JPH10310977A - Shrinkproof silk product and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart shrink resistance without deteriorating the touch feeling essential to silk by carrying out the cross-linking treatment of a silk product with a specific compound under acidic conditions. SOLUTION: This shrink-resistant silk product is obtained by carrying out the cross-linking treatment of a silk cloth in an acidic aqueous treating liquid, containing a compound represented by the formula [R1 , R2 , R3 and R4 are each an alkyl or R1 and R2 or R3 and R4 each an alkylene forming a ring; R5 is H or an alkyl; (m) is an integer of 2-10], e.g. 1,1,9,1-bisethylenedioxynonane present therein and regulated to pH 0.8-7.0 with a polycarboxylic acid type organic acid such as tartaric acid at 30-180 deg.C, preferably 60-150 deg.C temperature and imparting the shrink resistance thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silk product excellent in shrink resistance and a method for producing the same.

[0002]

2. Description of the Related Art Various methods have been proposed and attempted to improve the shrinkage resistance and wash and wear properties of a silk product by reacting a reactive resin on the product. However, all have problems in workability, and since crosslinking or polymerization reaction of resin occurs only on the fiber surface, the feeling of silk itself is impaired, and only products having problems in thread resistance etc. can be obtained. Was.

[0003] For example, the exhaustion method of adsorbing a resin to a fiber from a large amount of solution has disadvantages in that a resin that is not exhausted remains in the solution, and that a large amount of solvent must be treated as a waste liquid. In addition, after the resin solution is impregnated into silk, the method of drying and hardening requires a relatively small amount of the resin solution,
Heating causes the solvent to evaporate first, followed by drying and hardening of the resin.Therefore, with the evaporation of the solvent, the resin migrates to the silk surface, and the cured resin covers the silk surface. Often loses.

Further, in addition to the above-mentioned problems, even silk products that have been processed with resin undergo shrinkage of 3% or more due to washing, ironing, and the like. Further, in the case where a silk product of white fabric is subjected to resin processing, there is also a problem that processing unevenness generated at the time of resin processing in post-dyeing becomes a stain, and as a matter of course, the degree of the resin processing described above is strengthened, that is, shrink-proof processing If the degree of is increased, the texture of the dough tends to become harder with this, so that it is not possible to apply a very strong shrink-proofing process. Therefore, the silk product has many problems, such as insufficient shrinkage resistance and easy breakage and wrinkles of the fabric.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the problem of imparting shrink resistance to silk products, makes it possible to impart suitable shrink resistance, and suppresses wrinkles as much as possible. An object is to provide a product and a method for manufacturing the product.

[0006]

Means for Solving the Problems The present invention provides the following formula (1)
This is a shrink-preventing silk product which has been treated with the compound represented by the formula:

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[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a silk product means a fiber product containing silk, and even if it is made of silk alone, a blend of silk with other natural fibers, synthetic fibers, etc.
It may be a cross-woven or knitted product. Further, the shape may be any of a thread, a woven fabric, a nonwoven fabric, a knitted fabric, and a sewn product thereof, and is not particularly limited.

The compound represented by the following formula (1) in the present invention, that is, the compound to be subjected to a shrink-proof treatment of a silk product will be described in detail.

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In the formula, as the alkyl group represented by R _{1 to} R ₄ , a lower alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable in terms of ease of use. The alkyl group may be substituted with an alkyleneoxy group such as an ethyleneoxy group, and all of R _{1 to} R ₄ may be the same type of alkyl group or different. Further, as the alkylene group forming a ring, a lower alkylene group having 1 to 4 carbon atoms is preferable, but a 5-membered ring,
A 6-membered ring is preferable, and therefore, an ethylene group or a propylene group having 2 to 3 carbon atoms is preferable. Any of these alkyl groups and alkylene groups may have a substituent. In the formula, m is a value calculated in light of the composition ratio when treating using a plurality of the compounds,
Not necessarily an integer.

It is preferable that the compound does not have a branched chain at the time of crosslinking treatment, and R ₅ is preferably hydrogen. However, the compound has R ₅ having 1 carbon atom.
A lower alkyl group of ~ 4, a compound having a so-called branched chain, and a compound of a compound having no branched chain may be used, but only a compound having no branched chain in terms of imparting shrink resistance to silk, Alternatively, it is more preferable to use a mixture having a large ratio of the compound having no branched chain.

When R ₅ is an alkyl group, the number thereof may be up to m. However, in the present invention, it is not necessary that all m are alkyl groups. And the remainder is hydrogen, ie
This includes the case where the sum of the alkyl group and hydrogen is m. Further, the alkyl groups may be the same kind of group or different kinds of groups.

The compound is extremely stable because its terminal is blocked with an alkyl group or an alkylene group forming a ring, and is not oxidized even when contacted with oxygen such as air. Therefore, the end blocking allows the silk product to react with the amino group of the silk even under the conditions described later, thereby imparting excellent shrink resistance to the silk product. When the compound is used as an aqueous solution since it is hardly soluble in water, an anionic surfactant such as sodium dodecylbenzenesulfonate or sodium oxyalkylene modified with polycyclic phenol is used. It can be used in an emulsified state. Alternatively, a mixed solvent of water and alcohol can be used.

The concentration of the compound in the shrinkproofing solution is preferably in the range of 0.0001 to 50% by weight, particularly 0.001 to 10% by weight, based on the weight of the silk product to be treated. When the amount is out of this range, the silk product has no shrinkage-preventing effect, and when the amount of the compound is too large, the texture of the silk product deteriorates, that is, the silk product becomes hard and cannot be put to practical use.

Specific examples of the compound include 1,1,6,
6 tetramethoxyhexane, 1,1,6,6 tetraethoxyhexane, 1,1,7,7 tetramethoxyheptane, 1,1,7,7 tetraethoxyheptane, 1,1,
8,8 tetramethoxyoctane, 1,1,8,8 tetraethoxyoctane, 1,1,9,9 tetramethoxynonane, 1,1,9,9 tetraethoxynonane, 1,1,
9,9 bisethylenedioxynonane, 1,1,10,1
0 tetramethoxydecane, 1,1,10,10 tetraethoxydecane, 1,1,11,11 tetramethoxyundecane, 1,1,11,11 tetraethoxyundecane and the like can be mentioned. Among them, 1,1,9,9 tetramethoxy nonane, 1,1,9,9 tetraethoxy nonane, 1,1,1
It is preferable to use 9,9 bisethylenedioxynonane, and it is possible to use not only one kind but also two or more kinds.

In the present invention, it is essential that the cross-linking treatment is performed under an acidic condition, and the hydrogen ion concentration (pH) is adjusted to 0.1.
It is preferable to adjust to a range of 8 to 7.0. The acidity can be adjusted with mineral acids such as hydrochloric acid and sulfuric acid; and organic acids such as formic acid, acetic acid, maleic acid, tartaric acid, lactic acid, citric acid, malic acid, and succinic acid. Among them, organic acids are preferred from the viewpoint of the corrosion resistance of the treatment apparatus, and polycarboxylic acids are preferably used from the viewpoint of imparting staining spots when dyeing a white silk product. The polycarboxylic acid has at least one carboxyl group and at least one hydroxyl group per molecule. Specifically, tartaric acid, malic acid, lactic acid, citric acid, salicylic acid,
Glycolic acid and the like can be mentioned. Among them, water-soluble polycarboxylic acids such as tartaric acid, lactic acid, malic acid and citric acid are preferably used because of their good workability. The above-mentioned acids may be used alone or in combination of two or more.

If the acid concentration is out of the range, satisfactory shrinkage-prevention treatment cannot be performed, and shrinkage due to washing and ironing may increase. Further, since the bonding rate between the compound represented by the formula (1) and the amino group of the silk greatly depends on the acid concentration, an inorganic salt composed of a strong acid and a strong base, such as sodium hydroxide and bicarbonate, is used as a regulator thereof. Sodium, sodium carbonate, sodium percarbonate, sodium borate, sodium metaborate, sodium hydrogen perboronate, sodium sulfate, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium silicate, sodium metasilicate, sodium phosphate, sodium metaphosphate , Sodium polyphosphate, sodium pyrophosphate, sodium phosphite, sodium hypophosphite, sodium formate, sodium acetate and the like. These regulators may be used alone or in combination of two or more. It is preferable to use sodium sulfate from the viewpoint of versatility.

The processing temperature is preferably in the range of 30 to 180 ° C., particularly preferably in the range of 60 to 150 ° C. If the temperature is outside the above range, the effect of improving the shrink-prevention treatment of the silk product is small, and the silk product is often colored. The processing time varies depending on the processing temperature, but is preferably in the range of 3 to 60 minutes in consideration of the economic effect.

In the present invention, the silk product subjected to the shrink-proofing treatment may be subjected to the treatment as it is, but it is preferable that the silk product is pre-treated with a swelling agent in advance. Such swelling treatment may be performed simultaneously with the shrink-prevention treatment. By performing the swelling treatment, the above-mentioned compound penetrates into the silk product, and the shrinkage-preventing effect becomes extremely high. Further, for example, a softening agent such as a polyethylene emulsion, a dimethyl silicone emulsion, and a silicone softener, and a wrinkle-proofing agent such as a melamine resin can be used.

In the present invention, since the compound represented by the formula (1) is used, when dyeing a silk product of white fabric, the dyeing can be performed simultaneously with the shrink-proofing treatment.

