CN105556026B - Crosslink propylene acid esters series fiber and the fiber structure containing the fiber - Google Patents
Crosslink propylene acid esters series fiber and the fiber structure containing the fiber Download PDFInfo
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- CN105556026B CN105556026B CN201480051788.7A CN201480051788A CN105556026B CN 105556026 B CN105556026 B CN 105556026B CN 201480051788 A CN201480051788 A CN 201480051788A CN 105556026 B CN105556026 B CN 105556026B
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/32—Side-by-side structure; Spinnerette packs therefor
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Multicomponent Fibers (AREA)
Abstract
Known crosslink propylene acid esters series fiber has high hygroscopic property, is utilized in dress material field, industry Material Field.However, the fiber has hygroscopicity more high, fluffy degree, morphological stability become lower characteristic, therefore there is a problem of being difficult to take into account high hygroscopic property and combing processability, bulkiness.It is an object of the invention to, it is that offer cannot be provided by prior art, have concurrently in dress material/bedding field and to reduce moisture absorption exothermicity, the moisture pick-up properties of feeling of oppression and heat and improve the fluffy degree of heat insulating ability, and the moisture-absorbing fibre and the fiber structure containing the fiber of good net can be obtained in carding step.The purpose of the present invention is reached by with the carboxyl with cross-linked structure and 2~10mmol/g, crimp percent being more than the 7% crosslink propylene acid esters series fiber being characterized.
Description
Technical field
The present invention relates to have crimp property concurrently, wherein especially with the excellent characteristic of bulkiness and complexing and high hygroscopic property
Crosslink propylene acid esters series fiber.
Background technology
Known crosslink propylene acid esters series fiber have pH resiliencies, charging property, water-retaining property etc. reconcile function, high hydroscopicity,
Highly hygroscopic speed, high hydroscopicity difference or the conditioning function (such as patent document 1,2) from it, in dress material field, industry
Utilized in Material Field.
However, crosslink propylene acid esters series fiber has high hydroscopicity, therefore with the low spy of fluffy degree and morphological stability
Levy.Therefore, present situation is combing processing difficulties, and not yet propulsion application in purposes of bulkiness etc. is required in cotton-wool etc..
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 7-216730 publications
Patent document 2：Japanese Unexamined Patent Publication 5-132858 publications
The content of the invention
Problems to be solved by the invention
It is an object of the present invention to provide cannot be provided by prior art, take into account high wet absorption and discharging and processability or fluffy
The fiber of looseness.In addition, it is a further object to, there is provided useful in such as dress material/bedding field etc.,
Have the fiber structure of the fluffy degree for reducing moisture absorption exothermicity, the moisture pick-up properties of feeling of oppression and heat and improving heat insulating ability concurrently.
The scheme for solving problem
Above-mentioned purpose of the invention is reached by following means.
(1) a kind of crosslink propylene acid esters series fiber, it is characterised in that the carboxyl with cross-linked structure and 2~10mmol/g,
Crimp percent is more than 7%.
(2) the crosslink propylene acid esters series fiber according to (1), it is characterised in that carboxyl amount is 5~10mmol/g.
(3) the crosslink propylene acid esters series fiber according to (1) or (2), it is characterised in that crimp percent is more than 10%.
(4) according to the crosslink propylene acid esters series fiber that (1) to any one of (3) is described, it is characterised in that with multivalence
Metal ion as carboxyl counter ion counterionsl gegenions.
(5) according to the crosslink propylene acid esters series fiber that (1) to any one of (4) is described, it is characterised in that fiber entirety
There is carboxyl.
(6) according to (1) to any one of (5) described crosslink propylene acid esters series fiber, it is characterised in that its be to by
It is more than 2 that the acrylic fibre with parallel construction of 2 kinds of acrylic polymer formation is implemented using the nitrogen number in 1 molecule
Nitrogen-containing compound crosslinking Treatment and hydrolysis process obtained from.
(7) a kind of fiber structure, it contains (1) to any one of (6) described crosslink propylene acid esters series fiber.
(8) a kind of cotton-wool, it contains (1) to any one of (6) described crosslink propylene acid esters series fiber.
