CN103184607B - A kind of anti-yellowing nylon sewing thread and manufacture method thereof - Google Patents
A kind of anti-yellowing nylon sewing thread and manufacture method thereof Download PDFInfo
- Publication number
- CN103184607B CN103184607B CN201110454977.7A CN201110454977A CN103184607B CN 103184607 B CN103184607 B CN 103184607B CN 201110454977 A CN201110454977 A CN 201110454977A CN 103184607 B CN103184607 B CN 103184607B
- Authority
- CN
- China
- Prior art keywords
- sewing thread
- polyamide
- acid
- yellowing
- nylon
- 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.)
- Expired - Fee Related
Links
- 238000009958 sewing Methods 0.000 title claims abstract description 82
- 238000004383 yellowing Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 229920001778 nylon Polymers 0.000 title claims description 32
- 239000004677 Nylon Substances 0.000 title claims description 27
- 239000004952 Polyamide Substances 0.000 claims abstract description 84
- 229920002647 polyamide Polymers 0.000 claims abstract description 84
- 239000011528 polyamide (building material) Substances 0.000 claims abstract description 79
- 239000000835 fiber Substances 0.000 claims abstract description 48
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 125000003277 amino group Chemical group 0.000 claims abstract description 41
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000009987 spinning Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 8
- 239000001384 succinic acid Substances 0.000 claims description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N Suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N Sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 claims description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Azelaic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N Glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N Pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing Effects 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N Phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 1
- LCJRHAPPMIUHLH-UHFFFAOYSA-N 1-$l^{1}-azanylhexan-1-one Chemical compound [CH]CCCCC([N])=O LCJRHAPPMIUHLH-UHFFFAOYSA-N 0.000 description 19
- 229920002292 Nylon 6 Polymers 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000011068 load Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- MWOOGOJBHIARFG-UHFFFAOYSA-N Vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 12
- 210000003491 Skin Anatomy 0.000 description 11
- 239000007921 spray Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920000933 poly (ε-caprolactam) Polymers 0.000 description 8
- 229940117960 vanillin Drugs 0.000 description 6
- 235000012141 vanillin Nutrition 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 206010023126 Jaundice Diseases 0.000 description 3
- LOCYSVHOSYQGOV-UHFFFAOYSA-N N-hexyl-6-$l^{1}-azanyl-6-oxohexanamide Chemical compound [CH]CCCCCNC(=O)CCCCC([N])=O LOCYSVHOSYQGOV-UHFFFAOYSA-N 0.000 description 3
- 229910002089 NOx Inorganic materials 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 210000004247 Hand Anatomy 0.000 description 2
- 241000322338 Loeseliastrum Species 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000003078 antioxidant Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000003405 preventing Effects 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- -1 -tert-butyl paracresol Chemical compound 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N Succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 210000001138 Tears Anatomy 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002045 lasting Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004642 transportation engineering Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The invention discloses a kind of Fypro sewing thread and production method thereof, the end of the fibre-forming polymer polyamide molecule chain of this Fypro sewing thread contains terminal amino group and a kind of nitrogenous end structure, and this nitrogenous end structure is by C2～C20The terminal amino group of carboxylic acid and polyamide polymer strand by occurring chemical reaction to be formed.The manufacture method of the anti-yellowing polyamide fiber sewing yarn of the present invention, is the porch in screw extruder, adds the C through metering in polyamide polymer continuously2～C20Carboxylic acid, enter mixed melting, spinning in screw extruder, batch, the high-elastic processing of false twisting.The Fypro sewing thread of the present invention is possible not only to effectively suppress xanthochromia, and has good dyeability, colorfastness, fibre whiteness, the most soft.
Description
Technical field
The present invention relates to a kind of sewing thread, be specifically related to a kind of anti-yellowing nylon sewing thread.
Background technology
Sewing thread is main line class material, is used for sewing up various dress materials, has practical and decoration dual-use function concurrently.Existing
Some sewing threads such as common problem such as polyester-cotton blend, cotton textiles is: the intensity that filoplume sense is good is the lowest, wear no resistance；Intensity is high
Feel is poor.Its strength of pure polyster fibre sewing thread is high, and during hygrometric state, intensity does not declines, and washing shrinkage is the least, after suitably sizing
Shrink less than 1%, the most attractive in appearance flat, the feature of pucker-free can be remained after accordingly acting as sewing thread, instead of cotton in many occasions
Sewing thread.But in terms of dressing, pure polyester thread sewing also exist the brightest, feel is the most uncomfortable, the defect of poor air permeability.
Directly contacting the clothes of skin, when wearing, the sewing thread at the position such as shoulder or neck also can directly contact skin, skin
Infant that skin is tender or skin quality, than more sensitive crowd, are wearing sewing thread than cloth textile is also hard or sewing thread is the thickest
During clothes, skin is easily subject to stimulate, and produces prodding and itching feeling, the most uncomfortable.Therefore, soft Fypro sewing yarn
The use of line is very important.
Fypro sewing thread is again nylon wire or chinlon line, is to be formed by nylon continuous filament yarn twisted, smooth-going, soft
Soft, elongation percentage is generally 20%～35%, has preferable elasticity, and abrasion resistance is high, and light fastness is good, mildew-resistant, 100 degree of left sides of degree of staining
The right side, low temperature dyeing.And its linear slit strength is the highest, durable, sealing is calm, be suitable for the needs of difference sewing industrial products and extensively made
With.
