CN116394635A - Preparation method of ultrathin non-cloth electronic packaging leather material - Google Patents

Preparation method of ultrathin non-cloth electronic packaging leather material Download PDF

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Publication number
CN116394635A
CN116394635A CN202310332250.4A CN202310332250A CN116394635A CN 116394635 A CN116394635 A CN 116394635A CN 202310332250 A CN202310332250 A CN 202310332250A CN 116394635 A CN116394635 A CN 116394635A
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parts
layer
wear
electronic packaging
resin
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李炎
高航
李超
韩立业
张哲�
裴莹
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Suzhou Greentech Co ltd
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Suzhou Greentech Co ltd
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    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • 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
    • B32B27/065—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 of foam
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/24—Layered products comprising a layer of synthetic resin characterised by the use of special additives using solvents or swelling agents
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/73—Hydrophobic
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/754—Self-cleaning
    • 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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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

The application relates to the technical field of packaging leather materials, in particular to a preparation method of an ultrathin non-cloth electronic packaging leather material, which comprises the following steps: coating a wet-process base foaming layer material on the base cloth, and obtaining the base cloth with the base cloth after solidification, water washing and drying; coating PU layer mixture on the surface of release paper, drying to obtain a PU layer, attaching the PU layer on a base cloth bass, and stripping the release paper to form a semi-finished product; sequentially printing a wear-resistant layer and an oil stain-resistant layer on the surface of the semi-finished product; and separating the base cloth after printing to obtain a final product. According to the method, the material meets the physical property requirements of wear resistance, stain resistance and the like through the independently developed cloth-free leather technology, the thickness of a synthetic leather finished product is greatly reduced, the limit requirement of an electronic packaging product on the thickness of the material is met, and meanwhile, the technological difficulty and the material cost of the product in the subsequent processing and forming process can be greatly reduced due to the introduction of the cloth-free leather.

Description

Preparation method of ultrathin non-cloth electronic packaging leather material
Technical Field
The application relates to the technical field of packaging leather materials, in particular to a preparation method of an ultrathin non-cloth electronic packaging leather material.
Background
In recent years, with the improvement of the physical properties of synthetic leather, the surface yield is improved and the service life is prolonged. From the beginning of China, more and more electronic product brands adopt synthetic leather as packaging materials, and polyurethane synthetic leather with waterproof and antifouling properties, soft handfeel, high wear resistance and lower cost is gradually spreading on the market of packaging materials such as glass, plastic materials and the like in the field of electronic packaging.
However, at present, the limit requirement of the electronic product on the thickness ultrathin finished product cannot be met by directly processing the synthetic leather material with the base cloth.
Therefore, the preparation of the ultrathin non-cloth electronic packaging leather material has important significance on the limit requirement of electronic products on the thickness ultrathin finished products.
Disclosure of Invention
In order to prepare an ultrathin non-cloth electronic packaging leather material to meet the limit requirement of electronic products on the thickness ultrathin of finished products, the application provides a preparation method of the ultrathin non-cloth electronic packaging leather material.
The application provides a preparation method of an ultrathin non-cloth electronic packaging leather material, which adopts the following technical scheme:
the preparation method of the ultrathin non-cloth electronic packaging leather material comprises the following steps of:
s1, coating a wet bass foaming layer material on base cloth, and solidifying, washing and drying to obtain a base cloth-carrying bass;
s2, coating a PU layer mixture on the surface of release paper, drying to obtain a PU layer, attaching the PU layer on a base cloth bass, and stripping the release paper to form a semi-finished product;
s3, sequentially printing a wear-resistant layer and an oil stain-resistant layer on the surface of the semi-finished product;
s4, separating the base cloth after printing to obtain a final product.
Through adopting above-mentioned technical scheme, the application makes the material satisfy wear-resisting antifouling isophysical property requirement simultaneously greatly reduced synthetic leather finished product's thickness through independently developing's no cloth leather technique, satisfies the limit requirement of electronic packaging product to material thickness, and the introduction of no cloth leather also can greatly reduced product at the technology degree of difficulty and the material cost of follow-up processing shaping process simultaneously.
