CN108823679A - A kind of preparation method of aqueous wet process woven fabric bass - Google Patents
A kind of preparation method of aqueous wet process woven fabric bass Download PDFInfo
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- CN108823679A CN108823679A CN201810649182.3A CN201810649182A CN108823679A CN 108823679 A CN108823679 A CN 108823679A CN 201810649182 A CN201810649182 A CN 201810649182A CN 108823679 A CN108823679 A CN 108823679A
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- aqueous
- water
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- woven
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
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- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
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- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
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- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
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- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Abstract
The present invention provides a kind of preparation method of aqueous wet process woven fabric bass, includes the following steps:Non-woven base fabric prepares;Water-soluble polyester preshrunk handles non-woven base fabric;Aqueous polyurethane wet process impregnation processing;It squeezes;Wet coagulation:Fibrillation decrement;The step of post-processing, key of the invention be how in entire manufacturing process without using organic solvent, with aqueous wet processing, the design feature of artificial leather can be reached by reaching process materials environmental protection and prepared bass;Use the island Liao Ding sea-island staple fiber substrate, the superfine fibre that fineness is 0.05D is obtained because it dissolves Hai Houneng, manufactured leather hand feeling is soft, drapability is good, plentiful, good permeability, the performances such as its strength, folding strength and corium are equally matched, the fungi-proofing property of its waterproofness, anti-mildew is better than natural leather, therefore is a kind of vital new material of artificial leather, synthetic leather industry.
Description
Technical field
The invention belongs to the production fields that water-base resin is used for synthetic leather, are specifically related to a kind of aqueous wet process woven fabric bass
Preparation method.
Background technique
Island microfiber leather as forth generation synthetic leather leather on physicochemical property well beyond corium, at present in shoes
The fields such as class, sofa furniture, automobile interior decoration, luggage gloves gradually replace corium, and dosage respectively accounts for half river with corium
Mountain, it is believed that following as microfiber leather items environmental-protecting performance improves, microfiber leather dosage can be increasing.People's living standard
It is continuously improved, causes the requirement to quality of life higher and higher, especially under national strength energy-saving and emission-reduction policy, for substitution
The microfiber leather product feature of environmental protection of corium proposes requirements at the higher level, the especially feature of environmental protection, the feature of environmental protection of technique of the exploitation from material,
Entire process of manufacture does not use organic solvent, this aqueous technology is the emphasis direction of the following leather products exploitation, and
Major subjects are studied by each scientific research institutions.
Country's superfine fiber leather is produced at present, but is all non-environment-friendly products, due to common superfine islands-in-sea bicomponent
The technology features of fiber leather not can solve the material of the product feature of environmental protection itself and environmental friendly property problem, especially skin
The technical problems such as the nuisances such as DMF, toluene, smell, VOC in leather volatilization can not solve always, and described the said goods can not be real
Existing environment protection requirement, is also just unable to reach the environmental protection index requirement of top-grade furniture, footwear and automobile leather.
Common people can be referred to as the synthetic leather other than corium rtificial leather or imitation leather, such as PVC, PU leather.And show
Having in technology using Synthetic Leather is solvent based product, there is different degrees of solvent environment in process of production,
It has greater environmental impacts.Determining island microfiber leather is used as synthetic leather of new generation on physicochemical property well beyond corium, at present
Gradually replace corium in fields such as footwear, sofa furniture, automobile interior decorations, it is believed that future is with the microfiber leather items feature of environmental protection
The raising of energy, microfiber leather dosage can be increasing.The microfiber leather product feature of environmental protection for substituting corium proposes higher want
It asks.From the feature of environmental protection of material, the feature of environmental protection of technique, entire process of manufacture has not used the woven fabric bass that the present invention is developed
Solvent, this aqueous technology are the major fields of the following leather products research and development.This product solves DMF in leather from source,
The technical issues of toluene, the unwanted volatiles such as VOC.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of aqueous wet process woven fabric bass
Preparation method, entire manufacturing process do not use organic solvent, and obtained water-based microfiber bass reaches absolutely environmentally protective and zero
DMF replaces traditional PVA with water-soluble polyester, effectively reduces non-degradable problem caused by PVA, and water-soluble polyester
Cost is relatively low, and the rate of sizing is high, has many advantages, such as to reduce production cost, protection animal and ecological environment.Using aqueous wet coagulation
Technique, zero solvent in production process, zero DMF are generated, and are just really reaching the requirement of environmental protection.
