CN109689951A - Modified propylene nitrile series fiber, the manufacturing method of the fiber and the fiber construct containing the fiber - Google Patents
Modified propylene nitrile series fiber, the manufacturing method of the fiber and the fiber construct containing the fiber Download PDFInfo
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- CN109689951A CN109689951A CN201680089157.3A CN201680089157A CN109689951A CN 109689951 A CN109689951 A CN 109689951A CN 201680089157 A CN201680089157 A CN 201680089157A CN 109689951 A CN109689951 A CN 109689951A
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- fiber
- modified propylene
- carboxyl
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
Abstract
The object of the present invention is to provide: it can be with the modified propylene nitrile series fiber than the process production with contact simplicity.Reach foregoing purpose by following modified propylene nitrile series fiber, the modified propylene nitrile series fiber has the carboxyl of 0.2~4.0mmol/g, and the dissolubility to 58% sodium thiocyanate water solution is 95% or more, and is 50% or less to the dissolubility of dimethylformamide.
Description
Technical field
The present invention relates to modified propylene nitrile series fiber, the fiber manufacturing method and contain the fiber construct of the fiber.
Background technique
Since the consciousness in recent years to comfort improves, it is therefore desirable to the raw material with moisture absorption function are developed, it is fine
It is developed in dimension field also prevailing.Such as it has been known that there is: crosslink propylene acid esters obtained from chemical modification is carried out to acrylic fiber
Series fiber (patent document 1).The fiber contains cross-linked structure and carboxyl, for the fiber with excellent moisture pick-up properties.
However, in the manufacture of the fiber, the process for needing that hydrazine is utilized to import cross-linked structure and the hydrolysis for importing carboxyl
Process, in addition, after each process, need to react used in medicament removing residues process.Moreover, these each process
In, need high temperature, long-time.Accordingly, it is difficult to carry out the manufacture of the fiber, with continuous processing for point low with productivity of having to
The case where batch processing carries out.
In addition, on this point of acrylic fiber with carboxyl, it is known to: comprising there is carboxyl with acrylic acid etc.
Monomer is the acrylic fiber of the acrylic polymer of copolymer composition.However, if being copolymerized acrylic acid largely, spinning
It becomes difficult, accordingly, it is difficult to embody high hygroscopicity.In addition, the alkalinity in dyeing is soaped towards dress material purposes
Etc. become easy dissolution etc. under alkaline conditions and become problem.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 5-132858 bulletin
Summary of the invention
Problems to be solved by the invention
As above-mentioned, conventionally, there is known imparting hygroscopic fiber to acrylic fiber, but manufacturing process is more and produces
Rate is low or is difficult to improve hygroscopicity.The present invention is founded in view of the above-mentioned state of the art, it is intended that providing:
It can be with the hygroscopicity acrylic fibre than the process production with contact simplicity.
The solution to the problem
The present inventor in order to achieve the above objectives, has made intensive studies, as a result, it has been found that: it will polymerize dissolved with acrylic
After the spinning solution of object is spun from nozzle, through solidification, washing, stretching each process and obtain unseasoned fiber, will obtain not
Dry fiber hydrolysis, to can also keep practical fibrous physical property even if not implementing crosslinking Treatment and obtain with modification
Acrylic fibre completes the present invention.
That is, the present invention is reached by scheme below.
(1) a kind of modified propylene nitrile series fiber, which is characterized in that the carboxyl with 0.2~4mmol/g, to 58% sulphur cyanogen
The dissolubility of acid sodium aqueous solution is 95% or more, and is 50% or less to the dissolubility of dimethylformamide.
(2) a kind of modified propylene nitrile series fiber, which is characterized in that the carboxyl with 0.2~4mmol/g, to 58% sulphur cyanogen
The dissolubility of acid sodium aqueous solution is 95% or more, and is 5% or less to the dissolubility of 1g/L aqueous sodium carbonate.
(3) the modified propylene nitrile series fiber according to (1) or (2), which is characterized in that the saturation under 20 DEG C × 65%RH
Hydroscopicity is 3% or more.
(4) the modified propylene nitrile series fiber according to any one of (1)~(3), which is characterized in that carboxyl spreads fiber
Integrally exist.
