CN106958148A - Dry-spun polyurethane elastic fiber - Google Patents
Dry-spun polyurethane elastic fiber Download PDFInfo
- Publication number
- CN106958148A CN106958148A CN201610962929.1A CN201610962929A CN106958148A CN 106958148 A CN106958148 A CN 106958148A CN 201610962929 A CN201610962929 A CN 201610962929A CN 106958148 A CN106958148 A CN 106958148A
- Authority
- CN
- China
- Prior art keywords
- silicone
- polyurethane series
- mass
- agent
- series elastomer
- 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.)
- Granted
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)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (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 assigning excellent unwinding
Property, the easy zbility with the 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 contains 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 contains the various fibers such as mineral oil and aliphatic ester compound (referring for example to patent document 4).So
And, there are the following problems in these conventional dry spinning polyurethane series elastomers：To (following by differential scanning calorimetry (DSC)
Referred to as DSC) determine easy zbility that obtained thermal discharge assigns for the polyurethane series elastomer of particular range, it is unwinding with the time
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 that there is provided to determining the polyurethane series that obtained thermal discharge is particular range by DSC
Elastomer is done obtained from assigning excellent easy zbility, the easy zbility with the time, resistance to hand pick and resistance to scum silica frost accumulation property simultaneously
Formula spinning polyurethane series elastomer.
Method for solving problem
The present inventor etc. are studied to solve aforementioned problems, are as a result found correctly and it is appropriate that to being surveyed by DSC
Surely the thermal discharge obtained adheres to particular procedure agent, the specific place for the polyurethane series elastomer of particular range with special ratios
Reason 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 0.1 ~ 10 mass % ratio,
Polyurethane series elastomer：Determining the thermal discharge at 150 ~ 300 DEG C obtained by differential scanning calorimetry (DSC) (DSC) is
150 ~ 450mJ/mg polyurethane series elastomer；
Inorganic agent：Contain comprising following smooth agents and following easy zbility improvers and with 85 ~ 99.7 mass % ratio following
Smooth agent and the inorganic agent for containing following easy zbility improvers (total 100 mass %) with 0.3 ~ 15 mass % ratio；
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 be used as knot in molecule
The silicone resin that structure unit and matter average molecular weight are 3000 ~ 100000 and the fatty acid alkali that carbon number is 10 ~ 22
At least one of 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 determined by DSC at 150 ~ 300 DEG C obtained is 150 ~ 450mJ/mg
Property fiber.For polyurethane series elastomer DSC determine, exist 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 elastomers is determined 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, determine 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
Using the trade name DSC6200 of Seiko Instruments Inc. manufactures, the sampling amount for making polyurethane series elastomer is
3mg, object of reference uses Al2O3, so as to be measured.
It is attached to the poly- ammonia that the foregoing thermal discharge determined by DSC at 150 ~ 300 DEG C obtained is 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 of chemical industrial company of SHIN-ETSU HANTOTAI manufacture 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 the viscosity at 25 DEG C for 2 ~
100mm2/ s dimethyl silicone polymer, 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, 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
The trade name YUBASE 4 of Lubricants companies manufacture, the trade name ダ イ ア Na Off レ シ ア of light extraction Xing Chan companies manufacture
W8, the 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 ~ 100mm2/ s spindle oil, liquid stone
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
The ester that fat acid and alcohol are manufactured, they can use one kind or two or more, but viscosity at preferably 25 DEG C is 2 ~ 100mm2/ s ester.
In the aliphatic acid of raw material as 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 the aliphatic acid of ring-type, 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 the alcohol of ring-type, 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 be used 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 obtained by way of gel permeation chromatography (hereinafter referred to as GPC) is determined and converted with polystyrene.
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.Should illustrate, be preced with M before silicone resin, D,
T, Q are the form of presentations usually used as the expression method for the siloxane unit for constituting silicone resin, and M is that formula is
R1R2R3SiO1/21 shown functional silicone's unit, D is that formula is R4R5SiO2/22 shown functional silicone's units, T
It is that formula is R6SiO3/23 shown functional silicone's units, Q is that formula is SiO4/24 shown functional silicone's units.