The effect of invention
Crosslink propylene acid esters series fiber of the invention has moisture pick-up properties and fluffy degree high concurrently, reduces from coming that body is produced
From the feeling of oppression and heat of body fluid, and comfortable humiture environment is realized based on heat insulating ability.In addition, having complexing, can easily make
Into the net in carding step.The crosslink propylene acid esters series fiber of the invention described above can be suitable for the cotton of dress material, bedding
Wadding etc..
Specific embodiment
Hereinafter, the present invention is described in detail.It is with cross-linked structure that crosslink propylene acid esters series fiber of the invention is characterized
With the fiber that the carboxyl and crimp percent of 2~10mmol/g are more than 7%.Carboxyl is to make crosslink propylene acid esters series fiber embody suction to put
The principal element of the characteristics such as moist, moisture absorption exothermicity, in the fibre with 2~10mmol/g, more preferably 5~10mmol/g, enter one
The step preferably scope of 5~8mmol/g contains.When carboxyl amount is less than 2mmol/g, fiber blended fiber structure with other
Etc. moisture pick-up properties cannot be obtained, become fragile during more than 10mmol/g, when moisture absorption or water suction, it is impossible to maintain fiber shape, moisture absorption
Performance.
Crimp percent is prescribed in JIS L1015, and crimp percent is higher, fiber and the easier complexing of fiber, forms net, nonwoven
Become fluffy during the fiber assemblies such as cloth, spun yarn.In fiber of the invention, crimp percent be more than 7%, be preferably 10% with
On.When crimp percent is less than 7%, the mutual link of fiber in carding step is deteriorated, and fluffy during formation fiber assembly
Degree is low, and the shape with abundant thickness cannot be obtained with other fiber blended cotton-wools etc..
As the bulkiness of crosslink propylene acid esters series fiber of the invention, when being used in bed clothes, the cotton-wool purposes of clothes,
As specific volume described later, expect that preferably there is 35cm3/ more than g, more preferably have 40cm3/ more than g.
As the moisture pick-up properties of crosslink propylene acid esters series fiber of the invention, fiber blended fibre structure with other
In thing, from from the viewpoint of significant moisture pick-up properties is obtained with practical mixed rate level, as hydroscopicity described later, expect preferably
It is more than 15%, more preferably more than 25%, more preferably more than 35%.The upper limit of above-mentioned hydroscopicity is not limited especially
It is fixed, because there is limit, therefore the upper limit substantially 70% in carboxyl import volume.
Can be by acrylic as the acrylic fibre of the raw fibre of crosslink propylene acid esters series fiber of the invention
Polymer matrix is manufactured in known method.Used as the composition of the polymer, acrylonitrile is preferably more than 40 weight %, more preferably
It is more than 50 weight %, more preferably more than 80 weight %.As described later, by make to form acrylic fibre third
The nitrogen-containing compound reactions such as the itrile group of alkene nitrile based copolymer and hydrazine based compound, such that it is able to importing cross-linked structure in fiber.
Cross-linked structure has considerable influence to fibrous physical property.When the copolymerization composition of acrylonitrile is very few, cross-linked structure has to tail off, and has fiber
Physical property becomes insufficient possibility, but is set to above range by the way that the copolymerization of acrylonitrile is constituted, and can be readily obtained good
Result.
As the copolymer composition in addition to acrylonitrile in acrylic polymer, can be with acrylonitrile compolymer as long as being
Monomer, be not particularly limited, specifically, can enumerate：Methallyl sulfonic acid, p styrene sulfonic acid etc. contain sulfonic acid
Carboxyl group-containing monomer and its salt, styrene, vinyl acetate, (methyl) third such as base monomer and its salt, (methyl) acrylic acid, itaconic acid
Monomers such as olefin(e) acid ester, (methyl) acrylamide etc..