Preferably, in the step S1, the wet-process bass foaming layer material is prepared from the following raw materials in parts by weight: 100 parts of resin, 45 parts of solvent, 2-4 parts of color paste, 2-5 parts of flame retardant, 1-3 parts of foaming agent, 1-3 parts of foam stabilizer, 0.2-0.5 part of flatting agent and 3-10 parts of filler.
By adopting the technical scheme, the wet bass of the application has the following advantages compared with the traditional wet bass: compared with the traditional synthetic leather, the synthetic leather has softer hand feeling and is close to 'boneless feeling'; has a high bass thickness; has a regular cell structure; the peeling strength is high; has wide application range and large market potential.
Preferably, the resin is oily polyurethane resin, and the filler is extra-white powder or calcium carbonate.
By adopting the technical scheme, the oily polyurethane resin is a polyurethane system with a thermoplastic linear structure, has better stability, chemical resistance, rebound resilience and mechanical property than TPU resin, has smaller compression deformation property, and has good heat insulation, sound insulation, shock resistance and gas defense performance. The polyurethane has elasticity between plasticity and rubber, oil resistance, wear resistance, low temperature resistance, aging resistance and high hardness.
The special powder is nontoxic, has extremely stable chemical properties, hardly acts with any substance at normal temperature, is insoluble in water, dilute acid and organic matters, and is slightly soluble in alkali and hot acid; high decoloring power, high covering power and high lustrousness. The calcium carbonate as the filler can reduce the cost of the product, improve the production efficiency and obtain good economic benefit; the rigidity of the product is improved, and the weight of the product is increased; reducing shrinkage and shrinkage-induced deformation of the product; the dispersibility is good: meanwhile, the compatibility of the calcium carbonate and the resin is good, and even if a large amount of filler is added, good appearance can be obtained; under the condition of larger filling quantity, the product can still keep good mechanical property and has stronger process applicability.
Preferably, in the step S2, the PU layer mixture is prepared from the following raw materials in parts by weight: 100 parts of polyurethane resin, 110 parts of solvent, 0-0.2 part of flatting agent, 1-2 parts of wear-resistant auxiliary agent, 1-3 parts of yellowing-resistant auxiliary agent and 8-15 parts of color paste.
By adopting the technical scheme, the PU layer has the characteristics of wear resistance, solvent resistance, low temperature resistance, good waterproof and moisture permeability, wind resistance, softness and the like. PU is artificial leather, has the texture of leather, is very firm and durable, is low in cost, does not use plasticizer, and does not harden or become brittle and has soft property; meanwhile, the leather has the advantages of rich colors and various patterns, keeps the advantages of ventilation, moisture absorption, softness, wear resistance, strong comfort and the like of natural leather, has texture similar to leather, is stronger than leather, is durable and easy to maintain, and is popular with consumers.
Preferably, in the step S3, the wear-resistant layer is made from the following raw materials in parts by weight: 100 parts of aqueous resin and 3-5 parts of cross-linking agent.
By adopting the technical scheme, the wear-resistant layer adopts the aqueous resin, the aqueous resin has higher adhesive force with the base material after film formation, and the cured coating has excellent corrosion resistance and chemical resistance, small film shrinkage, high hardness and good wear resistance; meanwhile, the water-based resin adopts water instead of an organic solvent as a diluent, so that the resin does not contain toxic chemical substances and has environmental protection.
Preferably, the aqueous resin is aqueous polyurethane, and the wear-resistant layer further comprises 5-10 parts by mass of modified glass fibers;
by adopting the technical scheme, the water-based polyurethane is used as the base paint, and the glass fiber is added into the water-based polyurethane to improve the wear resistance of the paint and the air tightness after the wear-resistant layer is formed, but the glass fiber and the base paint have the problem of poor compatibility, so that the glass fiber is modified, the binding force between the glass fiber and the base paint is improved, the complexity of a molecular network in the wear-resistant layer is enhanced, and the air tightness of the coating is enhanced.
Preferably, the preparation method of the modified glass fiber comprises the following steps: ultrasonically mixing glass fibers with acetone, refluxing for 20-22h at 70-80 ℃, then adding a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:1, and reacting for 2-3h at 90-100 ℃ to obtain etched glass fibers; putting the etched glass fiber into a 75wt% ethanol solution for ultrasonic treatment for 15-25min, and washing with deionized water for 2-3 times to obtain pretreated glass fiber; and carrying out radio frequency magnetron sputtering treatment by taking the pretreated glass fiber as a substrate and titanium dioxide as a target, and carrying out annealing treatment at 500-600 ℃ on the treated sample to obtain the modified glass fiber.
