CN115503320A - Artificial imitation leather film and preparation method thereof - Google Patents
Artificial imitation leather film and preparation method thereof Download PDFInfo
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- CN115503320A CN115503320A CN202211172058.5A CN202211172058A CN115503320A CN 115503320 A CN115503320 A CN 115503320A CN 202211172058 A CN202211172058 A CN 202211172058A CN 115503320 A CN115503320 A CN 115503320A
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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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
- 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
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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
- 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
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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
- 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
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
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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
- B32B2437/00—Clothing
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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
- B32B2457/00—Electrical equipment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2601/00—Upholstery
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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
- B32B2605/00—Vehicles
- B32B2605/08—Cars
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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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 Kinetics & Catalysis (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
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Abstract
The application relates to the technical field of artificial leather, in particular to an artificial leather-like film and a preparation method thereof. An artificial leather-like membrane is sequentially provided with a first protective layer, a leather-like composite layer and a second protective layer from the upper surface to the lower surface, wherein the leather-like composite layer is sequentially provided with an organic silicon layer, a binding layer and a polyurethane layer from the inner surface to the outer surface; the laminating layer is obtained by curing adhesive glue, and the adhesive glue comprises the following raw materials in parts by weight: 48-100 parts of silane coupling agent, 48-100 parts of ethyl acetate, 2-5 parts of platinum catalyst and 2-5 parts of curing agent, and the artificial leather-like composite layer of the artificial leather-like film has the advantages of soft hand feeling, good toughness, water resistance, tearing resistance, puncture resistance and the like, and more importantly, is not easy to absorb moisture and decay.
Description
Technical Field
The application relates to the technical field of artificial leather, in particular to an artificial leather-like film and a preparation method thereof.
Background
Artificial leather is a plastic product that looks and feels like leather and can replace it. Usually, the fabric is used as a substrate and coated with synthetic resin and various plastic additives. Mainly comprises PVC artificial leather and PU synthetic leather. Because the price and price of the real leather are high, the artificial leather imitating the leather is adopted, and the artificial leather is widely applied to the fields of home decoration, clothes, shoes and the like because the artificial leather has the leather-like hand feeling.
At present, the artificial leather taking the fabric as the base is large in thickness and limited in the using process, so that the fabric is proposed to act as the base by people, the release film is taken as the base, and the artificial leather is peeled after the synthetic resin is coated and cured, so that the leather film is obtained.
However, the existing leather film has the defects of easy moisture decay, easy tearing and tearing when meeting water, or easy rupture when contacting sharp objects, and the like, so further research on the leather film is needed.
Disclosure of Invention
In order to solve the above technical problems, the present application provides an artificial leather-like film and a method for preparing the same.
In a first aspect, the application provides an artificial leather-like membrane, which adopts the following technical scheme:
an artificial leather-like film is sequentially provided with a first protective layer, a leather-like composite layer and a second protective layer from the upper surface to the lower surface, wherein the leather-like composite layer is sequentially provided with an organic silicon layer, a bonding layer and a polyurethane layer from the inner surface to the outer surface; the laminating layer is obtained by curing adhesive glue, and the adhesive glue comprises the following raw materials in parts by weight:
48-100 parts of silane coupling agent
48-100 parts of ethyl acetate
2-5 parts of platinum catalyst
2-5 parts of a curing agent.
The artificial imitation leather film is mainly used in the fields of electronic products, automobiles, home furnishings, garment materials and the like, and comprises a first protective layer, a second protective layer and an imitation leather composite layer, wherein the imitation leather composite layer has the advantages of soft hand feeling, good toughness, water resistance, tearing resistance, puncture resistance and the like, and more importantly, the artificial imitation leather film is not easy to absorb moisture, is not easy to rot and the like.
Through setting up first protective layer and second protective layer, can protect the imitation leather layer, and make its save stable form, reduce the imitation leather layer and receive the pollution of dust, perhaps reduce and receive scraping and grinding etc. at the transportation imitation leather, and the imitation leather layer is because organosilicon layer, bonding layer and polyurethane layer constitute, wherein, organosilicon layer and polyurethane layer all have better compliance, toughness and tear resistance, and the bonding layer can be with organosilicon layer and polyurethane layer bonding stability, reduce organosilicon layer and polyurethane layer and take place the possibility that breaks away from, and then reduce the imitation leather composite bed and appear the delaminating, the foaming, phenomenons such as ftractures.