As the method for obtaining crimp percent crosslink propylene acid esters series fiber high, acrylic of more than two kinds is gathered
The means that compound is compound and forms the acrylic fibre of raw fibre are effective.For example, being gathered by the way that acrylonitrile will be compounded with
Used as raw fibre, each acrylic is polymerized the acrylic fibre of the discrepant 2 kinds of acrylic polymer of composition and division in a proportion example
The import volume of the cross-linked structure in the region of thing produces difference, and shrinkage degree during hydrolysis process produces difference and can embody volume
It is bent.The composite construction of acrylic polymer can be engaged side by side, it is also possible to randomly be mixed, preferably by 2 kinds of acrylics
Polymer is engaged side by side.In the case of above-mentioned, in order to obtain sufficient crimp percent, by 2 kinds of acrylonitrile of acrylic polymer
The difference of polymerization ratio is preferably set to 1~10%, is further preferably set to 1~5%, by 2 kinds of compound ratios of acrylic polymer
Rate is preferably set to 20/80~80/20, is further preferably set to 30/70~70/30.
In addition, can be chopped fiber, tow, silk, braiding as the form of the acrylic fibre used in the present invention
Any forms such as thing, non-woven fabrics, alternatively, it is also possible in middle uses such as the intermediate product of manufacturing process, useless fibers.
As for the crosslinking agent that cross-linked structure is imported in acrylic fibre, it is also possible to using known any
Crosslinking agent, it is preferred from the efficiency of cross-linking reaction and the easiness aspect of operation during using nitrogen-containing compound.The nitrogen
Compound must have more than 2 nitrogen-atoms in 1 molecule.This is because, when the quantity of the nitrogen-atoms in 1 molecule is less than 2, no
Cross-linking reaction can be produced.As the concrete example of above-mentioned nitrogen-containing compound, as long as cross-linked structure can be formed, do not limit especially
It is fixed, preferably with more than 2 amino-compounds of primary amino radical, hydrazine based compounds.As with more than 2 aminations of primary amino radical
Compound, can enumerate：The amine compound of ethylenediamine, hexamethylene diamine etc. two, diethylenetriamines, 3,3 '-imino group double (third
Base amine), three amine compounds, trien, the N, N '-bis- (3- amino such as -3,3 '-imino group of N- methyl double (propyl group amine)
Propyl group) -1,3- propane diamine, N, four amine compounds, polyvinylamine, the polyene third such as N '-bis- (3- aminopropyls) -1,4- butanediamine
Base amine etc. is with more than 2 polyamine based compounds of primary amino radical etc..In addition, as hydrazine based compound, can enumerate：Hydrazine hydrate,
Hydrazine sulfate, hydrazine hydrochloride, hydrobromic acid hydrazine, hydrazine carbonic ester etc..It should be noted that the upper limit of the nitrogen-atoms numbers in 1 molecule is without spy
Do not limit, preferably less than 12, more preferably less than 6, particularly preferably less than 4.Nitrogen-atoms numbers in 1 molecule
During more than the above-mentioned upper limit, cross-linker molecules become big, are difficult to sometimes to importing cross-linked structure in fiber.
As the condition for importing cross-linked structure, it is not particularly limited, it may be considered that the crosslinking agent and acrylic of use are fine
The reactivity of dimension, the amount of cross-linked structure, hydroscopicity, the poor, fibrous physical property of hydroscopicity etc. and suitably select.For example, using hydrazine system
When compound is as crosslinking agent, can enumerate：Aforesaid propylene nitrile series fiber impregnated in 0.5~40 weight % is reached with hydrazine densimeter
Mode be added with the aqueous solution of above-mentioned hydrazine based compound, in method for being processed within 50~120 DEG C, 5 hours etc..
Hydrolysis process is implemented to the fiber for having imported cross-linked structure using alkaline metal cpds.By the treatment, fiber
Present in itrile group be hydrolyzed and form carboxyl.As specific treatment conditions, it may be considered that above-mentioned carboxyl amount etc. and suitably set
The various conditions such as concentration, reaction temperature, the reaction time of reagent treatment are determined, in preferably 0.5~10 weight %, further preferred 1
It is industrially right with 50~120 DEG C of means for process for 1~10 hour of temperature in the reagent treatment aqueous solution of~5 weight %
It is also preferred in fibrous physical property.It should be noted that above-mentioned crosslinking imports treatment and hydrolysis process can be each using being mixed with
The aqueous solution of reagent treatment is processed in the lump.
