JPH0253912A - Acrylic synthetic fiber and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title fiber of high durability having animal hair-toned feel and gloss by homogeneously dispersing, in advance, specific metallic compound(s) in an organic solvent solution of cellulose derivative followed by adding the resultant solution to an organic solvent solution of acrylonitrile copolymer and then making a spinning of the resultant final solution. CONSTITUTION:Firstly, at least one kind of metallic compound selected from SiO2, TiO2, ZrO2, Al2O3, Sb2O3, MgO, CaO, ZnO, SnO, Ti(OH)4, ZrO(OH)2, Al(OH)3, Mg(OH)2, Zn(OH)2, AlPO4, Ca3(PO4)2, CaSO4, BaSO4, ZnS, CaCO3, 2PbCO3.Pb(OH)2, 2PbO.PbPHO3.1/2H2O is homogeneously dispersed, in advance, in an organic solvent solution of cellulose derivative. Thence, the resultant solution is added to an organic solvent solution of acrylonitrile copolymer and the resultant solution is put to spinning, thus obtaining the objective fiber with the cellulose derivative present in a phase-separated state.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a synthetic fiber having a durable animal hair-like texture and luster, and a method for producing the same.

(Prior art) Acrylic synthetic fibers have traditionally been recognized as the fibers with the most animal hair-like texture and luster, and have been widely used in the field of imitation fur and high veils, such as pores and seals, which are designed for natural fur. There is.

In recent years, post-processing has been used to improve the texture and gloss in order to bring the texture and gloss closer to those of natural animal hair, but from the viewpoint of spinnability, it is not desirable to add a large amount of processing agents, and the effect is It is also temporary and has no durability after washing or dry cleaning. In order to overcome these drawbacks, it is preferable to make some kind of improvement at the spinning dope stage. For example, Japanese Patent Publication No. 56-44163, Japanese Patent Publication No. 564416
Publication No. 4 describes a manufacturing method in which a metal compound and a cellulose derivative are added to a spinning stock solution in which a copolymer of acryl-1-conitrile (hereinafter abbreviated as AN) is dissolved in an organic solvent. This is a synergistic effect of the interference effect of the metal compound and the phase separation effect of the AN copolymer caused by the cellulose derivative to bring the texture and luster closer to those of natural animal hair. Although it has superior washing resistance and dry cleaning resistance compared to post-processing, it is necessary to add metal compounds, especially metal compounds among cellulose derivatives, in multiple amounts to achieve a luster similar to that of natural animal hair. However, such fibers
It has the disadvantage that a large amount of metal compounds are exposed on the fiber surface, causing a significant decrease in spinnability and spinnability.

As a result of intensive research to improve the above drawbacks, the present inventors found that
The present invention was completed.

(Problems to be Solved by the Invention) An object of the present invention is to provide an acrylic synthetic fiber that is durable and has a texture and gloss closely resembling natural animal hair. Still another object is to provide a method for manufacturing such animal hair-like acrylic synthetic fibers into industrial products at low cost.

(Means for Solving the Problems) The acrylic synthetic fiber of the present invention is an acrylic synthetic fiber comprising a copolymer of AN and a cellulose derivative.
It is characterized in that the cellulose derivative exists in a phase-separated state and contains one or more selected from the following metal compounds (1). In addition, in the method of the present invention, when manufacturing acrylic synthetic fibers by wet spinning, one or more metal compounds selected from the following (1) are uniformly dispersed in advance in an organic solvent solution of a cellulose derivative, and then AN The method is characterized in that it is added to an organic solvent solution of the copolymer and then spun.

(I) S i 02. T i 02. Z r
02. A1zO3S b20a, S b209. Mg
O, CaO.

ZnO, SnO, Ti (OH)4゜Zr○(OH)
2. A7! (OH)3 M g (OH) 2. 2 n (OI() 2AI
P○4. CaJ(P 04) 2Ca S Oa
, B a S Oa Z n S , Ca
CO32PbCO,・Pb(OH)z 2 P b O-P b P I-I O3・1 /
2 H20 The A'N copolymer component used in the present invention is:
Preferably, the material contains at least 40% by weight of AN and has fiber-forming ability. That is, 40% by weight of AN
The above and other vinyl monomers, such as acrylic acid, methacrylic acid, or their alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, sodium allylsulfonate, sodium methallylsulfonate, sodium vinylsulfonate, styrene Examples include those copolymerized with a suitable combination of sodium sulfonate and the like at a ratio of 60% by weight or less. In particular, a copolymer of 80% by weight or more of AN and 20% by weight or less of a vinyl monomer and a sulfonic acid group-containing monomer, or a copolymer of 40% by weight or more of AN and 20 to 60% by weight of vinylidene chloride and a monone containing a sulfonic acid group. Copolymers containing these are preferred.

