CN117188178A - Manufacturing method of high-stripping and release paper-saving type organic silicon synthetic leather - Google Patents
Manufacturing method of high-stripping and release paper-saving type organic silicon synthetic leather Download PDFInfo
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- CN117188178A CN117188178A CN202311190848.0A CN202311190848A CN117188178A CN 117188178 A CN117188178 A CN 117188178A CN 202311190848 A CN202311190848 A CN 202311190848A CN 117188178 A CN117188178 A CN 117188178A
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- organosilicon
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- organic silicon
- synthetic leather
- vinyl
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 37
- 239000010703 silicon Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000004744 fabric Substances 0.000 claims abstract description 46
- 229920002545 silicone oil Polymers 0.000 claims abstract description 35
- 239000000853 adhesive Substances 0.000 claims abstract description 30
- 230000001070 adhesive effect Effects 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 239000002344 surface layer Substances 0.000 claims abstract description 18
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 229920002635 polyurethane Polymers 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 36
- 229920002554 vinyl polymer Polymers 0.000 claims description 36
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 29
- 238000005470 impregnation Methods 0.000 claims description 27
- 229920001296 polysiloxane Polymers 0.000 claims description 26
- -1 polysiloxane Polymers 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012744 reinforcing agent Substances 0.000 claims description 12
- 238000004513 sizing Methods 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 238000004049 embossing Methods 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 3
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001410 Microfiber Polymers 0.000 claims description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003658 microfiber Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010985 leather Substances 0.000 abstract description 9
- 239000000835 fiber Substances 0.000 abstract description 5
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 239000006255 coating slurry Substances 0.000 abstract 1
- 238000006459 hydrosilylation reaction Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000011229 interlayer Substances 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a manufacturing method of high-stripping and release paper saving type organic silicon synthetic leather. Firstly, pretreating base cloth by using polyurethane modified organosilicon adhesive with polarity mutual recognition, then directly coating slurry consisting of vinyl-terminated, hydrogen-containing silicone oil, catalyst, auxiliary agent and the like on the pretreated base cloth, and preparing an organosilicon intermediate layer and a surface layer in situ by hydrosilylation polymerization to prepare the high-stripping organosilicon synthetic leather. According to the invention, the base cloth is pretreated by the polarity-intercommunicating modified organosilicon adhesive, an interpenetrating network is formed between the adhesive macromolecules and the base cloth fibers, the polar polyurethane component of the base cloth is identified with the polar component of the base cloth, the nonpolar organosilicon component is identified with the middle layer organosilicon component, and strong intermolecular acting force is formed through a similar compatibility mechanism respectively, so that the peeling strength between the coating and the base cloth is greatly improved. In addition, the middle layer and the surface layer are directly coated on the pretreatment base cloth, so that expensive release paper resources are saved, and the cost of the organic silicon leather is reduced.
Description
Technical Field
The invention relates to a manufacturing method of high-stripping and release paper saving type organic silicon synthetic leather, and belongs to the field of organic silicon material application.
