CN114149644B - Environment-friendly synthetic leather and preparation method thereof - Google Patents

Environment-friendly synthetic leather and preparation method thereof Download PDF

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Publication number
CN114149644B
CN114149644B CN202111344065.4A CN202111344065A CN114149644B CN 114149644 B CN114149644 B CN 114149644B CN 202111344065 A CN202111344065 A CN 202111344065A CN 114149644 B CN114149644 B CN 114149644B
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porous material
layer
synthetic leather
parts
deodorant
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CN114149644A (en
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徐青
赵建明
徐雪明
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Kunshan Achilles New Material Technology Co ltd
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Kunshan Achilles New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/20—Oxides; Hydroxides
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The application relates to the field of synthetic leather, and particularly discloses environment-friendly synthetic leather and a preparation method thereof. The environment-friendly synthetic leather comprises a base layer, a foaming layer and a resin layer which are sequentially arranged from inside to outside, wherein the resin layer comprises the following substances in parts by weight: 50-80 parts of polyvinyl chloride resin A, 1-2 parts of a stabilizer, 5-25 parts of a deodorant and 40-80 parts of an o-benzene plasticizer, wherein the deodorant is a porous material, the inner walls of pores of the porous material are loaded with a reinforcing layer, the reinforcing layer is coated on the inner walls of the pores of the porous material through reinforcing liquid coating treatment, and the reinforcing liquid comprises silica sol; the preparation method comprises the following steps: s1, mixing raw materials; s2, preparing a resin layer; s3, preparing a foaming layer; and S4, preparing synthetic leather. The environment-friendly synthetic leather composition can be used for clothes, home decoration, ornaments and the like, and has the advantages of small smell, difficulty in causing harm to the environment and human bodies and good flexibility.

Description

Environment-friendly synthetic leather and preparation method thereof
Technical Field
The application relates to the field of synthetic leather, in particular to environment-friendly synthetic leather and a preparation method thereof.
Background
The leather product is firm and durable, but the manufacturing process is complex, the mass production cannot be realized, on one hand, the yield is not enough to meet the market demand, on the other hand, the price of the leather is high, and part of consumers cannot bear the burden, so that the synthetic leather can be produced at the discretion.
Synthetic leather is a plastic product generally made of a fabric as a base on which synthetic resin, various plastics, additives, etc. are coated. Because a large amount of chemical raw materials are required to be added in the manufacturing process of the synthetic leather, the synthetic leather has a relatively strong smell, and in order to solve the problem of the smell of the synthetic leather, a deodorant is usually added in the manufacturing process of the synthetic leather to adsorb the smell of the synthetic leather. The odor eliminator is typically a porous material that adsorbs odors through the larger pores of the odor eliminator.
In view of the above-mentioned related art, the inventors believe that the deodorant is more easily broken during the process of adding the deodorant to the synthetic leather raw material, so that the deodorant has a poor deodorizing effect, resulting in the drawback of a synthetic leather having a large odor.
Disclosure of Invention
In order to overcome the defect that bad odor removal effect causes large odor of synthetic leather, the application provides environment-friendly synthetic leather and a preparation method thereof.
In a first aspect, the present application provides an environment-friendly synthetic leather, which adopts the following technical scheme: the environment-friendly synthetic leather comprises a base layer, a foaming layer and a resin layer which are sequentially arranged from inside to outside, wherein the resin layer comprises the following substances in parts by weight: the polyvinyl chloride composite material comprises, by weight, 50-80 parts of polyvinyl chloride resin A, 1-2 parts of a stabilizer, 5-25 parts of a deodorant and 40-80 parts of an o-benzene plasticizer, wherein the deodorant is a porous material, a reinforcing layer is loaded on the inner wall of pores of the porous material, the reinforcing layer is coated on the inner wall of the pores of the porous material through reinforcing liquid coating treatment, and the reinforcing liquid comprises silica sol.
Through adopting above-mentioned technical scheme, the adoption is loaded with silica sol at porous material's pore inner wall, on the one hand, through the intensity in silica sol reinforcing porous material pore, reduce the possibility that porous material's pore collapses, porous material is difficult for taking place to break, the gas that the guarantee smell removal agent produced synthetic leather through the pore carries out the absorption effect, on the other hand, silica sol self has certain adsorption effect, and then porous material and silica sol mutually support, improve the adsorption effect of smell removal agent to the gas that synthetic leather produced in coordination, thereby reduce the smell of synthetic leather in coordination.
In addition, after the silica sol is loaded in the pores of the porous material, the silica sol has certain absorption effect on water vapor in the air, so that the water vapor permeability effect of the synthetic leather is improved, and the comfort of the synthetic leather is improved. In addition, in the process of absorbing water vapor by the silica sol, the water vapor can absorb and dissolve the gas loaded on the silica sol and the porous material through the pores of the porous material, namely, the time effect of the porous material on odor absorption is prolonged, so that the odor can be absorbed by the deodorant for a long time, and the influence of the gas generated in the synthetic leather on the human body and the environment is reduced.
Preferably, the reinforcing liquid also comprises the following substances in parts by weight: 30-40 parts of aluminum salt solution, 2-4 parts of aluminum magnesium spinel powder and 10-20 parts of titanium dioxide sol, wherein the mass ratio of the silicon dioxide sol to the titanium dioxide sol is 1:5-10.
By adopting the technical scheme, firstly, the inner walls of the pores of the porous material are loaded with the aluminum element, so that the adsorption mode of the porous material is converted from physical adsorption to physical-chemical adsorption, and the adsorption effect of the deodorant on the odor is synergistically improved; secondly, through the cooperation of the magnesium element in the aluminum-magnesium spinel powder, the aluminum element in the aluminum salt solution and the silica sol, a continuous high-strength interface layer is formed, namely the strength of the enhancement layer is improved, the supporting effect of the enhancement layer on the inner walls of the pores of the porous material is further improved, and the odor removal effect of the odor removal agent is guaranteed;
in addition, the titanium dioxide sol is stably grafted on the enhancement layer through the matching of the titanium dioxide sol and the aluminum element, on one hand, the support effect of the enhancement layer on the inner wall of the pore of the porous material is improved due to the good hardness of the titanium dioxide sol; on the other hand, due to the visible light activity of the titanium dioxide sol, gas generated by the synthetic leather can be decomposed, and the adsorption speed of the porous material to saturation is slowed down. Therefore, the smell removing agent can adsorb and decompose the smell at the same time, the smell removing effect of the smell removing agent is improved synergistically, and the influence of the smell generated by the synthetic leather on the environment and the human body is reduced.
Preferably, the coating treatment comprises the following steps: (1) Taking the porous material in the formula, stirring and mixing the porous material and an aluminum salt solution to prepare a mixed solution, adding silicon dioxide sol, aluminum-magnesium spinel powder and titanium dioxide sol into the mixed solution, continuously stirring, and carrying out oscillation treatment to prepare an intermediate solution; (2) And filtering the intermediate solution, reserving a filter cake, drying, calcining and cooling the filter cake, and taking out to obtain the porous material coated with the enhancement layer.
By adopting the technical scheme, the porous material is firstly placed in the aluminum salt solution, so that the aluminum element is loaded on the inner walls of the pores of the porous material, the absorption of the gas generated by the synthetic leather by the porous material is changed from physical adsorption to physical-chemical adsorption, and the adsorption effect of the porous material on the smell is improved. In addition, the activity of the porous material is improved, and the combination effect of the enhancement layer and the inner wall of the pore of the porous material is improved when the enhancement layer is loaded on the inner wall of the pore of the porous material subsequently, so that the enhancement layer stably supports the pore of the porous material, and the absorption effect of the porous material on gas generated by synthetic leather is ensured.
Preferably, the coating treatment further comprises a pretreatment, and the pretreatment comprises the following steps: placing the porous material in the formula in nitric acid, oscillating for reaction, filtering, retaining a filter cake, washing and drying to obtain the pretreated porous material.
By adopting the technical scheme, the porous material is pretreated, the nitric acid can eliminate some ash on the surface of the porous material, the number of oxygen-containing functional groups on the surface of the porous material is increased, the surface activity of the porous material is further improved, namely, the bonding strength and the bonding stability between the enhancement layer and the inner wall of the pore of the porous material are improved, the enhancement layer stably supports the inner wall of the pore of the porous material, namely, the odor removing effect of the odor removing agent on the odor of the synthetic leather is ensured. In addition, in the process of treating the porous material by the nitric acid, the pores on the porous material can be deepened to a certain degree, and the inner walls of the pores of the porous material are subjected to surface etching, so that the adsorption effect of the porous material on gas generated by the synthetic leather is further improved, and the odor volatilization of the synthetic leather is reduced.
Preferably, the frequency of the shaking reaction is 50-200rpm for 2-6h.
By adopting the technical scheme, under a proper oscillation rate, the nitric acid is fully contacted with the porous material, the activity of the porous material is stably improved, and the stable connection of the subsequent enhancement layer and the inner wall of the pore of the porous material is ensured; too fast oscillation speed causes the impact force between the porous material and the nitric acid to be larger, the pores of the porous material are easy to collapse, and the adsorption effect of the porous material is reduced; too slow oscillation speed, the contact effect between the porous material and nitric acid is poor, and further, oxygen-containing functional groups loaded on the porous material are few, so that the activity of the porous material is poor, and the loading effect between a subsequent enhancement layer and the inner wall of the pore of the porous material is poor.
Preferably, the porous material comprises one or more of activated carbon, zeolite, mesoporous material.
By adopting the technical scheme, the activated carbon has a good peculiar smell adsorption effect, has relatively developed pores and an ultra-large surface area, and has no selectivity on adsorbed gas, so that the smell generated by the synthetic leather can be absorbed, and the smell removal effect of the deodorant is guaranteed;
the zeolite has a stable crystal structure, so that the internal pore maintenance rate of the porous material is high, namely the odor removal effect of the odor removal agent is guaranteed, and a plurality of channels are arranged among the pores in the zeolite, the diameter of each channel is relatively single, so that certain selection can be performed on odor, formaldehyde in the synthetic leather can be stably absorbed, the possibility of formaldehyde emission in the synthetic leather is reduced, and the influence of the synthetic leather on a human body and the environment is reduced;
the pore size in the mesoporous material can be adjusted, so that the type of gas generated by the synthetic leather can be correspondingly adjusted, the gas generated in the synthetic leather can be accurately absorbed, and the influence of the odor of the synthetic leather on the environment and the human body can be reduced.
In addition, through the mutual cooperation among the activated carbon, the zeolite and the mesoporous material, the porous material can not only carry out more accurate absorption on the gas in the synthetic material, but also improve the adsorption loading capacity and the adsorption stability of the porous material, and synergistically improve the absorption effect of the deodorant on the gas generated by the synthetic leather.
Preferably, the porous material is further loaded with a connecting layer, the connecting layer and the reinforcing layer are coated on the porous material from inside to outside, and the connecting layer comprises any one of epoxy resin, phenolic resin and polyurethane.
By adopting the technical scheme, the connecting layer is loaded on the inner wall of the pore of the porous material, and the porous material has higher surface activity after being pretreated, so that the inner wall of the pore of the porous material is stably connected with the connecting layer, and the reinforcing layer is stably loaded on the inner wall of the pore of the porous material through the bonding effect of the connecting layer, so that the inner wall of the pore of the porous material is stably supported, the gas generated by the synthetic leather is stably adsorbed by the porous material, and the smell of the synthetic leather is reduced.
The epoxy resin has a relatively excellent bonding effect, and the bonding strength between the reinforcing layer and the inner walls of the pores of the porous material is stably improved. The phenolic resin has a good bonding effect, so that the loading effect between the reinforcing layer and the inner walls of the pores of the porous material is improved, and the compatibility between the porous material and the base material of the resin layer is improved to a certain extent, so that the deodorant is uniformly dispersed in the resin layer, and the odor of the synthetic leather is stably reduced. The waterborne polyurethane has a certain bonding effect, and after the polyurethane is loaded on the inner walls of the pores of the porous material, the bonding strength between the reinforcing layer and the inner walls of the pores of the porous material can be improved, certain elasticity is provided for the inner walls of the pores of the porous material, and the possibility of pore collapse of the porous material can be reduced to a certain extent.
In a second aspect, the present application provides a method for preparing an environmentally friendly synthetic leather, which adopts the following technical scheme:
a preparation method of environment-friendly synthetic leather comprises the following preparation steps of S1, mixing raw materials: taking the polyvinyl chloride resin A, the stabilizer, the deodorant and the o-benzene plasticizer in the formula, and stirring and mixing to prepare a mixed material; s2, preparing a resin layer: mixing and plasticating the mixed material, and performing calendering treatment at 100-200 ℃ to obtain a resin layer; s3, preparing a foaming layer: weighing the following substances in parts by weight: 50-80 parts of polyvinyl chloride resin B, 1-2 parts of stabilizer, 5-25 parts of deodorant, 40-80 parts of o-benzene plasticizer and 1-3 parts of foaming agent, stirring and mixing to prepare a foaming paste, coating the foaming paste on release paper, and drying to prepare a foaming layer; s4, preparing synthetic leather: coating an adhesive on the substrate layer, then attaching the foaming layer to the substrate layer, continuously coating the adhesive on the side of the foaming layer far away from the substrate layer, attaching the resin layer to the foaming layer, and applying pressure on the resin layer to prepare the synthetic leather.
By adopting the technical scheme, the mixing and plastication are carried out after the materials are mixed in advance, the dispersion uniformity of the deodorant among the base materials of the resin layer is effectively enhanced, and then the gas generated by the formed resin layer can be uniformly absorbed by the deodorant, so that the smell of the synthetic leather is reduced. The resin layer is prepared by adopting a rolling mode, the resin layer has better toughness through rolling treatment, and the resin layer, the foaming layer and the substrate layer are compounded through a coating mode, so that the prepared synthetic leather has the advantages of soft texture and high strength.
In summary, the present application has the following beneficial effects:
1. because the silica sol is loaded on the inner wall of the pore of the porous material and has certain strength, the silica sol supports the inner wall of the pore of the porous material, so that the stability of the pore of the porous material is ensured, namely the adsorption effect of the porous material on the odor generated by the synthetic leather is ensured; secondly, the silica sol has certain adsorbability, so that the adsorption effect of the porous material on the odor generated by the synthetic leather is synergistically improved; in addition, the silica sol can absorb water vapor to a certain extent, so that the absorbed gas can be dissolved by the water vapor to a certain extent, the adsorption capacity of the porous material is improved, the effect of the deodorant on absorbing the odor generated by the synthetic leather is improved, and the prepared synthetic leather has a small odor effect.
2. In the application, the enhancement layer is preferably prepared by compounding the silicon dioxide sol, the titanium dioxide sol, the aluminum-magnesium spinel powder and the aluminum salt solution, and as the porous material is loaded with the aluminum element, the surface activity of the porous material is improved, and the bonding strength between the inner wall of the pore of the porous material and the enhancement layer is improved; secondly, an interface layer with higher strength can be formed among the silica sol, the aluminum-magnesium spinel powder and the aluminum element, so that the supporting strength of the reinforcing layer on the inner wall of the pore of the porous material is improved, and the porous material can be ensured to stably absorb gas generated by synthetic leather;
the titanium dioxide sol is added into the enhancement layer and can be stably loaded on the porous material under the connection of the aluminum element, and the smell generated by the synthetic leather can be decomposed through the visible light activity of the titanium dioxide sol, so that the smell removing agent can absorb and decompose the gas generated by the synthetic leather at the same time, and the smell generated by the synthetic leather is reduced, therefore, the prepared synthetic leather has less smell and is not easy to harm the environment and the human body.
3. According to the method, the raw materials of the resin layer are premixed in advance, and the dispersing effect of the deodorant in the resin layer is improved through mixing and plastication, so that the deodorant can be absorbed on the synthetic leather uniformly, the odor emitted by the synthetic leather is reduced, and the resin layer is prepared through calendering, so that the synthetic leather obtains excellent flexibility, and the comfort of the synthetic leather is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
In the embodiment of the present application, the selected apparatuses are as follows, but not limited thereto:
medicine preparation: the foaming agent is foaming agent OBSH-75 with the cargo number of 965845 of Shanghai Kayin chemical Co., ltd; the Al-Mg spinel powder is 101 of Yixing summer refractory material Co., ltd; silica sol with a product number of 24567 from chemical technology ltd, shannon english; TA33 type titanium dioxide sol of hangzhou wanjing new materials ltd; the adhesive is a water-based polyurethane adhesive with a product number of AL-559005422729 from Jining Nissin Daizhi Biotechnology Limited; the polyvinyl chloride resin A is a 5G-5 type polyvinyl chloride resin of Zhengzhou Xidan chemical industry Co., ltd, and the polyvinyl chloride resin B is a CP-430 type polyvinyl chloride resin of Shanghai Kangyin chemical industry specialized shop.
Preparation example
Examples of preparation of porous Material
Preparation examples 1 to 7
Respectively taking active carbon, zeolite and a mesoporous material to prepare the porous material 1-7, wherein the mesoporous material is cobalt oxide, and the specific mass is shown in table 1.
TABLE 1 porous Material Components in preparation examples 1-7
Figure 102956DEST_PATH_IMAGE001
Examples of preparation of connecting layer
Preparation example 8
Epoxy resin was taken as the tie layer 1.
Preparation example 9
Phenolic resin was used as the tie layer 2.
Preparation example 10
Aqueous polyurethane is used as the connecting layer 3.
Preparation example of deodorant
Preparation example 11
Coating treatment: taking 2kg of silica sol as the enhancing solution 1, soaking 1kg of the porous material 1 in the enhancing solution 1, oscillating at the frequency of 100rpm for 1h, filtering to retain a filter cake, and then placing in an oven to dry at 45 ℃ for 24h to obtain the deodorant 1, wherein the enhancing layer 1 is loaded on the inner wall of the pore of the porous material in the deodorant 1.
Preparation examples 12 to 14
Coating treatment: placing 1kg of porous material 1 in an aluminum salt solution, stirring and mixing to prepare a mixed solution, wherein the aluminum salt solution is an aluminum chloride solution with the mass fraction of 3%, adding silicon dioxide sol, aluminum-magnesium spinel powder and titanium dioxide sol into the mixed solution, continuously stirring and mixing to prepare a reinforcing solution 2-4, placing the reinforcing solution 2-4 in an oscillating box, and oscillating at the frequency of 200rpm for 2 hours to prepare an intermediate solution; and filtering the intermediate solution, reserving a filter cake, drying the filter cake at 105 ℃ for 2h, calcining the filter cake at 300 ℃ for 2h, cooling to room temperature to obtain a deodorant 2-4, wherein the inner walls of pores of a porous material in the deodorant 2-4 are loaded with enhancement layers 2-4. The specific qualities of the aluminum salt solution, the silica sol, the aluminum magnesium spinel powder and the titanium dioxide sol in the reinforcing layers 2 to 4 are shown in table 2.
TABLE 2 composition of reinforcing layers in preparations 12 to 14
Figure 967007DEST_PATH_IMAGE002
Preparation example 15
The difference from preparation 13 is that: before coating treatment, pretreating the porous material 1, placing the porous material 1 in nitric acid with the mass fraction of 1% and placing the mixture in an oscillator, adjusting the oscillation frequency to 50rpm, oscillating for 2 hours, filtering, keeping a filter cake, carrying out deionization washing until washing liquid is neutral, stopping washing the filter cake, placing the filter cake in an oven to dry at 100 ℃, obtaining the pretreated porous material 1, and preparing the deodorant 5, wherein the rest preparation conditions and preparation environments are the same as those in the preparation example 13.
Preparation example 16
The difference from preparation 14 is that: the oscillating frequency was adjusted to 100rpm, and the oscillating treatment was carried out for 4 hours to prepare an odor eliminating agent 6, and the other preparation conditions and preparation environment were the same as those in preparation example 14.
Preparation example 17
The difference from preparation 14 is that: the oscillating frequency was adjusted to 200rpm, and the oscillating treatment was carried out for 6 hours to prepare deodorant 7, and the other preparation conditions and preparation environment were the same as those in preparation example 14.
Preparation examples 18 to 20
The difference from preparation 16 is that: respectively placing the pretreated porous material 1 in the connecting layers 1-3, stirring and mixing, oscillating for 30min at 100rpm, filtering, retaining a filter cake, placing the filter cake in an oven, and drying to obtain the deodorant 8-10, wherein the rest preparation conditions and preparation environment are the same as those in preparation example 16.
Preparation examples 21 to 26
The difference from preparation example 20 is that: the porous materials 2 to 7 in production examples 2 to 7 were used in place of the porous material 1 in production example 20, and the odorants 11 to 16 were prepared under the same conditions and in the same environment as in production example 20.
Preparation example of foaming paste
Preparation example 27
80kg of polyvinyl chloride resin B, 2kg of a stabilizer, 25 parts of a deodorant 1, 40kg of an o-benzene plasticizer and 3kg of a foaming agent were taken, stirred and mixed to prepare a foaming paste.
Examples
Examples 1 to 3
Preparing a resin layer: respectively weighing polyvinyl chloride resin A, a stabilizer, a deodorant 1 and an o-benzene plasticizer, wherein the specific mass is shown in Table 3, placing the materials in a high-speed stirring mixer, and stirring the materials at 100 ℃ for 10 to 20min to prepare a mixed material 1 to 3; and (2) placing the mixed materials 1-3 into an internal mixer, mixing for 5-15min at 120 ℃, conveying to an open mill after mixing, plasticating for 30min at 120 ℃, repeating for two times, conveying to a calender after plasticating, and carrying out calendaring molding at 140 ℃ to obtain the resin layers 1-3.
Preparing a foaming layer: and coating the foaming paste on release paper, and drying to obtain the foaming layer.
Preparing synthetic leather: coating an adhesive on the substrate layer, wherein the adhesive is waterborne polyurethane in the embodiment, bonding the foaming layer on the substrate layer, coating the adhesive on the surface of the foaming layer far away from the substrate layer, bonding the resin layer on the foaming layer, and uniformly applying a pressure of 800Pa on the resin layer to obtain the synthetic leather 1-3 compounded by the substrate layer, the foaming layer and the resin layer which are sequentially arranged from inside to outside.
Table 3 compositions of mixtures in examples 1-3
Figure 843696DEST_PATH_IMAGE003
Examples 4 to 5
The difference from example 3 is that: synthetic leathers 4 to 5 were prepared by selecting the deodorant 2 to 4 in place of the deodorant 1 in example 3, and the other preparation conditions and preparation environments were the same as those in example 3.
Example 6
The difference from example 4 is that: synthetic leather 6 was produced by using deodorant 5 in place of deodorant 4 in example 4, and the other production conditions and production environment were the same as in example 4.
Examples 7 to 8
The difference from example 6 is that: synthetic leathers 7 to 8 were prepared by selecting the deodorant 6 to 7 in place of the deodorant 5 in example 6, and the other preparation conditions and preparation environments were the same as those in example 6.
Examples 9 to 11
The difference from example 7 is that: synthetic leathers 9 to 11 were produced by using the deodorant 8 to 10 in place of the deodorant 7 in example 7, and the other production conditions and production environments were the same as in example 7.
Examples 12 to 17
The differences from example 11 are: synthetic leathers 12 to 17 were produced by selecting the deodorizing agents 11 to 16 in place of the deodorizing agent 6 in example 11, and the other production conditions and the production environment were the same as those in example 11.
Performance test
(1) Detecting the amount of formaldehyde volatilized from the synthetic leather: according to GB/T19941-2005 determination standard of formaldehyde content in leather and fur chemical test, synthetic leather is sampled according to QB/T2706 leather chemical, physical, mechanical and color fastness test sampling part, and the sample is detected, and is determined and recorded by a liquid chromatograph.
(2) And (3) detecting the volatile VOC (volatile organic compound) amount of the synthetic leather: the synthetic leathers were cut and sampled and cut to pieces of 5mm by 5mm and mixed well. Weighing 2.00g of sample from the mixed sample, placing the sample into a staring control sample injection bottle until the sample is accurate to 0.01g, covering a silicon rubber pad and an aluminum cover, sealing the sample by using a sealing tool, placing the sample into an automatic headspace sample injector to be measured, and measuring and recording the sample by using a gas chromatograph-mass spectrometer.
Table 4 examples 1-17 performance testing
Figure 259634DEST_PATH_IMAGE004
Comparative example
Comparative example 1
The differences from example 17 are: the deodorant 18 was prepared by preparing the synthetic leather 18 without coating the inner wall of the porous material with the reinforcing layer, and the other preparation conditions and preparation environments were the same as those in example 17.
Comparative example 2
The difference from example 17 is that: a copper chloride solution with a mass fraction of 3% was used in place of the aluminum chloride solution of example 17 to prepare an odor eliminating agent 19, and in place of the odor eliminating agent 16 of example 17 to prepare a synthetic leather 19, and the other preparation conditions and preparation environments were the same as those of example 17.
Comparative example 3
The difference from example 17 is that: a synthetic leather 20 was produced by replacing the deodorant 16 of example 17 with the deodorant 20 produced without adding a titanium dioxide sol to the reinforcing layer, and the other production conditions and production environments were the same as those of example 17.
Comparative example 4
The difference from example 17 is that: synthetic leather 21 was produced by using the deodorant 21 prepared without pretreating the porous material instead of the deodorant 16 of example 17, and the other production conditions and production environment were the same as those of example 17.
Comparative example 5
The differences from example 17 are: synthetic leather 22 was prepared by using a deodorant 22 prepared without supporting a connecting layer on a porous material, instead of the deodorant 16 of example 17, and the other preparation conditions and preparation environments were the same as those of example 17.
