CN100412241C - Acrylic shrinkable fiber and method for production thereof - Google Patents
Acrylic shrinkable fiber and method for production thereof Download PDFInfo
- Publication number
- CN100412241C CN100412241C CNB2004800376419A CN200480037641A CN100412241C CN 100412241 C CN100412241 C CN 100412241C CN B2004800376419 A CNB2004800376419 A CN B2004800376419A CN 200480037641 A CN200480037641 A CN 200480037641A CN 100412241 C CN100412241 C CN 100412241C
- Authority
- CN
- China
- Prior art keywords
- polymer
- weight
- shrinkable fiber
- dyeing
- acrylic shrinkable
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/14—Dyeability
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2904—Staple length fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
Abstract
An object of the present invention is to provide a dyeable acrylic shrinkable fiber that only slightly shrinks when dyed and has a high shrinkage percentage even after dyeing. By spinning an incompatible spinning solution, the above object can be achieved, and a dyeable acrylic shrinkable fiber that only slightly shrinks when dyed and has a high shrinkage percentage even after dyeing can be provided.
Description
Technical field
Even the present invention relates to a kind of stainable acrylic compounds high-shrinkage fibre and manufacture method that after dyeing, also can have high shrinkage.
Background technology
In the past, acrylic fiber had the same feel of animal hair, was used to owing to this feature in the lint commodity such as toy, dress material.Wherein,, see in appearance in order to make it to have the outward appearance of lint sense, natural style, by high shrinkage constitute fine hair part, to constitute the example of pin hair part by non-high shrinkage a lot.In the lint cloth and silk, owing to require appearance characteristics, high shrinkage also requires various tones, but only there is the high shrinkage that only limits at the painted tone of spinning process in high shrinkage.
Acrylic shrinkable fiber of the present invention is shunk by dry heat treatment in the tentering operation of flocking processing (lint processing) through behind the dyeing process.Before this, once obtained to belong to the copolymer that unsaturated monomer 0～10 weight % constitutes and had the more vinyl cyanide synthetic fiber of highly shrinkable (spy opens clear 60-110911 communique) by acrylonitrile 30～58 weight %, vinylidene chloride and vinyl chloride 70～42 weight % and the ethene more than a kind or a kind, but the inventor's etc. opinion is, above-mentioned high shrinkage shrinks when dyeing more than 70 ℃ or 70 ℃, bonding agent is adhered at the lint back side that adds man-hour in flocking, can not produce big contraction because of the heat of the tentering operation of drying.In addition,, can shrink, can not obtain sufficient dyeability by the heat of tentering operation though the dyeing of 70 ℃ of less thaies can suppress to shrink.
In order to improve low temperature dyeing, by by acrylonitrile (ア Network リ ロ ニ ト ニ Le) 40 weight % or more than the 40 weight % and vinylidene chloride and containing in polymer (I) 95～60 weight portions that monomer 20～60 weight % of sulfonic acid constitute mix by having polymer (II) 5～40 weight portions that high chromatic acrylonitrile 30～75 weight % and methyl acrylate 25～70 weight % constitute, obtain the high shrinkage (No. 2566890 communiques of patent) that can dye.Though this high shrinkage can suppress the shrinkage factor that dyes by the dyeability that improves under the low temperature, thereby obtains the high shrinkage more than dyeing after-contraction 20% or 20%, polymer (I) and polymer (II) mix.The inventor's etc. opinion is, polymer (I) and polymer (II) are when mixing, owing in fiber, exist continuously and have dyeability character that improves and the polymer (II) that reduces stable on heating character that makes under the low temperature, therefore, be difficult to clearly reflect the contraction behavior of fiber, and under low dyeing temperature, suppress the dyeing shrinkage factor.Shrink during dyeing when big, the shrinkage factor after the dyeing diminishes, and in addition, if shrink when dyeing, the packed density of the fiber in the dyeing machine diminishes, thereby produces shunting (バ イ パ ス), therefore becomes the reason of specking (dying the め spot).In addition, what produce when exist shrinking is crimped onto shortcomings such as being difficult to stretching in the glazing operation that flocking adds man-hour, thereby can not obtain having the outward appearance of expectation, the lint cloth and silk of feel.These problems also do not solve now, even the contraction when obtaining dyeing yet is little and also have the acrylic shrinkable fiber that can dye of high shrinkage after dyeing.
Summary of the invention
Therefore, the invention reside in and solve above-mentioned prior art problems, thereby even the contraction when obtaining dyeing is little and also have an acrylic shrinkable fiber that can dye of high shrinkage after dyeing.
What the inventor etc. furtherd investigate found that, by the non-spinning solution that mixes of spinning, and the acrylic shrinkable fiber that can dye of the shrinkage factor after can obtaining reducing to dye contraction and having high dyeing.
Promptly, the present invention relates to a kind of acrylic shrinkable fiber, this acrylic shrinkable fiber is the acrylic shrinkable fiber that can dye by the spinning solution manufacturing, described spinning solution is included in the polymeric compositions that has mixed 1～50 parts by weight polymer (B) in the polymer (A) of 50～99 weight portions, and polymer (A) and polymer (B) are immiscible, wherein, polymer (A) contains the monomer of halogen by 40～80 weight % acrylonitrile and 20～60 weight % and monomer that 0～5 weight % contains sulfonic acid constitutes, polymer (B) by 5～70 weight % acrylonitrile and 20～94 weight % other can copolymerization monomer and the monomer that 1～40 weight % contains sulfonic acid constitute.
In the aforesaid propylene acids high shrinkage other can copolymerization the monomer preferred acrylate.
Spinning solution in the aforesaid propylene acids high shrinkage preferably is separated into the above particle shape of 0.1～30 μ m.
In aforesaid propylene acids high shrinkage, preferred dyeing shrinkage factor below 80 ℃ or 80 ℃ is below 10% or 10% and the shrinkage factor after the dyeing is more than 20% or 20%.
