CN101608349B - Polylactic fiber with high hydrolytic resistance and abrasion resistance - Google Patents
Polylactic fiber with high hydrolytic resistance and abrasion resistance Download PDFInfo
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- CN101608349B CN101608349B CN2008101230560A CN200810123056A CN101608349B CN 101608349 B CN101608349 B CN 101608349B CN 2008101230560 A CN2008101230560 A CN 2008101230560A CN 200810123056 A CN200810123056 A CN 200810123056A CN 101608349 B CN101608349 B CN 101608349B
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Abstract
The invention discloses a novel polylactic fiber with high hydrolytic resistance and abrasion resistance, which is prepared by mixing epoxy compounds, phosphorus serial inorganic salts, and a composition of fatty acid diamide and/or alkyl substitution fatty acid monoamide in a composition of polylactic acid through melt spinning extension. The prepared polylactic fiber has good hydrolytic resistance, can obtain higher strength conservation rate after hot water treatment and constant temperature and humidity treatment, can improve the dyeing performance of the polylactic fiber under the conditions of high temperature and pressurizing, and improves the abrasion resistance and the spinning performance of the polylactic fiber.
Description
Technical field:
The present invention relates to a kind of acid fiber by polylactic.
Background technology:
In recent years; The enhancing of Along with people's growth in the living standard and environmental consciousness; People more and more pay attention to the research of natural Biodegradable fibers, and new environmental protection fiber is is competitively researched and developed in countries in the world, have wherein realized just that in late nineteen nineties the acid fiber by polylactic (PLA fiber) of industrialized developing is the most noticeable; It can be obtained from cereal; The discarded back of its goods can be decomposed into carbon dioxide and water through microbial action in soil, and can not distribute poison gas during burning, can not pollute.
But the hydrolytic resistance of pure acid fiber by polylactic can be relatively poor, in the coloration of textile materials process, handles through pressurized high-temperature, and the intensity of its fabric can descend, and has influenced the extensive use of acid fiber by polylactic.
Owing to contain a large amount of carboxyls among the PLA, the increasing of carboxyl when causing hydrolysis, the intensity of fiber descends significantly.So adopt the method for envelope terminal groups, the content of carboxyl in the PLA fiber is descended significantly, reach and improve the hydrolytic resistance ability.Adding carbodiimides hydrolysis-resisting agent according to putting down in writing in No. the 3122485th, Japanese Patent Laid and No. 3393752 patent of special permission can improve hydrolytic resistance; But carbodiimides itself is virose; The special gas that decomposes the back generation is carcinogenic; Human body is harmful to, so large-scale production cannot.This patent uses the hydrolysis-resisting agent with epoxide group to substitute carbodiimides, can well reach the effect of envelope carboxyl simultaneously again, and intensity can not descend significantly after the fiber hydrolysis.
PLA belongs to natural degradable property fiber simultaneously, and ABRASION RESISTANCE is poor, and is difficult when weaving.Toray Co., Ltd. reports in Chinese patents (application number is 03820140.2); This technology is aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide that in acid fiber by polylactic, adds with respect to fabric integer 0.1-5% weight; Can improve the rub resistance of PLA after the adding, but can not improve the anti-water-based that adds of PLA.
Summary of the invention:
The object of the present invention is to provide a kind of hydrolytic resistance ability is good, anti-wear performance is superior high hydrolysis resistance, high friction resistance polylactic acid fibre.
Technical solution of the present invention is:
A kind of high hydrolysis resistance, high friction resistance polylactic acid fibre; It is characterized in that: in this acid fiber by polylactic; Contain epoxide composition, phosphorus serial inorganic salts compound and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition; Wherein epoxide is 0.5～5% of a PLA weight item, and the addition of preferred epoxide is 0.8-2%, and epoxide can contain an epoxide group or a plurality of epoxide groups.Phosphorus serial inorganic salts compound is the 50ppm-1500ppm of PLA weight item, and the preferably phosphate addition is 100-500ppm.
