CN114058276A - Solvent-free high-folding-resistance high-wear-resistance organic silicon leather and preparation method thereof - Google Patents
Solvent-free high-folding-resistance high-wear-resistance organic silicon leather and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/26—Presence of textile or fabric
- C09J2400/263—Presence of textile or fabric in the substrate
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a solvent-free, high-folding-resistance and high-wear-resistance organic silicon leather and a preparation method thereof, relating to the technical field of organic silicon leather, and the key points of the technical scheme are that (1) a surface layer adhesive is prepared; (2) preparing middle layer glue and adhesive layer glue; (3) coating surface layer glue on the release paper, wherein the thickness of the surface layer glue is 20-50 μm, and then baking for 2-5min at the temperature of 130-150 ℃; (4) coating an intermediate layer adhesive on the surface of the surface layer adhesive, wherein the thickness of the intermediate layer adhesive is 100-250 μm, and then baking for 2-5min at 30-150 ℃; (5) coating adhesive layer glue on the surface of the middle layer glue, wherein the thickness of the adhesive layer glue is 80-200 μm, then attaching the base cloth to the adhesive layer, baking for 3-8min at 30-150 ℃, and stripping the release paper to obtain the organic silicon leather. Has the effects of improving the processing performance, the strength, the wear resistance and the interlayer bonding performance of the organic silicon leather.
Description
Technical Field
The invention relates to the technical field of organic silicon leather, in particular to solvent-free high-folding-resistance high-wear-resistance organic silicon leather and a preparation method thereof.
Background
Leather materials have been widely used in many fields such as automobiles, aviation, medical treatment, clothing, bags, furniture, decoration and the like because of their good physical and mechanical properties, excellent hygienic properties and exquisite appearance and texture, and are indispensable materials in various aspects such as daily life, work, travel and the like. Leather materials are generally classified into natural leathers and artificial leathers according to the source of the material. According to the data of related websites, the annual output and sales volume of natural leather in China currently accounts for about 5 hundred million square meters and about 20 percent of the total global amount, the annual output and sales volume of artificial leather accounts for about 40 hundred million square meters and about 60 percent of the total global amount, and the market space is huge. However, the current leather industry faces development bottlenecks in the aspects of environmental protection and product performance, and cannot meet the requirements of national green environmental protection policies and the requirements of people on high-performance leather.
The organic silicon synthetic leather is a novel artificial leather emerging in recent years, Liquid Silicone Rubber (LSR) is used as a main raw material, a hydrosilylation curing mode is adopted, no small molecules are released in the production process, and the organic silicon synthetic leather conforms to the concept of green development of China. Because of the unique-Si-O-Si-main chain and the outward methyl spiral structure of the polysiloxane, the organic silicon leather has the characteristics of weather resistance, pollution prevention, skin friendliness, high and low temperature resistance, flame retardance, chemical corrosion resistance, air permeability and the like. However, the production of the organic silicon leather needs LSR with lower viscosity, solvent-free LSR is difficult to simultaneously meet low viscosity and high strength, and the LSR has low surface energy and lacks of additional active groups acting with base cloth, so the organic silicon leather has the problems of poor processability, strength, wear resistance, interlayer bonding performance and the like.
Patent CN 108221398 discloses an organosilicon leather with good wear resistance, which realizes wear resistance by using a solvent to dilute high-viscosity glue and adding silicone resin, breaks through the concept of solvent-free environmental protection, and does not investigate the peeling strength; patent CN 109056357 discloses a preparation method of wear-resistant organic silicon leather, which uses a liquid silicon rubber-based glue containing a large amount of fumed silica to match with phenyl silicone resin, so as to improve the wear-resistant performance of the organic silicon leather, but the viscosity, the construction performance and the stripping performance of the organic leather are not examined; patent CN103821008 discloses a three-layer organic silicon synthetic leather, which has better slip property and wear resistance, but the surface layer glue contains solvent, which does not meet the requirement of green environmental protection, and the viscosity and the construction performance of the middle layer glue added with a large amount of white carbon black are not investigated.
The organic silicon leather glue which is solvent-free, environment-friendly and has excellent construction performance cannot be obtained through the researches, and the organic silicon leather with high folding resistance, high wear resistance and high peeling strength can be prepared.
Disclosure of Invention
The invention aims to provide a preparation method of solvent-free, high-folding-resistance and high-wear-resistance organic silicon leather, and solves the problems of poor processability, strength, wear resistance, interlayer bonding performance and the like of the organic silicon leather.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of solvent-free, high-folding-resistance and high-wear-resistance organic silicon leather comprises the following steps: coating surface layer glue on release paper, wherein the thickness of the surface layer glue is 20-50 mu m, and then baking for 2-5min at the temperature of 130-150 ℃; coating an intermediate layer adhesive on the surface of the surface layer adhesive, wherein the thickness of the intermediate layer adhesive is 100-250 μm, and then baking for 2-5min at 30-150 ℃; and step three, coating adhesive layer glue on the surface of the middle layer glue, wherein the thickness of the adhesive layer glue is 80-200 microns, then attaching the base cloth to the adhesive layer, baking for 3-8min at 30-150 ℃, and stripping the release paper to obtain the organic silicon leather.
Further, the surface layer adhesive is prepared by the following method: adding 80-100 parts of vinyl-terminated silicone oil, 5-25 parts of hydrophobic white carbon black and 30-70 parts of methacryloyloxy MQ resin into a planetary stirrer or a high-speed dispersion machine, stirring for 0.5-2 hours in vacuum, then adding 6-30 parts of a cross-linking agent, 1-10 parts of a chain extender, 1-10 parts of a tackifier and 0.1-5 parts of an inhibitor, stirring for 0.5 hour in vacuum, finally adding 0.2-5 parts of a catalyst, stirring uniformly, removing bubbles, and filtering impurities to obtain a surface layer adhesive;
the middle layer glue and the bonding layer glue are prepared by the following method: adding 80-100 parts of vinyl-terminated silicone oil, 25-50 parts of hydrophobic white carbon black and 15-40 parts of methacryloyloxy MQ resin into a planetary stirrer or a high-speed dispersion machine, stirring for 0.5-2 hours in vacuum, then adding 5-25 parts of a cross-linking agent, 1-10 parts of a chain extender, 1-10 parts of a tackifier and 0.1-5 parts of an inhibitor, stirring for 0.5 hour in vacuum, finally adding 0.2-5 parts of a catalyst, stirring uniformly, removing bubbles, and filtering impurities to obtain the middle layer adhesive and the adhesive layer adhesive.
Further, the vinyl-terminated silicone oil has a vinyl content of 0.1 wt% to 0.4 wt% and a viscosity of 2000-100000mPa · s.
Further, the methacryloyloxy MQ resin has a vinyl content of 2 wt% -3 wt%, and a structural formula shown in formula (1):
wherein R1 is
n is an integer of 1 to 10; r2 can be methyl, ethyl, propyl, phenyl, hydroxy.
Compared with the traditional vinyl MQ resin, the vinyl reactivity in the methacryloxy MQ resin is lower, and in the initial stage of vulcanization reaction, the acryloxy MQ resin does not compete with terminal vinyl silicone oil for the reaction point of terminal hydrogen silicone oil to realize the chain extension of terminal vinyl silicone oil, but along with the consumption and temperature increase of the terminal vinyl silicone oil, the acryloxy MQ resin and the hydrogen-containing silicone oil are subjected to crosslinking reaction to play a reinforcing effect.
Further, the methacryloyloxy MQ resin is prepared by the following steps: adding tetraethoxysilane into a reaction bottle, dropwise adding an HCl solution, carrying out hydrolytic polymerization reaction under the catalysis of acid, adding hexamethyldisiloxane, bis-3-methacryloxypropyltetramethyldisiloxane, or methacryloxypropyltrimethoxysilane and other silane monomers containing methacryloxy, continuing hydrolytic polymerization reaction, adding isoparaffin after the reaction is finished, extracting, standing and separating liquid to obtain an upper prepolymer solution; adding the upper prepolymer solution into a reaction bottle, adding KOH methanol solution, carrying out alkali condensation reaction, and adding NaHCO3Neutralizing and filtering to obtain a methacryloxy MQ resin solution, and then carrying out reduced pressure distillation and drying to obtain the methacryloxy MQ resin.
