JPH09188973A - Durable stabilization of shape in protein textile product and feather - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve surface smoothness and touch feeling in protein textile products and feathers after processing and to stably maintain their bulky shape even after exposed to steam or water vapor. SOLUTION: This purpose is accomplished by the following processes: (a) a solution is prepared by blending cysteine, its derivative and chitosan in the weight ratio cysteine/chitosan of 5/1 to 40/1 for protein textile products or of 5/1 to 30/1 for feathers (where chitosan has an average molecular weight of 5000 to 400000 and acetyl group content of 35 to 65mol%), followed by dissolving the blend in a solvent and adjusting the pH of the solution to 3.5 to 9.0; and (b) the solution is applied in quantities of 0.15 to 6.5wt.% onto the protein textile products or 0.8 to 6.5wt.% onto feathers based on the net weight of the principal components and drying the solution-applied protein textile products or feathers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for stabilizing the durable shape of feathers used for protein fiber products such as clothes and bedding. More specifically, even when the protein fiber product or the feather is compressed or exposed to water vapor, the shape once applied to the protein fiber product or the feather can be stably retained, and the surface of the fiber product or the feather surface can be maintained. The present invention relates to a durable shape stabilizing method for smoothly finishing with a good texture.

[0002]

2. Description of the Related Art A conventional setting method for permanently imparting a crease or a planar shape to a wool fiber product, which is a protein fiber product, involves heating the wool fiber product in the presence of a setting agent containing a thiol compound, The disulfide bond in the fiber is cleaved, and at the same time, the disulfide bond is rebonded while being fixed in a predetermined shape. As a conventional setting method of this kind, a method of using a setting agent containing an amino acid thiol compound such as cysteine or a cysteine derivative has also been proposed.

When setting a protein fiber product, cysteine or a cysteine derivative which cleaves the disulfide bond in the protein fiber in a recombinable state and an oxirane compound capable of binding active hydrogen in the protein fiber are used in combination, Alternatively, it is known to use a durable shape-fixing agent containing an oxirane compound and a protein hydrolysis product as main components. Further, in bulky processing of feathers, a method is known in which a glutaraldehyde solution is sprayed onto feathers, particularly down, and the spray solution is attached to the barbs or twigs and then dried.

[0004]

The conventional durable shape stabilizing treatment for protein fiber products has some disadvantages such as insufficient processing effect, lack of smoothness of protein fiber products, and partial lack of shape stability. It was In addition, in the conventional bulky processing of feathers using glutaraldehyde, there was a problem that the problem of odor and sufficient durability could not be obtained, and particularly when moisture was obtained, the recovery power was significantly reduced. The object of the present invention is to improve the surface smoothness of processed protein fiber products and feathers, and to further improve the texture, and to maintain a bulky shape stably even when exposed to steam or steam. It is to provide a durable shape stabilization method.

[0005]

The invention according to claim 1 of the present invention is characterized in that chitosan having an average molecular weight of 50,000 to 400,000 and an acetyl group content of 35 to 65 mol%, cysteine and a cysteine derivative are cysteine. / Chitosan = 5
A solution having a pH adjusted to 3.5 to 9.0 by mixing at a weight ratio of -40 to 40 is prepared, and the solution is added to a protein fiber product in a pure content of 0.
It is a durable shape stabilizing method for protein fiber products, which comprises depositing 15 to 6.5% by weight and drying the protein fiber product to which this solution is attached. Cysteine and cysteine derivatives, which are components of the above solution, cleave the disulfide bond in the protein fiber in a recombinable state. Chitosan, another component of the above solution, binds to active hydrogen in protein fibers. By these, the shape of the protein fiber product is stably stabilized.

The invention according to claim 2 of the present application comprises a polyoxirane type derivative such as ethylene or polyethylene glycol diglycidyl ether type derivative or propylene or polypropylene glycol diglycidyl ether type derivative, an epoxy modified silicone, and an acrylic ester derivative as main components. To prepare a prepolymerized solution by mixing one or more polymer resin compounds selected from the group consisting of fluorine-containing polymer compounds with the solution according to claim 1 to prepare a protein fiber product. A durable shape stabilizing method for a protein fiber product, which comprises depositing 0.15 to 7.0% by weight of the prepolymerized solution in a pure content and drying the protein fiber product to which the solution is deposited. . A polymer resin compound such as a polyoxirane type derivative, a silicone resin compound or a fluororesin compound, which is a component of the above solution, crosslinks with chitosan to further improve the moisture resistance and water repellency of the protein fiber product. The amount used may be small, but varies depending on the use of the protein fiber product.

In the invention according to claim 3 of the present application, chitosan having an average molecular weight of 50,000 to 400,000 and an acetyl group content of 35 to 65 mol% and cysteine and a cysteine derivative are cysteine / chitosan = 5 to 30. Prepare a solution of which the pH is adjusted to 3.5 to 9.0 by mixing it at a weight ratio of 0.8 to 6.5% by weight of the solution, and the solution is attached to the feathers. Is a method for stabilizing the shape of a feather in a durable manner. Cysteine and cysteine derivatives, which are components of the above solution, cleave the disulfide bond in feathers in a recombinable state.
Chitosan, which is another component of the above solution, binds to active hydrogen in feathers. By these, the shape of the feather is stably stabilized.

The invention according to claim 4 of the present application comprises as a main component a polyoxirane type derivative such as ethylene or polyethylene glycol diglycidyl ether type derivative or propylene or polypropylene glycol diglycidyl ether type derivative, epoxy modified silicone, and acrylic acid ester derivative. A solution obtained by mixing one or two or more polymer resin compounds selected from the group consisting of fluorine-based polymer compounds with the solution according to claim 3 to form a prepolymer. Is prepared, 1.1 to 7.0% by weight of the prepolymerized solution is attached to the feathers in a pure amount, and the feathers to which the solution is attached are dried to stabilize the shape of the feathers. Is. A polyoxirane type derivative which is a component of the above solution, a silicone resin compound,
A polymer resin compound such as a fluororesin compound crosslinks with chitosan to further improve the moisture resistance and water repellency of feathers.
The amount used may be small, but varies depending on the use of the feather.

According to the present invention, the shape once applied to the protein fiber product or the feather can be stably maintained even when exposed to steam or steam, and a smooth surface having a good texture is obtained. To be It does not cause an offensive odor at the time of fixing the shape or after fixing the shape, does not cause embrittlement of the protein fiber, has no effect on the dye, and does not change the hue of the fiber product.

Especially, the effect on feathers is great, and the mixed solution of cysteine and cysteine derivative and chitosan sprayed on the surface of feathers is mainly adhered to the barbs or twigs of the feathers, which react with the proteins of the feathers. By creating a bond, it prevents the barbs or twigs from flexing, which is manifested as waist strength. That is, bulkiness is increased and durability is also exhibited.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The protein fiber product of the present invention is a woven fabric, knitted fabric, non-woven fabric or the like made of wool, mohair, cashmere, silk or the like. Further, the present invention is not limited to a fabric made of only these fibers, but includes a fabric made of a blended fabric with other fibers such as polyester fiber, cellulose fiber, acrylic fiber, a mixed knitted fiber, and a mixed twist. Further, the feathers of the present invention include various kinds of feathers such as feathers of waterfowl such as goose and duck eider, and feathers of land birds such as chicken and turkey. The feathers of waterfowl have down and feathers, but land birds have only feathers. The major protein of feathers is β-keratin, which contains a large number of intramolecular S—S bonds. The amino acid composition of each part of the feather is different, but serine, glycine, cystine,
It contains the most proline residues. Cysteine used in the present invention includes D-cysteine, L-cysteine, and their racemates. Also, cysteine derivatives include N
There are N-acyl cysteines such as -acetyl-L-cysteine, N-caproyl-L-cysteine or salts thereof, and esters.

The deacetylated chitosan capable of binding to active hydrogen in protein fibers or feathers has an average molecular weight of 50,000 to 400,000, preferably 150,000 to 300,000 and an acetyl group content of 40 to 60 mol. It is a percentage. The mixed solution of chitosan with cysteine and a cysteine derivative is an aqueous solution having a pH of 3.5 to 9.0, preferably 6.0 to 8.0. When the average molecular weight of chitosan is less than 50,000, the bulkiness and morphological stability of the protein fiber product and the feather are poor, and when the average molecular weight exceeds 400,000, the molecular weight is too large and the texture of the protein fiber product and the feather becomes poor. Furthermore, 3.5 to 9.0
When used in the pH range of 1, the chitosan aqueous solution becomes stable and the shape of the protein fiber product is stably fixed.

In the present invention, cysteine and cysteine derivatives and chitosan are used as a durable shape stabilizer. The amount of this durable shape-stabilizing adhesion to protein fiber products or feathers is 1.2 for cysteine and cysteine derivatives.
It is set to be not less than × 10 ^-1 wt% owf and not more than 6.0 wt% owf, and that for chitosan is not less than 1.2 × 10 ^-2 wt% owf and not more than 0.8 wt% owf. When the amount of cysteine and cysteine derivative attached is less than 1.2 × 10 ^-1 wt% owf, overall sufficient durable shape stability cannot be obtained, and the amount of cysteine and cysteine derivative exceeds 6.0 wt% owf. In this case, cystine may be precipitated after the treatment and white powder may be generated. The attached amount of chitosan is 1.2 × 10 ^-2 wt% o
If it is less than wf, sufficient durable shape stability cannot be obtained, and if it exceeds 0.8 wt% owf, the texture becomes hard.

The polyoxirane type derivative according to claim 2 or 4 of the present application is an ethylene or polyethylene glycol diglycidyl ether type derivative represented by the following formula (1), or a propylene or polypropylene glycol diglycic acid derivative represented by the following formula (2). Is a luether type derivative,
These have an addition mole number of ethylene glycol or propylene glycol in the range of 1 to 4, respectively, and a water solubility of 90% by weight or more.

[0015]

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[0016]

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The silicone resin compound according to claim 2 or 4 of the present application has two or more alicyclic epoxy groups represented by the following formula (3) in the side chain and is highly reactive with epoxy modification. It is silicone.

[0018]

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The fluororesin compound according to claim 2 or 4 of the present application is an acrylic resin prepared by esterifying acrylic acid, methacrylic acid or the like with a compound having a fluoroalkyl group having 3 to 20 carbon atoms and a hydroxyl group. It is a copolymer whose main component is an acid ester derivative (perfluoromonomer). As the copolymerization component, a monomer such as alkyl (meth) acrylate and vinyl chloride, and a crosslinkable monomer such as 2-hydroxyethyl methacrylate and N-methylol acrylamide are used together. An example thereof is shown in the following formula (4).

[0020]

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The durable shape stabilizer is applied to the protein fiber product or the feather by a conventionally known method such as impregnation, coating, or spraying, and the durable shape stabilizer is further added with a POE alkyl ether as a wetting agent and a swelling agent. Addition of surfactants such as anionic nonionic surfactants and anionic surfactants such as sulfosuccinic acid ester salts further improves the exhaustion to protein fibers or feathers, and provides sufficient durable shape stability performance at low concentrations. To be

[0022]

【Example】

<Preparation of treatment liquid> -SH / -SS-exchange reaction agent N-acetyl-L-cysteine 6% by weight, L-cysteine 3% by weight, L-cysteine hydrochloride-hydrate 1% by weight L-cysteines An aqueous solution containing a total of 10% by weight of a catalyst consisting only of was prepared. 50% acetylated chitosan 1% aqueous solution Chitosan CLH manufactured by Yaizu Suisan Co., Ltd. is washed and deproteinized, and an acetylating agent is added so that the acetylation degree becomes 50%, and finally the acetylation degree is 51%. 1% aqueous solution was prepared. The acetylation degree is an index of solubility in acid. Epoxy-modified silicone has an epoxy equivalent of 3.8.
^{× 10 3 (g / eqlv.} ), Was used an average molecular weight 65,000 about manufactured by Dai-ichi Kogyo Seiyaku Co. Heras guard M1045. As the fluororesin compound, perfluoroacrylate having an average molecular weight of 10,000 to 20,000 (Asahi Guard LS-317 manufactured by Asahi Glass Co., Ltd.) was used. As a penetrant (surfactant), a perfluoroalkylethylene oxide adduct of Surflon SA-100 under the trade name of Asahi Glass Co., Ltd. was used.

The evaluation according to the present invention is based on the following method. (a) 5% elongation fixation ratio First, 20c in each of the warp direction and the weft direction with respect to the test cloth.
Mark at m intervals. Then, after impregnating this test cloth with the test treatment liquid, the test cloth was squeezed so that the pick-up rate of the treatment liquid was 60%, and stretched 5% each in the warp direction and the weft direction based on the length between the markings. The measured length (hereinafter, this length is referred to as L _5W ) is measured. In this state, it is dried at 100 ° C. for 10 minutes. After being dried, the test cloth released from the fixed state was immersed in an aqueous solution containing 0.1% of a nonionic surfactant at 25 ° C. for 30 minutes, and then the test cloth was taken out and water was lightly removed. After standing for 24 hours in a relative humidity of 65%, the length between the markings is measured (hereinafter, this length is referred to as L _5D ). The 5% stretch fixing rate is calculated from the following formula. 5% elongation fixation ratio (%) = L _5D / L _5W × 100 (%) (b) Shape fixation ratio The appearance of the test cloth at the time of measuring L _5D in the above (a) was measured by I.
Based on the bubbling judgment criteria of the collection of "standard judgment photographs of appearance retention of men's suits" issued by WS (International Wool Secretariat),
It was carried out according to the judgment of 1 to 5 grade (5 grade; best, 1 grade; poor).

(C) Bulkiness of feathers (JIS L-190
3) Put 50 g of feather in a cylinder with an inner diameter of 30 cm, and
A doughnut-shaped disk having a weight of 0 g and a diameter of 29.5 cm and having a material having good air permeability attached to the center is placed on the feather. The disc is suspended by a string so that the disc can be lowered inside the cylinder while keeping the disc horizontal. Lower the disc onto the feathers and check the looseness of the support cord. Read the disc height one minute after the lapse of time. After raising the disc and stirring the feathers in the cylinder, the disc is lowered again, the height of the disc is read in the same manner as above, and this is repeated three times to obtain the average value.

(D) Durability of feathers 2 g of feathers are put into a cylinder of 73 mm in diameter, a disk having good air permeability is placed on the feathers, and a weight of 200 g is placed thereon. After 30 seconds have passed, remove the weight and
After a second, put the weight on again. This operation is repeated 10 times, and the weight of the disc is finally left for 30 minutes and removed, and the height of the disc is read. (e) Moisture durability of feathers 2 g of feathers are put in a cylinder with a diameter of 73 mm and the relative humidity is 8
After left in a 7% box overnight, the same durability as in (d) above is measured. (f) Feather recovery property After the treatment of (e) above, the weight is removed, the feathers are thoroughly stirred, and dried thoroughly in a dryer at 100 ° C. Then 2
After applying a load of 00 g and leaving it for 30 minutes, remove the weight and read the height of the disc.

<Example 1> 2/72 meter count (hereinafter referred to as mN) worsted yarn was used as a warp to produce 1/48 mN.
The worsted yarn of is used as a weft and woven into a 2/3 diagonal weave with a warp density of 52 yarns / cm and a weft yarn density of 32 yarns / cm, and a basis weight of 234 g /
to obtain a cashmere cloth of m ^2. The cashmere cloth is impregnated with the following treatment liquid, and the treatment liquid is uniformly applied to the cashmere cloth at a pickup rate of 60% using a two-roll mangle padder, and then stretched and fixed by 5% in each of the warp direction and the weft direction. Then, it was dried at 100 ° C. for 10 minutes to obtain the treated cloth of Example 1.

In Example 1- (1), a 1% aqueous solution of 50% acetylated chitosan and a --SH /-SS-exchange reaction agent were used, and in Example 1- (2), the epoxy-modified silicone was used in Example 1- (1). In Example 1- (3).
A working fluid prepared by mixing the fluororesin compound with (1) was used. Furthermore, in Example 1- (4), a working liquid prepared by mixing both the epoxy-modified silicone and the fluororesin compound with the solution of Example 1- (1) was used. The prescription is shown in Table 1.

Comparative Example 1 For comparison with the treated cloth obtained in Example 1, a cloth treated with only a 50% acetylated chitosan aqueous solution (Comparative Example 1- (1)), and -SH / -SS-.
A cloth treated with only the exchange reaction agent (Comparative Example 1- (2)) and an untreated cloth (Comparative Example 1- (3)) were obtained in the same manner as in the Example.

[0029]

[Table 1]

Table 2 shows the results of evaluation of the above-mentioned 5% elongation fixation ratio and shape fixation ratio for this treated cloth.

[0031]

[Table 2]

As is clear from Table 2, Example 1-
The test cloth obtained in (1) had a good stretch-fixing ratio and had a large flat setting property without bubbling even after soaking in water. The test cloths obtained in Examples 1- (2), (3) and (4) had stable shapes. On the other hand, the test cloths obtained in Comparative Example 1 all had bad bubbling, and in particular, in Comparative Example 1- (1), the stability was worse than that of the untreated cloth soaked in water and dried.

<Example 2> The treated solution was uniformly sprayed and adhered on the feathers of Neo Eider species that had been scoured and dried so as to be in the ratio shown in Table 3, and dried in a dryer at 100 ° C for 30 minutes. The treated feathers were measured for bulkiness, durability, wet durability and recoverability. Table 4 shows the results. The epoxy-modified silicone, fluororesin compound and penetrant used here are the same as those used in Example 1.

Comparative Example 2 In order to compare the results obtained in Example 2, untreated feathers that had just been scoured and dried and 5
25% by weight owf of 1% aqueous solution of 0% acetylated chitosan
Feather just attached at a rate of, and feather to which -SH / -SS-exchange reaction agent is attached at a rate of 6.7 wt% owf,
Further, feathers to which glutaraldehyde was attached at a ratio of 5 wt% owf were obtained in the same manner as in the example. Table 3 shows the detailed prescription. Also, the bulkiness and durability of the treated feathers,
Table 4 shows the measurement results of wet durability and recoverability.

[0035]

[Table 3]

[0036]

[Table 4]

As is clear from Table 4, Example 2-
The bulkiness of the feathers obtained in (1) increased by 67% compared to the untreated one, and the durability was 42% compared to the untreated one.
Increased. The feathers obtained in Example 2- (2) have particularly excellent moisture durability, can maintain a bulky state even when moist, and become even bulky after drying. Further, the feathers obtained in Example 2- (4) are excellent in both bulkiness and wet durability, and the bulkiness is increased by 70% as compared with the untreated feathers. Especially, the recovery is much better than other feathers,
If treated in this way, even if it is exposed to moisture, it can be dried again to obtain bulky feathers again. On the other hand, when glutaraldehyde was treated, the aldehyde odor was felt unpleasant during the treatment, and the odor remained on the treated feathers.
The bulkiness was increased by 40%, but the durability was found in Example 2.
-It was 2 cm inferior to the feather obtained in (1) and 0.7 cm smaller than the untreated feather. Further, it was found that when it was moistened, it became less bulky and felt sticky, and once feathers had no recovery power, the imparted shape was not fixed.

[0038]

As described above, according to the method of the present invention, the shape once applied to the protein fiber product or the feathers is particularly resistant to hot water and steam, and also has a bad odor, discoloration, protein fiber. Brittleness and yellowing can be avoided, which contributes to stable quality. Furthermore, according to the method of the present invention, a particularly bulky and durable feather is obtained, and the effect is remarkably exhibited when the amount of adhesion to the feather is smaller than that of the conventional technique, and the grade is higher than that of the untreated one. You can get feathers.

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Claims (4)

[Claims] 1. Chitosan having an average molecular weight of 50,000 to 400,000 and an acetyl group content of 35 to 65 mol%, cysteine and a cysteine derivative are combined with cysteine / cysteine derivative.
Chitosan = 5 to 40 by mixing in a weight ratio of 3.5 to pH.
Prepare a solution adjusted to 9.0, and add 0.15 to 6.5% by weight of the above solution to the protein fiber product as a pure component.
A method for stabilizing a shape of a protein fiber product, which comprises depositing and drying the protein fiber product to which the solution is attached. 2. A fluorine-based polymer compound containing as a main component a polyoxirane type derivative such as ethylene or polyethylene glycol diglycidyl ether type derivative or propylene or polypropylene glycol diglycidyl ether type derivative, epoxy modified silicone, and acrylic acid ester derivative. A prepolymerized solution is prepared by mixing one or more polymer resin compounds selected from the group consisting of and the solution according to claim 1, and the prepolymerized solution is added to the protein fiber product. 0 for pure content.
A durable shape stabilizing method for a protein fiber product, which comprises depositing 15 to 7.0% by weight and drying the protein fiber product to which the solution is attached. 3. Chitosan having an average molecular weight of 50,000 to 400,000 and an acetyl group content of 35 to 65 mol%, cysteine and a cysteine derivative are cysteine /
Chitosan = 5 to 30 in a weight ratio to mix to a pH of 3.5 to
A durable solution of feathers, characterized in that a solution adjusted to 9.0 is prepared, 0.8 to 6.5% by weight of the solution is attached to the feathers, and the feathers to which the solution is attached are dried. Stabilization method. 4. A fluorine-based polymer compound containing ethylene or a polyethylene glycol diglycidyl ether type derivative or a polyoxirane type derivative such as propylene or a polypropylene glycol diglycidyl ether type derivative, an epoxy-modified silicone, and an acrylic acid ester derivative as a main component. A prepolymerized solution is prepared by mixing one or more polymer resin compounds selected from the group consisting of and the solution according to claim 3, and the feather is mixed with the prepolymerized solution in a pure content. Then 1.1 ~
A method for stabilizing the durable shape of feathers, which comprises depositing 7.0% by weight, and drying the feathers to which the solution has adhered.