In aforesaid propylene acids high shrinkage, preferred relative saturation value more than 60 ℃ or 60 ℃ is more than 0.1 or 0.1, and the relative saturation value more than 70 ℃ or 70 ℃ is more than 0.8 or 0.8.
In the manufacture method of aforesaid propylene acids high shrinkage, preferably carry out 1～20% relaxation processes.
The polymer (A) that uses when making acrylic shrinkable fiber of the present invention is to contain acrylonitrile 40～80 weight % and contain monomer 20～60 weight % of halogen and the polymer that contains monomer 0～5 weight % of sulfonic acid.
In above-mentioned polymer (A), preferably use the acrylonitrile of 40～80 weight %, but acrylonitrile contain quantity not sufficient 40 weight % the time, the heat resistance step-down of the fiber that obtains.In addition, when the content of acrylonitrile surpassed 80 weight %, heat resistance uprised, and can not obtain sufficient dyeability, shrinkage factor.
In polymer of the present invention (A), the said monomer that contains halogen, preferred vinyl chloride, vinylidene chloride, bromine ethene, inclined to one side bromine ethene etc. are the vinyl halides of representative and meta-halo ethylene class etc., can use separately or mix more than 2 kinds or 2 kinds and use.This contains monomer preferred 20～60 weight % of use in polymer (A) of halogen.When surpassing 60 weight %, hydrophobicity uprises, and can not obtain sufficient dyeability.In addition, during less than 20 weight %, fiber becomes rough (Ga I つ I), and the sense of touch variation.
In polymer of the present invention (A), the said monomer that contains sulfonic acid, preferred allyl sulphonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid or their metallic salt and amine salt class etc. can be used separately or mix more than 2 kinds or 2 kinds and be used.In polymer of the present invention (A), preferably use the monomer that contains sulfonic acid of 0～5 weight % content, when surpassing 5 weight %, in fiber, produce space or deadlocked, intensity reduces.
The polymer (B) that uses when making acrylic shrinkable fiber of the present invention be contain the acrylonitrile of 5～70 weight % and 20～94 weight % other can copolymerization monomer and the polymer of monomers that 1～40 weight % contains sulfonic acid.
In above-mentioned polymer (B), preferably use the acrylonitrile of 5～70 weight %.When surpassing 70 weight %, heat resistance uprises, and can not obtain sufficient dyeability, shrinkage factor.
In polymer of the present invention (B), as other can copolymerization monomer, preferred acrylic or methacrylic acid and their lower alkyl esters, N or N, aminoalkyl ester or ethylene oxidic ester that the N-alkyl replaces, acrylamide or Methacrylamide and their N or N, N-alkyl substituent, acrylic acid, methacrylic acid or itaconic acid etc. are the vinyl monomer that contains carboxyl of representative and their sodium, anionic property such as potassium or ammonium salt vinyl monomer, with the cationic vinyl monomer headed by the quaternary ammonium Arrcostab (4 Gradeization ア ミ ノ ア Le キ Le エ ス テ Le) of acrylic or methacrylic acid, the lower alkyl ether that perhaps contains vinyl, vinyl acetate is the low-carbon carboxylate that contains vinyl of representative, vinyl chloride, vinylidene chloride, bromine ethene, inclined to one side bromine ethene etc. is the vinyl halides of representative and the inclined to one side vinyl of halo, be more preferably styrene etc., these monomers can use separately or mix more than 2 kinds or 2 kinds and use.Other can copolymerization preferred 20～94 weight % of monomer.During less than 20 weight %, heat resistance uprises, and can not obtain sufficient dyeability.Particularly, on this aspect of dyeability, as other can copolymerization monomer, preferably use acrylate.As acrylate, preferred methyl acrylate, ethyl acrylate, butyl acrylate etc., these monomers can use separately or mix more than 2 kinds or 2 kinds and use.
In polymer (B), the said monomer that contains sulfonic acid, preferred allyl sulphonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid or their metallic salt and amine salt class etc. can be used separately or mix more than 2 kinds or 2 kinds and be used.In polymer of the present invention (B), contain preferred 1～40 weight % of monomer of sulfonic acid, when surpassing 40 weight %, in fiber, produce space or deadlocked, intensity reduces.
For dyeability is improved, 0.1～10 weight portion of the total content preferred polymers (A) that contains sulfonic monomer in polymer that contains in the fiber of acrylic shrinkable fiber of the present invention (A) and the polymer (B) and the monomer total amount of polymer (B) is more preferably 0.2～5 weight portion.During less than 0.1 weight portion, can not obtain sufficient dyeability, when surpassing 10 weight portions, produce space or deadlocked in fiber, intensity reduces, and is therefore not preferred.In addition, be 10 weight % or more than the 10 weight %, polymer (A) and polymer (B) have immiscible tendency by the monomer that contains sulfonic acid that contains polymer (B).
Polymer of the present invention (A), polymer (B) can use compound known, for example peroxide compounds, azo compound or various redox compounds obtain by common vinyl polymerization methods such as emulsion polymerisation, suspension polymerization, polymerisation in solutions as initator.
Polymer of the present invention (A), polymer (B) are dissolved in organic solvent, and for example acetone, acetonitrile, dimethyl formamide, dimethylacetylamide, methyl-sulfoxide or inorganic solvent are for example made spinning solution in zinc chloride, nitric acid, the rhodanate.Only otherwise spinning is brought obstacle, can also in this spinning solution, use titanium oxide or be used for inorganic and/or organic pigment such as painted pigment, to effective stabilizer such as antirust, coloring spinning, weatherabilities etc.
The mixed proportion of polymer of the present invention (A) and polymer (B) when polymer (B) less than 1 weight %, can not obtain sufficient dyeability, when surpassing 50 weight %, produces space or deadlocked in fiber, and intensity, dyeability reduce, and be therefore not preferred.