The general formula of phosphorus series inorganic salt compound is M
AH
BPO
4, A=1 or 2 wherein, B=1 or 2, M are alkali metal or alkali earth metal, can be NaH
2PO
4, Na
2HPO
4, KH
2PO
4, K
2HPO
4, MgHPO
4, BaHPO
4Deng in one or more.Aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition account for the 0.1-5% of PLA weight item, and preferred EBS addition is 0.7-2.0%.The aliphatic acid diamides is EBS (ethylene bis stearic amide) or EBL (the two lauryl amines of ethylene), and alkyl substituted type aliphatic acid monoamide composition is EBO (the two oleamides of ethylene).
Add the hydrolysis-resisting agent 0.5-5% that contains epoxy, the carboxyl of acid fiber by polylactic is significantly reduced, reach 1-20eq/t.But PLA hydrolysis under wet heat condition can make the Acidity of Aikalinity of environmental treatment liquid change, and impels the hydrolysis of PLA.To this problem; In PLA, add 50-1500ppm phosphoric acid salt compound simultaneously,, suppressed the alkalescence of treatment fluid as buffer solvent; Make Acidity of Aikalinity reach balance, the intensity of 120 degree processing acid fiber by polylactic after 30 minutes can remain to 50-90% under wet heat condition.Constant temperature 70 degree, humidity 90% handle 7 round the clock the intensity of (168 hours) back acid fiber by polylactic can remain to 40-85%.
The shortcoming that acid fiber by polylactic has the skin-friction coefficient height, wears no resistance; The crock fastness of for example stipulating according to JIS L0849; The general requirement of garment material is more than 3 grades, but present acid fiber by polylactic has only 1 grade low-level, has influenced the extensive use of acid fiber by polylactic.
Adding aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition can improve in acid fiber by polylactic.Aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition account for 0.1%～5% of PLA weight; Rub resistance that can acid fiber by polylactic is improved; In the evaluation of fabric, the dyeing back is through the evaluation of friction colorfastness, and the friction fastness of fabric reaches the 4-5 level.The friction fastness evaluation method of above-mentioned fabric adopts A-I method among the JIS L 0849 (friction colorfastness test method).
The preparation method of high hydrolysis resistance of the present invention, high friction resistance polylactic acid fibre is earlier with processing the section of PLA master batch through extruder in epoxy radicals hydrolysis-resisting agent and phosphate compounds and aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide adding PLA; Make pre-oriented yarn through melting high-speed spinning equipment after polylactic acid slice and the master batch section blend, make high hydrolysis resistance, high friction resistance polylactic acid fibre through the extension device extension again.
Below be this high hydrolysis resistance, high friction resistance polylactic acid fibre evaluation method:
Fibre strength before the method one, measurement processing is S1, and hot water 120 degree handle that fibre strength is S2 after 30 minutes, and its strength retention is S2/S1.
Fibre strength before method two, the measurement processing is S1, and constant temperature 70 degree, constant humidity 90% processing 7 be (168 hours) back fibre strength S3 round the clock, and strength retention is S3/S1.
The evaluation method of ABRASION RESISTANCE adopts A-I method among the JIS L 0849 (friction colorfastness test method).
Below in conjunction with embodiment the present invention is described further:
The spinnability evaluation method is zero: 24 hour no fracture of wire, and pressure is normal
There is pressure transient in 24 hours fracture of wires of △
Fracture of wire rose fast 10 times with upward pressure in * 24 hours
Embodiment 1:
Raw material: A polylactic acid slice: molecular weight (Mn) is that 100,000 fusing points are 170 degree
B epoxide: three epoxide group compound TGIC
C phosphate compounds: sodium dihydrogen phosphate
D aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide: EBS (ethylene bis stearic amide)
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.The above-mentioned raw materials consumption: the epoxide consumption is 0.6% of a PLA weight, and the phosphate compounds consumption is the 100ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.7cn/dtex, and dimension terminal carboxyl group content is 16eq/ton.The former silk fiber of PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 50%; Fiber is that its strength retention was 40% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
Embodiment 2:
Raw material C phosphate compounds: potassium dihydrogen phosphate other with embodiment 1.
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3500m/min., 1.3 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 1.0% of a PLA weight, and the phosphate compounds consumption is the 100ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1% of PLA weight.
The acid fiber by polylactic intensity that makes is 4.1cn/dtex, and dimension terminal carboxyl group content is 11eq/ton.The former silk fiber of PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 70%; Fiber is that its strength retention was 70% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
Embodiment 3:
Raw material C phosphate compounds: sodium hydrogen phosphate other with embodiment 1
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 225 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 4000m/min., 1.2 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 2.0% of a PLA weight, and the phosphate compounds consumption is the 100ppm of PLA weight, and EBS (ethylene bis stearic amide) consumption is 1% of a PLA weight.
The acid fiber by polylactic intensity that makes is 4.2cn/dtex, and dimension terminal carboxyl group content is 7eq/ton.。The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 75%; Fiber is that its strength retention was 75% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
Embodiment 4:
Raw material is with embodiment 1
Raw material A, B, C, D are made the PLA master batch through blend; Just gained PLA master batch and polylactic acid slice make pre-oriented yarn through high speed melt-spinning equipment after mixing; Wherein spinning temperature is 230 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 4500m/min., 1.16 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 3.0% of a PLA weight, and the phosphate compounds consumption is the 100ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.8cn/dtex, and dimension terminal carboxyl group content is 6eq/ton.The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 80%; Fiber is that its strength retention was 80% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
Embodiment 5:
Raw material is with embodiment 1
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 230 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 2500m/min., 1.45 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 4.5% of a PLA weight, and the phosphate compounds consumption is the 100ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.8cn/dtex, and dimension terminal carboxyl group content is 3eq/ton.The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 80%; Fiber is that its strength retention was 80% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
Embodiment 6:
Raw material is with embodiment 1
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 230 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 2500m/min., 1.45 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 4.5% of a PLA weight, and the phosphate compounds consumption is the 500ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 5% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.8cn/dtex, and dimension terminal carboxyl group content is 3eq/ton.The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 85%; Fiber is that its strength retention was 85% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
| Epoxide content | Phosphate content | EBS content | Strength retention after the hot water treatment | Constant temperature and humidity is handled the back strength retention | ABRASION RESISTANCE | Spinnability | Tone (b value) | |
| Embodiment 1 | 0.6％ | 100ppm | 1％ | 50％ | 40％ | More than 4 grades | ○ | Below 4 |
| Embodiment 2 | 1.0％ | 100ppm | 1％ | 70％ | 70％ | More than 4 grades | ○ | Below 4 |
| Embodiment 3 | 2.0％ | 100ppm | 1％ | 75％ | 75％ | More than 4 grades | ○ | Below 4 |
| Embodiment 4 | 3.0％ | 100ppm | 1％ | 80％ | 80％ | More than 4 grades | △ | Below 4 |
| Embodiment 5 | 4.5％ | 100ppm | 1％ | 80％ | 80％ | More than 4 grades | △ | Below 4 |
| Embodiment 6 | 4.5％ | 500ppm | 5％ | 85％ | 85％ | More than 4 grades | △ | Below 4 |
| Comparative example 1 | 0 | 0 | 0 | 0％ | 0％ | 1 grade | ○ | Below 4 |
| Comparative example 2 | 0.3％ | 100ppm | 1％ | 25％ | 30％ | More than 4 grades | ○ | Below 4 |
| Comparative example 3 | 6％ | 100ppm | 1％ | 85％ | 80％ | More than 4 grades | × | Below 4 |
Embodiment 7:
Raw material: A polylactic acid slice: molecular weight (Mn) is that 100,000 fusing points are 170 degree
B epoxide: diepoxy group compound MADGIC and three epoxide group compound TGIC ratios 1/1
C phosphate compounds: sodium dihydrogen phosphate
D aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide: EBO (the two oleamides of ethylene)
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 1% of a PLA weight, and the phosphate compounds consumption is the 60ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1.5% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.7cn/dtex, and dimension terminal carboxyl group content is 12eq/ton.。The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 60%; Fiber is that its strength retention was 60% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
Embodiment 8:
Raw material D aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide: EBO (the two oleamides of ethylene) and both ratios 1/1 of EBS (ethylene bis stearic amide)
Other raw materials are with embodiment 7
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 1% of a PLA weight, and the phosphate compounds consumption is the 130ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1.5% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.7cn/dtex, and dimension terminal carboxyl group content is 11eq/ton.The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 70%; Fiber is that its strength retention was 70% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
Embodiment 9
Raw material is with embodiment 7
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 1% of a PLA weight, and the phosphate compounds consumption is the 300ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1.5% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.7cn/dtex, and dimension terminal carboxyl group content is 10eq/ton.The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 70%; Fiber is that its strength retention was 75% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
Embodiment 10
Raw material is with embodiment 7
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 1% of a PLA weight, and the phosphate compounds consumption is the 480ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1.5% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.7cn/dtex, and dimension terminal carboxyl group content is 9eq/ton.The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 80%; Fiber is that its strength retention was 85% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.