The cellulose derivatives used in the present invention are acetylcellulose, acetylpropionylcellulose, and acetylbutyrylcellulose.
．． The content is 0 to 20.0% by weight, preferably 2.0 to 10.0% by weight. If the amount of cellulose derivative is less than 1.0% by weight, a good animal hair-like texture cannot be obtained, while if it exceeds 20% by weight, it becomes difficult to produce the product industrially easily and at low cost.

The metal compound used in the present invention is silicon oxide (Si20),
Titanium oxide ("Fi 02), zirconium oxide (Z
rO□), aluminum oxide (A7!203), antimony oxide (SbzOz), magnesium oxide (MgO),
Calcium oxide (Cab), zinc oxide (ZnO), tin oxide (Sn○), titanium hydroxide (T i (OH)
4).

Zirconium hydroxide (Z r O(OH) z), aluminum hydroxide (Aρ (01()3), magnesium hydroxide (Mg(○I(>2>), zinc hydroxide (Zn(O
H)z), aluminum phosphate (A7!P○4),
Calcium phosphate (Ca, , (PO2) 3. Calcium sulfate (CaSO3)
) Barium sulfate (B a SO,l), zinc sulfide (
Z n S) Calcium carbonate (Ca COi), basic lead carbonate (2PbCQ3・Pb(OH)2), dibasic lead phosphite (2PbO-PbPHO3・1/2H20)
and 0.1 to 10.0 to the AN copolymer.
The content is preferably 0.8 to 8.0% by weight. If the amount of the metal compound is less than 0.1% by weight, good animal hair-like gloss cannot be obtained. On the other hand, if it exceeds 10% by weight, spinnability and spinnability will be reduced, and the mechanical properties of the yarn and color development during dyeing will not be adversely affected.

In the method of the present invention, most of the metal compounds are contained in the cellulose derivative by uniformly dispersing the metal compound in an organic solvent solution of a cellulose derivative in advance, and then adding it to an organic solvent solution of an AN-based copolymer and spinning. It is.

In the method of the present invention, examples of the solvent used for wet spinning include dimethylformamide, dimethylacetamide, dimethylsulfoxide, and acetone.

In the method of the present invention, the concentration of the organic solvent solution of the cellulose derivative is usually 10 to 40% by weight, or 15 to 30% by weight.
Weight%. If this concentration is less than 10% by weight, depending on the amount of cellulose derivative added, the concentration of the spinning stock solution will be lowered, which will not only make it difficult to manufacture at a low cost, but also cause a decrease in strength and elongation due to the generation of voids. etc. occur. 40 again
If it exceeds % by weight, not only will it be difficult to uniformly disperse the metal compound due to an increase in viscosity, but it will also be difficult to easily produce it industrially.

The other conditions for wet spinning are similar to those for ordinary acrylic synthetic fibers, and the spinning process is carried out through several stages of baths, sequential stretching,
Wash with water, dry, and post-process.

(Effects of the Invention) The animal hair-like acrylic synthetic fiber of the present invention has a texture that closely resembles natural animal hair, a full-dull gloss, and has the same fiber properties as ordinary acrylic synthetic fibers, and is resistant to washing. There is almost no decrease in effectiveness due to dryness or try-cleaning resistance.

The method for producing animal hair-like acrylic synthetic fibers of the present invention allows such fibers to be produced industrially easily and inexpensively using normal acrylic synthetic fiber production conditions and equipment.

Hereinafter, preferred embodiments of the present invention will be summarized.

(a) The fiber according to claim 1, wherein the acrylonitrile copolymer comprises 80% by weight or more of acrylonitrile and 20% by weight or less of a vinyl monomer and a sulfonic acid group-containing monomer, or the fiber according to claim 2. Method.

(b) The fiber according to claim 1, or the method according to claim 2, wherein the acrylonitrile copolymer comprises 40% by weight or more of acrylonitrile and 20 to 60% by weight of vinylidene chloride and a sulfonic acid group-containing monomer. .

(c) The solvent for wet spinning is dimethylborumamide.

5. The manufacturing method according to claim 4, wherein the organic solvent is dimethylace I amide or dimethyl sulfoxide.

(Example) Examples of the present invention will be described below while comparing them with comparative examples. As a comparative example, the addition amount different from the above-described addition amount and the metal compound added to the AN-based copolymer without uniformly dispersing it in the organic solvent solution of the cellulose derivative were added.
1.

