JP2937677B2 - Durable shape fixing method for protein fiber products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a durably shaped solid titration of the protein fiber product, such as wool fiber or wool fiber products.
More specifically, a flat protein fiber product is permanently set on a flat surface, or a pleat is formed on the protein fiber product.
The or folds relates permanently imparted shape solid conventional method.

[0002]

2. Description of the Related Art Conventionally, as a fixing agent used in a durable shape fixing method for a protein fiber product of this kind, a setting agent containing a reducible sulfur-containing organic compound capable of cleaving disulfide bonds of wool fiber is disclosed in Japanese Patent Publication No. 37 (1988). No. -3099. This shape fixing agent is a setting agent containing a thiol compound such as ammonium thioglycolate. By heating the wool fiber product in the presence of this shape fixing agent to cleave the disulfide bond of the wool fiber and simultaneously recombining the disulfide bond in a state where the wool fiber is fixed in a predetermined shape, the wool fiber product is permanently Can be set to It has also been proposed to use monoethanolamine bisulfite or monoethanolamine sulfite instead of ammonium thioglycolate.

Further, JP-A-4-163369 discloses a durable shape fixing agent for protein fiber products mainly containing cysteine or a cysteine derivative. This cysteine or cysteine derivative is a setting agent containing a sulfur-containing amino acid thiol compound. Examples of the sulfur-containing amino acid-based thiol compound include D-cysteine, L-cysteine, a mixture thereof such as a racemate, or a cysteine derivative thereof. This cysteine derivative includes N
N-acyl-cysteine such as -acetyl-L-cysteine, N-caproyl-L-cysteine, N-propionyl-L-cysteine, N-palmitoyl-L-cysteine, or a salt thereof (sodium salt, potassium salt, ammonium salt) , Hydrochloride, etc.), organic acid salts (acetate, etc.) and esters (methyl, ethyl, propyl, etc.).

Although ammonium thioglycolate contained in the setting agent of Japanese Patent Publication No. 37-3099 certainly acts on wool fibers, it causes damage to the fibers due to swelling and has a large effect on dyes. The hue of the product may be changed. In addition, ammonium thioglycolate has the property of causing a color reaction due to metal ions such as iron, and has a disadvantage of discoloring under the influence of a trace amount of metal in dirt on containers and textiles, causing discoloration of textiles. . Further, ammonium thioglycolate easily oxidizes upon contact with air, and therefore has the drawback of extremely poor solution stability and poor workability.

When reducing wool fibers using a durable shape fixing agent containing monoethanolamine bisulfite or monoethanolamine sulfite, hydrogen sulfide,
In particular, sulfur dioxide gas, ammonia and the like were generated little by little over a long period of time, giving rise to the disadvantage of giving off odor. This bad smell disappears temporarily due to drying, but it becomes odor again when it absorbs water, and monoethanolamine bisulfite and monoethanolamine sulfite have strong reducing properties, causing discoloration and disulfide bonding. This caused embrittlement of wool fibers during cutting. In addition, either monoethanolamine bisulfite or monoethanolamine sulfite generates aminoacrylic acid residues during the reaction, which residues not only result in poor shape fixation of the wool fiber product, but also Increased radicals have led to yellowing of wool fiber products.

[0006] Cysteine or a derivative thereof, which is a sulfur-containing amino acid thiol compound described in JP-A-4-163369, is recombined with a disulfide bond to form the setting agent of JP-B-37-3099. Although the drawbacks can be improved, there is still a problem with the durable fixation of bonds involving active hydrogen, which is an important factor in durably fixing the shape of protein fiber products, and the treatment effect is still insufficient There was no problem. In addition, as with ammonium thioglycolate, cysteine is easily oxidized by contact with air or water, resulting in extremely poor solution stability and poor workability. There was a drawback to make it a good product.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a protein fiber product which can stably retain its shape even when the shape once applied to the protein fiber product is exposed to hot water or steam. and to provide a durable shape solid titration. Another object of the present invention is to provide after the time of form-locking and form-locking discoloration of protein fiber products, durably shaped solid titration not cause malodor or embrittlement. Still another object of the present invention is to provide a durable shape solid titration of never cause precipitation of white powdery substance on the protein fiber product protein fiber product.

