CN106958148B - Dry-spun polyurethane elastic fiber - Google Patents
Dry-spun polyurethane elastic fiber Download PDFInfo
- Publication number
- CN106958148B CN106958148B CN201610962929.1A CN201610962929A CN106958148B CN 106958148 B CN106958148 B CN 106958148B CN 201610962929 A CN201610962929 A CN 201610962929A CN 106958148 B CN106958148 B CN 106958148B
- Authority
- CN
- China
- Prior art keywords
- silicone
- mass
- polyurethane series
- agent
- improver
- 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
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided is a dry-spun polyurethane elastic fiber which has excellent unwinding properties, unwinding properties over time, yarn skipping resistance and scum deposition resistance, and which is simultaneously imparted to a polyurethane elastic fiber having a DSC heat release value in a specific range. A fiber having 0.1 to 10 mass% of a treatment agent attached to a polyurethane elastic fiber is used: the polyurethane elastic fiber has a DSC heat release of 150 to 450mJ/mg at 150 to 300 ℃; the treating agent contains 85 to 99.7 mass% of a smoothing agent and 0.3 to 15 mass% of a reelability improving agent (total 100 mass%); the smoothing agent is at least one selected from silicone oil, mineral oil and ester; the unwinding property-improving agent is at least one selected from the group consisting of a silicone resin having a 3-functional and/or 4-functional siloxane unit as a structural unit in the molecule and having a mass average molecular weight of 3000 to 100000, and a fatty acid alkaline earth metal salt having 10 to 22 carbon atoms.
Description
Technical field
The present invention relates to dry spinning polyurethane series elastomer, more specifically, it is related to while assigns excellent unwinding
Property, with the easy zbility of time, resistance to hand pick and resistance to scum silica frost (scum) accumulation property dry spinning polyurethane series elastomer.
Background technology
In the past, as dry spinning polyurethane series elastomer, it is known that：It is attached with the fiber of inorganic agent, the place
Manage agent and include the modified silicone with end group end-sealed type polyether-based (referring for example to patent document 1)；It is attached with inorganic agent
Fiber, the inorganic agent contain water-soluble silicone (referring for example to patent document 2)；It is attached with the fiber of inorganic agent, the processing
Agent contains polyalkylene ether glycols, higher alcohol, mineral oil and dimethyl silscone (referring for example to patent document 3)；It is attached with processing
The fiber of agent, the inorganic agent contain the various fibers such as mineral oil and aliphatic ester compound (referring for example to patent document 4).So
And in these conventional dry spinning polyurethane series elastomers, there are the following problems：To (following by differential scanning calorimetry (DSC)
Referred to as DSC) easy zbility, unwinding with the time that is assigned for the polyurethane series elastomer of particular range of the obtained thermal discharge of measure
Property, resistance to hand pick and resistance to scum silica frost accumulation property it is insufficient.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 9-296377
Patent document 2：Japanese Unexamined Patent Publication 10-158938
Patent document 3：Japanese Unexamined Patent Publication 2005-344215 publications
Patent document 4：Japanese Unexamined Patent Publication 2011-42891 publications.
The content of the invention
Problems to be solved by the invention
The problem to be solved in the present invention is, there is provided to the poly- ammonia that the thermal discharge measured by DSC is particular range
Ester system elastomer assigns excellent easy zbility, is obtained with the easy zbility of time, resistance to hand pick and resistance to scum silica frost accumulation property at the same time
Dry spinning polyurethane series elastomer.
The method for solving problem
The inventors of the present invention are studied to solve aforementioned problems, it turns out that correctly and it is appropriate that to passing through
The thermal discharge that DSC is measured adheres to particular procedure agent for the polyurethane series elastomer of particular range with special ratios, described
Particular procedure agent contains specific smooth agent and specific easy zbility improver with special ratios.
That is, the present invention relates to dry spinning polyurethane series elastomer, it is characterised in that fine to following polyurethane series elasticity
Dimension, adheres to following inorganic agents with the ratio of 0.1 ~ 10 mass %,
Polyurethane series elastomer：Thermal discharge at 150 ~ 300 DEG C obtained is measured by differential scanning calorimetry (DSC) (DSC)
For the polyurethane series elastomer of 150 ~ 450mJ/mg；
Inorganic agent：Contained comprising following smooth agents and following easy zbility improvers and with the ratio of 85 ~ 99.7 mass %
Following smooth agents and the inorganic agent for containing following easy zbility improvers (total 100 mass %) with the ratio of 0.3 ~ 15 mass %；
Smooth agent：Selected from least one of silicone oil, mineral oil and ester；
Easy zbility improver：There are 3 functional silicone's units and/or 4 functional silicone's units to make in molecule
The silicone resin for being 3000 ~ 100000 for construction unit and matter average molecular weight and the aliphatic acid alkaline earth that carbon number is 10 ~ 22
At least one of metal salt.
Embodiment
In dry spinning polyurethane series elastomer (hereinafter referred to as elastomer of the invention) of the present invention, poly- ammonia
Ester system elastomer is the polyurethane series bullet that the thermal discharge at 150 ~ 300 DEG C measured by DSC is 150 ~ 450mJ/mg
Property fiber.For polyurethane series elastomer DSC measure, there are it is multiple report (Japanese Unexamined Patent Application Publication 2010-509512 publications,
International Publication WO2004/113599 etc.).In the elastomer of the present invention, polyurethane series elastomer is measured by DSC
To 150 ~ 300 DEG C at thermal discharge can be obtained by following manner：Sample is cooled to 10 DEG C/min from 25 DEG C-
After 50 DEG C, measure with 10 DEG C/min of thermal discharges at 150 ~ 300 DEG C when being warming up to 300 DEG C for -50 DEG C., can be with as DSC
The trade name DSC6200 manufactured using Seiko Instruments Inc., the sampling amount for making polyurethane series elastomer are
3mg, object of reference use Al2O3, so as to be measured.