In addition, when the artificial leather-like film is used for an electronic product, the first protective layer and the second protective layer need to be peeled off to obtain a leather-like composite layer, and one surface of the leather-like composite layer is attached to a case of the electronic product.
Furthermore, the bonding layer is obtained by coating and curing bonding glue, the bonding glue is composed of a silane coupling agent, ethyl acetate, a curing agent and a platinum catalyst, wherein the silane coupling agent has good adhesion, high temperature resistance and water resistance, the curing agent has a good curing effect, the silane coupling agent is rapidly cured to form the bonding layer, the polyurethane layer and the organic silicon layer can be stably connected through the bonding layer, meanwhile, the formed bonding layer has good water resistance, high temperature resistance and the like, and the phenomena of water absorption, corrosion and the like of the leather imitation composite are reduced. Thereby reducing the phenomena of water absorption, corrosion and the like of the artificial imitation leather film. The ethyl acetate can play a role in diluting as a diluent, so that the obtained adhesive glue can be easily coated, the curing agent preferably adopts diethylenetriamine to have a better curing effect, and the platinum catalyst can play a role in catalysis.
Preferably, the wet glue thickness of the laminating layer is 3-8 μm.
The thickness of the attaching layer enables the polyurethane layer and the organic silicon layer to be bonded stably, when the thickness is smaller than 3 mu m, the thickness is too low, the bonding is unstable, the polyurethane layer and the organic silicon layer are easy to crack, and when the thickness is larger than 8 mu m, the using amount is too large, so that the cost is increased.
Preferably, the wet glue thickness of the polyurethane layer is 100-120 μm.
The polyurethane layer with the thickness range has good toughness and good flexibility, when the thickness of the polyurethane layer is less than 100 mu m, the toughness is reduced, and when the artificial leather-like film is used, the leather-like composite layer can be easily punctured, so that the attractiveness of the product is influenced; when the thickness is more than 120 μm, the thickness is too large, the amount is large, the cost is high, and the toughness and the like are not obviously increased.
Preferably, the polyurethane layer is obtained by photocuring polyurethane acrylate glue.
The polyurethane acrylate adhesive is prepared from polyurethane acrylate and a photoinitiator 184 according to the weight part ratio of (95-100): (5-10) mixing to obtain; wherein, the molecule of the polyurethane acrylate (PUA) contains acrylic acid functional group and urethane bond, and after being cured, the polyurethane acrylate (PUA) has high wear resistance, adhesion, flexibility, high peeling strength and excellent low-temperature resistance. And the photoinitiator 184 can better promote the polyurethane acrylate adhesive to carry out photocuring, and the processing efficiency is improved. The urethane acrylate has an average molecular weight of 2800 and a viscosity (60 ℃) of 20000 to 35000CPS.
Preferably, the organic silicon layer is obtained by curing organic silicon leather surface paste, and the organic silicon leather surface paste comprises the following raw materials in parts by weight:
49-100 parts of organic silicon epoxy resin and 1-5 parts of curing agent
49-100 parts of ethyl acetate.
The organic silicon epoxy resin has the performances of toughness, heat resistance, water resistance, high bonding strength and the like, the viscosity of the organic silicon epoxy resin is 2000-3000mPa.s, and the organic silicon epoxy resin has good bonding property in the viscosity range. The curing agent preferentially adopts diethylenetriamine and ethyl acetate as a diluent, and has a good diluting effect, so that the organosilicon leather surface slurry obtained by the organosilicon epoxy resin, the curing agent and the ethyl acetate is used for preparing the organosilicon layer, the organosilicon layer has good water resistance and heat resistance, and is easily connected with the laminating layer, the layer structure stability, the water resistance, the toughness and the like of the imitation leather composite layer of the artificial imitation leather film are improved, and the phenomena of delaminating, foaming, cracking, moisture absorption, rotting and the like are reduced.
Preferably, the wet glue thickness of the silicone layer is 100-120 μm.
The thickness in the range can ensure that the organic silicon layer and the polyurethane layer are bonded stably, and the organic silicon layer has better water resistance, temperature resistance, toughness and the like, and is too thin when the thickness of the organic silicon layer is less than 100 mu m, so that the organic silicon layer is easy to puncture in the processing process and the processing efficiency is influenced; when the thickness is more than 120 μm, the thickness is too large, the amount is large, the cost is high, and the water resistance and the like are not obviously changed.
