun yarn is further dyed.
The fabric was fully aligned and fed to a 7G flat knitting machine, knitted into a jersey texture, then stretched 4% in the warp direction and subjected to a Hoffman set. Next, as a comparative example, a cationic softener manufactured by Matsumoto Yushi Co., Ltd. was used without the treatment recommended in the present invention.
The same conditions as above were followed except that a non-shrinkable acrylic fiber to which only TA460-15 was attached was used as a substitute for Sample No. 1, except that the netting of the jersey texture was omitted. (Knitted Fabric 2) Table 5 shows the stress reduction rate and sensory texture evaluation results during dynamic friction of these knitted fabrics before and after washing. 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.

For washing, use a household electric washing machine, New Beads 1y/1
10 at a bath ratio of 1:200 in hot water at 40"C with the addition of
After rinsing with water for 10 minutes, the mixture was centrifuged and dried naturally on a flat plate.

Chapter 5 Table

[Brief explanation of drawings]

Figure 1 (A-) is an explanatory diagram of the fabric friction test device used to measure the slimy feeling, and Figure 1 (B) is the frictional resistance force and sample surface displacement recorded by the test device. FIG. 2 is a rectangular coordinate diagram illustrating the relationship between Purification of the drawing (no change in content) City + m = 8) Notes are the main correct reading (method) % formula % 1. Indication of the incident Legal patent application 1960-184519 2. Name of the invention Soft treatment agent 3 , Relationship with the case of the person making the amendment Patent application colonel Address: 2-2-8-4 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture;
Date of amendment order

Claims (1)

[Claims] 1. Primary and secondary compounds represented by the general formula -RNHR'NH_2 (where R and R' are alkylene groups having 1 to 6 carbon atoms)
Organopolysiloxane (A
), POE (l) alkylphenyl ether or POE (m) sec-alkyl ether (
However, l and m are partial phosphoric acid ester (B) of polyoxyethylene polymerization degree), and P with a phosphorylation degree of 0.5 or more.
OE(n) Completely or partially neutralized salt of phosphoric acid ester of alkyl ether (where n is the degree of polymerization of polyoxyethylene) (C) contains 0.1 to 0.5 parts of B per 1 part by weight of A. A softening agent comprising C stably dispersed in an aqueous medium in a proportion of 0.1 to 4.0 parts. 2. The bond content of amino groups in A is 0.1 to 2.
The softening agent according to claim 1, which has a content of 0 mmol/g. 3. The softening agent according to claim 1, wherein the bond content of amino groups in A and the acid value of B satisfy the following relational expression. 38N≦X≦105N N: Bond content of amino groups in A (mmol/g) X: The softening agent according to claim 1, wherein the acid value of B is 4 and the acid value of C is 14 or less. .