The thermal discharge being attached at 150 ~ 300 DEG C measured as previously described by DSC is the poly- ammonia of particular range
Inorganic agent on ester system elastomer includes smooth agent and easy zbility improver.Used smooth agent is selected from silicone oil, ore deposit
At least one of thing oil and ester.
As the concrete example of the silicone oil as smooth agent, the trade name that chemical industrial company of SHIN-ETSU HANTOTAI manufactures can be enumerated
KF-96-10cs, the trade name KF-96-20cs of chemical industrial company of SHIN-ETSU HANTOTAI manufacture, the commodity of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
Name KF-96-50cs, the trade name KF-50-100cs of chemical industrial company of SHIN-ETSU HANTOTAI manufacture, the business of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
Name of an article KF-4003, trade name KF-4917, the Momentive Performance of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
Trade name TSF451-10, the Momentive Performance Materials Inc. manufactures of Materials Inc. manufactures
Trade name TSF451-20, Dow Corning Toray Co., trade name SH200-10CS, Dow of Ltd. manufactures
Trade name SH510-100CS of Corning Toray Co., Ltd. manufactures etc..They are viscosity at 25 DEG C for 2 ~
100mm2The dimethyl silicone polymer of/s, polyalkylsiloxane, polyalkylphenylsilox,ne etc., can use a kind or 2 kinds with
On.
In addition, the mineral oil as smooth agent is also not particularly limited, it can use commercially available product, as described commercially available
Product, can enumerate Witoco companies manufacture trade name Semtol40, Witoco company manufacture trade name Carnation,
Trade name U ス モ ピ ュ ア ス ピ Application D, COSMO OIL of COSMO OIL LUBRICANTS CO., LTD. manufactures
Trade name U ス モ ピ ュ ア ス ピ Application RC, the COSMO OIL LUBRICANTS of LUBRICANTS CO., LTD. manufactures
CO., the trade name U ス モ ピ ュ ア ス ピ Application RB of LTD. manufactures, the trade name Off ッ U ー Le of Xing Chan companies of Fuji manufacture
The trade name Ultra-S2 for trade name Off ッ U ー Le NT-100, S-OIL companies manufacture that NT-60, Xing Chan companies of Fuji manufacture,
Trade name YUBASE 3, the SK of trade name Ultra-S3, the SK Lubricants companies manufacture of S-OIL companies manufacture
Trade name YUBASE 4, the trade name ダ イ ア Na Off レ シ ア of light extraction Xing Chan companies manufacture of Lubricants companies manufacture
W8, trade name ダ イ ア Na Off レ シ ア W32 of light extraction Xing Chan companies manufacture, the trade name ダ イ ア of light extraction Xing Chan companies manufacture
Na Off レ シ ア G9, trade name ダ イ ア Na Off レ シ ア K8, the Exxon Mobil of the manufacture of light extraction Xing Chan companies
Viscosity at 25 DEG C of trade name Network リ ス ト ー Le N72 of Corporation manufactures etc. is 2 ~ 100mm2Spindle oil, the liquid stone of/s
Wax etc., they can use one kind or two or more.
Further, the ester as smooth agent is also not particularly limited, and can enumerate as illustrated below by various fat
Fat acid and the ester of alcohol manufacture, they can use one kind or two or more, but the viscosity at preferably 25 DEG C is 2 ~ 100mm2The ester of/s.
In aliphatic acid as the raw material of foregoing ester, for its carbon number, whether there is branch, valence mumber etc. and do not limit especially
It is fixed, it can be higher fatty acids or cricoid aliphatic acid, can also be the aliphatic acid with aromatic ring.As described
Aliphatic acid, can enumerate octanoic acid, 2 ethyl hexanoic acid, capric acid, laurate, different tridecanoic acid, myristic acid, palmitic acid, stearic acid,
Isostearic acid, oleic acid, arachidic acid, behenic acid, lignoceric acid, adipic acid, decanedioic acid, benzoic acid etc..
In addition, the alcohol of the raw material as foregoing ester, for its carbon number, whether there is branch, valence mumber etc. and be not particularly limited,
It can be higher alcohol or cricoid alcohol, can also be the alcohol with aromatic ring.As the alcohol, can enumerate octanol,
2-Ethylhexyl Alcohol, decyl alcohol, laruyl alcohol, isotrideyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, isooctadecanol, oleyl alcohol, second two
Alcohol, hexylene glycol, glycerine, trimethylolpropane, pentaerythrite, D-sorbite, sorbitan etc..
For the easy zbility improver used in inorganic agent, using have in molecule 3 functional silicone's units and/
Or 4 functional silicone's unit as the silicone resin and carbon atom that construction unit and matter average molecular weight are 3000 ~ 100000
Number is the easy zbility improver of 10 ~ 22 fatty acid alkali salt.They can use one kind or two or more.Matter average molecular weight
It can be measured gel permeation chromatography (hereinafter referred to as GPC) in a manner of polystyrene conversion to obtain.