In order to achieve the above objects and other related objects, the present invention provides a kind of preparation side of aqueous wet process woven fabric bass
The preparation of method, the aqueous wet process woven fabric bass includes the following steps:
1) non-woven base fabric prepares:Extra large, polyamide fibre is made using modified dacron to do island and be made and determine island island superfine fiber, this is determined
Non-woven cloth is made by combing needle point method in island island superfine fiber, using the non-woven base fabric as the skeleton of superfine fiber leather
Material;
2) water-soluble polyester preshrunk handles non-woven base fabric:Non-woven base fabric in step 1) is handled with water-soluble polyester
Shrink product sufficiently, eliminating eedle-punched non-wovens internal stress makes its dimensionally stable, and wraps up layer protecting film in fiber surface;
3) impregnation of aqueous polyurethane wet process is handled:Step 2) is passed through into the processed non-woven distributing of water-soluble polyester preshrunk
Water-base resin dipping is carried out to wet production line, four leachings four are carried out using aqueous polyurethane slurry and roll dipping;
4) it squeezes:The base fabric that step 3) has been impregnated with squeezes, and extrusion time is 5~10min, and pressure is 1~2Mpa;
5) wet coagulation:Step 4) base fabric after extruding is put into solidification liquid and carries out solidification sizing;
6) fibrillation is reduced:Aqueous base fabric after sizing is passed through continuous type water washing machine again, continous way water-washing process is:40~
50 DEG C of one slot, 60~70 DEG C of one slot, 80~95 DEG C of two slot, then carrying out the processing of Alkali reduction fibrillation reaches out the thorough fine of fiber
Fibre, base fabric after fibrillation again shaping and drying aqueous superfine islands-in-sea bicomponent bass.
Preferably, the invention also includes post-processing step, by the aqueous superfine islands-in-sea bicomponent bass of step 6) shaping and drying half at
Product carry out wash water soft treatment, carry out veneer, mill skin, printing, embossing and gold stamping post-processing.
Preferably, the volume density of the step 1) non-woven base fabric is 200~600 grams/m.
Water-base resin impregnation formula and conventional organic solvents formula of the present invention are entirely different, and water-base resin refers to hydrophily
Group, can be miscible with water.Four rolled during impregnation using four leachings, be in order to make resin is full and uniform to penetrate among base fabric,
Four times are the technological parameters optimized, and number, which lacks resin, to permeate completely, and often effect weakens instead, are squeezed by adjusting roll
Press gap, control band liquid measure.
Preferably, the formula of the aqueous polyurethane slurry in the step 3) is:100 parts of aqueous polyurethane, water 40~50
Part, 0.2~0.4 part of defoaming agent, 0.1~0.5 part of wetting agent, 0.5~1.0 part of thickener, waterborne polyurethane resin dipping, solidification
Without organic solvent DMF, ecological, environmental protective.
Preferably, alkali selects concentration molten for 1.2~1.5% sodium hydroxide in the processing of Alkali reduction fibrillation in the step 6)
Liquid, fibrillation temperature are 85~95 DEG C, and the fibrillation time is 40~50min, and the base fabric after fibrillation is neutralized washing repeatedly again, are cleaned
Remaining sodium hydroxide, then shaping and drying aqueous island woven fabric bass, handle and need for next procedure.
Preferably, the base fabric in the step 6) after Alkali reduction fibrillation passes through 60~85 DEG C of 3~4 slot of rinsing bowl, cleans
Remaining alkali.
Preferably, the step 5) solidification liquid includes demulsification crosslinking agent and water;Mixed proportion is demulsification crosslinking agent 5~20
Part, 80~95 parts of tap water.
Preferably, demulsification crosslinking agent include phosphoric acid, sulfuric acid, carbonic acid, lactic acid, citric acid, sodium chloride, calcium chloride, ferric sulfate,
One or more of aluminium chloride.
Preferably, it is dried in the step 6) using baking oven, speed is 10~25 meters/min, and temperature is 160~200
℃。
It is highly preferred that the length of baking oven is 10~25 meters.
As described above, the preparation method of aqueous wet process woven fabric bass of the invention, has the advantages that:
1. present invention use determines island sea-island staple fiber and does substrate, is pre-processed by water-soluble polyester base fabric, keep base fabric abundant
It shrinks, eliminates needle and pierce stress, then contain resin pickup.Water-soluble polyester is washed away in water-washing process makes substrate contain aqueous polyurethane tree
Rouge and possess ventilating porous structure.
2. the present invention handles non-woven base fabric using water-soluble polyurethane preshrunk.It is non-woven instead of traditional PVA processing
Cloth largely reduces production cost, and water-soluble polyester is a kind of degradable environmentally friendly high molecular material,
It is biodegradable, no pollution to the environment.PVA all prices of tradition are higher, the wastes non-degradable such as clout of generation, to ring
There is certain pollution in border.
3. the aqueous wet process woven fabric bass technique of product of the present invention uses aqueous wet processing, it is solidifying to carry out wet process using water as medium
Gu there is no any organic solvent, zero DMF into use process from production.
4. the aqueous wet coagulation technology of the aqueous wet process woven fabric bass of product of the present invention is domestic initiation, solidifying by wet process
Gu technique bass produced has the advantages that dimensionally stable, skin sense, flexibility, elasticity has been restored.Permeability is very superior,
Significantly larger than corium, properties can meet the requirement of environmental protection, be the aqueous, environmental protective woven fabric bass in a kind of positive meaning.
Specific embodiment
The present invention is further explained combined with specific embodiments below, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Embodiment 1
A kind of preparation method of aqueous wet process woven fabric bass, includes the following steps:
1) non-woven base fabric prepares:
Extra large, polyamide fibre is made using modified dacron to do island and be made and determine island island superfine fiber, this is determined into island island superfine fiber and is led to
It crosses combing needle point method and non-woven cloth is made, using the non-woven base fabric as the framework material of superfine fiber leather, volume density 500
Gram/m;
2) water-soluble polyester preshrunk handles non-woven base fabric:
Non-woven base fabric in step 1) is handled with water-soluble polyester shrinks product sufficiently, and eliminating eedle-punched non-wovens internal stress makes
Its dimensionally stable, and layer protecting film is wrapped up in fiber surface;
3) impregnation of aqueous polyurethane wet process is handled:
By the non-woven cloth of step 2) be sent to wet production line carry out water-base resin dipping, using aqueous polyurethane slurry into
Dipping is rolled in the leaching of row four four;The formula of aqueous polyurethane slurry is:100 parts of aqueous polyurethane, 40 parts of water, 0.2 part of defoaming agent, wetting
0.1 part of agent, 0.5 part of thickener;
4) it squeezes:The base fabric that step 3) has been impregnated with squeezes, extrusion time 5min, pressure 1Mpa;
5) wet coagulation:Step 4) base fabric after extruding is put into solidification liquid and carries out solidification sizing, solidification liquid includes
Lactic acid and water;Mixed proportion is 15 parts of lactic acid, 80 parts of tap water;
6) fibrillation is reduced:Aqueous base fabric after sizing is passed through continuous type water washing machine again, continous way water-washing process is:40℃
One slot, 60 DEG C of one slot, 80 DEG C of two slot, water-soluble polyester, then 1.5% sodium hydroxide for being 85 DEG C in temperature are cleaned in washing repeatedly
Solution carries out the processing of Alkali reduction fibrillation, and the thorough fine of fiber is made to reach fibrillation, and the fibrillation time is 40mim.Base fabric after fibrillation
Again in 15 meters of long baking ovens, 160 DEG C at a temperature of, speed be 15 meters/min in speed carry out shaping drying it is aqueous
Superfine islands-in-sea bicomponent bass.
Embodiment 2
A kind of preparation method of aqueous wet process woven fabric bass, includes the following steps:
4) non-woven base fabric prepares:
Extra large, polyamide fibre is made using modified dacron to do island and be made and determine island island superfine fiber, this is determined into island island superfine fiber and is led to
It crosses combing needle point method and non-woven cloth is made, using the non-woven base fabric as the framework material of superfine fiber leather, volume density 400
Gram/m;
5) water-soluble polyester preshrunk handles non-woven base fabric:
Non-woven base fabric in step 1) is handled with water-soluble polyester shrinks product sufficiently, and eliminating eedle-punched non-wovens internal stress makes
Its dimensionally stable, and layer protecting film is wrapped up in fiber surface;
6) impregnation of aqueous polyurethane wet process is handled:
By the non-woven cloth of step 2) be sent to wet production line carry out water-base resin dipping, using aqueous polyurethane slurry into
Dipping is rolled in the leaching of row four four;The formula of aqueous polyurethane slurry is:100 parts of aqueous polyurethane, 45 parts of water, 0.3 part of defoaming agent, wetting
0.3 part of agent, 0.8 part of thickener;
4) it squeezes:The base fabric that step 3) has been impregnated with squeezes, extrusion time 8min, pressure 1Mpa;
5) wet coagulation:Step 4) base fabric after extruding is put into solidification liquid and carries out solidification sizing, solidification liquid includes
Lactic acid and water;Mixed proportion is 15 parts of lactic acid, 80 parts of tap water;
6) fibrillation is reduced:Aqueous base fabric after sizing is passed through continuous type water washing machine again, continous way water-washing process is:45℃
One slot, 65 DEG C of one slot, 85 DEG C of two slot, water-soluble polyester is cleaned in washing repeatedly, then at a temperature of 90 °C 1.5% sodium hydroxide
Solution carries out the processing of Alkali reduction fibrillation, and the thorough fine of fiber is made to reach fibrillation, and the fibrillation time is 45mim.Base fabric after fibrillation
Again in 15 meters of long baking ovens, 160 DEG C at a temperature of, speed be 15 meters/min in speed carry out shaping drying it is aqueous
Superfine islands-in-sea bicomponent bass.
Embodiment 3
A kind of preparation method of aqueous wet process woven fabric bass, includes the following steps:
7) non-woven base fabric prepares:
Extra large, polyamide fibre is made using modified dacron to do island and be made and determine island island superfine fiber, this is determined into island island superfine fiber and is led to
It crosses combing needle point method and non-woven cloth is made, using the non-woven base fabric as the framework material of superfine fiber leather, volume density 400
Gram/m;
8) water-soluble polyester preshrunk handles non-woven base fabric:
Non-woven base fabric in step 1) is handled with water-soluble polyester shrinks product sufficiently, and eliminating eedle-punched non-wovens internal stress makes
Its dimensionally stable, and layer protecting film is wrapped up in fiber surface;
9) impregnation of aqueous polyurethane wet process is handled:
By the non-woven cloth of step 2) be sent to wet production line carry out water-base resin dipping, using aqueous polyurethane slurry into
Dipping is rolled in the leaching of row four four;The formula of aqueous polyurethane slurry is:100 parts of aqueous polyurethane, 50 parts of water, 0.4 part of defoaming agent, wetting
0.5 part of agent, 1.0 parts of thickener;
4) it squeezes:The base fabric that step 3) has been impregnated with squeezes, extrusion time 10min, pressure 1Mpa;
5) wet coagulation:Step 4) base fabric after extruding is put into solidification liquid and carries out solidification sizing, solidification liquid includes
Lactic acid and water;Mixed proportion is 15 parts of lactic acid, 80 parts of tap water;
6) fibrillation is reduced:Aqueous base fabric after sizing is passed through continuous type water washing machine again, continous way water-washing process is:50℃
One slot, 70 DEG C of one slot, 95 DEG C of two slot, water-soluble polyester, then 1.5% sodium hydroxide for being 95 DEG C in temperature are cleaned in washing repeatedly
Solution carries out the processing of Alkali reduction fibrillation, and the thorough fine of fiber is made to reach fibrillation, and the fibrillation time is 45mim.Base fabric after fibrillation
Again in 15 meters of long baking ovens, 160 DEG C at a temperature of, speed be 15 meters/min in speed carry out shaping drying it is aqueous
Superfine islands-in-sea bicomponent bass.
To sum up, this case is a kind of preparation method of the aqueous wet process woven fabric bass of environmental protection, key of the invention be how
Entire process of manufacturing does not use organic solvent, with aqueous wet processing, reaches process materials environmental protection and can reach imitative
The design feature of corium.Using the island Liao Ding sea-island staple fiber substrate, the ultra-fine fibre that fineness is 0.05D is obtained because it dissolves Hai Houneng
Dimension, it has excellent performance, and manufactured leather hand feeling is soft, and drapability is good, plentiful, good permeability, strength, folding strength etc.
Performance is equally matched with corium.Its waterproofness, the fungi-proofing property of anti-mildew are better than natural leather, therefore are artificial leather, synthetic leather industry
A kind of vital new material, wide market.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (7)
1. a kind of preparation method of aqueous wet process woven fabric bass, which is characterized in that the preparation packet of the aqueous wet process woven fabric bass
Include following steps:
1) non-woven base fabric prepares:Extra large, polyamide fibre is made using modified dacron to do island and be made and determine island island superfine fiber, this is determined into island sea
Non-woven cloth is made by combing needle point method in island ultrafine fiber, the skeleton material using the non-woven base fabric as superfine fiber leather
Material;
2) water-soluble polyester preshrunk handles non-woven base fabric:Non-woven base fabric water-soluble polyester processing in step 1) is made to produce
Product are sufficiently shunk, and eliminating eedle-punched non-wovens internal stress makes its dimensionally stable, and wraps up layer protecting film in fiber surface;
3) impregnation of aqueous polyurethane wet process is handled:Step 2) is sent to by the processed non-woven cloth of water-soluble polyester preshrunk wet
Method production line carries out water-base resin dipping, carries out four leachings four using aqueous polyurethane slurry and rolls dipping;
4) it squeezes:The base fabric that step 3) has been impregnated with squeezes, and extrusion time is 5~10min, and pressure is 1~2Mpa;
5) wet coagulation:Step 4) base fabric after extruding is put into solidification liquid and carries out solidification sizing;
6) fibrillation is reduced:Aqueous base fabric after sizing is passed through continuous type water washing machine again, continous way water-washing process is:40~50 DEG C
One slot, 60~70 DEG C of one slot, 80~95 DEG C of two slot, then carrying out the processing of Alkali reduction fibrillation makes the thorough fine of fiber reach fibrillation,
Base fabric after fibrillation again shaping and drying aqueous superfine islands-in-sea bicomponent bass.
2. a kind of preparation method of aqueous wet process woven fabric bass according to claim 1, it is characterised in that:The step 3)
In the formula of aqueous polyurethane slurry be:100 parts of aqueous polyurethane, 40~50 parts of water, 0.2~0.4 part of defoaming agent, wetting agent
0.1~0.5 part, 0.5~1.0 part of thickener.
3. a kind of preparation method of aqueous wet process woven fabric bass according to claim 1, it is characterised in that:The step 6)
Alkali selects concentration for 1.2~1.5% sodium hydroxide solution in middle Alkali reduction fibrillation processing, and fibrillation temperature is 85~95 DEG C, is opened
The fine time is 40~50min.
