WO1998058104A1 - Fibre cellulosique apte a la teinture par colorant a dispersion - Google Patents

Fibre cellulosique apte a la teinture par colorant a dispersion Download PDF

Info

Publication number
WO1998058104A1
WO1998058104A1 PCT/JP1998/002729 JP9802729W WO9858104A1 WO 1998058104 A1 WO1998058104 A1 WO 1998058104A1 JP 9802729 W JP9802729 W JP 9802729W WO 9858104 A1 WO9858104 A1 WO 9858104A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
fine particles
cellulose
polymer
particles
Prior art date
Application number
PCT/JP1998/002729
Other languages
English (en)
Japanese (ja)
Inventor
Ryu Taniguchi
Shuji Takasu
Toru Morita
Original Assignee
Asahi Kasei Kogyo Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Kogyo Kabushiki Kaisha filed Critical Asahi Kasei Kogyo Kabushiki Kaisha
Publication of WO1998058104A1 publication Critical patent/WO1998058104A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either

Definitions

  • the present invention provides a cellulose fiber suitable for compounding with a polyester fiber, and more specifically, a color development equivalent to that of a polyester fiber when one-bath single-stage dyeing with a disperse dye is performed under ordinary polyester dyeing conditions.
  • TECHNICAL FIELD The present invention relates to a disperse dyeable cellulose fiber exhibiting excellent properties and hue, and having excellent spinning properties, fiber properties, and high glossiness and high coloring properties, and a fiber product thereof. Background art
  • JP-A-58-75686 discloses a compound having an alcohol or carboxylic acid group in a cellulose hydroxyl group using an acylating agent.
  • a technology has been disclosed in which cellulose is reacted to modify the cellulose to a cellulose ether derivative / senorelose ester derivative, thereby reducing the amount of hydrophilic cellulose hydroxyl groups, making the fibers hydrophobic, and having an affinity for disperse dyes. I have.
  • a cellulose compound is impregnated with a vinyl compound, and then heat-treated or irradiated with an electron beam in the presence of a polymerization initiator to convert the vinyl compound into cellulose.
  • a technique has been disclosed in which the compound has an affinity for a disperse dye.
  • post-processing technologies a technology for reacting an aromatic compound with cellulose has been disclosed, but these post-processing modifications involve the modification of the hydroxyl group in the cell opening or the carbon atom adjacent to the hydroxyl group.
  • WO 95/238388 and JP-A-1997-33836 disclose polyester fine particles, acryl'styrene polymer fine particles, and acrylic polymer fine particles. A technique has been disclosed in which fine particles that can be dyed with a disperse dye are added to an undiluted spinning solution and spun to dye the disperse dye.
  • the cellulose fiber is dyed first. As the temperature rises and the dyeing time elapses, the dye is transferred from the cellulose fibers to the polyester fibers. In order to sufficiently develop the color of the polyester fiber, it is necessary to dye under general polyester dyeing conditions, for example, at 130 ° C. for 60 minutes.However, in the technology disclosed in these patents, the cellulose fiber is dyed. Most of the dye is transferred to polyester fibers, cellulose fibers are lightly dyed, and polyester fibers are deeply dyed, increasing the color difference between the two.
  • the polymer fine particles disclosed in these patents are hydrophobic and are nearly neutral in terms of electrical properties, so that they tend to agglomerate in the cell solution with high alkali concentration.
  • the physical properties (especially elongation) of the obtained fiber are reduced because the agglomerated coarse particles act as a foreign substance inside the fiber.
  • methyl methacrylate Polymers containing acid components such as acrylic acid copolymers, methylmetaphthalate, methacrylic acid / styrene copolymers, and acrylic acid / styrene copolymers
  • the dispersion technique using these surfactants ensures that the particle diameter of the fine particles in the fiber is 0.1 m or less, particularly 0.05 m or less, while maintaining good spinning properties and fiber properties. It was difficult to achieve ultra-fine dispersion.
  • the particle diameter in the fiber is as large as 0.05 to 5 zm, the dispersion state of the particles in the fiber becomes sparse, and the uniform cross-section of the fiber cannot be performed, and the dyed spots are easily generated. there were.
  • the size of these particles is equal to or larger than the wavelength of visible light in the submicron to micron order, the yarn becomes cloudy when the amount of addition increases.
  • Japanese Patent Publication No. 37-124, No. 44-1320 and Japanese Patent Publication No. 431,1111 disclose a vinyl polymer obtained by copolymerizing a monomer having an acidic group.
  • a technique has been disclosed which suppresses agglomeration and deterioration of physical properties due to the addition of a polymer by adding it to a stock solution.
  • the fiber properties are improved by the addition of these polymers, the polymer becomes alkaline soluble or highly water-swellable due to the large copolymerization amount of the acidic monomer, and the dyed product is washed with water or washed with reduction. As a result, the color is greatly faded, and it is not possible to obtain a fiber having high color development and high robustness.
  • the temperature of the dyeing is raised.
  • the cellulosic fiber which can be dyed with a dispersible dye is dyed, and dye exhaustion of the polyester fiber occurs at around 130 ° C.
  • the disperse dye was transferred from the cellulosic fiber to the polyester fiber over time, and eventually the polyester fiber was deeply dyed and the cellulose fiber was pale. It dyes, and the color difference between them increases.
  • the amount of disperse dye-dyeable components (fine particles) in the cellulose fibers is at most 10% based on the amount of the polyester fibers. ⁇ 20%, and the number of dyed seats is overwhelmingly small. In this case, even if the addition rate of the polymer fine particles is increased or the mixing rate of the polyester fibers is reduced, the dye transfer to the polyester fibers cannot be suppressed, and the dyeing difference is hardly improved. If ⁇ ⁇ * of the same color evaluation method in the same bath dyeing with a disperse dye having an average hardness described later is 10 or less, particularly 5 or less, humans do not feel much irritability or discomfort.
  • polyester fibers are not sufficiently colored by short-time dyeing, and dyed in the same color due to high transfer speed. The point is the only point, and the dyeing level and color difference will change greatly due to differences in simple conditions such as variations in dyeing temperature and dyeing time.
  • a polymer that has only an ester bond without an aromatic ring eg, cellulose acetate, polymethyl acrylate
  • the degree of exhaustion varies greatly depending on the type of disperse dye used, when dyeing with a combination of multiple types of dyes, the dyes dyed under the same conditions are used.
  • the hue will be different from the hue of the ester.
  • the dyeing rate of the yellow dye is lower than that of polyester fibers, and the brown or reddish color is strong. The color becomes hue, and it looks strange.
  • Another object of the present invention is to provide a dispersible dyeable cellulose fiber having satisfactory mechanical properties, and excellent glossiness capable of fast dyeing with high clarity, deep color and coloring. is there.
  • Another object of the present invention is to provide cellulose dyeable dyeable cellulose fibers having excellent light fastness and wet rub fastness and improved as described above.
  • the migration phenomenon and the occurrence of color differences in the composite fiber product of disperse dye-dyed cellulose fiber / polyester fiber are due to the fact that the polymer added to the cellulose fiber has a higher affinity for the disperse dye than that of the polyester fiber. Is also inferior.
  • the present inventors have proposed a compound having an ester bond and / or an ester bond at an aromatic ring and an aromatic ring or a carbon atom adjacent to the aromatic ring in the same molecule as the polymer fine particles added to the cellulose fiber.
  • a polymer containing 0 to 95% by weight is used, the transfer speed of the disperse dye to the polyester fiber is reduced, the difference in dyeing color from the polyester fiber is reduced, and the ordinary polymer is used.
  • the same color can be dyed in one bath and one step, and the same hue as in the case of polyester fiber dyeing can be obtained in multiple types of compound dyeing. That is, in the present invention, 20 to 95% by weight of the repeating unit has an aromatic ring, and the aromatic ring or a carbon atom adjacent to the aromatic ring has an ester bond (—C 0 0—) and / or Contain 1 to 40% by weight of fine particles of a polymer composed of a compound having at least one or more ether bond (10-), and have a heat-up dye exhaustion rate of 70% or more.
  • the cellulose fiber means a chemical cellulose fiber other than natural cellulose fibers such as cotton, and includes both short fibers and long fibers. Specifically, cellulose is directly dissolved in an aqueous solvent such as regenerated cellulose fiber such as copper ammonia rayon fiber, pisco rayon fiber, or cellulose carbamate fiber, or cold sodium hydroxide or sulfuric acid. Cellulose fibers obtained by spinning.
  • the fiber product includes a yarn, a hollow yarn, a porous yarn, a cotton, a string, and a knitted fabric composed of only the disperse dye-dyeable cellulose fiber of the present invention.
  • fiber products containing at least a part of the cellulose fibers are also included.
  • the polymer constituting the fine particles contained in the cellulose fiber of the present invention has at least one ester bond and / or ether bond at an aromatic ring or at a carbon atom adjacent to the aromatic ring. It is a compound obtained by polymerizing a compound having at least one compound (hereinafter, this repeating unit is called the same color unit) in the range of 20 to 95% by weight.
  • Polymers constituting polymers are roughly classified into vinyl polymers and polycondensation polymers.
  • the vinyl polymer include an aromatic vinyl ester polymer, an aromatic vinyl ether polymer, an aromatic vinyl ketone polymer, and an aromatic methacrylate polymer.
  • polystyrene-derivative polymers aromatic maleic acid ester-based polymers, and the like.
  • the polycondensed yarn polymer include aromatic polymer copolymers.
  • the same color unit may have any number of at least one aromatic ring. Further, the same color unit may have any number of at least one ester bond or ether bond.
  • the aromatic ring may be a monocyclic or polycyclic aromatic ring such as a benzene ring, a naphthalene ring, and an anthracene ring. It may be. In terms of affinity with the disperse dye, polycyclic aromatic rings having high planarity are excellent, but benzene ring compounds which are relatively inexpensive industrially are preferred.
  • the repeating unit of the polymer refers to a monomer having at least one ethylenic unsaturated bond in the case of a vinyl polymer, and in the case of a polycondensation polymer. Is a unit from which one water molecule is eliminated by condensation.
  • Examples of the same color unit that can be used in the present invention include a radical polymerizable compound and a polycondensation compound.
  • Examples of the radical polymerizable compound (monomer) include vinyl benzoate and toluene. Vinyl acetate, ethoxyquin vinyl benzoate, vinyl ethyl benzoate, P—hydroxy benzoate, m—vinyl hydroxy benzoate, vinyl ethoxypropionate, vinyl anilate, ⁇ —naphthoic acid Vinyl, ⁇ — vinyl naphthoate, vinyl cinnamate, ⁇ — vinyl vinyl ester derivatives such as vinyl methoxycinnamate, diaryl terephthalate, diaryl isophthalate, etc.
  • Aromatic aryl ester derivative 2 — (meta) acryloyl phenol oxylate 2 — hydroxypropyl phthalate, 2 — (meta) acrylate Quintile-1 2 — Hydroxiceti norephthalic acid, 2 — (Meth) acryloi roxshetylphthalic acid, 2 — (Metha) acryloi noreoxypro pill high drogenphtalate, 2 —Aclylo iloxekityl 2 — hydroxypropyl phthalate, 2 — hydroxypropyl phthalate 2 — hydroxypropyl phthalate, ⁇ — (meta) acryloylochysylhydrazine phthalate, fue Nil (meta) acrylate, methylphenyl (meta) acrylate, nitrophenyl (meta) acrylate, methoxyphenyl (meta) acrylate , Benzil (meta) acrylate, 2-phenoxy
  • Aromatic (meth) acrylic acid ester derivatives such as (meth) acrylates, acetylstyrene, vinylsalicylic acid, p-phenoxystyrene, p-methoxystyrene , P-Styrene derivatives such as acetyl styrene, aromatic vinyl ketone derivatives such as acetyl benzylvinylketone, benzyl maleate, dibenzyl maleate, Examples thereof include aromatic maleic acid ester derivatives such as phenyl phthalate and diphenyl phthalate. If necessary, a plurality of these monomers may be used in combination.
  • Most preferred vinyl polymers include aromatic methyl acrylate polymers and aromatic vinyl ester polymers.
  • polycondensation systems include terephthalic acid Z adipic acid / ethylene glycol / polyethylene glycol, and terephthalic acid / adipic acid Z ethylene glycol.
  • / 5 Disperse dyes such as sodium perfluorophthalic acid and the like, which are easily dyeable polyethylene phthalate.
  • Polymer fine particles are finely dispersed inside the fiber It is preferable in terms of coloring.
  • a polycondensation polymer it is difficult to obtain submicron-order fine particles by mechanical pulverization of the polymer. Therefore, dispersion polymerization, suspension polymerization, and microemulsion It is preferable to use fine particles of a radical polymerization type polymer, which can directly produce polymer fine particles by a polymerization method or an emulsion polymerization method.
  • any other monomer may be used as long as the same color unit is copolymerized in the range of 20 to 95% by weight.
  • styrene methyl methacrylate, ethyl methacrylate, butyl (meth) acrylate, cyclohexyl (meta) acrylate
  • Monomers such as acrylate, ethylhexyl (meta) acrylate, and vinyl acetate are preferably used.
  • halogenates such as vinylidene chloride and trichloroethylene are used.
  • a conventionally known radically polymerizable compound such as a vinylketone derivative such as vinylenephthalene, a polycyclic monomer such as vinylnaphthalene or vinylanthracene may be copolymerized.
  • the fine particles of the polymer of the present invention need to have a degree of polymerization such that the polymer is not eluted during a treatment such as a dyeing step, a post-processing step, washing, and dry cleaning.
  • a treatment such as a dyeing step, a post-processing step, washing, and dry cleaning.
  • the degree of polymerization of the polymer is preferably 10 or more, and more preferably 30 or more.
  • polymer microparticles can be used in one or more polymer types. It may be a mixture of particles, and may contain fine particles having a different average particle size, particle size distribution, or molecular weight.
  • the copolymerization ratio of the same color unit when the copolymerization ratio of the same color unit is less than 20% by weight, the affinity for the disperse dye is insufficient, the dye transfer to the polyester fiber occurs, and the dyeing difference becomes large. Since the hue at the time of compound dyeing is greatly different from that of polyester fiber, it is preferably at least 30% by weight, more preferably at least 40% by weight, particularly preferably at least 50% by weight. It is desirable to copolymerize at a rate of not less than weight%.
  • Cellulose fibers containing polymer fine particles used in the present invention have a heating dye exhaustion rate of 70% or more.
  • the thermal dye exhaustion is measured by the method defined below.
  • the heating dye exhaustion rate is defined as the point at which a disperse dye dyeable cellulose fiber is poured into a dyeing solution, and the dyeing bath is heated at a specific heating rate to a predetermined dyeing temperature (130 ° C). It is the dye exhaustion rate of the fiber. In the present invention, the heating dye exhaustion rate is measured by a measuring method described later.
  • polyester fiber In the same bath dyeing of disperse dye dyeable cellulosic fiber / polyester fiber (weight ratio: 1/1), polyester fiber is more in the equilibrium dyeing state because of the number of disperse dye dyeing seats. Dyes and dyes deeply. For this reason, if the polyester fiber adsorbs the dye before the cellulose fiber, the dye transfer from the polyester fiber to the cellulosic fiber does not seem to occur, so that the cellulose and the polyester fiber are dyed from the start to the end of the dyeing. There is no point where the amount of dye dyeing is equal, and the same color can be achieved. Absent. To achieve the same coloration, the cellulose side needs to dye more dye first.
  • the heat-up dye exhaustion rate of the cellulose containing polymer fine particles must be 70% or more, and is preferably 80% or more, particularly preferably, in order to obtain sufficient coloration. Preferably, it is 90% or more.
  • the amount of the polymer fine particles contained in the cellulose fiber is from 1 to 40% by weight from the viewpoints of dyeing properties, coloring properties, fiber properties, process passability and the like. If the content of the polymer fine particles is less than 1% by weight, the amount of the disperse dye per unit weight of the fiber becomes small, so that a fiber having a clear color cannot be obtained. If the content of the polymer particles exceeds 40% by weight, the particles tend to agglomerate due to collisions between the particles, causing single yarn breakage and fluff in the manufacturing process, and the tensile strength of the obtained fibers. Physical properties, such as cell-mouth fiber, and the functions such as hygroscopicity and water-absorbing property are reduced.
  • the content of the polymer fine particles is preferably 5 to 30% by weight, more preferably 10 to 10% by weight, based on the balance between the color of the obtained fiber after dyeing with a disperse dye, the process passability, and the physical properties of the fiber. 20% by weight. Within this range, it is possible to obtain a cellulose fiber having good coloring properties and mechanical properties.
  • the content of the polymer fine particles in the cellulose fiber may be determined by dissolving the cellulose component in an aqueous solution of copper ammonia and performing centrifugation, and determining the content of the fine particles from the amount of the centrifuged sediment.
  • the fine particle content G (% by weight) in the fiber is calculated by the following formula. I do.
  • the transfer rate in this case is proportional to the product of the copolymerization amount of the same color unit and the amount of polymer fine particles contained in the cellulose fiber. It is necessary to select the addition amount of the polymer fine particles according to the copolymerization amount of the same color unit.
  • the copolymerization ratio of the unit of the same color should be X (weight%), Assuming that the content of the polymer fine particles is Y (% by weight), it is desirable that the product XY of the two is 400 or more.
  • the higher the XY value the slower the transfer speed can be.However, if the XY value is too high, the transfer speed becomes too slow, and the cell mouth fiber becomes densely dyed or lightfast. Therefore, it is desirable that the value be less than 2000. From the viewpoint of homochromaticity and fastness, the preferred range of XY is 500 to 100000.