For used silicone resin, as long as it is foregoing resin, then its species is not particularly limited, preferably
Selected from MQ silicone resins, MDQ silicone resins, T silicone resins and MTQ silicone resins, MQ silicone resins, MDQ silicon are more preferably selected from
Ketone resin and MTQ silicone resins.Wherein, as silicone resin, using selected from MQ silicone resins, MDQ silicone resins and MTQ silicone
During the resin of resin, particularly preferably using the resin that M/Q ratios are 0.5 ~ 1.1.It should illustrate that be preced with M, D before silicone resin,
T, Q is form of presentation as the expression method for the siloxane unit for forming silicone resin and usually used, and M is that general formula is
R1R2R3SiO1/21 shown functional silicone's unit, D are that general formula is R4R5SiO2/22 shown functional silicone's units, T
It is that general formula is R6SiO3/23 shown functional silicone's units, Q are that general formula is SiO4/24 shown functional silicone's units.
Here, R1~R6Alkyl, general formula for carbon number 1 ~ 24 are-R7NHR8NH2(R7And R8For the alkyl of carbon number 2 or 3) ,-
R9NH2(R9For the alkyl of carbon number 2 or 3) etc. shown in organic amino, vinyl, carbitol base etc..
For the fatty acid alkali salt that the carbon number as easy zbility improver is 10 ~ 22, also without more
It is particularly limited to, capric acid, laurate, myristic acid, palmitic acid, Heptadecanoic acide, stearic acid, oleic acid, linoleic acid etc. can be enumerated
Calcium salt, magnesium salts etc., wherein preferably magnesium stearate.Commercially available product can be used as magnesium stearate, can be with as the commercially available product
Enumerate the trade name of trade name SAK-MS-P, the SUN ACE CORPORATION manufactures of SUN ACE CORPORATION manufactures
Trade name マ グ ネ シ ウ system ス テ ア レ ー ト G, the commodity of You companies manufacture of SAK-MS-P/USP, You company manufacture
Name マ グ ネ シ ウ system ス テ ア レ ー ト GF-200, the trade name マ グ ネ シ ウ system ス テ ア レ ー ト of You companies manufacture
GR, You company manufacture trade name work マ グ ネ シ ウ system ス テ ア レ ー ト, You companies manufacture day office magnesium stearate,
Trade name Mg-LF of trade name Mg-St, Dong chemical conversion industry company manufacture of Dong chemical conversion industries company manufacture etc..
Inorganic agent includes the smooth agent and easy zbility improver of described above, is contained smoothly with the ratio of 85 ~ 99.7 mass %
Agent and easy zbility improver (total 100 mass %) is contained with the ratio of 0.3 ~ 15 mass %, preferably with 90 ~ 99.7 mass %'s
Ratio contains smooth agent and contains easy zbility improver (total 100 mass %) with the ratio of 0.3 ~ 10 mass %.
Inorganic agent includes the smooth agent and easy zbility improver of described above, can also be combined as needed according to its purpose
Use other components.For example, wettability improving agent, ultra-violet absorber, antioxidant, preservative etc. for it.It is described its
The content of its component can suitably be determined according to purpose within the scope without prejudice to the object of the present invention, as preferably be few as possible
Amount.
The preparation method of the inorganic agent of described above is not particularly limited, it can apply known method.
Inorganic agent as described above can be made to be attached to polyurethane series elasticity under without diluted undiluted state fine
Dimension.As adherence method, can with application roll to oil process, yarn guide to oil process, spray to method known to oil process etc..Attachment steps
Preferably spinning process.As the spinning process in spinning process, dry spinning method, melt spinning method, wet type can be enumerated and spun
Silk method etc., wherein, using dry spinning method.The adhesion amount of inorganic agent for polyurethane series elastomer reaches 0.1 ~
10 mass %, preferably reach 1 ~ 8 mass %.It should illustrate that the form of polyurethane series elastomer is not particularly limited, can apply
The fiber of long filament system, can also apply the fiber of short fine system.
The effect of invention
The present invention according to the above description, has the effect that：Can obtain to measured by DSC 150 ~ 300
The polyurethane series elastomer that thermal discharge at DEG C is 150 ~ 450mJ/mg assigns excellent easy zbility, unwinding with the time at the same time
Property, resistance to hand pick and resistance to scum silica frost accumulation property obtained from dry spinning polyurethane series elastomer.
Embodiment
Hereinafter, in order to make the composition of the present invention and effect more specifically enumerate embodiment etc., but the present invention is from these realities
Apply the limitation of example.It should illustrate that in following embodiment etc., part refers to mass parts, in addition, % refers to quality %.
Experiment 1 (preparation as the silicone resin of easy zbility improver) of packet
The preparation of SIR-1
By trimethylmethoxysilane 823.338g (7.9 moles), water 800g, methanesulfonic acid 2.0g and tetraethoxysilane
(10 moles) of 2083.3g input is into reaction vessel, and heating is so as to keep the temperature of reaction system to 65 DEG C, heating stirring 24
Hour.Then, after adding sodium acid carbonate 1.78g so as to be neutralized, when reflux 5 is small, cured.Further add dimethylbenzene
2000g, by water and because of reaction and after the methanol of by-product and ethanol distillation removed so as to be replaced as xylene solution, carries out full dose
Filtering.The valid density (the silicone resin concentration in xylene solution) of obtained filtrate is adjusted to after 50%, by its total amount
Put into N- (2- amino-ethyls) -3- amino propyl methyl dimethoxysilanes 20.636g (0.1 mole) and water 10g to another
In reaction vessel, reacted when progress 1 is small at 80 DEG C.Dimethylbenzene, water, methanol are distilled off from reaction solution, so as to obtain
Silicone resin SIR-1.For silicone resin SIR-1, when carrying out following analysis, silicone resin SIR-1 is matter average molecular weight
For 20000 silicone resin, wherein R1、R2、R3General formula when being methyl is R1R2R3SiO1/21 shown functional silicone
Unit/R4For N- (2- amino-ethyls) -3- aminopropyls and R5For methyl when general formula be R4R5SiO2/22 shown functionality silicon
Oxygen alkane unit/general formula is SiO4/2Shown 4 functional silicone's units=7.9/0.1/10 (molar ratio).