Examples 1-3. Comparative Examples 1-2 Acrylonitrile (AN/methyl acrylate) (MA
)/methallyl sodium sulfonate (SMAS) = 91.
4. / 8.0 / 0.6 acrylic copolymer dimethylformamide (DMF)? Then, a DMF solution of a cellulose derivative in which a metal compound uniformly dispersed with a metal compound whose amount is shown in Table 1 below relative to the acrylic copolymer was added to the acrylic copolymer in the amount shown in Table 1. The mixture was added to the mixture and thoroughly stirred with a homomixture to obtain a spinning stock solution.

” 1 using the stock solution, 0.336 × O, 056 mm
20'C, 50% through 25002 hole flat type I'' gold
DMF water? It was spun into 8 liquids. After spinning, the solvent was removed in three baths in which the DMF concentration sequentially decreased to 30%, 20%, and 15%, and at the same time, the first stretching of 4.0 mm was performed.
Thoroughly wash in a washing tank at 60°C and apply oil 4 in the front oil tank.
81, and then dried and densified using a pot roller at 140°C. After drying, it was subjected to a 1.3x secondary stretching at 117°C sputum heat, and a 1.3x stretching at 120°C. After carrying out tension contraction of 0.9 times under heat, oiling, drying, and drying, a product of 7d was obtained.

The acrylic synthetic fibers thus obtained were passed through a corner to obtain open cotton. A sensory test was conducted by five judges using open cotton wool, and those that resembled natural animal hair in texture and luster were rated 1-◎1, and those that were somewhat similar to natural animal hair were rated ``○''.
” The difference was marked “×” and judged in two stages. In addition, the operability was judged by comprehensively evaluating the overpressure in the trench, single yarn breakage, roller winding, etc. when manufactured under the conditions described in the examples [-◎-
It was carried out in three steps: 1 [○j, rXl.

The determination results are also shown in Table 1 below.

Examples 4-6. Comparative Examples 3 to 5 AN/vinylidene chloride (VC7!2/sodium allylsulfonate (SAS) = 56.0/42.0
/ 2.0 of acrylic copolymer I) M
The F solution was subjected to semi-(+Ri).Then, the amount of the acrylic copolymer was as shown in Table 2 below. Add it to the acrylic copolymer and mix thoroughly with a homomixer! This was used as l'L spinning stock solution.

-] Using the stock solution mentioned above, 0.336 X O, 056rn
19°C159% through a flat type mouthpiece with m1000 hole
+1) MF water? It was spun into the liquid. After spinning, D
M The oil agent (=J) was applied in an oil bath, and then dried and densified with a roller at 155°C. After drying, it was subjected to secondary stretching of 1.6 times with steam heat at 115°C and] 25° The opened cotton of -C7d was subjected to tension contraction of 0.9 times under steaming of C and subjected to the usual post-treatment.The opened cotton of the acrylic synthetic fiber obtained in this way was Inspection and judgment of operation were carried out in the same manner as above.

The determination results are shown in Table 2 with -U.

[Brief explanation of the drawing]

FIG. 1 is a phase contrast micrograph (magnification: 400 mm) showing the side surface of the acrylic synthetic fiber (first bath) obtained in the present invention. Figure 1

Claims (1)

[Claims] (1) In an acrylic synthetic fiber consisting of a copolymer of acrylonitrile and a cellulose derivative, the cellulose derivative exists in a phase-separated state and one or more selected from the following metal compounds (I) are combined with cellulose. An acrylic synthetic fiber characterized by being contained in a derivative. (I) SiO_2, TiO_2, ZrO_2, Al_
2O_3, Sb_2O_3, Sb_2O_5, MgO,
CaO, ZnO, SnO, Ti(OH)_4, ZrO(OH)_2, Al(OH)_3 Mg(OH)_2, Zn(OH)_2, AlPO_4, Ca_3(PO_4)_2, CaSO_
4, BaSO_4, ZnS, CaCO_3, 2PbCO
_3・Pb(OH)_2, 2PbO・PbPHO_3・1/2H_2O (2) When manufacturing acrylic synthetic fiber by wet spinning, one or two selected from the following (I) is added to the organic solvent solution of the cellulose derivative in advance. 1. A method for producing acrylic synthetic fibers, which comprises uniformly dispersing at least one metal compound, then adding it to an organic solvent solution of an acrylonitrile copolymer, and spinning the resulting solution. (I) SiO_2, TiO_2, ZrO_2, Al_
2O_3, Sb_2O_3, MgO, CaO, ZnO,
SnO, Ti(OH)_4, ZrO(OH)_2, Al
(OH)_3, Mg(OH)_2, Zn(OH)_2, AlPO_4, Ca_3(PO_4)_2, CaSO_4, BaSO_
4, ZnS, CaCO_3, 2PbCO_3・Pb(OH)_2, 2PbO・PbPHO_3・1/2H_2O