Bulk yarn and method for producing same

Abstract

The present invention relates to a bulked yarn having a bulkiness of 10 cm < 3 > / g or more, the bulked yarn comprising a first fiber and a second fiber, the first fiber comprising an artificial protein fiber which contains an artificial protein and which can shrink after contact with water, and the second fiber having a lower shrinkage rate after contact with water than the first fiber, and the bulked yarn having a bulkiness of 10 cm < 3 > / g or more.

Description

Technical Field

[0001] The present invention relates to bulked yarn and a method for making the same. Background Art

[0002] Patent document 1 discloses an acrylic fiber bulked yarn processing device and a manufacturing method thereof for bulking acrylic fibers. Patent document 2 discloses a knitted fabric composed of high-shrinkage acrylic fibers having a boiling water shrinkage of 15% or more and a single fiber fineness of 0.7 to 2.2 dtex and low-shrinkage fibers having a boiling water shrinkage of 10% or less, and a specific volume of 6 to 12 cm 3 / g, and a heat retention rate of 28 to 60%. Patent Document 2 states that the knitted fabric has an excellent hand feel, a soft surface touch, excellent dimensional stability, is lightweight and fluffy, and has good heat retention.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2003-328241

[0006] Patent Document 2: Japanese Patent Application Publication No. 2014-101601 Summary of the invention

[0007] Problems to be solved by the invention

[0008] The object of the present invention is to provide a novel bulked yarn using fibers containing artificial protein and a method for producing the same, as well as a novel fabric using the bulked yarn containing artificial protein fibers.

[0009] Methods used to solve problems

[0010] The present invention relates to, for example, the following inventions. [1]

[0012] Contains first and second fibers and has a bulkiness of 10 cm 3 / g or more bulked yarn, wherein the first fiber contains artificial protein and can shrink after contacting with water, and the shrinkage rate of the second fiber after contacting with water is lower than that of the first fiber. [2]

[0014] The bulkiness is 50cm 3 / g or less bulked yarn as described in [1]. [3]

[0016] The bulked yarn according to [1] or [2] has a shrinkage rate of 15% or more after the first fiber comes into contact with water. [4]

[0018] The bulked yarn according to any one of [1] to [3], wherein the number of crimps of the first fiber is 5 or more. [5]

[0020] The bulked yarn according to any one of [1] to [4], wherein the content of the first fiber is 5% by mass or more based on the total mass of the bulked yarn. [6]

[0022] The bulked yarn according to [5], wherein the content of the first fiber is 90% by mass or less based on the total mass of the bulked yarn. [7]

[0024] The bulked yarn according to any one of [1] to [6], wherein the average length of the first fibers is 48 mm to 170 mm. [8]

[0026] The first fiber and the second fiber are the bulked yarn described in any one of [1] to [7] and are of different types. [9]

[0028] The first fiber and the second fiber are the same type of bulked yarn described in any one of [1] to [7].

[10]

[0030] The second fiber is the bulked yarn described in [8], which is at least one of animal hair fiber and silk.

[11]

[0032] The second fiber is the bulked yarn described in

[10] , which is animal hair fiber or silk.

[12]

[0034] The bulked yarn according to any one of [1] to

[11] woven by a wool spinning method.

[13]

[0036] A method for manufacturing bulked yarn is provided, the method comprising the steps of blending a first sliver comprising a first fiber containing an artificial protein and shrinkable upon contact with water and a second sliver comprising a second fiber having a shrinkage rate lower than that of the first fiber upon contact with water to obtain a raw blended yarn, and a step of bringing the raw blended yarn into contact with an aqueous medium and shrinking at least the first fiber to obtain a bulked yarn.

[14]

[0038] The method described in

[13] further comprises the step of obtaining the first wool top.

[15]

[0040] The process of obtaining the blended yarn is carried out by combing wool spinning as described in

[13] or

[14] .

[16]

[0042] A fabric containing the bulked yarn described in any one of [1] to

[12] .

[0043] Effects of the Invention

[0044] The present invention can provide a novel bulked yarn containing artificial protein fiber and a method for producing the same, and can also provide a novel fabric using the bulked yarn containing artificial protein fiber.

[0045] The bulked yarn of the present invention contains artificial protein and thus has good water absorption. Furthermore, since the bulked yarn of the present invention includes the first fiber containing the artificial protein that can be molecularly designed and the second fiber different from the first fiber, the bulked yarn of the present invention can ensure diversified properties. Furthermore, the fabric of the present invention also contains the bulked yarn and thus has good water absorption and can ensure diversified properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is an explanatory diagram schematically showing an example of a spinning device for producing the first fiber (artificial protein fiber). DETAILED DESCRIPTION

[0047] Hereinafter, specific embodiments of the present disclosure will be described in detail with reference to the accompanying drawings as appropriate. However, the following embodiments are examples for describing the present disclosure, and the present disclosure is not limited to the following contents.

[0048] Unless otherwise specified, the materials exemplified in this specification may be used alone or in combination of two or more. When there are multiple substances equivalent to each component in the composition, unless otherwise specified, the content of each component in the composition refers to the total amount of the multiple substances present in the composition.

[0049] [Bulked Yarn]

[0050] The bulked yarn according to the present embodiment includes first fibers that contain artificial protein and are shrinkable when in contact with water, and second fibers that have a shrinkage rate lower than that of the first fibers when in contact with water.

[0051] The bulkiness of bulked yarn is 10cm 3 / g or more. The bulkiness of bulked yarn can be 15cm 3 / g or more, 20cm 3 / g or more, 25cm 3 / g or more, 30cm 3 / g or more, 35cm 3 / g or more, 40cm3 / g or more, 45cm 3 / g or more, 50cm 3 / g or above or 55cm 3 / g or more. The bulkiness of bulked yarn can be 70cm 3 / g or less, 65cm 3 / g or less, 60cm 3 / g or less, 55cm 3 / g or less, 50cm 3 / g or less, 45cm 3 / g or less or 40cm 3 / g or less. The higher the fluffiness, the better the softness, heat preservation, water absorption and anti-pilling properties of the bulked yarn.

[0052] The bulkiness of the bulked yarn was measured according to the JIS L 1095A test method.

[0053] The bulkiness of the bulked yarn can be adjusted, for example, by controlling the shrinkage rate of the first fiber after contact with water and the shrinkage rate of the second fiber after contact with water. The bulkiness shows a tendency that the larger the difference between the shrinkage rate of the first fiber after contact with water and the shrinkage rate of the second fiber after contact with water, the higher the bulkiness.

[0054] <First Fiber>

[0055] The first fiber is a fiber containing artificial protein (artificial protein fiber). The artificial protein-containing fiber mentioned here includes: a fiber containing only artificial protein, a fiber containing components other than artificial protein that are not physically or chemically bonded to artificial protein, a fiber containing components that are physically or chemically bonded to artificial protein, etc. In addition, artificial protein includes chemically modified artificial protein, artificial protein derivatives, etc.

[0056] (Artificial protein)

[0057] "Artificial protein" in this specification refers to artificially produced protein. Artificial proteins include recombinant proteins and synthetic proteins. Artificial proteins can be proteins whose domain sequences are different from the amino acid sequences of proteins of natural origin, or proteins whose amino acid sequences are the same as those of proteins of natural origin. "Artificial protein" can be a protein that directly uses the amino acid sequence of a protein of natural origin, or a protein whose amino acid sequence is modified based on the amino acid sequence of a protein of natural origin (for example, a protein obtained by modifying the amino acid sequence of a cloned gene sequence of a protein of natural origin), or a protein that is artificially designed and synthesized without relying on proteins of natural origin (for example, a protein having a desired amino acid sequence by chemically synthesizing a nucleic acid encoding the designed amino acid sequence).