By adopting the technical scheme, the glass fiber is acidified, and the surface of the glass fiber is etched to form micropores, so that the surface is roughened; meanwhile, the pretreated glass fiber is used as a substrate, the titanium dioxide is used as a target material to carry out radio frequency magnetron sputtering treatment, and a relatively continuous titanium dioxide film is deposited on the surface of the glass fiber, so that the strength of the glass fiber is improved; meanwhile, the titanium dioxide is effectively coated on the surface of the glass fiber, and hydroxyl groups on the surface of the titanium dioxide participate in the solidification of the aqueous polyurethane, so that the interface effect between the glass fiber and the aqueous polyurethane is improved, the compatible combination of the modified glass fiber and the aqueous polyurethane is facilitated, and the wear resistance of the wear-resistant layer is improved.
Preferably, in the step S3, the oil stain resistant layer is made from the following raw materials in parts by weight: 100 parts of oleoresin, 8-12 parts of cross-linking agent and 0.5-2 parts of wear-resistant auxiliary agent.
Further preferably, the oily resin is fluorine-silicon modified polyester resin, and the wear-resistant auxiliary agent is organic silicon wear-resistant auxiliary agent.
The fluorosilicon modified polyester resin is formed by connecting fluorosilicon resin with hydroxyl groups and branched polyester resin with hydroxyl active groups together through dehydration polycondensation.
By adopting the technical scheme, the hydroxyl-containing fluorosilicone modified polyester resin is used as the main resin, has the excellent characteristics of organic silicon and organic fluororesin and extremely low surface energy, and the hydroxyl-containing fluorosilicone modified polyester resin and the polyisocyanate prepolymer are crosslinked and cured to form the coating with extremely high hydrophobicity and oleophobicity, stain resistance and self-cleaning property and high weather resistance.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the packaging leather material formed by the preparation method does not contain base cloth, meets the limit requirement of electronic products on ultrathin thickness of finished products, and simultaneously sets a wear-resistant layer and an oil stain-resistant layer on the PU layer, so that the packaging leather has good wear resistance and oil stain resistance;
2. according to the modified glass fiber coating, the modified glass fiber is added into the wear-resistant layer, so that the complexity of a molecular network in the wear-resistant layer is enhanced, and the air tightness of the coating is enhanced;
3. the oleoresin selects the fluorosilicone modified polyester resin, has excellent characteristics of organic silicon and organic fluororesin and extremely low surface energy, and the fluorosilicone modified polyester resin containing hydroxyl and polyisocyanate prepolymer are crosslinked and cured to generate the coating with extremely strong hydrophobicity, oleophobicity, stain resistance, self cleaning property and strong weather resistance.
Drawings
Fig. 1 is a schematic structural diagram of an ultrathin non-woven electronic packaging leather material prepared by the method.
Reference numerals illustrate:
1. a bass foam layer; 2. a PU layer; 3. a wear-resistant layer; 4. an oil stain resistant layer.
Detailed Description
The present application is described in further detail below by way of examples and accompanying drawings.
The structure of the ultrathin non-cloth electronic packaging leather material prepared by the method is shown in figure 1, wherein the structure is as follows from bottom to top: a bass foaming layer 1, a PU layer 2, a wear-resistant layer 3 and an oil stain-proof layer 4.
Preparation example
Preparation example 1
The preparation example discloses a preparation method of modified glass fiber, which comprises the following steps:
s10, ultrasonically mixing glass fibers with acetone, refluxing for 22 hours at 70 ℃, then adding a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:1, and reacting for 3 hours at 90 ℃ to obtain etched glass fibers; glass fibers were purchased from Kinchang plasticization Inc., suzhou;
s20, placing the etched glass fiber into a 75wt% ethanol solution for ultrasonic treatment for 15min, and washing the ultrasonic treated etched glass fiber with deionized water for 2 times to obtain a pretreated glass fiber;
s30, performing radio frequency magnetron sputtering treatment by taking the pretreated glass fiber as a substrate and titanium dioxide as a target, wherein the sputtering pressure is 1.1Pa, the sputtering power is 140W, and the sputtering time is 1.5h; in the sputtering treatment, the vacuum degree was controlled to be 4.5X10 -3 Pa, controlling the flow rate of argon to be 30ml/min, and annealing the treated sample at 500 ℃ to obtain the modified glass fiber.
