A non-reducing process for manufacturing bio-based microfiber base cloth

Abstract

The application discloses a kind of non-reduction process biobased microfiber base cloth manufacturing method, specific implementation is: with biobased nylon or biobased PET as A component material, with TPU as B component material, composite spinning process is prepared to obtain biobased microfiber, and the microfiber is sequentially cut off, carding, net, needle punching and prepared microfiber needle felt, needle felt is heated and softened after oven, and cooling ironing, the non-woven fabric after ironing is first immersed in pure DMF, TPU in fiber is pre-dissolved, the non-woven fabric immersed in DMF is immersed again polyurethane resin, and finally prepared non-reduction process biobased microfiber base cloth after coagulation, washing, drying.The application uses TPU that can be dissolved in DMF as B component, before immersion polyurethane, first use DMF solution to pre-dissolve TPU in fiber, so that TPU is dissolved and stripped from fiber, so that the reduction process of traditional microfiber industry is removed, a large amount of waste solid is not generated, and energy consumption is significantly reduced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of artificial leather preparation, and particularly relates to a manufacturing method of a non-reduction process bio-based microfiber base cloth. BACKGROUND

[0002] The high mechanical performance, high durability performance and high imitation leather characteristics of the microfiber synthetic leather are well-known, and the microfiber synthetic leather is widely applied to sofa furniture, luggage and shoe materials and automotive interior industries. However, with the increasing environmental protection requirements in recent years, customers not only care about the high performance of the material, but also care about whether the material production process is green, energy consumption and the like, which are factors considered by customers when purchasing. At present, the production of microfiber mainly adopts two processes. One is a mixed spinning-toluene reduction method, which adopts a mixed mode of nylon and polyethylene at a ratio of about 50 / 50, tows the base cloth by dissolving polyethylene in the fiber with toluene, and separates the polyethylene by evaporation. The produced polyethylene can be sold as plastic for the second time, and the raw material cost is low, but the energy consumption is large. The other is a composite spinning-alkali reduction method, which adopts a composite spinning of nylon and alkali-soluble polyester at a ratio of about 65 / 35, and hydrolyzes the alkali-soluble polyester in the fiber with about 5% sodium hydroxide solution. The waste liquid is discharged after sewage treatment, and the advantages are no evaporation separation and low energy consumption. The disadvantages are that a large amount of high-salt wastewater and waste solid are produced, and the environment is greatly affected. SUMMARY

[0003] In view of the above problems, the purpose of the present application is to provide a manufacturing method of a non-reduction process bio-based microfiber base cloth.

[0004] The specific technical solutions are as follows:

[0005] A manufacturing method of a non-reduction process bio-based microfiber base cloth, comprising the following steps:

[0006] 1) preparing bio-based microfiber: bio-based nylon or bio-based PET is used as A component material, and TPU is used as B component material, and a composite spinning process is adopted to prepare bio-based microfiber;

[0007] 2) the bio-based microfiber prepared by step 1) is sequentially cut, carded, laid and needled to prepare microfiber needle-punched cloth;

[0008] 3) the microfiber needle-punched cloth prepared by step 2) is heated and softened in an oven, and then is ironed by a mirror surface roller with cooling water;

[0009] 4) the ironed non-woven fabric is first immersed in pure DMF to pre-dissolve TPU in the fiber, and the pre-dissolution time is greater than or equal to 5 min;

[0010] 5) The non-woven fabric soaked in DMF is soaked in polyurethane resin, and finally coagulation, water washing and drying are carried out to obtain a bio-based microfiber base fabric without the weight reduction process.

[0011] Further, the bio-based nylon in step 1) is one or more of PA56, PA410, PA510, PA610, PA1010, PA1012, PA11, and the bio-based PET is one or more of the dehydration polymers of bio-based 1,3-propanediol, 1,4-butanediol, purified terephthalic acid and isophthalic acid.

[0012] Further, the TPU in step 1) is a bio-based TPU containing bio-based polyether or polyester polyol and isocyanate polymerization, with a softening point of 110-170℃, preferably a softening point of 120℃±10℃, wherein the polyester polyol is one or both of bio-based 1,3-propanediol and 1,4-butanediol and bio-based 1,4-butyric acid or 1,6-hexanoic acid dehydration polymer.

[0013] Further, the bio-based microfiber prepared in step 1) is in an island structure, a rice-shaped structure or an orange segment structure.

[0014] Further, the temperature of the oven in step 3) is determined according to the melting point of the TPU, and the temperature of the oven is higher than the melting point of the TPU by 30℃.

[0015] Further, the polyurethane resin in step 5) is one or both of bio-based polyether and bio-based polyester polyol and diphenylmethane diisocyanate polymerization.

[0016] Further, the bio-based polyether is bio-based 1,3-propanediol ether or 1,4-butanediol ether, and the bio-based polyester polyol is a dehydration condensate of one or both of bio-based 1,3-propanediol and 1,4-butanediol and bio-based 1,4-butyric acid or 1,6-hexanoic acid.

[0017] The beneficial effects of the present application are:

[0018] In the process of microfiber spinning, the present application uses TPU soluble in DMF as component B, and uses DMF solution to pre-dissolve TPU in the fiber before soaking in polyurethane, so that TPU is dissolved and stripped from the fiber, thereby eliminating the weight reduction process in the traditional microfiber industry, without generating a large amount of waste solid, and the energy consumption is significantly reduced. DETAILED DESCRIPTION

[0019] The present application will be further described below in conjunction with examples, but the scope of protection of the present application is not limited thereto.

[0020] Example 1

[0021] 1) Using bio-based nylon PA11 as island component and bio-based TPU with softening point of 120±10℃, which is polymerized from bio-based 1,3-propanediol ether and isocyanate, as sea component, sea-island composite fibers with a mass ratio of 65 / 35 are prepared;

[0022] 2) The sea-island composite fibers of step 1) are cut, carded, laid, and needled to prepare a microfiber needle felt;

[0023] 3) The microfiber needle felt of step 2) is heated and softened in an oven at a temperature of 150℃±2℃, and is cooled and ironed flat by mirror surface rollers through which cooling water is passed to prepare a microfiber non-woven fabric;

[0024] 4) The non-woven fabric is immersed in an organic solvent DMF, and the vehicle speed is controlled so that the non-woven fabric stays in the DMF for 5 minutes;

[0025] 5) The non-woven fabric immersed in the DMF is put into a polyurethane resin solution polymerized from bio-based 1,3-propanediol ether with a molecular weight of 500 and diphenylmethane diisocyanate, so that the polyurethane resin solution completely fills the non-woven fabric;

[0026] 6) The non-woven fabric filled with polyurethane is coagulated in a DMF aqueous solution, washed with water, and dried to obtain a bio-based microfiber base cloth without a weight reduction process.

[0027] Example 2

[0028] 1) Using bio-based nylon PA510 as component A and bio-based TPU with a softening point of 140±10℃, which is polymerized from a polyester polymerized from bio-based 1,3-propanediol and 1,6-hexanedioic acid and isocyanate, as component B, segmented orange peel type composite fibers with a mass ratio of 70 / 30 are prepared;

[0029] 2) The segmented orange peel type composite fibers of step 1) are cut, carded, laid, and needled to prepare a microfiber needle felt;

[0030] 3) The microfiber needle felt of step 2) is heated and softened in an oven at a temperature of 170℃±2℃, and is cooled and ironed flat by mirror surface rollers through which cooling water is passed to prepare a microfiber non-woven fabric;

[0031] 4) The non-woven fabric is immersed in an organic solvent DMF, and the vehicle speed is controlled so that the non-woven fabric stays in the DMF for 8 minutes;

[0032] 5) The non-woven fabric immersed in the DMF is put into a polyurethane solution polymerized from a polyester polymerized from bio-based 1,3-propanediol with a molecular weight of 2000 and 1,6-hexanedioic acid and diphenylmethane diisocyanate, so that the polyurethane resin solution completely fills the non-woven fabric;

[0033] 6) The nonwoven fabric filled with polyurethane is solidified in DMF aqueous solution, washed with water, and dried to obtain a bio-based microfiber base cloth by non-reduction process.

[0034] Example 3

[0035] 1) Use bio-based PET as component A and bio-based TPU polymerized from polyester synthesized from bio-based 1,3-propanediol and bio-based 1,4-succinic acid and isocyanate with a softening point of 130±10℃ as component B to prepare segmented orange peel composite fibers with a mass ratio of 70 / 30;

[0036] 2) Use the segmented orange peel composite fibers of step 1) to prepare microfiber needle-punched fabric by cutting, carding, laying, and needling;

[0037] 3) Heat and soften the microfiber needle-punched fabric of step 2) in an oven at a temperature of 160℃±2℃, and cool and iron the fabric using mirror surface rollers with cooling water to obtain microfiber nonwoven fabric;

[0038] 4) The nonwoven fabric is immersed in organic solvent DMF, and the vehicle speed is controlled to make the nonwoven fabric stay in DMF for 7 minutes;

[0039] 5) The nonwoven fabric immersed in DMF is placed in a polyurethane solution containing polyester synthesized from bio-based 1,3-propanediol and bio-based 1,4-succinic acid and diphenylmethane diisocyanate, and the polyurethane resin solution is completely filled into the nonwoven fabric;

[0040] 6) The nonwoven fabric filled with polyurethane is solidified in DMF aqueous solution, washed with water, and dried to obtain a bio-based microfiber base cloth by non-reduction process.