(5) a kind of manufacturing method of modified propylene nitrile series fiber, which is characterized in that acrylic polymer will be dissolved with
After spinning solution is spun from nozzle, through solidification, washing, stretching each process and obtain unseasoned fiber, it is unseasoned by what is obtained
Fiber hydrolysis.
(6) manufacturing method of the modified propylene nitrile series fiber according to (5), which is characterized in that the water of unseasoned fiber
Dividing rate is 20~250%.
(7) a kind of fiber construct contains modified propylene nitrile series fiber described in any one of (1)~(4).
The effect of invention
What is worth mentioning effect is answered for of the invention, discovery will be by that will be dissolved with the spinning of acrylic polymer
After stoste is spun from nozzle, through solidification, washing, stretching each process and obtain unseasoned fiber, the unseasoned fiber that will be obtained
Hydrolysis also keeps practical fibrous physical property and available has hygroscopic acrylonitrile thus even if not implementing crosslinking Treatment
Series fiber.The fiber can continuously be produced, productivity according to above-mentioned manufacturing method using common fiber manufacturing apparatus
It is high.In addition, the fiber can not only embody hygroscopicity, as be described hereinafter, moreover it is possible to embody deodorization, anti-flammability, antibiotic property, antiviral property,
Therefore the characteristics such as antianaphylaxis can be used for various products, purposes.
Specific embodiment
Modified propylene nitrile series fiber of the invention can obtain as follows: will be dissolved with the spinning solution of acrylic polymer
After spinning from nozzle, through solidification, washing, stretching each process and obtain unseasoned fiber, obtained unseasoned fiber is hydrolyzed,
So as to obtain.Hereinafter, being described in detail to the method for obtaining modified propylene nitrile series fiber of the invention.
Firstly, become raw material acrylic polymer contain preferably 40 weight % or more, more preferable 50 weight % or more,
The acrylonitrile as polymerization composition of further preferred 85 weight % or more.Therefore, as the acrylic polymer, propylene is removed
Except nitrile homopolymer, the copolymer of acrylonitrile and other monomers can also be used.As the other monomers in copolymer, without spy
It does not limit, vinyl halide and vinylidene halide can be enumerated；(methyl) acrylate is (it should be noted that (first
Base) statement expression attached the term person of the methyl and do not add both terms of the methyl)；Methallylsulfonic acid,
P styrene sulfonic acid etc. contains sulfonic monomer and its salt, acrylamide, styrene, vinyl acetate etc..
Then, using above-mentioned acrylic polymer, fibrosis is carried out by wet spinning, is using the nothings such as Luo Dan acid sodium
Machine salt as solvent in the case where be illustrated, such as it is following.Firstly, above-mentioned acrylic polymer is made to be dissolved in solvent and make
Spinning solution.After the spinning solution is spun from nozzle, each process through solidification, washing, stretching makes the unseasoned fibre after stretching
The moisture rate of dimension (hereinafter also referred to as gel acrylic fiber) is 20~250 weight %, preferably 25~130 weight %, more
It is preferred that 30~100 weight %.
Herein, in the case that the moisture rate of gel acrylic fiber is lower than 20 weight %, in aftermentioned hydrolysis process
Medicament will not infiltrate into fibrous inside, become integrally generate carboxyl throughout fiber sometimes.The case where more than 250 weight %
Under, fibrous inside includes a large amount of moisture, and fibre strength becomes too low, and therefore, spinnability is reduced without preferred.More pay attention to fiber
In the case where the height of intensity, it is expected that being set as in the range of 25~130 weight %.In addition, by gel acrylic fiber
There are many ways to moisture rate control is in above range, such as coagulation bath temperature, it is desired for -3 DEG C~15 DEG C, preferably -3
DEG C~10 DEG C, as stretching ratio, it is desired for 5~20, preferably 7~15 times or so.
Hydrolysis process is then implemented to above-mentioned gel acrylic fiber.Through this process, gel acrylic compounds are fine
Itrile group in dimension is hydrolyzed, generates carboxyl.