[0058] Artificial proteins are different from natural proteins in that the amino acid sequence can be freely designed. Therefore, the first fiber containing artificial proteins and the bulked yarn containing the first fiber can arbitrarily control the functions, characteristics, physical properties, etc. by appropriately designing the amino acid sequence of the artificial protein. Artificial proteins can always achieve uniform molecular design, so artificial proteins that are highly identical to the target protein and suitable for the purpose can be stably obtained. Therefore, it is beneficial to achieve the quality stability of the first fiber containing artificial proteins and the bulked yarn containing the first fiber. From this point of view, it is very advantageous to use artificial structural proteins as artificial proteins.

[0059] The number of amino acid residues of the artificial protein is not particularly limited, but may be, for example, 50 or more. The number of amino acid residues may be, for example, 100 or more, 150 or more, 200 or more, 250 or more, 300 or more, 350 or more, 400 or more, 450 or more, or 500 or more. The number of amino acid residues may be, for example, 5000 or less, 4500 or less, 4000 or less, 3500 or less, 3000 or less, 2500 or less, 2000 or less, 1500 or less, or 1000 or less. There is a tendency that the smaller the number of amino acid residues, the higher the solubility in a solvent.

[0060] The molecular weight of the artificial protein is not particularly limited, and may be, for example, 2 kDa or more and 500 kDa or less. The molecular weight of the artificial protein may be, for example, 2 kDa or more, 3 kDa or more, 4 kDa or more, 5 kDa or more, 6 kDa or more, 7 kDa or more, 8 kDa or more, 9 kDa or more, 10 kDa or more, 20 kDa or more, 30 kDa or more, 40 kDa or more, 50 kDa or more, 60 kDa or more, 70 kDa or more, 80 kDa or more, 90 kDa or more, or 100 kDa or less, or 500 kDa or less, or 400 kDa or less, or less than 360 kDa, or less than 300 kDa, or less than 200 kDa.

[0061] As artificial proteins, for example, artificial proteins having physical properties close to those required for the desired use can be used. As artificial proteins, artificial proteins that can be used for industrial use can be exemplified. The term "can be used for industrial use" means, for example, various general-purpose materials that can be used indoors and / or outdoors. As specific examples of artificial proteins that can be used for industrial use, artificial structural proteins can be exemplified.

[0062] <Artificial structural protein>

[0063] Artificial proteins can be, for example, artificial structural proteins. In this specification, the so-called "artificial structural protein" refers to artificially produced structural proteins. The so-called structural protein is an artificial protein that can be used for industrial purposes, which refers to proteins related to the structure of an organism, or proteins produced by an organism to form a structure, or proteins derived from them. Structural proteins refer to proteins that self-aggregate under certain conditions to form structures such as fibers, films, resins, gels, micelles, nanoparticles, etc. In addition, structural proteins can also refer to proteins that are composed of a characteristic amino acid sequence or a motif consisting of a number of amino acid residues that repeats to form the skeleton of organisms and materials.

[0064] Artificial structural proteins can be structural proteins produced by microorganisms using genetic recombination technology, or proteins having the same amino acid sequence as natural structural proteins, or proteins having an amino acid sequence that has been improved from the perspectives of productivity or formability.

[0065] Specific examples of artificial structural proteins include spider silk (spider silk), silkworm silk, keratin, collagen, elastin, elastic protein, and proteins derived from these.

[0066] The number of amino acid residues of the artificial structural protein according to the present embodiment may be 150 or more. The number of amino acid residues may be, for example, 200 or more or 250 or more, preferably 300 or more, 350 or more, 400 or more, 450 or more, or 500 or more.

[0067] When forming artificial structural proteins, amino acids with relatively small side chains are easy to hydrogen bond, and the strength is easy to become higher. From the viewpoint of obtaining better strength, the alanine residue content is, for example, 10 to 40%, and can be 12 to 40%, 15 to 40%, 18 to 40%, 20 to 40% or 22 to 40%. From the viewpoint of obtaining better strength, the glycine residue content is, for example, 10 to 55%, and can be 11 to 55%, 13 to 55%, 15 to 55%, 18 to 55%, 20 to 55%, 22 to 55% or 25 to 55%.

[0068] In the present specification, the "alanine residue content" refers to the ratio of the number of alanine residues to the number of all amino acid residues constituting a protein, and is a value represented by the following formula.

[0069] Alanine residue content = (number of alanine residues contained in the protein / total number of amino acid residues in the protein) x 100 (%)

[0070] The glycine residue content and the serine residue content, threonine residue content, proline residue content and tyrosine residue content described later have the same meanings as those obtained by replacing the alanine residue in the above formula with a glycine residue, a serine residue, a threonine residue, a proline residue and a tyrosine residue, respectively.

[0071] The artificial structural protein is based on the number of amino acid residues, as long as the total content (total content) of at least one amino acid residue selected from the group consisting of serine, threonine and tyrosine (i.e., the serine residue content, the threonine residue content, the tyrosine residue content, the sum of the serine residue content and the threonine residue content, the sum of the serine residue content and the tyrosine residue content, the sum of the serine residue content and the threonine residue content, and the sum of the tyrosine residue content), the alanine residue content and the glycine residue content is 40% or more. The total content can be, for example, 45% or more, 50% or more, 55% or more, or 60% or more. The upper limit of the total content is not particularly limited, for example, it can be 90% or less, 85% or less, or 80% or less.

[0072] In one embodiment, the sum of the serine residue content, the threonine residue content, and the tyrosine residue content of the artificial structural protein may be 4% or more, 4.5% or more, 5% or more, 5.5% or more, 6% or more, 6.5% or more, or 7% or more based on the number of amino acid residues. The sum of the serine residue content, the threonine residue content, and the tyrosine residue content may be, for example, less than 35%, less than 33%, less than 30%, less than 25%, or less than 20%.

[0073] The distribution of serine residues, threonine residues or tyrosine residues in the artificial structural protein involved in this embodiment is even, and in any consecutive 20 amino acid residues, the total content of serine residues, threonine residues and tyrosine residues can be more than 4%, more than 5%, more than 10% or more than 15%, or less than 50%, less than 40%, less than 30% or less than 20%.

[0074] In addition, the artificial structural protein preferably contains amino acids with larger side chains or amino acids with bending to a certain extent in the overall sequence homogeneously. Specifically, the artificial structural protein can also be a motif containing tyrosine residues, threonine residues and proline residues that are repeatedly and periodically added. If it is such an artificial structural protein, it is easy to hinder the formation of stable intermolecular hydrogen bonds during processing after molding, and it is easy to improve processability. For example, in any continuous 20 amino acid residues, the sum of the contents of proline residues, threonine residues and tyrosine residues can be more than 5%, more than 5.5%, more than 6.0%, more than 6.5%, more than 7.0%, more than 7.5%, more than 8.0%, more than 8.5%, more than 9.0%, more than 10.0% or more than 15.0%. For example, in any continuous 20 amino acid residues, the sum of the contents of proline residues, threonine residues and tyrosine residues can be less than 50%, less than 40%, less than 30% or less than 20%.

[0075] The artificial structural protein can be a protein with a repeating sequence. That is, the artificial structural protein can have multiple amino acid sequences (repeating sequence units) with high sequence consistency in the artificial structural protein. The number of amino acid residues in the repeating sequence unit is preferably 6 to 200. The total number of glycine residues, serine residues, glutamic acid residues and alanine residues relative to the total number of amino acid residues in the repeating sequence unit can be 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more or 70% or more. In addition, the sequence consistency between repeating sequence units can be, for example, 85% or more, 90% or more, 95% or more, 96% or more, 97% or more, 98% or more or 99% or more.