[0041] Example 4

[0042] 1) Use bio-based nylon PA56 and PA510 with a mass ratio of 1:1 as component A and bio-based TPU polymerized from polyester synthesized from bio-based 1,3-propanediol and 1,6-hexanedioic acid and isocyanate with a softening point of 120±10℃ as component B to prepare segmented orange peel composite fibers with a mass ratio of 70 / 30;

[0043] 2) Use the segmented orange peel composite fibers of step 1) to prepare microfiber needle-punched fabric by cutting, carding, laying, and needling;

[0044] 3) Heat and soften the microfiber needle-punched fabric of step 2) in an oven at a temperature of 150℃±2℃, and cool and iron the fabric using mirror surface rollers with cooling water to obtain microfiber nonwoven fabric;

[0045] 4) The nonwoven fabric is immersed in organic solvent DMF, and the vehicle speed is controlled to make the nonwoven fabric stay in DMF for 6 minutes;

[0046] 5) The non-woven fabric after DMF soaking enters into the polyurethane solution containing polyester synthesized by bio-based 1,3-propanediol and 1,6-hexanedioic acid with molecular weight of 2000 and bio-based 1,3-propanediol ether with molecular weight of 2000 and diphenylmethane diisocyanate, and the polyurethane solution completely fills into the non-woven fabric;

[0047] 6) The non-woven fabric after polyurethane filling is coagulated by DMF aqueous solution, washed by water, and dried to obtain bio-based microfiber base cloth without weight reduction process.

[0048] Example 5

[0049] 1) Bio-based nylon PA510 and PA11 with mass ratio of 1:1 are used as A component, and bio-based TPU synthesized by bio-based 1,3-propanediol ether and isocyanate with softening point of 120±10℃ is used as B component, and a mizuki type composite fiber with mass ratio of 70 / 30 is prepared;

[0050] 2) The mizuki type composite fiber of step 1) is cut, carded, laid, and needled to prepare a microfiber needle-punched fabric;

[0051] 3) The microfiber needle-punched fabric is heated and softened by an oven with temperature of 150℃±2℃, and is cooled and ironed by a mirror surface roller with cooling water to prepare a microfiber non-woven fabric;

[0052] 4) The non-woven fabric is soaked in an organic solvent DMF, and the vehicle speed is controlled to make the non-woven fabric stay in DMF for 6 minutes;

[0053] 5) The non-woven fabric after DMF soaking enters into the polyurethane solution containing polyester synthesized by bio-based 1,4-butanediol and 1,6-hexanedioic acid with molecular weight of 1000 and bio-based 1,3-propanediol ether with molecular weight of 2000 and diphenylmethane diisocyanate, and the polyurethane solution completely fills into the non-woven fabric;

[0054] 6) The non-woven fabric after polyurethane filling is coagulated by DMF aqueous solution, washed by water, and dried to obtain bio-based microfiber base cloth without weight reduction process.

Claims

1. A method for manufacturing a non-reducing process bio-based microfiber base cloth, comprising the following steps: 1) preparing bio-based microfibers: using bio-based nylon or bio-based PET as component A material, and TPU as component B material, bio-based microfibers are prepared by using a composite spinning process; 2) the bio-based microfibers prepared by step 1) are sequentially cut, carded, laid, and needled to prepare microfiber needle-punched cloth; 3) the microfiber needle-punched cloth prepared in step 2) is heated and softened in an oven, and then is ironed by mirror surface rollers with cooling water; 4) the ironed non-woven fabric is first immersed in pure DMF to pre-dissolve TPU in the fibers, and the pre-dissolution time is 5-8 minutes; 5) the non-woven fabric immersed in DMF is then immersed in polyurethane resin, and finally is prepared into a non-reducing process bio-based microfiber base cloth after coagulation, washing, and drying; The TPU in step 1) is polymerized from bio-based polyether or polyester polyol and isocyanate, and the softening point is 110-170℃, wherein the polyester polyol is one or both of bio-based 1,3-propanediol and 1,4-butanediol, and the dehydration polymer of bio-based 1,4-butyric acid or 1,6-hexanoic acid.

2. The production method according to claim 1, wherein The bio-based nylon in step 1) is one or more of PA56, PA410, PA510, PA610, PA1010, PA1012, and PA11, and the bio-based PET is the dehydration polymer of one or more of bio-based 1,3-propanediol, 1,4-butanediol, purified terephthalic acid, and isophthalic acid.

3. The production method according to claim 1, wherein The TPU in step 1) is bio-based TPU with a softening point of 120℃±10℃.

4. The production method according to claim 1, wherein The bio-based microfibers prepared in step 1) have island structure, rice-shaped structure, or orange-segment structure.

5. The production method according to claim 1, wherein The temperature of the oven in step 3) is 30℃ higher than the melting point of TPU.

6. The production method according to claim 1, wherein The polyurethane resin in step 5) is polymerized from one or both of bio-based polyether and bio-based polyester polyol and diphenylmethane diisocyanate.

7. The production method according to claim 6, wherein The bio-based polyether is bio-based 1,3-propanediol ether or 1,4-butanediol ether, and the bio-based polyester polyol is the dehydration condensation product of one or both of bio-based 1,3-propanediol and 1,4-butanediol and bio-based 1,4-butyric acid or 1,6-hexanoic acid.