Preparation example 2
The preparation example discloses a preparation method of modified glass fiber, which comprises the following steps:
s10, ultrasonically mixing glass fibers with acetone, refluxing for 20 hours at 80 ℃, then adding a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:1, and reacting for 2 hours at 100 ℃ to obtain etched glass fibers;
s20, placing the etched glass fiber into a 75wt% ethanol solution for ultrasonic treatment for 25min, and washing the ultrasonic treated etched glass fiber with deionized water for 3 times to obtain a pretreated glass fiber;
s30, performing radio frequency magnetron sputtering treatment by taking the pretreated glass fiber as a substrate and titanium dioxide as a target, wherein the sputtering pressure is 1.2Pa, the sputtering power is 150W, and the sputtering time is 1.5h; in the sputtering treatment, the vacuum degree was controlled to be 4.5X10 -3 Pa, controlling the flow rate of argon to be 35ml/min, and annealing the treated sample at 600 ℃ to obtain the modified glass fiber.
Examples
Example 1
The embodiment discloses a preparation method of an ultrathin non-cloth electronic packaging leather material, which comprises the following steps:
s1, mixing 45Kg of solvent and 100Kg of oily polyurethane resin, adding the mixture into a stirrer, and then sequentially adding 2Kg of color paste, 2Kg of flame retardant, 1Kg of foaming agent, 1Kg of foam stabilizer, 0.2Kg of leveling agent and 3Kg of extra powdery mildew, dispersing and stirring for 1h, vacuumizing, and removing bubbles in the slurry to obtain the Bayes foaming layer slurry; impregnating a base cloth in a 3wt% hydrophilic auxiliary agent solution, then drying at 150 ℃, impregnating the base cloth in a 7wt% DMF aqueous solution, controlling the moisture content on the base cloth to be 30% by quantitative extrusion roll extrusion and hot roll scalding, coating a base foaming layer slurry on the base cloth by a knife coating method, controlling the coated knife clearance according to the product requirement to realize adjustment of the knife coating thickness, solidifying the base cloth to form a film by 15wt% dimethylformamide solidifying solution, washing, drying and shaping to obtain a wet base layer with the base cloth, wherein the drying temperature is 130 ℃, and the production line speed is 10m/min; the solvent is selected from ethanol but is not limited thereto; the viscosity of the oily polyurethane resin is 9000-25000CPS/25 ℃; the color paste is purchased from the cable materials limited company of Yuan county; flame retardant CAS: k-522, available from Jiayi chemical Co., ltd., suzhou; the foaming agent is purchased from the Huishun insulation engineering Co., ltd; the foam stabilizer is purchased from Fuda daily chemical Co., ltd; the leveling agent is purchased from Qian you chemical industry Co., buddha; the extra white powder is purchased from Tuoyi New Material (Guangzhou) limited company;
s2, mixing 100Kg of polyurethane resin, 110Kg of solvent, 1Kg of wear-resistant auxiliary agent, 1Kg of yellowing-resistant auxiliary agent and 8Kg of color paste to form a PU layer mixture, coating the surface of release paper with the PU layer mixture, sequentially drying at a temperature of 60 ℃, 70 ℃, 80 ℃ and 110 ℃ at a speed of 6m/min to obtain a PU layer, attaching the PU layer on a base cloth base, and stripping the release paper to form a semi-finished product; wear aids were purchased from the company Staer fine coatings (Suzhou); the yellowing resistant additive is purchased from Dongguan enterprise plastic jade plastic raw material limited company;
s3, mixing 100Kg of waterborne polyurethane and 3Kg of cross-linking agent to form a wear-resistant layer raw material, and printing the wear-resistant layer raw material on a semi-finished product by adopting a plate roller gravure printing method to form a wear-resistant layer; mixing 100Kg of fluorine-silicon modified polyester resin, 12Kg of cross-linking agent and 2Kg of organosilicon wear-resistant auxiliary agent to form an oil-stain-resistant layer raw material, printing the oil-stain-resistant layer raw material on the wear-resistant layer by adopting a plate roller gravure printing method to form an oil-stain-resistant layer, wherein the rotating speed of a plate roller is 1000rpm and the pressure of the plate roller is 0.3Mpa in the gravure printing process; the fluorosilicone modified polyester resin is a resin formed by connecting together fluorosilicone resin and polyester resin through dehydration polycondensation, in the embodiment, the fluorosilicone modified polyester resin is a fluorosilicone modified polyester resin containing hydroxyl group formed by connecting together fluorosilicone resin with hydroxyl and branched polyester resin with hydroxyl active group through dehydration polycondensation, and the hydroxyl value of the fluorosilicone modified polyester resin is 50-150mg KOH/g; the hydroxyl group is only contained in the finally prepared fluorosilicone modified polyester resin, and the specific type of the branched polyester resin with the hydroxyl active group of the fluorosilicone modified resin with the hydroxyl group is not particularly limited; aqueous polyurethane CAS:9009-54-5; crosslinking agent CAS:110-18-9; organosilicon wear-resistant auxiliary agent is purchased from Shanghai De obtained trade Limited company;
s4, stripping the base cloth after printing to obtain a final product.
Example 2
The embodiment discloses a preparation method of an ultrathin non-cloth electronic packaging leather material, which comprises the following steps:
s1, mixing 45Kg of solvent and 100Kg of oily polyurethane resin, adding the mixture into a stirrer, and then sequentially adding 4Kg of color paste, 5Kg of flame retardant, 3Kg of foaming agent, 3Kg of foam stabilizer, 0.5Kg of leveling agent and 10Kg of extra powdery mildew, dispersing and stirring for 1h, vacuumizing, and removing bubbles in the slurry to obtain the Bayes foaming layer slurry; impregnating a base cloth in a 3wt% hydrophilic auxiliary agent solution, then drying at 150 ℃, impregnating the base cloth in a 7wt% DMF aqueous solution, controlling the moisture content on the base cloth to be 30% by quantitative extrusion roll extrusion and hot roll scalding, coating a base foaming layer slurry on the base cloth by a knife coating method, controlling the coated knife clearance according to the product requirement to realize adjustment of the knife coating thickness, solidifying the base cloth to form a film by 15wt% dimethylformamide solidifying solution, washing, drying and shaping to obtain a wet base layer with the base cloth, wherein the drying temperature is 130 ℃, and the production line speed is 10m/min;
s2, mixing 100Kg of polyurethane resin, 110Kg of solvent, 0.2Kg of flatting agent, 2Kg of wear-resistant auxiliary agent, 3Kg of yellowing-resistant auxiliary agent and 15Kg of color paste to form PU layer mixture, coating the PU layer mixture on the surface of release paper, sequentially drying at a speed of 6m/min through a temperature zone of 60 ℃, 70 ℃, 80 ℃ and 110 ℃ to obtain a PU layer, attaching the PU layer on a base cloth bass, and stripping the release paper to form a semi-finished product;
s3, mixing 100Kg of waterborne polyurethane and 5Kg of cross-linking agent to form a wear-resistant layer raw material, and printing the wear-resistant layer raw material on a semi-finished product by adopting a plate roller gravure printing method to form a wear-resistant layer; mixing 100Kg of fluorosilicone modified polyester resin, 8Kg of cross-linking agent and 0.5Kg of wear-resistant auxiliary agent to form an oil-resistant layer raw material, printing the oil-resistant layer raw material on the wear-resistant layer by adopting a plate roller gravure printing method to form an oil-resistant layer, wherein the rotating speed of the plate roller is 1000rpm and the pressure of the plate roller is 0.3Mpa in the gravure printing process;
s4, stripping the base cloth after printing to obtain a final product.
Example 3
This example is essentially the same as example 1, except that in S1, the extra white powder is equivalently replaced with calcium carbonate; calcium carbonate was purchased from Hangzhou Kota biotechnology Co.