What is called of the present invention is immiscible, and preferred spinning solution is separated into the granular state of 0.1～30 μ m, is more preferably the granular state that is separated into 6～12 μ m.The phase-separated state of less than 0.1 μ m, the character of polymer (B) is reflected that the shrinkage factor during dyeing uprises, and surpasses the phase-separated state of 30 μ m, produces space or deadlocked in fiber, intensity, dyeability reduce, and be therefore not preferred.
Acrylic shrinkable fiber of the present invention can think that the polymer of taking to exist ratio high in the fiber (A) is the sea, exists the low polymer of ratio (B) to be the island structure on island owing to be made of polymer (A) and the immiscible spinning solution of polymer (B).Therefore, because existence continuously in fiber of polymer (B).Though have the low character of heat resistance, the contraction behavior do not had big influence.Therefore, compare with the fiber that constitutes by the spinning solution that mixes, can reduce the dyeing shrinkage factor by the fiber that immiscible spinning solution constitutes.In addition, because the shrinkage factor of high shrinkage is made up of resin and the spinning process decision, therefore, when contraction was big in dyeing process, the shrinkage factor in flocking manufacturing procedure thereafter diminished.Therefore, by reducing the shrinkage factor that dyes, the shrinkage factor after more XXL dyes.
In addition, in the present invention, by contain vinyl chloride in polymer (A), the intermiscibility of polymer (A) and polymer (B) reduces, and thus, can promote immiscibleization.
Said dyeing shrinkage factor among the present invention is that fiber produces the index of great contraction when dyeing, can as described belowly try to achieve.Mensuration is handled the length L of the fiber after 60 minutes with the fiber of length L o in the water-bath of arbitrary temp, and tries to achieve according to following formula.
Dyeing shrinkage factor (%)=((Lo-L)/Lo) * 100
Shrinkage factor among the present invention after the said dyeing is that the fiber after the dyeing produces the index of great contraction in the tentering operation, can as described belowly try to achieve.The fiber that uses the length L do after equal oven heat will dye is measured the length L d of fiber after handling 5 minutes under 130 ℃, and tries to achieve according to following formula.
Shrinkage factor after the dyeing (%)=((Ldo-Ld)/Ldo) * 100
The manufacture method of acrylic shrinkable fiber of the present invention is, spins from nozzle with common wet type or dry spinning method, stretches, drying.In addition, optionally also can further stretch, heat treatment.In addition, the fiber that obtains can be stretched 1.3～4.0 times down at 70～140 ℃, obtain high shrinkage.
When the dyeing shrinkage factor of acrylic shrinkable fiber of the present invention is big,, preferably in fiber manufacturing process, carry out the relaxation processes more than 1% or 1% in order to suppress to shrink.Relaxation processes is preferably carried out under damp and hot or xeothermic 70 ℃～140 ℃.Though can suppress the shrinkage factor that dyes by raising treatment temperature, increase mitigation rate, but because the shrinkage factor of the relaxation processes under the superfluous condition after also can suppressing to dye, therefore, preferably under the temperature about 110 ℃, carry out 20% or 20% following relaxation processes.
Acrylic shrinkable fiber of the present invention shrinks in the tentering operation of flocking processing.Preferred xeothermic 110～150 ℃ of tentering operation is because normally about 130 ℃, therefore, the shrinkage factor after the dyeing is measured under xeothermic 130 ℃, 5 minutes condition.
If acrylic shrinkable fiber dyeing temperature of the present invention uprises, the shrinkage factor that then dyes uprises.Therefore, when dyeing temperature surpasses 90 ℃, because the dyeing shrinkage factor becomes big, so not preferred.In addition, if shrink greatly in when dyeing, remaining shrinkage factor diminishes, and therefore, being difficult to make the shrinkage factor after the dyeing is more than 20% or 20%.In addition, the dyeing shrinkage factor surpasses at 10% o'clock, and the packed density of the fiber in the dyeing machine diminishes, thereby produces bypass, therefore becomes the reason of specking easily.In addition, what produce when exist shrinking is crimped onto shortcomings such as being difficult to stretching in the glazing operation that flocking adds man-hour, thereby can not obtain having the outward appearance of expectation, the lint cloth and silk of feel.
During shrinkage factor less than 20% after the dyeing of acrylic shrinkable fiber of the present invention, when being processed into the lint cloth and silk, owing to the length difference with non-contraction raw cotton diminishes, therefore, length difference can not be given prominence to, thereby the lint cloth and silk of the appearance characteristics of natural style or intention can not be obtained having.
The index that said relative saturation value is the colouring power of fiber among the present invention, the Malachite Green that uses supersaturation amount coloured fibre 60 minutes under temperature is arbitrarily obtained saturated dyeing amount, and is obtained the relative saturation value by saturated dyeing amount.Saturated dyeing amount, relative saturation value are obtained by following formula.
Saturated dyeing amount=((Ao-A)/Ao) * 2.5)
A: the absorbance of the dye liquor after the dyeing (618nm)
Ao: the absorbance (618nm) of the dye liquor before the dyeing
Relative saturation value=saturated dyeing amount * 400/463
Acrylic shrinkable fiber of the present invention can be 0.1 or 0.1 above time dyeing light color in the relative saturation value.
In addition,, can be coloured to light color and arrive heavy colour because the relative saturation value is 0.8 or 0.8 when above, in addition black, therefore, more than the relative saturation value preferred 0.8 or 0.8.
Below, before narration embodiment, the method for evaluating performance etc. for the fiber of test is described in detail.
(1) phase-separated state
Phase-separated state is to use phase contrast microscope (ア リ オ テ Network ノ Co., Ltd. make ANS30) to observe with the spinning solution of mixed basis rubber cement and mixed polymer arbitrarily, measure the grain system that 10 places separate the mixed polymer that granulates randomly, estimate with its mean value.