Here, R1~R6It is-R for the alkyl of carbon number 1 ~ 24, formula7NHR8NH2(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
The commodity of trade name マ グ ネ シ ウ system ス テ ア レ ー ト G, You companies manufacture of SAK-MS-P/USP, You company manufacture
The trade name マ グ ネ シ ウ system ス テ ア レ ー ト of name マ グ ネ シ ウ system ス テ ア レ ー ト GF-200, 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 85 ~ 99.7 mass % ratio
Agent and easy zbility improver (total 100 mass %) is contained with 0.3 ~ 15 mass % ratio, preferably with 90 ~ 99.7 mass %'s
Ratio contains smooth agent and contains easy zbility improver (total 100 mass %) with 0.3 ~ 10 mass % ratio.
Inorganic agent includes the smooth agent and easy zbility improver of described above, can also as needed be combined according to its purpose
Use other compositions.For example, wettability improving agent, ultra-violet absorber, antioxidant, preservative etc. for it.It is described its
The content of its composition 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, and it can be using known method.
Inorganic agent as described above can be made to be attached to polyurethane series elasticity under the undiluted state without dilution 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, the form of polyurethane series elastomer is not particularly limited, can apply
The fiber of long filament system, can also be using the short fine fiber for being.
The effect of invention
The present invention according to the above description, has the effect that：Result in being determined by DSC at 150 ~ 300 DEG C obtained
Thermal discharge for 150 ~ 450mJ/mg polyurethane series elastomer simultaneously assign excellent easy zbility, the easy zbility with the time,
Dry spinning polyurethane series elastomer obtained from resistance to hand pick and resistance to scum silica frost accumulation property.
Embodiment
Hereinafter, in order that the composition and effect of the present invention are more specific and enumerate embodiment etc., but the present invention is not by these realities
Apply the limitation of example.It should illustrate, in following embodiment etc., part refers to mass parts, in addition, % refers to quality %.
Experiment 1 (being used as the preparation of the silicone resin of easy zbility improver) of packet
SIR-1 preparation
By trimethylmethoxysilane 823.338g (7.9 moles), water 800g, methanesulfonic acid 2.0g and tetraethoxysilane
(10 moles) inputs of 2083.3g are into reaction vessel, and heating is so that the temperature of reaction system is kept to 65 DEG C, heating stirring 24
Hour.Then, addition sodium acid carbonate 1.78g is so as to which after being neutralized, backflow 5 hours is cured.Further add dimethylbenzene
2000g, by water and because of reaction, the methanol of by-product and ethanol distillation remove to be replaced as after xylene solution, carry out full dose
Filtering.The valid density (the silicone resin concentration in xylene solution) of resulting 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, carry out reacting for 1 hour 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、R3Formula when being methyl is R1R2R3SiO1/21 shown functional silicone
Unit/R4For N- (2- amino-ethyls) -3- aminopropyls and R5Formula during for methyl is R4R5SiO2/22 shown functionality silicon
Oxygen alkane unit/formula is SiO4/2Shown 4 functional silicone's units=7.9/0.1/10 (mol ratio).
Constitute the analysis of the siloxane unit of silicone resin
Silicone resin SIR-1 is analyzed for H NMR spectroscopy, the mol ratio for the siloxane unit for constituting silicone resin is calculated.With same
Mode, for other silicone resins, calculate the mol ratio for constituting respective siloxane unit.
SIR-2 preparation
By trimethylmethoxysilane 729.54g (7 moles), water 800g, methanesulfonic acid 2.0g and tetraethoxysilane 2083.3g
(10 moles) inputs are into reaction vessel, and heating is so that the temperature of reaction system is kept to 65 DEG C, heating stirring 24 hours.Connect
, addition sodium acid carbonate 1.78g is so as to which after being neutralized, backflow 5 hours is cured.Dimethylbenzene 2000g is further added,
By water and because of reaction, the methanol of by-product and ethanol distillation remove to be replaced as after xylene solution, carry out full dose filtering,
Dimethylbenzene is further distilled off, so as to obtain silicone resin SIR-2.When being analyzed for silicone resin SIR-2, it is
Matter average molecular weight is 11000 silicone resin, wherein R1、R2、R3Formula when being methyl is R1R2R3SiO1/21 shown official
Energy property siloxane unit/formula is SiO4/24 shown functional silicone unit=7/10 (mol ratio).
