JP2922797B2 - Method for producing colored silk thread - Google Patents

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 a colored silk thread for discharging colored silk thread from silkworm larvae, and more particularly to a method for producing a colored silk thread having excellent light fastness and washing fastness.

[0002]

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

[0003] Also, instead of dyeing the produced cocoons after the fact,
When producing a cocoon, a method of obtaining an already colored cocoon has been attempted. For example, a dye is applied to the respiratory tract of a grown silkworm from the time before entering 4 sleep to the age of 5 after 4 sleep, several times, and the dye is adsorbed to the silk wire inside the silkworm body, and the dyed silk thread is discharged from the mouth of the silkworm. A method for producing a colored cocoon is known (Japanese Patent Publication No. 54-30944).

Further, as another method for producing a colored cocoon, a silkworm larva is immersed in a dye solution to adsorb the dye from the larva of the larva to a silk wire inside the body, and the dyed silk thread is discharged from the mouth of the silkworm. A method for producing colored cocoons is known (Japanese Unexamined Patent Application Publication No.
193904).

[0005]

However, in the above-mentioned dyeing method in which the silk thread is immersed in a dye solution, a large number of work steps are required, and one work requires a considerable amount of time and labor. Since a dye solution about 50 times the weight of the silk to be dyed is required, large-scale equipment and a large amount of dye are required. In addition, it is very difficult to control the temperature and time, and if proper management is not performed, the color may be discolored. In addition, since the density of the color changes subtly depending on the ratio between the dye and water, it was extremely difficult to dye the color as desired.

Further, a dye solution is applied to the respiratory tract of the silkworm larvae described above, or the silkworm larva is immersed in the dye solution to allow the dye to be adsorbed on the silk wire within the silkworm, and the silk thread dyed from the mouth of the silkworm is removed. In the method of producing a colored silk thread by discharging and obtaining a colored cocoon, a colored cocoon is obtained,
The color of the dye used in the cooked cocoon is severely discolored, and colored silk yarn is produced from this cocoon, so that the color of the dye is largely lost even in the processing step. Further, since a dye is used, there is a defect that light fastness and washing fastness are weak. Further, in the step of repeatedly immersing the silkworm larvae in the dye solution, there is a problem that about 30% of the silkworm larvae die.

The inventors of the present invention have conducted various studies to solve the above-mentioned deficiencies. As a result, the use of an aqueous pigment dispersion from which coarse pigment particles have been removed by a centrifugal separation process or the like as a colorant solution has made it possible to use silkworm silkworms. The larvae of the silkworms hardly died at all even when the larvae were immersed in this coloring solution, and it was found that a colored silk thread excellent in light fastness and washing fastness was obtained, thereby completing the present invention. .

[0008]

That is, the present invention relates to a method for producing a colored silk thread, wherein a coloring agent solution is absorbed from a larva of a silkworm larva and a colored thread is discharged from the mouth of the larva. A method for producing a colored silk thread, comprising using 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.

[0009]

When a larva of a silkworm, which has grown about five years old, is immersed in an aqueous pigment dispersion in which a pigment is finely dispersed in an aqueous medium, an aqueous pigment dispersion solution is formed from the respiratory organs of the silkworm larva. Absorbed. At this time, the pigment fine particles that have entered the larvae of the larva from the respiratory tract are uniformly adsorbed to the protein that is the raw material of the silk thread. When the larva transforms into a 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 with hot water because the coloring component is a pigment, and it is possible to obtain a colored silk yarn having gloss and excellent light fastness and washing fastness.

[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 obtained by finely dispersing a pigment 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, for example, azo pigments, anthraquinone pigments, copper phthalocyanine pigments, quinacridone pigments, indigo pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, azomethine azo pigments Pigments, perylene pigments, perinone pigments, composite oxide pigments, and the like.