  • the polymer contained in the cellulose fiber of the present invention is in the form of fine particles.
  • the polymer is molecularly dispersed (alloyed) in the fiber, not only the dyeability and the fastness of the disperse dye are reduced, but also the post-processing step such as alkaline hot water treatment is performed. The problem that the coalescence elutes occurs.
  • the present inventors have found that 1-3 0 weight% Chikaraku of repeating units constituting the polymer, One C_ ⁇ OR, - S 0 3 R, - P 0 R (R is a hydrogen atom or alkali metal or NH, It has been found that, by having at least one kind of ionizing functional group selected from ( 4 ), the polymer fine particles are finely dispersed without agglomeration in the fiber.
  • the proportion of the repeating unit having an ionizable functional group in the polymer is from 1 to 30% by weight, preferably from 2 to 20% by weight, and more preferably from 3 to 10% by weight. .
  • the content of the repeating unit is less than 1% by weight, the surface potential of the particles does not increase and aggregation cannot be sufficiently suppressed.
  • the content exceeds 30% by weight aggregation can be suppressed, but alkali swelling occurs. Properties and hydrophilicity become too strong, becoming alkaline soluble or significantly swelling in water, weakening the affinity with disperse dyes, lowering the dye dyeing rate and fastness I do.
  • the disperse dyeable cellulose fiber needs to have the mechanical properties of a practical cellulose fiber.
  • the present inventors have found that the repeating units constituting the polymer constituting the fine particles, (A) - COOR, - S 03 R and P 0 3 R (where, R represents water atom, an alkali metal or NH 4 (B) —OH group, 1 NHR 1 group and —CONHR 1 group (R 1 is a hydrogen atom or an organic group having 1 to 6 carbon atoms)
  • R represents water atom, an alkali metal or NH 4
  • B —OH group, 1 NHR 1 group and —CONHR 1 group
  • R 1 is a hydrogen atom or an organic group having 1 to 6 carbon atoms
  • the stock solution for spinning cellulose fibers is an alkaline solution such as a sodium hydroxide solution or a copper ammonium solution, and positively charged ions such as sodium ions, copper ions, and ammonium ions are used. It is a solution that exists in excess. Under these excess ions, aggregation is more likely to occur than in the nonionic state.
  • the potential of the polymer particle surface in the stock solution for spinning cellulosic fibers is used. (Negative charge) can be increased.
  • Methods for incorporating an ionizable functional group in a polymer include polymers.
  • Polymers having an ionizable functional group formed by hydrolysis include polymers having a bond such as a carboxylic acid ester, a sulfonate ester, a phosphate ester, or an amide in a main chain or a side chain. No.
  • Examples of the polymer whose main chain is hydrolyzed to form an ionizable terminal include the above-mentioned easily dyeable polyester such as polyethylene phthalate and the like, and phthalic acid diaryl phthalate.
  • Examples include a vinyl polymer obtained by copolymerizing disophthalic acid diaryl.
  • Polymers whose side chains are hydrolyzed to form ionizable functional groups include methyl (meth) acrylate, ethynole (meta) acrylate, and pill ( Meth) acrylate, n-butyl (meth) acrylate, is 0—butyl (meta) acrylate, sec—butyl (meta) acrylate, tert —Butyl (meta) acrylate, phenyl (meta) acrylate, octyl (meta) acrylate, pentyl (meta) acrylate, 4 Monocarboxyphenyl (meta) acrylate, hydroxyxetil (meta) acrylate, 3 —Hydroxy (meta) propylacrylate, hydroxybutyl (meta) acrylate RELAY, 1, 1—Dimethyltilethyl (meta) Petil (methyl) acrylate, 1 — methoxethyl (meta)
  • hydrolysis may be carried out by any method, but from the viewpoint of cost and treatment efficiency, in the case of a polymer having an ester bond, alkali hydrolysis and amide bond In the case of a polymer having the general formula (I), acid hydrolysis is common.
  • Examples of a method for imparting an ionizable functional group to a polymer in advance include a method of copolymerizing a monomer having an ionizable functional group.
  • Examples of copolymerized monomers of polycondensation polymers include, for example, 5-sodium sulfeusophthalic acid, 2-sodium sulfoisophtalic acid, 1,8-dicarboxynaphthalene-13 —Sulfonate sodium or these Compounds include sulfonate-containing dicarboxylic acids such as lithium salts and lithium salts.
  • Examples of the copolymerized monomer of a vinyl polymer include (meth) acrylic acid, crotonic acid, isocrotonic acid, and cis-2-pentenoic acid trans_ 2 — pentenoic acid, 2 — ethyl (meth) acrylic acid, angelic acid, tiglic acid, 3, 3 — dimethyl acrylic acid, 23 — getinole (meta) Acrylic acid, 3 3 — Getyl (meth) acrylic acid, 3 — Propyl (meth) acrylic acid, 2 — Isopropyl (meta) acrylic acid, 3 —Isopropyl (meta) acrylic acid, trimethyl (meta) acrylic acid, 2 —butyl (meta) acrylic acid, 3 —butinole (meta) Acrylic acid, 3-tert-butyl (meth) acrylic acid cis — 3 —methyl-3- (ethynole) (meth) acrylic acid, trans — 3 — methyl 3 —Ethy
  • Methods for substituting and adding a functional group after copolymerization include vinyl benzolechloride, 2-cyclohexyl acrylate, 2-cycloethyl acrylate, and the like. Methods include copolymerization of an epoxy group-containing vinyl monomer such as a halogen-containing vinyl derivative glycidyl (meth) acrylate, followed by reaction with sodium sulfite to replace or add sodium sulfonate.
  • an epoxy group-containing vinyl monomer such as a halogen-containing vinyl derivative glycidyl (meth) acrylate
  • a method in which an ionizable functional group is copolymerized and then hydrolyzed is preferable, and in the case of a vinyl polymer, reactivity, polymerization cost, and particles are preferred. From the viewpoint of charge uniformity and reduction in particle size, a method of directly copolymerizing a monomer containing an ionizable functional group is preferred.
  • the polymerization of these monomers containing an ionizable functional group may be carried out by any of block copolymerization, graphite copolymerization, and random copolymerization.
  • the surface of the polymer particles can be negatively charged.
  • an activator which causes problems such as deterioration of physical properties and bath contamination.
  • the average particle size of the polymer fine particles is 0.05 m or less, aggregation cannot be suppressed even if an excessive amount of a surfactant is added in order to finely disperse the fine particles. Occurs.
  • a surfactant is used, a large amount of foam is generated in the spinning solution or coagulation bath.
  • the surfactant and the particles be chemically bonded so that they do not dissolve in the alkaline aqueous solution, since they may be produced or adversely affect the fiber structure formation, resulting in a significant decrease in the physical properties of the resulting fiber.
  • the reactive surfactants that chemically bond to the particles include polyquinethylene alkylpropenyl phenyl ether and sulfonates of alkyl methacrylate. And a sulfonate of a polyalkyloxy methacrylate, a sulfonate of an alkyl aryl renoconate diester, a sulfonate of a succinate diester, and the like.
  • the terminal of the polymer is sulfuric acid. It is preferable because it becomes the base and increases the surface charge of the particles.
  • the proportion of the repeating unit having an ionizable functional group in the polymer is from 1 to 25% by weight, preferably from 2 to 20% by weight, more preferably from 3 to 10% by weight. is there. If the content of the repeating unit is less than i% by weight, the surface potential of the particles does not increase and aggregation cannot be sufficiently suppressed. If the content exceeds 25% by weight, the aggregation can be suppressed, but the alkali swelling property and hydrophilicity become too strong, and the alkali swelling property and the swelling degree in water become remarkably high. The affinity with the dye is weakened, and the dye dyeing rate and fastness are reduced.
  • Copolymerization of the monomer having an ionizable functional group can suppress aggregation and finely disperse in a stock solution of cellulose, but furthermore, one OH group, one NHR group and —CONHR ′ (R ′)
  • a monomer having at least one hydrophilic functional group selected from the group consisting of a hydrogen atom and an organic group having 1 to 6 carbon atoms is copolymerized, further fine dispersion can be achieved. It is possible to express the same fiber properties as fibers without particles.
  • the cellulose fiber in the present invention is mainly used as a synthetic fiber such as polyester or polyamide, or a force used as a composite product with cellulose acetate or the like. Can be provided with fiber properties equivalent to those of conventionally known viscose fibers and cuprammonium rayon fibers.
  • the monomers used in the direct copolymerization of the vinyl polymer include 2-hydroxyhydroxyvinyl ether, 2-aminovinyl ether, vinylethylamine, vinylbutylamine, and 2-n-butyl.
  • Vinyl derivatives such as aminoethyl vinyl ether, (meth) acrylic acid derivatives such as 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N — Such as methyl (meta) acrylamide Meta) Acrylamide derivatives and the like.
  • monomers which become cellulophilic by hydrolysis after polymerization include vinyl acetate, vinyl butyrate, vinyl laurate, and pallate. And vinyl esters such as vinyl titanate and vinyl stearate.
  • the repeating unit of the polymer may contain two or more hydrophilic functional groups, or may contain two or more kinds of functional groups.
  • maleamidic acid N-methylmaleamic acid, / S-diaminoaminoacrylic acid, 2-acrylamide-2-sodium methylprononsulfonate
  • a monomer having both an ionizable functional group and a hydrophilic functional group, such as the above, may be used. Since these amphoteric monomers can exhibit the effects of both functional groups in one molecule, in the present invention, when these amphoteric monomers are used, half of the amount of the ionizable functional group-containing monomer is used. The other half is treated as hydrophilic functional group-containing monomer.
  • the polymer has both functional groups in order to achieve perfect fine dispersion and achieve the same physical properties as those of the particle-free fiber.
  • the amount of the monomer having an ionizable functional group and the monomer having a hydrophilic functional group are in the range of 1 to 25% by weight, respectively. However, if the total amount of each monomer is too large, the hydrophilicity becomes strong.
  • the ionizable functional group-containing monomer used for the copolymerization is hydrophilic.
  • the total amount with the functional group-containing monomer is in the range of 2 to 30% by weight, preferably 4 to 20% by weight, and more preferably 6 to 10% by weight.
  • the fiber properties (copper ammonia rayon: dry strength 2.4 g / d or more, dry elongation 1 2% or more, wet strength 1.4 g / d or more, Viscos Rayon: dry strength 1.7 g / d or more, dry elongation 17% or more, wet strength 0.7 g / d or more ) Can be achieved.
  • the cross-linking monomer can be copolymerized to maintain the form and suppress the swelling. It is preferable in terms of dyeability and fastness.
  • a crosslinkable monomer is copolymerized by a direct copolymerization method such as emulsion polymerization or microemulsion polymerization, an ionizable functional group or a hydrophilic functional group is used. It is preferable to add these functional group-containing monomers near the end of the polymerization, because they hardly appear on the particle surface and the effect of suppressing aggregation and the effect of expressing physical properties are reduced.
  • the average particle size of the polymer fine particles used in the present invention there is no particular limitation on the average particle size of the polymer fine particles used in the present invention, but if the particle size is too large, the particles act as foreign matter even if dispersed well, so that the particle size is 1 m or less. Is preferred.
  • a polymer containing an ionizable functional group and a hydrophilic functional group is used, even if very fine particles are added to the stock solution of cellulose, aggregation does not occur and coarse secondary particles are formed. do not do.
  • the average particle diameter of the fine particles contained in the cellulose fiber is in the range of 0.01 to 0.05 zm, making it possible to finely disperse the ultrafine particles, which could not be achieved with the conventional technology. Became possible.
  • the shape of the polymer fine particles but it is preferable that the shape of the particle is not flat and it is not a flat shape when the particle has any cross section. Especially a spherical shape is more preferable.
  • the polymer fine particles mean both primary particles of polymer particles contained in cellulose fibers and aggregated particles (secondary particles) formed by aggregation of the primary particles.
  • the secondary particles are defined as i polymer fine particles.
  • the secondary particles are those in which five or more primary particles are aggregated, and the shape of each primary particle is deformed by joining.
  • Cellulose fibers containing polymer fine particles of 0.1 m or less, especially 0.05 m or less have a transparency and gloss close to that of particles-free fibers, and when dyed with a disperse dye, It is possible to develop vivid, deep and high-colored colors.
  • ultra-fine particles with an average particle size of less than 0.05 // m are applied to viscose rayon fiber, the characteristics of rayon fiber such as glossiness, beautiful hue when dyed, and It can be fully utilized.
  • the cellulose fiber becomes more deeply dyed than when the particle size is large, so it appears apparently.
  • the transfer speed to the polyester fiber is slowed, and higher color uniformity and clearer hue can be achieved.
  • the fibers have a dull tone, and even when dyed, the average particle diameter is within the wavelength of visible light (0.3811 to 0.3811). 0.75 ⁇ m) or more, and the amount of primary particles on the large particle size side of the particle size distribution increases, scattering visible light, devitrifying, clouding, When dyed, the amount of light that irradiates the dye inside the particles decreases, resulting in a faint, faded color.
  • the average particle diameter is 0.055 // m or less
  • the scattering and reflection of visible light of the fine particles are almost eliminated, and the amount of light irradiated on the dye coloring groups in the particles increases, so that higher homochromaticity is obtained. It is considered that the sharpness of the hue is achieved.
  • fibers having an average particle diameter of 0.05 m or less have higher coloring performance than fibers having a large average particle diameter even if the fibers have the same amount of dye. Is shown.
  • the amount of dye transferred from the cellulose fiber to the polyester fiber does not change depending on the particle size, and is transferred to the disperse dyeable dyeable cellulose fiber after the dyeing.
  • the amount of the dye dyed does not greatly differ depending on the particle size.
  • the average particle size of the particles is 0.05 m or less, the coloring property is particularly good, and the same coloring property as that of the polyester fiber is higher.
  • the average particle size of the polymer fine particles is small, sedimentation, separation, and concentration caused by the density difference between the fine particles and the cellulose stock solution in the cell-mouth undiluted solution It is difficult to generate a gradient, and the cell mouth fiber having a uniform distribution state of the fine particles and a small number of irregularities can be obtained even inside the fiber. Further, as described later, when the number of fine particles present inside the fiber is large, the distribution state of the fine particles in the fiber becomes dense, and the dye after dyeing is not localized but densely distributed, so that a more uniform dye is obtained. Dyeing becomes possible.
  • the average particle diameter of the fine particles is small, the dyeing ability is clearer and deeper, although the dyeing ability is the same as when fine particles having a large average particle diameter are contained.
  • the amount of added fine particles can be reduced by almost half, and the adverse effects of increasing the amount of added fine particles (deterioration of physical properties, deterioration of process passage properties, increase in cost) ) Can be reduced.
  • the average particle diameter of the polymer particles inside the fiber is 0.01 to 0.05 m
  • a fiber with mechanical properties (strength and elongation) exactly equivalent to existing cellulose fibers can be obtained.
  • the reason for this is that, in addition to the formation of hydrogen bonds between the particles and the cellulose by the hydrophilic functional groups, when the average particle size is large, the stress applied at one point is large due to the reduction of the stress concentration points, and large defects are created. This is likely because stress concentration is less likely to occur when particles with a small particle diameter are finely dispersed.
  • the average particle size of the fine particles present in the fiber the better the gloss, sharpness, and deep color, and the decrease in strength is small. The better the passability of the fiber is obtained. Therefore, the average particle size of the fine particles is
  • the lower limit of the particle diameter is 0.01 / 1/1, considering the dyeing of the disperse dye (the size of the disperse dye molecule is about 0 • 001 to 0.002 m) inside the particle. / m is preferred.
  • the more preferable average particle diameter of the polymer fine particles is from 0.01 to 0.045 m, more preferably from 0.02 to 0.04 zm.
  • the average particle size of the polymer fine particles refers to the average particle size of the polymer fine particles in the cross section of the cellulosic fiber.
  • the average particle diameter may be determined, for example, by pre-processing an image obtained by observing the cross section of the cellulose fiber with an electron microscope at a magnification of 50,000 to 500,000 using a commercially available image analyzer, The average particle diameter equivalent to a circle can be calculated and obtained using the particle analysis mode of the apparatus.
  • the number of polymer fine particles contained in the cellulose fiber is preferably from 10 to 100/1: 1: 12, more preferably from the cross section of the cellulose fiber. 5 0-5 0 0 Z m 2, is rather to favored the al 1 0 0-3 0 0 / // m 2.
  • the number of particles in the fiber increases, the localization of the particles in the cross-sectional direction and the yarn length direction is reduced, and a fiber with less staining spots can be obtained.
  • the amount is too large, agglomeration tends to occur, and the concentration of fine particles in the cellulose stock solution needs to be reduced.
  • the number of coarse aggregated particles (secondary particles) formed by the aggregation of the primary particles is preferably 10 // m 2 or less, more preferably 5 / f m 2 hereinafter, the rather then favored by et 3 /; m 2 or less, is rather especially preferred is 1 or less.
  • the smaller the number of secondary particles the higher the gloss, sharpness and deep color of the fiber. The reason is that the average particle Even if a group of particles has a small diameter, if there are coarse secondary particles having a size (0.1 to 1 zm) that scatters light in the wavelength range of visible light, reflection and scattering of visible light will occur. It is considered that the amount increases. Also, as the number of secondary particles increases, the fibers become cloudy, devitrified, and lose their luster, as in the case of adding an anti-glare agent such as titanium dioxide. Color is difficult to develop.
  • a functional group that enhances the affinity with the cellulose fiber is introduced into the surface of the polymer particles used in the present invention.
  • Polymer fine particles are dispersed in a stock solution of cellulose fiber, but a polymer capable of being dyed with a disperse dye has a high hydrophobicity and generally has a small interaction with cellulose, so that physical properties of the fiber are likely to be reduced. It is.
  • By suppressing agglomeration of polymer fine particles and reducing the average particle diameter of the fine particles inside the fiber it is possible to suppress a decrease in the physical properties of the fiber. Further, it is possible to suppress a decrease in physical properties of the fiber.
  • the disperse dye-dyeable cellulose fiber of the present invention When used for a lining binder or the like, the light fastness of the dyed product does not matter. However, when used in outer applications such as blouses and scarts, it is desirable that the light fastness is 3 or higher. Particularly in the case of ultrafine particles having a polymer particle diameter of 0.05 m or less in the fiber, the probability of irradiating the polymer particles with ultraviolet rays increases because the fine particles are finely dispersed, and the light resistance is high. Toughness tends to decrease.
  • the present inventors have made it possible to copolymerize 1 to 30% by weight of a repeating unit having a cyano group (—C 3 N group) in fine particles of a polymer having the same color unit of 20 to 95% by weight. It was found that light fastness was good.
  • the repeating unit having a cyano group copolymerized for this purpose may be (meta) acrylonitrile, 3 — Acetoxyacrylonitrile, 2—Acetoxymethylonitrile, 2—Ethylacrylonitrile, 2—Propylacrylonitrile, 2—Isopro Pirua Crylonitrile, 2—Propoxy Crylonitrile, 2—Isobutyl Acrylonitrile, 2—Pentyl Crylonitrile, 2—Methoxy Crylonitrile , 2-ethoxyquinylonitrile, 3-ethoxyacrylonitrile, 2-ethylone 3-methacrylonitrile, 3-ethoxy2-methacrylonitrile (Meta) filters such as nitrile, 2, 3—dimethylacrylonitrile, 3,3—dimethylacrylonitrile, 2—phenylacrylonitrile Chloronitrile derivative, cyanomethyl acrylate Rate, 2-cyanoethyl (meth) acrylate, 2-cyano
  • the copolymerization amount of the monomer having a cyano group is too small, the effect of absorbing ultraviolet light becomes insufficient, so that it is preferably at least 1% by weight, more preferably at least 5% by weight.
  • the content is preferably 30% by weight or less, more preferably 15% by weight or less.
  • the required amount of the cyano group-containing monomer varies depending on the copolymerization amount of the same color unit.
  • the copolymerization ratio of the same color unit is X (% by weight)
  • the copolymerization ratio of the cyano group-containing monomer is Z (% by weight). It is particularly desirable from the viewpoints of properties, polymerization stability, disperse dye dyeing properties, coloring properties, and homochromaticity.
  • the ultraviolet light absorbing compound and the solder are added to the fine particles of the polymer.
  • the light fastness can be improved by adding a specific amount of a tomine-based light stabilizer.
  • Usable UV absorbers include salicylic acid derivatives, benzophenone-based compounds, benzotriazole-based compounds, oxalic acid anilide-based compounds, triazine-based compounds, and cyanoacrylate-based compounds.
  • Compounds and benzoic acid derivatives include phenylsalicylate, p-octylphenylsalicylate, and p-tert-butylphenylsalicylate.
  • Examples of benzophenone-based compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-14-methoxybenzophenone, and 2,2'-dihydroxy-14-methoxybenzophenone.
  • UV absorbers examples include resorcinol monobenzoate, 2,4-di-tert-butynolef-butane-3,5-di-tert-butyl-4-hydroxybenzoate, 0-methyl benzoyl benzoate And the like.
  • UV absorbers may be used alone or in combination of plural kinds.
  • Usable hindered amine light stabilizers include ADK STAB LA-77 (manufactured by Asahi Denka), Sunol LS770 (manufactured by Sankyo), Tinu Vin 123 ( C iba—Geigy), Tinuvin 144 (Ciba-Geigy), Tinuvin440 (Ciba—Geigy), Goof-rite UV304 (BF -Adeka Stub LA—87 (Asahi Denka), Adeka Stub LA—82 (Asahi Denka), Adeka Stub LA—57 (Asahi Denka), Adeka Stab LA—52 ADK STAB LA-6 (made by Asahi Denka Co., Ltd.) ADK STAB LA-6 made by Asahi Denka 3, Cyasorb UV3334 (Cytec), Chlmassorb 944 (Ciba-Geigy), Tinuvin 622 (Ciba-Geigy) and the
  • the amount of the ultraviolet absorber or the solder amine-based light stabilizer is too small, sufficient effects cannot be obtained. If the amount is too large, the polymerizability is reduced or the cost is high. Respectively, in the range of 0.1 to 5% by weight (based on the polymer fine particles), preferably 0.3 to 3% by weight, and more preferably 0.5 to 1% by weight. Desirable. The required amount of these additives also changes according to the copolymerization ratio of the same color unit.
  • the addition ratio of the ultraviolet absorber is Z ′ ( Weight%)
  • the addition ratio of the hindered amine light stabilizer is defined as Z ", and Z 'and Z" are within the range of the following formula, which indicates light fastness, polymerization stability, and cost. It is particularly desirable in that respect.
  • an anti-glazing agent such as titanium dioxide / silicon dioxide, a lubricant, a cellulose modifying agent, a viscosity reducing agent, etc. may be used alone or separately. Multiple types Can be added.
  • the cell mouth fiber according to the present invention has a fiber strength required for post-processing and consumption performance in practical use.
  • the dry strength is 2.2 g / d or more, It is desirable that the wet strength is 11 g or more, and the wet strength is 1.3 gZd or more, particularly preferably the dry strength is 2.4 gZd or more, the dry elongation is 12% or more, and the wet strength is 1.4 g. It is desirable that it be at least / d.
  • the dry strength is preferably 1.6 g / d or more, the dry elongation is 15% or more, and the wet dry strength is 0.5 gZd or more, and particularly preferably the dry strength is 1.7. Desirably, it should be gZd or more, dry elongation 17% or more, and wet strength 0.7 g / d or more. It is surprising that the cellulose fibers of the present invention exhibit the above-mentioned physical properties despite adding 10% by weight or more of polymer fine particles which are foreign substances to the fibers.
  • the disperse-dye-dyeable cellulose fiber of the present invention obtained as described above can be dyed with a disperse dye, and has a high coloring property, a clear deep color, excellent gloss, and a polyester fiber.
  • a resin treatment to the cellulose fiber or to make the disperse dye-dyeable cellulose fiber substantially chemically reactive with a compound having two or more functional groups that react with the hydroxyl groups of cellulose.
  • By being crosslinked it is possible to obtain a cellulose fiber having excellent wet-rubbing fastness and a fiber product thereof.
  • a resin usually used for resin processing of a cellulose fiber such as a polyacrylate emulsion and a polyvinyl acetate resin emulsion
  • Conventionally known resin processing methods such as a method of applying a resin onto a fiber, a method of impregnating a fiber surface with a compound having reactivity or polymerizability and then heating to form a resin, can be applied as they are.
  • urea formaldehyde dimethylol urea, trimethylol melamine, dimethylol ethyl urea, dimethylol triazone, methylated dimethylol ureon, dimethyl mono-l-hydroxyethyl urea
  • a compound that causes a cross-linking reaction with an aldehyde group such as dimethylene propylene urea, epichlorohydrin, diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, butane diol diglycidyl ether, vinylene cyclohex
  • substantially chemically cross-linked means that the cross-linking agent reacts with a hydroxyl group between cellulose molecules, and a portion insoluble in a cellulose solvent is present.
  • a solvent having a high ability to dissolve cellulose for example, a copper 'ethylenediamine complex
  • the presence of swollen insoluble portions (gels) is substantially confirmed by visual inspection. It can be determined that it has been chemically crosslinked.
  • the invention product is hydrolyzed with a cellulase enzyme or other chemicals to hydrolyze the type 1 and 4 bonds of cellulose to obtain a liquid chromatograph or a mass spectrometer. It can also be determined by detecting a portion where two glucoses are bound via one cross-linking agent when analyzed using the same.
  • reaction treatment method of the crosslinking agent is performed by a known method.
  • Reaction catalysts include hydrochloric acid, sulfuric acid, acetic acid, lactic acid, tartaric acid, citric acid, aluminum chloride, aluminum sulfate, zinc chloride, zinc nitrate, zinc fluoride, magnesium chloride, magnesium borofluoride, etc.
  • acidic catalyst include those which are suitable for each epoxy compound, or may be used alone or in combination of two or more.
  • the epoxy compound and the reaction catalyst are used after being dissolved in water. If the solubility of the epoxy compound is low, the epoxy compound and the reaction catalyst are used after being dissolved in an aqueous solution to which a small amount of an organic solvent such as dioxane or isopropyl alcohol is added.
  • the amounts of the epoxy compound and the reaction catalyst in the aqueous solution are appropriately determined in consideration of the method of applying the fibers to the fabric, the degree of the effect of the wet friction fastness, the texture of the fabric, and the like. At 0% by weight, the amount of the reaction catalyst is preferably 6 to 20% of the amount of the epoxy compound.
  • a stabilizer such as magnesium acetate, zinc acetate, or aqueous ammonia is added to the above mixture so that the solution PH becomes 5 to 7 from the time the epoxy compound is prepared. It is preferable from the viewpoint of suppressing decomposition of the compound.
  • the following method is used as a processing step of substantially chemically crosslinking hydroxyl groups of the disperse dye-dyeable cellulose fibers using the crosslinking reaction solution.
  • the fabric is immersed in an epoxy compound mixture and allowed to fully blend. Squeeze with a mangle or the like to adjust the rate of adhesion of the crosslinking reaction liquid to the fabric.
  • the adhesion rate varies depending on the mixing ratio of the dispersible dyeable dyeable cellulose fiber and the fabric form of the fabric, but is usually adjusted to be 40 to 120% owf.
  • pre-drying is usually performed at 80 to 150 ° C for 20 seconds to 2 minutes, and then 130 to 20 ° C.
  • Examples of solving agents include surfactants such as sodium hydroxide and sodium carbonate, and surfactants such as nonionic polyalkylene alkyl ethers and alkyl thioethers.
  • a cross-linking reaction liquid is applied to the fiber before drying using a Tactile roll blow-up nozzle or the like. It can be obtained by passing it through a dryer and performing drying and heat treatment.
  • cellulose fibers that are difficult to fibrillate such as viscose rayon fibers
  • it has a water-soluble property, the separation of the fine particles exposed on the fiber surface by the cross-linking treatment can be suppressed, further improving the wet dyeing fastness.
  • ⁇ 5th grade fiber Powerful can be stained with the above-mentioned ultra-dense black disperse dye without cross-linking, and can be rubbed with a 3 to 4 class wet friction.
  • the fiber product of the present invention is obtained by processing and commercializing the above-mentioned cellulose fiber by a known method, for example, knitting, weaving or the like, and may have any form.
  • the cellulose fiber of the present invention contains a thermoplastic polymer, it exhibits heat-setting properties and heat-fusing properties that cannot be obtained with conventional cellulose fibers, and has a false twisting process, a crimping process, and a pseudo hemp. Processing such as processing can be performed.
  • the average particle diameter of the fine particles in the fiber is 0.01 zm or more! In the range of .05 zm, the number of polymer particles on the fiber surface becomes very large, and the polymers are fused and shrunk, so that the workability for these post-processings is increased.
  • the cellulose fiber of the present invention can be developed with a product using 100% cellulose or a high mixing ratio of cellulose fiber, even in applications where it could not be used until now, In particular, in the field of blouse such as blouse paste for women, it is significant to expand the use rate of cellulose fiber, which has a unique feel and hygroscopicity, and to expand the field of application.
  • the dye exhaustion rate under ordinary disperse dye dyeing conditions is preferably 70% or more, and more preferably 70% or less. Desirably, the fiber is 80% or more, particularly preferably 90% or more.
  • the fibers applicable to the composite product with the fiber of the present invention include fibers that can be dyed with disperse dyes such as polyester, polyamide, and cellulose acetate, as well as acrylic fibers and spandex. Gas fiber or cellulose fiber may be used. Polyester fibers (polyethylene terephthalate, polymethylentele phthalate, polybutylene terelate) may be used as the composite material with the fiber of the present invention.
  • isophthalic acid 2-sodium Dicarboxylic acids such as rutheisophthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, naphthalene dicarboxylic acid, bisphenol 8, bisphenol Dialcohols such as Knoll F, Bisphenol S, Neopentyl alcohol, Polyethylene glycol, etc., Trimeritic acid, Pyromelitic acid, Glycerin, Pentaerylic Polycarboxylic acids such as toluene and trimethylolpropane, and polyols may be copolymerized.
  • 2-sodium Dicarboxylic acids such as rutheisophthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, naphthalene dicarboxylic acid, bisphenol 8, bisphenol Dialcohols such as Knoll F, Bisphenol S, Neopentyl alcohol, Polyethylene glycol, etc.,
  • Polyester forms include composite fibers produced by sheath-core spinning and side-by-side spinning, irregular cross-section fibers, hollow fibers, ultrafine fibers, split fibers, thick fibers, and spontaneously stretched yarns. Special fibers such as mixed-shrink yarns, composite yarns, etc. may be used, and conventional spinning, spin-drawing, spinning heating, high-speed spinning, etc. Fibers manufactured by a known spinning method can be used.
  • the cellulosic fiber of the present invention can be dyed in a clear and deep color with a disperse dye, and exhibits the same hue as that of a polyester fiber when dyed with a compound color disperse dye. It has functions not found in cellulose fiber, and it can be developed as a product of cellulose fiber alone.It is powerful and can disperse polyester fiber, polyamide fiber, cellulose acetate fiber, etc. The effect is most effective when used as a composite product with dye-dyeable fibers. In other words, the dyeing process is streamlined from the conventional two-stage two-bath dyeing to one-bath one-stage dyeing, reducing the dyeing time and dyeing cost, and further increasing the color of the cellulose and the counterpart material after dyeing.
  • the disperse-dye-dyeable cellulose fiber of the present invention is produced by a spinning method using a spinning dope obtained by mixing and dispersing the aforementioned polymer fine particles into a spinning dope commonly used in the production of known artificial cell mouth fibers.
  • the cellulose concentration of the spinning dope is 3 to 15% by weight, and preferably 5 to 12% by weight, although there are slight differences depending on the spinning system.
  • wood pulp, cotton linters, and cotton lint are preferably used as cell mouth raw materials.
  • the polymerization degree of cellulose in the spinning stock solution is from 200 to 110, preferably from 250 to 100, particularly preferably from 300 to 900.
  • the spinning dope 1 to 40% by weight of polymer fine particles are added, mixed and dispersed with respect to cell mouth.
  • the method for preparing the fine particles of the polymer to be mixed and the mixing method will be described later.
  • the spinning solution is specifically, for example, in the case of viscose rayon, cellulose? 110% by weight, 1 to 4% by weight of carbon disulfide, 5 to 9% by weight of sodium hydroxide, 1 to 40% by weight of fine particles with respect to cellulose at a temperature of 20 to 50 ° C.
  • the composition of the copper ammonia array solution is 5 to 12% by weight of cellulose, 2 to 5% by weight of copper, 5 to 9% by weight of ammonia, and 1 to 40% by weight of fine particles.
  • the spinning dope prepared in this way has no significant difference in coagulation and coagulation speed from the conventional spinning dope, so that a commonly used spinning method can be used as it is.
  • viscose rayon 8 to 12% by weight of sulfuric acid, 12 to 30% by weight of sodium sulfate, 1 to 3% by weight of zinc sulfate, and 0.03% in a coagulation bath at a temperature of 45 to 65 ° C.
  • a spinning stock solution is discharged at a discharge linear speed of 50 to 120 Om / min from a spinneret of 1 to 0.2 mm ⁇ (diameter, the same applies hereinafter), and a spinning speed of 50 to 120 OmZ Spun in minutes.
  • spinning device a conventionally known device can be used.
  • centrifugal spinning machines hank spinning machines, bobbin spinning machines, Hoffman continuous spinning machines, Duretta continuous spinning machines, Nelson continuous spinning machines, drum continuous spinning machines, net processes
  • a continuous spinning machine, an industrial continuous spinning machine, an Oscar Kohon continuous spinning machine, a Kurdish continuous spinning machine, and the like can be used.
  • continuous spinning machines with little difference in physical property unevenness, shrinkage unevenness, fiber structure difference, etc. from the viewpoint of uniformity of yarn characteristics in the yarn length direction such as shrinkage and dyeability. The use of is preferred.
  • scouring, washing and drying after spinning conventionally known devices and conditions can be applied as they are.
  • the fiber of the present invention is produced by using a composite fiber produced by known sheath-core spinning or side-by-side spinning, or by using a modified spinneret. Triangular cross section, flat cross section, star cross section, cross cross section, C cross section, T-shaped cross section, Y cross section, etc. It can be applied to special fibers such as hollow fibers produced by spinning.
  • the fine particles of the polymer added to the cellulose can be prepared by a pulverization monohydrolysis method or a direct polymerization method.
  • the pulverization monohydrolysis method is used when producing fine particles of a polycondensation polymer such as easily dyed polyester fiber.
  • Polymers that have been pre-treated, such as swelling, crystallization, or degradation are physically pulverized by a known wet pulverizer or dry pulverizer, then classified, and then hydrolyzed with alkali or acid.
  • Fine particles can be obtained by disintegration, but pre-treatment and post-treatment, multiple pulverization treatments are required, and when producing ultra-fine particles of submicron order or less, the yield of fine particles Therefore, a method of forming particles in the polymerization process is preferable from the viewpoint of production cost.