4. a kind of preparation method of aqueous wet process woven fabric bass according to claim 1, it is characterised in that:The step 6)
Base fabric after middle Alkali reduction fibrillation passes through 60~85 DEG C of 3~4 slot of rinsing bowl, cleans remaining alkali.
5. a kind of preparation method of aqueous wet process woven fabric bass according to claim 1, it is characterised in that:The step 5)
Middle solidification liquid includes demulsification crosslinking agent and water;Mixed proportion is 5~20 parts of crosslinking agent, 80~95 parts of tap water of demulsification.
6. a kind of preparation method of aqueous wet process woven fabric bass according to claim 5, it is characterised in that:Be demulsified crosslinking agent
Including one or more of phosphoric acid, sulfuric acid, carbonic acid, lactic acid, citric acid, sodium chloride, calcium chloride, ferric sulfate, aluminium chloride.
7. a kind of preparation method of aqueous wet process woven fabric bass according to claim 1, it is characterised in that:The step 6)
Middle to be dried using baking oven, speed is 10~25 meters/min, and temperature is 160~200 DEG C.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109622293A (en) * | 2018-12-10 | 2019-04-16 | 威尔尼装饰材料(江苏)有限公司 | A kind of fabric processing method of elastic force bass |
CN112553915A (en) * | 2020-11-12 | 2021-03-26 | 浙江吉利控股集团有限公司 | Preparation method of microfiber leather and microfiber leather |
CN113417151A (en) * | 2021-07-08 | 2021-09-21 | 江苏聚杰微纤科技集团股份有限公司 | Environment-friendly PU artificial leather with oily-like cellular structure and preparation method thereof |
CN113862931A (en) * | 2021-11-02 | 2021-12-31 | 上海华峰超纤科技股份有限公司 | Splitting process of water-soluble sea-island fiber base cloth |
CN114292383A (en) * | 2022-02-14 | 2022-04-08 | 山东天庆科技发展有限公司 | Alkali deweighting resin for water-based microfiber synthetic leather and preparation method and application thereof |
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62149986A (en) * | 1985-12-17 | 1987-07-03 | 金井 宏之 | Production of base material for artificial leather made of polyester |
CN101725052A (en) * | 2009-11-04 | 2010-06-09 | 烟台万华超纤股份有限公司 | Waterborne polyurethane resin superfiber leather and manufacturing method thereof |
CN102115983A (en) * | 2011-01-26 | 2011-07-06 | 烟台华大化学工业有限公司 | Aqueous polyurethane superfine fiber synthetic leather and preparation method thereof |
CN102877323A (en) * | 2012-10-11 | 2013-01-16 | 福建可利达合成纤维有限公司 | Production method for waterborne polyurethane synthetic leather wet process impregnated bass |
CN102877322A (en) * | 2012-10-11 | 2013-01-16 | 福建可利达合成纤维有限公司 | Method for preparing suede waterborne polyurethane superfine fiber synthetic leather |
CN104963211A (en) * | 2015-07-24 | 2015-10-07 | 江苏尚科聚合新材料有限公司 | Preparation method of figured islands-in-sea wool suedette interior trim leather of car |
CN105803816A (en) * | 2016-05-25 | 2016-07-27 | 山东同大海岛新材料股份有限公司 | Preparation method of easy-dyeing microfiber leather |
CN106544883A (en) * | 2016-10-27 | 2017-03-29 | 泉州众信超纤科技股份有限公司 | Hot light prepares the preparation technology of the woven fabric material and product of stereo natural light |
CN106868880A (en) * | 2017-04-10 | 2017-06-20 | 合肥科天水性科技有限责任公司 | A kind of aqueous polyurethane imitates woven fabric and its manufacture method |
CN107881798A (en) * | 2017-11-28 | 2018-04-06 | 浙江昶丰新材料有限公司 | Waterborne polyurethane synthetic leather and preparation method thereof |
CN107956134A (en) * | 2017-11-28 | 2018-04-24 | 浙江昶丰新材料有限公司 | Aqueous polyurethane superfine fiber synthetic leather and preparation method thereof |
-
2018
- 2018-06-22 CN CN201810649182.3A patent/CN108823679A/en active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62149986A (en) * | 1985-12-17 | 1987-07-03 | 金井 宏之 | Production of base material for artificial leather made of polyester |
CN101725052A (en) * | 2009-11-04 | 2010-06-09 | 烟台万华超纤股份有限公司 | Waterborne polyurethane resin superfiber leather and manufacturing method thereof |
CN102115983A (en) * | 2011-01-26 | 2011-07-06 | 烟台华大化学工业有限公司 | Aqueous polyurethane superfine fiber synthetic leather and preparation method thereof |
CN102877323A (en) * | 2012-10-11 | 2013-01-16 | 福建可利达合成纤维有限公司 | Production method for waterborne polyurethane synthetic leather wet process impregnated bass |
CN102877322A (en) * | 2012-10-11 | 2013-01-16 | 福建可利达合成纤维有限公司 | Method for preparing suede waterborne polyurethane superfine fiber synthetic leather |
CN104963211A (en) * | 2015-07-24 | 2015-10-07 | 江苏尚科聚合新材料有限公司 | Preparation method of figured islands-in-sea wool suedette interior trim leather of car |
CN105803816A (en) * | 2016-05-25 | 2016-07-27 | 山东同大海岛新材料股份有限公司 | Preparation method of easy-dyeing microfiber leather |
CN106544883A (en) * | 2016-10-27 | 2017-03-29 | 泉州众信超纤科技股份有限公司 | Hot light prepares the preparation technology of the woven fabric material and product of stereo natural light |
CN106868880A (en) * | 2017-04-10 | 2017-06-20 | 合肥科天水性科技有限责任公司 | A kind of aqueous polyurethane imitates woven fabric and its manufacture method |
CN107881798A (en) * | 2017-11-28 | 2018-04-06 | 浙江昶丰新材料有限公司 | Waterborne polyurethane synthetic leather and preparation method thereof |
CN107956134A (en) * | 2017-11-28 | 2018-04-24 | 浙江昶丰新材料有限公司 | Aqueous polyurethane superfine fiber synthetic leather and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
高士刚 等: "《鞋靴材料》", 31 January 2012, 中国轻工业出版社 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109622293A (en) * | 2018-12-10 | 2019-04-16 | 威尔尼装饰材料(江苏)有限公司 | A kind of fabric processing method of elastic force bass |
CN112553915A (en) * | 2020-11-12 | 2021-03-26 | 浙江吉利控股集团有限公司 | Preparation method of microfiber leather and microfiber leather |
CN113417151A (en) * | 2021-07-08 | 2021-09-21 | 江苏聚杰微纤科技集团股份有限公司 | Environment-friendly PU artificial leather with oily-like cellular structure and preparation method thereof |
CN113417151B (en) * | 2021-07-08 | 2023-01-03 | 江苏聚杰微纤科技集团股份有限公司 | Environment-friendly PU artificial leather with oily-like cellular structure and preparation method thereof |
CN113862931A (en) * | 2021-11-02 | 2021-12-31 | 上海华峰超纤科技股份有限公司 | Splitting process of water-soluble sea-island fiber base cloth |
CN113862931B (en) * | 2021-11-02 | 2023-12-29 | 上海华峰超纤科技股份有限公司 | Fiber opening process of water-soluble island fiber base cloth |
CN114292383A (en) * | 2022-02-14 | 2022-04-08 | 山东天庆科技发展有限公司 | Alkali deweighting resin for water-based microfiber synthetic leather and preparation method and application thereof |
CN115612060A (en) * | 2022-08-22 | 2023-01-17 | 明新梅诺卡(江苏)新材料有限公司 | Preparation method and application of high-continuity waterborne polyurethane |
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