Example 4
This example is substantially the same as example 3 except that 100Kg of aqueous polyurethane, 5Kg of a crosslinking agent and 5Kg of modified glass fiber are mixed to form a raw material for the abrasion-resistant layer, and the raw material for the abrasion-resistant layer is printed on a semi-finished product by a gravure printing method of a plate roller to form an abrasion-resistant layer; the modified fiber was obtained in preparation example 1.
Example 5
This example is substantially the same as example 4 except that the modified glass fiber is added in an amount of 10Kg.
Example 6
This example is essentially the same as example 5, except that the modified glass fiber was obtained in preparation example 2.
Comparative example
Comparative example 1
The comparative example is different from example 6 in that the wet-process base foaming layer is replaced by a TPU layer, specifically, S1 and S2 are omitted, 100Kg TPU particles and 3Kg color master batch are extruded and melted by a double screw at 170-200 ℃ and then coated on the back of the PU layer, and the TPU layer is obtained by cooling and solidifying by a cooling roller.
Comparative example 2
This comparative example differs from example 6 in that in S3, the modified glass fiber is replaced with a glass fiber in equal amount.
Comparative example 3
The comparative example is different from example 6 in that in S3, the oleoresin was selected from the group consisting of model 3311F available from the company Prime polymer Co., ltd.
Performance detection
1. Wear resistance
The test results are recorded in table 1, with a load of 175g, and the products prepared in each example and comparative example were fixed to a jig so that the surface to be tested was perpendicular to the rollers and able to be rubbed 200 times or more as acceptable.
1. Greasy dirt resistance
The stain resistance of the products prepared in each example and comparative example to an oil pen was measured with reference to QB/T5070-2017 test method for synthetic leather test method for stain resistance, and the test results are recorded in Table 1.
2. Hand feel
50 volunteers (average consumers) were found to score the softness rating of the products prepared for each example and comparative example, with a score of 5 full scale, and the average was taken and the scoring results for each example and preparation example are reported in Table 1.
TABLE 1 Performance test data sheets for examples 1-6 and comparative examples 1-3
Figure BDA0004155282030000071
Referring to table 1, in combination with examples 1-2, it can be seen that the prepared packaging leather materials have better wear resistance, oil stain resistance and soft hand feeling by changing the addition amounts of the components of the wet-process bass foaming layer, the PU layer, the wear-resistant layer and the oil stain-resistant layer within a proper range.
Referring to table 1, in combination with examples 3 to 5, it can be seen that the abrasion resistance of the produced packaging leather material is improved after adding a proper amount of modified glass fiber to the abrasion-resistant layer; this is due to the fact that the modified glass fibers can enhance the complexity of the molecular network in the wear layer, enhancing the air tightness of the coating.
Referring to table 1, in combination with example 6 and comparative example 1, it can be seen that the abrasion resistance of the manufactured packaging leather material is reduced while the hand feeling is deteriorated by replacing the wet base foaming layer with the TPU layer; the resin in the wet-process base foaming layer adopts oily polyurethane resin, and the oily polyurethane resin is a polyurethane system with a thermoplastic linear structure, and has better stability, chemical resistance, rebound resilience and mechanical property than TPU resin, and simultaneously has excellent characteristics of good oil resistance, wear resistance, high hardness and the like. The wet-process bass has high bass thickness and a regular cell structure, and is softer in hand feel than the traditional synthetic leather.
Referring to table 1, in combination with example 6 and comparative example 2, it can be seen that when the modified glass fibers in the wear-resistant layer are replaced with glass fibers in equal amounts, the wear-resistant layer of the produced packaging leather material is lowered and the feel is poor; although the glass fiber can improve the wear resistance of the coating, the glass fiber has poor compatibility with other components such as resin and the like; the glass fiber is etched to form micropores, the surface is roughened, and meanwhile, the titanium dioxide film is deposited on the surface of the glass fiber, so that the strength of the glass fiber is improved, the interface effect between the glass fiber and the aqueous polyurethane is improved, and the wear resistance of the coating and the overall hand feeling of the product are improved.
Referring to table 1, in combination with example 6 and comparative example 3, it can be seen that the oil stain resistance of the produced packaging leather material is lowered after the oleoresin in the oil stain resistant layer is replaced with the ordinary oleoresin. The hydroxyl-containing fluorosilicone modified polyester resin used in the application is taken as a main resin, has excellent characteristics of organic silicon and organic fluororesin and extremely low surface energy, and is crosslinked and cured with polyisocyanate prepolymer to form the coating with extremely high hydrophobicity and oleophobicity, stain resistance, self cleaning property and weather resistance.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (9)

1. A preparation method of an ultrathin non-cloth electronic packaging leather material is characterized by comprising the following steps of: the method comprises the following steps:
s1, coating a wet bass foaming layer material on base cloth, and solidifying, washing and drying to obtain a base cloth-carrying bass;
s2, coating a PU layer mixture on the surface of release paper, drying to obtain a PU layer, attaching the PU layer on a base cloth bass, and stripping the release paper to form a semi-finished product;
s3, sequentially printing a wear-resistant layer and an oil stain-resistant layer on the surface of the semi-finished product;
s4, separating the base cloth after printing to obtain a final product.
2. The method for preparing the ultrathin non-woven electronic packaging leather material according to claim 1, which is characterized in that: in the step S1, the wet-process base foaming layer material is prepared from the following raw materials in parts by weight: 100 parts of resin, 45 parts of solvent, 2-4 parts of color paste, 2-5 parts of flame retardant, 1-3 parts of foaming agent, 1-3 parts of foam stabilizer, 0.2-0.5 part of flatting agent and 3-10 parts of filler.
3. The method for preparing the ultrathin non-woven electronic packaging leather material according to claim 2, which is characterized in that: the resin is oily polyurethane resin, and the filler is extra-white powder or calcium carbonate.
4. The method for preparing the ultrathin non-woven electronic packaging leather material according to claim 1, which is characterized in that: in the step S2, the PU layer mixture is prepared from the following raw materials in parts by weight: 100 parts of polyurethane resin, 110 parts of solvent, 0-0.2 part of flatting agent, 1-2 parts of wear-resistant auxiliary agent, 1-3 parts of yellowing-resistant auxiliary agent and 8-15 parts of color paste.
5. The method for preparing the ultrathin non-woven electronic packaging leather material according to claim 1, which is characterized in that: in the step S3, the wear-resistant layer is prepared from the following raw materials in parts by weight: 100 parts of aqueous resin and 3-5 parts of cross-linking agent.
6. The method for preparing the ultrathin non-woven electronic packaging leather material, as claimed in claim 5, is characterized in that: the water-based resin is water-based polyurethane, and the wear-resistant layer further comprises 5-10 parts by mass of modified glass fibers;
the method for preparing the ultrathin non-woven electronic packaging leather material, as claimed in claim 6, is characterized in that: the preparation method of the modified glass fiber comprises the following steps: ultrasonically mixing glass fibers with acetone, refluxing for 20-22h at 70-80 ℃, then adding a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:1, and reacting for 2-3h at 90-100 ℃ to obtain etched glass fibers; putting the etched glass fiber into a 75wt% ethanol solution for ultrasonic treatment for 15-25min, and washing with deionized water for 2-3 times to obtain pretreated glass fiber; and carrying out radio frequency magnetron sputtering treatment by taking the pretreated glass fiber as a substrate and titanium dioxide as a target, and carrying out annealing treatment at 500-600 ℃ on the treated sample to obtain the modified glass fiber.
7. The method for preparing the ultrathin non-woven electronic packaging leather material according to claim 1, which is characterized in that: in the step S3, the oil stain resistant layer is prepared from the following raw materials in parts by weight: 100 parts of oleoresin, 8-12 parts of cross-linking agent and 0.5-2 parts of wear-resistant auxiliary agent.
8. The method for preparing the ultrathin non-woven electronic packaging leather material, which is disclosed in claim 8, is characterized in that: the oily resin is fluorine-silicon modified polyester resin, and the wear-resistant auxiliary agent is organic silicon wear-resistant auxiliary agent.
9. The method for preparing the ultrathin non-woven electronic packaging leather material, as claimed in claim 9, is characterized in that: the fluorosilicon modified polyester resin is formed by connecting fluorosilicon resin with hydroxyl groups and branched polyester resin with hydroxyl active groups together through dehydration polycondensation.
CN202310332250.4A 2023-03-31 2023-03-31 Preparation method of ultrathin non-cloth electronic packaging leather material Pending CN116394635A (en)

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