Preferably, the silane coupling agent is a silane complexing agent, and the silane complexing agent comprises the following raw materials in parts by weight:
3-5 parts of water white rosin resin
4.8-10 parts of silane coupling agent
1-3 parts of silicone-acrylic emulsion
0.01 to 0.05 portion of catalyst
60-80 parts of 55-75% ethanol
0.5-1.5 parts of ethoxylated trimethylolpropane triacrylate.
The raw materials and the weight parts of the raw materials are in a better range of the application, wherein the water white rosin resin is hydrogenated natural tackifying resin, has almost water white color, better adhesive property, heat resistance and compatibility, can be matched with various high polymers in any proportion, and has the softening point of 95-125 ℃ and the average molecular weight of 1000-250.
The silane coupling agent has good adhesion and heat resistance; the silicone-acrylate emulsion is prepared by adding an organic silicon monomer containing unsaturated bonds and an acrylic monomer into a proper assistant and polymerizing by a core-shell coating polymerization process. The silicone acrylic emulsion combines the high temperature resistance, weather resistance, chemical resistance, hydrophobicity, low surface energy and difficult pollution, and the high color retention, flexibility and adhesiveness of acrylic resin, the solid content of the silicone acrylic emulsion is 53.5%, and the viscosity is 1000 (S). The ethoxylated trimethylolpropane triacrylate has better adhesion and water resistance. The catalyst is as follows. The 55-75 mass percent ethanol can dissolve the rosin resin and the silane coupling agent, so that the silane compound agent obtained by compounding the raw materials has good water resistance, temperature resistance and adhesiveness, can stably adhere the organic silicon layer and the polyurethane layer, and reduces the phenomena of delamination, bubbling, cracking, moisture absorption, decay and the like of the artificial leather composite layer in the use process of the artificial leather-like film.
Preferably, the silane complexing agent is prepared by the following method:
step 1: weighing water white rosin resin and a silane coupling agent according to parts by weight, dissolving the water white rosin resin and the silane coupling agent in 55-75% of ethanol by mass, dropwise adding a catalyst, heating to 178-188 ℃, and mixing for 1-3 hours to obtain a mixture A;
step 2: and (2) weighing the ethoxylated trimethylolpropane triacrylate and the silicone-acrylate emulsion according to the parts by weight, adding the weighed ethoxylated trimethylolpropane triacrylate and the silicone-acrylate emulsion into the mixture A obtained in the step (1), stirring for 15-25min, cooling to 95-105 ℃, and carrying out reduced pressure distillation for 30-50min to obtain the silane complexing agent.
Preferably, the silane coupling agent consists of isobutyl triethoxy silane, gamma-tert-butyl peroxy propyl trimethoxy silane and methacryloxypropyl trimethoxy silane in the weight ratio of 1 (1.2-1.5) to 1.3-1.8.
The silane coupling agent is formed by isobutyl triethoxy silicon, gamma-tertiary butyl peroxy propyl trimethoxy silane and methacryloxypropyl trimethoxy silane which are all silane coupling agents and have better adhesion, when the silane coupling agent is formed by compounding isobutyl triethoxy silicon, gamma-tertiary butyl peroxy propyl trimethoxy silane and methacryloxypropyl trimethoxy silane according to the weight ratio of 1 (1.2-1.5) to (1.3-1.8), the obtained adhesive glue has better adhesion and water resistance, so that a polyurethane layer and an organic silicon layer are bonded stably, and the phenomena of cracking, foaming, moisture absorption, corrosion and the like of a leather-like composite layer of the artificial leather-like film are reduced.
In a second aspect, the present application provides an artificial leather-like membrane, which adopts the following technical scheme:
step 1: weighing 49-100 parts of organic silicon epoxy resin and 49-100 parts of ethyl acetate, uniformly stirring, adding 1-5 parts of curing agent, stirring for 8-15min to obtain organic silicon leather surface slurry, coating organic glue on a stripping layer, heating to 125-135 ℃ with the wet glue thickness of 100-120 mu m, curing for 40-60s, and forming an organic silicon layer on the surface of the stripping layer.