Performance test
(1) Detecting the amount of formaldehyde volatilized from the synthetic leather: according to GB/T19941-2005 measuring standard of formaldehyde content in leather and fur chemical test, the synthetic leather is sampled according to QB/T2706 leather chemical, physical, mechanical and color fastness test sampling part, and the sample is detected, measured and recorded by a liquid chromatograph.
(2) And (3) detecting the volatile VOC (volatile organic compound) amount of the synthetic leather: the synthetic leather was cut and sampled and cut to pieces of 5mm x 5mm or less and mixed well. Weighing 2.00g of sample from the mixed sample, placing the sample into a staring and controlling sample feeding bottle until the sample is accurate to 0.01g, covering a silicon rubber pad and an aluminum cover, sealing by using a sealing tool, placing the sample into an automatic headspace sample feeder to be measured, and measuring and recording by using a gas chromatograph-mass spectrometer.
TABLE 5 comparative examples 1-5 Performance test
Figure 995509DEST_PATH_IMAGE005
Comparing the performance tests in table 4 and table 5, it can be found that:
(1) By combining examples 1-3 and comparative example 1, the following can be found: the synthetic leathers prepared in examples 1-3 produced reduced formaldehyde and VOC, which indicates that the present application employs a reinforced layer loaded on the inner walls of the pores of the porous material, and further, the pores of the porous material are always stable and not easy to collapse during the mixing, milling, plasticating and calendering processes, thereby improving the adsorption effect of the deodorant on the gas produced by the synthetic leather. Meanwhile, the silicon dioxide sol can absorb water vapor to a certain extent, so that gas generated by the synthetic leather is effectively dissolved, the gas adsorption quantity of the deodorant is increased, the deodorizing effect of the deodorant is further improved, and the smell of the synthetic leather is reduced. As can be seen from tables 4 and 5, the synthetic leather produced in example 3 emitted less formaldehyde and VOC, indicating that the ratio of each component in the resin layer was appropriate.
(2) By combining the comparison of examples 4-5 and comparative examples 2-3, it can be found that: the formaldehyde and VOC generated by the synthetic leathers prepared in examples 4-5 are reduced, which shows that the present application forms a higher strength interface layer by compounding silica sol, titania sol, spinel powder of aluminum and magnesium, and aluminum chloride, that is, the strength of the reinforcement layer is increased, so that the reinforcement layer stably supports the inner walls of the pores of the porous material, and the porous material absorbs the gas generated by the synthetic leathers. By adding the titanium dioxide sol, the strength of the enhancement layer is further improved, and the gas generated by the synthetic leather can be decomposed through the visible light activity of the titanium dioxide sol, so that the deodorant can be adsorbed and decomposed cooperatively, the odor removing effect of the deodorant is further improved, and the odor of the synthetic leather is reduced. As can be seen from tables 4 and 5, the synthetic leather obtained in example 3 emitted less formaldehyde and VOC, indicating that the ratio of the components in the reinforcing layer was more suitable.
(3) A comparison of example 6, examples 7 to 8 and comparative example 4 shows that: the synthetic leathers prepared in examples 6 to 8 produced reduced formaldehyde and VOC, which indicates that the pretreatment of the porous material according to the present application can increase the depth of the pores in the porous material and improve the deodorizing effect of the deodorant, and can increase the number of oxygen-containing functional groups on the inner wall of the porous material and improve the bonding strength between the reinforcing layer and the inner wall of the porous material, thereby ensuring the adsorption effect of the porous material. The proper oscillation speed enables the nitric acid to be fully contacted with the porous material, the surface area of the porous material is stably improved, and the bonding strength between the enhancement layer and the porous material is guaranteed. As can be seen from tables 4 and 5, the synthetic leather produced in example 7 emitted less formaldehyde and VOC, indicating that the frequency and time of the shaking treatment were appropriate.
(4) A comparison of examples 9 to 11 with comparative example 5 shows that: the synthetic leathers prepared in examples 9 to 11 produced reduced formaldehyde and VOC, which indicates that the application improves the bonding strength between the reinforcing layer and the inner walls of the pores of the porous material by supporting the connection layer on the porous material, and increases the dispersion degree of the porous material in the resin layer by coating the connection layer on the porous material, so that the resin layer has a more uniform deodorizing effect. As can be seen from tables 4 and 5, the synthetic leather produced in example 11 emitted less formaldehyde and VOC, indicating that the tie layer was suitable.
(5) A comparison with examples 12 to 17 shows that: the formaldehyde and VOC generated by the synthetic leathers prepared in examples 13 to 14 are reduced, which indicates that the present application uses a mixture of activated carbon, mesoporous material and zeolite as a porous material, the activated carbon has many and dense pores, and the mesoporous material and zeolite have certain selectivity, so that the gas generated by the synthetic leathers is selectively absorbed, the odor removal effect of the odor remover is effectively improved, and the odor of the synthetic leathers is reduced. As can be seen from tables 4 and 5, the synthetic leather obtained in example 17 emitted less formaldehyde and VOC, indicating that the ratio of the components in the porous material was appropriate.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (7)

1. An environment-friendly synthetic leather is characterized in that: the foaming material comprises a substrate layer, a foaming layer and a resin layer which are sequentially arranged from inside to outside, wherein the resin layer comprises the following materials in parts by weight: 50-80 parts of polyvinyl chloride resin A, 1-2 parts of stabilizer, 5-25 parts of deodorant and 40-80 parts of o-benzene plasticizer, wherein the deodorant is a porous material, the inner walls of pores of the porous material are loaded with a reinforcing layer, the reinforcing layer is coated on the inner walls of the pores of the porous material through reinforcing liquid coating treatment, and the reinforcing liquid comprises silica sol;
the enhancement solution also comprises the following substances in parts by weight: 30-40 parts of aluminum salt solution, 2-4 parts of aluminum magnesium spinel powder and 10-20 parts of titanium dioxide sol, wherein the mass ratio of the silicon dioxide sol to the titanium dioxide sol is 1:5-10.
2. The eco-friendly synthetic leather according to claim 1, wherein the coating process comprises the steps of:
(1) Taking a porous material in the formula, stirring and mixing the porous material and an aluminum salt solution to prepare a mixed solution, adding a silicon dioxide sol, aluminum-magnesium spinel powder and a titanium dioxide sol into the mixed solution, continuously stirring, and performing oscillation treatment to prepare an intermediate solution;
(2) And filtering the intermediate solution, keeping a filter cake, drying, calcining and cooling the filter cake, and taking out to obtain the porous material coated with the enhancement layer.
3. The eco-friendly synthetic leather of claim 2, wherein the coating treatment further comprises a pretreatment comprising the steps of: and (3) putting the porous material in the formula into nitric acid, oscillating to react, filtering, retaining a filter cake, washing and drying to obtain the pretreated porous material.
4. The eco-friendly synthetic leather of claim 3, wherein: the frequency of the shaking reaction is 50-200rpm, and lasts for 2-6h.
5. The eco-friendly synthetic leather according to claim 1, wherein: the porous material comprises one or more of activated carbon, zeolite and mesoporous material.
6. The eco-friendly synthetic leather of claim 1, wherein: the porous material is also loaded with a connecting layer, the connecting layer and the reinforcing layer are coated on the porous material from inside to outside, and the connecting layer comprises any one of epoxy resin, phenolic resin and polyurethane.
7. The method for preparing environment-friendly synthetic leather according to any one of claims 1 to 6, comprising the following preparation steps:
s1, mixing raw materials: taking the polyvinyl chloride resin A, the stabilizer, the deodorant and the o-benzene plasticizer in the formula, and stirring and mixing to prepare a mixed material;
s2, preparing a resin layer: mixing and plasticating the mixed materials, and performing calendering treatment at 100-200 ℃ to obtain a resin layer;
s3, preparing a foaming layer: weighing the following substances in parts by weight: 50-80 parts of polyvinyl chloride resin B, 1-2 parts of stabilizer, 5-25 parts of deodorant, 40-80 parts of o-benzene plasticizer and 1-3 parts of foaming agent, stirring and mixing to obtain a foaming paste, coating the foaming paste on release paper, and drying to obtain a foaming layer;
s4, preparing synthetic leather: coating an adhesive on the substrate layer, then adhering the foaming layer on the substrate layer, continuously coating the adhesive on one side of the foaming layer away from the substrate layer, adhering the resin layer on the foaming layer, and applying pressure on the resin layer to obtain the synthetic leather.
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CN111733605A (en) * 2020-06-30 2020-10-02 昆山阿基里斯新材料科技有限公司 Polyvinyl chloride artificial leather with adsorption and decomposition functions and preparation method thereof

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