While Fypro sewing thread has above advantage, it still has some Fypros itself and is carried
The shortcoming come.It is poor that is exactly its anti-yellowing property, as during in outdoor for a long time by sun exposure, or in transportation, and fiber
Easily there is xanthochromia in itself, has influence on the outward appearance of sewed clothing, and time on the most lily clothing of light color, xanthochromia is outstanding
For substantially so that it is be limited by very large in purposes.For above-mentioned xanthochromia problem, prior art has and adds at dyeing process
Add the solution of xanthochromia preventing agent, but exist and can not control preventing property of xanthochromia and the bad defect of durability well.
For polyamide nylon fiber easy xanthochromia problem, insider has carried out various research, poly-about discovery
The content of the terminal amino group in the mainly Fypro of nylon xanthochromia.
Contained coming as antioxidant in terminal amino group in fiber and the packaging material used in the process of circulation
The produced sublimate of BHT (di-tert-butyl paracresol) distillation of the phenol series used is in the catalysis of NOx (oxidation nitrogen)
Under effect, generating a series of inductor, in this series therein, a certain inductor is coloring matter so that fiber occurs Huang
Cash as.
Another is exactly, vanillin contained in packaging material used in terminal amino group and the process of circulation in fiber
There is dehydration in (Vanillin), gained material, next under the effect of oxygen, finally produces coloured
Quinoid structure so that fiber generation Yellowing.
The xanthochromia that both the above reacts occurred in the process of circulation with the Cucumber in the packaging material used is existing
As so that fiber turns to be yellow.
It addition, in the stage used by consumer, some attachments of attachment on fibre, as washing agent, dirty etc. one
A little materials, under the catalytic action of extraneous NOx (oxidation nitrogen), with the amino terminal base phase contained by polyamide nylon fiber
In conjunction with, generate coloring matter, fiber generation Yellowing.
For above-mentioned by the xanthochromia problem caused by amino terminal base in polyamide nylon fiber, carried out in the past below
Processing mode.
In the stage of polyamide nylon polymer polymerizing, by adding acidic materials, allow terminal amino group at polymerization stage quilt
React away, thus reduce the content of terminal amino group in polymer, thus reach to suppress fiber jaundice.But, come at polymerization stage
The reactive mode of suppression terminal amino group so that the content of the terminal amino group in polymer is wayward, terminal amino group content excess
Minimizing can cause in the textile dyeing stage, is difficult to colouring, affects color emissivity, thus affect the use of fiber.Also have and be exactly, add
The unreacted small-molecule substance of the excess entered can affect fibrous matter in fiber stage；In the control mode of polymerization stage, meeting
More significantly increase polymerization cost, thus have impact on competitiveness commercially of fiber itself.
If post-processing stages suppresses xanthochromia problem by post processing processing mode, by postprocessing working procedures, right
Polyamide nylon sewing thread carries out organic acid or organic acid anhydride (such as, acetic acid or acetic anhydride) processes, and suppresses a part of end ammonia
Base ensures that fiber is non-yellowing, retains a part of amino terminal base to ensure dyeability.At the reality place to amino terminal base
In reason, there is error relatively big, the problem that product properties can not control very well, post processing processing mode is not a good place
Reason mode.
Have again and be exactly, the packaging material used are processed, screen or improve, such as by do not use vanillin,
Phenol series antioxidant BHT, ensures that polyamide nylon fiber does not occur jaundice problem.But, this kind of mode expense be huge,
Poor feasibility, and can not fundamentally solve Fypro xanthochromia problem.
With regard to above-mentioned processing mode institute produced problem, a kind of low cost of research and development, technique simply and neither affects polyamides
Amine fiber sewing thread performance can solve again the technology of xanthochromia problem and becomes the most necessary.
Summary of the invention
It is an object of the invention to provide a kind of anti-xanthochromia function admirable, lasting and soft the gathering of xanthochromia rejection
Nylon sewing thread and manufacture method thereof.
The technical solution of invention is:
A kind of anti-yellowing nylon sewing thread, the end of its fibre-forming polymer polyamide molecule chain contains 1.0 × 10-5
~3.0×10-5The terminal amino group content of mol/g and nitrogenous end structure as follows:
,
And R1 be carbon atom be the saturated or undersaturated aliphatic alkyl of 2 ~ 20；Described fibre-forming polymer polyamide molecule
The nitrogenous end structure of chain is by C2～C20The terminal amino group of carboxylic acid and polyamide polymer strand by there is chemical reaction
And formed；The boiling water shrinkage of described anti-xanthochromia polyamide sewing thread and yarn be 0.5～2.0%, damp and hot return rate of crispaturaing be 30～
50%, xeothermic return rate of crispaturaing is 30～50%.
The anti-yellowing nylon sewing thread whiteness of the present invention is 75～85, and whiteness is anti-higher than not carrying out amino terminal base
The Fypro sewing thread 2～about 10 answered.