  • vinyl polymer fine particles can be produced by any method such as dispersion polymerization, suspension polymerization, emulsion polymerization, and microemulsion polymerization.
  • the emulsion polymerization method is preferable.
  • the solids concentration increases, aggregation tends to occur due to collisions between particles, so a polymerization method with a low solids content of preferably 35% or less, more preferably 30% or less, should be used. Is desirable.
  • the solids concentration is too low, the fine particle content of the cellulose fibers will not be high, and sufficient dyeing will not be possible, or the cellulose concentration after mixing the fine particles will decrease. As a result, a problem arises in that the strength of the obtained fiber is reduced, so that the solid content concentration is 10% or more, preferably 15% or more, and more preferably 20% or more. It is desirable that there be.
  • These fine particles may be hollow, and the number of hollows may be one or porous.
  • the average particle diameter of the polymerized fine particles may be controlled by alkaline treatment and partial dissolution in the presence of a nonionic surfactant to control the average particle size of the fine particles (for example, C 0110 id & P 0). lymer S cience, 2 7 2: 1 5 2 1-1 5 2 5 (1 9
  • fine particles of the polymer used in the present invention can be obtained by lowering the solid content concentration to 40% or less using a conventionally known method.
  • the catalyst include sodium persulfate, potassium persulfate, ammonium persulfate and the like, hydrogen peroxide Z ferrous salt, tert-butyl hydroperoxide Z ferrous salt, p — Cumene hydroperoxide donoferrous salt, cumene hydroperoxide Z natriformaldehyde sulphoxylate, cumene hydroperoxide / N_alkylethylene diamine, benzoic peroxide Redox initiators such as le / dimethylaniline can be used.
  • n-butyl menolecaptan, n-octynolemercaptan, n-dodecinolemercaptan, t-dodecylmercaptan, chain transfer agents such as mercaptopropionate, thioglycolic acid, ⁇ - A polymerization retarder such as methyl styrene dimer can be used.
  • a cross-linking agent can be used.
  • examples of usable crosslinking agents include, for example, aryl (meta) acrylate, ethylene (meta) acrylate, and ethylene glycol (meta) acrylate. Rate, triethylene glycol (meta) acrylate, tetraethyl glycol (meta) acrylate, dipropylene glycol (Meta) acrylate, glycerol triacrylate (meta) acrylate, neopentinole glycolate (meta) acrylate, 1,4-butanedioldi (meta) Acrylate, 1,3—butyrene glycol (meta) acrylate, 1,6—hexane didiol (meta) acrylate (meta) acrylate Rate, N, N'-methyl acrylamide, 1, 1-bis (meta) acrylamide, 1, 2—bis (methyl) A) Acrylamide doethan, 1,3—bis (meta) acrylamide doprono.
  • diaryl terephthalate divinyl isophthalate, vinyl cinnamate, trimethylolpropane Di (meth) acrylic acid benzoate ester, bisphenol A di (meta) acrylate, bisphenol F di (meta) acrylate Aromatic ring and ester group or ether group
  • arbitrary use of crosslinking compound that satisfies the same color Yuni' Bok requirements of the present invention is preferred.
  • emulsifiers examples include nonionic surfactants, surfactants, and anionic surfactants.
  • Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyquinethylene derivatives, sorbin fatty acid esters, and polyoxyethylene sorbitas Fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene fatty acid esters Alcohols, polyoxyethylenealkylamines, alkylalkanolamides, polyquinethylene castor oil derivatives and the like.
  • anionic surfactants include fatty acids (for example, Uric acid, myristic acid, stearic acid, oleic acid), alkyl sulphonic acid (for example, cetyl sulphonic acid), alkyl sulphate (for example, phenyl sulphate, myristyl sulphate) , Palmityl sulphate, stearyl sulphate, oleyl sulphate), alkylsulphosuccinoic acid (for example, dioctylsulphosuccinic acid, sulphoconoic acid di-2-ethylhexyl ester) ), Alkylbenzenesulfonate (eg, dodecylbenzenesulfonate), alkyldiphenylate Rusulphonic acid (for example, Lauryl diphenyl ether sulphonic acid), Alkyl naphthalene sulphonic acid, Alkyl phosphoric acid, Polyoxyethylene
  • a reactive surfactant having a vinyl group may be used.
  • the active agent even if it is subjected to chemical or physical force, the active agent does not easily peel off from the particles. It is preferred from the viewpoint of fiber properties without giving.
  • anionic reactive surfactant examples include sulfonates of polyoxyethylene phenylpropenyl phenyl ether, sulfonic acids of styrene, and sulfonates of alkyl methacrylate.
  • nonionic reactive surfactants include phenyl ethers from polyoxyethylene carboxylic acids, esters of polyoxyethylene alkyl ethers from acrylic acid, and methyl acrylates.
  • surfactants may be used alone or in combination with a plurality of surfactants, and differ in types such as anionic surfactants, nonionic surfactants, and non-reactive / reactive surfactants.
  • Activators can also be used in combination.
  • additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an antioxidant, and an ozone deterioration inhibitor may be used.
  • the polymer fine particles are finally obtained as an aqueous emulsion having a solid content concentration of 1 to 40% by weight, and after adding water or a compound as necessary, an appropriate amount is added to the cellulose stock solution. . It is desirable that emulsion be added to the stock cellulose solution immediately after preparation. If there is a delay before addition, store in a dark room at a constant temperature of 10 to 40 ° C, avoiding heat, cooling, and light in terms of deterioration and dispersion stability. You It is desirable that
  • the concentration of the fine particles in the dispersion is too high, the dispersion itself tends to agglomerate, and if the concentration is too low, the cellulose concentration of the undiluted spinning solution will be low. %, Particularly preferably 10 to 30% by weight.
  • the solvent and the solvent of the spinning dope are preliminarily added to the fine particle dispersion so that the cellulose concentration and the solvent concentration of the final spinning dope become the desired concentrations.
  • An additional substance may be added.
  • a cationic compound such as a sodium hydroxide solution or a copper ammonia solution, from the viewpoint of dispersion stability of the fine particles, it is necessary to uniformly add the dispersion while stirring. Desirable.
  • the method of finely dispersing the fine particles stably in the dispersion is not particularly limited, and a conventional fine dispersion method, for example, a fine dispersion method using a stirrer, ultrasonic waves, a pulverizing medium, or the like can be used.
  • the fine particle dispersion should be stirred in a device having both a grinding medium and a rotating means for stirring the grinding medium or in a usual stirrer until the dispersion is prepared and added to the undiluted spinning solution.
  • the stirring after the preparation is preferably performed at a low speed, and especially after the preparation of the dispersion with a high-speed stirrer, the stirring is preferably performed at a low speed.
  • the addition of the polymer fine particles can be performed in any step from the step of charging the cellulose raw material to the spinning step in which the spinning solution is spun. It may be added before or after dissolving cellulose, or may be added stepwise in multiple steps if necessary.
  • the fine particle dispersion may be mixed with the spinning dope by filtering the fine particle dispersion as necessary, and then adding the fine particle dispersion to the dope containing cellulose.However, after the fine particle dispersion is added, the fine particles are uniformly added to the dope. Further, it is preferable to perform stirring and kneading treatment.
  • a known mixing device can be used for mixing and stirring the fine particles. In a mixing device such as a homomixer or an in-line mixer, the fine particles are stirred and mixed at a high speed immediately after the addition of the fine particle dispersion, so that the fine particles are aggregated. Homogeneous dope can be prepared without occurrence of odor.
  • an in-line mixer with high airtightness.
  • air bubbles are not mixed, and the defoaming treatment can be omitted after adding fine particles.
  • spinning can be performed, making it easy to change brands of fibers with different fine particle content and fibers without added fine particles, etc., and reduce the loss at the time of brand change, making it possible to manufacture at lower cost. Become.
  • the mixing temperature of the fine particles and the stock solution of cellulose the better the dispersibility of the fine particles.
  • the mixing temperature is preferably in the range of -5 ° C to 10 ° C.
  • the spinning be performed promptly without adding time after adding the dispersion liquid of the fine particles to the spinning solution.
  • spinning after adding fine particles from the viewpoints of spinning properties and fiber properties
  • the stock solution may be defoamed.For a low-viscosity stock solution such as a viscose solution, vacuum degassing for 1 to 10 hours, and for a high-viscosity stock solution such as a copper ammonia cellulose solution, 10 to 100 hours. It is preferable to carry out static degassing for 40 hours.
  • the spinning stock solution it is preferable to filter the spinning stock solution to remove mixed foreign matter and coarse particles, so that a fine pore having a pore diameter of 1 to 20 m is required before being discharged from the spinneret. It is particularly preferred to filter one or more stages with a filter.
  • a surfactant may be used in order to stabilize the dispersion state of the fine particles in the dispersion liquid or the spinning solution.
  • a surfactant When a surfactant is added, if the amount is small, the dispersing effect will not be sufficiently exhibited, and if added in a large amount, the defoaming property and the fiber properties will be reduced. % Is preferably added.
  • the surfactant the above-mentioned emulsifiers and the like can be used.
  • the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
  • % in the examples means% by weight unless otherwise indicated.
  • the average particle diameter of the emulsion, the solid content of the emulsion, the fine particle addition rate, the fineness, the dry strength, the elongation, the wet strength, the glossiness, the dye exhaustion rate, the sharpness, and the color depth The light fastness, light fastness, the same color, the average particle diameter of the fine particles in the fiber, the number of secondary particles, the number of particles and the wet friction fastness were measured by the following methods.
  • the particle size distribution of the polymer fine particle emulsion before addition of the stock solution at the cell opening was measured using a microphone opening track particle size distribution analyzer, and the highest peak point particle size (MV value) was taken as the average particle size. did.
  • Emulsion ion solids concentration 10.0 g of polymer fine particle emulsion was precisely weighed, dried with 105 for 18 hours, and the weight of the dried nonvolatile matter was precisely weighed.
  • the solid content concentration was calculated from the nonvolatile content weight (Ag) according to the following equation.
  • the mixing amount of the polymer fine particle dispersion is C (g or g / z), the solid content concentration of the polymer fine particle dispersion is D (% by weight), and the cellulose stock solution is mixed.
  • the total amount was E (g or gZ), and the concentration of cellulose in the cellulose stock solution was F (% by weight).
  • Fine particle addition rate C X D / (EX F) X 100 (%)
  • scouring is carried out according to the same formulation as in (8).
  • the dyed liquor is added to the scoured fabric, and the temperature is raised from 40 ° C to 130 ° C at a rate of 1 ° C / min.After reaching 130 ° C, the dyeing pot is removed. Quickly cool in cold water.
  • the dye, the dyeing concentration owf, and the bath ratio were also the same as in (8). Measurement and calculation were performed in the same manner as (8).
  • As the absorbance a value at 580 nm, which is the maximum absorption wavelength of the dye, was used.
  • Sharpness (10) Sharpness (a measure of sharpness): Uses Michelon Polyester Red FL (Disperse Dye, Mitsui Toatsu Co., Ltd., CID isperse Red 72) as the dye, and sets the dye concentration to 2, 4, 8, or 16% 0 wf. Was stained, reduced-washed and dried in the same manner as in (8), and dried, and then colorimetrically measured.
  • Colorimetry was performed using a color computer (SM-4) manufactured by Suga Test Instruments Co., Ltd., and the color density C * and the sharpness B * of the four dyeings obtained by changing the dye density were measured.
  • the measurement results were plotted on the ordinate and on the abscissa, and graphs were created with the scales of the ordinate and abscissa being 2 to 6 and 9 to 15 respectively.
  • the lengths of the vertical and horizontal axes were set to 12 cm and 20 cm, respectively.
  • the curve obtained by plotting the obtained data of the four points shows a shape that is convex to the upper right.
  • the chroma was evaluated for two types of colors, chromatic and achromatic. 1 Chromatic chromaticity:
  • KZ S is a chromatic deep color. Defined as degrees. The spectral reflectance was measured at 580 nm, which is the maximum absorption wavelength of the dye.
  • the obtained deep color has a very good correlation with the deep color that humans perceive.
  • Dyeing, reduction washing and drying were carried out in the same manner as in (8) except that Sumikalon Black S-BF (Sumitomo Chemical Co., Ltd. disperse dye) was used as the dye and the dye concentration was 16% owf. After that, colorimetry was performed.
  • Sumikalon Black S-BF Suditomo Chemical Co., Ltd. disperse dye
  • the L value was measured using a color computer (SM-4) manufactured by Suga Test Instruments Co., Ltd.
  • SM-4 color computer
  • this L value is defined as achromatic chromaticity. This deep chromaticity indicates that the smaller the number, the higher the deep chromaticity. The depth color obtained in this way has a very good correlation with the depth color perceived by humans.
  • the dyes used are the three primary colors of Dinik Snevi Blue UN—SE200Z Z Dainik Surbin UN-1SE / Dianix Orange UN—SE (all manufactured by Dystar Japan).
  • E * [(Lc * -L E *) 2 + (a c * — a E *) 2 + (b c * — b E *) 2 ⁇ 0 5
  • E * the smaller the hue difference
  • the E * is 10 or less, people will not be able to feel flickering or discomfort in the hue. If it is 5 or less, it looks the same hue.
  • Cellulose fiber is immersed in a mixed solution of epoxy monomer (Ketol 812 (made by New EM)) and curing agent (Dodecylzak Sonic Anhydride, Methylnadic Anhydride), and then the initiator is used. (DMP-30 (manufactured by Nisshin EM)), and the mixture is treated under heating at 60 ° C for 24 hours to carry out polymerization, and the fibers are embedded in a resin. Prepare a cross section of the fiber embedded resin with a thickness of 70 nm in the fiber length direction using a microtome. Using a transmission electron microscope, a photograph (image) of the obtained section at a magnification of 50,000 to 50,000 was photographed. If the contrast with an electron microscope was insufficient, the particles were stained with ruthenium tetroxide and observed. The photographed negative image was measured by the following method using an image analyzer (IP100-PC: manufactured by Asahi Kasei Corporation).
  • IP100-PC manufactured by Asah
  • gamma correction value 2.2
  • the capturing area was selected from the range of 1 ⁇ 1 m to 10 ⁇ 10 ⁇ m according to the photographing magnification.
  • Binary processing was performed on the captured 256-tone image.
  • small figure area removal of 300 nm or less. From the obtained binarized image, particles that were in contact with the measurement area and some of which were out of the measurement range were removed, and particle analysis was performed to determine the equivalent circle diameter of the target particles. After performing five visual field measurements, the arithmetic mean value was calculated for the measured circle equivalent diameters of all the particles, and the result was taken as the average particle diameter of the particles.
  • secondary particles were visually measured from the electron micrograph obtained in (14), and the average value of five observations was taken as the number of secondary particles.
  • secondary particles are defined as those in which five or more primary particles are aggregated, and the form of each primary particle is deformed by joining.
  • the number of particles was measured using the same image and image analyzer as in (14), and the average of five observations was taken as the number of particles.
  • control fiber without addition of polymer fine particles
  • control cellulose fiber usually cellulosic fiber
  • fineness, physical properties and glossiness to which no polymer fine particles obtained by spinning under the same apparatus and conditions as in the following examples were added were as follows.
  • Copper ammonia rayon Fineness 76.5 d / 45 f, dry strength 2.6 2 g / d, dry elongation 13.
  • a polymer fine particle emulsion having a solid content of 26.5% and an average particle diameter of 0.039 m.
  • This emulsion was mixed with a copper ammonia cell solution (cellulose: 10%, copper: 3.5%, ammonia: 7%, sodium hydroxide: 0.5%) prepared by a conventional method. ), Using an in-line mixer, mixing at a mixing temperature of 10 ° C and a mixer rotation speed of 100 rpm, mixing and mixing. A liquid is prepared, and after mixing, a coagulation bath (primary spinning water) is continuously passed through a 20-mm sintered filter and a 5-mm sintered filter through a 0.7 mm x 45 hole spinneret.
  • a coagulation bath primary spinning water
  • the resulting yarn has a fineness of 80.3 dZ45 f, dry strength of 2.5 g / d, dry elongation of 13.2%, wet strength of 1.53 g / d and fiber without added particles. Had the same physical properties as. The glossiness was as high as 41.2.
  • the average particle diameter of the fine particles in the fiber cross section is 0. 0 4 3 m in a non-pre-treatment method, the secondary particles is not present, fully differential dispersed particle number 1 0 8. eight / zm 2 Had been converted.
  • the dye exhaustion rate and the heat-up dye exhaustion rate were 94.2% and 87.6%, indicating sufficient dyeability and dye dyeing speed, and the resulting dyed product had a sharpness
  • the chromatic and achromatic chromaticities were 18.8, 38.9 and 16.4, showing excellent vivid and deep chromaticity.
  • the homochromaticity was also high, with ⁇ E * of 4.5.
  • the light fastness of the dyed cellulose fiber was 3 or 4 grade.
  • This emulsion was spun with the same formulation as in Example 1.
  • the resulting yarn has excellent physical properties of fineness of 80.2 d45 f, dry strength of 2.49 g / d, dry elongation of 13.3%, wet strength of 152 g / d.
  • I was The gloss is as high as 40.2, the average particle diameter of the fine particles in the fiber cross section is 0.047 m, the number of secondary particles is 0.2 / m 2 , and the number of particles is extremely high, 17.6. It showed excellent dispersibility.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate are 95.1% and 90.5%, indicating sufficient dyeability and dyeing speed, and the resulting dyed product has sharpness, chromatic color depth, The achromatic deep chromaticity was 19.4, 39.3, and 16.2.
  • ⁇ E * was as high as 3.9.
  • the light fastness of the dyed cell mouth fiber was 4th grade.
  • Emulsion polymerization was carried out according to the same formulation as in Example 1 except that benzyl methacrylate was used instead of vinyl benzoate to obtain a polymer having a solid content of 27.2% and an average particle diameter of 0.046 m. Obtained a coalesced fine particle emulsion
  • the resulting yarn has a fineness of 81.4 d / 45 f and a dry strength of 2.48 g / d It had excellent physical properties of a dry elongation of 13.5% and a wet strength of 1.48 g Zd.
  • Glossiness 4 1. 5 the average particle diameter of the fine particles in the fiber cross-section is 0. 0 4 6 / m, the secondary particles is not, the number of particles 1 0 5.
  • Outstanding dispersion and 0 / / zm 2 Showed sex.
  • Dye exhaustion rate, warming dye exhaustion rate is 93.88.89.4%, indicating sufficient dyeability and dyeing speed, and the resulting dyed product has sharpness, chromatic deep color, and achromatic color.
  • the deep chromaticity is also 18.7 and 37.
  • Emulsion polymerization was carried out according to the same formulation as in Example 1 except that vinyl benzoate was replaced with phenoxydiethylene glycol acrylate, and the solid content concentration was 26.4% and the average particle size was 0.04. A polymer emulsion of 4 m was obtained.
  • the resulting yarn has a fineness of 81.2 dZ 45 f, dry strength of 2.61 g / d, dry elongation of 13.6%, and wet strength of 1.62 g Zd. I had it.
  • the gloss is 39.3, the average particle size of the fine particles in the fiber cross section is 0.048 ⁇ m, the number of secondary particles is 0.4 / m 2 , and the number of particles is 103.8 zm 2 showed excellent dispersibility.
  • the dye exhaustion rate and thermal dye exhaustion rate show sufficient dyeability and dyeing rate of 91.9% and 82.1%, respectively, and the obtained dyed product has sharpness, chromatic deep color, and none.
  • the coloring deep chromaticity was 18.6, 36.3, and 16.9, showing excellent clear and deep coloring. For the same color, ⁇ E * is 5.3, and the light fastness of the dyed cellulose fiber is class 2. I got it.
  • Example 2 Except that vinyl benzoate was replaced with phenoxyshethylmethacrylate, emulsion polymerization was carried out according to the same formulation as in Example 1 to obtain a polymer having a solid content of 26.3% and an average particle diameter of 0.032. A fine particle emulsion was obtained.
  • the resulting yarn has excellent physical properties such as fineness of 82.5 ld Z45i, dry strength of 2.57 g / d, dry elongation of 13.6%, and wet strength of 1.59 g / d.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate are 94.1% and 89.3%, indicating sufficient dyeability and dyeing speed.
  • Achromatic deep chromaticity is also 19.8, 38.
  • Emulsion polymerization was carried out according to the same formulation as in Example 1 except that vinyl benzoate was replaced with P-cumylquinoquinethyl acrylate.
  • the solid content concentration was 26.5% and the average particle size was 0.03.
  • a 9 m polymer microparticle emulsion was obtained.
  • the resulting yarn has a fineness of 80.9 d / 45 f, a dry strength of 2.39 g / d, a dry elongation of 12.9%, a wet strength of 1.44 g, and a gloss of 3 It was 8.8. 0
  • the average particle diameter of the fine particles in the fiber cross-section. 0 4 5 m, secondary particle is not, the number of particles 1 0 7.
  • Six / // m 2 and excellent dispersibility shows, dye adsorption ratio
  • the thermal dye exhaustion rate was 91.3% and 85.7%, indicating sufficient dyeability and dyeing speed, and the resulting dyed product had sharpness, chromatic color depth, and achromatic color depth. Also, they exhibited excellent vivid and deep-colored properties of 18.9, 35.5, and 17.0.
  • ⁇ E * was 4.3, which was high.
  • the light fastness of the dyed cellulose fiber was 2nd to 3rd grade.
  • Emulsion polymerization was carried out according to the same formulation as in Example 1 except that vinyl benzoate was replaced with 2-hydroxy-3-propyl acrylate.
  • the solid content was 26.4%, and the average particle size was 27.5%.
  • a fine particle emulsion of a polymer having a diameter of 0.043 im was obtained.
  • the resulting yarn has a fineness of 81.2 d / 45 i, a dry strength of 2.45 g / d, a dry elongation of 13.2%, a wet strength of 1.48 g / d, and a gloss of 4 Was 0.3.
  • the average particle diameter of the fine particles in the fiber cross-section is 0. 0 4 2 m, the secondary particles not, indicates the number of particles 1 1 4.2 pieces / / m 2 and excellent dispersibility, dye exhaustion rate, The thermal dye exhaustion rate was 91.9% and 89.3%, indicating sufficient dyeability and dyeing speed, and the resulting dyed product also had sharpness, chromatic deep color, and achromatic deep color. , 19.0, 34.7, 17.3 and excellent clarity It exhibited deep color. ⁇ E * was 5.6, indicating good color consistency.
  • the light fastness of the dyed cellulose fiber was second class.
  • Emulsion polymerization was carried out according to the same formulation as in Example 1 except that vinyl benzoate was replaced with 2-methacryloyloxyshethyl-1 2-hydroxypropyl phthalate, and the solid content concentration was 27.0%, average A polymer emulsion of 0.047 m in particle size was obtained.
  • the resulting yarn has a fineness of 80.3 d / 45 f, a dry strength of 2.54 / d, a dry elongation of 13.4%, a wet strength of 1.51 gZd, and a gloss of 38.2. Met.
  • the average particle diameter of the fine particles in the fiber cross section is 0 0 5;... / M, the number of secondary particles 0 4 m 2, the number of particles 1 0 1 represents 0 or Z / zm 2 and excellent dispersibility
  • the dye exhaustion rate and the warming-up dye exhaustion rate are 88.5% and 70.2%, indicating the fastest dyeability and dyeing speed, and the resulting dyed product has sharpness and chromatic deep color.
  • the achromatic deep chromaticity was 18.7, 32.2, and 17.7, showing excellent vivid deep color.
  • ⁇ E * was 6.1, indicating good homochromaticity.
  • the light fastness of the dyed cellulose fiber was second class.
  • Emulsion polymerization was carried out according to the same recipe as in Example 1 except that the amount of vinyl benzoate was reduced from 350 parts to 300 parts, and 50 parts of diaryl phthalate was newly added. A fine particle emulsion of a polymer having a concentration of 25.4% and an average particle diameter of 0.047 m was obtained.
  • the resulting yarn has a fineness of 8 to 2 dZ 45 f, a dry strength of 2.48 g / d, a dry elongation of 12.5%, a wet strength of 1.45 g Zd, and a gloss of 38.
  • the average particle diameter of the fine particles in the fiber cross section is 0.05 m
  • the number of secondary particles is 0.2 Z ⁇ m 2
  • the number of particles is 99.8 Z zm 2
  • Exhaust rate and thermal dye exhaustion rate show excellent dyeability and dyeing rate of 91.0% and 88.5%, respectively, and the resulting dyed product has sharpness, chromatic deep color, and achromatic color.
  • the color depth was 18.8, 36.3, and 16.6, showing excellent vivid color depth.
  • ⁇ * also showed a good homochromaticity of 5.5, and the light fastness of the dyed cellulose fiber was grade 3 or 4.
  • Example 3 the benzyl methacrylate was reduced to 250 parts, and instead of adding styrene, the methyl methacrylate was increased to 170 parts and a new 2,2-bis (monobis) methacrylate was added.
  • the resulting yarn has a fineness of 82.0 d / 45 f, a dry strength of 2.47 g / d, a dry elongation of 12.3%, a wet strength of 39 g, and a gloss of 40 Was one.
  • Adekaly soap SE 100 10 parts of 25% by weight aqueous solution of Anion emulsifier manufactured by Asahi Denka Co., Ltd., 10 parts of 25% by weight aqueous solution of Emulgen 920 (nonionic surfactant manufactured by Kao Corporation), 10 parts of Emulgen 950 (Kao Corporation) 30 parts by weight of a 25% by weight aqueous nonionic surfactant), 3.73 parts of persulfuric acid, and 400 parts of distilled water were added, and the mixture was stirred with a homomixer to prepare a pre-emulsified product.
  • the resulting yarn has a fineness of 81.5 dZ 45 f, a dry strength of 2.61 / d, a dry elongation of 13.4%, a wet strength of 1.55 g, and a fine particle-free copper ammonia. It was a level comparable to rayon yarn. Glossiness It has a perfect brightness of 40.9, and the average particle diameter of the fine particles in the fiber cross section is 0.044 m, the number of secondary particles is 0.2 Zm 2 , and the number of particles is 109 . was favorably finely dispersed six "m 2. Further, the dye exhaustion rate, Atsushi Nobori dye adsorption ratio is 9 2.
  • the clarity, chromatic color depth and achromatic color depth of the obtained dyed product are 18.7, 34.9 and 17.5, indicating excellent clarity and color depth.
  • the same color property was as good as 6.8, and the light fastness of the dyed cellulose fiber was class 3 or 4.
  • Polymerization was carried out in the same manner as in Example 11 except that 100 parts of vinyl benzoate was replaced with 100 parts of fluorinated methacrylate. A polymer fine particle emulsion having a diameter of 0.045 / m was obtained.
  • the resulting yarn had a fineness of 82.1 d / 45 d and exhibited high physical properties of a dry strength of 2.47 gZd, a dry elongation of 12.9%, and a wet strength of 1.49 gZd.
  • the glossiness is a bright tone of 38.3, the average particle size of the fine particles in the fiber cross section is 0.045 m, there are no secondary particles, and the number of particles is 104.2 /; It was finely dispersed as well as um 2 .
  • the dye exhaustion rate and heating dye exhaustion rate show excellent dyeability and dyeing speed of 91.5% and 88.9%, respectively, and the resulting dyed product has sharpness and chromatic color depth.
  • the chromaticity, achromatic deep chromaticity, and ⁇ E * were 19.0, 35.8, 17.2, and 6.4, indicating excellent clarity, deep color, and homochromaticity.
  • the light fastness of the dyed cellulose fiber was grade 4.
  • Example 11 polymerization was carried out in the same manner except that styrene 22.5 parts was replaced with acrylonitrile 22.5 parts, and the solid content concentration was 22.2%. A polymer fine particle emulsion having an average particle diameter of 0.050 was obtained.
  • the resulting yarn has a fineness of 81.7 d / 45 f, a high dry strength of 2.44 g / d, a dry elongation of 12.7% and a wet strength of 1.44 g / d. showed that.
  • the glossiness is a bright tone of 36.3
  • the average particle diameter of the fine particles in the fiber cross section is 0.052 m
  • the number of secondary particles is 0.2 Zm2
  • the number of particles is 10 It was finely dispersed as 3.2 pieces / // m 2 .
  • the dye exhaustion rate and the heat-up dye exhaustion rate show excellent dyeability and dyeing rate of 90.9% and 85.1%, respectively.
  • the achromatic deep chromaticity and homochromaticity were 18.3, 34.3, 17.8, and 6.6, indicating excellent color developing and homochromaticity.
  • the light fastness of this dyed cellulosic fiber was as high as 4 to 5 grades.
  • Example 13 is the same as Example 13 except that methyl methacrylate was reduced to 62.5 parts, vinyl benzoate was increased to 125 parts, and 25 parts of diaryl phthalate was newly added. Polymerization was carried out according to the following formula to obtain a polymer fine particle emulsion having a solid content of 21.3% and an average particle diameter of 0.048 Aim.
  • the obtained yarn has a fineness of 80.5 d / 45 f, a dry strength of 2.33 g / d, a dry elongation of 12.5%, and a wet strength of 1.42 g Zd. showed that.
  • the dye exhaustion rate and the warming-up dye exhaustion rate show high dyeability and dyeing rate of 91.8% and 87.0%, and the obtained dyed product has sharpness, chromatic
  • the achromatic deep chromaticity and homochromaticity were 19.2, 35.1, 17.4, and 5.8, indicating excellent clear deep chroma and homochromaticity.
  • the light fastness of the dyed cellulose fiber was as high as 4-5 class.
  • Example 12 the vinyl methacrylate was increased to 175 parts, the methyl methacrylate was reduced to 30 parts, and instead of adding styrene, the acrylonitrile was added. Polymerization was carried out in the same manner except that 30 parts of the polymer was used, to obtain a polymer fine particle emulsion having a solid content of 22.3% and an average particle diameter of 0.048 m.
  • the obtained yarn had a fineness of 80.3 dZ45f, a dry strength of 2.61 g / d, a dry elongation of 14.0%, and a wet strength of 62 d, indicating high physical properties.
  • the dye exhaustion rate and the heat-up dye exhaustion rate are 94.2%, It shows excellent dyeability and dyeing speed of 90.3%, and the obtained dyed product has sharpness, chromatic deep color and achromatic deep color of 18.6, 40.2 and 16 2 and excellent vivid color depth. ⁇ ⁇ * also showed very good homochromaticity of 3.9.
  • the light fastness of the dyed cellulose fiber was a good grade of 4-5 class.
  • Example 12 the same formulation was used except that the methyl methacrylate was reduced to 60 parts, the styrene was increased to 25 parts, and 50 parts of acrylonitrile were newly used. Polymerization was carried out to obtain a polymer fine particle emulsion having a solid content of 22.5% and an average particle diameter of 0.042 / m.
  • the obtained yarn has a fineness of 81.2 d / 45 f, a dry strength of 2.49 / d, a dry elongation of 13.1%, and a wet strength of 1.43 g / d.
  • Glossiness 3 8.9 average particle diameter of the fine particles in the fiber cross-section is 0. 0 4 7 m, the secondary particles rather than, the number of particles 1 0 7.6 pieces / m 2 and satisfactorily finely dispersed I was
  • the dye exhaustion rate and the heat-up dye exhaustion rate are 91.1% and 85.3%, showing excellent dyeability and dyeing speed, and the resulting dyed product has sharpness and chromatic deep color.
  • the degree of achromatic color depth was 18.8, 34.3, and 17.5, indicating excellent vivid color depth.
  • E * also showed good homogeneity of 5.8.
  • the light fastness of the dyed cellulose fiber was as good as 5th grade.
  • Example 16 the same formulation was used except that acrylonitrile was reduced to 12.5 parts and methyl methacrylate was increased to 97.5 parts. Polymerization was carried out to obtain a polymer fine particle emulsion having a solid concentration of 22.4% and an average particle diameter of 0.046 m.
  • the resulting yarn had a fineness of 82.1 d / 45 f, a dry strength of 2.52 g / d, a dry elongation of 13.5%, and a wet strength of 1.51 g / d.
  • Gloss 3 9.6 an average particle diameter of the fine particles in the fiber cross section is 0. 0 4 9 / m, secondary particle number is 0.2 pieces / m 2, the number of particles 1 0 2 2 / m 2 And it was finely dispersed.
  • the dye exhaustion rate and the heat-up dye exhaustion rate are 90.5% and 83.9%, respectively.
  • the degree was 18.6, 33.7, 17.5, showing excellent clear and deep color.
  • ⁇ ⁇ * also showed fairly good color matching with 6.3.
  • the light fastness of the dyed cellulose fiber was as good as grades 4 and 5.
  • Example 2 the amount of vinyl methacrylate was reduced to 200 parts, the amount of methyl methacrylate was increased to 220 parts, and Tinuvin 328 (Ciba-Geigy) was used.
  • a similar formulation except that 1.5 parts of benzotriazole-based UV absorber and 1.5 parts of Tinuvinl 44 (a hindered amine light stabilizer manufactured by Ciba-Geigy) are used. Polymerization was performed to obtain a polymer fine particle emulsion having a solid content of 26.3% and an average particle diameter of 0.043 m.
  • the resulting yarn had a fineness of 81.7 d / 45 f, a dry strength of 2.53 g / d, a dry elongation of 13.7%, and a wet strength of 1.55 g / d.
  • the dye exhaustion rate and heat-up dye exhaustion rate are 90.0% and 84.5%, respectively, and the dyeability, the sharpness of the obtained dyed product, the chromatic color depth, and the achromatic color As for the degree, 19.2, 34.1, 17.1 showed excellent clear and deep color, and E * also showed a good same color of 6.2. Further, the light fastness of the dyed cellulose fiber was as good as 4 to 5 grade.
  • Example 18 the emulsion polymerization was carried out by the same formulation except that the methyl methacrylate was reduced to 175 parts, and 45 parts of acrylonitrile was newly used. A polymer fine particle emulsion having 6.4% and an average particle diameter of 0.050 Zm was obtained.
  • the resulting yarn had a fineness of 81.2 d / 45 f, a dry strength of 2.47 g / d, a dry elongation of 12.6%, and a wet strength of 1.49 g / d.
  • Glossiness 3 5.3 an average particle diameter of the fine particles in the fiber cross-section is 0. 0 5 3 m, secondary particle instead, the number of particles were finely dispersed with 9 6.8 pieces Z im 2.
  • the dye exhaustion rate and the heat-up dye exhaustion rate are 91.1% and 83.3%, respectively, and the dyeability, the sharpness of the obtained dyed product, the chromatic color depth, The chromaticity is 18.4, 32.8, and 17.9, showing excellent clear and deep color. E * also showed a reasonable color balance of 5.8.
  • the light fastness of the dyed cellulose fiber was good, at class 5.
  • Emulsion polymerization and spinning were carried out in the same manner as in Example 2 except that the addition ratio of the fine particles of the polymer was 5% relative to cellulose.
  • the spinnability was good, the pressure of the gear pump did not increase during spinning for 5 hours, and no problems such as filter clogging, clogging of the spout, and yarn breakage occurred.
  • the resulting yarn has a fineness of 77.3 d / 45 f, dry strength of 2.63 g / d, dry elongation of 13.7%, wet strength of 1.62 g Zd, and no fine particles added. It was completely equivalent to copper ammonia rayon yarn.
  • the glossiness is completely bright with 41.7, the average particle diameter of the fine particles in the fiber cross section is 0.041 m, there are no secondary particles, and the number of particles is 62.4 Z / m 2 was well differentiated.
  • the dye exhaustion rate and the heat-up dye exhaustion rate were 90.2% and 86.5%, showing good dyeing properties and dyeing speeds.
  • the degree and achromatic deep chromaticity were 16.8, 24.7, and 18.8, indicating a moderate color development.
  • the homochromaticity ⁇ * was also at a reasonable level of 9.0, and the light fastness of the dyed cellulose fiber was 3 or 4 grade.
  • Emulsion polymerization and spinning were carried out in the same manner as in Example 2 except that the addition ratio of the polymer fine particles was 25% relative to cellulose.
  • the spinnability was good, there was no pressure increase in the gear pump during the 5-hour spinning, and no problems such as filter clogging, spinning clogging, and thread breakage occurred.
  • the resulting yarn has a fineness of 84.5 d Z 45 f, a dry strength of 2.29 g / d, a dry elongation of 1 to 1%, a wet strength of 1.39 g / d, and a gloss of 32 .
  • 1 In average particle diameter of the fine particles in the fiber cross-section is 0. 0 4 9 nm secondary particles number is 0.8 pieces / 11 2, the number of particles are well dispersed and 1 4 3.6 cells / / m 2 Was.
  • the dye exhaustion rate and heat-up dye exhaustion rate were 95.3% and 90.5%, indicating good dyeability and dyeing speed, and the resulting dyed product had sharpness and chromatic deep color.
  • the degree and achromatic deep chromaticity were 20.9, 41.5 and 16.1, indicating excellent color development.
  • the ⁇ * was also excellent at 3.7, and the light fastness of the dyed cellulose fiber was 4-5.
  • Emulsion polymerization and spinning were carried out in the same manner as in Example 2 except that the addition ratio of the fine particles of the polymer was set to 40% of cellulose.
  • the spinnability was slightly poor, and during 5 hours of spinning, the gear pump pressure increased by 2 kg Z cm2 and two single yarn breaks occurred, but serious troubles such as thread breakage and clogging of the spout occurred. Did not.
  • the resulting yarn has a fineness of 87.5 d / 45 f, a dry strength of 81 g Zd, a dry elongation of 9.8%, a wet strength of 0.83 g Zd and a low gloss.
  • 2 0.5, an average particle diameter of the fine particles in the fiber cross-section 0. 0 6 3 ⁇ 111, secondary number of grains 1. 8 / m 2, the number of particles 1 5 2. six Z im 2
  • the particle density was too high and some aggregation occurred.
  • the dye exhaustion rate and the heat-up dye exhaustion rate show good dyeability and dyeing speed of 96.1% and 92.2%, respectively.
  • the chromaticity and achromatic deep chromaticity were 21.2, 42.3, and 15.8, indicating excellent color development.
  • the homochromaticity ⁇ E * was also excellent at 2.9.
  • the light fastness of the dyed cell opening fiber was 4 to 5 grade.
  • a fine particle emulsion of the polymer polymerized in Example 1 was mixed with a viscose rayon solution (cellulose: 8.7, sodium hydroxide 6.1%, carbon disulfide 1) prepared by a conventional method. 8%) The mixture was added at a mixing temperature of 15 ° C. and a mixer rotation speed of 100 rpm, and mixed to obtain a fine particle-nocellulose mixed liquid having a fine particle-to-cellulose addition ratio of 13% by weight. After mixing, the mixture was continuously filtered through a 20 m filter, and then coagulated from a single-array spinneret of 0.06 mm x 50 holes (coagulation bath (sulfuric acid: 140 gZl, sodium sulfate).
  • coagulation bath sulfuric acid: 140 gZl, sodium sulfate
  • the resulting yarn has a fineness of 120.ld Z50i and a dry strength of 1.85 gZ d, a dry elongation of 17.5%, a wet strength of 0.78 g / d, showing excellent physical properties and a gloss of 51.2.
  • the average particle diameter of the fine particles in the fiber cross section was 0.05 m, the number of secondary particles was 0.6 Zm 2 , and the number of particles was 101.2 Zm 2, which was well dispersed.
  • the dye exhaustion rate and the warming dye exhaustion rate were 94.5% and 90.3%, indicating good dyeing properties and dyeing speed, and the resulting dyed product had sharpness and chromatic color.
  • the deep chromaticity and achromatic deep chromaticity were 19.0, 38.1, and 16.9, indicating excellent sharpness and deep color.
  • the homochromaticity ⁇ E * was fairly 7.1, and the dyed viscose rayon light fastness was grade 3 or 4.
  • Example 18 Using the emulsion prepared in Example 18, spinning of viscos rayon was carried out in the same manner as in Example 23. The spinnability was good, and no problems such as fluff and breakage and no filter clogging occurred after 5 hours of spinning.
  • the resulting yarn has excellent physical properties of fineness of 18.2 d / 50 f, dry strength of 1.72 g Zd, dry elongation of 19.1%, and wet strength of 0.69 g / d.
  • the glossiness was 48.0, high gloss, the average particle diameter of the fine particles in the fiber cross section was 0.048 m, the number of secondary particles was 0.4 // m 2 , and the number of particles was 101.8 Zm 2 were well dispersed.
  • the dye exhaustion rate and the heat-up dye exhaustion rate show good dyeability and dyeing speed of 89.5% and 84.2%, respectively.
  • the degree of color and achromatic deep color were 19.5, 33.3, and 17.5, indicating excellent sharpness and deep color.
  • the homochromaticity ⁇ E * was a reasonable 8.5, and the light fastness of the dyed visco rayon fiber was grade 4.
  • Example 2 A similar procedure was performed in Example 2 except that the phenyl methacrylate was reduced to 125 parts and the methyl methacrylate was increased to 295 parts. Polymerization was carried out according to the formulation to obtain an emulsion having a solid content of 26.1% and an average particle diameter of 0.031 m.
  • the obtained yarn has excellent physical properties such as fineness of 81.3 d45 mm, dry strength of 2.65 g / d, dry elongation of 13.6%, and wet strength of 1.62 g Zd. , glossiness 4 1 5, an average particle diameter of the fine particles in the fiber cross section is 0 0 3 7 ⁇ m, secondary particle is not, the number of particles 1 2 4 6 /;... m 2 and good fine Was dispersed.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate were 91.5% and 83.2%, indicating reasonable dyeing properties and dyeing speeds, and the resulting dyed product had sharpness and chromatic depth.
  • the chromaticity and achromatic deep chromaticity were 18.3, 31.5, and 17.9, indicating excellent sharpness and deep color.
  • ⁇ E * was the same as 7.8, indicating the same color, and the light fastness of the dyed cellulose fiber was 4 to 5.
  • Example 2 polymerization was carried out in the same manner except that methyl acrylate was increased to 470 parts and methyl methacrylate and styrene were not used. An emulsion having a solid content of 25.2% and an average particle diameter of 0.15 m was obtained.
  • the resulting yarn has excellent physical properties of fineness of 80.2 d, dry strength of 2.4 g g d, dry elongation of 12.7%, wet strength of 1.39 g / d, and gloss. Is 15.5, and the average particle diameter of the fine particles in the fiber cross section is 0.13 / m, which is slightly coarse, but there are no secondary particles, and the number of particles is 11.2 / m 2 and sparsely distributed.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate show high dyeability and dyeing rate of 95.0% and 90.3%, respectively, and the clarity and chromatic
  • the degree and achromatic deep chromaticity were 17.1, 30.2 and 18.1, indicating a fairly high sharpness and deep color.
  • the homochromaticity ⁇ * was excellent at 3.7, and the light fastness of the dyed cellulose fiber was 4 or 5 grade.
  • the resulting yarn has a fineness of 8 2.ld Z 45 f, a dry strength of 2.40 g / d, a dry elongation of 12.9%, a wet strength of 38 g Zd, and exhibits excellent physical properties.
  • gloss 3 6.2 an average particle diameter of the fine particles in the fiber cross section is 0. 0 5 H m. secondary particle number is 0.6 or Z m 2, the number of particles 9 8. zero or Roh m 2 It was well dispersed.
  • the dye exhaustion rate and the warming-up dye exhaustion rate are 93.3% and 90.4%, indicating sufficient dyeability and dyeing speed, and the obtained dyed product has sharpness and chromatic color depth.
  • the resulting yarn has excellent physical properties of fineness of 80.3 dZ45 f, dry strength of 2.53 g / d, dry elongation of 13.5%, wet strength of 1.33 g / d. shows, glossiness 4 0.2 and higher, the average particle diameter of the fine particles in the fiber cross-section is 0. 0 4 3 m, secondary particle is not, the number of particles 1 0 9.6 pieces / / m 2 and good Was finely dispersed.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate are 9
  • the fastness to light of the dyed cellulose fiber was 4 and was excellent.
  • Polymerization was carried out in the same manner as in Example 2, except that 60 parts of methacrylic acid was used instead of itaconic acid and the amount of methyl methacrylate was reduced to 25 parts. An emulsion having a solid content of 25.0% and an average particle size of 0.052 m was obtained.
  • the resulting yarn has a fineness of 80.4 dZ 45 f, a dry strength of 2.42 g / d, a dry elongation of 12.3%, a wet strength of 1.25 g / d and a glossiness of
  • the average particle diameter of the fine particles in the fiber cross section is 0.055 m, the number of secondary particles is 0.2 m 2 , and the number of particles is 89.8 Z / m 2 . It was finely dispersed well.
  • the dye exhaustion rate, 91.5% 87.2%, showing sufficient dyeability and dyeing speed, and the resulting dyed product has sharpness, chromatic deep color, and achromatic deep color of 18.2, 3 4 4. Highly clear and deep-colored with 17.4.
  • the homochromaticity E * was excellent at 5.5, and the light fastness of the dyed cellulose fiber was 3 or 4 o
  • Example 2 Polymerization was carried out in the same manner as in Example 2 except that the amounts of the initiator and the emulsifier used were reduced to obtain an emulsion having a solid content of 24.9% and an average particle diameter of 0.075 ⁇ m. Was. Using this emulsion, spinning was carried out in the same manner as in Example 1. Good spinnability, no problems such as fluff and yarn breakage after 5 hours of spinning No clogging of filter o
  • the obtained yarn had a fineness of 81.ldZ45f, a dry strength of 2.51 g / d, a dry elongation of 12.9%, and a wet strength of 50 g / d.
  • the dye exhaustion rate and heating dye exhaustion rate are 94.5% and 90.1%, indicating sufficient dyeability and dyeing speed, and the resulting dyed product has sharpness, chromatic color depth, The achromatic deep chromaticity was slightly lower at 17.2, 31.3, and 18.0.
  • the homochromaticity ⁇ E * was excellent at 4.4, and the light fastness of the dyed cellulosic fiber was grade 4.
  • Example 2 Polymerization was carried out in the same manner as in Example 2 except that the amounts of the initiator and the emulsifier used were reduced, to obtain an emulsion having a solid content of 26.3% and an average particle diameter of 0.11 m.
  • spinning was carried out in the same manner as in Example 1. The spinnability was good, and no trouble or filter clogging such as fluff or yarn breakage occurred after 5 hours of spinning.
  • the resulting yarn had a fineness of 80.5 dZ45f, a dry strength of 2.45 g / d, a dry elongation of 12.4%, and a wet strength of 1.44 g / d.
  • the average particle diameter of the fine particles in the fiber cross section is 0. 1 1 m, the secondary particles not, well dispersed particles number 1 6. the four Z // m 2
  • the dye exhaustion rate and the temperature rise dye exhaustion rate are 95.3% and 90.3%, respectively.
  • the sharpness, chromatic deep color, and achromatic deep color of the obtained dyed product are 16. It was slightly lower at 9, 29.8 and 18.8 i.
  • the homochromaticity E * was 5.2, and the light fastness of the dyed cellulose fiber was 4-5.
  • Example 2 Polymerization was carried out in the same manner as in Example 2 except that the amounts of the initiator and the emulsifier used were reduced to obtain an emulsion having a solid content of 25.5% and an average particle diameter of 0.21 m.
  • spinning was carried out in the same manner as in Example 1. The spinnability was good, and no problems such as fluff and breakage and no filter clogging occurred after 5 hours of spinning.
  • the resulting yarn had a fineness of 8 to 2 dZ45 f, a dry strength of 2.39 g / d, a dry elongation of 11.8%, and a wet strength of 29 gd.
  • the dye exhaustion rate and the warming-up dye exhaustion rate are 93.9% and 88.8, indicating sufficient dyeability and dyeing speed, and the obtained dyed product has sharpness, chromatic color depth, and none The coloring deep chromaticities were 15.7, 27.8, and 18.5.
  • the homochromaticity ⁇ E * was 6.0, and the light fastness of the dyed cellulose fiber was 4 to 5 grade.
  • Example 2 Polymerization was carried out in the same manner as in Example 2 except that the amounts of the initiator and the emulsifier used were reduced. The solid content concentration was 25.4%, and the average particle size was 0.4. 2 / m emulsion was obtained. Using this emulsion, spinning was carried out in the same manner as in Example 1. The spinnability was good, and no troubles such as fluff and thread breakage were found in the filter after 5 hours of spinning. The resulting yarn had a fineness of 81.4 d / 45 f, a dry strength of 2.31 g / d, a dry elongation of 11.4%, and a wet strength of 1.27 g / d.
  • the gloss at 1 4.3 and dull, the average particle diameter of the fine particles in the fiber cross-section is 0. 3 9 m, the secondary particles rather than, the number of particles 1.8 pieces / m 2 and well dispersed However, the distribution was sparse.
  • the dye exhaustion rate and the heat-up dye exhaustion rate are 95.3% and 89.9%, respectively.
  • the sharpness, chromatic deep chromaticity and achromatic deep chromaticity of the obtained dyed product are 15. It was a little lower at 5, 26.3 and 19.0.
  • the homochromaticity ⁇ * was 6.8, and the lightfastness of the dyed cellulose fiber was 4 to 5 grade.
  • Example 2 the amount of used itaconic acid was increased to 20 parts, and instead of acrylamide, 90 parts of 2—hydroxyquinethyl methacrylate was used, and methyl methacrylate was used. Polymerization was carried out in the same manner except that the amount of styrene was reduced to 20 parts and the amount of styrene was reduced to 20 parts, respectively, to obtain an emulsion having a solid content of 25.3 and an average particle diameter of 0.051 m.
  • the resulting yarn had a fineness of 80.9 d / 45 f, a dry strength of 2.49 g / d, a dry elongation of 12.3%, and a wet strength of 1.23 g Zd.
  • the glossiness was 38.1, the average particle size of the fine particles in the fiber cross section was 0.
  • the dye exhaustion rate and the warming-up dye exhaustion rate are 90.5% and 88.3%, indicating sufficient dyeability and dyeing speed, and the obtained dyed product has sharpness and chromatic deep color. Every time, The achromatic deep chromaticities were 18.2, 32.9, and 17.7, the homochromaticity E * was 6.5, and the light fastness of the dyed cellulose fiber was grade 3 or 4. o
  • the resulting yarn had a fineness of 82.2 d / 45 f, a dry strength of 2.38 g / d, a dry elongation of 11.8%, and a wet strength of 39 g / d.
  • the gloss is 39.8, the average particle diameter of the fine particles in the fiber cross section is 0.048 m, the number of next particles is 0.4 Zm 2 , and the number of particles is 103.2 / nm 2 It was finely dispersed.
  • the dye exhaustion rate and the heat-up dye exhaustion rate are 92.2% and 89.7%, respectively, and the resulting dyed product has a sharpness, chromatic deep chromaticity and achromatic deep chromaticity of 18. 9, 36.5 and 17.1.
  • E * was 4.3, and the light fastness of the dyed cellulose fiber was class 4.
  • Example 2 Polymerization was carried out in the same manner as in Example 2, except that itaconic acid was not used, the acrylamide used was increased to 20 parts, and the methyl methacrylate was increased to 80 parts. An emulsion having a solid content of 26.1% and an average particle diameter of 0.043 m was obtained. Using this emulsion, spinning was performed with the same formulation as in Example 1. Spinnability somewhat upset, there is a gear pump pressure increase LKG Z cm 2 at a spinning for 5 hours, a single yarn breakage once occurred. The resulting yarn had a fineness of 8 to 5 dZ 45 f, a dry strength of 2.19 g / d, a dry elongation of 10.2%, and a wet strength of 1.25 g Zd.
  • the glossiness is dull to 16.1, the average particle diameter of the fine particles in the fiber cross section is 0.18 ⁇ m, the number of secondary particles is 5.2 Zm 2 , and the number of particles is 7.6 / / m 2 to have been aggregated.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate were 93.5% s and 90.3%, showing good dyeability.However, the obtained dyed product had clearness, chromatic deep color, and achromatic color.
  • the deep chromaticity was as low as 15.5, 29.3 and 18.2.
  • the homochromaticity was fair with ⁇ E * of 5.9, and the colorfastness of the dyed cellulose fiber was class 4.
  • Example 2 the same formulation was used except that the amount of the itaconic acid used was increased to 20 parts, the acrylamide was not used, and the methyl methacrylate was used at 80 parts.
  • the polymerization was carried out to obtain an emulsion having a solid content of 25.5% and an average particle diameter of 0.048 m.
  • spinning was carried out in the same manner as in Example 1. The spinnability was good, and no problems such as clogging of the filter, fluff, and yarn breakage occurred after 5 hours of spinning.
  • the resulting yarn had a slightly lower fineness of 80.3 dZ45 f, a dry strength of 2.28 g / d, a dry elongation of 1 to 6%, and a wet strength of 33 g d.
  • Glossiness 3 7. 3, 0 average particle size of the fine particles in the fiber cross-section. 0 5 u rn, the secondary particle number is 0. 8 / m 2, the number of particles 9 6.
  • Eight Z m 2 It was in a fairly dispersed state.
  • the dye exhaustion rate and heating dye exhaustion rate are 94.3% and 90.2%, and the obtained dyed product has sharpness, chromatic deep color and achromatic deep color of 19.0%. , 34.7 and 17.3.
  • the homochromaticity was as excellent as ⁇ * of 4.2, and the light fastness of the dyed cellulose fiber was class 4.
  • Example 3 9 Using the emulsion prepared in Example 33, spinning was carried out in the same manner as in Example 23. The spinnability was good, and no problems such as filter clogging, fluff, and yarn breakage occurred after 5 hours of spinning.
  • the obtained viscose rayon yarn has a fineness of 18.5 d / 50 f, a dry strength of 1.75 g / d, a dry elongation of 17.1%, and a wet strength of 0.70 g / d.
  • Met. Gloss 1 7. 5 and dull the average particle diameter of the fine particles in the fiber cross-section is 0. 2 0 m, the secondary particles rather than the number of particles 4.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate are 95.19.5%, indicating sufficient dyeability and dyeing speed, and the resulting dyed product has clearness, chromatic deep color, and achromatic color.
  • the deep chromaticities were 16.0, 28.2, and 18.2.
  • the homochromaticity ⁇ E * is 8.0, and the light fastness of the dyed cellulose fiber is 4
  • Example 2 Polymerization was carried out in the same manner as in Example 2 except that the amount of vinyl methacrylate used was reduced to 50 parts and the amount of methyl methacrylate was increased to 370 parts. An emulsion of 0.2% and an average particle diameter of 0.038 m was obtained. Using this emulsion, spinning was carried out in the same manner as in Example 1. Good spinnability, no problems such as filter clogging, fluff, and yarn breakage after 5 hours of spinning
  • the obtained yarn had a fineness of 80.0 dZ45f, a dry strength of 2.58 g / d, a dry elongation of 13.8%, and a wet strength of 1.53 gZd. .
  • Light Sawado 4 1.2 and higher the average particle diameter of the fine particles in the fiber cross-section is 0. 0 4 u rn, secondary particles rather than, the number of particles 1 1 6.8 pieces / m 2 and finely dispersed was.
  • the dye exhaustion rate and the heat-up dye exhaustion rate were 92.3% and 75.2%, and the exhaustion rate was slightly slow.
  • the sharpness and chromatic depth of the dyed material obtained The chromaticity and achromatic deep chromaticity were 18.9, 37.2, and 17.3. As for the homochromaticity, ⁇ E * was 10.3 and the color difference was large. The light fastness of the dyed cellulose fiber was class 4.
  • Example 2 except that 500 parts of phenyl methacrylate was used and no itaconic acid, acrylamide, methyl methacrylate, and styrene were used at all. Was polymerized with the same formulation. The polymerizability was slightly poor and some sedimentation occurred. The emulsion after filtration through the 80 # filter had a solid content of 25.5% and an average particle diameter of 0.062 m. When spinning was carried out using this emulsion in the same manner as in Example 1, yarn breakage occurred frequently immediately after the start of spinning and spinning was impossible. Oleyl sulfate sodium and emalgen as surfactants
  • Spinning was carried out by adding 9 20 to each of 5% of the fine particles. However, spinning in the coagulation bath occurred frequently and spinning was impossible.
  • Example 9 Polymerization was carried out in the same manner as in Example 9 except that 37 parts of methyl methacrylate was used instead of not using vinyl benzoate, and the solid content concentration was 26.3%. A 0.049 m emulsion was obtained. Using this emulsion, spinning was performed with the same formulation as in Example 1. The spinnability was good, and troubles such as filter clogging, fluff, and yarn breakage did not occur after 5 hours of spinning.
  • the resulting yarn had a fineness of 80.3 d / 45 f, a dry strength of 2.56 g / d, a dry elongation of 13.2%, and a wet strength of 55 g / d.
  • the gloss is as high as 37.9, the average particle size of the fine particles in the fiber cross section is 0.053 m, the number of secondary particles is 1.2 Zm 2 , and the number of particles is 93.2 particles / m 2 and dispersed.
  • Dye exhaustion rate, warming dye exhaustion rate is 89.7%, 65.4%, the dyeing speed is slow, the sharpness of the obtained dyed product, chromatic color depth
  • the chromaticity and achromatic deep chromaticity were 18.1, 34.1, and 17.7.
  • the homochromaticity ⁇ * was 10.9, which was a large color difference, and the light fastness of the dyed cellulose fiber was class 4.
  • Example 2 Polymerization was carried out in the same manner as in Example 1 except that 370 parts of cyclohexyl methacrylate was used instead of using benzoyl butyl. The solid content was 26.0% and the average particle size was 20.0%. An emulsion of 0.041 / m in diameter was obtained. Using this emulsion, spinning was performed according to the same formulation as in Example 1. The spinnability was good, and no problems such as filter clogging, fluffing, and yarn breakage occurred after 5 hours of spinning.
  • the resulting yarn had a fineness of 81.2 d / 45 f, a dry strength of 2.63 g / d, a dry elongation of 14.0%, and a wet strength of 1.60 g / d.
  • the gloss is as high as 39.8, the average particle diameter of the fine particles in the fiber cross section is 0.043 m, the number of secondary particles is 0.2 / m 2 , and the number of particles is 11.4 / ⁇ m 2 and had been finely dispersed.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate are 89.5% and 67.4%, and the dyeing speed is slow, and the obtained dyed product has sharpness, chromatic color depth, and achromatic color deep.
  • the degrees were 17.9, 33.5 and 17.6.
  • the homochromaticity ⁇ * was 10.1, which was a large color difference, and the light fastness of the dyed cellulose fiber was class 4.
  • Example 2 Polymerization was carried out in the same manner as in Example 1 except that 370 parts of methylstyrene was used instead of not using vinyl benzoate, and the solid component concentration was 25.6% and the average particle diameter was 0. 0.38 m of emulsion was obtained. Using this emulsion, spinning was carried out with the same formulation as in Example 1. The spinnability was good, and no problems such as filter clogging, fluff, and yarn breakage occurred after 5 hours of spinning.
  • the resulting yarn has a fineness of 80.2 dZ 45 f and a dry strength of 2.65 g / d
  • the dry elongation was 13.8% and the wet strength was 1.61 g / d.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate are particularly low at 81.5% and 54.7%, and the dyeing speed is particularly slow.
  • the chromaticity was 17.5, 31.2, 18.3.
  • the color difference ⁇ * was 12.6, which was a large color difference, and the light fastness of the dyed cellulose fiber was 3 or 4.
  • Example 2 Polymerization was carried out in the same manner as in Example 1 except that vinyl benzoate was not used and the amount of methyl methacrylate used was increased to 420 parts, and the solid content concentration was 26.5%, average An emulsion having a particle size of 0.029 ⁇ m was obtained. Using this emulsion, spinning was performed with the same formulation as in Example 1. The spinnability was good, and no problems such as filter clogging, fluff, and yarn breakage occurred after 5 hours of spinning.
  • the resulting yarn had a fineness of 81.3 d / 45 f, a dry strength of 2.59 g / d, a dry elongation of 13.8%, and a wet strength of 1.53 g / d.
  • Glossiness 4 1.5 average particle diameter of the fine particles in the fiber cross-section is 0. 0 3 8 zm, secondary particles rather than, the number of particles were finely dispersed with 1 1 9.8 pieces Z m 2 .
  • the dye exhaustion rate and heating dye exhaustion rate are as low as 91.8% and 63.2%, respectively, and the dyeing speed is slow.
  • the degrees were 19.1, 35.8, and 17.0.
  • the color difference E * was as large as 11.0 and the color fastness of the dyed cellulose fiber was 4-5.
  • Example 1 the amount of methyl methacrylate and the amount of styrene were increased to 235 parts each without using vinyl benzoate. Outside, polymerization was carried out in the same manner to obtain an emulsion having a solid content concentration of 26.2% and an average particle diameter of 0.035 zm. Using this emulsion, spinning was carried out in the same formulation as in Example 1. Good spinnability, no trouble such as filter clogging, fluff, thread breakage, etc. after 5 hours of spinning.
  • the resulting yarn had a fineness of 8 to 2 d / 45 f, a dry strength of 2.61 g / d, a dry elongation of 13.5%, and a wet strength of 55 g / d.
  • the glossiness was 41.3, the average particle diameter of the fine particles in the fiber cross section was 0.04 m, there were no secondary particles, and the number of particles was 11.1.2, which was finely dispersed.
  • the dye exhaustion rate and the thermal dye exhaustion rate are 90.5% and 65.5%, and the resulting dyed product has a sharpness, chromatic deep color, and achromatic deep color of 18 8, 34.9 and 17.3.
  • the color difference E * was 10.9, which was a large color difference, and the light fastness of the dyed cellulose fiber was 4th grade.
  • Example 2 Polymerization was carried out in the same manner as in Example 1 except that vinyl benzoate was not used, methyl methacrylate was reduced to 50 parts, and the amount of styrene was increased to 420 parts. An emulsion having a solid content of 25.3% and an average particle diameter of 0.033 zm was obtained. Using this emulsion, spinning was performed with the same formulation as in Example 1. The spinnability was good, and no troubles such as clogging, fluff, and yarn breakage occurred during 5 hours of spinning.
  • the resulting yarn had a fineness of 80.5 d / 45 f, a dry strength of 2.60 g / d, a dry elongation of 13.9%, and a wet strength of 1.58 g / d.
  • the gloss was 38.9, the average particle size of the fine particles in the fiber cross section was 0.041 m, there were no secondary particles, and the number of particles was finely dispersed at 11.0 particles / m 2 .
  • the dye exhaustion rate and the temperature rise dye exhaustion rate were 86.5% and 66.3%, and the resulting dyed product had sharpness, chromatic deep color and achromatic deep color of 17 . 9 , 34.0, 17.2.
  • the homochromaticity ⁇ E * was as large as 11.3 and the color difference was large.
  • the light fastness of the dyed cellulose fiber was grade 3 or 4.
  • Example 11 the composition of the pre-emulsified product was 200 parts of methyl methacrylate, 25 parts of styrene, 7.5 parts of sodium styrene sulfonate, and acrylamide. Polymerization was carried out in the same manner except that the amount was 10 parts, to obtain polymer fine particles having a solid content of 20.9% and an average particle diameter of 0.023 / m.
  • the resulting viscose rayon yarn has a fineness of 15.7 d / 50 f, a dry strength of 1.85 gd, a dry elongation of 17.0%, and a wet strength of 0.72 g / d.
  • the glossiness is 49.7, which is a completely bright tone.
  • the average particle size of the fine particles in the fiber cross section is 0.04 3 // m
  • the number of secondary particles is 0.2 / m 2
  • the particles The number was i 07.4 Zm 2 , which was a very good finely dispersed state.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate were 92.7% and 68.3%, respectively, and the sharpness, They were 17.7, 31.2 and 17.7.
  • the homochromaticity ⁇ * was as large as 11.9, and the dyed cellulose fiber had a light fastness of class 4.
  • Example 11 the amount of methyl methacrylate used was increased to 270 parts without using itaconic acid or acrylamide, and styrene was not used. Polymerization was carried out in the same manner except that the amount was increased to 30 parts, to obtain an emulsion having a solid concentration of 21.8% and an average particle diameter of 0.035 m.
  • the emulsifier of the pre-emulsified product was changed to 5 parts of a 25% by weight aqueous solution of Eleminor JS-12 (anionic surfactant manufactured by Sanyo Kasei Co., Ltd.) and 25 parts by weight of Emulgen 985 14 parts of a 25% aqueous solution of emalgen 950, 30 parts of a 25% aqueous solution of emalgen 950, and 6 parts of a 25% aqueous solution of Eleminor JS-2 as an emulsifier to be charged into a flask equipped with a stirrer. Except for the addition, polymerization was carried out in the same manner to obtain an emulsion having a solid content of 22.2% and an average particle diameter of 0.18 m.
  • Eleminor JS-12 anionic surfactant manufactured by Sanyo Kasei Co., Ltd.
  • the resulting yarn has a fineness of 80.1 (5/45, dry strength of 1.02 g Zd, dry elongation of 8.8%, wet strength of 0.69 g / d, a property unsuitable for practical use.
  • the glossiness was 12.1, which was not glossy.
  • the average particle diameter of the fine particles in the fiber cross section was 0.58 / zm by the non-pretreatment method, and the number of secondary particles was 0.28 Z / zm 2 were observed and the number of particles was 0.95 / m 2 , and most of the particles were aggregated.
  • a stock solution was prepared and spun in the same manner as in Example 23 except that the addition amount of the fine particles was 25% based on cellulose.
  • the spinnability was four single yarn breaks with a spinning time of 5 hours.
  • the resulting piscose yarn had a fineness of 122.0 d / 50 f, a dry strength of 43 g / d, a dry elongation of 8.8%, and a wet strength of 0.51 g Zd.
  • the obtained fiber had a dullness of 15.3.
  • the average particle diameter of the fine particles in the fiber cross-section is 0. 3 9 m, the number of secondary particles 1 to 8. 4 Z m 2, the number of particles 3 4. 6 / m 2 and aggregation stood.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate are 93.2% and 64.5%, respectively, and the obtained dyed product has a sharpness, chromatic deep chromaticity and achromatic deep chromaticity of 17.
  • the color developability was reduced to 4, 33.3, and 18.0.
  • ⁇ E * was 12.7, which was a large color difference.
  • the light fastness of the dyed cellulosic fiber was 4 to 5.
  • Comparative Example 13 the amount of metaacrylic acid was increased to 140 parts and added dropwise. Polymerization was carried out in the same manner except that the monomer was changed to 130 parts of methyl methacrylate, 31.2 parts of styrene, and 24 parts of neopentyl glycol dimethacrylate. An emulsion with 19.9% and an average particle diameter of 0.049 m was obtained.
  • the resulting yarn has a fineness of 19.8 d / 50 i, a dry strength of 1.21 g "d, a dry elongation of 9.6%, a wet strength of 0.30 g Zd and a particularly high wet strength.
  • the gloss was 29.9, the average particle diameter of the fine particles in the fiber cross section was 0.049 m, the number of secondary particles was 2.4 / m 2 , and the number of particles was 10 1.0 Zm 2 was good, but the dye exhaustion rate and temperature rise The dye exhaustion rate was as low as 66.3% and 65.2%.
  • the brightness of the obtained dyed material cannot be measured, and the chromatic and achromatic deep chromaticities are as low as 5.3 and 19.7, so that a sufficient dye can be obtained.
  • the color difference was also large, that is, ⁇ E * was 16.1
  • the light fastness of this dyed cellulose fiber was grade 4.
  • Example 16 The same formulation as in Example 1 was used, except that vinyl benzoate and acrylamide were not used, but styrene was increased to 30 parts and methyl methacrylate was increased to 210 parts. The polymerization was performed to obtain an emulsion having a solid content of 19.6% and an average particle diameter of 0.041 zm. Using this emulsion, a stock solution was prepared and spinned in the same manner as in Example 23, except that the amount of fine particles added to the cell mouth was adjusted to 100%. Single yarn breakage occurred frequently and spinning was impossible. Comparative Example 16
  • Polyethylene terephthalate was polymerized from dimethyl terephthalate ethylene glycol by an ordinary method to obtain a polymer having a specific viscosity of 0.60 in 0-chlorophenol. This polymer was heat-treated at 110 ° C for 3 hours under reduced pressure at 76 mmHg, and then heat-treated at 170 ° C for 4 hours. After the preliminary pulverization, pulverization was further performed using a wet media mill. After the resulting particle dispersion was diluted, the dispersion was filtered through a 80-mesh filter.
  • sodium oleyl sulfate and emulgen 920 were added as surfactants in an amount of 5% with respect to the fine particles, respectively, to give a solid content of 10.3% and an average particle diameter of 2.5 m. A dispersion of fine particles was obtained.
  • Example 2 Using this dispersion, spinning was carried out in the same manner as in Example 1 except that the amount of added fine particles was 10% based on cellulose. The spinnability was poor, and filter clogging occurred immediately after the start of spinning, and extrusion was impossible.Therefore, the 5 / m sintered letter was removed, and only the 20 meter letter was filtered. Was done. However, during the spinning for 3 hours, there was a pressure increase of 10 kg Z cm 2 or more, fuzz or single yarn breakage occurred 20 times or more, and frequent yarn breakage also occurred during tube knitting.
  • the obtained yarn had a fineness of 79.2 dZ 45 f, a dry strength of 0.82 g Zd, a dry elongation of 8.9%, and a wet strength of 0.61 gd, which were unpractical physical properties. .
  • the gloss was 9.6, which was not glossy at all.
  • the average particle diameter of the fine particles in the fiber cross section was 4.3 m, and coarse aggregate particles with a diameter of 10 ⁇ or more were observed in some places. Secondary particle number 0.0 0 1 /; m 2, The number of particles was sparse and 0.0 0 5 Bruno ⁇ m 2.
  • the dye exhaustion rate and the temperature rise dye exhaustion rate are 97.5% and 46.9%, and the dyeing speed is slow, and the resulting dyed product has sharpness, chromatic deep color, and achromatic deep color.
  • ⁇ ⁇ * has a large color difference of 1 1.3 It was terrible.
  • the light fastness of this dyed cellulose fiber was grade 6.
  • HyPhPrA 2-Hydroxy-3-phenoxyb mouth building acrylate
  • ZMAOEHyEP 2-methylacryloyloxetil-2-Hydroxypropyl phthalate
  • UVA / HALS Tinuv i n328 / Ti nuv i n l44
  • ZCHMA Cyclohexyl methacrylate / MeSt: Methylstyrene
  • NaSS Sodium styrenesulfonate
  • Example 1 0.043 108.8 0 80.3 2, 55 13.2 1.53 ⁇ 41.2 94.2 87.6 18.8 38.9 16.4 4.5 3-4
  • Example 2 0.047 107.6 0.2 80.2 2.49 13.3 1.52 ⁇ 40.2 95.1 90.5 19.4 39.3 16.2 3.9
  • Example 3 0.046 105 0.0 81.4 2.48 13.5 1.48 ⁇ 41.5 93.8 89.4 18.7 37.5 16.7 4.7 2-3
  • Example 4 0.048 103.8 0.4 81.2 2.61 13.6 1.62 ⁇ 39.3 91.9 82.
  • Example 15 0.05 103.4 0 80.3 2.61 14.0 1.62 ⁇ 37.7 94.2 90.3 18.6 40.2 16.2 3.9 4 to 5
  • Example 16 0.047 107.6 0 81.2 2.49 13.1 1.43 ⁇ 38.9 91.i 85.3 18.8 34.3 17.5 5.8 5
  • Example 19 0.053 96,8 0 81.2 2.47 12.6 1.49 ⁇ 35.3 91.1 83.3 18.4 32.8 17.9 5.8 5
  • Example 20 0.0 1 62.4 0 77.3 2.63 13.7 1.62 ⁇ 41,7 90.2 86.5 16.8 24.7 18.8 9.0 3-4
  • Example 21 0.049 143.6 0.8 84.5 2.29 11.1 1.39 ⁇ 32.J 95.3 90.5 20.9 41.5 16.1 3.7 4-5
  • Example 22 0.063 152.6 1.8 87.5 1.81 9.8 0.83 ⁇ 20.5 96.1 92.2 21.2 42.3 15.8 2.9 4 ⁇ 5
  • Example 23 0.049 99.0 0.4 118.3 1.83 17.2 0.73 ⁇ 49.2 93.3 86.6 20.1 37.7 17.1 7.5 3
  • Example 24 0.05 101.2 0.6 120.1 1.85 17.5 0.78 ⁇ 51.2 94.5 90.3 19.0 38.1 16.9 7.1 3 ⁇ 4
  • Example 25 0.048 101.8 0.4 118
  • Comparative example 12 0.19 5.2 0 81.9 2.49 12.9 1.55 ⁇ 18.5 91.7 64.3 15.3 26.2 18.9 13.5 4-5 Comparative example 13 0.39 34.6 18.4 122.0 1.43 8.8 0.51 ⁇ 15.3 93.2 64.5 17.4 33,3 18.0 12.7 4-5 Comparative example 14 0.049 101.0 2.4 119.8 1.21 9,6 0.30 X 29.9 66.3 65.2 5.3 19.7 16.1 4 Comparative example 15 X
  • the cell mouth fibers containing fine particles of a polymer having an aromatic ring and an ester bond or an aromatic ring and an ether bond in a specific ratio have a hue, a polyester and a
  • the polymer fine particles have a CN group or an ultraviolet ray absorbent and a solder-to-mine light stabilizer
  • the polymer has excellent light fastness and excellent light fastness.
  • the fiber has excellent spinning properties and mechanical properties, and particularly, the average particle diameter of the polymer fine particles in the fiber is 0.
  • the number of particles can be increased while suppressing the generation of secondary particles in the cellulose fiber, and the gloss, sharpness and deep color, and Have good color matching with polyester. Understand o
  • the single-knit fabric of the fiber obtained in Example 2 was scoured and dried, and a cross-linking reaction solution (ethylene glycol diglycidyl ether: 5.0%, magnesium borofluoride: 1%, magnesium acetate: 1%, water: 9 3%), squeeze it to 100% with a mangle (5 kgcm 2 ), pre-dry at 100 ° C for 1 minute, and heat-treat at 160 ° C for 3 minutes. did.
  • a cross-linking reaction solution ethylene glycol diglycidyl ether: 5.0%, magnesium borofluoride: 1%, magnesium acetate: 1%, water: 9 3%
  • Example 2 One-mouth knitted fabric of the fiber obtained in Example 2 was scoured and dried, and a cross-linking reaction solution, polyethylene glycol diglycidyl ether (uniresin Z-135; manufactured by DUNICA GIKEN): 5%, Hofu After immersion in magnesium nitrate: 3%, magnesium acetate: 1.5%, water: 90.5%), squeeze it to 90% with a mangle (5 kg / cm 2 ), and extract it to 90%. Preliminary drying was performed at 00 ° C for 1 minute and heat treatment was performed at 160 ° C for 3 minutes. The wet rub fastness of this fabric was as good as 4 to 5 grade.
  • Example 4 2 One-mouth knitted fabric of the fiber obtained in Example 2 was scoured and dried, and a cross-linking reaction solution, polyethylene glycol diglycidyl ether (uniresin Z-135; manufactured by DUNICA GIKEN): 5%, Hofu After immersion in magnesium nitrate: 3%, magnesium acetate
  • the knitted fabric was dyed with a reactive dye Sumifix B lack B (disperse dye manufactured by Sumitomo Chemical Co., Ltd.) at 5% 0 wf and a bath ratio of 1:50.
  • the aid, sulfuric acid was used na Application Benefits um (5 0 g Z l), carbonate Na Application Benefits ⁇ beam (1 5 g / / l). After dyeing, sufficient soaping, dehydration and drying were performed.
  • this fabric was evaluated for wet rub fastness according to JIS-L0849, it was unsatisfactory of grade 2 to 3.
  • Example 42 Using a one-piece knitted fabric (knitting gauge / 28 GG, flat knitting) made of copper ammonia cellulose fiber prepared by a conventional method, the same cross-linking reaction treatment as in Example 42 was performed.
  • the present invention is excellent in process passability and fiber physical properties, has high gloss, exhibits high color development and excellent color when dyed with a disperse dye, and is excellent in the same bath dyeing with polyester fiber. It is intended to provide a cellulose fiber exhibiting the same color.
  • Cellulose i As a 100% woven or knitted fabric, or as a woven or knitted fabric mixed with disperse dye dyeable fiber, especially polyester fiber, it is applied to the garment field such as the inner field, outer field, sports clothing field and lining field. Extremely useful.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Abstract

Cette fibre cellulosique contient de 1 à 40 % en poids de particules fines d'un polymère pourvu de 20 à 95 % en poids de motifs répétitifs ayant un noyau aromatique. Ce polymère est préparé à partir d'un composé ayant un noyau aromatique ou un atome de carbone adjacent au noyau aromatique ayant au moins une liaison ester et/ou éther. L'évacuation du colorant par dispersion à chaud par la fibre est égale ou supérieure à 70 %. Cette fibre cellulosique, qui fait montre d'une remarquable aptitude à tenir la coloration avec un seul bain, se colorant en une seule étape avec une fibre polyester, est dotée d'une transparence et d'une brillance remarquables ainsi que de caractéristiques de couleurs profondes et est également pourvue de propriétés de transfert et de qualités mécaniques excellentes.
PCT/JP1998/002729 1997-06-18 1998-06-18 Fibre cellulosique apte a la teinture par colorant a dispersion WO1998058104A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/161082 1997-06-18
JP16108297 1997-06-18

Publications (1)

Publication Number Publication Date
WO1998058104A1 true WO1998058104A1 (fr) 1998-12-23

Family

ID=15728288

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/002729 WO1998058104A1 (fr) 1997-06-18 1998-06-18 Fibre cellulosique apte a la teinture par colorant a dispersion

Country Status (1)

Country Link
WO (1) WO1998058104A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018178303A1 (fr) * 2017-03-31 2018-10-04 Innovia Films Ltd Fibre comprenant des fibres composites de cellulose et d'acétate de cellulose
CN115652474A (zh) * 2022-09-28 2023-01-31 清华大学 由酰胺酸共聚物制备酰亚胺共聚物的纤维的方法和由其制备的纤维

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0874118A (ja) * 1994-06-29 1996-03-19 Kuraray Co Ltd 分散染料に可染性の再生セルロース繊維及びその製造方法
JPH08170219A (ja) * 1994-12-16 1996-07-02 Kuraray Co Ltd 分散染料による内外層染色差のないレーヨン・ケーク糸
JPH0978336A (ja) * 1995-09-05 1997-03-25 Kuraray Co Ltd 分散染料に可染性の再生又は溶剤紡糸セルロース繊維および該繊維を含む繊維製品

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0874118A (ja) * 1994-06-29 1996-03-19 Kuraray Co Ltd 分散染料に可染性の再生セルロース繊維及びその製造方法
JPH08170219A (ja) * 1994-12-16 1996-07-02 Kuraray Co Ltd 分散染料による内外層染色差のないレーヨン・ケーク糸
JPH0978336A (ja) * 1995-09-05 1997-03-25 Kuraray Co Ltd 分散染料に可染性の再生又は溶剤紡糸セルロース繊維および該繊維を含む繊維製品

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018178303A1 (fr) * 2017-03-31 2018-10-04 Innovia Films Ltd Fibre comprenant des fibres composites de cellulose et d'acétate de cellulose
CN115652474A (zh) * 2022-09-28 2023-01-31 清华大学 由酰胺酸共聚物制备酰亚胺共聚物的纤维的方法和由其制备的纤维

Similar Documents

Publication Publication Date Title
EP0080099B1 (fr) Fibres synthétiques à surface irrégulière et procédé pour leur obtention
KR20140053966A (ko) 개질된 나노입자, 그의 제조, 및 섬유질 기재의 양이온성 염색성을 개선하기 위한 용도
WO1995023882A1 (fr) Fibre de cellulose regeneree pouvant etre teinte avec un colorant dispersable et produit textile contenant cette fibre
JPS5831113A (ja) 吸水性アクリル繊維
KR20060111351A (ko) 저온 가염 수축성 아크릴 섬유
WO1998058104A1 (fr) Fibre cellulosique apte a la teinture par colorant a dispersion
JP2000038492A (ja) 分散染料可染用のラテックス
US4999245A (en) Multi-layered conjugated acrylic fibers and the method for their production
JPH1181033A (ja) 分散染料可染性セルロース繊維およびその製造方法ならびに繊維製品
JP2001049519A (ja) カチオン染料可染セルロース繊維
JP2008013877A (ja) 染色性に優れたアクリル系合成繊維
JP3466339B2 (ja) 分散染料に可染性の再生又は溶剤紡糸セルロース繊維および該繊維を含む繊維製品
JP2989751B2 (ja) ポリエステル繊維と再生セルロ−ス繊維からなる繊維製品およびその染色方法
JP2014084535A (ja) 染色機能を増強した天然タンパク質繊維製品及びその製造方法
JP2843519B2 (ja) 分散染料に可染性の再生セルロース繊維及びその製造方法
JP4338574B2 (ja) 着色吸放湿発熱繊維及び同混紡糸の製造方法
JPH11217722A (ja) 分散染料可染用のラテックス
JP2005314841A (ja) 染色及び抜染性が改善されたアクリル系合成繊維
JP2837408B2 (ja) アクリル系繊維の処理方法
JP2005336631A (ja) 着色混紡糸の製造方法
JP3626561B2 (ja) 分散染色性改良剤
JP2908046B2 (ja) 抗ピリング性アクリル系繊維及びその製造方法
JPH11217721A (ja) 分散染料可染用ラテックス
JP3452691B2 (ja) 耐候性に優れた難燃アクリル系合成繊維
JP2004256936A (ja) 高難燃性アクリル系繊維の製造法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP KR RU TR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase