CN106917298B - A kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass - Google Patents

A kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass Download PDF

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CN106917298B
CN106917298B CN201710264897.2A CN201710264897A CN106917298B CN 106917298 B CN106917298 B CN 106917298B CN 201710264897 A CN201710264897 A CN 201710264897A CN 106917298 B CN106917298 B CN 106917298B
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bass
preparation
superfine fiber
base fabric
color fastness
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CN106917298A (en
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王玉路
靳丽强
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Shandong Jiqing Technology Service Co ltd
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Qilu University of Technology
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/32Treating 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
    • D06M11/36Treating 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
    • D06M11/38Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32Polyesters
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34Polyamides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/08Properties of the materials having optical properties
    • D06N2209/0807Coloured
    • D06N2209/0823Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/08Properties of the materials having optical properties
    • D06N2209/0807Coloured
    • D06N2209/083Multi-coloured
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/16Properties of the materials having other properties
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00Specially adapted uses
    • D06N2211/12Decorative or sun protection articles
    • D06N2211/28Artificial leather

Abstract

The present invention relates to a kind of preparation methods of high color fastness dyeing-free superfine fiber chemical leather bass.The preparation method includes base fabric decrement, impregnates color aqueous polyurethane, polyurethane solidification, post-treating and other steps.Prepared superfine fiber chemical leather bass color is full, and color fastness is high, is not required to be dyed again.Preparation process dye dosage is few, and dye utilization rate is high, is a kind of preparation method of environment-friendly type superfine fiber chemical leather bass without using organic solvents such as toluene, dimethylformamides.

Description

A kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass
Technical field
The present invention relates to a kind of preparation methods of high color fastness dyeing-free superfine fiber chemical leather bass, and it is raw to belong to synthetic leather Produce technical field.
Background technique
In recent years, superfine fibre-Synthetic Leather (MPSL) development is swift and violent, is widely used in sporting goods, household, vapour The fields such as automobile-used product.High density " sea-island " type superfine fibre imparts the excellent physical mechanical strength of MPSL, has open type micropore The polyurethane of structure imparts MPSL similar to the texture of corium, becomes the excellent substitute of natural leather;Meanwhile MPSL high The mass uniformity of degree and higher utilization rate become the contenders of natural leather.
But the design feature of superfine fibre causes technical problem of the MPSL in terms of dyeing.On the one hand, too small fibre Degree makes that Dye Adsorption speed is fast, consumption is big, level-dyeing property is poor, and apparent that color is shallow.On the other hand, active in superfine fibre molecule Group is seldom, causes the poor color fastness of product.In addition, superfine fibre and the qualitative difference of polyurethane, and easily cause synthetic leather Occurs the problems such as " PU spot " when product is washed.
In order to solve the dyeing problem of MPSL, scientific research personnel has carried out a large amount of research work.The research of early stage mainly collects In in the improvement to superfine fiber synthetic leather dyeing, such as screen suitable dyestuff, optimization bath raio, temperature, time, pH etc. Process conditions etc., these research work provide important technological parameter to improve the color fastness of superfine fiber chemical leather.Synthesis With the important way for using novel dyeing assistant being also improvement superfine fiber synthetic leather coloring and color fastness, double fiber tip table Face activating agent, the levelling agent with amide structure, weak cation type dye deep-dyeing agent, rare earth element, chitin modified product etc. help Agent improve dyestuff level-dyeing property, it is beautiful in colour degree and in terms of play certain effect.It is modified to superfine fibre, increase Add fiber polar groups content to improve the tinctorial property of superfine fibre, and improves superfine fiber synthetic leather dyeability Can a kind of important means, appropriateness hydrolysis, hydrolysis are carried out to superfine fibre using acid, enzyme etc. and carry out graft modification or crosslinking etc. It is common modification mode.Soft, hard segment structure by changing polyurethane molecular chain prepare easy dyeing or can dye polyurethane simultaneously Preparation and a kind of very important modification mode applied to synthetic leather bass.
On the other hand, dimethylformamide, acetone, butanone, toluene equal solvent will be used in synthetic leather production process, and Solvent volatilizees the health for not only having polluted to atmosphere, but also having compromised site operation personnel in process of production, therefore develops and make It is the direction of synthetic leather future development with waterborne polyurethane resin.Superfine fibre often also uses solvent type in impregnating polyurethane Then polyurethane is promptly fixed polyurethane using the difference of solvent and polyurethane solvability in water, is obtained simultaneously Good microcellular structure.But it is only gone back for synthetic leather cleanly production from the use that the subsequent covering with paint stage reduces solvent It is far from enough.Therefore, develop that solvent usage amount in entire production process is few, dye distribution is uniform, beautiful in colour, good color fastness Environment-friendly type technique is imperative.
Chinese patent document CN105155297A discloses a kind of aqueous polyurethane impregnation superfine fiber chemical leather bass Preparation method, comprising the following steps: coat aqueous polyurethane slurry in release paper, paste superfine fibre nonwoven cloth, carry out red External heat and heated-air drying;After cooling, then carry out being impregnated with obtained aqueous polyurethane impregnation superfine fiber chemical leather bass.It is producing There was only moisture evaporation in the process, there is environmental-protecting performance.Production environment will not generate pernicious gas, not will cause to operator Health hazard;Contain hydrophilic radical in water-based material due to using in aqueous ultrafine fiber synthetic leather bass, makes it have preferably Penetrability;Aqueous ultrafine fiber synthetic leather has good airing function after Alkali reduction fibrillation.But this method not can solve Dye distribution is uneven between superfine fibre and polyurethane when bass dyes, and the problems such as " PU spot " easily occurs.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of system of high color fastness dyeing-free superfine fiber chemical leather bass Preparation Method.The present invention prepares dyeing-free superfine fiber chemical leather bass using color aqueous polyurethane impregnated superfine fiber fabric, To solve the problems, such as current superfine fiber chemical leather bass poor color fastness, while solvent use is reduced, improves synthetic leather and produce work Skill cleans degree.
Term explanation:
Bath raio: refer to the quality of textile and the mass ratio of dye liquor or treatment fluid.For example, 100 grams of textile dye liquor 1000 Gram, then bath raio is 1:10.
Technical scheme is as follows:
A kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass, includes the following steps:
(1) superfine fiber fabric is added in aqueous slkali and is reduced, the bath raio of base fabric and aqueous slkali is 1:5~1: 50, the alkali content in aqueous slkali is 3~30g/L;Being reduced reaction temperature is 70~130 DEG C, and the decrement time is 20~180min;Subtract Water washing after the completion of amount is dried at 20~100 DEG C, and loss of weight base fabric is made;
(2) loss of weight base fabric is soaked with deionized water, color aqueous polyaminoester emulsion (CWPU) is then impregnated, so that CWPU It is fully penetrated into loss of weight base fabric, obtain bass sample;The mass ratio of loss of weight base fabric and CWPU are 1:0.05~1:5, in CWPU Polyether polyols mass content is 15%~35%;Bass sample is placed on plate, it is with spreader that bass sample is uniform Flattening;
(3) then plate and bass sample are placed in together in the acetum that concentration is 0.005~0.3mol/L, to It is taken out after CWPU solidification, bass sample is separated with plate and is sufficiently washed, spontaneously dried again after removing surface moisture;
(4) the bass sample of natural drying is ultra-fine to get high color fastness dyeing-free in 30~120 DEG C of dry 0.1~3h Fiber synthetic leather bass.
Preferred according to the present invention, superfine fibre described in step (1) is essentially sea-island composite fiber base fabric, into one Step is preferred, and the sea-island composite fiber base fabric is made of polyamide and polyester.
Preferred according to the present invention, aqueous slkali described in step (1) is NaOH or KOH solution.Initial mass can be used Concentration is 10%~40%, and further preferred 15%~25% aqueous slkali is configured, and when decrement can add water or water is not added Required alkali content and liquor ratio when reaching decrement.
Preferred according to the present invention, base fabric and the bath raio of lye are 1:10~1:20 in step (1);Alkali in aqueous slkali contains Amount is 5~20g/L.
Preferred according to the present invention, decrement reaction temperature is 70~90 DEG C in step (1), the decrement time is 40~ 120min。
Preferred according to the present invention, abundant water washing after the completion of decrement in step (1) is dried at 40~90 DEG C.
Preferred according to the present invention, the mass ratio of loss of weight base fabric and CWPU are 1:0.1~1:3 in step (2);
Preferably, the polyether polyols mass content in CWPU is 15%~25%, and dye content is polyurethane polymerization The 1%~10% of amount of substance.
According to the present invention, color aqueous polyaminoester emulsion (CWPU) described in step (2) is commercially available, can also be by existing skill Art be prepared (reference can be made to: Wang Yulu, Jin Liqiang, poly- (amine -ester) chain extension of the quick superbrnaching end-hydroxy of Jiao Li prepare color aqueous Polyurethane the 11st national leather chemicals seminar, 2016, Jinan).That is, modified using hyperbranched poly (amine -ester) Aqueous polyurethane is reacted with reactive dye prepares color aqueous polyurethane, and the color that dyestuff is added does not require, preferred dyestuff For reactive brilliant red k-2g, Reactive Light Yellow K-4G, the emerald green orchid KN-G of activity etc..
Preferred according to the present invention, the concentration of acetum is 0.1~0.3mol/L in step (3);
Preferably, the time of natural drying is 1~12h, further preferred 3~6h.
It is preferred according to the present invention, the bass sample of natural drying is placed in baking oven at 60~120 DEG C in step (4) Dry 0.1~0.5h.
Beneficial effects of the present invention
1, high color fastness dyeing-free superfine fiber chemical leather bass color produced by the present invention is full uniformly, Bearable dry and wet wipe color Fastness can reach 5 grades.
2, high color fastness dyeing-free superfine fiber chemical leather bass dyestuff produced by the present invention is mainly distributed on polyurethane tree In rouge, superfine fibre is substantially not colored, therefore can substantially reduce dye dosage, while substantially reducing Wastewater Dyes content.
3, compared with conventional production methods, the bass of analogous color saturation degree is obtained, dye dosage of the present invention is about tradition The 57% of method, dye utilization rate is up to 99%, and the dye utilization rate of conventional method is only 32% or so.
4, ultra-fine fibre is greatly reduced without using organic solvents such as toluene, dimethylformamides in production process of the present invention Tie up the VOC content in synthetic leather bass production process.
Detailed description of the invention
Fig. 1 is the pattern photo on dyeing-free superfine fiber chemical leather bass surface made from embodiment 2.
Fig. 2 is the pattern photo in dyeing-free superfine fiber chemical leather bass section made from embodiment 2.
Fig. 3 is the pattern photo on comparative example dyeing bass surface obtained.
Fig. 4 is the pattern photo in comparative example dyeing bass section obtained.
Specific embodiment
The present invention is described further combined with specific embodiments below, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously;The reagent and material Material, unless otherwise specified, commercially obtains.Sea-island composite fiber, Zhejiang He Xin Industry Co., Ltd etc. There is sale.
Wherein color aqueous polyurethane can refer to following document and be prepared: (Wang Yulu, Jin Liqiang, the quick terminal hydroxy group of Jiao Li Hyperbranched poly (amine -ester) chain extension prepares the national leather chemicals seminar of color aqueous polyurethane the 11st, and 2016, Jinan), dyestuff is reactive brilliant red k-2g, Reactive Light Yellow K-4G, the emerald green orchid KN-G of activity etc..Its specific preparation process is as follows: by 50 Mass parts polyalcohol is added in four-hole bottle, and 100~130 DEG C vacuumize 2~3h to remove moisture, after being cooled to 50~95 DEG C, drop Add 15~30 mass parts diisocyanate;The organotin catalysts of 0.1wt%~1wt% are added after dripping off, the reaction was continued 1~ Dihydromethyl propionic acid the reaction was continued the 0.5~2h for accounting for monomer gross mass 2%~6% is added in 3h later.Then 40~70 are cooled to DEG C, 0.1~2 mass parts 1,4-butanediol and 0.1~10 mass parts first generation hyperbranched poly (amine -ester) is added, the reaction was continued 0.5 After~2h, triethylamine is added and is neutralized to pH=7~8.Viscosity is adjusted using proper amount of acetone in reaction process, is added after the reaction was completed Deionized water emulsifies 0.5~2h, then vacuumizes removing acetone, obtains the poly- ammonia of modified water-soluble that solid content is about 30wt% blueing light Ester lotion (WPU-H).Then it takes the WPU-H of certain mass to be added in four-hole bottle, the reactive brilliant red k-2g of certain mass is dissolved in Four-hole bottle is added after deionized water, is greater than 8 with the pH of a small amount of sodium hydroxide solution regulation system, is warming up to 60~90 DEG C of reactions 1 The color aqueous polyaminoester emulsion (CWPU) that~5h is about 20wt% to get solid content.
Embodiment 1
A kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass, preparation step are as follows:
(1) sea-island composite fiber base fabric is placed in reactor, the NaOH solution that mass fraction is 10% is then added It is reduced, the bath raio of base fabric and NaOH solution is 1:10, and the alkali content in NaOH solution is 5g/L.Being reduced reaction temperature is 70 DEG C, the decrement time is 180min.Abundant water washing after the completion of decrement is dried at 50 DEG C, and loss of weight base fabric is made.
(2) a small amount of deionized water of loss of weight base fabric is soaked, then impregnates color aqueous polyaminoester emulsion (CWPU), so that CWPU is fully penetrated into loss of weight base fabric, obtains bass sample;The mass ratio of loss of weight base fabric and CWPU are 1:2, the poly- ammonia in CWPU Ester polymer mass content is 15%, and dye content is the 5% of polyether polyols quality.Bass sample is placed on plate, Bass sample is uniformly flattened with spreader.
(3) then plate and bass sample are placed in together in the acetum that concentration is 0.1mol/L, are solidified to CWPU After take out, bass sample is separated with plate and is sufficiently washed, remove surface moisture after spontaneously dry 2h.
(4) the bass sample of natural drying is placed in baking oven at 60 DEG C dry 0.5h, obtains high color fastness and exempts to contaminate Color superfine fiber chemical leather bass.
Embodiment 2
A kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass, preparation step are as follows:
(1) sea-island composite fiber base fabric is placed in reactor, the NaOH solution that mass fraction is 20% is then added It is reduced, the bath raio of base fabric and NaOH solution is 1:20, and the alkali content in NaOH solution is 10g/L.Being reduced reaction temperature is 90 DEG C, the decrement time is 60min.Abundant water washing after the completion of decrement is dried at 60 DEG C, and loss of weight base fabric is made.
(2) a small amount of deionized water of loss of weight base fabric is soaked, then impregnates color aqueous polyaminoester emulsion (CWPU), so that CWPU is fully penetrated into loss of weight base fabric, obtains bass sample;The mass ratio of loss of weight base fabric and CWPU are 1:1, the poly- ammonia in CWPU Ester polymer content is 20%, and dye content is the 3% of polyether polyols quality.Bass sample is placed on plate, with painting Cloth device uniformly flattens bass sample.
(3) then plate and bass sample are placed in together in the acetum that concentration is 0.2mol/L, are solidified to CWPU After take out, bass sample is separated with plate and is sufficiently washed, remove surface moisture after spontaneously dry 4h.
(4) the bass sample of natural drying is placed in baking oven at 110 DEG C dry 0.1h, obtains high color fastness and exempts to contaminate Color superfine fiber chemical leather bass.
Embodiment 3
A kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass, preparation step are as follows:
(1) sea-island composite fiber base fabric is placed in reactor, the NaOH solution that mass fraction is 40% is then added It is reduced, the bath raio of base fabric and NaOH solution is 1:20, and the alkali content in NaOH solution is 20g/L.Being reduced reaction temperature is 70 DEG C, the decrement time is 30min.Abundant water washing after the completion of decrement is dried at 100 DEG C, and loss of weight base fabric is made.
(2) a small amount of deionized water of loss of weight base fabric is soaked, then impregnates color aqueous polyaminoester emulsion (CWPU), so that CWPU is fully penetrated into loss of weight base fabric, obtains bass sample;The mass ratio of loss of weight base fabric and CWPU are 1:5, the poly- ammonia in CWPU Ester polymer content is 15%, and dye content is the 6% of polyether polyols quality.Bass sample is placed on plate, with painting Cloth device uniformly flattens bass sample.
(3) then plate and bass sample are placed in together in the acetum that concentration is 0.005mol/L, it is solidifying to CWPU It takes out after Gu, bass sample is separated with plate and sufficiently washes, spontaneously dry 8h after removing surface moisture.
(4) the bass sample of natural drying is placed in baking oven at 40 DEG C dry 2.5h, obtains high color fastness and exempts to contaminate Color superfine fiber chemical leather bass.
Embodiment 4
A kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass, preparation step are as follows:
(1) sea-island composite fiber base fabric is placed in reactor, the mass fraction that certain mass is then added is 30% KOH solution be reduced, the bath raio of base fabric and KOH solution is 1:15, and the alkali content in KOH solution is 20g/L.Decrement reaction Temperature is 75 DEG C, and the decrement time is 40min.Abundant water washing after the completion of decrement is dried at 60 DEG C, and loss of weight base fabric is made.
(2) a small amount of deionized water of loss of weight base fabric is soaked, then impregnates color aqueous polyaminoester emulsion (CWPU), so that CWPU is fully penetrated into loss of weight base fabric, obtains bass sample;The mass ratio of loss of weight base fabric and CWPU are 1:0.8, poly- in CWPU Urethane polymers content is 25%, and dye content is the 8% of polyether polyols quality.Bass sample is placed on plate, is used Spreader uniformly flattens bass sample.
(3) then plate and bass sample are placed in together in the acetum that concentration is 0.01mol/L, are solidified to CWPU After take out, bass sample is separated with plate and is sufficiently washed, remove surface moisture after spontaneously dry 3h.
(4) the bass sample of natural drying is placed in baking oven at 70 DEG C dry 0.6h, obtains high color fastness and exempts to contaminate Color superfine fiber chemical leather bass.
Embodiment 5
A kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass, preparation step are as follows:
(1) sea-island composite fiber base fabric is placed in reactor, then be added mass fraction be 18% KOH solution into The bath raio of row decrement, base fabric and KOH solution is 1:12, and the alkali content in KOH solution is 22g/L.Being reduced reaction temperature is 110 DEG C, the decrement time is 35min.Abundant water washing after the completion of decrement is dried at 55 DEG C, and loss of weight base fabric is made.
(2) a small amount of deionized water of loss of weight base fabric is soaked, then impregnates color aqueous polyaminoester emulsion (CWPU), so that CWPU is fully penetrated into loss of weight base fabric, obtains bass sample;The mass ratio of loss of weight base fabric and CWPU are 1:1.05, poly- in CWPU Urethane polymers content is 18%, and dye content is the 2% of polyether polyols quality.Bass sample is placed on plate, is used Spreader uniformly flattens bass sample.
(3) then plate and bass sample are placed in together in the acetum that concentration is 0.25mol/L, are solidified to CWPU After take out, bass sample is separated with plate and is sufficiently washed, remove surface moisture after spontaneously dry 2.4h.
(4) the bass sample of natural drying is placed in baking oven at 115 DEG C dry 0.15h, obtains high color fastness and exempts from Dyed ultrafine fiber synthetic leather bass.
Comparative example
Dyeing bass is prepared using conventional method, preparation process is as follows:
Superfine fiber fabric impregnates common solvent type polyurethane (being dissolved in dimethylformamide), then makes polyurethane in water Then quick solidification is dried at a certain temperature.Superfine fibre-PU composite sheet after drying is placed in certain density lye In be reduced at a certain temperature, washing after the completion of decrement neutralizes, is dry, obtains superfluorescent fiber synthetic leather bass.Then comparison carries out Normal dyeing, dyestuff use acid red, dye dosage 2%, bath raio 1:30, formic acid adjusting pH3~4.
Test example
High color fastness dyeing-free superfine fiber chemical leather bass made from testing example 2 and comparative example dyeing shellfish obtained This performance indicator, the results are shown in Table 1.
1 dyeing-free superfine fiber chemical leather bass of table and conventional method dyeing bass comparison
A: value of chromatism, by formulaIt calculates and obtains.
As shown in Table 1, the dyeing-free superfine fiber chemical leather bass dye content in embodiment 2 is lower than tradition in comparative example Method is obtained to dye bass, and the utilization rate embodiment 2 of dyestuff is much higher than comparative example.As it can be seen that made from the method for the present invention High color fastness dyeing-free superfine fiber chemical leather bass substantially reduces dye dosage, while substantially reducing Wastewater Dyes content.
Dyeing-free superfine fiber chemical leather bass colorfastness to rubbing obtained is 5 grades in embodiment 2, and color fastness is compared to comparison Example conventional method increases.
The pattern photo on bass surface and section in testing example 2 and comparative example, as shown in Figs 1-4.Wherein, Fig. 1 For the pattern photo on dyeing-free superfine fiber chemical leather bass surface made from embodiment 2, Fig. 2 is to exempt to contaminate made from embodiment 2 The pattern photo in color superfine fiber chemical leather bass section, Fig. 3 are the pattern photo on comparative example dyeing bass surface obtained, figure 4 be the comparative example pattern photo obtained for dyeing bass section.
Comparison diagram 1 and Fig. 3 and comparison diagram 2,4 are it is found that the embodiment of the present invention 2 is fuller compared to comparative example color It is even.

Claims (9)

1. a kind of preparation method of high color fastness dyeing-free superfine fiber chemical leather bass, includes the following steps:
(1) superfine fiber fabric is added in aqueous slkali and is reduced, the bath raio of base fabric and aqueous slkali is 1:5 ~ 1:50, alkali soluble Alkali content in liquid is 3 ~ 30g/L;Being reduced reaction temperature is 70 ~ 130 DEG C, and the decrement time is 20 ~ 180min;Water after the completion of decrement It washs, is dried at 20 ~ 100 DEG C, loss of weight base fabric is made;
(2) loss of weight base fabric is soaked with deionized water, then dipping utilizes hyperbranched polyamine -ester modified aqueous polyurethane and activity The color aqueous polyaminoester emulsion of dyestuff reaction preparation, so that color aqueous polyaminoester emulsion is fully penetrated into loss of weight base fabric, Obtain bass sample;The mass ratio of loss of weight base fabric and color aqueous polyaminoester emulsion is 1:0.05 ~ 1:5, color aqueous polyurethane cream Polyether polyols mass content in liquid is 15% ~ 25%, and dye content is the 1% ~ 10% of polyether polyols quality;By bass Sample is placed on plate, is uniformly flattened bass sample with spreader;
(3) then plate and bass sample are placed in together in the acetum that concentration is 0.005 ~ 0.3mol/L, to color water Property polyaminoester emulsion solidification after take out, bass sample is separated with plate and is sufficiently washed, remove surface moisture after again naturally do It is dry;
(4) the bass sample of natural drying is closed in 30 ~ 120 DEG C of dry 0.1 ~ 3h to get high color fastness dyeing-free superfine fibre Finished leather bass.
2. the preparation method of high color fastness dyeing-free superfine fiber chemical leather bass according to claim 1, feature exist In superfine fiber fabric as described in step (1) is sea-island composite fiber base fabric;The sea-island composite fiber base fabric by Polyamide and polyester composition.
3. the preparation method of high color fastness dyeing-free superfine fiber chemical leather bass according to claim 1, feature exist In aqueous slkali as described in step (1) is NaOH or KOH solution.
4. the preparation method of high color fastness dyeing-free superfine fiber chemical leather bass according to claim 1, feature exist In base fabric and the bath raio of lye are 1:10 ~ 1:20 in step (1);Alkali content in aqueous slkali is 5 ~ 20g/L.
5. the preparation method of high color fastness dyeing-free superfine fiber chemical leather bass according to claim 1, feature exist In decrement reaction temperature is 70 ~ 90 DEG C in step (1), and the decrement time is 40 ~ 120min.
6. the preparation method of high color fastness dyeing-free superfine fiber chemical leather bass according to claim 1, feature exist The abundant water washing after the completion of decrement in, step (1) is dried at 40 ~ 90 DEG C.
7. the preparation method of high color fastness dyeing-free superfine fiber chemical leather bass according to claim 1, feature exist In the mass ratio of loss of weight base fabric and color aqueous polyaminoester emulsion is 1:0.1 ~ 1:3 in step (2).
8. the preparation method of high color fastness dyeing-free superfine fiber chemical leather bass according to claim 1, feature exist In the concentration of acetum is 0.1 ~ 0.3mol/L in step (3);The time of natural drying is 1 ~ 12h.
9. the preparation method of high color fastness dyeing-free superfine fiber chemical leather bass according to claim 1, feature exist In the bass sample of natural drying is placed in baking oven at 60 ~ 120 DEG C dry 0.1 ~ 0.5h in step (4).
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CN108385404A (en) * 2018-03-09 2018-08-10 昌邑誉华纺织材料有限公司 Water-based microfiber shoe lining leather technique
CN108360187B (en) * 2018-04-28 2020-02-07 四川大学 Dyeing method of polyester type superfine fiber synthetic leather

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CN101629387A (en) * 2009-07-30 2010-01-20 山东同大纺织印染有限公司 Micro-fiber knitted fabric synthetic leather and manufacturing method thereof
CN102899918A (en) * 2012-10-11 2013-01-30 福建可利达合成纤维有限公司 Method for producing wet-process waterborne polyurethane synthetic leather coating base
CN105155297A (en) * 2015-08-25 2015-12-16 浙江繁盛超纤制品有限公司 Method for preparation of waterborne polyurethane impregnated superfine fiber synthetic leather base

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101629387A (en) * 2009-07-30 2010-01-20 山东同大纺织印染有限公司 Micro-fiber knitted fabric synthetic leather and manufacturing method thereof
CN102899918A (en) * 2012-10-11 2013-01-30 福建可利达合成纤维有限公司 Method for producing wet-process waterborne polyurethane synthetic leather coating base
CN105155297A (en) * 2015-08-25 2015-12-16 浙江繁盛超纤制品有限公司 Method for preparation of waterborne polyurethane impregnated superfine fiber synthetic leather base

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