Further, the cross-linking agent is side chain hydrogen-containing silicone oil, the mass fraction of hydrogen is 0.3-1.2%, the viscosity is 30-500 mPa.s, and the structural formula is shown as the formula (2):
wherein R is3Is methyl, ethyl or phenyl, p and q are positive integers, p + q is more than or equal to 20 and less than or equal to 230, m is more than or equal to 2.5 and n is less than or equal to 0.25. The larger the value of p + q, the larger the molecular weight of the side chain hydrogen-containing silicone oil, the larger the viscosity, and the larger the value of p: q, the lower the hydrogen-containing mass fraction of the side chain hydrogen-containing silicone oil.
Further, the chain extender is hydrogen-terminated silicone oil, the mass fraction of hydrogen is 0.08-0.15%, the viscosity is 5-15mPa & s, and the structural formula is shown as the formula (3):
wherein m is a positive integer from 4 to 18.
When the viscosity of the hydrogen-terminated silicone oil is too low, the hydrogen-terminated silicone oil is easy to volatilize in the high-temperature vulcanization process, and the chain extension effect is influenced; when the viscosity of the hydrogen-terminated silicone oil is too high, the degree of freedom of molecules is reduced, and the chain extension reaction rate is influenced.
Further, the structural formula of the tackifier is shown as a formula (4):
wherein R is methoxy or ethoxy.
The tackifier can improve the adhesion between the organic silicon leather glue layers and between the glue and the base cloth.
Further, the inhibitor is polyvinyl siloxane, alkynol compounds and maleate compounds; the platinum catalyst is a platinum-vinyl complex or a platinum-alkynyl complex.
A solvent-free, highly fold-resistant, highly abrasion-resistant silicone leather produced by the method of any one of claims 1-9.
The beneficial effect of this scheme lies in: the acryloxy MQ resin has good compatibility with silicon rubber and has small influence on viscosity. Compared with the traditional vinyl MQ resin, the vinyl reaction activity in the acryloxy MQ resin is lower, and in the initial stage of vulcanization reaction, the silicon resin does not compete with the terminal vinyl silicone oil for the reaction point of the terminal hydrogen silicone oil to realize the chain extension of the terminal vinyl silicone oil, but along with the consumption and temperature increase of the terminal vinyl silicone oil, the acryloxy MQ resin and the hydrogen silicone oil have a crosslinking reaction to play a reinforcing effect. By matching the acryloyloxy MQ resin with the white carbon black and using the terminal hydrogen silicone oil to carry out chain extension on the terminal vinyl silicone oil, the surface layer adhesive with lower viscosity and higher hardness, tensile strength and elongation and the middle layer adhesive and the bonding layer adhesive with lower viscosity and higher tensile strength, tearing strength and elongation can be prepared.
Detailed Description
Example 1
A preparation method of solvent-free, high-folding-resistance and high-wear-resistance organic silicon leather comprises the following steps:
(1) preparing a surface layer adhesive: adding 100 parts of terminal vinyl silicone oil, 15 parts of hydrophobic white carbon black and 50 parts of methacryloyloxy MQ resin into a planetary stirrer or a high-speed dispersion machine, stirring for 1.5 hours in vacuum, adding 20 parts of cross-linking agent, 6 parts of chain extender, 4 parts of tackifier and 0.4 part of inhibitor, stirring for 0.5 hour in vacuum, finally adding 2 parts of catalyst, stirring uniformly, removing bubbles, and filtering impurities to obtain a surface layer adhesive;
(2) preparing middle layer glue and adhesive layer glue: adding 100 parts of terminal vinyl silicone oil, 30 parts of hydrophobic white carbon black and 30 parts of methacryloxy MQ resin into a planetary stirrer or a high-speed dispersion machine, stirring for 1.5 hours in vacuum, adding 15 parts of cross-linking agent, 6 parts of chain extender, 4 parts of tackifier and 0.4 part of inhibitor, stirring for 0.5 hour in vacuum, finally adding 2 parts of catalyst, stirring uniformly, removing bubbles, and filtering impurities to obtain an intermediate layer adhesive and a bonding layer adhesive;
(3) coating surface layer glue on the release paper, wherein the thickness of the surface layer glue is 30 mu m, and then baking for 2min at 130 ℃;
(4) coating middle layer adhesive on the surface of the surface layer adhesive, wherein the thickness of the middle layer adhesive is 150 mu m, and then baking for 2min at 130 ℃;
(5) and coating adhesive layer glue on the surface of the middle layer glue, wherein the thickness of the adhesive layer glue is 100 mu m, then attaching the base cloth and the adhesive layer, baking for 4min at 130 ℃, and stripping the release paper to obtain the organic silicon leather.
The hydrophobic white carbon black is hydrophobic white carbon black subjected to surface treatment of organic silicon such as Wake H2000, Yingchuang R8200, R974, Kabot TS720 and the like. The white carbon black can improve the hardness and strength of the silicone rubber, but the viscosity of the silicone rubber is too high, and the operation is difficult.
The methacryloxy MQ resin is prepared by the following steps: adding tetraethoxysilane into a reaction bottle, dropwise adding an HCl solution, carrying out hydrolytic polymerization reaction under the catalysis of acid, adding hexamethyldisiloxane and bis-3-methacryloxypropyltetramethyldisiloxane, or methacryloxypropyltrimethoxysilane and other silane monomers containing methacryloxy groups, continuing hydrolytic polymerization reaction, adding isoparaffin after the reaction is finished, extracting, standing and separating liquid to obtain an upper prepolymer solution; adding the upper prepolymer solution into a reaction bottle, adding KOH methanol solution, carrying out alkali condensation reaction, and adding NaHCO3Neutralizing and filtering to obtain a methacryloxy MQ resin solution, and then carrying out reduced pressure distillation and drying to obtain the methacryloxy MQ resin.
The tackifier is prepared by the following method: adding trimethyl borate, allyl alcohol, hydroxyethyl acrylate and hydroxymethyl triethoxysilane (or hydroxymethyl trimethoxysilane) into a reaction bottle according to a certain molar ratio, reacting under the protection of nitrogen, collecting distilled methanol by using constant-pressure dropping liquid, reacting for 4 hours, observing that no methanol is distilled out, and stopping the reaction to obtain the tackifier.
Examples 2-6 are largely identical to example 1 with the differences detailed in tables 1 and 2.
Table 1 examples 1-3
Table 2 examples 4-6
Comparative example 1
Comparative example 1 differs from example 1 in that: no methacryloxy MQ resin was added.
Comparative example 2
Comparative example 2 differs from example 1 in that: the methacryloxy MQ resin was replaced with a common vinyl MQ resin of the same vinyl content.
Comparative example 3
Comparative example 3 differs from example 1 in that: no hydrogen terminated silicone oil is added.
Comparative example 4
Comparative example 4 differs from example 1 in that: and replacing the hydrogen-terminated silicone oil with the hydrogen content of 0.04% and the viscosity of 30mPa & s.
Comparative example 5
Comparative example 5 differs from example 1 in that: no tackifier was added.
Comparative example 6
Comparative example 6 differs from example 1 in that: the adhesion promoter was replaced with glycidoxypropyltrimethoxysilane.
The performance of the silicone leather glue and the silicone leather is tested by referring to test standards such as GB/T2794, GB/T531.1, GB/T528, GB/T529, GB/T8949, GB/T19089, GB/T1695, GB/T1693, GB/T1692, GB/T9286 and the like, and the results are shown in Table 3.
Table 3 examples 1-6 and comparative examples 1-6 performance tests
As can be seen from the above Table 3, the silicone leathers prepared in examples 1-6 were not cracked 10 ten thousand times, had a peeling load of 60N or more and a Martindale abrasion resistance of 15 ten thousand times (12kPa) according to the folding fastness test (-20 ℃). The adhesion of the organosilicon leather surface layer prepared in the examples 1-6 is less than or equal to 40000 mPas, the hardness is more than or equal to 75Shore A, the tensile strength is more than or equal to 6MPa, and the elongation at break is more than or equal to 200 percent; the adhesive strength of the middle layer and the bonding layer is less than or equal to 80000mPa & s, the tensile strength is more than or equal to 7MPa, the elongation at break is more than or equal to 400 percent, and the tearing strength is more than or equal to 35 kN/m.
Comparative example 1 no methacryloxy MQ resin is added, the tensile strength and tear strength of the top layer glue and the middle and bonding layer glues prepared in comparative example 1 are lower, and the peel strength of the prepared leather is lower; comparative example 2 uses common vinyl MQ resin as reinforcing filler, because the vinyl of the vinyl MQ resin competes with terminal vinyl silicone oil for the reaction point of terminal hydrogen silicone oil, causing chain extension failure, the prepared surface layer glue, the intermediate layer glue and the bonding layer glue have low elongation at break, low tearing strength and low tensile strength, and the prepared leather has poor wear resistance, folding resistance and stripping performance; comparative example 3 does not use a chain extender, and the molecular weight of the basic polymer cannot be increased in the vulcanization reaction process, so that the prepared surface layer adhesive, the prepared middle layer adhesive and the prepared bonding layer adhesive have low elongation at break, the tear strength and the tensile strength are also reduced, and the prepared leather has poor wear resistance, folding resistance and peeling performance; comparative example 4 the hydrogen-terminated silicone oil is replaced by the hydrogen-terminated silicone oil with the hydrogen content of 0.04% and the viscosity of 30mPa & s, the prepared surface layer adhesive, the prepared middle layer and the prepared bonding layer have very low elongation at break, the tear strength and the tensile strength are also reduced, and the prepared leather has poor wear resistance, folding resistance and peeling performance; comparative example 5 no tackifier is added, so the adhesion performance between the glue layers of the leather and between the glue layers and the base cloth is poor, so the peeling load of the prepared leather is very low, and the wear resistance is reduced due to the poor adhesion performance between the glue layers; comparative example 6 the adhesion promoter was replaced with glycidoxypropyltrimethoxysilane, and the leather produced was poor in both abrasion resistance and release properties. By adopting the schemes of the embodiments 1 to 6, the organosilicon leather with better performance can be prepared.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, 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 invention.
Claims (10)
1. A preparation method of solvent-free, high-folding-resistance and high-wear-resistance organic silicon leather is characterized by comprising the following steps: coating surface layer glue on release paper, wherein the thickness of the surface layer glue is 20-50 mu m, and then baking for 2-5min at the temperature of 130-150 ℃; coating an intermediate layer adhesive on the surface of the surface layer adhesive, wherein the thickness of the intermediate layer adhesive is 100-250 μm, and then baking for 2-5min at 30-150 ℃; and step three, coating adhesive layer glue on the surface of the middle layer glue, wherein the thickness of the adhesive layer glue is 80-200 microns, then attaching the base cloth to the adhesive layer, baking for 3-8min at 30-150 ℃, and stripping the release paper to obtain the organic silicon leather.
2. The preparation method of the solvent-free, high-folding-resistance and high-abrasion-resistance organic silicon leather as claimed in claim 1, wherein the surface layer adhesive is prepared by the following method: adding 80-100 parts of vinyl-terminated silicone oil, 5-25 parts of hydrophobic white carbon black and 30-70 parts of methacryloyloxy MQ resin into a planetary stirrer or a high-speed dispersion machine, stirring for 0.5-2 hours in vacuum, then adding 6-30 parts of a cross-linking agent, 1-10 parts of a chain extender, 1-10 parts of a tackifier and 0.1-5 parts of an inhibitor, stirring for 0.5 hour in vacuum, finally adding 0.2-5 parts of a catalyst, stirring uniformly, removing bubbles, and filtering impurities to obtain a surface layer adhesive;
the middle layer glue and the bonding layer glue are prepared by the following method: adding 80-100 parts of vinyl-terminated silicone oil, 25-50 parts of hydrophobic white carbon black and 15-40 parts of methacryloyloxy MQ resin into a planetary stirrer or a high-speed dispersion machine, stirring for 0.5-2 hours in vacuum, then adding 5-25 parts of a cross-linking agent, 1-10 parts of a chain extender, 1-10 parts of a tackifier and 0.1-5 parts of an inhibitor, stirring for 0.5 hour in vacuum, finally adding 0.2-5 parts of a catalyst, stirring uniformly, removing bubbles, and filtering impurities to obtain the middle layer adhesive and the adhesive layer adhesive.