Background
The organosilicon is polysiloxane for short, and is a polymer formed by connecting a silicon-oxygen bond (Si-O-Si) as a framework and a side group with an organic group through a silicon atom. Because of its unique structure, silicone polymers have excellent properties of aging resistance, weather resistance, abrasion resistance, flame retardance, hydrophobicity, stain resistance, insulation, and the like, and have been widely used as leather, synthetic leather, and textile coating materials in recent years. Compared with the traditional polyurethane, acrylic resin and polyvinyl chloride coating materials, the organic silicon material is independent of petroleum resources and carbon-based materials, the crust is rich in content, the raw materials are easy to obtain, and the silicon-based material is used for replacing the carbon-based material to meet the strategic requirements of national green sustainable development; meanwhile, the organic silicon material is utilized to develop leather and synthetic leather coatings, a silicon-hydrogen addition reaction system can be adopted, the reaction condition is mild, no by-products such as waste water, waste residue and the like are generated in the preparation process, and the pollution to the environment can be greatly reduced. At present, an addition type liquid silicone rubber system is mainly adopted as an organosilicon coating material for synthetic leather, such as organosilicon slurry prepared by Chinese patent CN112522965A (an organosilicon synthetic leather and a preparation method thereof), and the organosilicon synthetic leather is prepared by veneering by a dry method (also called a transfer coating method). Although the organic silicon synthetic leather has soft hand feeling, wear resistance, scratch resistance, hydrophobicity and stain resistance, the organic silicon belongs to a nonpolar polymer, and has large interfacial energy difference with polar substrates such as substrates composed of leather collagen fibers, nylon fibers, polyester fibers and spandex fibers and the like and poor polarity mutual recognition, so that the organic silicon coating and the substrates have low peeling strength (mostly lower than 30N/3 cm) and cannot meet the industry requirement of 50N/3cm, not to mention the high peeling requirement of 80-100N/3cm of vamp leather and the like; secondly, the existing leather making process takes the traditional dry synthetic leather transfer coating process, takes expensive release paper (average price of 50 yuan/meter) as a carrier, and the service life of the release paper is not longer than 50 times, thereby seriously pushing high cost. The problems of low peeling strength and large release paper loss lead to the lack of competitiveness of the organic silicon synthetic leather in the market.
Disclosure of Invention
The invention aims to provide a manufacturing method of high-stripping and release paper saving type organic silicon synthetic leather aiming at the defects of the prior art. Aiming at the problem of low peeling strength between an organosilicon coating and base cloth, the polyurethane modified organosilicon adhesive is prepared and used as impregnation liquid to impregnate the base cloth to form an interpenetrating network, and meanwhile, the adhesive contains both polar polyurethane components and nonpolar organosilicon components, has compatibility to the polar and nonpolar components, and is beneficial to improving the interaction force between the organosilicon coating and a base material, thereby improving the peeling strength between the base material and the organosilicon coating; and then, aiming at the problem of high price of release paper, the middle layer and surface layer sizing agent are directly coated on the base cloth pretreated by the impregnation liquid to obtain the organic silicon synthetic leather, so that expensive release paper resources are saved, the cost is reduced, and the combination technology provides a new thought for developing the organic silicon synthetic leather with high quality, high physical property and low cost, and greatly improves the international market competitiveness of the product.
The invention provides a manufacturing method of high-stripping release paper saving type organic silicon synthetic leather, which is characterized by comprising the following steps of:
(1) Preparation of adhesive impregnation liquid pretreatment base cloth:
(1) preparation of polyurethane modified organosilicon adhesive: adding 50 parts of polypropylene glycol with the molecular weight of 1000-2000 and 5-10 parts of polysiloxane blocked by dihydroxyl with the viscosity of 1000-5000 mPa.s into a reaction kettle, adding 15-20 parts of diisocyanate, heating to 80-85 ℃, stirring for reaction 2h, adding 0.5-1.0 part of butanediol, controlling the molar ratio of-NCO/-OH of the system to 1:1, continuously reacting for 2h at 80-85 ℃, cooling to 60 ℃, and adding a proper amount of methanol to block for 0.5h to obtain the polyurethane modified organosilicon adhesive;
(2) preparation of pretreatment base cloth: diluting the adhesive prepared in the step (1) into 5-8% concentration impregnation liquid by using a solvent, placing the impregnation liquid into an impregnation tank, impregnating, extruding and drying the base fabric by using the impregnation liquid to obtain a pretreated base fabric;
(2) Preparation of organosilicon slurry:
(1) preparation of organosilicon middle layer slurry: sequentially adding 40-50 parts of vinyl-terminated silicone oil, 10-20 parts of side vinyl silicone oil, 30-40 parts of hydrogen-containing silicone oil, 0.02-0.05% of platinum catalyst and 0.01-002% of inhibitor into a mixer, controlling the mole ratio of a system-C=C/-Si-H to be 1:1, fully stirring, adding 20-30 parts of reinforcing agent, and uniformly mixing the materials to obtain organosilicon intermediate layer slurry;
(2) preparation of organosilicon surface layer slurry: sequentially adding 40-50 parts of polyvinyl silicone oil, 30-40 parts of hydrogen-containing silicone oil, 0.02-0.05% of platinum catalyst and 0.01-002% of inhibitor into a mixer, controlling the molar ratio of a system-C=C/-Si-H to be 1:1, fully stirring, adding 30-40 parts of reinforcing agent, and uniformly mixing the materials to obtain organosilicon surface layer slurry;
preparation of high-peel organic silicon synthetic leather:
uniformly coating the organosilicon intermediate layer slurry prepared in the step (2) on the surface of the pretreated base cloth prepared in the step (1), controlling the sizing amount to be 50-60g/m < 2 >, placing the base cloth in a baking oven at 120-130 ℃, heating and curing for 5-10 min, then coating the organosilicon surface layer slurry prepared in the step (2), controlling the sizing amount to be 30-40g/m < 2 >, placing the base cloth in a baking oven at 120-130 ℃ for continuous curing for 5-10 min, and then carrying out optional vacuum grain suction or embossing and other process treatment to obtain the high-stripping organosilicon synthetic leather;
the double-hydroxyl end-capped polysiloxane is double-hydroxyl polysiloxane with double hydroxyl groups in a main chain, and the polysiloxane is in a side chain and a Y-shaped structure.
The diisocyanate is one of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate which are liquid at normal temperature.
The base fabric is one of knitted fabric, non-woven fabric or reduced microfiber base fabric.
The solvent is one or a combination of cyclohexane, normal hexane and tetrahydrofuran with weak polarity.
The reinforcing agent is one of MQ resin or fumed silica.
The platinum catalyst is one of a platinum-1, 3-divinyl-1, 3-tetramethyl disiloxane complex or an isopropanol solution of chloroplatinic acid.
The inhibitor is one or a combination of methylbutynol, ethynyl cyclohexanol and alkynyl-containing maleic acid/fumonic acid.
The hydrogen-containing silicone oil is hydrogen-containing polysiloxane with the viscosity of 100-150 mPa.s and the hydrogen content of 0.18-1.6%, and the hydrogen atoms are positioned at the chain end or side chain of the polysiloxane; the vinyl-terminated silicone oil is vinyl-terminated polysiloxane with the viscosity of 10000 mPa.s~80000 mPa and the vinyl content of 0.05-0.5%; the side vinyl silicone oil is side vinyl polysiloxane with viscosity 100 mPa.s~150 mPa and vinyl content of 1.5-2.3%; the polyvinyl silicone oil comprises 0.2-2.3% of vinyl by mass, wherein the vinyl is positioned at the end and branched chains.
Compared with the prior art, the invention has the following positive effects:
according to the principle of polarity mutual recognition, the prepared polyurethane modified organosilicon adhesive agent contains both polar polyurethane components and nonpolar organosilicon components, so that mutual recognition force is formed on polar substrates and nonpolar organosilicon coatings respectively, and the action force between molecular chains is improved; meanwhile, the base cloth is impregnated with the adhesive, and an interpenetrating network is formed between the adhesive macromolecules and the base cloth fibers, so that the peeling strength between the coating and the base material is further improved;
in the selection of the raw materials of the modified adhesive, the dihydroxyl polysiloxane with the dihydroxyl group in the main chain and the polysiloxane in the side chain and the Y-shaped structure is selected, because the polysiloxane in the side chain is favorable for the structural reconstruction of the adhesive after drying, stronger polarity mutual recognition is formed, and the peeling strength is improved.
(3) The organosilicon intermediate layer and the surface sizing agent are directly coated on the surface of the pretreated base fabric, so that expensive release paper resources are saved, and the cost is reduced.
Detailed Description
The present invention is specifically described below by way of examples, which are given for the purpose of illustration only and are not to be construed as limiting the scope of the present invention, as many insubstantial modifications and variations will be apparent to those skilled in the art in light of the foregoing disclosure, while still falling within the scope of the present invention.
Example 1: preparation of high-stripping organic silicon sofa leather
(1) Preparation of adhesive impregnation liquid pretreatment base cloth:
(1) preparation of polyurethane modified organosilicon adhesive: adding 50 parts of polypropylene glycol with the molecular weight of 1000 and 5 parts of polysiloxane with the viscosity of 1000mPa.s and blocked by dihydroxy into a reaction kettle, adding 15 parts of isophorone diisocyanate, heating to 80-85 ℃, stirring for reaction 2h, then adding 0.5 part of butanediol, controlling the molar ratio of-NCO/OH of the system to 1:1, continuously reacting for 2 hours at 80-85 ℃, cooling to 60 ℃, and adding a proper amount of methanol to block for 0.5 hour to obtain the polyurethane modified organosilicon adhesive;
(2) preparation of pretreatment base cloth: diluting the adhesive prepared in the step (1) into 5-8% concentration impregnation liquid by using a solvent, placing the impregnation liquid in an impregnation tank, impregnating, extruding and drying the woven cloth (base cloth) by using the impregnation liquid to obtain a pretreated base cloth;
(2) Preparation of organosilicon slurry:
(1) preparation of organosilicon middle layer slurry: sequentially adding 40 parts of vinyl-terminated silicone oil with the viscosity of 10000 mPas, the vinyl content of 0.05%, 10-20 parts of side vinyl silicone oil with the viscosity of 100 mPas and the vinyl content of 1.5%, 30 parts of hydrogen-containing silicone oil with the hydrogen content of 0.18%, 0.02% of catalyst platinum-1, 3-divinyl-1, 3-tetramethyl disiloxane complex and 0.01% of inhibitor methyl butynol into a mixer, controlling the mole ratio of a system-C=C/-Si-H to 1, fully stirring, adding 20 parts of reinforcing agent MQ resin, and uniformly mixing the materials to obtain organosilicon intermediate layer slurry;
(2) preparation of organosilicon surface layer slurry: sequentially adding 40 parts of polyvinyl silicone oil with the mass percentage of vinyl of 0.2-2.3%, the vinyl of which is positioned at the end and a branched chain, 40 parts of hydrogen-containing silicone oil with the viscosity of 100mPa.s and the hydrogen content of which is 1.6%, the hydrogen atoms of which are positioned at the chain end or a side chain of polysiloxane, 0.05% of isopropanol solution of catalyst chloroplatinic acid and 0.02% of inhibitor methylbutinol, controlling the mole ratio of a system-C=C/-Si-H to 1:1, fully stirring, adding 30 parts of reinforcing agent fumed silica, and uniformly mixing the materials to obtain the organosilicon surface layer slurry;
(3) Preparation of high-peel organic silicon synthetic leather:
uniformly coating the organosilicon interlayer slurry prepared in the step (2) on the surface of the pretreated base fabric prepared in the step (1), wherein the sizing amount is controlled to be 50g/m 2 Heating and curing the mixture in an oven at 120-130 ℃ for 5-10 min, and then coating the organosilicon surface layer slurry prepared in the step (2), wherein the sizing amount is controlled at 30g/m 2 Placing the high-peel organic silicon synthetic leather in an oven at 120-130 ℃ for continuous curing for 5-10 min, and then performing optional vacuum suction or embossing and other processes to obtain the high-peel organic silicon synthetic leather;
the organic silicon synthetic leather prepared by the method does not use release paper, has 58N/3cm peeling strength, a coating water contact angle higher than 110 DEG, can be wiped for more than or equal to 100 times by an oily pen, and has excellent hydrophobic and antifouling properties.
Example 2: preparation of high-peeling organic silicon vamp leather
(1) Preparation of adhesive impregnation liquid pretreatment base fabric
(1) Preparation of polyurethane modified organosilicon adhesive: adding 50 parts of polypropylene glycol with molecular weight of 2000 and 10 parts of polysiloxane with viscosity of 5000 mPa.s and end-capped by dihydroxy into a reaction kettle, adding 20 parts of hydrogenated diphenylmethane diisocyanate, heating to 80-85 ℃, stirring for reaction 2h, adding 1.0 part of butanediol, controlling the molar ratio of-NCO/-OH of the system to 1:1, continuing to react for 2 hours at 80-85 ℃, cooling to 60 ℃, and adding a proper amount of methanol for end-capping for 0.5 hour to obtain the polyurethane modified organosilicon adhesive.
(2) Preparation of pretreatment base cloth: and (3) diluting the adhesive prepared in the step (1) into 5-8% concentration impregnation liquid by using a solvent, placing the impregnation liquid in an impregnation tank, impregnating, extruding and drying the microfiber non-woven fabric by using the impregnation liquid to obtain the pretreatment base fabric.
(2) Preparation of organosilicon slurry
(1) Preparation of organosilicon middle layer slurry: sequentially adding 40 parts of vinyl-terminated silicone oil with the viscosity of 30000 mPas, the vinyl content of 0.05%, 20 parts of side vinyl silicone oil with the viscosity of 100 mPas and the vinyl content of 1.5%, 30 parts of hydrogen-containing silicone oil with the viscosity of 100 mPas and the hydrogen content of 0.18%, 0.02% of catalyst platinum-1, 3-divinyl-1, 3-tetramethyl disiloxane complex and 0.01% of inhibitor ethynyl cyclohexanol into a mixer, controlling the mole ratio of a system-C=C/-Si-H to be 1:1, fully stirring, adding 20 parts of reinforcing agent MQ resin, and uniformly mixing the materials to obtain the organosilicon interlayer slurry.
(2) Preparation of organosilicon surface layer slurry: sequentially adding 40 parts of polyvinyl silicone oil with 2.3 mass percent of vinyl and 40 parts of hydrogen-containing silicone oil with 150mPa.s viscosity, 1.6 parts of hydrogen-containing silicone oil with hydrogen atoms at chain ends or side chains of polysiloxane, 0.05% of isopropanol solution of catalyst chloroplatinic acid and 0.02% of inhibitor methylbutinol into a mixer, controlling the mole ratio of a system-C=C/-Si-H to be 1:1, fully stirring, adding 30 parts of reinforcing agent fumed silica, and uniformly mixing the materials to obtain the organosilicon surface layer slurry.
(3) Preparation of high-peel organic silicon synthetic leather:
uniformly coating the organosilicon interlayer slurry prepared in the step (2) on the surface of the pretreated base fabric prepared in the step (1), wherein the sizing amount is controlled to be 60g/m 2 Heating and curing the mixture in an oven at 120-130 ℃ for 5-10 min, and then coating the organosilicon surface layer slurry prepared in the step (2), wherein the sizing amount is controlled at 40g/m 2 And (3) placing the high-peel organic silicon synthetic leather in an oven at 120-130 ℃ for continuous curing for 5-10 min, and then carrying out optional vacuum suction or embossing and other processes to obtain the high-peel organic silicon synthetic leather.
The organic silicon synthetic leather prepared by the method does not use release paper, has the peel strength of 88N/3cm, has the coating water contact angle higher than 115 degrees, can be wiped for more than or equal to 150 times by writing with an oily pen, and has excellent hydrophobic and antifouling properties.
Example 3: preparation of high-peeling organic silicon automobile leather
(1) Preparation of adhesive impregnation liquid pretreatment base fabric
(1) Preparation of polyurethane modified organosilicon adhesive: adding 50 parts of polypropylene glycol with molecular weight of 2000 and 7.5 parts of polysiloxane blocked by dihydroxy with viscosity of 3000 mPa.s into a reaction kettle, adding 10 parts of isophorone diisocyanate and 1, 6-hexamethylene diisocyanate respectively, heating to 80-85 ℃, stirring for reacting 2h, adding 7.5 parts of butanediol, controlling the molar ratio of-NCO/-OH of the system to 1:1, continuously reacting for 2h at 80-85 ℃, cooling to 60 ℃, and adding a proper amount of methanol for blocking for 0.5h to obtain the polyurethane modified organosilicon adhesive.
(2) Preparation of pretreatment base cloth: and (3) diluting the adhesive prepared in the step (1) into 5-8% concentration impregnation liquid by using a solvent, placing the impregnation liquid in an impregnation tank, impregnating, extruding and drying the high-density non-woven fabric by using the impregnation liquid to obtain the pretreatment base fabric.
(2) Preparation of organosilicon slurry
(1) Preparation of organosilicon middle layer slurry: sequentially adding 45 parts of terminal vinyl silicone oil with the viscosity of 80000 mPas and the vinyl content of 0.2%, 15 parts of side vinyl silicone oil with the viscosity of 120 mPas and the vinyl content of 1.0%, the viscosity of 100 mPas, 35 parts of hydrogen-containing silicone oil with the hydrogen content of 0.8%, 0.02% of catalyst platinum-1, 3-divinyl-1, 3-tetramethyl disiloxane complex and 0.01% of inhibitor ethynyl cyclohexanol, controlling the mole ratio of a system-C=C/-Si-H to be 1:1, fully stirring, adding 25 parts of reinforcing agent MQ resin, and uniformly mixing the materials to obtain the organosilicon interlayer slurry.
(2) Preparation of organosilicon surface layer slurry: sequentially adding 40 parts of polyvinyl silicone oil with the mass percentage of vinyl of 1.8%, the vinyl of which is positioned at the end and a branched chain, 40 parts of silicone oil with the viscosity of 120mPa.s, the hydrogen content of which is 1.0%, the hydrogen atom of which is positioned at the chain end or a side chain of polysiloxane, 0.03% of isopropanol solution of catalyst chloroplatinic acid, 0.015% of inhibitor methylbutinol, and the mole ratio of-C=C/-Si-H of a system of 1:1 into a mixer, fully stirring, adding 35 parts of reinforcing agent fumed silica, and uniformly mixing the materials to obtain the organosilicon surface layer slurry.
(3) Preparation of high-peel organic silicon synthetic leather:
uniformly coating the organosilicon interlayer slurry prepared in the step (2) on the surface of the pretreated base fabric prepared in the step (1), wherein the sizing amount is controlled to be 55g/m 2 Heating and curing the mixture in an oven at 120-130 ℃ for 5-10 min, and then coating the organosilicon surface layer slurry prepared in the step (2), wherein the sizing amount is controlled at 35g/m 2 And (3) placing the high-peel organic silicon synthetic leather in an oven at 120-130 ℃ for continuous curing for 5-10 min, and then carrying out optional vacuum suction or embossing and other processes to obtain the high-peel organic silicon synthetic leather.
The organic silicon synthetic leather prepared by the method does not use release paper, has the peel strength of 65N/3cm, has the coating water contact angle higher than 120 DEG, can be wiped for more than or equal to 150 times by using an oily pen, and has excellent hydrophobic and antifouling properties.
Claims (4)
1. The manufacturing method of the high-stripping and release paper saving type organic silicon synthetic leather is characterized by comprising the following steps of:
(1) Preparation of adhesive impregnation liquid pretreatment base cloth:
(1) preparation of a polarity-mutual recognition polyurethane modified organosilicon adhesive: adding 50 parts of polypropylene glycol with the molecular weight of 1000-2000 and 5-10 parts of polysiloxane with the viscosity of 1000-5000 mPa.s and blocked by dihydroxy into a reaction kettle, adding 15-20 parts of diisocyanate, heating to 80-85 ℃, stirring for reaction 2h, adding 0.5-1.0 part of butanediol, controlling the molar ratio of-NCO/-OH of the system to 1:1, continuously reacting for 2h at 80-85 ℃, cooling to 60 ℃, and adding a proper amount of methanol to block for 0.5h to obtain the polar mutually-recognized polyurethane modified organosilicon adhesive;
(2) preparation of pretreatment base cloth: diluting the adhesive prepared in the step (1) into 5-8% concentration impregnation liquid by using a solvent, placing the impregnation liquid into an impregnation tank, impregnating, extruding and drying the base fabric by using the impregnation liquid to obtain a pretreated base fabric;
(2) Preparation of organosilicon slurry:
(1) preparation of organosilicon middle layer slurry: sequentially adding 40-50 parts of vinyl-terminated silicone oil, 10-20 parts of side vinyl silicone oil, 30-40 parts of hydrogen-containing silicone oil, 0.02-0.05% of platinum catalyst and 0.01-002% of inhibitor into a mixer, controlling the mole ratio of a system-C=C/-Si-H to be 1:1, fully stirring, adding 20-30 parts of reinforcing agent, and uniformly mixing the materials to obtain organosilicon intermediate layer slurry;
(2) preparation of organosilicon surface layer slurry: sequentially adding 40-50 parts of polyvinyl silicone oil, 30-40 parts of hydrogen-containing silicone oil, 0.02-0.05% of platinum catalyst and 0.01-002% of inhibitor into a mixer, controlling the molar ratio of a system-C=C/-Si-H to be 1:1, fully stirring, adding 30-40 parts of reinforcing agent, and uniformly mixing the materials to obtain organosilicon surface layer slurry;
preparation of high-peel organic silicon synthetic leather:
uniformly coating the organosilicon intermediate layer slurry prepared in the step (2) on the surface of the pretreated base fabric prepared in the step (1), wherein the sizing amount is controlled to be 50-60g/m 2 Heating and curing the mixture in an oven at 120-130 ℃ for 5-10 min, and then coating the organosilicon surface layer slurry prepared in the step (2), wherein the sizing amount is controlled to be 30-40g/m 2 Placing the high-peel organic silicon synthetic leather in an oven at 120-130 ℃ for continuous curing for 5-10 min, and then performing optional vacuum suction or embossing and other processes to obtain the high-peel organic silicon synthetic leather;
the double-hydroxyl end-capped polysiloxane is double-hydroxyl polysiloxane with double hydroxyl groups in a main chain, and the polysiloxane is in a side chain and a Y-shaped structure;
the diisocyanate is one of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate which are liquid at normal temperature;
the base fabric is one of knitted fabric, non-woven fabric or reduced microfiber base fabric;
the solvent is one or a combination of cyclohexane, normal hexane and tetrahydrofuran with weak polarity;
the reinforcing agent is one of MQ resin or fumed silica.
2. The method for manufacturing the high-peel-off release paper saving type organic silicon synthetic leather according to claim 1, wherein the platinum catalyst is one of a platinum-1, 3-divinyl-1, 3-tetramethyl disiloxane complex or an isopropanol solution of chloroplatinic acid.
3. The method for manufacturing the high-peel-off release paper-saving type organic silicon synthetic leather according to claim 1, wherein the inhibitor is one or a combination of methylbutynol, ethynyl cyclohexanol and alkynyl-containing maleic acid/fumonic acid.
4. The method for manufacturing the high-peel-off release paper-saving type organic silicon synthetic leather according to claim 1, wherein the hydrogen-containing silicone oil is hydrogen-containing polysiloxane with the viscosity of 100-150 mPa.s and the hydrogen content of 0.18-1.6%, and the hydrogen atoms are positioned at chain ends or side chains of the polysiloxane; the vinyl-terminated silicone oil is vinyl-terminated polysiloxane with the viscosity of 10000 mPa.s~80000 mPa and the vinyl content of 0.05-0.5%; the side vinyl silicone oil is side vinyl polysiloxane with viscosity 100 mPa.s~150 mPa and vinyl content of 1.5-2.3%; the polyvinyl silicone oil comprises 0.2-2.3% of vinyl by mass, wherein the vinyl is positioned at the end and branched chains.
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| CN202311190848.0A CN117188178A (en) | 2023-09-15 | 2023-09-15 | Manufacturing method of high-stripping and release paper-saving type organic silicon synthetic leather |
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| CN202311190848.0A CN117188178A (en) | 2023-09-15 | 2023-09-15 | Manufacturing method of high-stripping and release paper-saving type organic silicon synthetic leather |
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