Form the analysis of the siloxane unit of silicone resin
Silicone resin SIR-1 is analyzed for H NMR spectroscopy, calculates the molar ratio for the siloxane unit for forming silicone resin.With
Same mode, for other silicone resins, calculates the molar ratio for forming respective siloxane unit.
The preparation of SIR-2
By trimethylmethoxysilane 729.54g (7 moles), water 800g, methanesulfonic acid 2.0g and tetraethoxysilane
(10 moles) of 2083.3g input is into reaction vessel, and heating is so as to keep the temperature of reaction system to 65 DEG C, heating stirring 24
Hour.Then, after adding sodium acid carbonate 1.78g so as to be neutralized, when reflux 5 is small, cured.Further add dimethylbenzene
2000g, by water and because of reaction and after the methanol of by-product and ethanol distillation removed so as to be replaced as xylene solution, carries out full dose
Filtering, is further distilled off dimethylbenzene, so as to obtain silicone resin SIR-2.Analyzed for silicone resin SIR-2
When, it is the silicone resin that matter average molecular weight is 11000, wherein R1、R2、R3General formula when being methyl is R1R2R3SiO1/2Institute
The 1 functional silicone's unit/general formula shown is SiO4/24 shown functional silicone unit=7/10 (molar ratio).
The preparation of SIR-3
By trimethylmethoxysilane 1042.2g (10 moles), water 800g, methanesulfonic acid 2.0g and tetraethoxysilane
(10 moles) of 2083.3g input is into reaction vessel, and heating is so as to keep the temperature of reaction system to 65 DEG C, heating stirring 24
Hour.Then, after adding sodium acid carbonate 1.78g so as to be neutralized, when reflux 5 is small, cured.Further add dimethylbenzene
2000g, by water and because of reaction and after the methanol of by-product and ethanol distillation removed so as to be replaced as xylene solution, carries out full dose
Filtering, is further distilled off dimethylbenzene, so as to obtain silicone resin SIR-3.Analyzed for silicone resin SIR-3
When, it is the silicone resin that matter average molecular weight is 8000, wherein R1、R2、R3General formula when being methyl is R1R2R3SiO1/2It is shown
1 functional silicone's unit/general formula be SiO4/24 shown functional silicone unit=1/1 (molar ratio).
The preparation of SIR-4
By trimethylmethoxysilane 1042.2g (10 moles), water 800g, methanesulfonic acid 2.0g and tetraethoxysilane
(10 moles) of 2083.3g input is into reaction vessel, and heating is so as to keep the temperature of reaction system to 65 DEG C, heating stirring 24
Hour.Then, after adding sodium acid carbonate 1.78g so as to be neutralized, when reflux 5 is small, cured.Further add dimethylbenzene
2000g, by water and because of reaction and after the methanol of by-product and ethanol distillation removed so as to be replaced as xylene solution, carries out full dose
Filtering.The valid density (the silicone resin concentration in xylene solution) of obtained filtrate is adjusted to after 50%, by its total amount
Put into N- (2- amino-ethyls) -3- amino propyl methyl dimethoxysilanes 206.36g (1 mole) and water 10g to another anti-
Answer in container, reacted when progress 1 is small at 80 DEG C.Dimethylbenzene, water and methanol are distilled off from reaction solution, so as to obtain silicon
Ketone resin SIR-4.When being analyzed for silicone resin SIR-4, it is the silicone resin that matter average molecular weight is 7000, wherein
R1、R2、R3General formula when being methyl is R1R2R3SiO1/2Shown 1 functional silicone's unit/R4For N- (2- amino second
Base) -3- aminopropyls and R5For methyl when general formula be R4R5SiO2/2Shown 2 functional silicone's units/general formula is SiO4/2
4 shown functional silicone unit=10/1/10 (molar ratio).
The preparation of SIR-5
Hexyl trimethoxy silane 2063.5g (10 moles), water 800g, methanesulfonic acid 2.0g are put into reaction vessel,
Heating is so as to keeping the temperature of reaction system to 65 DEG C, when heating stirring 24 is small.Then, add sodium acid carbonate 1.78g so as to
After being neutralized, when reflux 5 is small, cured.Dimethylbenzene 2000g is further added, by water and the first of by-product because of reaction
After alcohol is distilled off so as to be replaced as xylene solution, full dose filtering is carried out, dimethylbenzene is further distilled off, so as to obtain silicon
Ketone resin SIR-5.When being analyzed for silicone resin SIR-5, it is the silicone resin that matter average molecular weight is 4500, it includes
R6For hexyl when general formula be R6SiO3/23 shown functional silicone's units.
The preparation of SIR-6
By N- (2- amino-ethyls) -3- TSL 8330s 2223.6g (10 moles) and water 800g put into
In reaction vessel, heating so as to keeping the temperature of reaction system to 65 DEG C, be heated at reflux stirring 24 it is small when.Then, by water with
And because of reaction and the methanol of by-product is distilled off, so as to obtain silicone resin SIR-6.Analyzed for silicone resin SIR-6
When, it is the silicone resin that matter average molecular weight is 5000, and it includes R6For N- (2- amino-ethyls) -3- aminopropyls when general formula
For R6SiO3/23 shown functional silicone's units.