These pigments are used in an aqueous pigment dispersion in an amount of from 0.5 to
Used in a concentration range of 30% by weight. The dispersing agent is adsorbed on the surface of the pigment particles and acts as a protective colloid in water. The dispersing agent is 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 ether of sugar, higher fatty acid ester of sugar, higher fatty acid ester of polyoxyalkylenated sugar, polyoxyalkylene-natural oil condensation Surfactant, nonionic surfactant such as oxyethylene-oxypropylene block polymer, sulfonate of naphthalene-formaldehyde condensate, higher fatty alcohol sulfate, alkylated sulfonate of higher fatty acid amide, alkylallyl sulfonic acid Anionic surfactant such as salt, polyvinyl Water-soluble polymers such as lolidone, polyacrylic acid, acrylic acid copolymer, and maleic acid, and further, a water-soluble polymer composed of a polymer having both a lipophilic portion, a cationic portion and a hydrophilic portion, for example, water-soluble Alkyl, cycloalkyl, arylalkyl and aryl esters of α, β-ethylenically unsaturated carboxylic acids, wherein the lipophilic portion of the polymer includes acrylic acid, methacrylic acid, itaconic acid, fumaric acid. Ester, styrene, α-methylstyrene, vinyltoluene or a mixture of two or more thereof, wherein the lipophilic portion is 10 to 93% by weight in the water-soluble polymer, preferably 30 to 93% by weight. 90% by weight.

As the monomer forming the cationic portion of the water-soluble polymer, a conventionally known monomer having a primary, secondary, tertiary amino group, quaternary ammonium group or pyridinium group in the molecule is used. Monomers are used. For example, N-alkylaminoalkyl esters, N, N-dialkylaminoalkyl esters, N,
N, N-trialkylammonium alkyl esters,
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 includes (a) an anionic hydrophilic group and a soluble salt thereof in an aqueous medium, (b) a cationic hydrophilic group and a soluble salt thereof in an aqueous medium, (c) a nonionic hydrophilic group, And a polymer part having a mixture thereof. Examples of the above-mentioned anionic hydrophilic group include a carboxyl group, a sulfonic acid group, a sulfate ester group and a phosphate ester group, and alkali metal salts such as a sodium salt, a potassium salt, and an ammonium salt.

The cationic hydrophilic groups include primary, secondary and tertiary amino groups, quaternary ammonium groups and pyridinium groups, wherein the primary amino group and the substituent have 1 to 4 carbon atoms.
Secondary and tertiary amino groups, quaternary ammonium salts and salts of lower fatty acids thereof, for example, formic acid, acetic acid, propionic acid salts and inorganic acid salts such as hydrochloride, bromate and sulfonic acid Salts, sulfates and phosphates.

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 portion in the water-soluble polymer is (a) 5 to 40% by weight in the anionic hydrophilic portion, and 10% in the (b) cationic hydrophilic portion.
~ 50% by weight, (c) 20 ~ in the nonionic hydrophilic part
60% by weight.

The above-mentioned water-soluble polymer used in the present invention is prepared by appropriately mixing the above-mentioned monomers and using any of the conventionally known mixed polymerization methods such as solution polymerization, suspension polymerization and emulsion polymerization. It can also be obtained by a polymerization method. The amount of the water-soluble polymer varies depending on the pigment.
It is 1 to 10 parts by weight, preferably 5 to 60 parts by weight based on 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 is composed of the above-mentioned components and blending, and various methods can be adopted for the production method. For example, a typical method is to mix the above components and mix and grind them with a conventionally known dispersing machine such as a ball mill, a homomixer, a sand grinder, a speed line mill, a roll mill or the like. 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 further removing coarse particles present therein.

In order to use a colorant solution comprising the above-mentioned aqueous pigment dispersion and absorb it from the larva of the silkworm larva,
Any method such as an immersion method, a brushing method, and a spray method may be used, but the immersion method is preferred from the viewpoint of working efficiency. The temperature of the colorant solution for immersing the silkworm is 10 to 45.
The temperature range is 20 ° C to 20 ° C and 37 ° C.
It is preferable because the absorption of the solution is improved.