The anti-yellowing nylon sewing thread of the present invention, its fibre-forming polymer polyamide is by C2～C20Carboxylic acid and polyamides
The terminal amino group generation chemical reaction of amine polymer strand, thus form above-mentioned nitrogenous end structure.
Namely polyamide polymer strand portion distal end amino is transformed into above-mentioned nitrogenous end structure, i.e. portion distal end
Amino is blocked, and loses chemism.
In the present invention, C2～C20Polymer before carboxylic acid-terminated preferably forms polyamides with p-phthalic acid as comonomer
Amine polymer, can be copolymerization caprolactam or copolymerization hexamethylene diamine adipate, preferably copolymerization caprolactam.
One important technology feature of the present invention is, adds p-phthalic acid comonomer at polymerization stage and carries out appropriate
End-blocking obtains the polyamide polymer of certain terminal amino group content, and the existence of p-phthalic acid simultaneously makes in spinning process permissible
Control C2～C20Carboxylic acid carries out the speed of further termination process to polyamide polymer, forms the nitrogenous end knot of ad hoc structure
Structure, controls the terminal amino group content of fibre-forming polymer polyamide molecule chain, and the anti-xanthochromia reaching the present invention has again good dyeing concurrently
Performance, the Fypro sewing thread of fibre whiteness.
In the present invention, C2～C20Polymer preferably terminal amino group content before carboxylic acid-terminated is 3.5 × 10-5~4.5×
10-5The polyamide polymer of mol/g.C can be made in such scope2～C20The capping process of carboxylic acid is the most successfully carried out, control
The terminal amino group content of fibre-forming polymer processed is in the range of setting, it is ensured that the anti-xanthochromia of fiber product has again good dyeability concurrently
Energy.The terminal amino group content of polyamide polymer is higher than 4.5 × 10-5If mol/g, C2～C20Fast reaction after carboxylic acid interpolation,
Uncontrollable fibre-forming polymer terminal amino group content is 1.0 × 10-5~3.0×10-5In the range of mol/g, xanthochromia inhibition
Bad, do not reach the vanillin xanthochromia 4 grades of target；The terminal amino group content of polyamide polymer is less than 3.5 × 10-5Mol/g's
Words, it can make the dyeability of Fypro sewing thread bad at the excessive end-blocking of polymerization process, it is impossible to reaches to use
Dye level.
The reason that the present invention uses carboxylic acid and do not uses anhydride to carry out end blockade is, owing to anhydride thermostability is poor, and end
The whiteness of the anti-xanthochromia fiber obtained by after end seal lock is poor, and far below non-end blockade polyamide, it is left that whiteness gap reaches 20
Right.
The present invention is for the C of end-blocking2～C20Carboxylic acid be preferably dicarboxylic acids, use dicarboxylic acids to polyamide polymer
Carry out end blockade, be because dicarboxylic acids and there is higher heat resistance, anti-xanthochromia fiber obtained after end blockade
There is the whiteness same with non-end blockade polyamide.Product after dicarboxylic acids of the present invention end-blocking, whiteness is 75～85, and it is white
Degree is compared with non-end blockade polyamide high 2～about 10.
C2～C20Carboxylic acid be more preferably ethanedioic acid, malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid,
Azelaic Acid or decanedioic acid.
C2～C20The addition of carboxylic acid be preferably polyamide polymer strand terminal amino group molar content 50～
150%.Such addition is so that the terminal amino group content of fibre-forming polymer polyamide of this fiber is 1.0 × 10-5~3.0
×10-5mol/g.The terminal amino group content of fibre-forming polymer polyamide controls in above-mentioned scope, it can be ensured that fiber sewing thread was both
Xanthochromia can be prevented to have again good dyeability.
The manufacture method of the anti-yellowing nylon sewing thread of the present invention, is the porch in screw extruder, to
Polyamide polymer adds C through metering continuously2～C20Carboxylic acid, enter mixed melting, spinning, volume in screw extruder
Take, the then high-elastic processing of false twisting, twisting, prepare anti-xanthochromia polyamide sewing thread and yarn.
Preferably in polyamide polymer, add the C through metering continuously by positive displacement powder body micro-adding device2~
C20Carboxylic acid.
The polyamide polymer formed with p-phthalic acid as comonomer is preferably cut by the manufacture method of the present invention
While sheet imports to be arranged on the feed bin directly over Screw Extrusion machine inlet, added continuously in feed bin by opening pipe arrangement
C2～C20Carboxylic acid；Described opening pipe arrangement is upwardly into section piling height being arranged on the lower section divided from accumulation portion of cutting into slices in feed bin
10%～50% position directly over position straight down.
According to the present invention, it is provided that a kind of molecule chain end amino reducing fibre-forming polymer polyamide in Fypro
The method of content, is the method for a kind of carboxylic acid process polyamide polymer, and preferably one carboxylic acid processes with to benzene two
Formic acid is the method for the polyamide polymer that comonomer is formed.