Herein, carboxyl includes：Its counter ion counterionsl gegenions be the cation in addition to hydrogen ion alkaline carboxyl and its contend with from
Son is hydrionic H types carboxyl.Its ratio can be adjusted arbitrarily, in order to obtain hydroscopicity high, expect by the 40% of carboxyl with
On be set to alkaline carboxyl.
As the species of the cation for constituting alkaline carboxyl, can enumerate：The alkaline earths such as the alkali metal such as lithium, sodium, potassium, magnesium, calcium
Other metals such as metal, manganese, copper, zinc, silver, NH4, the cation such as amine, characteristic that can be as needed and select one or more.
When being employed as magnesium, calcium, zinc of polyvalent metal ion etc., there is crimp percent and uprise, be particularly suitable for.For example, for by 2 kinds
The acrylic fibre that acrylic polymer is engaged side by side, implements above-mentioned crosslinking and imports, hydrolyzes and form carboxyl, and
During the polyvalent metal ions such as counter ion counterionsl gegenions selection magnesium, calcium, zinc, the crosslink propylene acid esters of crimp percent more than 10% can be readily obtained
Series fiber.
Method as the ratio of alkaline carboxyl and H type carboxyls is adjusted into above range, can enumerate：Using nitric acid
The slaines such as salt, sulfate, hydrochloride implement ion-exchange treatment；Implement acid treatment using nitric acid, sulfuric acid, hydrochloric acid, formic acid etc.；
Or implement the methods such as pH adjustment treatment using alkaline metal cpds etc..
In addition, in crosslink propylene acid esters series fiber of the invention, when fiber integrally has carboxyl, the crisp of fiber can be suppressed
Change, cohesive, and more carboxyls can be imported, therefore, it can to form the fiber that practicality is high, moisture pick-up properties is also high.Make big
Amount carboxyl is when concentrating and being present in a part for fiber, sometimes due to moisture absorption, water suction and the part is become fragile or with bonding
Property.
On the other hand, when carboxyl is existed only in fiber sheath portion, because fibrillar center portion is substantially absent from carboxyl, because
This can suppress by the caused embrittlement such as moisture absorption, and fiber becomes to be difficult to sagging, can be conducive to the raising of bulkiness.But, as above
State like that, from from the viewpoint of the brittle of fiber, cohesive, carboxyl amount is suppressed.
The crosslink propylene acid esters series fiber of the invention for obtaining as described above possesses following feature：With moisture absorption high
Rate, and there is sufficiently curling in order to obtain the fluffy degree and combing processability of practicality.It is understood that containing this hair
Bright crosslink propylene acid esters series fiber as fiber structure composition fiber when, the fluffy degree that is obtained by the curling and can carry
Heat insulating ability high, and the feeling of oppression and heat from body fluid produced from body is reduced, realize comfortable humidity environment.
Crosslink propylene acid esters series fiber of the invention can be used alone or form fiber knot with other combination of raw materials
Structure thing, becomes more useful.As the mode of appearance of above-mentioned fiber structure, have：Cotton, silk, knitted fabric, fabric, non-woven fabrics, fluffing
Fabric, paper-like thing etc..Contain form as the crosslink propylene acid esters series fiber of the invention in the works, have：By with
The mixing of other raw material, substantial equally distributed form；During structure with multilayer, make crosslink propylene acid esters of the invention
Series fiber is concentrated and is present in the form of random layer (can be that odd number can also be plural number)；Make crosslink propylene acid esters of the invention
Series fiber is distributed in form in each layer etc. with specific ratios.
As other raw material that can be applied in combination in fiber structure of the invention, it is not particularly limited, can makes
With public natural fiber, organic fiber, semisynthetic fibre, synthetic fibers, and then inorganic fibre can also be used according to purposes
Dimension, glass fibre etc..As specific example, can enumerate：Cotton, fiber crops, thin,tough silk, wool, nylon, artificial silk, polyester, acrylic compounds
Fiber etc..In addition, other raw material being applied in combination can be the raw material such as feather, resin, particle.
In fiber structure of the invention, as the mode of appearance of above-mentioned example, the group containing form and other raw material
Close, exist countless.Which kind of works is formed it is contemplated that the use form of end article (is used for example as seasonal, motility
Or the mode of underwear, underpants or coat, the mode as filter, curtain or carpet, bedding or mat, shoe-pad etc. etc.),
Required function, crosslink propylene acid esters series fiber help to embody Land use systems of above-mentioned functions etc. and suitably determine.For example,
If in the case that fiber structure is cotton-wool, the combination with polyester, wool, feather etc. can be enumerated.Bed clothes cotton-wool
In the case of, can enumerate：By crosslink propylene acid esters series fiber of the invention and feather according to weight ratio meter be 5:95~75:25
The mixed example of ratio.
The manufacture method of cotton-wool of the invention is not particularly limited, and can be applicable the manufacture of known general cotton-wool
Method.For example, can be applicable for raw material cotton pre- fibrillation mixing to be carried out with fibre separating machine, then netted side is machined to using combing
Method.In addition, in order to assign morphological stability, it is also possible to additional：Acupuncture or spun lacing (water punch) etc. are complexed the work of fiber
Sequence, bonding process between the fiber of thermal welding resin is used.
Embodiment
Hereinafter, the present invention is specifically described according to embodiment.Part and percentage in embodiment as long as no restriction, with
Weight basis are represented.The evaluation method of the characteristic in embodiment is as described below.
(1) carboxyl amount
About 1g fiber samples impregnated in 30 minutes in the 1mol/l aqueous hydrochloric acid solutions of 50ml.Then, by fiber samples with
Bath raio 1:500 impregnated in water.After 15 minutes, confirm the pH of bath and (when the pH of bath is less than 4, enter again to dry after more than 4, it
Water-filling is washed).Then, accurate weighing fully dried fiber samples about 0.2g (W1 [g]), add the water of 100ml, and then add
The 0.1mol/l sodium hydrate aqueous solutions of 15ml, the sodium chloride of 0.4g and phenolphthalein are simultaneously stirred.After 15 minutes, be isolated by filtration for
Sample fiber and filtrate, then wash sample fiber until the colour developing of phenolphthalein disappears.Washing water now and filtrate will be incorporated
Liquid with 0.1mol/l aqueous hydrochloric acid solutions titration until phenolphthalein colour developing disappear, obtain aqueous hydrochloric acid solution consumption (V1
[ml]).Total carboxyl amount is calculated according to following formula by gained measured value.
Carboxyl amount [mmol/g]=(0.1 × 15-0.1 × V1)/W1
The hydroscopicity of (2) 20 DEG C × 65%RH
By about 2.5g fiber samples in hot-air drier with 105 DEG C of dryings 16 hours, gravimetry (W2 [g]).Then,
The fiber samples are put into regulation to 24 hours in 20 DEG C of temperature, the Constant Temperature and Humidity Chambers of 65%RH.Determine the fiber of such moisture absorption
The weight (W3 [g]) of sample.20 DEG C × 65%RH hydroscopicities are calculated according to following formula by these measurement results.
Hydroscopicity [%]=(W3-W2)/W2 × 100 of 20 DEG C × 65%RH
(3) crimp percent
Determined by JIS L1015, calculated.
(4) specific volume (bulkiness)
Determined by JIS L1097, calculated.
(5) combing passes through property
In regulation to 30 ± 5 DEG C of temperature, the interior of 50 ± 10%RH, the sample roller manufactured using big and Ji Gong Co., Ltd.
Carding machine (model SC-300L), carded web is made by the sample fiber 50g of fibre length 70mm.Below gained mesh-shaped
Benchmark is stated to be evaluated.
○：Complexing fully, can obtain uniform net.
△：Complexing is slightly not enough, is produced in net uneven.
×：Complexing is substantially not enough, and fiber is not connected to each other, it is impossible to obtain net.
[embodiment 1]
By the weight % of acrylonitrile 90, the weight % of methyl acrylate 10 acrylic polymer Ap (in dimethyl at 30 DEG C
Inherent viscosity [η] in formamide=1.5), the weight % of acrylonitrile 88, the acrylic polymer of the weight % of vinyl acetate 12
Bp ([η]=1.5) is dissolved with the sodium thiocyanate water solution of 48 weight % respectively, prepares spinning solution.To Japanese Patent Publication 39-
Each spinning solution is imported in the compined spinning apparatus of No. 24301 in the way of the recombination rate of Ap/Bp reaches 1/1, according to routine
Method carry out spinning, washing, stretching, curling, heat treatment, obtain filament denier for 3.3dtex be compounded with polymer Ap and
The parallel type raw fibre of Bp.
The crosslinking importing treatment of 98 DEG C × 5 hours is carried out to the raw fibre in the 20 weight % aqueous solution of hydrazine hydrate simultaneously
Cleaning.The fiber impregnation that will be imported by crosslinking carries out the acid treatment of 90 DEG C × 2 hours in 3 weight % aqueous solution of nitric acid.Connect
, in 3 weight % sodium hydrate aqueous solutions, carry out the hydrolysis process of 90 DEG C × 2 hours, with 3.5 weight % aqueous solution of nitric acid
Processed and washed.By gained fiber impregnation in water, pH is adjusted to 11 by addition NaOH, then be dissolved with equivalent to
The dipping of 50 DEG C × 1 hour is carried out in the aqueous solution of the magnesium nitrate of 2 times of carboxyl amount contained in fiber, is implemented at ion exchange
Reason, washes, dries, so as to obtain the crosslink propylene acid esters series fiber of the embodiment 1 with Mg alkaline carboxyls.By gained fiber
Evaluation result is shown in table 1.In addition, the infrared ray absorbing for carrying out the fiber is determined, the 2250cm from itrile group is as a result had no-1Near
Absorption, can confirm that itrile group in fiber entirety hydrolysis propulsion, imported carboxyl.
[embodiment 2,3]
In embodiment 1, the recombination rate of acrylic polymer Ap/Bp is set to change in the scope shown in table 1, except this it
Outward, the parallel type raw fibre that filament denier is 3.3dtex is similarly obtained.Using the raw fibre, using with embodiment 1
Identical method carries out crosslinking and imports the later treatment for the treatment of, obtains the crosslink propylene of the embodiment 2 and 3 with Mg alkaline carboxyls
Acid esters series fiber.The evaluation result of these fibers is shown in table 1.In addition, during the infrared ray absorbing of these fibers is determined, also with reality
The crosslink propylene acid esters series fiber for applying example 1 similarly has no the 2250cm from itrile group-1Neighbouring absorption.
[embodiment 4]
In embodiment 1, magnesium nitrate is replaced using calcium nitrate, in addition, similarly obtain the reality with Ca alkaline carboxyls
Apply the fiber of example 4.The evaluation result of the fiber is shown in table 1.
[embodiment 5]
In the aqueous solution containing the weight % of hydrazine hydrate 0.5 and the weight % of NaOH 2 to embodiment 1 in gained parallel type
The crosslinking that raw fibre is carried out 100 DEG C × 1 hour simultaneously imports treatment and hydrolysis process, is carried out with 8 weight % aqueous solution of nitric acid
Process and wash.By gained fiber impregnation in water, NaOH is added, pH is adjusted to 9, be then dissolved with equivalent to fiber
In 2 times of contained carboxyl amount magnesium nitrate the aqueous solution in carry out the dipping of 50 DEG C × 1 hour, implement ion-exchange treatment,
Wash, dry, so as to obtain the fiber of the embodiment 5 with Mg alkaline carboxyls.The evaluation result of gained fiber is shown in table 1.
It should be noted that during the infrared ray absorbing of above-mentioned fiber is determined, it is thus identified that in the 2250cm from itrile group-1Nearby there is absorption,
The hydrolysis of the itrile group in fiber sheath portion is carried out, but has remained itrile group in fibrillar center portion.
[comparative example 1]
In embodiment 1, formed using only acrylic polymer Ap is dissolved with the sodium thiocyanate water solution of 48 weight %
Spinning solution, in addition, similarly obtain filament denier for the raw material that is only made up of polymer Ap of 3.3dtex is fine
Dimension.Using the raw fibre, carry out crosslinking using method same as Example 1 and import the later treatment for the treatment of, compared
The fiber of example 1.The evaluation result of the fiber is shown in table 1.
[embodiment 6]
In embodiment 1, do not implement, using the ion-exchange treatment of magnesium nitrate, in addition, similarly to obtain with Na alkali
The fiber of the embodiment 4 of type carboxyl.The evaluation result of the fiber is shown in table 2.
[comparative example 2]
In comparative example 1, do not implement, using the ion-exchange treatment of magnesium nitrate, in addition, similarly to obtain with Na alkali
The fiber of the comparative example 2 of type carboxyl.The evaluation result of the fiber is shown in table 2.
[table 1]
[table 2]
As shown in Table 1, embodiment 1~5 takes into account hydroscopicity and bulkiness high, therefore as holding heat insulating ability and can have
The cotton-wool of humidity conditioning function is used.On the other hand, it is equal hydroscopicity in comparative example 1, but bulkiness step-down.In addition, by table 2
Understand, in embodiment 6, good combing processability can be obtained, but crimp percent is low in comparative example 2, and combing processability is bad.
Claims (7)
1. a kind of crosslink propylene acid esters series fiber, it is characterised in that the carboxyl with cross-linked structure and 2~10mmol/g, curling
Rate is more than 7%,
The crosslink propylene acid esters series fiber is the acrylic with parallel construction to being formed by 2 kinds of acrylic polymer
Fiber is implemented obtained from the crosslinking Treatment and hydrolysis process of the nitrogen-containing compound that the nitrogen number in 1 molecule is more than 2.
2. crosslink propylene acid esters series fiber according to claim 1, it is characterised in that carboxyl amount is 5~10mmol/g.
3. crosslink propylene acid esters series fiber according to claim 1 and 2, it is characterised in that crimp percent is more than 10%.
4. crosslink propylene acid esters series fiber according to claim 1 and 2, it is characterised in that make with polyvalent metal ion
It is the counter ion counterionsl gegenions of carboxyl.
5. crosslink propylene acid esters series fiber according to claim 1 and 2, it is characterised in that fiber integrally has carboxyl.
6. a kind of fiber structure, it contains the described crosslink propylene acid esters series fiber of any one of claim 1 to 5.
7. a kind of cotton-wool, it contains the described crosslink propylene acid esters series fiber of any one of claim 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710433714.5A CN107237004B (en) | 2013-09-20 | 2014-09-18 | Crosslinked acrylate fiber and fiber structure containing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-194969 | 2013-09-20 | ||
| JP2013194969 | 2013-09-20 | ||
| PCT/JP2014/074646 WO2015041275A1 (en) | 2013-09-20 | 2014-09-18 | Cross-linked acrylate fiber and fiber structure containing same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710433714.5A Division CN107237004B (en) | 2013-09-20 | 2014-09-18 | Crosslinked acrylate fiber and fiber structure containing the same |
Publications (2)
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| KR (1) | KR102190232B1 (en) |
| CN (2) | CN105556026B (en) |
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| JP6228511B2 (en) * | 2014-05-29 | 2017-11-08 | 日本エクスラン工業株式会社 | Cross-linked acrylate fiber with good dispersibility |
| JP6247800B1 (en) * | 2016-09-26 | 2017-12-13 | 東洋紡株式会社 | Hygroscopic exothermic fiber |
| WO2018055868A1 (en) * | 2016-09-26 | 2018-03-29 | 東洋紡株式会社 | Hygroscopic heat-generating fiber |
| JP6247801B1 (en) * | 2016-09-29 | 2017-12-13 | 東洋紡株式会社 | Batting |
| WO2018061369A1 (en) * | 2016-09-29 | 2018-04-05 | 東洋紡株式会社 | Batting |
| TWI771378B (en) * | 2017-03-23 | 2022-07-21 | 日商日本Ｅｘｌａｎ工業股份有限公司 | Hygroscopic (moisture-absorption) granular cotton and batting (inner cotton) comprising the granular cotton thereof |
| CN110475924B (en) * | 2017-03-31 | 2022-08-16 | 东洋纺株式会社 | Filling cotton |
| JP7187911B2 (en) * | 2017-09-22 | 2022-12-13 | 日本エクスラン工業株式会社 | Hygroscopic acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber |
| CN111133137B (en) * | 2017-09-22 | 2022-05-10 | 日本爱克兰工业株式会社 | Hygroscopic acrylic fiber, method for producing the fiber, and fiber structure containing the fiber |
| JP7177986B2 (en) * | 2018-02-15 | 2022-11-25 | 日本エクスラン工業株式会社 | Shrinkable, moisture-absorbing acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber |
| JP7177987B2 (en) * | 2018-02-26 | 2022-11-25 | 日本エクスラン工業株式会社 | Easily de-crimpable and moisture-absorbing acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber |
| JP7177988B2 (en) * | 2018-03-09 | 2022-11-25 | 日本エクスラン工業株式会社 | Water-repellent and moisture-absorbing acrylonitrile-based fiber, method for producing said fiber, and fiber structure containing said fiber |
| JP7219418B2 (en) * | 2018-03-09 | 2023-02-08 | 日本エクスラン工業株式会社 | Crimped moisture-absorbing acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber |
| JP7166912B2 (en) * | 2018-12-25 | 2022-11-08 | 株式会社エアウィーヴ | Mattress covers, mattresses, and ventilated beds |
| JP7441429B2 (en) | 2019-06-20 | 2024-03-01 | 日本エクスラン工業株式会社 | Ion exchange fiber and ion exchange filter containing the fiber |
| JP7050365B2 (en) * | 2019-12-26 | 2022-04-08 | 学校法人神奈川大学 | Crosslinked polymer compounds and methods for producing them, absorbent articles, disposable diapers, sanitary products, processing containers, and processing methods. |
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| CN101023212A (en) * | 2004-09-07 | 2007-08-22 | 日本爱克兰工业株式会社 | Highly flame-retardant and hygroscopic fiber and fiber structure |
| CN102575415A (en) * | 2009-07-22 | 2012-07-11 | 日本爱克兰工业株式会社 | Moisture-absorbing fiber dyeable with acid dyes and method for producing same |
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| JPS55132754A (en) * | 1979-04-02 | 1980-10-15 | Japan Exlan Co Ltd | High water absorbable sheet like fiber product |
| JPS60194173A (en) * | 1984-12-13 | 1985-10-02 | 日本エクスラン工業株式会社 | Production of new water swellable fiber |
| JP2623771B2 (en) * | 1988-09-21 | 1997-06-25 | 日本エクスラン工業株式会社 | High hygroscopic fiber |
| JP3196855B2 (en) | 1991-11-11 | 2001-08-06 | 東洋紡績株式会社 | High moisture absorption and release fiber |
| JP3191278B2 (en) | 1994-02-08 | 2001-07-23 | 日本エクスラン工業株式会社 | pH buffering fiber and method for producing the same |
| JP4696724B2 (en) * | 2004-08-03 | 2011-06-08 | 日本エクスラン工業株式会社 | Method for dyeing cross-linked acrylate fibers and fiber products containing cross-linked acrylate fibers dyed by the dyeing method |
| JP5056358B2 (en) * | 2007-11-02 | 2012-10-24 | 日本エクスラン工業株式会社 | Dyeable cross-linked acrylate fiber, method for producing the same, and dyed cross-linked acrylate fiber obtained by dyeing the fiber |
| JP2009138296A (en) * | 2007-12-06 | 2009-06-25 | Mitsubishi Rayon Co Ltd | Acrylic conjugate fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023212A (en) * | 2004-09-07 | 2007-08-22 | 日本爱克兰工业株式会社 | Highly flame-retardant and hygroscopic fiber and fiber structure |
| CN102575415A (en) * | 2009-07-22 | 2012-07-11 | 日本爱克兰工业株式会社 | Moisture-absorbing fiber dyeable with acid dyes and method for producing same |
Also Published As
| Publication number | Publication date |
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| KR20160056849A (en) | 2016-05-20 |
| TWI645086B (en) | 2018-12-21 |
| JP6455680B2 (en) | 2019-01-23 |
| CN107237004B (en) | 2020-01-31 |
| CN105556026A (en) | 2016-05-04 |
| KR102190232B1 (en) | 2020-12-11 |
| CN107237004A (en) | 2017-10-10 |
| WO2015041275A1 (en) | 2015-03-26 |
| TW201512478A (en) | 2015-04-01 |
| JPWO2015041275A1 (en) | 2017-03-02 |
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