[0019]

The present invention will be specifically described below with reference to examples and comparative examples. In the Examples and Comparative Examples, parts and percentages are by weight. Example 1 (Preparation of aqueous pigment dispersion solution) Blue α-type copper phthalocyanine pigment (CI Pigmentable-15) 50 parts Anionic surfactant (condensate of formalin and sodium naphthalenedicarboxylate) 12.5 parts Water 182.5 copies

The above components are placed in a 1,000 ml beaker, mixed well for 10 minutes, the mixture is transferred to a 500 ml container, and a glass bead having a diameter of 2 mm is further filled therein to a filling rate of 40%. The mixture was shaken with a paint shaker for 1 hour to obtain a dispersion. Next, the dispersion was placed in a high-speed centrifugal separator and treated for 20 minutes to remove coarse particles, thereby obtaining 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%.

(Preparation of colored silk thread) A plurality of fifth-instar silkworm larvae (about 100) are immersed in the aqueous blue pigment dispersion solution (pigment concentration 8%) obtained above for about 2 to 3 seconds. Further, the above immersion operation is repeated 2 to 5 times.
At that time, no silkworm larva died. According to the above immersion, the blue aqueous pigment dispersion solution had good absorption from the respiratory tract, which is the respiratory organ of silkworm, and the blue pigment was uniformly adsorbed to the protein in the embryo of the silkworm. The larvae of the silkworm, in which the blue pigment was accumulated in the body, had no difference from the larvae of the normal silkworm.

Then, the larvae of the silkworm, which has completed the above operations, are bred by a normal breeding method. In this way, when the silkworm larva transformed into a pupa, the blue thread absorbed in the body was ejected to produce a blue cocoon. A blue silk thread without thread breakage was obtained by pinching the cocoon. The resulting blue silk thread is glossy, has the physical properties of copper phthalocyanine pigment-pigment, is extremely excellent in light fastness as compared with those using dyes, has no color fading, and has extremely high washing fastness. It was excellent.

For comparison, a blue aqueous pigment dispersion solution similar to that described above, which was not subjected to high-speed centrifugation, was used, and larvae of silkworms were immersed in this solution. It was not performed sufficiently, and the silk thread obtained from the silkworm cocoon was uneven in color and often broken.

Example 2 (Preparation of aqueous pigment dispersion solution) Red quinacridone pigment (CI Pigment Violet 19) 50 parts Polyoxyethylene nonylphenyl-based nonionic surfactant (HLB: 15) 10 parts Water 190 parts The components were placed in a 1,000 ml beaker, mixed well for 10 minutes, and the mixture was transferred to a 500 ml container. A glass bead having a diameter of 2 mm was further added thereto so that the filling rate became 40%. The mixture was shaken with a paint shaker for 1 hour to obtain a dispersion. Next, the dispersion was placed in a high-speed centrifuge and treated for 20 minutes to remove coarse particles, thereby obtaining 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) In the red aqueous pigment dispersion solution (pigment concentration: 8%) obtained as described above, a plurality of larvae (about 100 larvae) of a 5th-instar grown silkworm are immersed for about 2 to 3 seconds. Further, the above immersion operation is repeated 2 to 5 times.
At that time, no silkworm larva died. According to the above immersion, the red aqueous pigment dispersion solution had good absorption from the respiratory tract, which is the respiratory organ of the silkworm, and the red pigment was uniformly adsorbed to the protein in the embryo of the silkworm. The larva of the silkworm in which the red pigment was accumulated in the body in this way was not different from the larva of the normal silkworm. For comparison, the same red aqueous pigment dispersion solution as described above without high-speed centrifugation treatment was used, and the larvae of silkworms were immersed in this solution. As a result, the red pigment was sufficiently absorbed from the respiratory tract. However, the silk thread obtained from the silkworm cocoon was uneven in color and often broken.