[0076] The hydrophobicity degree (hydrophilic index) of the repeating sequence unit can be, for example, above -0.80, above -0.70, above -0.60, above -0.50, above -0.40, above -0.30, above -0.20, above -0.10, above 0.00, above 0.22, above 0.25, above 0.30, above 0.35, above 0.40, above 0.45, above 0.50, above 0.55, above 0.60, above 0.65 or above 0.70. The upper limit of the hydrophobicity degree of the repeating sequence unit is not particularly limited, for example, it can be below 1.0, or below 0.7.

[0077] The hydropathic index is obtained by a known method using a known hydrophobicity index of an amino acid residue. The known hydrophobicity index of an amino acid residue is shown in Table 1. For example, the hydrophobicity can also be calculated according to the method described in Kyte J, Doolittle R (1982) "A simple method for displaying the hydropathic character of a protein", J. Mol. Biol, 157, pp. 105-132.

[0078] [Table 1]

[0079]

[0080] The artificial structural protein may be a protein comprising (A) n In this specification, (A) n A motif is an amino acid sequence that is primarily composed of alanine residues. (A) n The number of amino acid residues in the motif may be 2 to 27, or may be an integer of 2 to 20, 2 to 16, or 2 to 12. (A) n The ratio of the number of alanine residues in the motif to the total number of amino acid residues may be 40% or more, and may be 60% or more, 70% or more, 80% or more, 83% or more, 85% or more, 86% or more, 90% or more, 95% or more, or 100%. (A) n The ratio of the number of alanine residues in the motif to the total number of amino acid residues is 100%, which means (A) n The motif consists only of alanine residues.

[0081] The ratio of the total number of alanine residues, serine residues, threonine residues and valine residues in the (A)n motif to the total number of amino acid residues in the (A)n motif may be 80% or more, preferably 85% or more, more preferably 90% or more, further preferably 95% or more, and even more preferably 100% (meaning that it is composed of only one or more amino acid residues selected from alanine residues, serine residues, threonine residues and valine residues). The multiple (A)n residues present in the recombinant structural protein according to the present embodiment n The motifs may be identical amino acid sequences or different amino acid sequences. n The motif mainly contains alanine residues, so it is easy to obtain α-helical structure or β-sheet structure. n The motif is contained in the repeating sequence unit, and the artificial structural protein involved in this embodiment repeatedly has these secondary structures. Therefore, as described later, when the artificial structural protein is made into a fiber form, it is expected to exert high strength due to these secondary structures.

[0082] The artificial structural protein may also be artificial silk fibroin. In the present specification, "artificial silk fibroin" refers to artificially produced silk fibroin (artificial silk fibroin). Artificial silk fibroin may be a silk fibroin having an amino acid sequence different from that of silk fibroin derived from nature, or a silk fibroin having an amino acid sequence identical to that of silk fibroin derived from nature.

[0083] As natural silk fibroin, for example, silk fibroin produced by insects or spiders can be cited. Natural silk fibroin is a fibrous protein with a molecular weight of about 370,000, consisting of two subunits, with high contents of glycine residues, alanine residues, serine residues and tyrosine residues, which account for nearly 90% of all amino acid residues. Natural silk fibroin has two different regions, namely a crystalline region rich in amino acid residues with smaller side chains such as glycine, alanine and serine, and an amorphous region rich in amino acid residues with larger side chains such as tyrosine.

[0084] As a more specific example of naturally derived silk fibroin, there can be cited silk fibroin for which sequence information is registered in NCBI GenBank. For example, it can be confirmed by extracting sequences containing INV as a classification code (DIVISION) in the sequence information registered in NCBI GenBank, in which spider silk protein, ampulla, silk fibroin, "silk and polypeptide" or "silk and protein" is recorded as a keyword in the definition (DEFINITION), extracting a character string specifying a product from the CDS, and extracting a sequence in which a specified character string is recorded in the tissue type (TISSUE TYPE) from the source (SOURCE).

[0085] Artificial silk fibroin can be produced by a known method, for example, by the method described in International Publication No. 2019 / 194263.

[0086] Artificial silk fibroin may be a fibrous protein having a structure suitable for natural silk fibroin, or may be a silk fibroin having a sequence identical to a repeating sequence possessed by natural silk fibroin. The so-called "sequence identical to a repeating sequence possessed by silk fibroin" may actually be a sequence possessed by natural silk fibroin, or may be a sequence similar thereto.

[0087] As long as the artificial silk fibroin has the amino acid sequence specified in the present disclosure, it can be a silk fibroin obtained by modifying the amino acid sequence of a silk fibroin from a natural source (for example, a silk fibroin obtained by modifying the amino acid sequence of a cloned natural silk fibroin gene sequence), or a silk fibroin with an artificially designed amino acid sequence independent of a natural silk fibroin (for example, a silk fibroin having a desired amino acid sequence by chemically synthesizing a nucleic acid encoding the designed amino acid sequence). Silk fibroin modified in the amino acid sequence of an artificial silk fibroin can be included in the artificial silk fibroin as long as its amino acid sequence is different from that of a natural silk fibroin.

[0088] As artificial silk fibroin, for example, artificial silk (silk) fibroin (fibroin in which the amino acid sequence of silk fibroin produced by silkworms is modified), artificial spider silk fibroin (fibroin in which the amino acid sequence of spider silk fibroin produced by spiders is modified), etc. Artificial silk fibroin preferably contains artificial spider silk fibroin, and more preferably consists of artificial spider silk fibroin, from the viewpoint of being relatively easy to fibrillate and having high fiber-forming ability.

[0089] Artificial silk fibroin may be a material comprising formula 1: [(A) n motif-REP] m Or formula 2: [(A) n motif-REP] m -(A) n The protein of the domain sequence represented by the motif. Artificial silk fibroin can further add an amino acid sequence (N-terminal sequence and C-terminal sequence) to either or both of the N-terminal side and the C-terminal side of the domain sequence. The N-terminal sequence and the C-terminal sequence are not limited thereto, and typically do not have a repeated region of the characteristic amino acid motif in silk fibroin, and are composed of about 100 amino acid residues.

[0090] In this specification, "domain sequence" refers to Formula 1: [(A) n motif-REP] m Or formula 2: [(A) n motif-REP] m -(A) n The amino acid sequence represented by the motif. Here, (A) n The motif indicates an amino acid sequence mainly composed of alanine residues, with the number of amino acid residues ranging from 2 to 27. (A) n The number of amino acid residues in the motif may be an integer of 2 to 20, 4 to 27, 4 to 20, 8 to 20, 10 to 20, 4 to 16, 8 to 16, or 10 to 16. In addition, as long as (A) n The ratio of the number of alanine residues in the motif to the total number of amino acid residues may be 40% or more, and may be 60% or more, 70% or more, 80% or more, 83% or more, 85% or more, 86% or more, 90% or more, 95% or more, or 100% (meaning that it is composed only of alanine residues). n At least 7 of the motifs may consist of only alanine residues. REP represents an amino acid sequence consisting of 2 to 200 amino acid residues. REP may be an amino acid sequence consisting of 10 to 200 amino acid residues. m represents an integer of 2 to 300, or may be an integer of 10 to 300. The presence of multiple (A) n The motifs may be identical amino acid sequences or different amino acid sequences. A plurality of REPs may be identical amino acid sequences or different amino acid sequences.