As the means of above-mentioned hydrolysis process, following means can be enumerated: infiltrate or be impregnated with alkali metal hydroxide,
Heated in the state of the aqueous solutions such as the alkaline aqueous solution or nitric acid of alkali carbonate, ammonia etc., sulfuric acid, hydrochloric acid.Make
For specific treatment conditions, it may be considered that the range etc. of the amount of above-mentioned carboxyl is suitable for concentration, the reaction temperature of setting processing medicament
Each condition such as degree, reaction time, it is however generally that, industrially, on fibrous physical property it is also preferred that making 0.5~20 weight %, preferably 1.0
The treatment agent of~15 weight % infiltrates and after drawing, under damp and hot atmosphere, in 100~140 DEG C of temperature, preferably 110~135 DEG C
It is set in the range of the condition of lower processing 10~60 minutes.It should be noted that damp and hot atmosphere refers to, with saturated steam or mistake
The atmosphere that hot steam is full of.
In such as above-mentioned fiber for implementing hydrolysis process, generate with the alkali metal hydroxide according to used in hydrolysis process
The cation such as alkali metal, ammonium of the type of object, alkali carbonate, ammonia etc. is the salt form carboxyl of gegenion, then, according to need
It wants, the processing for converting the gegenion of carboxyl can also be carried out.As long as utilizing the metal salts such as nitrate, sulfate, hydrochloride
Aqueous solution carries out ion-exchange treatment, can form the salt form carboxyl using desired metal ion as gegenion.In turn,
PH, metal salt concentrations type by adjusting aqueous solution, so that different kinds of gegenion can also be made to be mixed or adjust
Its whole ratio.
As more than, available modified propylene nitrile series fiber of the invention can also be washed, be dried as needed.
More than, it is illustrated in solvent using the case where inorganic salts such as Luo Dan acid sodium, but in the case where use organic solvent, it is above-mentioned
Condition is also identical.But since the type of solvent is different, for coagulation bath temperature, selection is suitable for the temperature of the solvent,
The moisture rate of gel acrylic fiber is controlled as in above range.
As modified propylene nitrile series fiber of the invention obtained above has the so far combination for no characteristic.That is, tool
Having the following characteristics that the carboxyl with 0.2~4.0mmol/g, the dissolubility to 58% sodium thiocyanate water solution is 95% or more, and
And it is 50% or less to the dissolubility of dimethylformamide or is 5% or less to the dissolubility of 1g/L aqueous sodium carbonate.
The structure that the fiber can be estimated by the characteristic of the modified propylene nitrile series fiber of aforementioned present invention is not knot below
Structure.That is, being 95% or more by the dissolubility of 58% sodium thiocyanate water solution to the good solvent as acrylic polymer
Characteristic thinks, constitutes in the acrylic polymer of the fiber, and there is no intermolecular cross-linking structures caused by covalent bond.
On the other hand, similarly, it is believed that, the rising of hydrophily caused by the carboxyl imported by hydrolysis can be to as propylene
The dissolubility of the dimethylformamide of the good solvent of nitrile based polymer is that 50% characteristic below has an impact.However, acrylic
In polymer, in the case where making the monomer copolymerization containing carboxyl such as methacrylic acid, it can be dissolved in dimethylformamide, therefore not
Easily think, above-mentioned characteristic, which depends on merely carboxyl, to be existed and bring.In manufacturing process of the invention, to gel acrylic compounds
Fiber is hydrolyzed, result, it is believed that successively being hydrolyzed from fiber surface, medicament also infiltrates into depths in fiber, spreads
Fiber is integrally hydrolyzed.Herein, and then if from it is microcosmic it is upper from, generally in acrylic fiber, be mixed
There are the crystal block section of acrylic polymer orientation and the amorphous fraction of structure disturbance.Result, it is believed that crystal block section is on the outside of it
It is hydrolyzed, but amorphous fraction is hydrolyzed on the whole.Its result thinks, after hydrolysis, on microcosmic, and in crystal block section, one portion
Divide and directly remained in the state of being not subjected to hydrolysis with the highly concentrated part of itrile group, amorphous fraction becomes the highly concentrated portion of carboxyl
Point.Moreover, the hydrophily of the highly concentrated part of the carboxyl is especially high, thus it is speculated that reducing the dissolubility to dimethylformamide.