Example 3 (Preparation of Aqueous Pigment Dispersion Solution) Azomethine azo black pigment (trade name: AMA Black, manufactured by Dainichi Seika Kogyo Co., Ltd.) 50 parts Anionic surfactant similar to that in Example 1 12 parts Water 188 Part 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 placed in a high-speed centrifugal separator and treated for 15 minutes to remove coarse particles, thereby obtaining 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 fifth-instar silkworm larvae (about 100) are immersed in the black aqueous pigment dispersion solution (pigment concentration 5%) obtained above for about 2 to 3 seconds. Further, the above immersion operation is repeated 2 to 5 times.
At that time, no silkworm larva died.

According to the above immersion, the black aqueous pigment dispersion solution has good absorption from the respiratory tract, which is the respiratory organ of silkworm,
The black pigment was uniformly adsorbed to the protein in the silkworm womb. The larva of the silkworm in which the black pigment was accumulated in the body in this way had no difference from the larva of the normal silkworm. For comparison, the same black aqueous pigment dispersion solution as described above without high-speed centrifugation was used, and the larvae of silkworms were immersed in this solution. As a result, the black pigment was sufficiently absorbed from the stomach. However, the silk thread obtained from the silkworm cocoon was uneven in color and often broken.

Example 4 (Preparation of Aqueous Pigment Dispersion Solution) Yellow Isoindolinone Pigment (CI Pigment Ero-110) 45 parts Nonionic surfactant similar to that in Example 2 10 parts Water 243 parts The components were ground and dispersed for 60 minutes using an attritor to obtain a yellow pigment dispersion. Next, this yellow pigment dispersion was placed in a high-speed centrifugal separator and treated for 15 minutes to remove coarse particles, thereby obtaining 276 parts of a yellow aqueous pigment dispersion solution.
Further, this pigment dispersion solution was diluted with water to obtain a pigment concentration of 3%.
% Of a yellow aqueous pigment dispersion solution.

(Preparation of colored silk thread) A plurality of fifth-instar silkworm larvae (about 100) are dipped in the yellow aqueous pigment dispersion solution (pigment concentration: 3%) obtained above for about 2 to 3 seconds. Further, the above immersion operation is repeated 2 to 5 times.
At that time, no silkworm larva died. According to the above immersion, the yellow aqueous pigment dispersion solution had good absorption from the respiratory tract, which is the respiratory organ of silkworm, and the yellow pigment was uniformly adsorbed to the protein in the embryo of the silkworm. The silkworm larva having the yellow pigment accumulated in the body in this way had no difference from the normal silkworm larva. For comparison, the same yellow aqueous pigment dispersion solution as above without high-speed centrifugation was used, and the larvae of silkworms were immersed in this solution. As a result, the yellow pigment was sufficiently absorbed from the respiratory tract. However, the silk thread obtained from the silkworm cocoon was uneven in color and often broken.

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

(Production of colored silk thread) A plurality of fifth-instar silkworm larvae (about 100) are dipped in the orange aqueous pigment dispersion solution (pigment concentration: 10%) obtained above for about 2 to 3 seconds. Further, the above immersion operation is repeated 2 to 5 times.
At that time, no silkworm larva died. According to the above immersion, the orange aqueous pigment dispersion solution had good absorption from the respiratory tract, which is the respiratory organ of the silkworm, and the orange pigment was uniformly adsorbed to the protein in the embryo of the silkworm. The silkworm larva in which the orange pigment was accumulated in the body in this way had no difference from the normal silkworm larva.

[0033]

According to the method for producing a colored silk thread of the present invention,
Pigments are adsorbed from the respiratory tract, the respiratory organ of the silkworm larva, to the protein, which is the raw material of the silk thread in the womb, and the silkworm larva does not die at that time. When the larva transforms into a pupa, a cocoon is produced by discharging a thread having a color tone of a pigment mixed in a protein in the fetus of the larva. By spinning this colored cocoon, a glossy colored silk thread having excellent light fastness and washing fastness can be obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor, Takae Ogiwara, 618-2 Horishita, Oazabori-cho, Sawa-gun, Gunma Prefecture (72) Inventor Yoshio Abe 5--11-32 Higashiiwatsuki, Iwatsuki-shi, Saitama (72) Invention Person Akira Hoshino 3-4 Koshigaya Honcho, Koshigaya City, Saitama Prefecture (56) References JP-A-51-85987 (JP, A) JP-A-55-125165 (JP, A) JP-B-54-30944 (JP, B2) (58) Field surveyed (Int.Cl. ⁶ , DB name) A01K 67/04 302 C09C 3/10

Claims (9)

(57) [Claims] 1. A method for producing a colored silk thread in which a colorant solution is absorbed from a larva of a silkworm larva and a colored thread is discharged from the mouth of the larva, wherein the colorant solution contains a surfactant and / or a highly water-soluble dye. A method for producing a colored silk thread, comprising using an aqueous pigment dispersion in which a pigment is finely dispersed in an aqueous medium having a molecule as a dispersant. 2. The colored silk yarn according to claim 1, wherein the surfactant is at least one selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Method. 3. The water-soluble polymer is a polymer having both a lipophilic portion, a cationic portion and a hydrophilic portion.
3. The method for producing a colored silk thread according to item 1. 4. The water-soluble polymer in which the lipophilic portion is an alkyl ester, a cycloalkyl ester, or an alkyl ester of an α, β-ethylenically unsaturated carboxylic acid including acrylic acid, methacrylic acid, itaconic acid, and fumaric acid. Or a mixture of two or more of them, wherein the lipophilic portion is 10 to 93% by weight in the water-soluble polymer. The method for producing a colored silk thread according to claim 1, wherein the colored silk thread comprises: 5. The method of claim 1, wherein the cationic portion 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 of these groups, wherein the cationic moiety is a polymer moiety in a water-soluble polymer.
The method for producing a colored silk yarn according to claim 1, wherein the colored silk yarn occupies about 50% by weight. 6. The aqueous medium-soluble salt of an anionic group such as (a) a carboxyl group, a sulfonic group, a sulfate group, or a phosphate group, wherein the hydrophilic portion of the water-soluble polymer is (a)
(B) an aqueous medium-soluble salt of a cationic group such as a primary, secondary, tertiary amino group, quaternary ammonium group or pyridinium group; (c) a nonion such as a hydroxyl group, a polyethylene oxide group or a carboxamide group A hydrophilic group or a polymer part having two or more of these groups. In the water-soluble polymer as a hydrophilic part, (a) an anionic hydrophilic part is 5 to 5.
40% by weight, (b) 10 to 5 in the cationic hydrophilic portion
0% by weight, (c) 20 to 60 in the nonionic hydrophilic portion.
2. The method for producing a colored silk thread according to claim 1, wherein the colored silk thread occupies a weight%. 7. The water-soluble polymer is polyvinylpyrrolidone,
The method for producing a colored silk thread according to claim 1, wherein the colored silk thread is at least one selected from polyacrylic acid, an acrylic acid copolymer, and maleic acid. 8. The azo pigment, anthraquinone pigment, copper phthalocyanine pigment, quinacridone pigment, indigo pigment, thioindigo pigment, dioxazine pigment, isoindolinone pigment, azomethine azo pigment,
2. The method for producing a colored silk thread according to claim 1, wherein one or more kinds selected from perylene pigments, perinone pigments, composite oxide pigments, and the like are used. 9. The method for producing a colored silk thread according to claim 1, wherein the aqueous pigment dispersion has been subjected to a centrifugal separation treatment to remove coarse particles.