Specifically, in the melt stage of the screw extruder of spinning-drawing machine, in polyamide polymer, add trace binary-component
Acid powder body, preferably adds trace binary-component acid powder body in the polyamide polymer formed for comonomer with p-phthalic acid, makes
Binary acid and polyamide polymer frit reaction, the specific nitrogenous end structure of generation, and it is poly-to reach to control fibre-forming polymer
The purpose of the terminal amino group content of the strand of amide, it is ensured that Fypro transport, use in there is not xanthochromia, meanwhile,
Fibre whiteness is excellent, it is ensured that the service life of fiber and the field of use；Meanwhile, end-blocking is added at spinning phase by powder body device
Agent, makes again the terminal amino group content of the strand of fibre-forming polymer polyamide in Fypro will not too be reduced to impact
The degree of dyeing.While ensuring a suppression of xanthochromia effect, it is possible to ensure that there is good dyeability.
The Fypro sewing thread of the present invention carries out the high-elastic processing of false twisting by Fypro and is formed, and its twist is 50
～350 sth. made by twisting/m, boiling water shrinkage be 0.5～2.0%, damp and hot return rate of crispaturaing be 30～50%, xeothermic return rate of crispaturaing be 30～
50%.When reality is worn, the sewing thread being sewn on clothes has the situation directly contacting skin, and sewing thread is the most soft to be produced skin
Excitement can be the least, wear the most comfortable, simultaneously taking account of processability and the seamability of sewing thread, the preferably twist is 100
～150 sth. made by twisting/m.This sewing thread has good retractility, bulkiness and flexibility, is sewn on clothes, even if touching skin also
Can feel the most soft.
The fabric that the Fypro sewing thread of the present invention is sewed has good anti-yellowing property, does not affect polyamides
The dyeability of amine fiber itself, excellent fibre whiteness, simultaneously, keep Fypro excellent handle.
The tensile strength of the sewing thread of the present invention is 8.4～15N, and degree of stretching is 20～40%；Meet JIS L 2510 standard
In specification requirement to Fypro sewing thread.
Sewing thread of the present invention, compared with ordinary sewing line, has a good retractility, bulkiness, soft, and by force
Degree of stretching is big, elastic big, improves comfortableness when wearing and because thermal finalization processes or transport the xanthochromia that the reasons such as preservation cause
Problem, is especially suitable for the fabric sewing the comfort levels such as underwear, sweater, sport shirt, underlinen, T-shirt, quality requirements is high.
In the present invention, the test mode of each physical parameter is as follows:
(1) amino terminal base content
The content of amino terminal base by being dissolved in the mixture of about 60ml phenol-methanol by about 2.0g polymer
(68:32) measure in.This solution, wherein terminal is titrated by the electrometric titration HCI of about 0.2N at about 25 DEG C
Determined by electromotive force increase drastically.
The xanthochromia performance that prevents of Fypro is divided into, anti-vanillin xanthochromia performance, NOx xanthochromia performance, anti-phenol xanthochromia
Performance.
(2) fibre whiteness
The test of fibre whiteness, by the aluminium sheet wide at 5cm, goes the winding of fibre compact, uses Computer color testing instrument
Carry out whiteness test.
(3) boiling water shrinkage
A. yarn sampling 10 circle × 1m/ circle, naturally droops yarn and is suspended on temperature 25 DEG C, adjusts in the environment of humidity 65%
Wet 12 hours；
B. surveying on long table, yarn is being hung and determines loading G, measure former long L
G=D × 0.9 × 0.1 × the number of turns × 2(D: denier count as received)；
C. being bound up with gauze by the yarn surveyed in the water being placed on 100 DEG C, keeping water temperature is 100 DEG C, 30min；
D. by gauze and yarn natural cooling, then take out yarn and hang over temperature 25 DEG C, damping 12 in the environment of humidity 65%
Hour；
E. the yarn that damping is good hangs determines loading G, measures L1.Boiling water shrinkage is calculated: boiling water shrinkage according to following equation
Rate=(L-L1)/L × 100%.
(4) damp and hot return rate of crispaturaing
A. yarn sampling 10 circle × 1m/ circle, naturally droops yarn and is suspended on temperature 25 DEG C, adjusts in the environment of humidity 60%
Wet 12 hours；
B. yarn is bound up with gauze, be placed in 90 DEG C of thermostatic water bath holding 20min；
C. by yarn and yarn natural cooling, hanging over temperature 25 DEG C after being taken out by yarn, in the environment of humidity 60%, damping 12 is little
Time；
D. yarn is hung in the measurement tank filling water, first suspension just loading+determine loading, after keeping 2min, read length
L；
Just loading=0.002g/d × D × 2 × volume number
Determine loading=0.1 g/d × D × 2 × volume number
Then will determine loading remove, keep just load state to hang 2min, read length L1；Measure according to formula below:
Crispatura percentage elongation=(L-L1)/L × 100%
(5) xeothermic flexible return rate
A. yarn sampling 10 circle × 1m/ circle, naturally droops yarn and is suspended on temperature 25 DEG C, adjusts in the environment of humidity 65%
Wet 12 hours；
B. the yarn sample taken is hung up the loading of 0.00167g/D × D × 2 × number of turns；
C. putting in drying baker by above-mentioned yarn sample, in keeping case, temperature is 150 DEG C, processes 5min；
D. yarn sample is handled well and is taken out afterwards, places 10 minutes under first loading in temperature adjusts room；
E. length L of yarn sample under just loading is measured1(unit: mm), then takes off just loading, hang up 0.1g/D × D × 2 ×
The number of turns determine loading, measure length L of yarn sample2, calculate dry shrinkage return rate according to following equation: dry shrinkage return rate %=
(L2-L1)/L2×100。
(6) anti-vanillin xanthochromia
Make the aqueous solution of vanillin 0.2wt%, choose test film and nylon staining calico gravimetry, each extract bath
Vanillin aqueous solution than 1:50, puts in the test chamber of 200～500cc, in 10 minutes, from room temperature, liquid temperature is warming up to 50
DEG C and after keeping 1 minute, take out test film and nylon staining calico, hang dry-air blast and do.Dried test film and nylon staining are white
Before and after cloth test, the degree change of xanthochromia is faded and is compared differentiation with gray scale.
(7) anti-phenol xanthochromia
X18 part is tested: material phenol jaundice probability is commented with reference to ISO 105-X18-2007 textile material color fastness
Estimate.
(8) feel (sense) is evaluated
20 estimator's handss and finger tip please go to touch the sewing thread position of clothes contact skin side, then inquire opposite joint
Thread the sensation of soft or hard degree at line position.
Detailed description of the invention
Below in conjunction with embodiment and comparative example, the invention will be further described.
Embodiment 1:
It is 4.2 × 10 by terminal amino group content-5The polyamide nylon 6 adding p-phthalic acid combined polymerization of mol/g
(poly-(ε caprolactam)) section feeding spinning-drawing machine screw extruder entrance before, by use micro powder drawing-in device to
N6 section add 0.4wt%(80mol%) succinic acid additive, both are melting mixing, reaction in screw extruder, passes through
The spinning manifold of 255 DEG C sprays through spinneret, cool down, wind and obtain 140T polyamide nylon 6 fiber preoriented yarn.Gained polyamides
The terminal amino group content of amine nylon 6 is 2.22 × 10-5Mol/g, and containing nitrogenous end structure as follows,
, R1 be carbon atom be the representative examples of saturated aliphatic alkyl of 2.
Gained polyamide preoriented yarn is carried out under conditions of processing temperature is 180 DEG C false twisting false-twist textured yarn processing, afterwards
Twist by the condition that the twist is 100 sth. made by twisting/m again, obtain the sewing thread of the present invention.The fiber number of gained sewing thread be 124dtex,
Boiling water shrinkage is 1.5%, damp and hot return rate of crispaturaing is 34.2%, xeothermic return rate of crispaturaing is 42.3%, average tensile strength is
9.32N, average tensile degree of stretching are 29.7%；Wash resistant fastness is that change fades 4～5 grades, pollutes 3～4 grades；Fastness to rubbing is dry
Formula rubs 4～5 grades, and anti-vanillin xanthochromia is 4～5 grades, and anti-phenol xanthochromia performance is 4 grades.
Embodiment 2:
It is 4.2 × 10 by the content of terminal amino group-5The polyamide nylon adding p-phthalic acid combined polymerization of mol/g
6 (poly-(ε caprolactam)) section feeding spinning-drawing machine screw extruder entrance before, by use micro powder drawing-in device to
N6 section add 0.65wt%(75mol%) decanedioic acid additive, both are melting mixing, reaction in screw extruder, passes through
The spinning manifold of 255 DEG C sprays through spinneret, cool down, wind and obtain 140T nylon 6 fiber preoriented yarn.Gained polyamide nylon
6 terminal amino group contents are 2.58 × 10-5Mol/g, and containing nitrogenous end structure as follows.
, R1 be carbon atom be the representative examples of saturated aliphatic alkyl of 8.
Gained polyamide preoriented yarn is carried out under conditions of processing temperature is 180 DEG C the high-elastic processing of false twisting, the most again
Twist by the condition that the twist is 100 sth. made by twisting/m, obtain the sewing thread of the present invention.The fiber number of gained sewing thread is 124dtex, boiling
Water shrinkage factor is 1.95%, damp and hot contraction return rate is 40.4%, dry shrinkage return rate is 47%, average tensile strength is 8.9N,
Average tensile degree of stretching is 30.7%；Wash resistant fastness is that change fades 4～5 grades, pollutes 3～4 grades；Fastness to rubbing is dry type friction 4
Level, anti-vanillin xanthochromia is 4～5 grades, and anti-phenol xanthochromia performance is 4 grades.
Embodiment 3:
It is 4.2 × 10 by the content of terminal amino group-5The polyamide nylon adding p-phthalic acid combined polymerization of mol/g
6 (poly-(ε caprolactam)) section feeding spinning-drawing machine screw extruder entrance before, by use micro powder drawing-in device to
N6 section add 0.6wt%(120mol%) succinic acid additive, both are melting mixing, reaction in screw extruder, passes through
The spinning manifold of 255 DEG C sprays through spinneret, cool down, wind and obtain 140T nylon 6 fiber preoriented yarn.Gained polyamide nylon
6 terminal amino group contents are 2.18 × 10-5Mol/g, contained nitrogenous end structure is with embodiment 1.
Gained polyamide preoriented yarn is carried out under conditions of processing temperature is 180 DEG C the high-elastic processing of false twisting, the most again
Twist by the condition that the twist is 100 sth. made by twisting/m, obtain the sewing thread of the present invention.The fiber number of gained sewing thread is 123dtex, boiling
Water shrinkage factor is 1.65%, damp and hot contraction return rate is 38.6%, dry shrinkage return rate is 46.5%, average tensile strength is
9.8N, average tensile degree of stretching is 30.2%；Wash resistant fastness is that change fades 4～5 grades, pollutes 3～4 grades；Fastness to rubbing is dry type
Rubbing 4 grades, anti-vanillin xanthochromia is 4～5 grades, and anti-phenol xanthochromia performance is 4 grades.
Embodiment 4:
It is 4.2 × 10 by the content of terminal amino group-5The polyamide nylon adding p-phthalic acid combined polymerization of mol/g
6 (poly-(ε caprolactam)) section feeding spinning-drawing machine screw extruder entrance before, by use micro powder drawing-in device to
N6 section add 0.25wt%(50mol%) succinic acid additive, both are melting mixing, reaction in screw extruder, passes through
The spinning manifold of 255 DEG C sprays through spinneret, cool down, wind and obtain 144T nylon 6 fiber preoriented yarn.Gained polyamide nylon
6 terminal amino group contents are 2.65 × 10-5Mol/g, contained nitrogenous end structure is with embodiment 1.
Gained polyamide preoriented yarn is carried out under conditions of processing temperature is 180 DEG C the high-elastic processing of false twisting, the most again
Twist by the condition that the twist is 100 sth. made by twisting/m, obtain the sewing thread of the present invention.The fiber number of gained sewing thread is 125dtex, boiling
Water shrinkage factor is 1.82%, damp and hot contraction return rate is 36.8%, dry shrinkage return rate is 45.2%, average tensile strength is
10.8N, average tensile degree of stretching is 30.2%；Wash resistant fastness is that change fades 4～5 grades, pollutes 3～4 grades；Fastness to rubbing is dry
Formula rubs 4 grades, and anti-vanillin xanthochromia is 4～5 grades, and anti-phenol xanthochromia performance is 4 grades.
Embodiment 5:
It is 4.2 × 10 by terminal amino group content-5The polyamide nylon 6 adding p-phthalic acid combined polymerization of mol/g
(poly-(ε caprolactam)) section feeding spinning-drawing machine screw extruder entrance before, by use micro powder drawing-in device to
N6 section add 0.7wt%(140mol%) succinic acid additive, both are melting mixing, reaction in screw extruder, passes through
The spinning manifold of 255 DEG C sprays through spinneret, cool down, wind and obtain 145T nylon 6 fiber preoriented yarn.Gained polyamide nylon
6 terminal amino group contents are 2.11 × 10-5Mol/g, contained nitrogenous end structure is with embodiment 1.
Gained polyamide preoriented yarn is carried out under conditions of processing temperature is 180 DEG C the high-elastic processing of false twisting, the most again
Twist by the condition that the twist is 100 sth. made by twisting/m, obtain the sewing thread of the present invention.The fiber number of gained sewing thread is 124dtex, boiling
Water shrinkage factor is 1.78%, damp and hot contraction return rate is 39.8%, dry shrinkage return rate is 48.2%, average tensile strength is
10.2N, average tensile degree of stretching is 32.2%；Wash resistant fastness is that change fades 4～5 grades, pollutes 3～4 grades；Fastness to rubbing is dry
Formula rubs 4 grades, and anti-vanillin xanthochromia is 4～5 grades, and anti-phenol xanthochromia performance is 4 grades.
Embodiment 6:
It is 3.5 × 10 by terminal amino group content-5The polyamide nylon 66 adding p-phthalic acid combined polymerization of mol/g
(PA 66) section feeding spinning-drawing machine screw extruder entrance before, by use micro powder drawing-in device to
N66 section add 0.4wt%(80mol%) succinic acid additive, both are melting mixing, reaction in screw extruder, passes through
The spinning manifold of 285 DEG C sprays through spinneret, cool down, wind and obtain 140T nylon 66 fiber.Gained polyamide nylon 66 end
Amino content is 2.31 × 10-5Mol/g, contained nitrogenous end structure is with embodiment 1.
Gained polyamide preoriented yarn is carried out under conditions of processing temperature is 180 DEG C the high-elastic processing of false twisting, the most again
Twist by the condition that the twist is 100 sth. made by twisting/m, obtain the sewing thread of the present invention.The fiber number of gained sewing thread is 122dtex, boiling
Water shrinkage factor is 1.68%, damp and hot contraction return rate is 35.8%, dry shrinkage return rate is 46.2%, average tensile strength is
10.4N, average tensile degree of stretching is 29.2%；Wash resistant fastness is that change fades 4～5 grades, pollutes 3～4 grades；Fastness to rubbing is dry
Formula rubs 4 grades, and anti-vanillin xanthochromia is 4～5 grades, and anti-phenol xanthochromia performance is 4 grades.
Comparative example 1:
It is 4.2 × 10 by terminal amino group content-5The polyamide nylon 6 adding p-phthalic acid combined polymerization of mol/g
(poly-(ε caprolactam)) section feeding spinning-drawing machine screw extruder, by the spinning manifolds of 255 DEG C through spinneret spray, cooling,
Winding obtains 140T nylon 6 fiber preoriented yarn.Gained polyamide nylon 6 terminal amino group content is 3.97 × 10-5Mol/g, institute
Containing nitrogenous end structure with embodiment 1.
Gained polyamide preoriented yarn is carried out under conditions of processing temperature is 180 DEG C the high-elastic processing of false twisting, the most again
Twist by the condition that the twist is 100 sth. made by twisting/m, obtain sewing thread.Its fiber number is 123dtex, and average tensile strength is 8.5N,
Average tensile degree of stretching is 30.8%.The terminal amino group content of this polyamide sewing thread is 3.97 × 10-5Mol/g, after tested, this seam
The anti-vanillin xanthochromia of line of threading is 3～4 grades, and anti-phenol xanthochromia performance is 3 grades.
Comparative example 2:
It is 4.2 × 10 by terminal amino group content-5The polyamide nylon 6 adding p-phthalic acid combined polymerization of mol/g
(poly-(ε caprolactam)) section feeding spinning-drawing machine screw extruder entrance before, by use micro powder drawing-in device to
N6 section add 0.85wt%(170mol%) succinic acid additive, both are melting mixing, reaction in screw extruder, passes through
The spinning manifold of 255 DEG C sprays through spinneret, and spinning pressure declines serious, from spinneret hole generation tear drop phenomenon, it is impossible to batch.
Comparative example 3:
It is 4.2 × 10 by terminal amino group content-5The polyamide nylon 6 adding p-phthalic acid combined polymerization of mol/g
(poly-(ε caprolactam)) section feeding spinning-drawing machine screw extruder entrance before, by use micro powder drawing-in device to
N6 section add 0.4wt%(80mol%) succinic anhydride additive, both are melting mixing, reaction in screw extruder, passes through
The spinning manifold of 255 DEG C sprays through spinneret, cool down, wind and obtain 140T nylon 6 fiber preoriented yarn.Gained polyamide nylon
6 terminal amino group contents are 1.97 × 10-5Mol/g, contained nitrogenous end structure is with embodiment 1.
Gained polyamide preoriented yarn is carried out under conditions of processing temperature is 180 DEG C the high-elastic processing of false twisting, the most again
Twist by the condition that the twist is 100 sth. made by twisting/m, obtain sewing thread.Its fiber number is 123dtex, and average tensile strength is 8.25N,
Average tensile degree of stretching is 33.9%.The anti-vanillin xanthochromia of this sewing thread is 4～5 grades, and anti-phenol xanthochromia performance is 4～5 grades.
Being evaluated by feel (sense), 20 estimator's handss and finger tip remove to touch the sewing thread of clothes contact skin side
Position, wherein, 17 estimators think that the sewing thread of embodiment is the most soft compared with the sewing thread of comparative example 1,3；20
Name estimator thinks that the sewing thread of embodiment is soft.
Claims (9)
1. an anti-yellowing nylon sewing thread, it is characterised in that: the end of fibre-forming polymer polyamide molecule chain contains
1.0×10-5~3.0×10-5The terminal amino group content of mol/g and nitrogenous end structure as follows:
,
And R1 be carbon atom be the saturated or undersaturated aliphatic alkyl of 2 ~ 20；Described fibre-forming polymer polyamide molecule chain
Nitrogenous end structure is by C2～C20The terminal amino group of carboxylic acid and polyamide polymer strand by there is chemical reaction and shape
Become；The boiling water shrinkage of described anti-xanthochromia polyamide sewing thread and yarn be 0.5～2.0%, damp and hot return rate of crispaturaing be 30～50%,
Xeothermic return rate of crispaturaing is 30～50%.
Anti-yellowing nylon sewing thread the most according to claim 1, it is characterised in that: described C2～C20Carboxylic acid be
Ethanedioic acid, malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid or decanedioic acid.
Anti-yellowing nylon sewing thread the most according to claim 1 and 2, it is characterised in that: C2～C20Adding of carboxylic acid
Dosage is the end reacting the polyamide polymer strand forming the fibre-forming polymer nitrogenous end structure of polyamide molecule chain
The 50～150% of Amino End Group molar content.
Anti-yellowing nylon sewing thread the most according to claim 1 and 2, it is characterised in that: described polymerizing polyamide
Thing is the copolymerization caprolactam or copolymerization hexamethylene diamine adipate formed with p-phthalic acid as comonomer.
Anti-yellowing nylon sewing thread the most according to claim 1 and 2, it is characterised in that: this sewing thread twist is
50～350 sth. made by twisting/m, boiling water shrinkage be 0.5～2.0%, damp and hot return rate of crispaturaing be 30～50%, xeothermic return rate of crispaturaing be 30
～50%.
Anti-yellowing nylon sewing thread the most according to claim 5, it is characterised in that: the twist of described sewing thread and yarn is
100～150 sth. made by twisting/m.
7. the manufacture method of anti-yellowing nylon sewing thread described in a claim 1, it is characterised in that: at Screw Extrusion
Porch in machine, adds the C through metering in polyamide polymer continuously2～C20Carboxylic acid, enter in screw extruder
Mixed melting, spinning, batch, then false twisting, twisting, prepare anti-xanthochromia polyamide sewing thread and yarn；Described anti-xanthochromia polyamide
Sewing thread and yarn is to carry out high-elastic false twisting processing under conditions of processing temperature is 150～185 DEG C to prepare false twist fibers, the vacation of gained
Twist with the fingers fiber and carry out the prepared anti-xanthochromia polyamide sewing thread and yarn of twisting processing.
The manufacture method of anti-yellowing nylon sewing thread the most according to claim 7, it is characterised in that: pass through positive displacement
Powder body micro-adding device adds the C through metering in polyamide polymer continuously2～C20Carboxylic acid.
9. according to the manufacture method of anti-yellowing nylon sewing thread described in claim 7 or 8, it is characterised in that: will be with right
Phthalic acid is that the polyamide polymer chips that comonomer is formed imports to be arranged on directly over Screw Extrusion machine inlet
Feed bin while, in feed bin, add C continuously by opening pipe arrangement2～C20Carboxylic acid；Described opening pipe arrangement is arranged on from material
Position straight down is acted directly over 10%～50% position being upwardly into section piling height in the lower section divided, accumulation portion of cutting into slices in storehouse
Put.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110454977.7A CN103184607B (en) | 2011-12-31 | A kind of anti-yellowing nylon sewing thread and manufacture method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110454977.7A CN103184607B (en) | 2011-12-31 | A kind of anti-yellowing nylon sewing thread and manufacture method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103184607A CN103184607A (en) | 2013-07-03 |
| CN103184607B true CN103184607B (en) | 2016-12-14 |
Family
ID=
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61102446A (en) * | 1984-10-24 | 1986-05-21 | 東洋紡績株式会社 | Polyamide fiber false twisted sewing yarn |
| CN1207055A (en) * | 1995-11-16 | 1999-02-03 | 埃尔夫·阿奎坦 | Oxidation process of organic substrates in the presence of metal complexes of tetra-, penta- and hexacoordinating ligands, and oxidation catalysts containing them |
| WO2011076085A1 (en) * | 2009-12-25 | 2011-06-30 | 东丽纤维研究所（中国）有限公司 | Yellowing-proof polyamide fiber and producing method thereof |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61102446A (en) * | 1984-10-24 | 1986-05-21 | 東洋紡績株式会社 | Polyamide fiber false twisted sewing yarn |
| CN1207055A (en) * | 1995-11-16 | 1999-02-03 | 埃尔夫·阿奎坦 | Oxidation process of organic substrates in the presence of metal complexes of tetra-, penta- and hexacoordinating ligands, and oxidation catalysts containing them |
| WO2011076085A1 (en) * | 2009-12-25 | 2011-06-30 | 东丽纤维研究所（中国）有限公司 | Yellowing-proof polyamide fiber and producing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2412287C2 (en) | Yarn containing siliconised ultrafine fibres of polyester | |
| JP4935695B2 (en) | Crimp yarn made of polyamide 56 and carpet comprising the same | |
| TW200844282A (en) | Conjugate fibers excellent in antistatic property, water absorption and cool feeling by contact | |
| EP3310948B1 (en) | Polyamide fiber with enhanced dyeing properties, process for obtaining such fiber and polyamide article made therefrom | |
| JP7173014B2 (en) | Polyamide fiber, woven and knitted fabric, and method for producing polyamide fiber | |
| CN102834556B (en) | Moisture-absorbing fibre and manufacture method thereof | |
| CN107075741B (en) | Ultrafine high-tenacity polyamide multifilament and core-spun yarn, stocking, and fabric using same | |
| CN1981078A (en) | Fabric and clothes for atopic dermatitis patients | |
| CN107354531A (en) | A kind of modified PBT fiber spinning process | |
| US20150159303A1 (en) | Core-Sheath Conjugated Fiber | |
| US9765450B2 (en) | Polyamide fabric enhancing body warming | |
| CN102666949B (en) | Yellowing-proof polyamide fiber and producing method thereof | |
| CN114250527B (en) | Polyamide 5X fully drawn yarn and preparation method and application thereof | |
| CN103184607B (en) | A kind of anti-yellowing nylon sewing thread and manufacture method thereof | |
| CN103122492A (en) | Anti-yellowing polyamide fiber and method for manufacturing same | |
| CN106574404A (en) | Polyamide fibers, fiber structure using same, and clothing | |
| CN102877182A (en) | Polyamide fiber sewing thread and method for producing same | |
| CN208118603U (en) | A kind of antibacterial thermal insulating cashmere-like fabric | |
| JP4955463B2 (en) | Composite fiber | |
| CN103184607A (en) | Anti-yellowing nylon sewing thread and manufacturing method thereof | |
| CN108350607A (en) | Can high-temperature dyeing Fypro | |
| JP5543748B2 (en) | Woven knitted fabric using nylon 11 yarn and dyeing method thereof | |
| CN105167211A (en) | Healthy and comfortable sock production process | |
| CN102613707A (en) | Preparation process of underwear with skin whitening effect | |
| CN114293278A (en) | Polyamide 5X fully drawn yarn and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161214 Termination date: 20181231 |