The shrink-preventing treatment of the present invention, that is, whether or not the compound represented by the formula (1) is bonded to the amino group of the silk is determined by measuring the increase in weight, change in specific gravity, etc. of the silk product after the treatment. Can be evaluated. The silk product thus shrink-proofed is much more excellent in shrink resistance and wrinkle resistance against washing, ironing and the like than conventional silk products.

[0021]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In addition, each measured value in an Example is a value measured and calculated by the following method. (1) Moisture Absorption (%) A sample was placed in an atmosphere of 65% RH and 20 ° C. for one week, its weight W was measured, and calculated by the following equation. Moisture absorption (%) = [(weight W-absolute dry weight) / absolute dry weight] x
100 (2) Washing shrinkage (%) It is a value measured in accordance with JIS L 1042G method.

(3) Iron shrinkage (%) This is a value measured in accordance with JIS L 1047A method. (4) Color fastness UV accelerated testing machine [Dainippon Plastics Co., Ltd. EYE
SUPER UVTESTER (SUV-W11)]
Was used to perform an acceleration test under the following conditions. UV intensity: 50 mW / cm ² Black panel temperature: 50 ° C. Humidity condition: 70% RH UV shielding irradiation irradiation: 16 hours Water injection: 6 hours Eight cycles were carried out with 2 hours of reset as one cycle. Next, the ΔE value is measured by a fading tester [color difference meter (Z-1001DP) manufactured by Nippon Denshoku Industries Co., Ltd.]. △ E
Is the difference between the L, a, and b values before and after the ultraviolet acceleration tester {L, △
a and △ b are measured and calculated by the following equation. ΔE = (ΔL ² + Δa ² + Δb ² ) ^1/2

(5) Hand A sensory test was conducted by touching the panel with five panelists.
The evaluation criteria are shown below. ◎: All five persons were judged good ○: Three to four of the five persons judged good Δ: Two of the five persons judged good ×: All the five persons judged bad

Example 1 150 g of an attached white cloth (silk No. 2-1 manufactured by Japan Standards Association) for dyeing fastness test was used and a shrinkproof treatment was carried out using a rotary dyeing machine (30 liters in volume) under the following conditions. Was done. Shrink-prevention treatment conditions; Treatment agent: 1,1,9,9-diethylethyleneoxyoxynonane 20% owf Dispersant: 5 g / liter aqueous solution of sodium decylbenzenesulfonate 30 ml Acid: succinic acid 3% owf Solvent: water Bath ratio 1: 50 temperature 100 ° C time 40 minutes After treatment, water washing for 30 minutes, centrifugal dehydration, air drying overnight,
Vacuum drying was performed at 70 ° C. × 15 hours. The rate of increase in the treatment (reaction) weight of the obtained silk product was calculated.
A sample for measurement was left overnight in an atmosphere of 0% RH.
Each sample was evaluated for this measurement sample, and the results are shown in Table 1.

Example 2 In Example 1, a dye and a dyeing aid shown below were added to the treatment solution to perform a simultaneous shrink-prevention treatment for the dyeing. Dye: Kayanol Milling Black TLB [manufactured by Nippon Kayaku Co., Ltd.] 5% owf Dyeing aid: sodium sulfate 2% owf ammonium acetate 5% owf After the treatment, 70% using a nonionic surfactant 1 g / liter aqueous solution concentration of 30 liter. The soaping was performed at 20 ° C. for 20 minutes. Then, after washing with water for 30 minutes, centrifugal dehydration, air drying and vacuum drying were performed in the same manner as in Example 1, and the temperature was reduced to 20 ° C-6.
A sample for measurement was left overnight in an atmosphere of 0% RH.
Each sample was evaluated for this measurement sample, and the results are shown in Table 1.

Comparative Example 1 Attached white cloth (silk 2-) for dyeing fastness test used in Example 1
No. 1 manufactured by the Japan Standards Association) as a measurement sample. Table 1 shows the results. It can be seen that the shrinkage-preventing treatment of the present invention greatly improves the shrinkage of washing and ironing.

Comparative Example 2 In Example 1, washing, centrifugal dehydration, air-drying overnight, and vacuum drying were performed in the same manner as in Example 1 except that the shrinking treatment was performed only with an acid, and left overnight in an atmosphere of 20 ° C.-60% RH. To obtain a measurement sample. Each sample was evaluated for this measurement sample, and the results are shown in Table 1. Although the shrinkage is improved only by the acid treatment, the improvement is not as great as that of the present invention.

[0028]

[Table 1]

[0029]

According to the present invention, it is possible to obtain a silk product having excellent shrink resistance, which is a great improvement as compared with the prior art.

Claims (2)

[Claims] 1. A shrink-preventing silk product which is treated with a compound represented by the following formula (1). Embedded image 2. A method for producing a silk product, comprising crosslinking a silk product with a compound represented by the following formula (1) under acidic conditions. Embedded image