JP2001262470A - Silk-processed acrylic blanket and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic blanket having excellent feeling and washing resistance, excellent in sweat-absorbing and warmth-keeping properties, and expected to have skincare effect, and to provide a method for manufacturing the same. SOLUTION: The first invention is a silk-processed acrylic blanket which is obtained by treating a porous acrylic blanket with a low-molecular weight silk fibroin having a molecular weight in the range from 5,000 to 50,000 together with a softening agent selected from the group of nonionic softening agents or anionic softening agents. The second invention is a method for manufacturing the silk-processed acrylic blanket comprising the processes that a low-molecular weight silk fibroin having a molecular weight in the range from 5,000 to 50,000 together with a softening agent is applied on a porous acrylic blanket, and the treated blanket is dried.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silk-processed acrylic blanket which is excellent in texture, has washing durability, is excellent in sweat absorption and moisture retention, and is expected to provide skin care, and a method for producing the silk-processed acrylic blanket.

[0002]

2. Description of the Related Art Conventional acrylic blankets are excellent in heat retention, but their moisture retention is inferior to those using natural fibers such as wool, cotton, rayon and silk. Therefore, in order to improve the heat retention and moisture absorption, a water-absorbing surfactant is provided, and other fibers having moisture absorption are blended or cross-woven. Also, at the stage of producing raw cotton, kneading of a moisture absorbing material such as silk is performed.

[0003] However, the application of a surfactant often lacks washing durability, and the method of mixing with other fibers also complicates dyeing and the like, and in the production of a silk-processed acrylic blanket and the like, the efficiency is reduced and the cost is high. There is a drawback that leads to conversion. In addition, the kneading method during the production of raw cotton also involves many technical problems, and it is extremely difficult to obtain the desired quality.

[0004]

In view of such circumstances, the inventors have made intensive studies to improve the problems of the prior art, and as a result, low-molecular weight silk fibroin was replaced with a nonionic or anionic softener. By processing it into a porous acrylic blanket in combination, it is possible to easily and stably apply low molecular weight silk fibroin to the acrylic blanket, to have excellent texture, excellent washing durability, and excellent sweat absorption and moisture retention. Heading, the present invention has been completed, the purpose of which is excellent in texture, excellent in washing durability,
Another object of the present invention is to provide an acrylic blanket excellent in sweat absorption and moisture retention and expected to provide skin care, and a method for producing the same.

[0005]

To achieve the above object, the present invention has the following arrangement. That is, the first invention is to process a porous acrylic blanket by using low molecular weight silk fibroin having a molecular weight of 5,000 to 50,000 in combination with a softener selected from the group of nonionic or anionic softeners. The second aspect of the present invention is a silk-processed acrylic blanket characterized by having a molecular weight of 5,000 to 5
A gist of the present invention is a method for producing a silk-processed acrylic blanket, which comprises applying a low-molecular-weight silk fibroin in the range of 000 in combination with a softening agent to a porous acrylic blanket and drying.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

[0007] The silk fibroin used in the present invention is obtained by refining silk waste fiber by-produced in a silk mill or silk spinning mill by a conventional method using Marcel soap and soda ash to reduce residual sericin to 1% by weight or less. Apply things. The solvent of silk fibroin is described in Japanese Patent Publication No. 58-38449, for example, a copper-ethylenediamine aqueous solution, a copper hydroxide-ammonia aqueous solution (Shweizer reagent), a copper hydroxide-alkali-glycerin aqueous solution (Rohe reagent), Examples thereof include an aqueous solution of lithium bromide, an aqueous solution of calcium or magnesium or zinc hydrochloride or nitrate or thiocyanate, and an aqueous solution of sodium thiocyanate. Of these, calcium or magnesium hydrochloride or nitrate is preferred in view of cost and use.

The average molecular weight cutoff used in the present invention is 5,0
As a method for preparing a low molecular weight silk fibroin of the fraction of 00 to 50,000, the silk fibroin aqueous solution is once treated with an acid (for example, hydrochloric acid, sulfuric acid or the like) as disclosed in JP-A-04-100976. , Alkali (eg, sodium hydroxide, potassium hydroxide, etc.) treatment, hydrolytic enzyme (eg, pronase obtained from actinomycetes, prolase obtained from papaya, etc.) to give a low molecular weight, and then cellophane etc. Dialysis membrane or hollow fiber dialyzer (average molecular weight cut off: 1,000-
5,000) by dialysis and removal of a low molecular weight fraction having an average molecular weight of 5,000 or less.