The preparation of SIR-7
By trimethylmethoxysilane 312.66g (3 moles), hexyl trimethoxy silane 206.35g (1 mole), water
800g, methanesulfonic acid 2.0g and (5 moles) of tetraethoxysilane 1041.65g input are into reaction vessel, and heating is so as to by reactant
The temperature of system is kept to 65 DEG C, when heating stirring 24 is small.Then, after adding sodium acid carbonate 1.78g so as to be neutralized, reflux 5
Hour, cured.Further add dimethylbenzene 2000g, by water and because of reaction and the methanol of by-product, ethanol distillation remove from
And after being replaced as xylene solution, full dose filtering is carried out, dimethylbenzene is further distilled off, so as to obtain silicone resin SIR-7.
When being analyzed for silicone resin SIR-7, it is the silicone resin that matter average molecular weight is 30000, wherein R1、R2、R3It is first
General formula during base is R1R2R3SiO1/2Shown 1 functional silicone's unit/R6For hexyl when general formula be R6SiO3/2Shown 3
Functional silicone's unit/general formula is SiO4/24 shown functional silicone unit=3/1/5 (molar ratio).
Experiment 2 (preparations of inorganic agent) of packet
The preparation of inorganic agent (E-1)
For the dimethyl silicone polymer (L-1 of the record of table 1 as smooth agent：The business of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
Name of an article KF-96-10cs) 69.5 parts and mineral oil (L-2：The trade name ダ イ ア Na Off レ シ ア W8 of light extraction Xing Chan companies manufacture)
30 parts and as easy zbility improver table 2 record 0.5 part of MDQ silicone resins (SIR-1), will it is above-mentioned uniformly mix, from
And prepare inorganic agent (E-1).
The preparation of inorganic agent (E-7)
For the dimethyl silicone polymer (L-1 of the record of table 1 as smooth agent：The business of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
Name of an article KF-96-10cs) 88 parts and mineral oil (L-2：The trade name ダ イ ア Na Off レ シ ア W8 of light extraction Xing Chan companies manufacture) 10
Part and 1 part of the MDQ silicone resins (SIR-1) of the record of table 2 and the magnesium stearate (S- of the record of table 3 as easy zbility improver
1：The trade name SAK-MS-P of SUN ACE CORPORATION manufactures) 1 part, after above-mentioned uniformly mixing, with wet type dispersion machine into
Row processing, so as to prepare inorganic agent (E-7).
The preparation of inorganic agent (E-8)
For the dimethyl silicone polymer (L-1 of the record of table 1 as smooth agent：The business of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
Name of an article KF-96-10cs) magnesium stearate (S-1 that records of 96 parts and the table 3 as easy zbility improver：SUN ACE
The trade name SAK-MS-P of CORPORATION manufactures) 4 parts, after above-mentioned uniformly mixing, handled with wet type dispersion machine, from
And prepare inorganic agent (E-8).
The preparation of inorganic agent (E-9)
For the dimethyl silicone polymer (L-1 of the record of table 1 as smooth agent：The business of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
Name of an article KF-96-10cs) 29 parts and mineral oil (L-2：The trade name ダ イ ア Na Off レ シ ア W8 of light extraction Xing Chan companies manufacture) 70
Part and the T silicone resins (SIR-5) 1 recorded of table 2 as easy zbility improver, will it is above-mentioned it is uniform mix, so as to prepare
Inorganic agent (E-9).It should illustrate that in experiment packet 3 described later, it is applied in combination using the inorganic agent (E-9) to every 100 parts
The material that 1 part of Lauryl Diethanolamine is obtained with the salt of cetanol di-phosphate ester.
The preparation of inorganic agent (E-10)
For the dimethyl silicone polymer (L-1 of the record of table 1 as smooth agent：The business of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
Name of an article KF-96-10cs) 87 parts and mineral oil (L-3：The trade name YUBASE 3 of SK Lubricants companies manufacture) 10 parts, with
And 3 parts of the T silicone resins (SIR-6) of the record of table 2 as easy zbility improver, uniformly mixed above-mentioned, so as to prepare processing
Agent (E-10).It should illustrate that in experiment packet 3 described later, it is applied in combination using the inorganic agent (E-10) to every 100 parts
The material that 0.5 part of amino modified silicone (the trade name KF-861 of chemical industrial company of SHIN-ETSU HANTOTAI manufacture) obtains.
The preparation of inorganic agent (E-2) ~ (E-6), (R-1) ~ (R-6) and (R-8)
By with inorganic agent (E-1) it is same in a manner of, smooth agent is uniformly mixed with easy zbility improver, so as to prepare processing
Agent (E-2) ~ (E-6), (R-1) ~ (R-6) and (R-8).
The preparation of inorganic agent (R-7), (R-9) and (R-10)
By with inorganic agent (E-7) it is same in a manner of, after smooth agent and easy zbility improver uniformly mixing, disperseed with wet type
Machine is handled, so as to prepare inorganic agent (R-7), (R-9) and (R-10).The content summary of each inorganic agent produced above is shown
In table 4.
Experiment 3 (evaluations) of packet
The manufacture of dry spinning polyurethane series elastomer
First, will by molecular weight be 2900 tetramethylene ether glycol, it is double-(to isocyanates root close phenyl)-methane and
The N for the polyurethane that ethylenediamine is formed, 35% solution of N'- dimethylacetylamides (hereinafter referred to as DMAc) is polymerize, so as to obtain
Solution (A).
Then, prepare what is generated by the reaction of tertiarybutyldiethanolamine and methylene-bis--(4- cyclohexyl isocyanates)
Polyurethane (the trade name メ タ Network ロ ー Le (registration mark) 2462 of Du Pont companies manufacture) and paracresol and divinylbenzene
The condensation polymer trade name メ タ Network ロ ー Le (registration mark) 2390 of manufacture (Du Pont companies) 2:1 (mass ratio) mixes
35% solution of the DMAc of thing, so as to obtain solution (B).
By previous solu (A) and solution (B) with 96:The ratio uniform mixing of 4 (mass ratioes), so that spinning solution be made.
Using the spinning solution obtained in this way, spun by dry type used in known spandex (spandex)
Silk method, carries out spinning, by the finish roll before batching directly with not to the polyurethane series elastomer of the multifilament of 44dtex/3fil
Inorganic agent (E-1) ~ (E-10) and (R-1) ~ (R-10) is carried out roller oil supply by diluted state.Then, using surface drive
The coiling machine of (surface drive), via assign 38mm volume width traverse guide by the fiber through roller oil supply with
On the cylindric paper tube that it is 58mm to length that the coiling speed of 600m/ minutes, which is batched, it is fine to obtain dry spinning polyurethane series elasticity
The package 500g of dimension.Polyurethane series elastomer with the adjusting of the adhesion amount of inorganic agent by adjusting finish roll rotating speed come into
OK, so that it is 5% that it, which reaches relative to polyurethane series elastomer,.In the step of spinning, DMAc is made by stream of nitrogen gas
Volatilization, but temperature at this time is higher, elongation multiplying power when batching in addition is higher, then and obtained polyurethane series elastomer is logical
The thermal discharge crossed at 150 ~ 300 DEG C that DSC is measured becomes smaller, conversely, temperature when making the DMAc volatilize is lower, rolls up in addition
Elongation multiplying power when taking is lower, then at 150 ~ 300 DEG C measured by DSC of obtained polyurethane series elastomer
Thermal discharge becomes bigger, by by its as table 4 it is described be changed, so as to obtain the thermal discharge with as described in table 4
Each example polyurethane series elastomer.For the package of obtained dry spinning polyurethane series elastomer, carry out following
Measure and evaluation, by result summarize be shown in table 5.
The measure of thermal discharge at 150 ~ 300 DEG C measured by DSC of polyurethane series elastomer
Sample is taken out by the package of the dry spinning polyurethane series elastomer after foregoing obtained immediately spinning, by institute
Sample is stated with 10 DEG C/min after 25 DEG C are cooled to -50 DEG C, 300 DEG C are warming up to from -50 DEG C with 10 DEG C/min, is measured at this time
Thermal discharge at 150 ~ 300 DEG C.It should illustrate that as DSC, the trade name manufactured using Seiko Instruments Inc.
DSC6200, the sampling amount for making polyurethane series elastomer are 3mg, and object of reference uses Al2O3。
The evaluation of easy zbility
One side by the first driven roller and it is normal with its when the first free roller for contacting form unloading part, in addition, in opposite side
Reeling end is formed by the second driven roller and with the second free roller that its is contacted when normal, which is arranged in the horizontal direction
Relative to unloading part distance 20cm.The poly- ammonia of dry spinning after foregoing obtained immediately spinning is installed in the first driven roller
The package of ester system elastomer, untill the unwinding thickness to silk volume reaches 2mm, is batched to the second driven roller.Will be by the first driving
The speed that roller sends out polyurethane series elastomer is fixed as 50m/ minutes, and on the other hand, slowly being improved from 50m/ minutes will be poly-
Urethane system elastomer is batched to the speed of the second driven roller, polyurethane series elastomer is forced from package unwinding.It is described
When forcing unwinding, batching when measuring at the time of the polyurethane series elastomer between submitting portion and reel-up no longer jumps
Speed V (m/ minutes), obtains easy zbility (%) by following numbers 1, is evaluated according to following benchmark.
[number 1]
Easy zbility (%)=(V-50) × 2.
The metewand of easy zbility
◎：Easy zbility is less than 120% (having no problem completely, can be stably unwinding)
○：Easy zbility for 120%, (slightly there are impedance without silk occurs break less than 180% by the pull-out to silk
Split, can be stably unwinding)
×：Easy zbility is for more than 180% (pull-out to silk there are impedance, also there are silk fracture, in the presence of asking in terms of operation
Topic).
With the evaluation of the easy zbility of time
After immediately spinning being replaced using the package for the dry spinning polyurethane series elastomer that 6 months are taken care of after spinning
Dry spinning polyurethane series elastomer package, in addition, carry out the evaluation identical with the evaluation of easy zbility.
The evaluation of resistance to hand pick
Obtain the package of the dry spinning polyurethane series elastomer after foregoing obtained immediately spinning with 20m/ points
Submitting speed, the coiling speed of 40m/ minutes of clock batch the fracture of wire number caused by the hand pick of package during 1000m, pass through
Following benchmark is evaluated.
The metewand of resistance to hand pick
◎：The fracture of wire caused by hand pick is 0 time
○：The fracture of wire caused by hand pick is for 1 time less than 3 times
×：The fracture of wire caused by hand pick is more than 3 times.
The evaluation of resistance to scum silica frost accumulation property
The package of dry spinning polyurethane series elastomer after 10 foregoing obtained immediately spinning is installed on small
Type warping machine, 1500km was batched under 25 DEG C, the atmosphere of 65%RH with the silk speed of 300m/ minutes.At this time, visually observe small
Come off state and the accumulated state of scum silica frost on the combed yarn guide of type warping machine, are evaluated by following benchmark.