(2) plush trial-production
After retractable fibre and the damping of noncontractile fiber mixed cotton, make the combing machine for fur wool top through opener, carding machine.Then, carry out sliver braiding, lint is cut off and made lint length, with the esters of acrylic acid bonding agent back side is carried out at the back side of lint and be coated with neatly for behind the certain-length with shearing machine with the plush braiding machine.Then, dry bonding agent is 5 minutes under 130 ℃, and retractable fibre is shunk.Then, carry out glazing processing and cropping, make plush.
(3) ocular estimate of plush
For length difference lint cloth and silk of in (2), making, viewpoint from vision and sense organ, according to 4 following grade evaluations the obvious degree of the appearance characteristics of the length difference of plush part and undercoat suede part is carried out the evaluation of sense, estimate according to following benchmark.
◎: in the lint cloth and silk of length difference, have the very tangible appearance characteristics of length difference of plush part and undercoat suede part.
Zero: in the lint cloth and silk of length difference, have the tangible appearance characteristics of length difference of plush part and undercoat suede part.
△: in the lint cloth and silk of length difference, the length difference of plush part and undercoat suede part is not too obvious.
*: in the lint cloth and silk of length difference, almost do not find the length difference of plush part and undercoat suede part.
Below, narration embodiment, unless otherwise specified, the part among the embodiment is the meaning of weight portion.
Embodiment
(Production Example 1)
In the withstand voltage polymerizing reactor of internal volume 20L, drop into 200 parts of ion exchange waters, 0.9 part of lauryl sodium sulfate, 0.43 part of sulfurous acid, 0.22 part of sodium hydrogensulfite, 0.001 part of ferric sulfate, 4.9 parts of acrylonitrile (below be designated as AN), 52.5 parts of vinyl chloride (below be designated as VC), carry out the nitrogen displacement.Temperature in the polymerization machine is adjusted into 50 ℃, drops into 0.035 part of ammonium persulfate as initator, initiated polymerization.Midway, Yi Bian append 42.1 parts of AN, 0.5 part of Sodium styrene sulfonate (below be designated as 3S), 0.23 part of ammonium persulfate, Yi Bian polymerization 5 hours 10 minutes.Then, reclaim unreacted VC, take out latex, saltout, heat treatment, filtration, washing, dehydration, drying, obtain polymer 1 from the polymerization machine.
Then, in the withstand voltage polymerizing reactor of internal volume 5L, drop into 187 parts of acetone, 47 parts of water, 40 parts of AN, 45 parts of methyl acrylates (below be designated as MA), 15 parts of 2-acrylamido-2-methyl propane sulfonic acid sodium (below be designated as SAM), carry out the nitrogen displacement.Temperature in the polymerization machine is adjusted into 65 ℃, drops into 0.5 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) is as initator, initiated polymerization.Midway, two (ア ゾ PVC ス) limit polymerizations of 1.0 parts of azos 2 hours are appended on the limit, are warmed up to 70 ℃ then, polymerization 2 hours, and obtaining polymer concentration is the solution of the polymer 2 of 30 weight %.Adding acetone and making polymer 1 is 30 weight %, in the solution of dissolved polymers 1, the solution of mixed polymer 2 and to make the weight ratio of polymer be polymer 1: polymer 2=9: 1 ratio, with the solution that obtains as spinning solution.With the spinning solution that obtains spinning head by 0.08mm φ, 8500 holes, be sprayed onto in 25 ℃, the aqueous acetone solution of 30 weight %, in 25 ℃, 20 weight % aqueous acetone solutions, be drawn into 2.0 times again after, 60 ℃ of washings down.Then, dry under 130 ℃, under 105 ℃, be drawn into 1.8 times again, obtain the drawn yarn of 4.4dtex.
Then, to the high shrinkage that obtains give curl and be cut into 32mm after, use Maxilon RedGRL (manufacturing of チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ Co., Ltd.) dyestuff of 0.2%omf and the dyeing assistant of ウ Le ト ラ MT#100 (manufacturing of ミ テ ジ マ KCC) 0.5g/L, dyeed 60 minutes down at 60 ℃, 70 ℃, 80 ℃.With the fiber of 70 weight % dyeing and 30 weight % " カ ネ カ ロ Application (registration mark) " RCL12.2dtex, 44mm (Kanegafuchi Chemical Industry Co., Ltd's manufacturings) mixed cotton, manufacturing plush as non-contraction raw cotton.At this moment, during cropping after sliver braiding, lint length is cut into 15mm, the lint length after the glazing processing is cut into 18mm, obtain plush.
(Production Example 2)
The drawn yarn that Production Example 1 is obtained is carried out 5% relaxation processes under 110 ℃.
In addition, use the fiber that will carry out relaxation processes to make plush with the same method of Production Example 1.
(Production Example 3)
In the withstand voltage polymerizing reactor of internal volume 20L, drop into 200 parts of ion exchange waters, 1.1 parts of lauryl sodium sulfate, 0.13 part of sulfurous acid, 0.17 part of niter cake, 0.002 part of ferric sulfate, 10.7 parts of acrylonitrile, 4.4 parts of vinylidene chlorides, carry out the nitrogen displacement.Temperature in the polymerization machine is adjusted into 55 ℃, drops into 0.012 part of ammonium persulfate, the beginning polymerization as initator.Midway, Yi Bian append 42.7 parts of acrylonitrile, 41.0 parts of vinylidene chlorides, 1.2 parts of Sodium styrene sulfonate, 0.135 part of ammonium persulfate, Yi Bian polymerization 6 hours 10 minutes.Then, take out latex, saltout, heat treatment, filtration, washing, dehydration, drying, obtain polymer 3 from the polymerization machine.Adding acetone and making polymer 3 is 30 weight %, and in the solution of dissolved polymers 3, mixing the solution of the polymer 2 that Production Example 1 makes and making the weight ratio of polymer is polymer 3: polymer 2=9: 1 ratio, with the solution that obtains as spinning solution.With the spinning solution that obtains spinning head by 0.08mm φ, 8500 holes, be sprayed onto in 25 ℃, the aqueous acetone solution of 30 weight %, in 25 ℃, 20 weight % aqueous acetone solutions, be drawn into 2.0 times again after, 60 ℃ of washings down.Then, 130 ℃ down dry, under 105 ℃, be drawn into 1.8 times again, and the drawn yarn of the 4.4dtex that obtains is carried out 5% relaxation processes under 110 ℃.Re-use the fiber that will carry out relaxation processes and make plush with the same method of Production Example 1.