As the low molecular weight silk fibroin used in the present invention, those having a molecular weight in the range of 5,000 to 50,000 are used. Preferably 20,000-40,
000. If the molecular weight is 50,000 or more, the water solubility decreases, the processability into fibers becomes unstable, and yellowing occurs. The whiteness of the fibers tends to decrease, which is not preferable. Further, the use of those having a molecular weight of not more than 5.000 improves the water solubility and improves the workability. However, the adhesiveness to the vertebra is reduced, and the texture of silk fibroin is deteriorated, so that the desired purpose cannot be obtained. Not preferred. The low molecular weight silk fibroin used in the processing method of the present invention is such that silk fibroin of the molecular weight size imparts high performance and high quality to the blanket.

The processing concentration of the low molecular weight silk fibroin used in the present invention is preferably 1 to 10% by weight.

The fibers used in the acrylic blanket of the present invention include fine wrinkles, fine irregularities,
It is particularly preferable to use porous acrylic fibers having pores and voids. The portion to be treated with low molecular weight silk fibroin is preferably used in a pile portion on a blanket surface, and the pile portion preferably contains 50% or more of the porous acrylic fiber.

The porous acrylic fiber used for the acrylic blanket used in the present invention is disclosed in JP-A-7-2290.
No. 65, a porous acrylic synthetic fiber may be used, and a polymer containing acrylonitrile as a main constituent unit (for example, acrylonitrile is 40% by weight)
(A) a copolymer containing the above and other vinyl monomers, methyl acrylate, etc. in a proportion of 60% or less, and a polymer miscible and incompatible with the polymer (acetyl cellulose, polyacetic acid) (B) etc.
And both exist in a phase-separated state, and the porosity V is 0.05 to
The surface area A of the pores is 15 m ² / g or less at 0.75 cm ³ · g.

As a method for producing the porous acrylic fiber, for example, a method disclosed in Japanese Patent Application Laid-Open No. 7-229065, that is, 2 to 20 parts by weight of the polymer (B) and 80 to 98 parts of the polymer (A) A spinning solution containing a polymer consisting of parts by weight is spun into a coagulation bath at a temperature of at most 30 ° C. to form fibers in which the formation of fine pores is suppressed, and then a large pore structure obtained by primary drawing Is dried by drying the fiber containing the polyisocyanate to substantially eliminate the fine pores, and then secondary stretching is performed to promote the large pore structure.

Examples of the softener used in the present invention include a nonionic softener and an anionic softener. Specifically, a handbook for dyeing and finishing (Nippon Textile Center Co., Ltd.
Examples of the nonionic softener described on page 45 include a polyhydric alcohol higher fatty acid ester and a softer component such as an Acobel-type nonylphenol ethylene oxide adduct (NP nonion) and a higher alcohol ethylene oxide adduct (higher alcohol). Examples thereof include those emulsified with a nonionic surfactant such as a nonionic surfactant, and examples of the anionic softening agent include an aerosol OT type (dialkyl sulfosuccinate). On the other hand, cationic softeners such as Akobel-type, imidazoline-type acid salts, and those obtained by converting them into quaternary ammonium salts with an alkylating agent, are used in processing silk. It is not preferable because it preferentially adheres to the acrylic fiber and inhibits the adhesion of silk, resulting in poor processability.

The concentration of the softener used in the present invention is preferably 0.1 to 7.0% by weight based on the total amount of the low molecular weight silk fibroin-treated solution.

The method for producing the silk-processed acrylic blanket in the present invention includes a padding method, a spraying method, a coating method, and the like. For example, in the padding step for adjusting the texture after dyeing or printing the acrylic blanket, one dipping process is performed. A method implemented by a nip padding method,
A spray method in which a mixture of low molecular weight silk fibroin and a softener is sprayed onto the surface of an acrylic blanket using a sprayer, and a coating method implemented by applying low molecular weight silk fibroin together with a softener to the entire surface of the fabric, etc. No. In terms of increasing sweat absorption and moisture absorption,
Coating methods are particularly preferred.

[0017]

The present invention will be described in detail below with reference to examples and comparative examples.