Embodiment 11
Raw material is with embodiment 7
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 1% of a PLA weight, and the phosphate compounds consumption is the 1300ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1.5% of acid fiber by polylactic weight.
The acid fiber by polylactic intensity that makes is that 3.6cn/dtex dimension terminal carboxyl group content is 8eq/ton.The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 85%; Fiber is that its strength retention was 85% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.But the PLA spinnability descends.
Embodiment 12
Raw material is with embodiment 7
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 4% of a PLA weight, and the phosphate compounds consumption is the 1300ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 2.5% of acid fiber by polylactic weight.
The acid fiber by polylactic intensity that makes is that 3.6cn/dtex dimension terminal carboxyl group content is 4eq/ton.The former silk fiber of PLA precursor PLA is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 90%; Fiber is that its strength retention was 85% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.Fiber ABRASION RESISTANCE (fastness promptly rubs) reaches more than 4 grades.But the PLA spinnability descends.
Embodiment 12
Raw material: A polylactic acid slice: molecular weight (Mn) is that 100,000 fusing points are 170 degree
B epoxide: three epoxide group compound TGIC
C phosphate compounds: sodium dihydrogen phosphate and sodium hydrogen phosphate ratio 1/1
D aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide: EBS (ethylene bis stearic amide)
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 1% of a PLA weight, and the phosphate compounds consumption is the 200ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 0.6% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.7cn/dtex, and dimension terminal carboxyl group content is 11eq/ton.The PLA precursor through hot water treatment after strength retention reach 70%, it is 75% that constant temperature and humidity is handled the back strength retention.ABRASION RESISTANCE reaches 3 grades.
Embodiment 13
Raw material is with embodiment 12
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 1% of a PLA weight, and the phosphate compounds consumption is the 200ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 1.8% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.6cn/dtex, and dimension terminal carboxyl group content is 10eq/ton.The PLA precursor through hot water treatment after strength retention reach 70%, it is 75% that constant temperature and humidity is handled the back strength retention.ABRASION RESISTANCE reaches more than 4 grades.
Embodiment 14
Raw material is with embodiment 12
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 25g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 1% of a PLA weight, and the phosphate compounds consumption is the 200ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 2.5% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.5cn/dtex, and dimension terminal carboxyl group content is 7q/ton.The PLA precursor through hot water treatment after strength retention reach 70%, it is 75% that constant temperature and humidity is handled the back strength retention.ABRASION RESISTANCE reaches more than 4 grades., be that spinning properties descends, the phenomenon of fracture of wire appears.
Embodiment 15
Raw material is with embodiment 12
Raw material A, B, C, D are made the PLA master batch through blend; Gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment; Wherein spinning temperature is 220 degree; Discharge-amount is 2g/min, and using the hole count of spinnerets is 24 holes, and spinning speed is 3000m/min., 1.4 times extension ratio makes high anti-hydrolysis, high-wearing feature acid fiber by polylactic through extension device after extending below again.
The above-mentioned raw materials consumption: the epoxide consumption is 2% of a PLA weight, and the phosphate compounds consumption is the 500ppm of PLA weight, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide consumption are 4.5% of PLA weight.
The acid fiber by polylactic intensity that makes is 3.5cn/dtex, and dimension terminal carboxyl group content is 6q/ton.The PLA precursor through hot water treatment after strength retention reach 85%, it is 85% that constant temperature and humidity is handled the back strength retention.ABRASION RESISTANCE reaches more than 4 grades., be that spinning properties descends, the phenomenon of fracture of wire appears.
Comparative example 1
Conventional polylactic acid slice is made pre-oriented yarn through high speed melt-spinning equipment, the acid fiber by polylactic that after elongator extends, makes.This PLA precursor through hot water treatment after strength retention be 0%, it is 0% that constant temperature and humidity is handled the back strength retention.ABRASION RESISTANCE reaches 1 grade.
Comparative example 2
Raw material: A polylactic acid slice: molecular weight (Mn) is that 100,000 fusing points are 170 degree
B epoxide: three epoxide group compound TGIC
C phosphate compounds: magnesium monohydrogen phosphate and barium hydrogen phosphate ratio 1/1
D aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide: EBS (ethylene bis stearic amide)
Raw material A, B, C, D are made the PLA master batch through blend, gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment, the high anti-hydrolysis, the high-wearing feature acid fiber by polylactic that after elongator extends, make.The phosphorus compound and 1% aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide that contain 0.3% epoxide and 100ppm in this acid fiber by polylactic; The PLA precursor through hot water treatment after strength retention be 25%, constant temperature and humidity is handled the back strength retention and is reached 30%.Dimension terminal carboxyl group content is 18eq/ton.ABRASION RESISTANCE reaches more than 4 grades.
Comparative example 3
Raw material is with comparative example 2
Raw material A, B, C, D are made the PLA master batch through blend, gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment, the high anti-hydrolysis, the high-wearing feature acid fiber by polylactic that after elongator extends, make.The phosphorus compound and 1% aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide that contain 6% epoxide and 100ppm in this acid fiber by polylactic; The PLA precursor through hot water treatment after strength retention be 70%, it is 75% that constant temperature and humidity is handled the back strength retention.Dimension terminal carboxyl group content is 2eq/ton.ABRASION RESISTANCE reaches 4 grades.But spinning properties descends.
Comparative example 4
Raw material: A polylactic acid slice: molecular weight (Mn) is that 100,000 fusing points are 170 degree
B epoxide: diepoxy group compound MADGIC and three epoxide group compound TGIC ratios 1/1
C phosphate compounds: sodium dihydrogen phosphate
D aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide: EBO (the two oleamides of ethylene)
Raw material A, B, C, D are made the PLA master batch through blend, gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment, the high anti-hydrolysis, the high-wearing feature acid fiber by polylactic that after elongator extends, make.The phosphorus compound and 1.5% aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide that contain 1% epoxide and 30ppm in this acid fiber by polylactic; The PLA precursor through hot water treatment after strength retention be below 60%, it is below 50% that constant temperature and humidity is handled the back strength retention.Dimension terminal carboxyl group content is 10eq/ton.ABRASION RESISTANCE reaches more than 4 grades.
Comparative example 5
Raw material is with comparative example 4
Raw material A, B, C, D are made the PLA master batch through blend, gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment, the high anti-hydrolysis, the high-wearing feature acid fiber by polylactic that after elongator extends, make.The phosphorus compound and 1.5% aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide that contain 1% epoxide and 1800ppm in this acid fiber by polylactic; The PLA precursor through hot water treatment after strength retention be 85%, it is 85% that constant temperature and humidity is handled the back strength retention.Dimension terminal carboxyl group content is 9eq/ton.ABRASION RESISTANCE reaches more than 4 grades.But spinnability descends.
Comparative example 6
Raw material is with embodiment 11
Raw material A, B, C, D are made the PLA master batch through blend, gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment, the high anti-hydrolysis, the high-wearing feature acid fiber by polylactic that after elongator extends, make.The phosphorus compound and 0.3% aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide that contain 1% epoxide and 200ppm in this acid fiber by polylactic; The PLA precursor through hot water treatment after strength retention be 70%, it is 75% that constant temperature and humidity is handled the back strength retention.Dimension terminal carboxyl group content is 10eq/ton.ABRASION RESISTANCE reaches 2 grades.
Comparative example 7
Raw material is with embodiment 11
Raw material A, B, C, D are made the PLA master batch through blend, gained PLA master batch and polylactic acid slice mixing back are made pre-oriented yarn through high speed melt-spinning equipment, the high anti-hydrolysis, the high-wearing feature acid fiber by polylactic that after elongator extends, make.The phosphorus compound and 6% aliphatic acid diamides and/or the alkyl substituted type aliphatic acid monoamide that contain 1% epoxide and 200ppm in this acid fiber by polylactic; The PLA precursor through hot water treatment after strength retention be 70%, it is 75% that constant temperature and humidity is handled the back strength retention.Dimension terminal carboxyl group content is 10eq/ton.ABRASION RESISTANCE reaches more than 4 grades.But occurring pressure during spinning rises and the serious phenomenon that breaks end.
Claims (7)
1. a high hydrolysis resistance, high friction resistance polylactic acid fibre; It is characterized in that: in this acid fiber by polylactic; Contain epoxide composition, phosphorus serial inorganic salts compound and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition; Wherein epoxide is 0.5～5% of a PLA weight item, and described epoxide is three epoxide group compound TGIC; Phosphorus serial inorganic salts compound is the 50ppm-1500ppm of PLA weight item, and aliphatic acid diamides and/or alkyl substituted type aliphatic acid monoamide composition account for the 0.1-5% of PLA weight item.
2. high hydrolysis resistance according to claim 1, high friction resistance polylactic acid fibre is characterized in that: the general formula of described phosphorus series inorganic salt compound is: M
AH
BPO
4,
A=1 or 2 wherein, B=1 or 2, M are alkali metal or alkali earth metal.
3. high hydrolysis resistance according to claim 1, high friction resistance polylactic acid fibre is characterized in that: the aliphatic acid diamides is the bimonthly osmanthus of an ethylene bis stearamide or ethylene acid amides, and alkyl substituted type aliphatic acid monoamide is the two oleamides of ethylene.
4. according to claim 1,2 or 3 described high hydrolysis resistances, high friction resistance polylactic acid fibre, it is characterized in that: the terminal groups content of fiber is 1-20eq/ton.
5. according to claim 1,2 or 3 described high hydrolysis resistances, high friction resistance polylactic acid hydrolysis-resisting fibre, it is characterized in that: fiber is after 120 ℃ of hot water are handled 30 minutes, and its strength retention is 50-95%.
6. according to claim 1,2 or 3 described high hydrolysis resistances, high friction resistance polylactic acid fibre, it is characterized in that: fiber is that its strength retention was 40-85% after 90% constant humidity was handled 168 hours through 70 ℃ of constant temperature, humidity.
7. according to claim 1,2 or 3 described high hydrolysis resistances, high friction resistance polylactic acid fibre, it is characterized in that: the dyeing back is through the evaluation of friction colorfastness, and the friction fastness of fabric is the 4-5 level.
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| CN2008101230560A CN101608349B (en) | 2008-06-20 | 2008-06-20 | Polylactic fiber with high hydrolytic resistance and abrasion resistance |
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| CN101608349B true CN101608349B (en) | 2012-06-27 |
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| CN105579630B (en) | 2013-09-30 | 2018-03-23 | 3M创新有限公司 | Fiber, cleaning piece and method |
| JP2016536474A (en) | 2013-09-30 | 2016-11-24 | スリーエム イノベイティブ プロパティズ カンパニー | Fiber and wipe with epoxidized fatty acid ester disposed thereon and method |
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