SIR-3 preparation
By trimethylmethoxysilane 1042.2g (10 moles), water 800g, methanesulfonic acid 2.0g and tetraethoxysilane 2083.3g
(10 moles) inputs are into reaction vessel, and heating is so that the temperature of reaction system is kept to 65 DEG C, heating stirring 24 hours.Connect
, addition sodium acid carbonate 1.78g is so as to which after being neutralized, backflow 5 hours is cured.Dimethylbenzene 2000g is further added,
By water and because of reaction, the methanol of by-product and ethanol distillation remove to be replaced as after xylene solution, carry out full dose filtering,
Dimethylbenzene is further distilled off, so as to obtain silicone resin SIR-3.When being analyzed for silicone resin SIR-3, it is
Matter average molecular weight is 8000 silicone resin, wherein R1、R2、R3Formula when being methyl is R1R2R3SiO1/21 shown function
Property siloxane unit/formula be SiO4/24 shown functional silicone unit=1/1 (mol ratio).
SIR-4 preparation
By trimethylmethoxysilane 1042.2g (10 moles), water 800g, methanesulfonic acid 2.0g and tetraethoxysilane 2083.3g
(10 moles) inputs are into reaction vessel, and heating is so that the temperature of reaction system is kept to 65 DEG C, heating stirring 24 hours.Connect
, addition sodium acid carbonate 1.78g is so as to which after being neutralized, backflow 5 hours is cured.Dimethylbenzene 2000g is further added,
By water and because of reaction, the methanol of by-product and ethanol distillation remove to be replaced as after xylene solution, carry out full dose filtering.
The valid density (the silicone resin concentration in xylene solution) of resulting filtrate is adjusted to after 50%, by its total amount and N-
(2- amino-ethyls) -3- amino propyl methyl dimethoxysilanes 206.36g (1 mole) and water 10g, which are put into another reaction, to be held
In device, carry out reacting for 1 hour at 80 DEG C.Dimethylbenzene, water and methanol are distilled off from reaction solution, so as to obtain silicone tree
Fat 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、R3Formula when being methyl is R1R2R3SiO1/2Shown 1 functional silicone's unit/R4For N- (2- amino-ethyls) -3-
Aminopropyl and R5Formula during for methyl is R4R5SiO2/2Shown 2 functional silicone's units/formula is SiO4/2Shown
4 functional silicone unit=10/1/10 (mol ratio).
SIR-5 preparation
Hexyl trimethoxy silane 2063.5g (10 moles), water 800g, methanesulfonic acid 2.0g are put into reaction vessel, heated
So as to which the temperature of reaction system is kept to 65 DEG C, heating stirring 24 hours.Then, addition sodium acid carbonate 1.78g is so as to carry out
After neutralization, flow back 5 hours, cured.Dimethylbenzene 2000g is further added, the methanol of by-product steams by water and because of reaction
Distillation goes to be replaced as after xylene solution, carries out full dose filtering, dimethylbenzene is further distilled off, so as to obtain silicone tree
Fat SIR-5.When being analyzed for silicone resin SIR-5, it is the silicone resin that matter average molecular weight is 4500, and it includes R6For
Formula during hexyl is R6SiO3/23 shown functional silicone's units.
SIR-6 preparation
N- (2- amino-ethyls) -3- TSL 8330s 2223.6g (10 moles) and water 800g are put into reaction
In container, heating is heated at reflux stirring 24 hours so as to which the temperature of reaction system is kept to 65 DEG C.Then, by water and because
Reaction and the methanol of by-product is distilled off, so as to obtain silicone resin SIR-6.When being analyzed for silicone resin SIR-6, its
The silicone resin for being 5000 for matter average molecular weight, it includes R6Formula during for N- (2- amino-ethyls) -3- aminopropyls is
R6SiO3/23 shown functional silicone's units.