Examples 1 to 4 and Comparative Examples 1 to 4 (Method for producing porous acrylic blanket) As a method for producing a porous acrylic blanket, for example, acrylonitrile (AN) / methyl acrylate (MA) / 2-acrylamide-2 −
Sodium methylpropanesulfonate (SAM) = 91.2
A dimethylformamide (DMF) solution containing 80 parts of an acrylic polymer having a composition of /8.0/0.8 and 20 parts of cellulose acetate and having a polymer concentration of 20% was used as a stock solution for spinning.
The fiber is spun into a 60% DMF aqueous solution at 0 ° C., subjected to primary stretching 5 times after spinning, dried in a hot roller dryer at 120 ° C. until the water content becomes 0.5%, and then heated to 100 ° C. Below 2
Next stretching was performed 1.1 times. After crimping and crimp setting, 3 denier fiber was obtained. The porosity V of the obtained fiber is 0.357 cm ³ / g, and the surface area A is 2.04 m ² / g.
g and V / A were 1 / 5.7. The obtained acrylic synthetic fiber was spun into a 30th single yarn by spinning according to a conventional method, and then subjected to warp knitting and opened to obtain a porous acrylic blanket. (Examples 1 to 4, Comparative Examples 1, 2 and 4)

(Production method of general acrylic blanket) As a method for producing a general acrylic blanket, a method disclosed in JP-A-08-337930 may be used. For example, acrylonitrile (AN) / vinylidene chloride (VC12) / 2- Acrylamide-2-methylpropanesulfonic acid sodium (SA
M) = dimethylformamide (D) such that the acrylic polymer concentration of 56/40/4 (% by weight) is 28%.
MF) to prepare a spinning stock solution. Then, 1.2% by weight of titanium oxide was added as a DMF dispersion liquid to the spinning stock solution, and DMF / water = 55/45 (% by weight) at 20 ° C. through a 0.336 mm × 0.056 mm, 25,000-hole flat die 3. After spinning into a coagulation bath and stretching 5.5 times,
The fibers were washed with water to obtain gel-swelled fibers. The obtained acrylic synthetic fiber was spun into a No. 30 single yarn by a conventional method to form a warp knit, and then opened to obtain a general acrylic blanket (Comparative Example 3).

(Preparation of low molecular weight silk fibroin) Using silk spun waste as a raw material of silk fibroin, 100 parts of the same were stirred and scoured with a solution of 30 parts of Marcel soap and 3000 parts of water at 95 to 98 ° C. for 3 hours, and the remainder was scoured. 0.1 glue
%, And washed with water and dried with hot air at 30 ° C.
100 parts of calcium chloride (CaCl ₂ .2H ₂ O)
Of the 38% by weight aqueous solution of calcium chloride.
0 parts were prepared and heated to 110 ° C. Forty parts of the refined silk spun were added to the kneader while stirring for 5 minutes using a kneader, and then stirred for 30 minutes to completely dissolve.

Next, the inner diameter is 200 μm, the film thickness is 20 μm, and the length is 5 μm.
Regenerated cellulose hollow fiber of 00 mm (2,000 bundles)
The lysate was flowed in at a rate of 0.2 l / hour using a holo-fiber dialysis apparatus (1) and dialyzed with deionized water to obtain an aqueous fibroin solution. The aqueous fibroin solution had a fibroin concentration of 11% and a residual calcium chloride of 0.001% by weight. The molecular weight of the obtained silk fibroin was about 150,000 as measured by HPLC under the following conditions.

Column: Asahipak GS-620 Eluent: 0.2 M phosphate buffer (pH 7.0) Elution conditions: flow rate 1.0 ml / min Standard substances: cytochrome, ovalbumin, transferrin Detection: absorbance at 280 nm

To 1000 parts of this was added sodium hydroxide 0.
Five parts of 10 parts of an aqueous solution were mixed, heated and stirred at 80 ° C. for 4 hours to hydrolyze silk fibroin. The fibroin aqueous solution was applied to an inner diameter of 50 μm, a film thickness of 10 μm, and a length of 500 m.
using a hollow fiber dialysis device (average molecular weight cut-off 5000) of the regenerated cellulose-based hollow fiber with a flow rate of 0.2 l / hour and dialyzed with deionized water to obtain a fibroin aqueous solution. I got The aqueous fibroin solution had a fibroin concentration of 15% and a residual calcium chloride of 0.0003% by weight. The molecular weight of the silk fibroin after hydrolysis was about 35,000 as measured by HPLC under the above conditions (Examples 1 and 2,
Comparative Examples 3 and 4).

(Preparation of silk fibroin) The conditions of hydrolysis treatment with sodium hydroxide carried out to obtain silk fibroin having a molecular weight of about 35,000, at 80 ° C.
Was replaced with 4 hours of heating and stirring, and about 500 silk fibroin was obtained under the conditions of heating and stirring at 95 ° C. for 20 hours (Comparative Example 1). Under the conditions of heating and stirring at 90 ° C. for 6 hours, about 5,000 silk fibroin was obtained (Example 3). Under the conditions of heating and stirring at 70 ° C. for 5 hours, about 50,000 silk fibroin was obtained (Example 4). Further, about 100,000 silk fibroin was obtained under the conditions of heating and stirring at 60 ° C. for 3 hours (Comparative Example 2).

Example 1 (Silk processing method) Low molecular weight silk fibroin (molecular weight: 3,5000)
A treatment solution comprising a softener and a softener (nonionic) was prepared with the following composition. Treatment liquid Low molecular weight silk fibroin (Example 1) 3% by weight Nonionic softener: 5% by weight polyethylene glycol in acrylonitrile copolymer Water 92% by weight Processing of low molecular weight silk fibroin into acrylic blanket is 1 dipping Performed by the one-nip padding method. The acrylic fiber blanket (porous acrylic blanket) was continuously immersed in a padding bath in a roll batter filled with a low molecular weight silk fibroin treatment solution through a guider (the padding squeezing rate was 45%), and then. The blanket is dehydrated with a mangle so as to have a squeezing ratio of 100%, and then dried by a non-touch method at a temperature of 100 to 120 ° C. using a denting machine. Low molecular weight silk fibroin was treated at 3% by weight based on fiber weight.

The silk adhesion rate A was calculated by the following equation. A (%) = [(weight after treatment−weight before treatment) / weight before treatment] × 100 The silk adhesion rate was determined to be 0.02% or less as poor.

The washing test is a practical washing test JISL021.
It followed the 7-103 method. Washing was repeated 5 times and evaluated. The wash-resistance rate was 20% or more as a passing point.

The texture was evaluated by five judges on the silk-treated surface after washing five times according to the following judgment items, and the five judgment points were averaged. 5: Significant change compared to unprocessed. 4: Changed compared to unprocessed. 3: Intermediate change between 2 and 4. 2: Slight change from unprocessed. 1: Same as unprocessed.

Examples 2-4, Comparative Examples 1-4 (Silk processing method) As shown in Table 1, molecular weight 500 (Comparative Example 1), molecular weight 5,000 (Example 3), 35,000 (Example 2, Comparative Examples 3 and 4), using a silk fibroin stock solution having a molecular weight of 50,000 (Example 4) or a molecular weight of 100,000 (Comparative Example 2), while using the same nonionic softener as in Example 1 ( Examples 3 and 4, Comparative Examples 1 and 2, a cationic softener (Acobel-type acid salt 0.7% by weight, Comparative Examples 3 and 4), and an anionic softener (Dialkyl sulfosuccinate 5.0% by weight) Using Example 2), silk fibroin of each molecular weight size and the softener were respectively combined to prepare a treatment liquid, and the treatment liquid was subjected to a 1-dip 1-nip padding method under the same conditions as in Example 1. Aku Attached to Le textiles blankets and processed. In addition, in the case of Comparative Example 3, the acrylic fiber material blanket was used in place of the porous acrylic blanket and the above-mentioned general acrylic blanket was used. In other cases, the porous acrylic blanket was used as in Example 1. . The silk adhesion rate, the washing test, and the texture were evaluated in the same manner as in Example 1.

As a result, as shown in Table 1, Examples 1-4
Compared to Comparative Examples 1 to 4, was excellent in texture, silk adhesion and washing resistance, and also had excellent effects in sweat absorption and moisture retention.

[0031]

[Table 1]

[0032]

As described in detail above, the silk-processed acrylic blanket obtained according to the present invention is excellent in texture, durable in washing, excellent in sweat absorption and moisture retention, can be expected for skin care, and is very useful. is there. Further, it can be easily carried out by the production method of the present invention.

Claims (2)

[Claims] 1. A process for producing a porous acrylic blanket using low molecular weight silk fibroin having a molecular weight of 5,000 to 50,000 in combination with a softening agent selected from the group consisting of nonionic and anionic softening agents. A characteristic acrylic blanket. 2. A process for producing a silk-processed acrylic blanket, comprising applying low-molecular-weight silk fibroin having a molecular weight in the range of 5,000 to 50,000 to a porous acrylic blanket in combination with a softening agent, and drying. .