[0091] Specific examples of artificial silk fibroin include artificial silk fibroin (first artificial silk fibroin) derived from the large silk tube dragline protein produced by the large ampulla gland of a spider described in International Publication No. 2021 / 187502, artificial silk fibroin having a domain sequence with a reduced content of glycine residues (second artificial silk fibroin), and artificial silk fibroin having a domain sequence with a reduced content of (A) n The artificial silk fibroin (artificial silk fibroin 3) with a domain sequence containing motifs, reduced glycine residue content and (A) n The fibroin having a motif content (the fourth fibroin), the fibroin having a domain sequence partially containing a region with a large hydrophobicity index (the fifth fibroin), and the fibroin having a domain sequence with a reduced glutamine residue content (the sixth fibroin). The definitions of each of the first to sixth fibroin are incorporated into this specification by referring to the contents described in International Publication No. 2021 / 187502.

[0092] Artificial silk fibroin may contain a tag sequence at either or both of the N-terminus and the C-terminus, thereby enabling separation, fixation, detection, and visualization of artificial silk fibroin. PRT966 is the sixth artificial silk fibroin containing a tag sequence.

[0093] As a tag sequence, for example, an affinity tag that utilizes specific affinity (binding property, affinity) with other molecules can be listed. As a specific example of an affinity tag, a histidine tag (His tag) can be listed. The His tag is a short peptide composed of about 4 to 10 histidine residues arranged in an array, and has the property of specifically binding to metal ions such as nickel, so it can be used for the separation of artificial silk core protein by metal chelating chromatography (chelating metal chromatography). As a specific example of a tag sequence, for example, the amino acid sequence shown in sequence number 8 (an amino acid sequence containing a His tag sequence and a hinge sequence) can be listed.

[0094] Alternatively, tag sequences such as glutathione-S-transferase (GST) that specifically binds to glutathione and maltose binding protein (MBP) that specifically binds to maltose may be used.

[0095] Furthermore, an "epitope tag" that utilizes an antigen-antibody reaction can also be used. By adding a peptide (epitope) for showing antigenicity as a tag sequence, an antibody against the epitope can be bound. As epitope tags, HA (peptide sequence of influenza virus hemagglutinin) tags, myc tags, FLAG tags, etc. can be listed. By utilizing epitope tags, artificial silk fibroin can be easily purified with high specificity.

[0096] Furthermore, a tag obtained by removing a tag sequence using a specific protease may be used. The artificial silk fibroin after the removal of the tag sequence may be recovered by treating the protein adsorbed via the tag sequence with a protease.

[0097] As specific examples of artificial silk fibroin, for example, artificial silk fibroin shown in sequence numbers 1 to 7 can be cited. The artificial silk fibroin can be the artificial silk fibroin shown in sequence numbers 1 to 7 or an artificial silk fibroin containing an amino acid sequence having a sequence identity of 90% or more with these amino acid sequences. The contents of alanine residues, glycine residues, serine residues, threonine residues, proline residues and tyrosine residues in the artificial silk fibroin shown in sequence numbers 1 to 7 are shown in Table 2 below.

[0098] [Table 2]

[0099]

[0100] The rayon may be a rayon having at least two or more characteristics among the characteristics of the first rayon, the second rayon, the third rayon, the fourth rayon, the fifth rayon, and the sixth rayon.

[0101] The molecular weight of the artificial silk fibroin involved in the present embodiment is not particularly limited, and can be, for example, 2 kDa or more and 700 kDa or less. The molecular weight of the artificial silk fibroin can be, for example, 2 kDa or more, 3 kDa or more, 4 kDa or more, 5 kDa or more, 6 kDa or more, 7 kDa or more, 8 kDa or more, 9 kDa or more, 10 kDa or more, 20 kDa or more, 30 kDa or more, 40 kDa or more, 50 kDa or more, 60 kDa or more, 70 kDa or more, 80 kDa or more, 90 kDa or more, or 100 kDa or more, or 700 kDa or less, 600 kDa or less, 500 kDa or less, 400 kDa or less, or 360 kDa or less, 300 kDa or less, or 200 kDa or less.

[0102] (Content of artificial protein)

[0103] The content of the artificial protein, based on the total mass of the first fiber, may be 30% by mass or more, 40% by mass or more, or 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, or 100% by mass or less, 95% by mass or less, or 90% by mass or less. The higher the protein content, the higher the shrinkage rate of the first fiber after contact with water. In addition, the range of the artificial protein content combining the upper limit and the lower limit mentioned above includes all ranges determined by arbitrarily selecting the upper limit and the lower limit mentioned above, respectively (e.g., 30 to 100% by mass and 40 to 95% by mass, etc.).

[0104] (Shrinkage after contact with water)

[0105] The first fiber is a fiber that shrinks after contact with water. The shrinkage rate of the first fiber after contact with water can be, for example, more than 10%, more than 15%, more than 20%, more than 25%, more than 30%, more than 35%, more than 40%, more than 45% or more than 50%. The shrinkage rate of the first fiber after contact with water can be, for example, less than 80%, less than 75%, less than 70%, less than 65%, less than 60% or less than 55%. The higher the shrinkage rate of the first fiber in contact with water, the higher the fluffiness of the blended yarn, thereby improving the softness, heat retention, pilling, water absorption and pilling resistance of the bulked yarn. In addition, the range of the shrinkage rate of the first fiber after contact with water formed by combining the above-mentioned upper limit and lower limit includes all ranges determined by arbitrarily selecting the above-mentioned upper limit and lower limit, respectively (for example, 10 to 80%, 15 to 80% and 20 to 75%, etc.).

[0106] The "shrinkage rate after contact with water" in this specification can be measured by the method shown below. First, obtain a fiber bundle formed by bundling multiple fibers of the same length, install a 0.8g plumb bob on the fiber bundle, and soak it in 95°C water for 10 minutes. After that, take out the fiber bundle from the water, and then dry it at room temperature for 2 hours while keeping the 0.8g plumb bob installed on the taken out fiber bundle, and measure the length of the fiber bundle after drying. Next, calculate the "shrinkage rate after contact with water (%)" of the fiber according to the following formula I. In formula I, L0 represents the length of the fiber bundle before contact with water, and Ld represents the length of the fiber bundle in the dry state after shrinkage due to contact with water.

[0107] Formula I: Shrinkage rate = {1-(Ld / L0)}×100(%)

[0108] The "shrinkage ratio after contact with water" in this specification can be adjusted by controlling the amino acid sequence of the artificial protein and the production conditions of the fiber (for example, the stretching conditions when a stretching treatment is performed during the production of the fiber).

[0109] (Number of curls)

[0110] The number of crimps of the first fiber may be, for example, 5 or more, 7 or more, 9 or more, 11 or more, 13 or more, 15 or more, or 16 or more. The number of crimps of the first fiber may be, for example, 20 or less, 19 or less, 18 or less, or 17 or less. The greater the number of crimps of the first fiber, the higher the fluffiness of the blended yarn, and the higher the softness, heat retention, pilling, water absorption, and pilling resistance of the bulked yarn. In addition, the range of the number of crimps of the first fiber formed by combining the above-mentioned upper limit and lower limit includes all ranges determined by arbitrarily selecting the above-mentioned upper limit and lower limit, respectively (for example, 5 to 20, 7 to 18, etc.).

[0111] The number of crimps can be measured according to the JIS L 1015 method.

[0112] The curl of the first fiber is mainly caused by the shrinkage of the blended yarn described later after contact with water. Therefore, the number of curls of the first fiber can be adjusted by controlling the amino acid sequence of the artificial protein and the manufacturing conditions of the fiber (for example, the stretching conditions when the stretching treatment is performed during the fiber manufacturing process, etc.) in the same way as the "shrinkage rate after contact with water" of the first fiber.

[0113] (Average length of first fiber)

[0114] The average length of the first fiber can be, for example, 48 mm or more, 50 mm or more, 60 mm or more, 70 mm or more, 80 mm or more, 90 mm or more, 100 mm or more, 110 mm or more, 120 mm or more, 130 mm or more, 140 mm or more, or 150 mm or more, and can be 170 mm or less or 160 mm or less. In addition, the longer the average length of the first fiber is, the higher the bulkiness of the blended yarn is, and the higher the softness, heat retention, pilling, water absorption, and pilling resistance of the bulked yarn are. The average length range of the first fiber formed by combining the above upper limit and lower limit includes all ranges determined by arbitrarily selecting the above upper limit and lower limit, respectively (for example, 48 to 170 mm and 70 to 160 mm, etc.).

[0115] The "average fiber length" in this specification refers to the length of short fibers randomly drawn from bulked yarns. Specifically, the "average fiber length" can be measured according to the JIS L 1015C test method.

[0116] (Fiber size of the first fiber)

[0117] The fineness of the first fiber may be, for example, 0.5 denier or more, 0.7 denier or more, 1.0 denier or more, 1.5 denier or more, or 2.0 denier or more. Furthermore, the fineness of the first fiber may be, for example, 5 denier or less, 4.5 denier or less, 4.0 denier or less, or 3.5 denier or less. For example, by controlling the molecular design of the artificial protein contained in the first fiber, a fiber having excellent mechanical strength even at a low fineness and a fiber having excellent softness even at a high fineness may be realized. In addition, the fineness range of the first fiber formed by combining the above-mentioned upper limit value and lower limit value includes all ranges determined by arbitrarily selecting the above-mentioned upper limit value and lower limit value, respectively (for example, 1.0 to 3.5 denier, etc.).

[0118] (Content of the first fiber)

[0119] The content of the first fiber, based on the total mass of the bulked yarn, can be, for example, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, or 80% by mass or more, or it can be 90% by mass or less or 85% by mass or less. If the content of the first fiber is too low, the bulkiness of the bulked yarn may be reduced. In addition, the content range of the first fiber formed by combining the above-mentioned upper limit and lower limit includes all ranges determined by arbitrarily selecting the above-mentioned upper limit and lower limit, respectively (for example, 5 to 90%, 10 to 85%, etc.). In addition, the content of the first fiber can be appropriately determined based on the difference between the shrinkage rate of the first fiber after contact with water and the shrinkage rate of the second fiber after contact with water, or based on the desired properties of the bulked yarn to be achieved by combining the properties of the first fiber and the properties of the second fiber.

[0120] (Method for producing the first fiber)

[0121] The first fiber can be produced by a common spinning method. The first fiber can be produced by a method including the steps of obtaining a spinning solution containing an artificial protein and spinning the spinning solution to obtain the first fiber containing the artificial protein.

[0122] The spinning solution can be obtained by dissolving the artificial protein using a solvent. Examples of the solvent include dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), hexafluoroisopropanol (HFIP), and the like. In order to dissolve the artificial protein, a dissolution accelerator may be used if necessary. Examples of the dissolution accelerator include inorganic salts, and the like.

[0123] The spinning method may be wet spinning, dry spinning, dry-wet spinning or melt spinning, etc. A preferred spinning method may be wet spinning or dry-wet spinning.

[0124] Figure 1 It is an explanatory diagram schematically showing an example of a spinning device for producing the first fiber. Figure 1 The spinning device 10 shown is an example of a spinning device for dry and wet spinning, and includes an extrusion device 1 , an undrawn yarn production device 2 , a wet heat drawing device 3 , and a drying device 4 .

[0125] The spinning method using the spinning device 10 is described. First, the spinning solution 6 stored in the storage tank 7 is extruded from the spinneret 9 by the gear pump 8. In a laboratory-level device, the spinning solution can also be filled into a cylinder and extruded from the nozzle using a syringe pump. Next, the extruded spinning solution 6 is supplied to the coagulation liquid 11 in the coagulation liquid tank 20 through the air gap 19, the solvent is removed, the artificial protein is coagulated, and a fibrous coagulant is formed. Next, the fibrous coagulant is supplied to the warm water 12 in the stretching bath 21 for stretching. The stretching ratio is determined by the speed ratio of the supply clamping roller 13 and the winding clamping roller 14. Then, the stretched fibrous coagulant is supplied to the drying device 4 and dried in the yarn path 22 to obtain the artificial protein fiber 36 in the form of a winding body 5. 18a~18g are yarn guides.

[0126] As the coagulation liquid 11, any solvent capable of desolvation may be used, and examples thereof include lower alcohols having 1 to 5 carbon atoms such as methanol, ethanol and 2-propanol, and acetone. The coagulation liquid 11 may contain appropriate water. The temperature of the coagulation liquid 11 is preferably 0 to 30°C. When a syringe pump having a nozzle with a diameter of 0.1 to 0.6 mm is used as the spinneret 9, the extrusion rate is preferably 0.2 to 6.0 ml / hour per hole, and more preferably 1.4 to 4.0 ml / hour. The distance that the coagulated protein passes through the coagulation liquid 11 (substantially the distance from the yarn guide 18a to the yarn guide 18b) is a length that can effectively desolvate, and may be, for example, 200 to 500 mm. The withdrawal speed of the unstretched yarn may be, for example, 1 to 20 m / minute, and preferably 1 to 3 m / minute. The residence time in the coagulation liquid 11 may be, for example, 0.01 to 3 minutes, and preferably 0.05 to 0.15 minutes. Furthermore, stretching (pre-stretching) may be performed in the coagulation liquid 11. The coagulation liquid tank 20 may be provided in a plurality of stages, and stretching may be performed in each stage or in a specific stage as required.

[0127] The stretching performed when obtaining the first fiber may be, for example, pre-stretching in the coagulation liquid tank 20 and wet heat stretching in the stretching bath 21, or dry heat stretching may be employed.

[0128] The wet heat stretching can be carried out in warm water, or in a solution of an organic solvent or the like added to warm water, or in steam heating. The temperature can be, for example, 50 to 90° C., preferably 75 to 85° C. In the wet heat stretching, the unstretched yarn (or pre-stretched yarn) can be stretched, for example, 1 to 10 times, preferably 2 to 8 times.

[0129] Dry heat stretching can be performed using a tubular electric heating furnace or a dry heat plate, etc. The temperature can be, for example, 140°C to 270°C, preferably 160°C to 230°C. In dry heat stretching, the unstretched yarn (or pre-stretched yarn) can be stretched, for example, 0.5 to 8 times, preferably 1 to 4 times.

[0130] Wet heat stretching and dry heat stretching may be performed separately, or they may be performed in multiple steps or in combination. That is, the first step of stretching may be performed by wet heat stretching, and the second step of stretching may be performed by dry heat stretching; or the first step of stretching may be performed by wet heat stretching, the second step of stretching may be performed by wet heat stretching, and the third step of stretching may be performed by dry heat stretching, etc., and wet heat stretching and dry heat stretching may be performed in appropriate combination.

[0131] The final stretch ratio is preferably greater than 1, 2, 3, 4, 5, 6, 7, 8, or 9 times the lower limit of the unstretched yarn (or pre-stretched yarn), and preferably 40, 30, 20, 15, 14, 13, 12, 11, or 10 times the upper limit of the final stretch ratio. If the first fiber is a fiber spun at a stretch ratio of 2 or more, the shrinkage rate of the first fiber after contact with water tends to be higher.