In addition, being that 5% characteristic below shows to constitute fiber of the invention to the dissolubility of 1g/L aqueous sodium carbonate
Polymer has carboxyl and is not easy to dissolve out in alkaline aqueous solution.It is such as above-mentioned in fiber of the invention, it is believed that itrile group concentration is high
Part integrally exist throughout fiber, there is alkali resistance in the highly concentrated part of itrile group, thus it is speculated that reducing to 1g/L sodium carbonate
The dissolubility of solution.
As speculating above: the structure of modified propylene nitrile series fiber of the invention does not have intermolecular friendship caused by covalent bond
It is coupled structure, spreads fiber integrally existing structure for the highly concentrated part of carboxyl and the highly concentrated part of itrile group.
It should be noted that it can be seen from the above, in the present invention, by the way that place is hydrolyzed to gel acrylic fiber
Reason, so as to obtain fiber with the above characteristics.Without using gel acrylic fiber, i.e. stretch after unseasoned fibre
Dimension and to after drying acrylic fiber implement hydrolysis process in the case where, medicament is impermeable to depths in fiber, from fiber
Surface successively hydrolyzes, therefore, derive it is more in fiber sheath portion carboxyl and in fiber the few structure of depths carboxyl.In this way
The fiber of structure cause fiber sheath portion to become intolerant in practical the dissolution etc. of water.
In addition, in modified propylene nitrile series fiber of the invention, the dissolubility to 58% sodium thiocyanate water solution be 95% with
On characteristic indicate to have in previous crosslink propylene acid esters system moisture-absorbing fibre and recycled caused by the dissolution that can not carry out
A possibility that.Dissolubility to dimethylformamide is that 50% characteristic below indicates there is organic solvent resistance.To 1g/L carbon
The dissolubility of acid sodium aqueous solution be 5% characteristic below be expressed as do not have covalent bond caused by intermolecular cross-linking structure and
Fiber with the high carboxyl of a large amount of hydrophilies, and also it is resistant to the processing of soaping in washing, dyeing process.
Then, the amount as the carboxyl of modified propylene nitrile series fiber of the invention is 0.2~4.0mmol/g, preferably 0.5
~3.5mmol/g, more preferable 1.0~3.5mmol/g.In the case that the amount of carboxyl is unsatisfactory for lower limit, it is unable to get sometimes sufficiently
Moisture pick-up properties, be more than the upper limit in the case where, the water-swellable of fiber becomes excessively high, it is sometimes practical on not preferably.
As the state of carboxyl, in the case where paying attention to moisture pick-up properties, preferably gegenion is the cation in addition to H.On
In the case of stating, as cation example, can enumerate the alkaline-earth metal such as the alkali metal such as Li, Na, K, Be, Ca, Ba, Cu, Zn,
The metals such as Al, Mn, Ag, Fe, Co, Ni, NH4, cations such as amine etc., a variety of cations can also be mixed.Wherein, Li, Na,
K, Mg, Ca, Zn etc. are suitable.
In addition, the excellent of the aldehyde such as the sour gas to acetic acid, isovaleric acid etc., formaldehyde can also be embodied under above situation
Deodoriging properties.In addition, flame retardant property is high if it is Mg, Ca ion, it can about anti-microbial property if it is Ag, Cu ion
To obtain high effect.
On the other hand, if gegenion is state of the form of H, i.e. COOH as carboxyl, especially with regard to ammonia, three second
Deodoriging properties, antiviral property, the antianaphylaxis energy of the amine-based gas such as amine, pyridine etc., embody excellent performance.
In the case that modified propylene nitrile series fiber of the invention is used as moisture-absorbing fibre, as 20 DEG C, it is opposite
Saturation moisture absorption under 65% atmosphere of humidity, it is generally desirable to, preferably 3 weight %, more preferable 5 weight %, further preferred 10 weight
Measure % or more.
In addition, in modified propylene nitrile series fiber of the invention, it is generally desirable to, carboxyl is whole throughout fiber and exists.Herein,
Exist and refer to throughout fiber entirety, the containing ratio of the magnesium elements in fibre section measured by aftermentioned measuring method
Coefficient of variation CV is 50% or less.In modified propylene nitrile series fiber of the invention, such as above-mentioned, the highly concentrated part of carboxyl and itrile group
Highly concentrated part is whole throughout fiber and exists, so as to inhibit the crisp of fiber caused by the hygroscopicity of carboxyl
Change, can have and be resistant to not having cross-linked structure in practical fibrous physical property.
Above-mentioned modified propylene nitrile series fiber of the invention can individually or with other combination of raw materials, can be a variety of
It uses and is utilized on the way as useful fiber construct.It as other raw material, is not particularly limited, common day can be used
Right fiber, organic fiber, semisynthetic fibre, synthetic fibers can also use inorfil, glass fibers depending on the application in turn
Dimension etc..As concrete example, cotton, fiber crops, silk, wool, nylon, artificial silk, polyester, acrylic fiber etc. can be enumerated.
As the mode of appearance of the fiber construct, have: silk, non-woven fabrics, paper-like object, tablet, laminated body, cotton like body
(including spherical, blocky person) etc..Contain form as the fiber of the invention in the works, by with other raw material
Mixing, has: not substantially being uniformly distributed person；In the case where with multilayer, in random layer (can be odd number or multilayer)
It concentrates and there are persons；In layers with specific ratios distribution person etc..
By the mode of appearance of the fiber construct of above-mentioned example, containing form, constitute other former materials of the fiber construct
Which kind of material and other components combined with the fiber construct are set as, it may be considered that modified propylene nitrile series fiber of the invention has
Help according to required by the type (such as dress material product, filter, curtain, carpet, bedding, cushion, insole etc.) of final product
Function, characteristic, shape, embody above-mentioned function mode etc. and be suitable for determining.
Embodiment
Hereinafter, show embodiment to facilitate the understanding of the present invention, but these only examples, purport of the invention is not
It is defined in these.It should be noted that part and percentage mean that weight basis unless otherwise specified in embodiment.
The measurement > of the total carboxyl amount of <
After addition 1mol/l aqueous hydrochloric acid solution makes pH 2 in the sample, is washed, dried, the examination that precision weighing obtains
The water of 200ml is added in sample about 1g (W1 [g]) thereto, finds out drop according to conventional method with 0.1mol/l sodium hydrate aqueous solution
Determine curve.Sodium hydrate aqueous solution consumption consumed by carboxyl (V1 [ml]) is found out as the titration curve, is calculated by following formula
Carboxyl amount.
Carboxyl amount [mmol/g]=0.1 × V1/W1
Deliquescent measurement > of the < to sodium thiocyanate water solution
The dried sample of precision weighing about 1g (W2 [g]), is added 58% sodium thiocyanate water solution of 100ml, with 80 DEG C
Dipping was filtered, washes, dries after 1 hour.Sample (W3 [g]) after precision weighing is dry, is calculated by following formula and is dissolved
Property.
Dissolubility [%]=(1-W3/W2) × 100
Deliquescent measurement > of the < to dimethylformamide
Solution is changed to DMF, immersion condition is changed to 30 DEG C, 1 hour, in addition to this, with < to sodium sulfocyanate water
The deliquescent measurement > of solution similarly calculates dissolubility.
Deliquescent measurement > of the < to aqueous sodium carbonate
Solution is changed to the aqueous sodium carbonate of 1g/L, immersion condition is changed to 95 DEG C, 30 minutes, in addition to this,
Dissolubility is calculated in the same manner as < is to the deliquescent measurement > of sodium thiocyanate water solution.
The measurement > of < saturation moisture absorption
Sample is 16 hours dry with 105 DEG C in air drier, it measures weight (W4 [g]).Then, by the sample thing
It is first put into the Constant Temperature and Humidity Chambers for the condition for being adjusted to 20 DEG C × 65%RH 24 hours.Measure the weight of the sample of such moisture absorption
(W5[g]).By above measurement result, calculated by following formula.
Saturation moisture absorption [%]=(W5-W4)/W4 × 100
The distribution > of carboxyl in < fibre structure
It is immersed in fiber samples dissolved with being equivalent in the aqueous solution of 2 times of magnesium nitrate of carboxyl amount contained in fiber
It 50 DEG C × 1 hour, to implement ion-exchange treatment, washed, dried, thus make the gegenion magnesium of carboxyl.For
As the fiber samples of magnesium salts type, using energy dispersion X-ray spectrometer (EDS), from the outer rim of fibre section to center with big
Cause selects 10 points of measuring point at equal intervals, measures the containing ratio of the magnesium elements in each measuring point.By the number of each measuring point of gained
Value calculates coefficient of variation CV [%] by following formula.
Coefficient of variation CV [%]=(standard deviation/average value) × 100
The measurement > of the moisture rate of unseasoned fiber after < stretching
Make stretch after unseasoned fiber impregnation in pure water after, with centrifugal dehydrator (domestic centrifuge Co. Ltd. system
TYPE H-770A), it is dehydrated within 2 minutes with centrifugal acceleration 1100G (G indicates acceleration of gravity) progress.Weight after measurement dehydration
It is after (being set as W6), the unseasoned fiber is 15 minutes dry with 120 DEG C, it measures weight (being set as W7), is calculate by the following formula.
Moisture rate (%)=(W6-W7)/W6 × 100 of unseasoned fiber after stretching
1 > of < embodiment
By in 90 parts of sodium thiocyanate water solution of 48% dissolved with being formed by acrylonitrile 90% and methyl acrylate 10%
The spinning solution that 10 parts of acrylic polymer is spun in -2.5 DEG C of coagulating bath, is solidified, is washed, 12 times of stretchings, obtained
To the gel acrylic fiber for the raw material that moisture rate is 35%.By the fiber impregnation in 1.0% sodium hydrate aqueous solution
In and drawing after, in damp and hot atmosphere, carry out 123 DEG C × 25 minutes hydrolysis process, washed, dried, obtained of the invention
Modified propylene nitrile series fiber.By gained fiber evaluation result is shown in table 1.
2~6 > of < embodiment
In the formula of embodiment 1, for the concentration of sodium hydrate aqueous solution, 2.5%, embodiment 3 is changed in embodiment 2
In be changed to be changed to be changed in 10%, embodiment 5 in 7.5%, embodiment 4 to be changed to 20% in 15%, embodiment 6, remove
Except this, modified propylene nitrile series fiber of the invention is got similarly.By gained fiber evaluation result is shown in table 1.
7~9 > of < embodiment
In the formula of embodiment 3, instead of 7.5% sodium hydrate aqueous solution, 7.5% hydroxide is used in embodiment 7
In aqueous solutions of potassium, embodiment 8 using 7.5% lithium hydroxide aqueous solution, use in embodiment 9 7.5% aqueous sodium carbonate,
In addition to this, modified propylene nitrile series fiber of the invention is got similarly.By gained fiber evaluation result is shown in table 1.
10 > of < embodiment
In the formula of embodiment 1, makes 10 DEG C of coagulation bath temperature, the moisture rate of gel acrylic fiber is adjusted to
67%, and the concentration of sodium hydrate aqueous solution is changed to 3.8%, in addition to this, get similarly modified propylene of the invention
Nitrile series fiber.By gained fiber evaluation result is shown in table 1.
< embodiment 11,12 >
In the formula of embodiment 3, for the temperature condition of hydrolysis process, 113 DEG C are set as in embodiment 11, in embodiment 12
135 DEG C are set as, in addition to this, gets similarly modified propylene nitrile series fiber of the invention.The evaluation result of gained fiber is shown
In table 1.
1 > of < comparative example
For the gel acrylic fiber that the formula with embodiment 1 obtains, instead of using sodium hydrate aqueous solution into
Row hydrolysis process in damp and hot atmosphere, heat within 123 DEG C × 25 minutes, obtains the fiber without carboxyl.By gained
Fiber evaluation result is shown in table 1.
2 > of < comparative example
It is formed being dissolved in 90 parts of sodium thiocyanate water solution of 48% by acrylonitrile 92.5% and methacrylic acid 7.5%
10 parts of acrylic polymer of spinning solution spin according to conventional method, after being solidified, washed, being stretched, dry, obtain
Acrylic fiber with carboxyl.By gained fiber evaluation result is shown in table 1.
3 > of < comparative example
By in 90 parts of sodium thiocyanate water solution of 48% dissolved with being formed by acrylonitrile 85% and methacrylic acid 15%
The spinning solution that 10 parts of acrylic polymer is spun according to conventional method, dry after being solidified, washed, being stretched, and is had
There is the acrylic fiber of carboxyl.By gained fiber evaluation result is shown in table 1.
4 > of < comparative example
It is infiltrated in the fiber obtained in comparative example 1 without carboxyl water-soluble containing 0.5% hydrazine and 2% sodium hydroxide
In liquid, heat within 115 DEG C × 2 hours, obtains the fiber with cross-linked structure and carboxyl.By the evaluation knot of gained fiber
Fruit is shown in table 1.
[table 1]
As shown in table 1 like that, the modified propylene nitrile series fiber for the embodiment 1~12 that manufacturing method through the invention obtains
Have following feature: the carboxyl with 0.2~4.0mmol/g, the dissolubility to 58% sodium thiocyanate water solution are 95% or more,
And it is 50% or less to the dissolubility of dimethylformamide or is 5% or less to the dissolubility of 1g/L aqueous sodium carbonate.
In addition, the fiber of comparative example 2 and 3 obtained from being copolymerized the monomer with carboxyl is dissolved completely in dimethyl formyl
Amine also has dissolubility in aqueous sodium carbonate.In contrast, it is known that, 3 He of embodiment of the carboxyl amount with equal extent
4 modified propylene nitrile series fiber of the invention is neither easily soluble in dimethylformamide, also not readily dissolves in aqueous sodium carbonate.
Claims (7)
1. a kind of modified propylene nitrile series fiber, which is characterized in that the carboxyl with 0.2~4mmol/g, to 58% sodium sulfocyanate water
The dissolubility of solution is 95% or more, and is 50% or less to the dissolubility of dimethylformamide.
2. a kind of modified propylene nitrile series fiber, which is characterized in that the carboxyl with 0.2~4mmol/g, to 58% sodium sulfocyanate water
The dissolubility of solution is 95% or more, and is 5% or less to the dissolubility of 1g/L aqueous sodium carbonate.
3. modified propylene nitrile series fiber according to claim 1 or 2, which is characterized in that the saturation under 20 DEG C × 65%RH
Hydroscopicity is 3% or more.
4. modified propylene nitrile series fiber described in any one of claim 1 to 3, which is characterized in that carboxyl spreads fiber
Integrally exist.
5. a kind of manufacturing method of modified propylene nitrile series fiber, which is characterized in that the spinning of acrylic polymer will be dissolved with
After stoste is spun from nozzle, through solidification, washing, stretching each process and obtain unseasoned fiber, the unseasoned fiber that will be obtained
Hydrolysis.
6. the manufacturing method of modified propylene nitrile series fiber according to claim 5, which is characterized in that the water of unseasoned fiber
Dividing rate is 20~250%.
7. a kind of fiber construct contains modified propylene nitrile series fiber according to any one of claims 1 to 4.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2016/076815 WO2018047344A1 (en) | 2016-09-12 | 2016-09-12 | Modified acrylonitrile-based fiber, method for producing said fiber, and fibrous structure containing said fiber |
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| CN109689951A true CN109689951A (en) | 2019-04-26 |
| CN109689951B CN109689951B (en) | 2022-03-22 |
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| CN201680089157.3A Active CN109689951B (en) | 2016-09-12 | 2016-09-12 | Modacrylic fiber, method for producing the fiber, and fiber structure containing the fiber |
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| JP (1) | JP6819686B2 (en) |
| CN (1) | CN109689951B (en) |
| TW (1) | TWI727079B (en) |
| WO (1) | WO2018047344A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111133137A (en) * | 2017-09-22 | 2020-05-08 | 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 |
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| JP7177982B2 (en) * | 2017-11-06 | 2022-11-29 | 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 |
| 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 |
| 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 |
| 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 |
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| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018047344A1 (en) | 2018-03-15 |
| TW201816211A (en) | 2018-05-01 |
| TWI727079B (en) | 2021-05-11 |
| JP6819686B2 (en) | 2021-01-27 |
| JPWO2018047344A1 (en) | 2019-06-27 |
| CN109689951B (en) | 2022-03-22 |
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