JPH08103189A - Production of colored silk yarn - Google Patents

Abstract

PURPOSE: To simply obtain colored silk yarns excellent in gloss and light and wash fastness by allowing silk worms to absorb a specific colorant solution through their spiracles and to discharge colored yarn from their mouth. CONSTITUTION: Silk worms are allowed to absorb, from their spiracles, a colorant solution such as an aqueous dispersion of a pigment such as azo pigment in an aqueous medium prepared from at least one of surfactant selected from anionic, cationic, nonionic or amphoteric surfactants and/or a water-soluble macromolecule such as polyvinyl pyrrolidone, polyacrylic acid and the like as a dispersant and colored yarns are discharged from the mouths of silk worms whereby this colored silk yarn is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing colored silk thread from which colored silk thread is discharged from silkworm larvae, and more particularly to a method for producing colored silk thread excellent in light resistance and washing fastness.

[0002]

2. Description of the Related Art Conventionally, the following methods are known as typical silk dyeing methods. First, the dye is dissolved in a small amount of hot water, the dye liquor is diluted to about 50 times the weight of the silk to be dyed, and soda sulfate is mixed to form a dye liquor. Next, silk which has been washed with hot water is put into this dye solution and gradually heated so as to boil after about 30 minutes. Furthermore, about 3
Allow the dye to completely adhere to the silk for 0 minutes, and when the dye has completely adhered to the silk, remove the silk from the dye solution,
Wash with water and dry to obtain colored silk thread.

Further, instead of dyeing the generated cocoons after the fact,
Attempts have also been made to produce cocoons that are already colored when producing them. For example, the dye is applied multiple times to the spiracles of a silkworm that has grown to 4 years after the start of 4 sleeps, and the dye is adsorbed to the silk thread inside the silkworm body, and the dyed silk thread is discharged from the mouth of the silkworm. A method for producing colored cocoons is known (Japanese Patent Publication No. 54-30944).

As another method for producing colored cocoons, the silkworm larvae are dipped in a dye solution to adsorb the dye from the larva's larvae to the silk thread inside the body, and the dyed silk thread is discharged from the silkworm's mouth. There is known a method for producing colored cocoons (Japanese Patent Laid-Open No. Hei 3)
No. 193904).

[0005]

However, in the above-mentioned dyeing method of immersing the silk thread in the dye solution, there are many working steps, and a considerable amount of time and labor is required for one work. Since a dye solution of about 50 times the weight of silk to be dyed is required, a large amount of equipment and a large amount of dye are required. Further, it is very difficult to control the temperature and time, and if proper control is not performed, discoloration may occur. Further, since the shade of the color changes subtly depending on the ratio of the dye and water, it was extremely difficult to dye the shade as desired.

[0006] Further, a dye solution is applied to the larvae of the silkworm larvae described above, or the silkworm larvae are dipped in the dye solution so that the dye is adsorbed to the silk thread in the silkworm's womb, and the silk thread dyed from the mouth of the silkworm is removed. In the method of producing a colored cocoon by discharging and producing a colored silk thread, although a colored cocoon is obtained,
The dye used during boiled cocoon is severely discolored, and since the colored silk yarn is manufactured from this cocoon, color loss is large even during the treatment process. Further, since the dye is used, there is a defect that light resistance and wash fastness are weak. Further, in the step of repeatedly immersing the silkworm larvae in the dye solution, there is a problem that the silkworm larvae die by about 30%.

The present inventors have conducted various studies in order to eliminate the above-mentioned defects, and as a result, by using an aqueous pigment dispersion from which coarse pigment particles have been removed by centrifugal separation or the like as a colorant solution, the silkworm The present invention has been completed by discovering that silkworm larvae do not die at all even when the larvae of No. 1 are soaked in this coloring solution, and colored silk yarns excellent in light resistance and wash fastness can be obtained. .

[0008]

Means for Solving the Problems That is, the present invention provides a method for producing a colored silk thread in which a colorant solution is absorbed from the larvae of the silkworm larvae and colored threads are discharged from the mouth of the larvae. The method for producing a colored silk yarn is characterized in that an aqueous pigment dispersion in which a pigment is finely dispersed in an aqueous medium containing a surfactant and / or a water-soluble polymer as a dispersant is used.

[0009]

[Function] When a silkworm larva grown at about 5th instar is immersed in an aqueous pigment dispersion in which a pigment is finely dispersed in an aqueous medium, an aqueous pigment dispersion solution is obtained from the respiratory tract of the silkworm larva Be absorbed. At that time, the fine particles of the pigment that have entered the larvae's womb from the spiracles are uniformly adsorbed by the protein, which is the raw material of the silk thread. Then, when this larva transforms into pupa, a cocoon composed of a colored thread mainly composed of a protein to which a pigment is adsorbed is produced. This colored cocoon does not fade even when spun in hot water because the coloring component is a pigment, and it is possible to obtain a colored silk thread having gloss and excellent light resistance and fastness to washing.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The aqueous pigment dispersion used as a colorant solution in the present invention is a pigment finely dispersed in an aqueous medium together with a dispersant such as a surfactant and / or a water-soluble polymer. Examples of the pigment used in the aqueous pigment dispersion include azo pigments, anthraquinone pigments, copper phthalocyanine pigments, quinacridone pigments, indigo pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, azomethine azo. Examples thereof include pigments, perylene pigments, perinone pigments, complex oxide pigments, and the like.

These pigments are added in an amount of 0.5 to 0.5 in the aqueous pigment dispersion.
Used in a concentration range of 30% by weight. The dispersant is adsorbed on the surface of the pigment particles and acts as a protective colloid in water. The dispersant has a polyoxyalkylene higher fatty acid alcohol ether having an HLB value of 8 to 15, a polyoxyalkylene alkylphenol ether, and a polyoxyalkylene alkylphenol ether. Oxyalkylene higher fatty acid ester, higher fatty acid partial ester of polyhydric alcohol, higher fatty alcohol alcohol of sugar, higher fatty acid ester of sugar, higher fatty acid ester of polyoxyalkylenated sugar, polyoxyalkylene-natural oil condensation Compounds, nonionic surfactants such as oxyethylene-oxypropylene block polymers, sulfonates of naphthalene-formaldehyde condensate, higher fatty alcohol sulfate esters, alkylated sulfonates of higher fatty acid amides, alkylallyl sulfonic acids Anionic surfactant such as salt, polyvinyl Water-soluble polymers such as loridone, polyacrylic acid, acrylic acid copolymers, maleic acid, etc., and polymers having a lipophilic portion, a cationic portion and a hydrophilic portion together, for example, water-soluble The lipophilic portion of the polymer includes acrylic acid, methacrylic acid, itaconic acid, fumaric acid, alkyl ester, cycloalkyl ester, arylalkyl ester and aryl ester of α, β-ethylenically unsaturated carboxylic acid. Is a polymer composed of a polyester, styrene, α-methylstyrene, vinyltoluene or a mixture of two or more thereof, and the lipophilic portion is 10 to 93% by weight in the water-soluble polymer, preferably 30 to 90% by weight.

As the monomer for forming the cationic part of the water-soluble polymer, there are conventionally known monomers having a primary, secondary, tertiary amino group, quaternary ammonium group or pyridinium group in the molecule. Monomers are used. For example, N-alkylaminoalkyl esters of the above-mentioned unsaturated carboxylic acids, N, N-dialkylaminoalkyl esters, N,
N, N-trialkylammonium alkyl ester,
γ- (N-alkylamino) -β-hydroxy-propyl ester and the like. The cationic portion is 2 to 50% by weight, preferably 7 to 40% by weight in the water-soluble polymer.

The hydrophilic portion of the water-soluble polymer is (a) an anionic hydrophilic group and its aqueous medium-soluble salt, (b) a cationic hydrophilic group and its aqueous medium-soluble salt, (c) a nonionic hydrophilic group, And a polymer portion having a mixture thereof. Examples of the above-mentioned anionic hydrophilic group include a carboxyl group, a sulfonic acid group, a sulfuric acid ester group and a phosphoric acid ester group, and alkali metal salts such as sodium salt, potassium salt and ammonium salt.

The cationic hydrophilic group is a primary, secondary, tertiary amino group, quaternary ammonium group or pyridinium group, and the primary amino group or substituent has 1 to 4 carbon atoms.
Secondary, tertiary amino groups, quaternary ammonium salts and lower fatty acid salts thereof, for example, formic acid, acetic acid, propionic acid salts and inorganic acid salts, for example, hydrochloride, hydrobromide, sulfonic acid Examples thereof include salts, sulfate ester salts, and phosphate salts.

Next, examples of the nonionic hydrophilic group include a hydroxyl group, a carboxamide group, an ether group and a hydroxyethyl group. The approximate content of the hydrophilic part in the water-soluble polymer is 5 to 40% by weight in the (a) anionic hydrophilic part, and 10 in the (b) cationic hydrophilic part.
˜50% by weight, 20% in the nonionic hydrophilic part (c)
It is 60% by weight.

The above-mentioned water-soluble polymer used in the present invention is prepared by appropriately blending the above-mentioned monomers, and any of the conventionally known mixed polymerization methods such as solution polymerization method, suspension polymerization method and emulsion polymerization method can be used. It can also be obtained by a polymerization method. The amount of this water-soluble polymer used depends on the pigment, but the amount of pigment 100
It is 1 to 10 parts by weight, preferably 5 to 60 parts by weight with respect to parts by weight.

The aqueous pigment dispersion of the present invention contains a preservative,
A dispersant or the like is added as needed. The aqueous pigment dispersion used in the present invention comprises the above-mentioned components and blends, and various production methods can be adopted. For example, a typical method is to mix the above components and mix and grind them with a conventionally known disperser such as a ball mill, a homomixer, a sand grinder, a speed line mill and a roll mill. The aqueous pigment dispersion used in the present invention is preferably subjected to a centrifugal separation treatment at a centrifugal acceleration of 25,000 G or less for the purpose of removing coarse particles existing therein.

To use a colorant solution consisting of the above aqueous pigment dispersion and to absorb it from the larvae of the silkworm larvae,
Any method such as a dipping method, a brush coating method and a spray method may be used, but the dipping method is preferable from the viewpoint of work efficiency. The temperature of the colorant solution in which the silkworm is dipped is 10 to 45.
It is in the range of ℃
It is preferable because the solution is well absorbed.

[0019]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. Parts or% in Examples or Comparative Examples are based on weight. Example 1 (Preparation of aqueous pigment dispersion solution) Blue α-type copper phthalocyanine pigment (CI Pigment Bull-15) 50 parts Anionic surfactant (condensate of formalin and sodium naphthalenedicarboxylate) 12.5 parts Water 182.5 copies

The above components were placed in a 1,000 ml beaker and mixed well for 10 minutes, the mixture was transferred to a 500 ml container, and a glass bead having a diameter of 2 mm was filled therein to a filling rate of 40%. In addition, the mixture was shaken with a paint shaker for 1 hour to obtain a dispersion liquid. Next, the above dispersion liquid was placed in a high-speed centrifugal separator and treated for 20 minutes to remove coarse particles, to obtain 225 parts of a blue aqueous pigment dispersion solution. Further, this pigment dispersion solution was diluted with water to prepare a blue aqueous pigment dispersion solution having a pigment concentration of 8%.

(Production of colored silk thread) A plurality of silkworm larvae (about 100) grown at the fifth instar are dipped in the blue aqueous pigment dispersion solution (pigment concentration 8%) obtained above for about 2 to 3 seconds. Further, the above dipping operation is repeated 2 to 5 times.
At that time, the silkworm larvae did not die at all. According to the above dipping, the blue aqueous pigment dispersion solution was well absorbed from the respiratory tract, the respiratory tract of the silkworm, and the blue pigment was uniformly adsorbed to the protein in the womb of the silkworm. Thus, the silkworm larvae in which the blue pigment was accumulated in the body were no different from normal silkworm larvae.

Then, the silkworm larvae which have completed the above-mentioned work are bred by a usual breeding method. By doing this, when the silkworm larvae metamorphose into pupae, the blue thread absorbed into the body was ejected to produce blue cocoons. By picking up the above cocoon, a blue silk thread without thread breakage was obtained. The obtained blue silk thread has luster and copper phthalocyanine bull-pigment original physical properties, is extremely excellent in light resistance as compared with the one using a dye, has no discoloration, and has very good wash fastness. Was excellent.

For comparison, the same blue aqueous pigment dispersion solution as described above, which was not subjected to high-speed centrifugation, was used, and the larvae of the silkworm were soaked in this solution. The silk thread obtained from the cocoons of the silkworm, which was not sufficiently performed, had uneven color and often had thread breakage.

Example 2 (Preparation of Aqueous Pigment Dispersion Solution) Red quinacridone pigment (CI Pigment Violet 19) 50 parts Polyoxyethylene nonylphenyl nonionic surfactant (HLB: 15) 10 parts Water 190 parts The above components were placed in a 1,000 ml beaker and mixed well for 10 minutes, the mixture was transferred to a 500 ml container, and glass beads having a diameter of 2 mm were added to the container so that the filling rate was 40%. The dispersion was obtained by shaking with a paint shaker for 1 hour. Next, the above dispersion liquid was put into a high-speed centrifugal separator and treated for 20 minutes to remove coarse particles to obtain 230 parts of a red aqueous pigment dispersion solution. Further, this pigment dispersion solution was diluted with water to prepare a red aqueous pigment dispersion solution having a pigment concentration of 8%.

(Production of colored silk thread) A plurality of silkworm larvae (about 100) grown at the fifth age are dipped in the red aqueous pigment dispersion solution (pigment concentration 8%) obtained above for about 2 to 3 seconds. Further, the above dipping operation is repeated 2 to 5 times.
At that time, the silkworm larvae did not die at all. According to the above-mentioned dipping, the red aqueous pigment dispersion solution was well absorbed from the respiratory tract, which is a respiratory organ of the silkworm, and the red pigment was uniformly adsorbed to the protein in the womb of the silkworm. In this way, the silkworm larvae in which the red pigment was accumulated in the body were no different from normal silkworm larvae. For comparison, as a result of using the same red aqueous pigment dispersion solution as described above, which was not subjected to the high-speed centrifugation treatment, as a result of immersing the silkworm larvae in this solution, the absorption of the red pigment from the air gate was sufficiently performed. However, the silk thread obtained from the silkworm cocoon had uneven color and often had thread breakage.

Example 3 (Preparation of Aqueous Pigment Dispersion Solution) Azomethine azo black pigment (trade name: AMA Black, product of Dainichiseika Kogyo Co., Ltd.) 50 parts Anionic surfactant similar to that of Example 1 12 parts Water 188 Parts The above components were ground and dispersed for 40 minutes using a desktop sand mill to obtain a black pigment dispersion. Next, this black pigment dispersion was put into a high-speed centrifugal separator and treated for 15 minutes to remove coarse particles to obtain 220 parts of a black aqueous pigment dispersion solution. Further, this pigment dispersion solution was diluted with water to obtain a black aqueous pigment dispersion solution having a pigment concentration of 5%.

(Production of colored silk thread) A plurality of silkworm larvae (about 100) grown at the 5th instar are dipped in the black aqueous pigment dispersion solution (pigment concentration 5%) obtained above for about 2 to 3 seconds. Further, the above dipping operation is repeated 2 to 5 times.
At that time, the silkworm larvae did not die at all.

According to the above-mentioned dipping, the black aqueous pigment dispersion solution has good absorption from the respiratory tract, which is a respiratory organ of the silkworm,
The black pigment was uniformly adsorbed on the protein in the womb of the silkworm. In this way, the silkworm larvae in which the black pigment was accumulated in the body were no different from normal silkworm larvae. For comparison, using a black aqueous pigment dispersion solution similar to the above, which was not subjected to high-speed centrifugation, and immersing the silkworm larvae in this solution resulted in sufficient absorption of the black pigment from the stomata. However, the silk thread obtained from the silkworm cocoon had uneven color and often had thread breakage.

Example 4 (Preparation of Aqueous Pigment Dispersion Solution) Yellow isoindolinone pigment (CI Pigmentero-110) 45 parts Nonionic surfactant similar to Example 2 10 parts Water 243 parts The component (1) was ground and dispersed for 60 minutes using an attritor to obtain a yellow pigment dispersion. Next, this yellow pigment dispersion was put into a high-speed centrifugal separator and treated for 15 minutes to remove coarse particles to obtain 276 parts of a yellow aqueous pigment dispersion solution.
Further, this pigment dispersion solution is diluted with water to adjust the pigment concentration to 3
% Yellow aqueous pigment dispersion solution.

(Production of colored silk thread) A plurality of larvae of silkworms (about 100) grown at the fifth instar are dipped in the yellow aqueous pigment dispersion solution (pigment concentration 3%) obtained above for about 2 to 3 seconds. Further, the above dipping operation is repeated 2 to 5 times.
At that time, the silkworm larvae did not die at all. According to the above dipping, the yellow aqueous pigment dispersion solution was well absorbed from the respiratory tract, the respiratory tract of the silkworm, and the yellow pigment was uniformly adsorbed to the protein in the womb of the silkworm. In this way, the silkworm larvae in which the yellow pigment was accumulated in the body were no different from normal silkworm larvae. For comparison, using the same yellow aqueous pigment dispersion solution as above, which was not subjected to high-speed centrifugation, the result of immersing the silkworm larvae in this solution was that absorption of the yellow pigment from the air gate was sufficiently performed. However, the silk thread obtained from the silkworm cocoon had uneven color and often had thread breakage.

Example 5 (Preparation of Aqueous Pigment Dispersion Solution) Azomethine azo orange pigment 50 parts Nonionic surfactant similar to that in Example 2 10 parts Water 100 parts The above components were used in a ball mill for 10 hours. It was ground and dispersed to obtain an orange pigment dispersion. Next, this orange pigment dispersion was put into a high-speed centrifugal separator and treated for 30 minutes to remove coarse particles to obtain 230 parts of an orange aqueous pigment dispersion solution. Further, this pigment dispersion solution is diluted with water to obtain a pigment concentration of 10
% Orange aqueous pigment dispersion solution.

(Production of colored silk thread) A plurality of silkworm larvae (about 100) grown at the 5th instar are immersed in the orange aqueous pigment dispersion solution (pigment concentration 10%) obtained above for about 2 to 3 seconds. Further, the above dipping operation is repeated 2 to 5 times.
At that time, the silkworm larvae did not die at all. According to the above dipping, the orange aqueous pigment dispersion solution was well absorbed from the respiratory tract, the respiratory tract of the silkworm, and the orange pigment was uniformly adsorbed to the protein in the womb of the silkworm. Thus, the silkworm larvae in which the orange pigment was accumulated in the body were no different from normal silkworm larvae.

[0033]

According to the method for producing colored silk yarn of the present invention,
Pigments are adsorbed from the respiratory organs of the silkworm larvae, the spleen, to the protein that is the source of silk thread in the womb, and the silkworm larvae never die. Then, when the larva transforms into pupa, cocoons are produced by discharging threads having the color tone of the pigment mixed in the protein in the womb of the larva. By spinning this colored cocoon, it is possible to obtain a glossy colored silk thread excellent in light resistance and fastness to washing.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kyoe Ogihara 618-2 Horishita, Akabori-cho, Sawa-gun, Gunma Prefecture (72) Inventor Yoshio Abe 5-chome 11-32, Higashiiwatsuki, Iwatsuki-shi, Saitama (72) Inventor Akira Hoshino 3-4 Koshigayahoncho, Koshigaya City, Saitama Prefecture

Claims (9)

[Claims] 1. A method for producing a colored silk thread in which a colorant solution is absorbed from the larvae of silkworm larvae and colored threads are discharged from the mouth of the larvae, wherein a surfactant and / or a highly water-soluble pigment is used as the colorant solution. A method for producing a colored silk yarn, which comprises using an aqueous pigment dispersion in which a pigment is finely dispersed in an aqueous medium having a molecule as a dispersant. 2. The production of colored silk yarn according to claim 1, wherein the surfactant is one or more selected from anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants. Method. 3. The water-soluble polymer is a polymer having both a lipophilic portion, a cationic portion and a hydrophilic portion.
The method for producing a colored silk thread according to 1. 4. A lipophilic moiety of a water-soluble polymer includes acrylic acid, methacrylic acid, itaconic acid and fumaric acid. Alkyl esters, cycloalkyl esters and ants of α, β-ethylenically unsaturated carboxylic acids. -Alkyl ester and aryl ester, styrene, α-methylstyrene, vinyltoluene or a polymer composed of a mixture of two or more thereof, wherein the lipophilic moiety is 10 to 93% by weight in a water-soluble polymer. The method for producing a colored silk yarn according to claim 1, wherein 5. The cationic part of the water-soluble polymer is a primary, secondary, tertiary amino group, quaternary ammonium group,
A polymer moiety having a pyridinium group or two or more groups thereof, wherein the cationic moiety is 2 in the water-soluble polymer.
The method for producing a colored silk thread according to claim 1, which accounts for ˜50% by weight. 6. A water-soluble salt of a water-soluble polymer, wherein the hydrophilic portion is (a) an anionic group such as a carboxyl group, a sulfonic acid group, a sulfuric acid ester group, or a phosphoric acid ester group.
(B) Aqueous medium-soluble salts of cationic groups such as primary, secondary, tertiary amino groups, quaternary ammonium groups or pyridinium groups, (c) nonionics such as hydroxyl groups, polyethylene oxide groups or carboxamide groups. Is a polymer moiety having a hydrophilic group or two or more groups thereof, and the hydrophilic moiety is (a) an anionic hydrophilic moiety of 5 to 5 in the water-soluble polymer.
40% by weight, 10 to 5 in (b) cationic hydrophilic part
0% by weight, 20 to 60 in the nonionic hydrophilic portion (c)
The manufacturing method of the colored silk thread according to claim 1, wherein the colored silk thread comprises 10% by weight. 7. The water-soluble polymer is polyvinylpyrrolidone,
The method for producing a colored silk thread according to claim 1, which is one kind or two or more kinds selected from polyacrylic acid, an acrylic acid copolymer, and maleic acid. 8. The pigment is an azo pigment, anthraquinone pigment, copper phthalocyanine pigment, quinacridone pigment, indigo pigment, thioindigo pigment, dioxazine pigment, isoindolinone pigment, azomethine azo pigment,
The method for producing a colored silk thread according to claim 1, wherein the colored silk thread is one or more selected from perylene pigments, perinone pigments, complex oxide pigments, and the like. 9. The method for producing a colored silk yarn according to claim 1, wherein the aqueous pigment dispersion is obtained by removing coarse particles by centrifugation.