3. The method as claimed in claim 2, wherein the vinyl-terminated silicone oil has a vinyl content of 0.1 wt% to 0.4 wt% and a viscosity of 2000-100000mPa · s.
4. The preparation method of the solvent-free, high-folding-resistance and high-abrasion-resistance silicone leather as claimed in claim 2, wherein the methacryloyloxy MQ resin has a vinyl content of 2 wt% to 3 wt%, and a structural formula shown in formula (1):
wherein R is1Is composed of
n is an integer of 1 to 10; r2Can be methyl, ethyl, propyl, phenyl and hydroxyl.
5. The method for preparing the solvent-free, high-folding-resistance and high-abrasion-resistance silicone leather according to claim 4, wherein the methacryloyloxy MQ resin is prepared by the following steps: (1) adding tetraethoxysilane into a reaction bottle, dropwise adding an HCl solution, carrying out hydrolytic polymerization reaction under the catalysis of acid, adding hexamethyldisiloxane and bis-3-methacryloxypropyltetramethyldisiloxane or methacryloxypropyltrimethoxysilane and other methacryloxy-containing silane monomers, continuing hydrolytic polymerization reaction, adding isoparaffin for extraction after the reaction is finished, and standing and separating liquid to obtain an upper prepolymer solution; (2) adding the upper prepolymer solution into a reaction bottle, adding KOH methanol solution, carrying out alkali condensation reaction, and adding NaHCO3Neutralizing and filtering to obtain a methacryloxy MQ resin solution, and then carrying out reduced pressure distillation and drying to obtain the methacryloxy MQ resin.
6. The preparation method of the solvent-free, high-folding-resistance and high-wear-resistance organosilicon leather as claimed in claim 2, wherein the cross-linking agent is side chain hydrogen-containing silicone oil, the mass fraction of hydrogen is 0.3% -1.2%, the viscosity is 30-500mPa · s, and the structural formula is as shown in formula (2):
wherein R is3Is methyl, ethyl or phenyl, p and q are positive integers, p + q is more than or equal to 20 and less than or equal to 230, and p is more than or equal to 2.5 and less than or equal to 0.25.
7. The preparation method of the solvent-free, high-folding-resistance and high-wear-resistance organosilicon leather according to claim 2, wherein the chain extender is hydrogen-terminated silicone oil, the mass fraction of hydrogen is 0.08-0.15%, the viscosity is 5-15mPa · s, and the structural formula is shown as formula (3):
wherein m is a positive integer from 4 to 18.
8. The preparation method of the solvent-free, high-folding-resistance and high-abrasion-resistance organosilicon leather according to claim 2, wherein the structural formula of the tackifier is shown as formula (4):
wherein R is methoxy or ethoxy.
9. The method for preparing the solvent-free, high-folding-resistance and high-abrasion-resistance organosilicon leather according to claim 2, wherein the inhibitor is a polyvinyl siloxane, an alkynol compound or a maleate compound; the platinum catalyst is a platinum-vinyl complex or a platinum-alkynyl complex.
10. A solvent-free, highly fold-resistant, highly abrasion-resistant silicone leather produced by the method of any one of claims 1-9.
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| CN115595800A (en) * | 2022-09-27 | 2023-01-13 | 唐山三友硅业有限责任公司（Cn） | Anti-adsorption, wear-resistant and scratch-resistant organic silicon leather and preparation method thereof |
| CN115652651A (en) * | 2022-11-24 | 2023-01-31 | 华懋（厦门）特种材料有限公司 | Manufacturing process of environment-friendly organic silicon leather |
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| CN115678454B (en) * | 2022-10-26 | 2024-03-22 | 皇冠新材料科技股份有限公司 | Silica gel protective film, preparation method thereof and electronic product |
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