[0008]

The invention according to claim 1 of the present invention provides a cysteine and a cysteine derivative.
Adhering a durable shape fixative containing a protein compound to protein fiber products
Durable shape fixing method for protein fiber products to be
The cysteine include <br/> emissions compound 39.0 wt% or more, the cysteine derivative when the cysteine compound 100 mol% when the shape fixing agent and 100 wt%
In a N- acyl - cysteine or a salt thereof comprises at least 50 mol%, and the protein fiber product, characterized in that to 0.1 to 1.2% owf attaching said durably form-locking agent to the protein fiber product Durable shape fixing method. According to a second aspect of the present invention, the durable shape fixing agent according to the first aspect further comprises an oxirane compound capable of binding to active hydrogen of the protein fiber, and the oxirane compound is added to the protein fiber product in an amount of 0.3%. It is a durable shape fixing method for protein fiber products to be adhered to 3.0% owf. Furthermore the invention according to the claims 3, durably form-locking agent according to claim 2 further comprises a protein hydrolyzate, from 0.12 to 4 the protein hydrolyzate with respect to the protein fiber product. This is a durable shape fixing method for protein fiber products to which 8% owf is attached.

Hereinafter, the present invention will be described in detail. The protein fiber product of the present invention includes wool, mohair, cashmere, alpaca and other animal hair fibers, silkworms, cocoon fibers obtained from cocoons of wild silkworms, etc., or wool, silk, or these fibers or yarns made from these fibers. Woven, knitted and non-woven fabrics. The protein fiber products include blended products with other fibers, for example, polyester fibers, cellulose fibers, acrylic fibers, etc .;

The cysteine compounds contained in the durable shape fixing agent are cysteine and cysteine derivatives. As cysteine, L-cysteine, D-cysteine, DL
-Cysteine or salts thereof. As cysteine derivatives, N-acetyl-cysteine,
Examples thereof include N-acyl-cysteine such as N-caproyl-cysteine and salts thereof, and cysteine esters such as cysteine methyl ester and salts thereof. These cysteine derivatives may be optically active or optically inactive racemic. The cysteine compound is a main component of the durable shape fixing agent,
39.0 when the durable shape fixing agent is 100% by weight.
It must be contained in an amount of at least% by weight. When the content is less than 39.0% by weight, -SH between the shape fixing agent and the protein fiber is reduced.
This is because the exchange reaction between the group and -SS- is not sufficiently performed, and the effect of fixing the shape is uncertain. Further
Cysteine compound consisting of stain and cysteine derivatives
It is necessary that the product contains 50 mol% or more of N-acyl-cysteine which is a cysteine derivative or a salt thereof when the cysteine compound is 100 mol%. This 50
The reason is that the cysteine is easily oxidized due to contact with air or water during the treatment to precipitate a white powdery substance, while the processing solution of the protein fiber product is stabilized.
Acyl-cysteine or a salt thereof dissolves white powder to prevent precipitation of white powder of cystine on the protein fiber product after shape fixation. When the amount of N-acetyl-L-cysteine is less than 50 mol%, the white powder of cystine has poor dissolving power and white powder remains. The remaining amount of the cysteine compound excluding N-acyl-cysteine or a salt thereof is not particularly limited.

The oxirane compound capable of binding to active hydrogen of the protein fiber is a polyglycidyl ether compound having a water solubility (dissolution rate of 10 parts of the oxirane compound in 90 parts of water at room temperature) of 20% or more. is there. Examples of this oxirane compound include polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, polypropylene glycol diglycidyl ether, and diglycerol polyglycidyl ether. The oxirane compound is a polyglycidyl ether compound having at least two epoxy groups, and needs to have a water solubility of 20% or more. When the water solubility is not 100%, a low-boiling solvent that is freely miscible with water is used and can be prepared by a known self-emulsification method.

[0012] Examples of the protein hydrolysis product include collagen and collagen derivatives, all of which must be water-soluble. The protein hydrolysis product is a hydrolyzed collagen derived from water-soluble collagen, and has a wide molecular weight distribution depending on the degree of hydrolysis. Therefore, in the present invention, the molecular weight is 1,500 to 15,000.
Are preferred. When the molecular weight is less than 1,500, it is difficult to obtain a sufficient treatment effect, and the protein fiber product may be yellowed during the adhesion treatment. Further, the molecular weight is 15.0.
If it exceeds 00, the treatment effect can be sufficiently obtained, but the texture of the treated cloth becomes coarse and hard, deviating from a practical range.

Use of the above fixing agent in a durable shape fixing method
Sometimes, the deposition amount of the protein fiber product of cysteine and cysteine derivatives 0.1% owf (on the weight of fib
er) At least 1.2% owf, or 0.1% of cysteine and cysteine derivative attached to protein fiber product
owf to 1.2% owf, and the adhesion amount of the oxirane compound to the protein fiber product is 0.3% owf to 3.0%
owf. When the durable shape fixing agent contains an oxirane compound and a protein hydrolyzate, the amount of cysteine and cysteine derivative attached to the protein fiber product is set to 0.1.
1% owf or more and 1.2% owf, and the adhesion amount of the oxirane compound to the protein fiber product is 0.3% owf or more and 3.0%
owf, the amount of protein hydrolyzate adhering to the protein fiber product is 0.12% owf or more and 4.8% owf, and the three are combined in these ranges.

If the amount of cysteine and cysteine derivative adhered to the protein fiber product is less than 0.1% owf, a sufficient and sufficient durable shape fixing performance cannot be obtained, and the amount of adhered cysteine and cysteine derivative is 1.2% owf. If it exceeds, the residual amount of cysteine and cysteine derivative increases after the treatment, which has an adverse effect.
0.3% o adhesion of oxirane compounds to protein fiber products
If it is less than wf, a sufficient durable shape fixing effect cannot be obtained, and if it exceeds 3.0% owf, a processing effect can be obtained but the texture becomes hard, which is not preferable. If the amount of the protein hydrolyzate adhered to the protein fiber product is less than 0.12% owf, a sufficient durable shape fixing effect cannot be obtained, and 4.8.
If it exceeds% owf, the processing effect is sufficiently obtained,
The texture of the treated cloth becomes coarse and hard, deviating from the practical range.

[0015] The durable shape fixing agent of the present invention is applied to a protein fiber product by spraying or spraying the same or by impregnating the protein fiber product with a padding mangle and impregnating the protein fiber product. Given to goods. The protein fiber product to which the durable shape fixative has been applied is then dried, heat-treated, boiled, steamed, embossed,
A predetermined shape is given by a conventionally known method such as twisting, crimping, and wrinkling.

[0016]

The reaction mechanism between the durable shape fixing agent of the present invention and protein fibers has not been clarified. However, an exchange reaction of -SH group and -SS- occurs between the shape fixing agent and the protein fiber, and -SH group and epoxy group, active hydrogen and epoxy group, active hydrogen and epoxy group of collagen, and -SH group It is considered that an interaction between the active hydrogen and the epoxy group and between the active hydrogen of the collagen and the epoxy group have occurred. As a result, sufficient durable shape fixing performance can be obtained at a low concentration. By adding surfactants, wetting agents, swelling agents, water repellents, etc. to this durable shape fixing agent, the exhaustion to protein fibers is further improved, and sufficient durable shape fixing performance at low concentrations Is obtained.

[0017]

Next, examples of the present invention will be described together with comparative examples. The embodiment shown here is an example and does not limit the technical scope of the present invention. <Contents of treatment agent> Molecular weight 121.1 manufactured by Ajinomoto Co. as cysteine
L-cysteine (hereinafter referred to as L-cys) of No. 6 as a cysteine derivative having a molecular weight of 16 from Ajinomoto Co., Inc.
3.2 N-acetyl-L-cysteine (hereinafter Ac-
That L-cys) or Ajinomoto Co., Ltd., having a molecular weight of 171.
66 L-cysteine-methyl ester hydrochloride (hereinafter, referred to as L-cysteine-methyl ester hydrochloride)
Me-L-cys) was used. As the oxirane compound, the trade name of polyethylene glycol diglycidyl ether series manufactured by Nagase Kasei Kogyo Co., Ltd. is Denacol E
X-850 (hereinafter referred to as 850) or Nagase Kasei Kogyo
The trade name of a glycerol polyglycidyl ether type manufactured by Co., Ltd. is Denacol EX-313 (hereinafter referred to as 313).
Were used. As a protein hydrolysis product, collagen W10K (hereinafter referred to as W10K) having a brand name of collagen acid hydrolyzate manufactured by Amano Pharmaceutical Co., Ltd. was used.
As a penetrating and wetting agent, a penetrant-based polyoxyethylene deseal ether (n = 6) (hereinafter referred to as Nonion) manufactured by NOF Corporation or a swelling agent-based ethylene glycol manufactured by NOF Corporation (hereinafter, referred to as Nonionic). EG).

<Example 1> A worsted yarn of 2/72 m count was used as a warp, and a worsted yarn of 2/60 m count was used as a weft. The warp density was 50 yarns / cm and the weft density was 28.
A wool gabardine cloth having a 1/3 structure with a basis weight of 210 g / m ² woven at a density of book / cm was prepared. A treatment solution having the formulation shown in Table 1 below was uniformly applied to the wool cloth at a pickup rate of 55% using a two-roll mangle padder.
Extend and fix 5% each in the longitudinal and weft directions and
The treated cloth of Example 1 was obtained by drying at 0 ° C. for 10 minutes.

[0019]

[Table 1]

<Comparative Example 1> The same wool cloth as in Example 1 was prepared, and a treatment solution having the formulation shown in Table 2 below was applied to this wool cloth. A treated cloth was obtained. That is, in Comparative Example 1, 850, 3 used in Example 1 were used.
13. In Formula 7, only L-cys was used without using cysteine derivatives without using W10K. (Hereafter, this page margin)

[0021]

[Table 2]

<Embodiment 2> A treatment liquid having the formulation shown in Table 1 above was applied to both sides of the same wool cloth as in Embodiment 1 by a hand spray gun using compressed air of 2.0 kg / cm ² at 40%.
It sprayed so that the amount of owf might be attached. The wool cloth to which the treatment liquid has adhered is applied to a steam press (Hoffman press).
After steaming for 0 seconds, baking was performed for 30 seconds, followed by vacuuming for 10 seconds. The steam pressure during steaming was 4.5 kg / cm ² , and steam was simultaneously sprayed on both sides of the wool cloth. After vacuuming, the wool cloth was air-dried to obtain a treated cloth of Example 2.

<Comparative Example 2> The same wool cloth as in Example 1 was prepared, and a treatment solution having the formulation shown in Table 2 was applied to this wool cloth. A treated cloth was obtained.

<Evaluation Method and Results> Example 1 and Comparative Example 1
The 9% test cloths obtained in the above were evaluated for 5% elongation fixing ratio, shape fixing ratio, and white powder deposition state by the following methods. The nine types of test cloths obtained in Example 2 and Comparative Example 2 were evaluated for the state of white powder deposition and the durability test of the fold by the following methods. (a) 5% elongation and fixing rate On a test cloth of about 25 cm x 25 cm, set it upright and 20 cm wide
Marking is made at intervals, and the test cloth is impregnated with test treatment liquids of 9 types. After squeezing the test cloth to 55%, the length of the test cloth stretched and fixed by 5% (hereinafter referred to as _L5w ) is measured based on the length between the markings. In this state, the test cloth dried at 100 ° C. for 10 minutes and then released from the fixed state after drying was dried, containing 0.1% of a nonionic surfactant.
After immersion in an aqueous solution of 30 ° C. for 30 minutes, the test cloth is taken out and the water is lightly removed. Then, after leaving for 24 hours at a temperature of 25 ° C. and a relative humidity of 65%, the length between the markings (hereinafter referred to as _L5D ) is measured. The above L _5w and L _5D are substituted into the following equation to obtain a 5% elongation fixed ratio. 5% stretch fixing rate (%) = (L _5D / L _5W ) × 100 (%) Table 3 shows the 5% stretch fixing rate of each test cloth of Example 1 and Comparative Example 1.

(B) Shape fixation ratio The appearance of the test cloth at the time of measuring the _L5D in the above (a) is shown in I.
W. S's “Gentleman Suit Appearance Retention Standard Judgment Photo Book”
Was evaluated in comparison with the first to fifth grades of bubbling judgment criteria. It should be noted that the higher the grade of the judgment criterion, the better, the fifth grade is the best, and the first grade is the worst. Table 3 shows the shape fixing ratio of each test cloth of Example 1 and Comparative Example 1.

(C) White Powder Precipitation State The state of generation of white powdery substances on the treatment liquid and the test cloth as the treatment cloth was visually examined. Table 3 shows the white powder deposition state of each test cloth of Example 1 and Comparative Example 1, and Table 4 shows the white powder precipitation state of each test cloth of Example 2 and Comparative Example 2.

(D) Fold durability test A total of 4 from the top and bottom of the two folds attached to the test cloth
Cut a piece of woven fabric from the book, i.e., 1 cm in the length direction of the fold and 2 cm in width from the fold. Five crimped pine needle-shaped threads are loosened from each piece of fabric. After immersing them in water at 25 ° C. containing 0.1% by weight of a penetrant for 2 minutes, the fold angle (opening angle) of the yarn in the water is measured from above using a protractor. Then, the average of the opening angles of a total of 20 yarns was determined.
The smaller the opening angle is, the more excellent the durability of the fold is.
It must be within 0 degrees. Table 4 shows the opening angles of the folds in Example 2 and Comparative Example 2.

[0028]

[Table 3] (Hereafter, this page margin)

[0029]

[Table 4]

As is clear from Tables 3 and 4, the 5% elongation fixing ratio of Comparative Example 1 was as low as less than 93%, whereas the 5% elongation fixing ratio of Example 1 was less than 93%. In each case, a high value of 93% or more was shown. In addition, the shape fixing ratios of Comparative Example 1 were all quaternary or less, whereas the shape fixing ratios of Example 1 were all quaternary to quintic. In Comparative Examples 1 and 2, white powder was precipitated in all cases except Formulation 6, whereas in Examples 1 and 2, no white powder was precipitated. Further, the fold opening angle of Comparative Example 2 exceeds 70 degrees, whereas the fold opening angle of Example 2 is 70 degrees.
Less than a degree. From these results, it was found that Examples 1 and 2 were superior to Comparative Examples 1 and 2 in shape fixation and appearance. Then

[0031]

As described above, by treating with the shape fixing agent of the present invention, even if the shape given to the protein fiber product is exposed to hot water or steam, the shape is stably maintained. be able to. In particular, N-acyl-cysteine or a salt thereof contained in this durable shape fixing agent has an ability to prevent the precipitation of white crystals of cystine, and the oxirane compound or the protein hydrolyzate has a higher shape than the conventional shape fixing agent. Improve the fixing ability and its durability. This durable shape fixing agent can avoid malodor due to its reduction reaction mechanism, discoloration, embrittlement and yellowing of protein fiber products. Furthermore,
By using this durable shape fixing agent for boiling, steaming, twisting, forming folds, and the like, it is possible to obtain an extremely high shape fixing processing ability as compared with the related art.

Continuation of the front page (72) Inventor Masazumi Date 1-15-1, Kyobashi, Chuo-ku, Tokyo Ajinomoto Co., Inc. (56) References JP-A-4-163369 (JP, A) JP-A-2-216263 (JP, A) JP-A-63-35885 (JP, A) JP-A-6-57631 (JP, A)

Claims (3)

(57) [Claims] (1) a cysteine and cysteine derivative;
Durable shape fixing agent containing cysteine compound
Durable shape fixing method for protein fiber products attached to
Te, wherein said cysteine compound 39.0 wt% or more when the durable shape fixing agent is 100 wt%, wherein the cysteine compounds when 100 mol%
A cysteine derivative N-acyl-cysteine or a salt thereof in an amount of 50 mol% or more , and the durable shape fixing agent is 0.1
A durable shape fixing method for a protein fiber product, characterized in that the fiber fiber is adhered by 1.2% owf. 2. A method comprising cysteine and cysteine derivatives.
Cysteine compound can bind to active hydrogen of protein fiber
Durable shape fixing agent containing oxirane compound
A durable shape fixation of the protein fiber product to be attached to, wherein the cysteine compounds 39.0 wt% or more when the durable shape fixing agent is 100 wt%, and 100 mol% of the cysteine compounds When said
Is cysteine derivative N- acyl - comprises cysteine or a salt thereof 50 mol% or more, 0.1 to the durably form-locking agent to the protein fiber product
1.2% owf adhered, and durable shape fixation of the protein fiber product, characterized in that to 0.3 to 3.0% owf adhesion relative to the oxirane compound the protein fiber product. 3. A method comprising cysteine and cysteine derivatives.
Cysteine compound can bind to active hydrogen of protein fiber
Durable containing oxirane compounds and protein hydrolysis products
Adhering shape fixative to protein fiber product durability of protein fiber product
A shape fixation comprises said cysteine compound 39.0 wt% or more when the durable shape fixing agent is 100 wt%, wherein the cysteine compounds when 100 mol%
Is cysteine derivative N- acyl - comprises cysteine or a salt thereof 50 mol% or more, 0.1 to the durably form-locking agent to the protein fiber product
1.2% owf adhere, 0.3 the oxirane compound to the protein fiber product
To 3.0% owf adhered, and durable shape fixation of the protein fiber product, characterized in that to from 0.12 to 4.8% owf adhesion relative to the protein hydrolyzate the protein fiber product.