The metewand of resistance to scum silica frost accumulation property
◎：Almost without the accumulation of scum silica frost.
○：Scum silica frost is slightly accumulated, but there is no problem in terms of the stable movement of silk.
×：Scum silica frost bulk deposition, silk stablize movement in terms of there are it is larger the problem of.
[table 1]
。
In table 1,
Viscosity：30 DEG C of kinematic viscosity
L-1：The trade name KF-96-10cs of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
L-2：The trade name ダ イ ア Na Off レ シ ア W8 of light extraction Xing Chan companies manufacture
L-3：The trade name YUBASE 3 of SK Lubricants companies manufacture.
[table 2]
。
In table 2,
M1：General formula R1R2R3SiO1/2Shown and R1、R2And R31 functional silicone's unit when being methyl
D1：General formula R4R5SiO2/2Shown and R4And R52 functional silicone's units when being methyl
D2：General formula R4R5SiO2/2Shown and R4For methyl, R5For N- (2- amino-ethyls) -3- aminopropyls when 2 functions
Property siloxane unit
T1：General formula R6SiO3/2Shown and R6For hexyl when 3 functional silicone's units
T2：General formula R6SiO3/2Shown and R6For N- (2- amino-ethyls) -3- aminopropyls when 3 functional silicone's units
Q1：General formula SiO4/24 shown functional silicone's units.
[table 3]
。
[table 4]
。
[table 5]
。
Also can be clear and definite as the result of the table 5 corresponding to 1 ~ table of table 4, according to the present invention it is possible to obtain to being measured by DSC
To thermal discharge assign excellent easy zbility, the easy zbility, resistance to the time at the same time for the polyurethane series elastomer of particular range
Dry spinning polyurethane series elastomer obtained from hand pick and resistance to scum silica frost accumulation property.
Claims (6)
1. dry spinning polyurethane series elastomer, it is characterised in that to following polyurethane series elastomers, with 0.1 ~ 10 matter
The ratio for measuring % adheres to following inorganic agents,
Polyurethane series elastomer：Measuring the thermal discharge at 150 ~ 300 DEG C obtained by differential scanning calorimetry (DSC) (DSC) is
The polyurethane series elastomer of 150 ~ 450mJ/mg
Inorganic agent：Contain comprising following smooth agents and following easy zbility improvers and with the ratio of 85 ~ 99.7 mass % following
Smooth agent and the inorganic agent for containing following easy zbility improvers with the ratio of 0.3 ~ 15 mass %, following smooth agents and following unwinding
The content of property improver adds up to 100 mass %,
Smooth agent：Selected from least one of silicone oil, mineral oil and ester
Easy zbility improver：There are 3 functional silicone's units and/or 4 functional silicone's units in molecule as knot
Structure unit and the silicone resin that matter average molecular weight is 3000 ~ 100000 and the fatty acid alkali that carbon number is 10 ~ 22
At least one of salt.
2. dry spinning polyurethane series elastomer according to claim 1, wherein, the silicone resin of easy zbility improver
For selected from least one of MQ silicone resins, MDQ silicone resins, T silicone resins and MTQ silicone resins.
3. dry spinning polyurethane series elastomer according to claim 1, wherein, the silicone resin of easy zbility improver
For selected from least one of MQ silicone resins, MDQ silicone resins and MTQ silicone resins.
4. dry spinning polyurethane series elastomer according to claim 3, wherein, the silicone resin of easy zbility improver
It is the resin in the case that M/Q ratios are 0.5 ~ 1.1.
5. the dry spinning polyurethane series elastomer according to any one of claim 1 ~ 4, wherein, easy zbility improver
Fatty acid alkali salt be magnesium stearate.
6. the dry spinning polyurethane series elastomer according to any one of claim 1 ~ 4, wherein, inorganic agent with 90 ~
The ratio of 99.7 mass % contains smooth agent, and contains easy zbility improver with the ratio of 0.3 ~ 10 mass %, in inorganic agent
The content of smooth agent and easy zbility improver adds up to 100 mass %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015097488 | 2015-05-12 | ||
| JP2015218771A JP5936293B1 (en) | 2015-05-12 | 2015-11-06 | Dry-spun polyurethane elastic fiber |
| JP2015-218771 | 2015-11-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106958148A CN106958148A (en) | 2017-07-18 |
| CN106958148B true CN106958148B (en) | 2018-05-15 |
Family
ID=56184649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610962929.1A Active CN106958148B (en) | 2015-05-12 | 2016-11-04 | Dry-spun polyurethane elastic fiber |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5936293B1 (en) |
| CN (1) | CN106958148B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6141554B1 (en) * | 2017-02-14 | 2017-06-07 | 竹本油脂株式会社 | Elastic fiber treatment agent and elastic fiber |
| CN111194364B (en) | 2017-10-18 | 2022-07-26 | 旭化成株式会社 | Polyurethane elastic fiber, yarn-wound body thereof, and article comprising same |
| WO2022034868A1 (en) | 2020-08-12 | 2022-02-17 | 旭化成株式会社 | Polyurethane elastic fiber, winding body therefor, gather member, and sanitary material |
| JP6877795B1 (en) * | 2020-09-07 | 2021-05-26 | 竹本油脂株式会社 | Elastic fiber treatment agent and elastic fiber |
| JP6870878B1 (en) * | 2020-09-23 | 2021-05-12 | 竹本油脂株式会社 | Elastic fiber treatment agent and elastic fiber |
| JP6910679B1 (en) * | 2020-12-21 | 2021-07-28 | 竹本油脂株式会社 | Elastomer fiber high-speed spinning process treatment agent with winding speed of 1000 m / min or more, and method for producing elastomer fiber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009287127A (en) * | 2008-05-27 | 2009-12-10 | Takemoto Oil & Fat Co Ltd | Modifier for producing elastic fiber |
| CN102787490A (en) * | 2011-05-16 | 2012-11-21 | 竹本油脂株式会社 | Coating-type treating agent for elastic fiber, method for treating elastic fiber, and elastic fiber |
| CN105088801A (en) * | 2014-05-13 | 2015-11-25 | 竹本油脂株式会社 | Treating agent for polyurethane elastomer fiber, method for treating polyurethane elastomer fiber, and polyurethane elastomer fiber |
| CN105178033A (en) * | 2014-05-14 | 2015-12-23 | 竹本油脂株式会社 | Treating agent for polyurethane elastomer fiber, method for treating polyurethane elastomer fiber, and polyurethane elastomer fiber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3393713B2 (en) * | 1994-08-31 | 2003-04-07 | 東レ・ダウコーニング・シリコーン株式会社 | Straight oil composition for fibrous filaments |
| DE19805153A1 (en) * | 1998-02-09 | 1999-08-12 | Bayer Ag | Biodegradable coating agents |
| JP5329843B2 (en) * | 2008-05-27 | 2013-10-30 | 東レ・オペロンテックス株式会社 | Modifier for elastic fiber production |
| WO2014148368A1 (en) * | 2013-03-22 | 2014-09-25 | 松本油脂製薬株式会社 | Elastic fiber treating agent and elastic fiber |
-
2015
- 2015-11-06 JP JP2015218771A patent/JP5936293B1/en active Active
-
2016
- 2016-11-04 CN CN201610962929.1A patent/CN106958148B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009287127A (en) * | 2008-05-27 | 2009-12-10 | Takemoto Oil & Fat Co Ltd | Modifier for producing elastic fiber |
| CN102787490A (en) * | 2011-05-16 | 2012-11-21 | 竹本油脂株式会社 | Coating-type treating agent for elastic fiber, method for treating elastic fiber, and elastic fiber |
| CN105088801A (en) * | 2014-05-13 | 2015-11-25 | 竹本油脂株式会社 | Treating agent for polyurethane elastomer fiber, method for treating polyurethane elastomer fiber, and polyurethane elastomer fiber |
| CN105178033A (en) * | 2014-05-14 | 2015-12-23 | 竹本油脂株式会社 | Treating agent for polyurethane elastomer fiber, method for treating polyurethane elastomer fiber, and polyurethane elastomer fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5936293B1 (en) | 2016-06-22 |
| JP2016211131A (en) | 2016-12-15 |
| CN106958148A (en) | 2017-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106958148B (en) | Dry-spun polyurethane elastic fiber | |
| CN106884225B (en) | Dry-spun polyurethane elastic fiber | |
| JP4805428B2 (en) | Treatment agent for polyurethane elastic fiber and polyurethane elastic fiber | |
| JP6026038B1 (en) | Elastic fiber treatment agent, elastic fiber treatment method, and elastic fiber | |
| WO2020102966A1 (en) | Block-modified polysiloxane and compositions formed thereof | |
| DE502008003340D1 (en) | Use of linear siloxanes and process for their preparation | |
| JP7218385B2 (en) | Radiation curable compositions for coating optical fibers via alternating oligomers and coatings produced therefrom | |
| US20140004359A1 (en) | Hydrosilylation reaction inhibitors and use thereof for preparing stable curable silicone compositions | |
| EP3577149A1 (en) | Method for the production of polyoxazolidinone polymer compounds | |
| US4578116A (en) | Organosilicon compounds and textile fiber finishes containing these | |
| TW201900771A (en) | Silicone composition, silicone emulsion composition, and fiber treatment agent | |
| CN103835128A (en) | Method for treating synthetic fiber, method for spinning synthetic fiber, and spun yarn | |
| CN113165971A (en) | Filled radiation curable compositions for coating optical fibers and coatings produced therefrom | |
| JP6083917B1 (en) | Treatment agent for elastic fiber, elastic fiber, and method for producing polyurethane-based elastic fiber | |
| JP5936292B1 (en) | Dry-spun polyurethane elastic fiber | |
| UA48168C2 (en) | Glass yarn sizing composition, method of application for the copmposition and products obtained | |
| JP6141554B1 (en) | Elastic fiber treatment agent and elastic fiber | |
| WO2003038182A1 (en) | Treating agent for elastic fibers and elastic fibers obtained by using the same | |
| JP5507868B2 (en) | Polyurethane elastic fiber and method for producing the same | |
| ES2286734T3 (en) | RAMIFIED POLYGANOSILOXANES CONTAINING QUATERNARY AMMONIA GROUPS. | |
| EP2831149A1 (en) | Amphiphilic resin-linear organosiloxane block copolymers | |
| JP7289469B1 (en) | Carbon fiber precursor treatment agent and carbon fiber precursor | |
| WO2024122372A1 (en) | Elastic fiber treatment agent and use thereof | |
| JP7525152B2 (en) | Treatment agent for synthetic fibers, and synthetic fibers | |
| TW201237230A (en) | Oil composition-adhered, acrylic precursor fiber bundle for carbon fibers and method of manufacturing thereof, oil composition for an acrylic precursor fiber for carbon fibers, and dispersion liquid of an oil composition for an acrylic precursor fiber fo |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |