CN114164675A - Preparation method of natural latex superfine fiber synthetic leather - Google Patents

Preparation method of natural latex superfine fiber synthetic leather Download PDF

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Publication number
CN114164675A
CN114164675A CN202111373570.1A CN202111373570A CN114164675A CN 114164675 A CN114164675 A CN 114164675A CN 202111373570 A CN202111373570 A CN 202111373570A CN 114164675 A CN114164675 A CN 114164675A
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China
Prior art keywords
natural latex
synthetic leather
mass
superfine fiber
fiber synthetic
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CN202111373570.1A
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Chinese (zh)
Inventor
戴家兵
张奥
祝彬
王刚
戴金伟
李维虎
朱保凌
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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Priority to CN202111373570.1A priority Critical patent/CN114164675A/en
Publication of CN114164675A publication Critical patent/CN114164675A/en
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial 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)
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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    • D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
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    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention provides a preparation method of natural latex superfine fiber synthetic leather, particularly relates to the technical field of synthetic leather preparation, and can solve the problem of poor air permeability of synthetic leather. The preparation method of the natural latex superfine fiber synthetic leather comprises the following steps: providing a sea-island superfine fiber synthetic leather base cloth; preparing modified natural latex; preparing filling resin; and adding the filling resin into an impregnation tank, padding the sea-island type superfine fiber synthetic leather base cloth in the impregnation tank, taking out the padded sea-island type superfine fiber synthetic leather base cloth, and heating and foaming to prepare the natural latex superfine fiber synthetic leather. The natural latex superfine fiber synthetic leather prepared by the method has high tearing strength, good oil resistance and solvent resistance, good acid and alkali resistance, good air permeability, high dyeing color fastness and soft hand feeling.

Description

Preparation method of natural latex superfine fiber synthetic leather
Technical Field
The invention relates to the technical field of synthetic leather preparation, in particular to a preparation method of natural latex superfine fiber synthetic leather.
Background
Superfine fiber synthetic leather is also called microfiber synthetic leather, is the third generation product in the synthetic leather field, is also the synthetic leather which is closest to genuine leather in structure at present, and can surpass genuine leather in performance, and the solvent type microfiber synthetic leather which is not environment-friendly is mainly used in the market at present, the environment-friendly microfiber synthetic leather is only waterborne polyurethane microfiber synthetic leather, and the waterborne polyurethane microfiber synthetic leather has hard hand feeling and poor air permeability, so that clothes and shoes made of the waterborne polyurethane microfiber synthetic leather are uncomfortable to wear, the market requirements cannot be met, and the development of the environment-friendly microfiber synthetic leather is limited. Natural latex may be used for microfiber impregnation as a partial substitute for polyurethane, but its use is also limited due to weather resistance. Therefore, it is very important to research and develop a microfiber synthetic leather with high tearing strength, particularly good oil resistance and solvent resistance, good acid and alkali resistance, good air permeability, high dyeing color fastness and good hand feeling.
Disclosure of Invention
The invention aims to provide a preparation method of natural latex superfine fiber synthetic leather. The natural latex superfine fiber synthetic leather prepared by the method has high tearing strength, good oil resistance and solvent resistance, good acid and alkali resistance and air permeability, high dyeing color fastness and soft hand feeling, and can meet the requirements of customers on environmental protection, water resistance and air permeability.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing natural latex superfine fiber synthetic leather, comprising the steps of:
providing a sea-island superfine fiber synthetic leather base cloth;
preparing modified natural latex, wherein the modified natural latex comprises natural latex, ammonia water, a stabilizer, a vulcanization accelerator, a vulcanization activator and an anti-aging agent;
preparing filling resin, wherein the filling resin comprises modified natural latex, a foaming agent H, dimethyl oxalate, a thickening agent and color paste;
and adding the filling resin into an impregnation tank, padding the sea-island type superfine fiber synthetic leather base cloth in the impregnation tank, taking out the padded sea-island type superfine fiber synthetic leather base cloth, and heating and foaming to prepare the natural latex superfine fiber synthetic leather.
In an example of the method for preparing the natural latex superfine fiber synthetic leather, the method further comprises: preparing a wear-resistant hydrophobic treatment agent, wherein the wear-resistant hydrophobic treatment agent is prepared by mixing modified natural latex, a defoaming agent, a wetting agent, a thickening agent, a wear-resistant auxiliary agent, a hydrophobic auxiliary agent, a cross-linking agent and color paste;
and treating the natural latex superfine fiber synthetic leather by using the wear-resistant hydrophobic treatment agent to prepare the suede natural latex superfine fiber synthetic leather.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the sea-island superfine fiber synthetic leather base fabric takes alkali-soluble polyester as a sea component and polyamide or polyester as an island component, wherein the sea component accounts for 25-49% of the total mass of the sea-island superfine fiber synthetic leather base fabric, and the balance is the island component.
In an example of the preparation method of the natural latex superfine fiber synthetic leather of the present invention, the preparation method of the sea-island superfine fiber synthetic leather base cloth comprises: the sea component and the island component are made into fixed island short fibers, and the fixed island short fibers are made into the sea-island superfine fiber synthetic leather base cloth after carding, lapping and needling.
In an example of the preparation method of the natural latex ultrafine fiber synthetic leather, in the modified natural latex, based on the mass of the natural latex, the mass of the ammonia water is 30-40% of the mass of the natural latex, the mass of the stabilizer is 0.05-0.2% of the mass of the natural latex, the mass of the vulcanization accelerator is 0.25-1.5% of the mass of the natural latex, the mass of the vulcanization activator is 0.05-0.2% of the mass of the natural latex, and the mass of the anti-aging agent is 0.05-0.2% of the mass of the natural latex.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the preparation method of the modified natural latex comprises the following steps: uniformly mixing the raw materials, heating to 55-60 ℃, preserving heat for 6-10 hours, and then cooling to room temperature.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, in the filling resin, based on the mass of the modified natural latex, the mass of the foaming agent H is 3-10% of the mass of the modified natural latex, the mass of the dimethyl oxalate is 0.2-1% of the mass of the modified natural latex, the mass of the thickening agent is 0.2-2% of the mass of the modified natural latex, and the mass of the color paste is 2-10% of the mass of the modified natural latex.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the padding treatment is two-in-two, the extra slurry of the base cloth of the sea-island superfine fiber synthetic leather after the padding treatment is removed by a scraper, the base cloth is placed into an oven for high-temperature foaming, and then the natural latex superfine fiber synthetic leather is prepared through decrement, splitting, dyeing, sanding and oiling.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the foaming temperature is 90-130 ℃.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, in the wear-resistant hydrophobic treatment agent, based on the mass of the modified natural latex, the mass of the defoaming agent is 0.15-0.5% of the mass of the modified natural latex, the mass of the wetting agent is 0.3-1.5% of the mass of the modified natural latex, the mass of the thickening agent is 0.2-2% of the mass of the modified natural latex, the mass of the wear-resistant assistant is 0.5-2% of the mass of the modified natural latex, the mass of the hydrophobic assistant is 2-10% of the mass of the modified natural latex, the mass of the cross-linking agent is 0.3-1% of the mass of the modified natural latex, and the mass of the color paste is 1-20% of the mass of the modified natural latex.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the thickener is one or more of a polyurethane associative thickener, a cellulose thickener and an alkali swelling thickener.
In one example of the method for preparing the natural latex superfine fiber synthetic leather, the stabilizer is one or more of casein and potassium hydroxide.
In one example of the preparation method of the natural latex superfine fiber synthetic leather, the vulcanization accelerator is one or more of ZDMC, ZDBC and ZMBT.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the vulcanization activator is one or more of zinc oxide and stearic acid.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the anti-aging agent is 2-mercaptobenzimidazole.
In one example of the preparation method of the natural latex superfine fiber synthetic leather, the defoaming agent is one or more of a mineral oil defoaming agent, an organic silicon defoaming agent and a polyether defoaming agent.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the wetting agent is one or more of an organic silicon wetting agent and an alkyne diol wetting agent.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the wear-resistant auxiliary agent is an organic silicon wear-resistant agent.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the hydrophobic auxiliary agent is an organic silicon hydrophobic agent.
In one example of the method for preparing the natural latex microfiber synthetic leather according to the present invention, the crosslinking agent is one or more of a carbodiimide crosslinking agent, an isocyanate crosslinking agent, and an aziridine crosslinking agent.
In one example of the preparation method of the natural latex superfine fiber synthetic leather, the wear-resistant hydrophobic treatment agent is used for treating the natural latex by an anilox roller printing methodThe sizing amount of the superfine fiber synthetic leather is 20-50 g/m2。
The invention also provides the natural latex superfine fiber synthetic leather prepared by the preparation method.
The natural latex superfine fiber synthetic leather prepared by the method is high in tear strength, good in oil resistance and solvent resistance, good in acid and alkali resistance and air permeability, high in dyeing color fastness and soft in hand feeling, is suitable for the fields of automotive interiors, gloves, sofas, clothes, electronic packaging and the like, and provides a high-quality choice for application of downstream customers.
Drawings
FIG. 1 is a flow chart of the preparation method of the natural latex superfine fiber synthetic leather of the invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those in the embodiments of the present invention may be used to practice the present invention.
Referring to fig. 1, fig. 1 is a flow chart of a method for preparing natural latex superfine fiber synthetic leather according to the present invention. The invention provides a preparation method of natural latex superfine fiber synthetic leather, which comprises the following steps:
step 1, providing a sea-island superfine fiber synthetic leather base cloth;
step 2, preparing modified natural latex, wherein the modified natural latex comprises natural latex, ammonia water, a stabilizer, a vulcanization accelerator, a vulcanization activator and an anti-aging agent;
step 3, preparing filling resin, wherein the filling resin comprises modified natural latex, a foaming agent H, dimethyl oxalate, a thickening agent and color paste;
and 4, adding the filling resin into an impregnation tank, padding the sea-island type superfine fiber synthetic leather base cloth in the impregnation tank, taking out the padded sea-island type superfine fiber synthetic leather base cloth, and heating and foaming to prepare the natural latex superfine fiber synthetic leather.
In an example of the method for preparing the natural latex superfine fiber synthetic leather, the method further comprises: preparing a wear-resistant hydrophobic treatment agent, wherein the wear-resistant hydrophobic treatment agent comprises modified natural latex, a defoaming agent, a wetting agent, a thickening agent, a wear-resistant auxiliary agent, a hydrophobic auxiliary agent, a cross-linking agent and color paste;
and treating the natural latex superfine fiber synthetic leather by using the wear-resistant hydrophobic treatment agent to prepare the suede natural latex superfine fiber synthetic leather.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the sea-island superfine fiber synthetic leather base fabric takes alkali-soluble polyester as a sea component and polyamide or polyester as an island component, wherein the sea component accounts for 25-49% of the total mass of the sea-island superfine fiber synthetic leather base fabric, and the balance is the island component.
In an example of the preparation method of the natural latex superfine fiber synthetic leather of the present invention, the preparation method of the sea-island superfine fiber synthetic leather base cloth comprises: the sea component and the island component are made into fixed island short fibers, and the fixed island short fibers are made into the sea-island superfine fiber synthetic leather base cloth after carding, lapping and needling.
In an example of the preparation method of the natural latex ultrafine fiber synthetic leather, in the modified natural latex, based on the mass of the natural latex, the mass of the ammonia water is 30-40% of the mass of the natural latex, the mass of the stabilizer is 0.05-0.2% of the mass of the natural latex, the mass of the vulcanization accelerator is 0.25-1.5% of the mass of the natural latex, the mass of the vulcanization activator is 0.05-0.2% of the mass of the natural latex, and the mass of the anti-aging agent is 0.05-0.2% of the mass of the natural latex.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the preparation method of the modified natural latex comprises the following steps: uniformly mixing the raw materials, heating to 55-60 ℃, preserving heat for 6-10 hours, and then cooling to room temperature. .
In an example of the preparation method of the natural latex superfine fiber synthetic leather, in the filling resin, based on the mass of the modified natural latex, the mass of the foaming agent H is 3-10% of the mass of the modified natural latex, the mass of the dimethyl oxalate is 0.2-1% of the mass of the modified natural latex, the mass of the thickening agent is 0.2-2% of the mass of the modified natural latex, and the mass of the color paste is 2-10% of the mass of the modified natural latex.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the thickener is one or more of a polyurethane associative thickener, a cellulose thickener and an alkali swelling thickener.
In step 4, the padding treatment is two-in-two, and after the excess slurry is removed from the base cloth of the sea-island type superfine fiber synthetic leather by a scraper after the padding treatment, the base cloth is put into an oven to be foamed at high temperature, and then the base cloth is subjected to decrement, splitting, dyeing, sanding and oiling to prepare the natural latex superfine fiber synthetic leather.
In the first example of the preparation method of the natural latex superfine fiber synthetic leather, in the step 4, the foaming temperature is 90-130 ℃.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, in the wear-resistant hydrophobic treatment agent, based on the mass of the modified natural latex, the mass of the defoaming agent is 0.15-0.5% of the mass of the modified natural latex, the mass of the wetting agent is 0.3-1.5% of the mass of the modified natural latex, the mass of the thickening agent is 0.2-2% of the mass of the modified natural latex, the mass of the wear-resistant assistant is 0.5-2% of the mass of the modified natural latex, the mass of the hydrophobic assistant is 2-10% of the mass of the modified natural latex, the mass of the cross-linking agent is 0.3-1% of the mass of the modified natural latex, and the mass of the color paste is 1-20% of the mass of the modified natural latex.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the thickener is one or more of a polyurethane associative thickener, a cellulose thickener and an alkali swelling thickener.
In one example of the method for preparing the natural latex superfine fiber synthetic leather, the stabilizer is one or more of casein and potassium hydroxide.
In one example of the preparation method of the natural latex superfine fiber synthetic leather, the vulcanization accelerator is one or more of ZDMC, ZDBC and ZMBT.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the vulcanization activator is one or more of zinc oxide and stearic acid.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the anti-aging agent is 2-mercaptobenzimidazole.
In one example of the preparation method of the natural latex superfine fiber synthetic leather, the defoaming agent is one or more of a mineral oil defoaming agent, an organic silicon defoaming agent and a polyether defoaming agent.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the wetting agent is one or more of an organic silicon wetting agent and an alkyne diol wetting agent.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the wear-resistant auxiliary agent is an organic silicon wear-resistant agent.
In an example of the preparation method of the natural latex superfine fiber synthetic leather, the hydrophobic auxiliary agent is an organic silicon hydrophobic agent.
In one example of the method for preparing the natural latex microfiber synthetic leather according to the present invention, the crosslinking agent is one or more of a carbodiimide crosslinking agent, an isocyanate crosslinking agent, and an aziridine crosslinking agent.
In the first example of the preparation method of the natural latex superfine fiber synthetic leather, the wear-resistant hydrophobic treatment agent is used for treating the natural latex superfine fiber synthetic leather by an anilox roller printing method, and the sizing amount is 20-50 g/m2。
The invention also provides the natural latex superfine fiber synthetic leather prepared by the preparation method.
The modified natural latex has good weather resistance, durability and water resistance, good toughness, good acid-base resistance and solvent resistance, and the filling resin prepared by the modified natural latex inherits the excellent performance. Dimethyl oxalate in the filling resin is decomposed at high temperature to generate organic acid, and the organic acid can catalyze the foaming agent H to release nitrogen at 90-130 ℃, so that the decomposition temperature of the foaming agent H is reduced. In the curing process of the modified natural latex, nitrogen released by the foaming agent H can enable the modified natural latex to generate a cellular structure, and the cellular structure can enable the natural latex superfine fiber synthetic leather prepared by the invention to have air permeability and cannot influence the waterproof performance of the natural latex superfine fiber synthetic leather. The wear-resistant hydrophobic treatment agent is used for performing roller coating treatment on the surface of the natural latex superfine fiber synthetic leather, so that a suede structure can be obtained, the waterproof performance and the wear resistance of the natural latex superfine fiber synthetic leather are further enhanced, and the application range of the natural latex superfine fiber synthetic leather is widened.
Example 1
The preparation method of the natural latex superfine fiber synthetic leather comprises the following steps:
step 1, providing a sea-island superfine fiber synthetic leather base cloth, wherein the sea-island superfine fiber synthetic leather base cloth adopts alkali-soluble polyester as a sea component and polyamide as an island component, wherein the sea component accounts for 25% of the total mass of the sea-island superfine fiber synthetic leather base cloth, and the island component accounts for 75% of the total mass of the sea-island superfine fiber synthetic leather base cloth.
The sea component and the island component are prepared into fixed island short fibers, and the fixed island short fibers are prepared into the sea-island superfine fiber synthetic leather base cloth after carding, lapping and needling.
And 2, preparing modified natural latex, wherein the raw materials of the modified natural latex comprise natural latex, ammonia water, a stabilizer, a vulcanization accelerator, a vulcanization activator and an anti-aging agent, the ammonia water accounting for 30% of the mass of the modified natural latex, the stabilizer accounting for 0.05%, the vulcanization accelerator accounting for 0.25%, the vulcanization activator accounting for 0.05% and the anti-aging agent accounting for 0.05% of the mass of the modified natural latex are added into the natural latex, the mixture is uniformly mixed, heated to 55 ℃, kept for 6 hours and cooled to room temperature to prepare the modified natural latex.
And 3, preparing filling resin, wherein the filling resin comprises modified natural latex, a foaming agent H, dimethyl oxalate, a thickening agent and color paste.
Adding 3% of foaming agent H, 0.2% of dimethyl oxalate, 0.2% of thickening agent and 2% of color paste into the modified natural latex, and uniformly mixing to prepare the filling resin.
And 4, adding filling resin into a soaking tank, carrying out padding treatment on the sea-island type superfine fiber synthetic leather base cloth in the soaking tank, wherein the padding treatment is two-padding and two-rolling, removing redundant slurry from the padded sea-island type superfine fiber synthetic leather base cloth by using a scraper, placing the base cloth into an oven for foaming at a high temperature of 90 ℃, and then carrying out decrement, splitting, dyeing, sanding and oiling to prepare the natural latex superfine fiber synthetic leather.
And 5, preparing the wear-resistant hydrophobic treatment agent, wherein the wear-resistant hydrophobic treatment agent comprises modified natural latex, a defoaming agent, a wetting agent, a thickening agent, a wear-resistant auxiliary agent, a hydrophobic auxiliary agent, a cross-linking agent and color paste.
Adding 0.15% of defoaming agent, 0.3% of wetting agent, 0.2% of thickening agent, 0.5% of wear-resistant additive, 2% of hydrophobic additive, 0.3% of cross-linking agent and 1% of color paste into the modified natural latex, and uniformly mixing to prepare the wear-resistant hydrophobic water treatment agent.
Step 6, treating the natural latex superfine fiber synthetic leather prepared in the step 4 by using the wear-resistant hydrophobic treatment agent through an anilox roller printing method, wherein the sizing amount is 20g/m2And obtaining the suede natural latex superfine fiber synthetic leather.
Example 2
The preparation method of the natural latex superfine fiber synthetic leather comprises the following steps:
step 1, providing a sea-island superfine fiber synthetic leather base cloth, wherein the sea-island superfine fiber synthetic leather base cloth adopts alkali-soluble polyester as a sea component and polyamide as an island component, wherein the sea component accounts for 30% of the total mass of the sea-island superfine fiber synthetic leather base cloth, and the island component accounts for 70% of the total mass of the sea-island superfine fiber synthetic leather base cloth.
The sea component and the island component are prepared into fixed island short fibers, and the fixed island short fibers are prepared into the sea-island superfine fiber synthetic leather base cloth after carding, lapping and needling.
And 2, preparing modified natural latex, wherein the raw materials of the modified natural latex comprise natural latex, ammonia water, a stabilizer, a vulcanization accelerator, a vulcanization activator and an anti-aging agent, the ammonia water accounting for 35% of the mass of the modified natural latex, the stabilizer accounting for 0.1%, the vulcanization accelerator accounting for 0.5%, the vulcanization activator accounting for 0.1% and the anti-aging agent accounting for 0.1% of the mass of the modified natural latex are added into the natural latex, the mixture is uniformly mixed, heated to 60 ℃, kept for 8 hours and then cooled to room temperature to prepare the modified natural latex.
And 3, preparing filling resin, wherein the filling resin is prepared by mixing modified natural latex, a foaming agent H, dimethyl oxalate, a thickening agent and color paste.
Adding 6% of foaming agent H, 0.5% of dimethyl oxalate, 0.8% of thickening agent and 5% of color paste into the modified natural latex, and uniformly mixing to prepare the filling resin.
And 4, adding filling resin into a soaking tank, carrying out padding treatment on the sea-island type superfine fiber synthetic leather base cloth in the soaking tank, wherein the padding treatment is two-padding and two-rolling, removing redundant slurry from the padded sea-island type superfine fiber synthetic leather base cloth by using a scraper, placing the base cloth into an oven for foaming at a high temperature of 100 ℃, and then carrying out decrement, splitting, dyeing, sanding and oiling to prepare the natural latex superfine fiber synthetic leather.
And 5, preparing the wear-resistant hydrophobic treatment agent, wherein the wear-resistant hydrophobic treatment agent comprises modified natural latex, a defoaming agent, a wetting agent, a thickening agent, a wear-resistant auxiliary agent, a hydrophobic auxiliary agent, a cross-linking agent and color paste.
Adding 0.3% of defoaming agent, 0.5% of wetting agent, 1% of thickening agent, 1% of wear-resistant additive, 4% of hydrophobic additive, 0.5% of cross-linking agent and 8% of color paste into the modified natural latex, and uniformly mixing to prepare the wear-resistant hydrophobic water treatment agent.
Step 6, treating the natural latex superfine fiber synthetic leather prepared in the step 4 by using the wear-resistant hydrophobic treatment agent through an anilox roller printing method, wherein the sizing amount is 30g/m2And obtaining the suede natural latex superfine fiber synthetic leather.
Example 3
The preparation method of the natural latex superfine fiber synthetic leather comprises the following steps:
step 1, providing a sea-island superfine fiber synthetic leather base cloth, wherein the sea-island superfine fiber synthetic leather base cloth adopts alkali-soluble polyester as a sea component and polyamide as an island component, wherein the sea component accounts for 40% of the total mass of the sea-island superfine fiber synthetic leather base cloth, and the island component accounts for 60% of the total mass of the sea-island superfine fiber synthetic leather base cloth.
The sea component and the island component are prepared into fixed island short fibers, and the fixed island short fibers are prepared into the sea-island superfine fiber synthetic leather base cloth after carding, lapping and needling.
And 2, preparing modified natural latex, wherein the raw materials of the modified natural latex comprise natural latex, ammonia water, a stabilizer, a vulcanization accelerator, a vulcanization activator and an anti-aging agent, the ammonia water accounting for 40% of the mass of the modified natural latex, the stabilizer accounting for 0.15%, the vulcanization accelerator accounting for 1%, the vulcanization activator accounting for 0.15% of the mass of the modified natural latex and the anti-aging agent accounting for 0.15% of the mass of the modified natural latex are added into the natural latex, the mixture is uniformly mixed, heated to 60 ℃, kept for 9 hours and then cooled to room temperature to prepare the modified natural latex.
And 3, preparing filling resin, wherein the filling resin is prepared by mixing modified natural latex, a foaming agent H, dimethyl oxalate, a thickening agent and color paste.
Adding 8% of foaming agent H, 0.8% of dimethyl oxalate, 1.5% of thickening agent and 8% of color paste into the modified natural latex, and uniformly mixing to prepare the filling resin.
And 4, adding filling resin into a soaking tank, carrying out padding treatment on the sea-island type superfine fiber synthetic leather base cloth in the soaking tank, wherein the padding treatment is two-padding and two-rolling, removing redundant slurry from the padded sea-island type superfine fiber synthetic leather base cloth by using a scraper, placing the base cloth into an oven for foaming at a high temperature of 110 ℃, and then carrying out decrement, splitting, dyeing, sanding and oiling to prepare the natural latex superfine fiber synthetic leather.
And 5, preparing the wear-resistant hydrophobic treatment agent, wherein the wear-resistant hydrophobic treatment agent comprises modified natural latex, a defoaming agent, a wetting agent, a thickening agent, a wear-resistant auxiliary agent, a hydrophobic auxiliary agent, a cross-linking agent and color paste.
Adding 0.4% of defoaming agent, 1% of wetting agent, 1.5% of thickening agent, 1.5% of wear-resistant additive, 8% of hydrophobic additive, 0.8% of cross-linking agent and 15% of color paste into the modified natural latex, and uniformly mixing to prepare the wear-resistant hydrophobic water treatment agent.
Step 6, treating the natural latex superfine fiber synthetic leather prepared in the step 4 by using the wear-resistant hydrophobic treatment agent through an anilox roller printing method, wherein the sizing amount is 40g/m2And obtaining the suede natural latex superfine fiber synthetic leather.
Example 4
The preparation method of the natural latex superfine fiber synthetic leather comprises the following steps:
step 1, providing a sea-island superfine fiber synthetic leather base cloth, wherein the sea-island superfine fiber synthetic leather base cloth adopts alkali-soluble polyester as a sea component and polyamide as an island component, wherein the sea component accounts for 49% of the total mass of the sea-island superfine fiber synthetic leather base cloth, and the island component accounts for 51% of the total mass of the sea-island superfine fiber synthetic leather base cloth.
The sea component and the island component are prepared into fixed island short fibers, and the fixed island short fibers are prepared into the sea-island superfine fiber synthetic leather base cloth after carding, lapping and needling.
And 2, preparing modified natural latex, wherein the raw materials of the modified natural latex comprise natural latex, ammonia water, a stabilizer, a vulcanization accelerator, a vulcanization activator and an anti-aging agent, the ammonia water accounting for 40% of the mass of the modified natural latex, the stabilizer accounting for 0.2%, the vulcanization accelerator accounting for 1.5%, the vulcanization activator accounting for 0.2% of the mass of the modified natural latex and the anti-aging agent accounting for 0.2% of the mass of the modified natural latex are added into the natural latex, the mixture is uniformly mixed, heated to 60 ℃, kept for 10 hours and then cooled to room temperature to prepare the modified natural latex.
And 3, preparing filling resin, wherein the filling resin comprises modified natural latex, a foaming agent H, dimethyl oxalate, a thickening agent and color paste.
Adding 10% of foaming agent H, 1% of dimethyl oxalate, 2% of thickening agent and 10% of color paste into the modified natural latex, and uniformly mixing to prepare the filling resin.
And 4, adding filling resin into a soaking tank, carrying out padding treatment on the sea-island type superfine fiber synthetic leather base cloth in the soaking tank, wherein the padding treatment is two-padding and two-rolling, removing redundant slurry from the padded sea-island type superfine fiber synthetic leather base cloth by using a scraper, placing the base cloth into an oven for foaming at a high temperature of 130 ℃, and then carrying out decrement, splitting, dyeing, sanding and oiling to prepare the natural latex superfine fiber synthetic leather.
And 5, preparing the wear-resistant hydrophobic treatment agent, wherein the wear-resistant hydrophobic treatment agent comprises modified natural latex, a defoaming agent, a wetting agent, a thickening agent, a wear-resistant auxiliary agent, a hydrophobic auxiliary agent, a cross-linking agent and color paste.
Adding 0.5% of defoaming agent, 1.5% of wetting agent, 2% of thickening agent, 2% of wear-resistant additive, 10% of hydrophobic additive, 1% of cross-linking agent and 20% of color paste into the modified natural latex, and uniformly mixing to prepare the wear-resistant hydrophobic water treatment agent.
Step 6, treating the natural latex superfine fiber synthetic leather prepared in the step 4 by using the wear-resistant hydrophobic treatment agent through an anilox roller printing method, wherein the sizing amount is 50g/m2And obtaining the suede natural latex superfine fiber synthetic leather.
Comparative example 1
Comparative example 1 is solvent type polyurethane superfine fiber synthetic leather, and its production process is in order: wet solvent type polyurethane impregnation, DMF aqueous solution solidification, water washing, toluene reduction, drying, splitting, dyeing, sanding, oiling and solvent type treatment agent surface treatment to prepare the solvent type polyurethane superfine fiber synthetic leather.
Comparative example 2
Comparative example 2 is waterborne polyurethane superfine fiber synthetic leather, and its production process is in order: impregnating waterborne polyurethane, drying and solidifying at high temperature, reducing alkali, drying, splitting, dyeing, sanding, oiling and performing surface treatment by using a waterborne treating agent to obtain the waterborne polyurethane superfine fiber synthetic leather.
Product performance testing
The products obtained in examples 1 to 4, comparative example 1 and comparative example 2 were tested as follows:
1. air permeability determination
The air permeability of the above products was measured according to the air permeability measurement of the standard QB/T5156-2017 synthetic leather test method.
2. Surface water splash rating
And (3) carrying out surface water repellent grade measurement on the product according to AATCC22-2017 water repellent performance test-spraying method.
3. Colour fastness to rubbing
The products were tested for crocking fastness according to standard QB/T2537-2001 leather fastness test-reciprocating crocking fastness.
The test results for each product are given in the following table:
table 1 product Performance test results
Figure BDA0003363242600000111
Figure BDA0003363242600000121
From the above table, it can be seen that the air permeability, the waterproof performance and the rubbing color fastness of the natural latex superfine fiber synthetic leather prepared by the invention are greatly superior to those of the comparative example 1 and the comparative example 2. The natural latex superfine fiber synthetic leather manufactured by the invention inherits the characteristics of good toughness, oil resistance, solvent resistance and acid and alkali resistance of a natural latex product, is soft in hand feeling, uses water-soluble materials in the production process, is environment-friendly and human-friendly, and can meet the requirements of customers on environmental protection, water resistance and air permeability.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. A preparation method of natural latex superfine fiber synthetic leather is characterized by comprising the following steps:
providing a sea-island superfine fiber synthetic leather base cloth;
preparing modified natural latex, wherein the modified natural latex comprises natural latex, ammonia water, a stabilizer, a vulcanization accelerator, a vulcanization activator and an anti-aging agent;
preparing filling resin, wherein the filling resin comprises modified natural latex, a foaming agent H, dimethyl oxalate, a thickening agent and color paste;
and adding the filling resin into an impregnation tank, padding the sea-island type superfine fiber synthetic leather base cloth in the impregnation tank, taking out the padded sea-island type superfine fiber synthetic leather base cloth, and heating and foaming to prepare the natural latex superfine fiber synthetic leather.
2. The method for preparing the natural latex superfine fiber synthetic leather according to claim 1, wherein the method for preparing the natural latex superfine fiber synthetic leather further comprises the following steps: preparing a wear-resistant hydrophobic treatment agent, wherein the wear-resistant hydrophobic treatment agent comprises modified natural latex, a defoaming agent, a wetting agent, a thickening agent, a wear-resistant auxiliary agent, a hydrophobic auxiliary agent, a cross-linking agent and color paste;
and treating the natural latex superfine fiber synthetic leather by using the wear-resistant hydrophobic treatment agent to prepare the suede natural latex superfine fiber synthetic leather.
3. The method for preparing the natural latex superfine fiber synthetic leather according to claim 1, wherein the sea-island superfine fiber synthetic leather base fabric takes alkali-soluble polyester as a sea component and polyamide or polyester as an island component, wherein the sea component accounts for 25-49% of the total mass of the sea-island superfine fiber synthetic leather base fabric, and the balance is the island component.
4. The method for preparing the natural latex superfine fiber synthetic leather according to claim 3, wherein the method for preparing the sea-island superfine fiber synthetic leather base cloth comprises the following steps: the sea component and the island component are made into fixed island short fibers, and the fixed island short fibers are made into the sea-island superfine fiber synthetic leather base cloth after carding, lapping and needling.
5. The method for preparing the natural latex ultrafine fiber synthetic leather according to claim 1, wherein in the modified natural latex, based on the mass of the natural latex, the mass of the ammonia water is 30 to 40% of the mass of the natural latex, the mass of the stabilizer is 0.05 to 0.2% of the mass of the natural latex, the mass of the vulcanization accelerator is 0.25 to 1.5% of the mass of the natural latex, the mass of the vulcanization activator is 0.05 to 0.2% of the mass of the natural latex, and the mass of the anti-aging agent is 0.05 to 0.2% of the mass of the natural latex.
6. The method for preparing the natural latex superfine fiber synthetic leather according to claim 1, wherein the method for preparing the modified natural latex comprises the following steps: uniformly mixing the raw materials, heating to 55-60 ℃, preserving heat for 6-10 hours, and then cooling to room temperature.
7. The method for preparing the natural latex superfine fiber synthetic leather according to claim 1, wherein in the filling resin, based on the mass of the modified natural latex, the mass of the foaming agent H is 3-10% of the mass of the modified natural latex, the mass of the dimethyl oxalate is 0.2-1% of the mass of the modified natural latex, the mass of the thickening agent is 0.2-2% of the mass of the modified natural latex, and the mass of the color paste is 2-10% of the mass of the modified natural latex.
8. The method for preparing the natural latex superfine fiber synthetic leather according to the claim 1, wherein in the step 4, the padding treatment is two-in-two, the extra slurry is removed from the sea-island superfine fiber synthetic leather base cloth after the padding treatment by a scraper, the sea-island superfine fiber synthetic leather base cloth is placed into an oven for high temperature foaming, and then the natural latex superfine fiber synthetic leather is prepared through decrement, splitting, dyeing, sanding and oiling.
9. The method for preparing the natural latex superfine fiber synthetic leather according to claim 2, wherein in the wear-resistant hydrophobic treatment agent, based on the mass of the modified natural latex, the mass of the defoaming agent is 0.15-0.5% of the mass of the modified natural latex, the mass of the wetting agent is 0.3-1.5% of the mass of the modified natural latex, the mass of the thickening agent is 0.2-2% of the mass of the modified natural latex, the mass of the wear-resistant auxiliary agent is 0.5-2% of the mass of the modified natural latex, the mass of the hydrophobic auxiliary agent is 2-10% of the mass of the modified natural latex, the mass of the crosslinking agent is 0.3-1% of the mass of the modified natural latex, and the mass of the color paste is 1-20% of the mass of the modified natural latex.
10. A natural latex microfine fiber synthetic leather produced by the production method according to any one of claims 1 to 9.
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