SIR-7 preparation
By trimethylmethoxysilane 312.66g (3 moles), hexyl trimethoxy silane 206.35g (1 mole), water 800g, first
Sulfonic acid 2.0g and (5 moles) of tetraethoxysilane 1041.65g inputs are into reaction vessel, and heating is so as to by the temperature of reaction system
Degree is kept to 65 DEG C, heating stirring 24 hours.Then, addition sodium acid carbonate 1.78g is so as to which after being neutralized, backflow 5 hours is entered
Row curing.Dimethylbenzene 2000g is further added, the methanol of by-product, ethanol distillation remove to replace by water and because of reaction
Into after xylene solution, full dose filtering is carried out, dimethylbenzene is further distilled off, so as to obtain silicone resin SIR-7.For silicon
When ketone resin SIR-7 is analyzed, it is the silicone resin that matter average molecular weight is 30000, wherein R1、R2、R3When being methyl
Formula is R1R2R3SiO1/2Shown 1 functional silicone's unit/R6Formula during for hexyl is R6SiO3/23 shown functionalities
Siloxane unit/formula is SiO4/24 shown functional silicone unit=3/1/5 (mol 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 trade name of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
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
Part and as easy zbility improver table 2 record 0.5 part of MDQ silicone resins (SIR-1), by above-mentioned uniform mixing so that
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 trade name of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
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 parts,
And 1 part of the MDQ silicone resins (SIR-1) and the magnesium stearate (S-1 of the record of table 3 of the record of table 2 as easy zbility improver：
The trade name SAK-MS-P of SUN ACE CORPORATION manufactures) 1 part, after above-mentioned uniform mixing, carried out with wet type dispersion machine
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 trade name of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
KF-96-10cs) 96 parts and as easy zbility improver table 3 record magnesium stearate (S-1：SUN ACE
The trade name SAK-MS-P of CORPORATION manufactures) 4 parts, after above-mentioned uniform 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 trade name of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
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 parts,
And the T silicone resins (SIR-5) 1 of the record of table 2 as easy zbility improver, by above-mentioned uniform mixing, so that at preparation
Manage agent (E-9).It should illustrate, in experiment packet 3 described later, 1 is applied in combination using the inorganic agent (E-9) to every 100 parts
The material that the Lauryl Diethanolamine of part 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 trade name of chemical industrial company of SHIN-ETSU HANTOTAI manufacture
KF-96-10cs) 87 parts and mineral oil (L-3：The trade name YUBASE 3 of SK Lubricants companies manufacture) 10 parts, Yi Jizuo
3 parts of the T silicone resins (SIR-6) recorded for the table 2 of easy zbility improver, by above-mentioned uniform mixing, so as to prepare inorganic agent (E-
10).It should illustrate, in experiment packet 3 described later, 0.5 part is applied in combination using the inorganic agent (E-10) to every 100 parts
The material that amino modified silicone (the trade name KF-861 of chemical industrial company of SHIN-ETSU HANTOTAI manufacture) obtains.
Inorganic agent (E-2) ~ (E-6), (R-1) ~ (R-6) and (R-8) preparation
In the mode same with inorganic agent (E-1), smooth agent is uniformly mixed with easy zbility improver, so as to prepare inorganic agent
(E-2) ~ (E-6), (R-1) ~ (R-6) and (R-8).
The preparation of inorganic agent (R-7), (R-9) and (R-10)
In the mode same with inorganic agent (E-7), after smooth agent and easy zbility improver are uniformly mixed, entered with wet type dispersion machine
Row processing, 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 be 2900 tetramethylene ether glycol, double-(phenyl is closed to isocyanates root)-methane and second two by molecular weight
The N of the polyurethane of amine formation, 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) is mixed
The DMAc of thing 35% solution, 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 is made.
Using the spinning solution obtained in this way, spun by dry type used in known spandex (spandex)
Silk method, spinning is carried out to the polyurethane series elastomer of 44dtex/3fil multifilament, by batching before finish roll directly with not
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
The coiling speed of 600m/ minutes is batched to length fine on 58mm cylindric paper tube, to obtain dry spinning polyurethane series elasticity
The package 500g of dimension.Polyurethane series elastomer is entered with the regulation of the adhesion amount of inorganic agent by adjusting the rotating speed of finish roll
OK, so that it reaches that relative to polyurethane series elastomer be 5%.In the step of spinning, DMAc is made by stream of nitrogen gas
Volatilization, but temperature now is higher, elongation multiplying power when batching in addition is higher, then and resulting polyurethane series elastomer is logical
Crossing the thermal discharge that DSC determined at obtain 150 ~ 300 DEG C becomes smaller, conversely, temperature when making the DMAc volatilize is lower, roll up in addition
Elongation multiplying power when taking is lower, then resulting polyurethane series elastomer is determined at obtain 150 ~ 300 DEG C by DSC
Thermal discharge becomes bigger, by the way that it is changed as described in table 4, so as to obtain with the thermal discharge as described in table 4
Each example polyurethane series elastomer.For the package of resulting dry spinning polyurethane series elastomer, carry out following
Measure and evaluation, by result summarize be shown in table 5.
The measure that the thermal discharge at 150 ~ 300 DEG C obtained is determined 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 the sample
Product are cooled to after -50 DEG C with 10 DEG C/min from 25 DEG C, and 300 DEG C are warming up to from -50 DEG C with 10 DEG C/min, determine now 150 ~
Thermal discharge at 300 DEG C.It should illustrate, as DSC, the trade name manufactured using Seiko Instruments Inc.
DSC6200, the sampling amount for making polyurethane series elastomer is 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 constitute unloading part, in addition, in opposite side by the
Two driven rollers and reeling end is constituted with the second free roller that its is contacted when normal, the reeling end is set to relative in the horizontal direction
In the unloading part apart from 20cm.Dry spinning polyurethane series after foregoing obtained immediately spinning are installed in the first driven roller
The package of elastomer, it is unwinding untill the thickness that silk is rolled up reaches 2mm, batch to the second driven roller.It will be sent by the first driven roller
The speed for going out polyurethane series elastomer is fixed as 50m/ minutes, on the other hand, slow from 50m/ minutes to improve polyurethane
It is that elastomer is batched to the speed of the second driven roller, polyurethane series elastomer is forced unwinding from package.It is described to force
When unwinding, the coiling speed when at the time of polyurethane series elastomer between submitting portion and reel-up no longer jumping is determined
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 be 120% less than 180% (slightly there is impedance to the pull-out of silk, but without occurring silk fracture, can
With stably unwinding)
×：Easy zbility is more than 180% (there is impedance to the pull-out of silk, also there is silk fracture, there is problem in terms of operation).
With the evaluation of the easy zbility of time
Replace dry after immediately spinning using the package for the dry spinning polyurethane series elastomer that 6 months are taken care of after spinning
The package of formula spinning polyurethane series elastomer, in addition, evaluate with the evaluation identical of easy zbility.
The evaluation of resistance to hand pick
The package by the dry spinning polyurethane series elastomer after foregoing obtained immediately spinning is obtained with 20m/ minutes
Fracture of wire number of times caused by the hand pick because of package when speed, the coiling speed of 40m/ minutes batch 1000m is sent out, by as follows
Benchmark is evaluated.
The metewand of resistance to hand pick
◎：Fracture of wire is 0 time caused by hand pick
○：Fracture of wire is 1 time less than 3 times caused by hand pick
×：Fracture of wire is more than 3 times caused by hand pick.
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-sized whole
Through machine, 1500km was batched with the silk speed of 300m/ minutes under 25 DEG C, 65%RH atmosphere.Now, visually observe small-sized whole
Come off state and the accumulated state of scum silica frost on combed yarn guide through machine, are evaluated by following benchmark.
The metewand of resistance to scum silica frost accumulation property
◎：The almost accumulation without 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, the problem of having larger in terms of the stable movement of silk.
[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 R3It is 1 functional silicone's unit during methyl
D1：General formula R4R5SiO2/2Shown and R4And R5It is 2 functional silicone's units during methyl
D2：General formula R4R5SiO2/2Shown and R4For methyl, R52 functionality silicon during for N- (2- amino-ethyls) -3- aminopropyls
Oxygen alkane unit
T1：General formula R6SiO3/2Shown and R63 functional silicone's units during for hexyl
T2：General formula R6SiO3/2Shown and R63 functional silicone's units during for N- (2- amino-ethyls) -3- aminopropyls
Q1：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 determined by DSC
To thermal discharge for the polyurethane series elastomer of particular range assign excellent easy zbility simultaneously, it is the easy zbility with the time, resistance to
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：Determining the thermal discharge at 150 ~ 300 DEG C obtained by differential scanning calorimetry (DSC) (DSC) is
150 ~ 450mJ/mg polyurethane series elastomer
Inorganic agent：Contain comprising following smooth agents and following easy zbility improvers and with 85 ~ 99.7 mass % ratio following
Smooth agent and the inorganic agent for containing following easy zbility improvers (total 100 mass %) with 0.3 ~ 15 mass % ratio
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 be used as knot in molecule
The silicone resin that structure unit and matter average molecular weight are 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
Be M/Q ratios be 0.5 ~ 1.1 in the case of resin.
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 ~ 5, wherein, inorganic agent with 90 ~
99.7 mass % ratio contains smooth agent, and contains easy zbility improver (total 100 matter with 0.3 ~ 10 mass % ratio
Measure %).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015097488 | 2015-05-12 | ||
| JP2015-218771 | 2015-11-06 | ||
| JP2015218771A JP5936293B1 (en) | 2015-05-12 | 2015-11-06 | Dry-spun polyurethane elastic fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106958148A true CN106958148A (en) | 2017-07-18 |
| CN106958148B 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116034192A (en) * | 2020-09-07 | 2023-04-28 | 竹本油脂株式会社 | Treating agent for elastic fiber and elastic fiber |
| CN116157569A (en) * | 2020-09-23 | 2023-05-23 | 竹本油脂株式会社 | Treating agent for elastic fiber and elastic fiber |
Families Citing this family (4)
| 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 |
| JP7050800B2 (en) | 2017-10-18 | 2022-04-08 | 旭化成株式会社 | Polyurethane elastic fiber, its winding body, and products containing it |
| JP7410307B2 (en) | 2020-08-12 | 2024-01-09 | 旭化成株式会社 | Polyurethane elastic fibers, spools thereof, gather members, and sanitary materials |
| 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 |
| CN105074081A (en) * | 2013-03-22 | 2015-11-18 | 松本油脂制药株式会社 | 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116034192A (en) * | 2020-09-07 | 2023-04-28 | 竹本油脂株式会社 | Treating agent for elastic fiber and elastic fiber |
| CN116034192B (en) * | 2020-09-07 | 2024-03-01 | 竹本油脂株式会社 | Treating agent for elastic fiber and elastic fiber |
| CN116157569A (en) * | 2020-09-23 | 2023-05-23 | 竹本油脂株式会社 | Treating agent for elastic fiber and elastic fiber |
| CN116157569B (en) * | 2020-09-23 | 2024-03-29 | 竹本油脂株式会社 | Treating agent for elastic fiber and elastic fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106958148B (en) | 2018-05-15 |
| JP5936293B1 (en) | 2016-06-22 |
| JP2016211131A (en) | 2016-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106958148B (en) | Dry-spun polyurethane elastic fiber | |
| CN106884225B (en) | Dry-spun polyurethane elastic fiber | |
| JP6026038B1 (en) | Elastic fiber treatment agent, elastic fiber treatment method, and elastic fiber | |
| CN1195919C (en) | Spin finish | |
| WO2020102966A1 (en) | Block-modified polysiloxane and compositions formed thereof | |
| US20050027094A1 (en) | Spandex compositions | |
| CA2773123A1 (en) | Anti-soiling agent composition for preventing pitch contamination in a paper making process | |
| CN103835128A (en) | Method for treating synthetic fiber, method for spinning synthetic fiber, and spun yarn | |
| EP3577149A1 (en) | Method for the production of polyoxazolidinone polymer compounds | |
| US20140004359A1 (en) | Hydrosilylation reaction inhibitors and use thereof for preparing stable curable silicone compositions | |
| CN102787490A (en) | Coating-type treating agent for elastic fiber, method for treating elastic fiber, and elastic fiber | |
| JP6083917B1 (en) | Treatment agent for elastic fiber, elastic fiber, and method for producing polyurethane-based elastic fiber | |
| JP5936292B1 (en) | Dry-spun polyurethane elastic fiber | |
| WO2003038182A1 (en) | Treating agent for elastic fibers and elastic fibers obtained by using the same | |
| JP6141554B1 (en) | Elastic fiber treatment agent and elastic fiber | |
| JP3283277B2 (en) | Organopolysiloxane composition | |
| US4496632A (en) | Process for lubricating synthetic fibers | |
| EP1451122B1 (en) | Sizing composition for glass yarns, the glass yarns thus obtained and composite materials comprising said yarns | |
| EP2831149A1 (en) | Amphiphilic resin-linear organosiloxane block copolymers | |
| CN103806271B (en) | fiber treatment agent | |
| JP2010236150A (en) | Polyurethane-based elastic fiber and method for producing the same | |
| WO2022138571A1 (en) | Treatment agent for elstomer fiber high speed spinning process, and method for producing elstomer fiber | |
| WO2024122372A1 (en) | Elastic fiber treatment agent and use thereof | |
| US20210032497A1 (en) | Anti-contamination agent composition | |
| 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 |