[0132] <Second Fiber>

[0133] The second fiber is a fiber having a shrinkage rate lower than that of the first fiber after contact with water. The second fiber, for example, can include at least one fiber selected from the group consisting of synthetic fibers (including chemical fibers and semi-synthetic fibers), natural fibers, regenerated fibers, and artificial protein fibers. The second fiber, for example, can include animal hair fibers such as wool, cashmere, angora goat hair, angora rabbit hair, alpaca hair, natural cellulose fibers such as silk (including regenerated silk), cotton, and hemp, regenerated cellulose fibers such as lyocell and rayon, artificial protein fibers, nylon fibers, polyester fibers, and synthetic fibers such as acrylic fibers. Synthetic fibers, natural fibers, regenerated fibers, and artificial protein fibers are selected to have a shrinkage rate lower than that of the first fiber after contact with water. In addition, when the second fiber is an artificial protein fiber, the second fiber is selected to have a shrinkage rate lower than that of the first fiber after contact with water, although it contains the same type of protein as the artificial protein contained in the first fiber, or to contain an artificial protein fiber of a different type of artificial protein from the artificial protein contained in the first fiber.

[0134] (Shrinkage after contact with water)

[0135] The shrinkage rate of the second fiber after contact with water may be, for example, 0% or more, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, or 30% or more. The shrinkage rate of the second fiber after contact with water may be, for example, 45% or less or 40% or less. The second fiber may also be a fiber that does not shrink at all after contact with water. In addition, the range of the shrinkage rate of the second fiber after contact with water formed by combining the above-mentioned upper limit and lower limit includes all ranges determined by arbitrarily selecting the above-mentioned upper limit and lower limit, respectively (for example, 0 to 45%, 5 to 40%, etc.).

[0136] The difference (X1-X2) between the shrinkage rate X1 of the first fiber after contact with water and the shrinkage rate X2 of the second fiber after contact with water can be, for example, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, or 40% or less, or 50% or less or 45% or less. The larger the difference (X1-X2) between the shrinkage rate X1 and the shrinkage rate X2, the higher the fluffiness of the blended yarn, and the higher the softness, heat retention, pilling, water absorption and pilling resistance of the bulked yarn. In addition, the range of the difference (X1-X2) between the shrinkage rate X1 and the shrinkage rate X2 formed by combining the above upper limit and lower limit includes all ranges determined by arbitrarily selecting the above upper limit and lower limit, respectively (for example, 5 to 50% and 10 to 45%, etc.).

[0137] (Number of curls)

[0138] The number of crimps of the second fiber may be, for example, 5 or more, 7 or more, 9 or more, 11 or more, 13 or more, 15 or more, 17 or more, 19 or more, or 20 or more. The number of crimps of the second fiber may be, for example, 25 or less, 23 or less, or 21 or less. In addition, the range of the number of crimps of the second fiber formed by combining the above upper limit and lower limit includes all ranges determined by arbitrarily selecting the above upper limit and lower limit, respectively (for example, 5 to 25, 7 to 23, etc.).

[0139] (Average length of the second fiber)

[0140] The average length of the second fiber may be, for example, 48 mm or more, 50 mm or more, 60 mm or more, 70 mm or more, 80 mm or more, 90 mm or more, 100 mm or more, 110 mm or more, 120 mm or more, 130 mm or more, 140 mm or more, 150 mm or more, or 160 mm or less, or 200 mm or less, 190 mm or less, 180 mm or less, or 170 mm or less. In addition, the average length range of the second fiber formed by combining the above-mentioned upper limit and lower limit includes all ranges determined by arbitrarily selecting the above-mentioned upper limit and lower limit, respectively (for example, 48 to 200 mm and 60 to 190 mm, etc.).

[0141] (Content of the second fiber)

[0142] The content of the second fiber may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, or 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less, based on the total mass of the bulked yarn. In addition, the range of the content of the second fiber formed by combining the above upper limit and lower limit includes all ranges determined by arbitrarily selecting the above upper limit and lower limit, respectively (e.g., 5 to 50%, 10 to 45%, etc.).

[0143] (Method for obtaining the second fiber)

[0144] The second fiber may be a commercially available product as it is, may be produced by a known general method, or may be produced by spinning in the same method as the first fiber.

[0145] <Purpose>

[0146] The bulked yarn can be used as, for example, fabrics for clothing and bedding.

[0147] [Method for producing bulked yarn]

[0148] The method for manufacturing bulked yarn involved in this embodiment includes a blending process and a shrinking process, wherein the blending process is to blend a first wool top containing a first fiber that contains artificial protein and can shrink after contact with water, and a second wool top containing a second fiber whose shrinkage rate after contact with water is lower than that of the first fiber to obtain a raw blended yarn, and the shrinking process is to make the raw blended yarn contact with water and shrink at least the first fiber to obtain a bulked yarn. This method can appropriately manufacture the above-mentioned bulked yarn. The details of the artificial protein, the first fiber and the second fiber can be as described above. Using this manufacturing method, the above-mentioned bulked yarn with bulkiness can be manufactured. In addition, as a weaving method used when obtaining the raw blended yarn, for example, a well-known weaving method such as wool spinning (including 2-inch spinning), wool spinning, cotton spinning and silk spinning can be used. From the perspective of obtaining a bulked yarn with higher bulkiness, among these weaving methods, for example, wool spinning is more advantageous. The reason why a bulked yarn with higher bulkiness can be obtained by using a raw textile yarn obtained by wool spinning is as follows. The raw material blended yarn obtained by combing wool spinning has less twist than the blended yarn obtained by other spinning methods, so the blended yarn is softer as a whole. As a result, the fluffy effect that can be obtained by the first water shrinkage is enhanced. In addition, the length of the short fibers used in combing wool spinning is also longer than that used in wool spinning, cotton spinning, etc. (for example, fibers with a length of 50 to 170 mm are used in combing wool spinning), so the force required for pulling when pulling the wool tops is greater. Therefore, a greater residual stress is generated in the first fiber in combing wool spinning, and the shrinkage rate increases after contact with water. These reasons ultimately make it possible to obtain higher fluffiness in bulked yarn. In addition, in combing wool spinning, a comb-like body is used to comb the wool tops when pulling the wool tops, and a large resistance is applied to the fibers at this time. It is speculated that this will also cause a greater residual stress in the first fiber, so that the bulked yarn finally obtained has a higher fluffiness.

[0149] The first top may be a top prepared in advance (already manufactured) or a top obtained by a process of manufacturing a tow containing the first fiber (a process of obtaining the first top). Furthermore, the second top may be a top prepared in advance (already manufactured) or a top obtained by a process of manufacturing a second fiber by a known method (a process of obtaining the second top).

[0150] In the first wool top obtaining process, for example, a tow of the first fiber can be supplied between two groups of rollers, front and rear, and the surface speed of the rear roller is made greater than the surface speed of the front roller to break the tow (stretching and cutting). In other words, the conventional method of obtaining the first wool top by breaking the tow can be used.

[0151] In the first sliver obtaining step, by adopting a method of breaking the tow containing the first fiber, the first sliver can be obtained in a state where the first fiber is not shrunk and not curled. As a result, it is easier to obtain a bulked yarn having a bulkiness within the above range. In addition, when the tow is broken, a higher residual stress can be obtained by stretching the first fiber. Therefore, the water shrinkage rate (shrinkage rate when in contact with water) of the first fiber will be further improved. As a result, it is expected that a more bulked yarn can be obtained.

[0152] In the blending process, the first top and the second top are blended to obtain a raw blended yarn. The second top contains a second fiber. The second top can be directly made of a commercial product or can be made of a second fiber having a shrinkage rate lower than that of the first fiber after contacting with water. Any known method can be used to obtain the second top using the second fiber.

[0153] The method of blending the first wool top and the second wool top can be carried out by a general method of blending wool top. For example, the blending can be carried out by a method including a step of forming a thick line with the first wool top and the second wool top, and a step of applying traction to the thick line and twisting the line at the same time, in order to improve the parallelism of the fibers and uniformly mix the fibers. The traction in the twisting process can also increase the residual stress of the first fiber and further improve the water shrinkage rate. As a result, it is expected that a more fluffy bulked yarn can be obtained.

[0154] By adopting the above blending process, in addition to the fluffiness, the elongation, heat retention, water absorption and anti-pilling properties also tend to be improved.

[0155] In the shrinking step, the raw material mixed yarn is brought into contact with an aqueous medium to shrink at least the first fiber, thereby obtaining a bulked yarn.

[0156] An aqueous medium refers to a medium of a liquid or gas (steam) containing water (including water vapor). The aqueous medium may be water or a mixed solution of water and a hydrophilic medium. As a hydrophilic medium, for example, volatile solvents such as ethanol and methanol or their vapors may also be used. The aqueous medium may be a mixed liquid of water and a volatile solvent such as ethanol or methanol, preferably water or a mixed liquid of water and ethanol. The ratio of water to a volatile solvent or its vapor is not particularly limited, for example, water: a volatile solvent or its vapor may be 10:90 to 90:10 in terms of mass ratio. The proportion of water is preferably 30% by mass or more, and may also be 40% by mass or 50% by mass or more.

[0157] The aqueous medium is preferably a liquid or gas containing water (including water vapor) at 10 to 230° C. The temperature of the aqueous medium may be 10° C. or higher, 25° C. or higher, 40° C. or higher, 60° C. or higher, or 100° C. or higher, or 230° C. or lower, 120° C. or lower, 100° C. or lower, or 90° C. or lower. More specifically, when the aqueous medium is a gas (steam), the temperature of the aqueous medium is preferably 100 to 230° C., and more preferably 100 to 120° C.

[0158] Examples of methods for bringing the raw blended yarn into contact with the aqueous medium include a method of spraying the aqueous medium on the raw blended yarn, a method of immersing the raw blended yarn in the aqueous medium, and a method of exposing the raw blended yarn to an environment filled with aqueous medium vapor.

[0159] The time of contact with the aqueous medium is appropriately adjusted according to the type of raw material blended yarn, the temperature of the aqueous medium, the method of contact with the aqueous medium, etc. The time of contact with the aqueous medium may be, for example, more than 1 minute, more than 5 minutes, more than 10 minutes, or more than 15 minutes, or less than 30 minutes, less than 20 minutes, or less than 15 minutes. The contact with the aqueous medium may be carried out under normal pressure or under reduced pressure (e.g., vacuum).

[0160] The raw material blended yarn after contact with the aqueous medium may be washed, if necessary. The washing may be performed, for example, using the above-mentioned aqueous medium. The temperature of the aqueous medium during washing may be, for example, 10°C or more, 20°C or more, or 30°C or less, or 50°C or less, 45°C or less, or 40°C or less.

[0161] The raw material blended yarn after contacting with the aqueous medium may be dried. The drying method is not particularly limited, and the drying may be natural drying or drying using hot air or a hot roller. The drying temperature is not particularly limited, and may be, for example, 20 to 150° C., preferably 40 to 120° C., and more preferably 60 to 100° C. The drying time may be, for example, 5 minutes or more or 10 minutes or more, or 30 minutes or less or 20 minutes or less.

[0162] The fabric containing the bulked yarn involved in this embodiment can be a fabric consisting of bulked yarn alone, or a fabric containing other yarns (such as spun yarn, twisted yarn, etc.). In addition, the fabric can be any one of knitted fabrics or woven fabrics, or a texture composed of these. In addition, the manufacturing method (knitting method and weaving method) of the knitted fabric or woven fabric constituting the fabric can adopt any known method.

[0163] [Example]

[0164] Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following examples.

[0165] <Preparation of artificial protein>

[0166] (1) Preparation of plasmid expression strains

[0167] An artificial protein (artificial silk fibroin) having the amino acid sequence shown in SEQ ID NO: 2 (PRT966) was designed.

[0168] Next, a nucleic acid encoding the designed artificial protein is synthesized. In the nucleic acid, an NdeI site is added to the 5' end and an EcoRI site is added downstream of the stop codon. The nucleic acid is cloned into a cloning vector (pUC118). Then, the nucleic acid is treated with restriction enzymes using NdeI and EcoRI and excised, and then recombined into a protein expression vector pET-22b (+) to obtain an expression vector.

[0169] (2) Protein expression

[0170] E. coli BLR (DE3) was transformed with the pET-22b (+) expression vector containing the nucleic acid encoding the designed artificial protein. The transformed E. coli was cultured in 2 mL LB medium containing ampicillin for 15 hours. The culture solution was added to 100 mL of seed culture medium (Table 3) containing ampicillin to a concentration of OD 600 The culture temperature was maintained at 30°C and the flask culture was continued until the OD 600 When the temperature reaches 5 (about 15 hours), a seed culture solution is obtained.

[0171] [Table 3]

[0172]

[0173] The seed culture was added to a fermenter containing 500 ml of production medium (Table 4) to obtain a OD 600 The culture medium temperature was maintained at 37°C and the pH value was constantly controlled at 6.9. In addition, the dissolved oxygen concentration in the culture medium was maintained at 20% of the saturated dissolved oxygen concentration.

[0174] [Table 4]

[0175]

[0176] After the glucose in the production medium is completely consumed, the feed solution (glucose 455g / 1L, yeast extract 120g / 1L) is immediately added at a rate of 1mL / min. The culture solution temperature is maintained at 37°C and the pH value is constantly controlled at 6.9 for cultivation. In addition, the dissolved oxygen concentration in the culture solution is maintained at 20% of the saturated dissolved oxygen concentration and cultured for 20 hours. Then, 1M isopropyl-β-thiogalactopyranoside (IPTG) is added to the culture solution to make its final concentration 1mM, and the expression of induced artificial protein is induced. At a time point of 20 hours after the addition of IPTG, the culture solution is centrifuged and the bacterial cells are recovered. SDS-PAGE is performed using bacterial cells prepared from the culture solution before and after the addition of IPTG. After the appearance of the target artificial protein size band depending on the addition of IPTG, the expression of the target artificial protein is confirmed.

[0177] (3) Protein purification

[0178] The cells recovered after 2 hours after adding IPTG were washed with 20mM Tris-HCl buffer (pH7.4). The washed cells were suspended in 20mM Tris-HCl buffer (pH7.4) containing about 1mM phenylmethylsulfonyl fluoride (PMSF), and the cells were disrupted using a high-pressure homogenizer (manufactured by GEA Niro Soavi). The disrupted cells were centrifuged to obtain a precipitate. The obtained precipitate was washed with 20mMTris-HCl buffer (pH7.4) until it reached a high purity. The washed precipitate was suspended in 8M guanidine buffer (8M guanidine hydrochloride, 10mM sodium dihydrogen phosphate, 20mM NaCl, 1mMTris-HCl, pH7.0) to a concentration of 100mg / mL, and stirred with a stirrer at 60°C for 30 minutes to dissolve it. After dissolution, it was dialyzed with water using a dialysis tube (cellulose tube 36 / 32 manufactured by Sanko Junyaku Co., Ltd.). The white aggregated protein obtained after dialysis was recovered by centrifugal separation, and the water was removed by a freeze dryer to recover a freeze-dried powder containing the artificial protein PRT966.

[0179] <Manufacturing of the first fiber (artificial protein fiber)>

[0180] (1) Preparation of spinning solution

[0181] A freeze-dried powder of artificial protein was added to dimethyl sulfoxide (DMSO) to a concentration of 24 mass %, and then LiCl was added as a dissolution accelerator to a concentration of 4.0 mass %. Then, a shaker was used to shake for 3 hours to dissolve the freeze-dried powder of artificial protein, and a DMSO solution of artificial protein was obtained. Insoluble matter and bubbles in the obtained DMSO solution were removed to prepare a spinning solution. The solution viscosity of the spinning solution was 5000 cP (centipoise) at 90°C.

[0182] (2) Spinning

[0183] Using the spinning solution obtained as described above and Figure 1 The spinning device 10 shown in the figure performs known dry-wet spinning to obtain artificial protein fibers. The obtained artificial protein fibers are wound onto a bobbin. The dry-wet spinning is performed under the following conditions.

[0184] Temperature of coagulation liquid (methanol): 5~10℃

[0185] Stretching ratio: 4.52 times

[0186] Drying temperature: 80℃

[0187] <Manufacturing of blended yarn>

[0188] The rayon fibers are broken to produce a first sliver containing the rayon fibers. The cut length of the rayon fibers cut at this time is about 150 to 250 mm. The blended yarn is produced by a wool spinning method.

[0189] <Example 1>

[0190] The first and second wool tops are used to carry out the pre-spinning process. This process is a process of processing the first and second wool tops into thick yarns for post-spinning. The purpose of this process is to improve the parallelism of the fibers and make them evenly mixed. In this process, wool tops are used as the second wool tops. Commercially available wool tops are used, and the fiber length is about 75 mm. In the pre-spinning process, for example, 6 to 8 wool tops and 2 to 4 artificial protein fibers out of 10 wool tops are stretched at a stretching ratio of 2 to 6 times. This process is repeated, for example, 5 times.

[0191] The post-spinning process is carried out using thick yarn. Specifically, this process is a process of twisting the thick yarn while stretching it. In this process, the number of twists is about 300 times / m, and the stretching ratio is 25 to 30 times. The twisting direction is twisting in the Z direction. When manufacturing a double-ply yarn, the number of twists is about 230 times / m, and the twisting direction is twisting in the S direction.

[0192] The raw material blended yarn obtained by the above method is made into a hank (2m40cm). The hank is installed in a hank dyeing machine. In the hank dyeing machine, 100°C water is sprayed on the hank for 15 to 20 minutes. The obtained hank is washed with 30 to 40°C water, dehydrated, and dried with hot air at about 90°C for 15 minutes. Thus, a bulked yarn composed of artificial protein fiber and wool is obtained.

[0193] <Content of the first fiber>

[0194] The content of the first fiber was 30% by mass based on the total mass of the blended yarn.

[0195] <Average fiber length>

[0196] The average length of the first fibers was 72.4 mm. The average length of the second fibers was 74.2 mm. The average length of the fibers was measured according to JIS L 1015C.

[0197] <Shrinkage after contact with water>

[0198] The shrinkage rate of the first fiber after contact with water is 45%. The shrinkage rate of the second fiber after contact with water is 10%. The "shrinkage rate after contact with water" of the first fiber and the second fiber are measured separately according to the following method. First, a fiber bundle in which multiple fibers of the same length are bundled is obtained. A 0.8g plumb bob is installed on the obtained fiber bundle, and it is immersed in water at 95°C for 10 minutes. After that, the fiber bundle is taken out of the water, and then the taken out fiber bundle is kept with a 0.8g plumb bob installed, and it is dried at room temperature for 2 hours, and the length of the fiber bundle is measured after drying. Next, the "shrinkage rate (%) after contact with water" of the fiber is calculated according to the following formula I. In formula I, L0 represents the length of the fiber bundle before contact with water, and Ld represents the length of the fiber bundle in the dry state after shrinkage due to contact with water.

[0199] Formula I: Shrinkage rate = {1-(Ld / L0)}×100(%)

[0200] <Number of curls>

[0201] The number of crimps of the first fiber was 8.0. The number of crimps of the second fiber was 11.8. The number of crimps was measured according to the JIS L 1015 test method.

[0202] <Fluffiness>

[0203] The bulkiness of the blended yarn obtained by the above method is 36.1 cm 3 / g. The bulkiness was measured according to the JIS L 1095A test method.

[0204] <Example 2>

[0205] A bulked yarn composed of rayon fiber and silk was obtained by the same method as in Example 1 except that silk top was used as the second top. The raw material blended yarn was produced by the wool spinning method.

[0206] <Content of the first fiber>

[0207] The content of the first fiber was 30% by mass based on the total mass of the blended yarn.

[0208] <Average fiber length>

[0209] The average length of the first fibers was 68.0 mm, and the average length of the second fibers was 86.2 mm.

[0210] <Shrinkage after contact with water>

[0211] The shrinkage rate of the first fiber after contact with water is 45%, and the shrinkage rate of the second fiber after contact with water is 10%.

[0212] <Number of curls after contact with water>

[0213] The number of crimps of the first fiber was 8.0. The number of crimps of the second fiber was 19.1. In addition, the average length, shrinkage rate after contact with water, and number of crimps of the first and second fibers were measured by the same method as in Example 1.

[0214] <Fluffiness>

[0215] The bulkiness of the blended yarn obtained by the above method is 22.0 cm 3 / g. In addition, the bulkiness was measured by the same method as in Example 1.

[0216] Explanation of symbols

[0217] 1Extrusion device

[0218] 2 Undrawn yarn manufacturing device

[0219] 3. Wet heat stretching device

[0220] 4 Drying device

[0221] 6 Spinning solution

[0222] 10 Spinning device

[0223] 20 solidification tank

[0224] 21Stretching bath

[0225] 36. Artificial protein fiber

Claims

1. A bulked yarn comprising: Contains artificial protein, the first fiber that shrinks when in contact with water, The second fiber has a lower shrinkage rate than the first fiber after contact with water, and the bulkiness is 10cm 3 / g or above.

2. The bulked yarn according to claim 1, wherein the bulkiness is 50 cm 3 / g or less. 3 . The bulked yarn according to claim 1 , wherein the shrinkage rate of the first fiber after contact with water is 15% or more. 4 . The bulked yarn according to claim 1 , wherein the first fiber has 5 or more crimps. 5 . The bulked yarn according to claim 1 , wherein the content of the first fiber is 5% by mass or more based on the total mass of the bulked yarn. 6 . The bulked yarn according to claim 1 , wherein an average length of the first fibers is not less than 48 mm and not more than 170 mm. 7 . The bulked yarn according to claim 1 , wherein the second fiber is at least one of animal hair fiber and silk.

8. A method for producing bulked yarn, comprising the following steps: A process of blending a first sliver including a first fiber containing artificial protein and shrinkable upon contact with water and a second sliver including a second fiber having a shrinkage rate lower than that of the first fiber upon contact with water to obtain a raw blended yarn, The step of bringing the raw material mixed yarn into contact with an aqueous medium to shrink at least the first fiber to obtain a bulked yarn.

9. A fabric comprising the bulked yarn according to claim 1 or 2.

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