(Production Example 4)
In the withstand voltage polymerizing reactor of internal volume 5L, drop into 187 parts of acetone, 47 parts of water, 40 parts of AN, 55 parts of MA, 5 parts of SAM, and the polymer 2 same methods of employing and Production Example 1 carry out polymerization, obtain the solution of polymer 4.Adding the polymer 1 that acetone obtains Production Example 1 is 30 weight %, in the solution of dissolved polymers 1, the solution of mixed polymer 4 and to make the weight ratio of polymer be polymer 1: polymer 4=7: 3 ratio, with the solution that obtains as spinning solution.Use the spinning solution that obtains with the same method spinning of Production Example 1, obtain drawn yarn.Use with the same method of Production Example 1 drawn yarn that obtains is made plush.
(Production Example 5)
The drawn yarn that Production Example 4 is obtained is carried out 5% relaxation processes under 110 ℃.In addition, use the fiber that will carry out relaxation processes to make plush with the same method of Production Example 1.
(Production Example 6)
The polymer 3 that adding acetone is made Production Example 3 is 30 weight %, the solution that in the solution of dissolved polymers 3, mixes the polymer 4 of Production Example 4 making, and the weight ratio that makes polymer is a polymer 3: polymer 4=7: 3 ratio, with the solution that obtains as spinning solution.Use with the same method of Production Example 3 and the spinning solution that obtains is made into the fiber that has carried out relaxation processes.Then, use with the same method of Production Example 1 and use the fiber that has carried out relaxation processes to make plush.
(Production Example 7)
In the withstand voltage polymerizing reactor of internal volume 5L, drop into 187 parts of acetone, 47 parts of water, 30 parts of AN, 55 parts of MA, 15 parts of SAM, and the polymer 2 same methods of employing and Production Example 1 carry out polymerization, obtain the solution of polymer 5.Adding the polymer 1 that acetone obtains Production Example 1 is 30 weight %, in the solution of dissolved polymers 1, the solution of mixed polymer 5 and to make the weight ratio of polymer be polymer 1: polymer 5=9: 1 ratio, with the solution that obtains as spinning solution.Use the spinning solution that obtains with the same method spinning of Production Example 1, obtain drawn yarn.Use with the same method of Production Example 1 drawn yarn that obtains is made plush.
(Production Example 8)
The drawn yarn that Production Example 7 is obtained is carried out 5% relaxation processes under 110 ℃.
In addition, use the fiber that will carry out relaxation processes to make plush with the same method of Production Example 1.
(Production Example 9)
In the withstand voltage polymerizing reactor of internal volume 5L, drop into 187 parts of acetone, 47 parts of water, 60 parts of AN, 25 parts of MA, 15 parts of SAM, and the polymer 2 same methods of employing and Production Example 1 carry out polymerization, obtain the solution of polymer 6.Adding the polymer 1 that acetone obtains Production Example 1 is 30 weight %, in the solution of dissolved polymers 1, the solution of mixed polymer 6 and to make the weight ratio of polymer be polymer 1: polymer 6=9: 1 ratio, with the solution that obtains as spinning solution.Use the spinning solution that obtains with the same method spinning of Production Example 1, obtain drawn yarn.Use with the same method of Production Example 1 drawn yarn that obtains is made plush.
(Production Example 10)
The drawn yarn that Production Example 9 is obtained is carried out 5% relaxation processes under 110 ℃.
In addition, use the fiber that will carry out relaxation processes to make plush with the same method of Production Example 1.
(Production Example 11)
In the withstand voltage polymerizing reactor of internal volume 5L, drop into 140 parts of acetone, 94 parts of water, 10 parts of AN, 60 parts of methyl acrylates (below, be designated as MA), 30 parts of SAM, and the polymer 2 same methods of employing and Production Example 1 carry out polymerization, obtain the solution of polymer 8.Adding the polymer 1 that acetone obtains Production Example 1 is 30 weight %, in the solution of dissolved polymers 1, the solution of mixed polymer 7 and to make the weight ratio of polymer be polymer 1: polymer 7=96: 4 ratio, with the solution that obtains as spinning solution.Use the spinning solution that obtains with the same method spinning of Production Example 1, obtain drawn yarn.Use with the same method of Production Example 1 drawn yarn that obtains is made plush.
(Production Example 12)
The drawn yarn that Production Example 11 is obtained is carried out 5% relaxation processes under 110 ℃.
In addition, use the fiber that will carry out relaxation processes to make plush with the same method of Production Example 1.
(Production Example 13)
In the withstand voltage polymerizing reactor of internal volume 5L, drop into 187 parts of acetone, 47 parts of water, 50 parts of AN, 35 parts of ethyl acrylates (below, be designated as EA), 15 parts of SAM, and the polymer 2 same methods of employing and Production Example 1 carry out polymerization, obtain the solution of polymer 8.Adding the polymer 1 that acetone obtains Production Example 1 is 30 weight %, in the solution of dissolved polymers 1, the solution of mixed polymer 8 and to make the weight ratio of polymer be polymer 1: polymer 8=9: 1 ratio, with the solution that obtains as spinning solution.Use the spinning solution that obtains with the same method spinning of Production Example 1, obtain drawn yarn.Use with the same method of Production Example 1 drawn yarn that obtains is made plush.
(Production Example 14)
The drawn yarn that Production Example 13 is obtained is carried out 5% relaxation processes under 110 ℃.
In addition, use the fiber that will carry out relaxation processes to make plush with the same method of Production Example 1.
(Production Example 15)
In the withstand voltage polymerizing reactor of internal volume 5L, drop into 187 parts of acetone, 47 parts of water, 50 parts of AN, 35 parts of methyl methacrylates (below, be designated as MMA), 15 parts of SAM, and the polymer 2 same methods of employing and Production Example 1 carry out polymerization, obtain the solution of polymer 9.Adding the polymer 1 that acetone obtains Production Example 1 is 30 weight %, in the solution of dissolved polymers 1, the solution of mixed polymer 9 and to make the weight ratio of polymer be polymer 1: polymer 9=9: 1 ratio, with the solution that obtains as spinning solution.Use the spinning solution that obtains with the same method spinning of Production Example 1, obtain drawn yarn.Use with the same method of Production Example 1 drawn yarn that obtains is made plush.
(Production Example 16)
The drawn yarn that Production Example 15 is obtained is carried out 5% relaxation processes under 110 ℃.
In addition, use the fiber that will carry out relaxation processes to make plush with the same method of Production Example 1.
(Production Example 17)
In the withstand voltage polymerizing reactor of internal volume 5L, drop into 187 parts of acetone, 47 parts of water, 50 parts of AN, 25 parts of MA, 10 parts of vinylidene chlorides (below be designated as VD), 15 parts of SAM, and the polymer 2 same methods of employing and Production Example 1 carry out polymerization, obtain the solution of polymer 10.Adding the polymer 1 that acetone obtains Production Example 1 is 30 weight %, in the solution of dissolved polymers 1, the solution of mixed polymer 10 and to make the weight ratio of polymer be polymer 1: polymer 10=9: 1 ratio, with the solution that obtains as spinning solution.Use the spinning solution that obtains with the same method spinning of Production Example 1, obtain drawn yarn.Use with the same method of Production Example 1 drawn yarn that obtains is made plush.
(Production Example 18)
The drawn yarn that Production Example 17 is obtained is carried out 5% relaxation processes under 110 ℃.
In addition, use the fiber that will carry out relaxation processes to make plush with the same method of Production Example 1.
The manufacture method of the fiber that Production Example 1～18 is obtained is shown in table 1.
(embodiment 1～16)
The high shrinkage that Production Example 1,2,4,5,7～18 is obtained dyeed 60 minutes down at 60 ℃, 70 ℃, 80 ℃.The value of the shrinkage factor after the relative saturation value of this moment, dyeing shrinkage factor, the dyeing is shown in table 2.When spinning solution is immiscible, when 60～80 ℃ dyeing, the dyeing shrinkage factor is below 10% or 10%, shrinkage factor after the dyeing is more than 20% or 20%, dyeing more than 60 ℃ or 60 ℃, the relative saturation value is more than 0.1 or 0.1, and the relative saturation value under the temperature more than 70 ℃ or 70 ℃ is more than 0.8 or 0.8.
In addition, carried out the ocular estimate of the plush that obtains in the Production Example 1,2,4,5,7～18.It the results are shown in table 2.As long as the shrinkage factor after the dyeing is more than 20% or 20%, then can obtain having the plush of plush part and the undercoat suede tangible appearance characteristics of length difference partly.
(comparative example 1,2)
The high shrinkage that Production Example 3,6 is obtained dyeed 60 minutes down at 60 ℃, 70 ℃, 80 ℃.The value of the shrinkage factor after the relative saturation value of this moment, dyeing shrinkage factor, the dyeing is shown in table 2.
When spinning solution mixes, 70～80 ℃ dyeing, being difficult to make the dyeing shrinkage factor is below 10% or 10%.
In addition, carried out the ocular estimate of the plush that Production Example 3,6 obtains.It the results are shown in table 2.Shrinkage factor after the dyeing is 20% or 20% when following, does not almost find plush part and undercoat suede length difference partly.
Industrial applicibility
Acrylic shrinkable fiber of the present invention, the contraction during dyeing is little, even also have height after dyeing Shrinkage factor, its result can be wide at dress material, toy (fabric doll etc.) and indoor decoration In the field, the commodity that design makes new advances.
Claims (14)
1. acrylic shrinkable fiber, this acrylic shrinkable fiber is the acrylic shrinkable fiber that can dye by the spinning solution manufacturing, described spinning solution comprises and mixes the polymeric compositions that 1～50 parts by weight polymer (B) forms in the polymer (A) of 50～99 weight portions, and polymer (A) and polymer (B) are immiscible, wherein, polymer (A) contains the monomer of halogen by 40～80 weight % acrylonitrile and 20～60 weight % and monomer that 0～5 weight % contains sulfonic acid constitutes, polymer (B) by 5～70 weight % acrylonitrile and 20～94 weight % other can copolymerization monomer and the monomer that 1～40 weight % contains sulfonic acid constitute.
2. according to the described acrylic shrinkable fiber of claim 1, wherein, the total content that contains sulfonic monomer in polymer (A) and the polymer (B) is 0.1～10 weight portion of the monomer total amount of polymer (A) and polymer (B).
3. according to the described acrylic shrinkable fiber of claim 1, wherein, in above-mentioned polymer (B), other can copolymerization monomer be acrylate.
4. according to the described acrylic shrinkable fiber of claim 2, wherein, in above-mentioned polymer (B), other can copolymerization monomer be acrylate.
5. according to the described acrylic shrinkable fiber of claim 1, it is characterized in that above-mentioned spinning solution is separated into the particle shape of 0.1～30 μ m.
6. according to the described acrylic shrinkable fiber of claim 2, it is characterized in that above-mentioned spinning solution is separated into the particle shape of 0.1～30 μ m.
7. according to the described acrylic shrinkable fiber of claim 3, it is characterized in that above-mentioned spinning solution is separated into the particle shape of 0.1～30 μ m.
8. according to each described acrylic shrinkable fiber in the claim 1～7, it is characterized in that the dyeing shrinkage factor below 80 ℃ or 80 ℃ is below 10% or 10%.
9. according to each described acrylic shrinkable fiber in the claim 1～7, it is characterized in that after dyeing below 80 ℃ or 80 ℃, the shrinkage factor after carrying out 5 minutes dry heat treatment under 130 ℃ is more than 20% or 20%.
10. according to the described acrylic shrinkable fiber of claim 8, it is characterized in that after dyeing below 80 ℃ or 80 ℃, the shrinkage factor after carrying out 5 minutes dry heat treatment under 130 ℃ is more than 20% or 20%.
11., it is characterized in that when dyeing more than 60 ℃ or 60 ℃, the relative saturation value is more than 0.1 or 0.1, and the relative saturation value more than 70 ℃ or 70 ℃ is more than 0.8 or 0.8 according to each described acrylic shrinkable fiber in the claim 1～7.
12., it is characterized in that when dyeing more than 60 ℃ or 60 ℃, the relative saturation value is more than 0.1 or 0.1, and the relative saturation value more than 70 ℃ or 70 ℃ is more than 0.8 or 0.8 according to the described acrylic shrinkable fiber of claim 8.
13., it is characterized in that when dyeing more than 60 ℃ or 60 ℃, the relative saturation value is more than 0.1 or 0.1, and the relative saturation value more than 70 ℃ or 70 ℃ is more than 0.8 or 0.8 according to the described acrylic shrinkable fiber of claim 9.
14. make the method for each described acrylic shrinkable fiber in the claim 1～13, it is characterized in that, carry out 1～20% relaxation processes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003435851 | 2003-12-26 | ||
| JP435851/2003 | 2003-12-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1894449A CN1894449A (en) | 2007-01-10 |
| CN100412241C true CN100412241C (en) | 2008-08-20 |
Family
ID=34736647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800376419A Active CN100412241C (en) | 2003-12-26 | 2004-12-24 | Acrylic shrinkable fiber and method for production thereof |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20070098982A1 (en) |
| EP (1) | EP1698718B1 (en) |
| JP (1) | JP4603486B2 (en) |
| KR (1) | KR101098809B1 (en) |
| CN (1) | CN100412241C (en) |
| AT (1) | ATE429530T1 (en) |
| DE (1) | DE602004020800D1 (en) |
| WO (1) | WO2005064050A1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2309102T3 (en) * | 2000-07-28 | 2008-12-16 | Kaneka Corporation | TEXTILE MATERIAL WITH STEELED HAIR. |
| US20040185222A1 (en) * | 2001-07-05 | 2004-09-23 | Minoru Kuroda | Pile cloth having animal hair style |
| US20040260034A1 (en) | 2003-06-19 | 2004-12-23 | Haile William Alston | Water-dispersible fibers and fibrous articles |
| US8513147B2 (en) | 2003-06-19 | 2013-08-20 | Eastman Chemical Company | Nonwovens produced from multicomponent fibers |
| US7892993B2 (en) | 2003-06-19 | 2011-02-22 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
| CN1890418B (en) * | 2003-12-26 | 2010-07-21 | 株式会社钟化 | Step pile fabric and process for producing the same |
| WO2006008990A1 (en) * | 2004-07-16 | 2006-01-26 | Kaneka Corporation | Acrylic shrinkable fiber and process for producing the same |
| WO2006051862A1 (en) * | 2004-11-12 | 2006-05-18 | Kaneka Corporation | Process for production of unleveled pile fabric |
| JP4745194B2 (en) * | 2006-10-19 | 2011-08-10 | 株式会社カネカ | Acrylic fiber and method for producing the same |
| US8512519B2 (en) | 2009-04-24 | 2013-08-20 | Eastman Chemical Company | Sulfopolyesters for paper strength and process |
| US9273417B2 (en) | 2010-10-21 | 2016-03-01 | Eastman Chemical Company | Wet-Laid process to produce a bound nonwoven article |
| US8840757B2 (en) | 2012-01-31 | 2014-09-23 | Eastman Chemical Company | Processes to produce short cut microfibers |
| WO2014046110A1 (en) * | 2012-09-24 | 2014-03-27 | 株式会社カネカ | Pile fabric and method for producing same |
| US9617685B2 (en) | 2013-04-19 | 2017-04-11 | Eastman Chemical Company | Process for making paper and nonwoven articles comprising synthetic microfiber binders |
| US9598802B2 (en) | 2013-12-17 | 2017-03-21 | Eastman Chemical Company | Ultrafiltration process for producing a sulfopolyester concentrate |
| US9605126B2 (en) | 2013-12-17 | 2017-03-28 | Eastman Chemical Company | Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion |
| CN105040151B (en) * | 2015-07-10 | 2017-08-04 | 东华大学 | A kind of polyacrylonitrile fibre of low temperature dyeing and preparation method thereof |
| CN105040150B (en) * | 2015-07-10 | 2017-03-22 | 东华大学 | Low temperature dyeable contractile polyacrylonitrile fibre and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383086A (en) * | 1979-06-02 | 1983-05-10 | Hoechst Aktiengesellschaft | Filaments and fibers of acrylonitrile copolymer mixtures |
| CN1143985A (en) * | 1994-01-26 | 1997-02-26 | 孟山都公司 | Fibre bundles including reversible crimp filaments having improved dyeability |
| JP2001303364A (en) * | 2000-04-24 | 2001-10-31 | Kanegafuchi Chem Ind Co Ltd | Acrylic synthetic yarn having excellent whiteness and dyeability |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2958670A (en) * | 1957-12-12 | 1960-11-01 | Du Pont | Compositions and fibers containing acrylonitrile polymer blends and method of making |
| US3963790A (en) * | 1972-08-09 | 1976-06-15 | Rhone-Poulenc-Textile | Non-inflammable filaments comprising acrylonitrile/vinylidene chloride copolymers |
| JPS5146857B2 (en) * | 1972-09-14 | 1976-12-11 | ||
| GB1517368A (en) * | 1974-11-15 | 1978-07-12 | Bayer Ag | Modacrylic filaments with colouristic properties |
| US4101621A (en) * | 1975-05-31 | 1978-07-18 | Kanebo, Ltd. | Method for producing flame resistant acrylic fibers |
| DE2554124C3 (en) * | 1975-12-02 | 1986-07-10 | Bayer Ag, 5090 Leverkusen | Process for the production of hydrophilic fibers and threads from acrylonitrile polymers |
| GB1549924A (en) * | 1976-11-03 | 1979-08-08 | Snia Viscosa | Polymer blends for making modacrylic fibres |
| US4301107A (en) * | 1978-08-30 | 1981-11-17 | American Cyanamid Company | Melt-spinning a plurality of acrylonitrile polymer fibers |
| FR2442901A1 (en) * | 1978-11-30 | 1980-06-27 | Rhone Poulenc Textile | DOUBLE CONSTITUENT ACRYLIC FIBERS |
| JPS6342911A (en) * | 1986-08-07 | 1988-02-24 | Kanebo Ltd | Production of modacrylic yarn of modified cross section |
| JP2566890B2 (en) * | 1987-08-17 | 1996-12-25 | 鐘紡株式会社 | Flame-retardant acrylic high shrink fiber |
| JP2566891B2 (en) * | 1987-08-24 | 1996-12-25 | 鐘紡株式会社 | Flame-retardant acrylic high shrink fiber |
| JPH06158422A (en) * | 1992-11-06 | 1994-06-07 | Kanebo Ltd | Flame-retardant acrylic fiber having high shrinkage |
| WO2000070133A1 (en) * | 1999-05-18 | 2000-11-23 | Kaneka Corporation | Hollow, shrinkable fiber for pile and method for production thereof and file product |
-
2004
- 2004-12-24 EP EP04808075A patent/EP1698718B1/en not_active Not-in-force
- 2004-12-24 US US10/583,182 patent/US20070098982A1/en not_active Abandoned
- 2004-12-24 CN CNB2004800376419A patent/CN100412241C/en active Active
- 2004-12-24 AT AT04808075T patent/ATE429530T1/en not_active IP Right Cessation
- 2004-12-24 JP JP2005516717A patent/JP4603486B2/en not_active Expired - Fee Related
- 2004-12-24 DE DE602004020800T patent/DE602004020800D1/en not_active Expired - Fee Related
- 2004-12-24 WO PCT/JP2004/019725 patent/WO2005064050A1/en not_active Application Discontinuation
-
2006
- 2006-06-15 KR KR1020067011818A patent/KR101098809B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383086A (en) * | 1979-06-02 | 1983-05-10 | Hoechst Aktiengesellschaft | Filaments and fibers of acrylonitrile copolymer mixtures |
| CN1143985A (en) * | 1994-01-26 | 1997-02-26 | 孟山都公司 | Fibre bundles including reversible crimp filaments having improved dyeability |
| JP2001303364A (en) * | 2000-04-24 | 2001-10-31 | Kanegafuchi Chem Ind Co Ltd | Acrylic synthetic yarn having excellent whiteness and dyeability |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2005064050A1 (en) | 2007-07-19 |
| KR20060118551A (en) | 2006-11-23 |
| KR101098809B1 (en) | 2011-12-26 |
| EP1698718A1 (en) | 2006-09-06 |
| WO2005064050A1 (en) | 2005-07-14 |
| CN1894449A (en) | 2007-01-10 |
| JP4603486B2 (en) | 2010-12-22 |
| EP1698718A4 (en) | 2008-03-19 |
| ATE429530T1 (en) | 2009-05-15 |
| EP1698718B1 (en) | 2009-04-22 |
| US20070098982A1 (en) | 2007-05-03 |
| DE602004020800D1 (en) | 2009-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100412241C (en) | Acrylic shrinkable fiber and method for production thereof | |
| CN100500958C (en) | Acrylic shrinkable fiber and process for producing the same | |
| JP4979175B2 (en) | Method for producing artificial hair fiber | |
| CN100415961C (en) | Acrylic shrinkable fiber | |
| CN109577021A (en) | A kind of good wig preparation method of simulated effect | |
| US3296341A (en) | Method for impregnating acrylonitrile polymer fibers to improve dyeability | |
| CN101166853B (en) | Acrylic shrinkable fiber | |
| CN104662216B (en) | Pile fabric and manufacture method thereof | |
| HU184214B (en) | Process for preparing copolymeric solutions for forming modacryl fibres | |
| JP3452691B2 (en) | Flame-retardant acrylic synthetic fiber with excellent weather resistance | |
| JP2008007909A (en) | Acrylic fiber and its production method | |
| JP2002309440A (en) | Raw cotton for pile | |
| JP2009228188A (en) | Acrylic dyed fiber and method for producing the same | |
| JPH05125615A (en) | Highly dense acrylic fiber | |
| JPH08269815A (en) | Flame retardant acrylic synthetic fiber excellent in light fastness | |
| JPH04370220A (en) | Deodorant fiber | |
| WO2007060943A1 (en) | Contractile acrylic fiber and method of piling the same | |
| WO2007060946A1 (en) | Acrylic shrinkable fiber and process for production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |