JPH06200475A - Durable shape fixer for protein fiber products - Google Patents

Abstract

(57) [Summary] [Purpose] Even if the shape given to a protein fiber product is exposed to hot water or steam, the shape is maintained stable and white powdery substance is deposited on the fiber product after fixing the shape. And does not cause discoloration, malodor or embrittlement of textiles. The present invention is an improvement of a durable shape-fixing agent for a protein fiber product containing a cysteine compound consisting of cysteine and a cysteine derivative that cleaves the disulfide bond of protein fiber in a recombinable state. This shape-fixing agent contains N-acyl-cysteine or a salt thereof in an amount of 50 mol% or more when the cysteine compound is 100 mol%. In addition to N-acyl-cysteine or its salt, it further contains an oxirane compound capable of binding to active hydrogen of protein fiber, or this oxirane compound and a protein hydrolysis product.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a durable shape fixing agent for protein fiber products such as wool fibers or wool fiber products.
More specifically, a flat protein fiber product is permanently set in a flat form, or pleats are provided for the protein fiber product.
The present invention relates to a shape-fixing agent that permanently gives folds and folds.

[0002]

2. Description of the Related Art Conventionally, as a durable shape-fixing agent for this type of protein fiber product, a setting agent containing a reducing sulfur-containing organic compound capable of cleaving the disulfide bond of wool fiber is disclosed in Japanese Patent Publication No.
No. 7-3099. 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 at the same time re-bonding the disulfide bond in a state of being fixed in a predetermined shape, the wool fiber product becomes permanent. 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. As the sulfur-containing amino acid-based thiol compound, D-cysteine, L-cysteine, a mixture of these racemates, or a cysteine derivative thereof is shown. This cysteine derivative contains N
-N-acyl-cysteine such as acetyl-L-cysteine, N-caproyl-L-cysteine, N-propionyl-L-cysteine, N-palmitoyl-L-cysteine or salts thereof (sodium salt, potassium salt, ammonium salt) , Hydrochloric acid salts, etc.), organic acid salts (acetic acid salts, etc.) and esters (methyl, ethyl, propyl, etc.) are described.

Ammonium thioglycolate contained in the setting agent of JP-B-37-3099 certainly acts effectively on wool fibers, but it causes damage to the fibers due to swelling and has a great influence on dyes. It sometimes changed the hue of the product. Ammonium thioglycolate also has the property of causing a color reaction due to metal ions such as iron, and has the drawback that it discolors under the influence of a trace amount of metal in the stains on containers and textiles, causing discoloration of textiles. . Further, ammonium thioglycolate is easily oxidized by contact with air, so that the stability of the solution is extremely poor and the workability is poor.

Further, in the case of reducing wool fiber using a durable shape-fixing agent containing monoethanolamine bisulfite or monoethanolamine sulfite, hydrogen sulfide,
In particular, there is a drawback that sulfurous acid gas, ammonia, and the like are generated little by little over a long period of time to give off a bad odor. This malodor disappears temporarily when it is dried, but when it absorbs water, it starts to smell again, and since monoethanolamine bisulfite and monoethanolamine sulfite have strong reducing properties, discoloration or disulfide bond formation occurs. The wool fiber was fragile at the time of cutting. Furthermore, neither monoethanolamine bisulfite nor monoethanolamine sulfite produces an aminoacrylic acid residue during the reaction, and this residue not only causes insufficient shape fixing of the wool fiber product, but also leaves this residue. The increase of the group has caused the yellowing of wool fiber products.

[0006] The sulfur-containing amino acid thiol compound cysteine or its derivative described in JP-A-4-163369 is used as a setting agent of JP-B-37-3099 by re-bonding a disulfide bond. Although the drawbacks can be improved, there remains a problem for the durable immobilization of bonds involving active hydrogen, which is an important factor for permanently fixing the shape of protein fiber products, and the treatment effect is still insufficient. There was a problem. Also, like ammonium thioglycolate, cysteine is easily oxidized by contact with air or water, so the stability of the solution is extremely poor and the workability is poor. There was a flaw in making it a good product.

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a protein fiber product capable of stably retaining the shape once applied to the protein fiber product, even when exposed to hot water or steam. To provide a durable shape-fixing agent. Another object of the present invention is to provide a durable shape-fixing agent that does not cause discoloration, malodor or embrittlement of a protein fiber product during and after shape-fixing. Still another object of the present invention is to provide a durable shape fixing agent for a protein fiber product which does not cause precipitation of a white powder on the protein fiber product.

[0008]

Means for Solving the Problems The present invention is an improvement in a durable shape-fixing agent for a protein fiber product containing a cysteine compound consisting of cysteine and a cysteine derivative capable of cleaving the disulfide bond of the protein fiber in a recombinable state. is there. The characteristic first constitution is that N-acyl-cysteine or a salt thereof is contained in an amount of 50 mol% or more when the cysteine compound contained in the durable shape fixing agent is 100 mol%. The characteristic second constitution is that, in addition to cysteine and a cysteine derivative, it further contains an oxirane compound capable of binding to active hydrogen of protein fiber, or an oxirane compound and a protein hydrolysis product.

The present invention will be described in detail below. The protein fiber product of the present invention includes animal hair fibers such as wool, mohair, cashmere, and alpaca, cocoon fibers obtained from cocoons such as domestic silkworms and wild silkworms, or yarns or silk yarns made from these fibers, or these fibers or yarns. Fabrics, knits and non-woven fabrics made from This protein fiber product also includes a blended product with other fibers such as polyester fiber, cellulose fiber, acrylic fiber, a mixed knitted woven product, and a mixed twisted product.

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 the cysteine derivative, N-acetyl-cysteine,
Examples thereof include N-acyl-cysteine such as N-caproyl-cysteine or salts thereof, or cysteine esters such as cysteine methyl ester or salts thereof. These cysteine derivatives may be optically active or optically inactive racemates. In addition, the cysteine compound contained in the durable shape fixing agent is 100 mol% of the cysteine compound contained in the durable shape fixing agent.
In this case, it is necessary to contain 50 mol% or more of N-acyl-cysteine which is a cysteine derivative or a salt thereof. This is for stabilizing the treatment liquid and for preventing the deposition of white powder of cystine on the protein fiber product after fixing the shape. The remaining cysteine compound excluding N-acyl-cysteine or a salt thereof is not particularly limited.

The oxirane compound capable of binding to the active hydrogen of the protein fiber is a polyglycidyl ether compound having a water solubility (solubility of 10 parts of oxirane compound dissolved 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 point solvent which is freely miscible with water can be used and prepared by a known method for producing a self-emulsifying solution.

Further, as the protein hydrolysis product, collagen or collagen derivative can be mentioned, but all of them must be water-soluble. The protein hydrolyzate is a hydrolyzed collagen originating from water-soluble collagen and has a broad molecular weight distribution depending on the degree of hydrolysis. Therefore, in the present invention, the molecular weight is 1,500 to 15,000.
Those in the range are preferred. If the molecular weight is less than 1,500, it is difficult to obtain sufficient treatment effect, and the protein fiber product may turn yellow during the adhesion treatment. The molecular weight is 15.0
When it exceeds 00, the treatment effect is sufficiently obtained, but the texture of the treated cloth becomes coarse and hard, which deviates from the practical range.

A preferred example of the use of the durable shape-fixing agent is that the amount of cysteine and cysteine derivative attached to the protein fiber product is 0.1% owf (on the weight of fiber) or more.
2% owf, the amount of the oxirane compound attached to the protein fiber product is 0.3% owf or more and 3.0% owf, and both are combined within these ranges. When the durable shape-fixing agent contains an oxirane compound and a protein hydrolysis product, the amount of cysteine and cysteine derivative attached to the protein fiber product is 0.1% owf or more and 1.2% owf. Of 0.3% owf on protein fiber products
3.0% owf or more, and the amount of protein hydrolysis product attached to the protein fiber product is 0.12% owf or more and 4.8% ow
f, and combine the three in these ranges.

When the amount of cysteine and cysteine derivative adhered to the protein fiber product is less than 0.1% owf, comprehensively sufficient durable shape fixing performance cannot be obtained, and the amount of adhered 1.2% owf. If it exceeds, the residual amount of cysteine and the cysteine derivative increases after the treatment, which adversely affects.
The amount of oxirane compound deposited on protein fiber products is 0.3% o
If it is less than wf, a sufficient durable shape fixing effect cannot be obtained, and if it exceeds 3.0% owf, a treatment effect can be obtained but the texture becomes hard, which is not preferable. Further, if the amount of the protein hydrolysis product attached to the protein fiber product is less than 0.12% owf, a sufficient durable shape fixing effect cannot be obtained, and 4.8.
When it exceeds% owf, the treatment effect is sufficiently obtained,
The texture of the treated cloth becomes coarse and hard and deviates from the practical range.

The durable shape-fixing agent of the present invention can be applied to a protein fiber product by spraying or spraying it, or by dipping the protein fiber product in the protein fiber product and squeezing it with a padding mangle or the like to impregnate the protein fiber product. It is given to the item. The protein fiber product to which the durable shape-fixing agent is added is then dried, heat-treated, boiled, steamed, embossed,
A predetermined shape is imparted by a conventionally known method such as anti-twist processing, crimping processing, and wrinkling processing.

[0016]

The reaction mechanism between the durable shape-fixing agent of the present invention and the protein fiber has not been clarified. However, an exchange reaction between -SH group and -SS- occurs between the shape fixative 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 a mutual reaction occurs between the active hydrogen and the epoxy group, and the active hydrogen of collagen and the epoxy group. As a result, it is possible to obtain sufficient durable shape fixing performance at a low concentration. By further adding a surfactant, a wetting agent, a swelling agent, a water repellent, etc. to this durable shape-fixing agent, the absorbability to protein fibers is further improved, and the durable shape-fixing performance at a low concentration is sufficient. Is obtained.

[0017]

EXAMPLES 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> L-Cysteine (hereinafter, referred to as L-cys) manufactured by Ajinomoto Co., Inc. is used as cysteine, and N-acetyl-L-cysteine (hereinafter Ac-L, manufactured by Ajinomoto Co., Inc.) is used as a cysteine derivative. -Cys) or L-Cysteine-methyl ester hydrochloride manufactured by Ajinomoto Co., Inc. (hereinafter Me-
L-cys) was used. As the oxirane compound, the trade name of polyethylene glycol diglycidyl ether type manufactured by Nagase Chemical Industries Co., Ltd. is Denacol EX-850 (hereinafter referred to as 850) or the trade name of glycerol polyglycidyl ether type manufactured by Nagase Chemical Industry Co., Ltd. Denacol EX-313 (hereinafter referred to as 313) was used. As a protein hydrolysis product, the product name of collagen acid hydrolyzate system manufactured by Amano Pharmaceutical Co., Ltd. is collagen W10K.
(Hereinafter referred to as W10K) was used. As a penetrating and wetting agent, a penetrant 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 “NONION”) EG).

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

[0019]

[Table 1]

Comparative Example 1 Comparative Example 1 was prepared in the same manner as in Example 1 except that the same woolen cloth as that used in Example 1 was prepared and the treatment liquid having the formulation shown in Table 2 below was applied to this woolen cloth. A treated cloth was obtained. That is, in Comparative Example 1, 850 and 3 used in Example 1 were used.
In Formulation 7, only L-cys was used without using a cysteine derivative, without using 13, W10K. (Hereafter, margins on this page)

[0021]

[Table 2]

<Example 2> A treatment liquid having the formulation shown in Table 1 above was applied with a hand spray gun using compressed air of 2.0 kg / cm ² to 40% of both sides of the same woolen fabric as in Example 1.
It was sprayed so that the attached amount of owf was reached. Use a steam press machine (Hoffman press) to apply the wool cloth with the treatment liquid to it 3
Steaming for 0 seconds, baking 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 onto both sides of the woolen cloth. After vacuuming, the wool cloth was naturally dried to obtain the treated cloth of Example 2.

<Comparative Example 2> The same wool cloth as in Example 1 was prepared, and the same procedure as in Example 2 was carried out except that the treating liquid having the formulation shown in Table 2 was applied to the wool cloth. A treated cloth was obtained.

<Evaluation Method and Results> Example 1 and Comparative Example 1
The 9% test cloths obtained in Step 1 were evaluated for 5% elongation fixation ratio, shape fixation ratio and white powder deposition state by the following methods. Moreover, the white powder deposition state and the fold durability test were evaluated for the nine types of test cloths obtained in Example 2 and Comparative Example 2 by the following methods, respectively. (a) 5% stretch fixing rate About 25 cm x 25 cm test cloth, vertical and horizontal 20 cm
The intervals are marked and the test cloth is impregnated with the test treatment liquid of 9 different formulations. After squeezing the test cloth to 55% of the pickup, the length (hereinafter referred to as L _5w ) fixed by 5% elongation is measured based on the length between the markings. In this state, the test cloth, which was dried at 100 ° C. for 10 minutes and released from the fixed state after drying, contained 25% of a nonionic surfactant.
After soaking in the aqueous solution at 30 ° C. for 30 minutes, the test cloth is taken out and water is lightly removed. Then, after leaving it for 24 hours at a temperature of 25 ° C. and a relative humidity of 65%, the length between markings (hereinafter referred to as L _5D ) is measured. By substituting the above L _5w and L _5D into the following equation, the 5% stretch fixing ratio is obtained. 5% elongation fixation ratio (%) = (L _5D / L _5W ) × 100 (%) Table 3 shows the 5% elongation fixation ratio of each test cloth of Example 1 and Comparative Example 1.

(B) Shape Fixing Ratio The appearance of the test cloth at the time of measuring L _5D in the above (a) was measured by I.V.
W. "Gentleman suit appearance retention standard judgment photograph collection" issued by S
The bubbling judgment standard was evaluated in comparison with the first to fifth grades. It should be noted that the higher the criterion series is, the better it is. The fifth grade is the best and the first grade is the worst. Table 3 shows the shape fixing ratios of the test cloths of Example 1 and Comparative Example 1.

(C) White Powder Precipitation State The generation status of white powdery substances on the treatment liquid and the test cloth as the treatment cloth was visually inspected. 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 deposition state of each test cloth of Example 2 and Comparative Example 2.

(D) Durability test of folds A total of 4 from two points above and below the two folds attached to the test cloth.
Cut a small piece of fabric from the book, 1 cm in the lengthwise direction of the fold and 2 cm wide from the fold. Unfold five pine needles from each piece of fabric. After immersing these in water containing 0.1% by weight of a penetrant at 25 ° C. for 2 minutes, the fold angle (open angle) of the yarn in water is measured from the top with a protractor. Then, the average of the open angles of 20 yarns in total was obtained.
The smaller the opening angle, the better the durability of the fold,
It must be within 0 degrees. Table 4 shows the opening angles of the folds of Example 2 and Comparative Example 2.

[0028]

[Table 3] (Hereafter, margins on this page)

[0029]

[Table 4]

As is clear from Tables 3 and 4, the 5% stretch-fixing rate of Comparative Example 1 was low at less than 93%, while the 5% stretch-fixing rate of Example 1 was low. All showed high values of 93% or more. Further, the shape fixing ratios of Comparative Example 1 were all below the fourth grade, whereas the shape fixing ratios of Example 1 were all the fourth to fifth grade. In addition, in Comparative Examples 1 and 2, white powder was precipitated in all 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.
It was less than degree. From these results, it was found that Example 1 and Example 2 were superior to Comparative Example 1 and Comparative Example 2 in shape fixing and appearance state. Then

[0031]

As described above, when the shape-fixing agent of the present invention is used for treatment, the shape imparted to the protein fiber product can be stably maintained even when exposed to hot water or steam. be able to. In particular, N-acyl-cysteine or a salt thereof contained in this durable shape-fixing agent has the ability to prevent the precipitation of white crystals of cystine, and the oxirane compound and protein hydrolyzate are more effective than conventional shape-fixing agents. Improving the fixing ability and its durability. This durable shape-fixing agent can avoid bad odor, discoloration, embrittlement and yellowing of protein fiber products due to its reduction reaction mechanism. Furthermore,
By using this durable shape-fixing agent for boiling, steaming, twisting prevention, making folds, etc., it is possible to obtain an extremely high shape-fixing treatment ability compared to the conventional case.

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Claims (5)

[Claims] 1. A durable shape-fixing agent for a protein fiber product containing a cysteine compound as a main component, wherein the cysteine compound contained in the durable shape-fixing agent is 1
A durable shape-fixing agent for a protein fiber product, which contains N-acyl-cysteine or a salt thereof in an amount of 50 mol% or more when the amount is 00 mol%. 2. The durable shape fixing agent for a protein fiber product according to claim 1, which contains an oxirane compound capable of binding to active hydrogen of the protein fiber. 3. The durable shape fixing agent for a protein fiber product according to claim 2, wherein the oxirane compound is a polyglycidyl ether compound having at least two epoxy groups and has a water solubility of 20% or more. 4. The durable shape-fixing agent for a protein fiber product according to claim 2, which contains a protein hydrolysis product. 5. The durable shape-fixing agent for a protein fiber product according to claim 4, wherein the protein hydrolysis product is water-soluble collagen or a water-soluble collagen derivative.