Step 2: weighing 48-100 parts of silane coupling agent and 48-100 parts of ethyl acetate, stirring for 15-30min, adding 2-5 parts of curing agent, stirring for 10-20min, adding 2-5 parts of platinum catalyst, stirring for 10-20min to obtain adhesive glue, coating the adhesive glue on the surface of the organic silicon layer, wherein the coating moisture content is 3-8 mu m, heating to 145-155 ℃, drying for 3-5min, and forming an adhesive layer on the surface of the organic silicon layer.
And 3, step 3: coating polyurethane acrylate glue on the surface of the bonding layer, wherein the thickness of wet glue is 100-120 mu m, carrying out UV curing at 50-80 ℃ for 5-6min, and forming a polyurethane layer on the surface of the bonding layer; and then tearing off the release layer, baking the release layer for 10-20min at 125-135 ℃ to obtain a leather-like composite layer, and then respectively coating the first protective layer and the second protective layer on the two sides of the leather-like composite layer to obtain the artificial leather-like film.
In summary, the present application has the following beneficial effects:
1. because this application obtains bonding glue through adopting silane coupling agent, ethyl acetate, curing agent, platinum catalyst mixture, this bonding glue has better adhesion, high temperature resistance, water proofness, and then can make quick-witted silicon layer and polyurethane layer bonding stable, and make its imitation leather composite bed that forms have better water proofness, high temperature resistance, and then make artificial imitation leather membrane be used for the goods after, difficult phenomenons such as moisture absorption, rotten appear, and have advantages such as soft handle, toughness is good, water proofness, tear-resistant, puncture-resistant.
2. The organosilicon leather facing paste obtained through organosilicon epoxy resin, curing agent, ethyl acetate is used for preparing the organosilicon layer, makes the organosilicon layer have better water proofness, heat resistance to bond with the laminating layer easily, improve the layer structure stability and water proofness, toughness etc. of the imitation leather composite layer of artificial imitation leather membrane, reduce and appear delaminating, bubble, chap, absorb moisture, phenomenons such as rotting.
3. When the artificial leather-like film is used by introducing isobutyl triethoxy silicon, gamma-tert-butyl peroxy propyl trimethoxy silane and methacryloxypropyl trimethoxy silane, the obtained bonding glue has better bonding property and water resistance, so that a polyurethane layer and an organosilicon layer are bonded stably, and the phenomena of cracking, foaming, moisture absorption, decay and the like of a leather-like composite layer of the artificial leather-like film are reduced.
4. The silane complexing agent obtained by compounding the water white rosin resin, the silane coupling agent, the silicone-acrylic emulsion, the catalyst, the ethanol with the mass fraction of 55-75% and the ethoxylated trimethylolpropane triacrylate has good water resistance, temperature resistance and adhesiveness, can stably adhere the organic silicon layer and the polyurethane layer, and reduces the phenomena of delamination, foaming, cracking, moisture absorption, decay and the like of the artificial leather composite layer in the use process of the artificial leather-like film.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples
Example 1
An artificial leather-like membrane is sequentially provided with a first protective layer, a leather-like composite layer and a second protective layer from the upper surface to the lower surface, wherein the leather-like composite layer is sequentially provided with an organic silicon layer, a binding layer and a polyurethane layer from the inner surface to the outer surface; the laminating layer is obtained by curing the adhesive glue,
the preparation method of the artificial leather-like film is prepared by the following steps:
step 1: weighing 4.9kg of organic silicon epoxy resin and 4.9kg of ethyl acetate, uniformly stirring, adding 0.1kg of curing agent, stirring for 8min to obtain organic silicon leather surface paste, coating organic glue on the stripping layer, heating to 125 ℃ to cure for 40s, and forming an organic silicon layer on the surface of the release layer;
and 2, step: weighing 1.38kg of isobutyl triethoxy silicon, 1.64kg of gamma-tert-butyl peroxy propyl trimethoxy silane, 1.78kg of methacryloxypropyl trimethoxy silane and 4.8kg of ethyl acetate, stirring for 20min, adding 0.2kg of curing agent, stirring for 10min, adding 0.2 part of platinum catalyst, stirring for 10min to obtain bonding glue, coating the bonding glue on the surface of the organic silicon layer, wherein the coating moisture content is 3 mu m, heating to 145 ℃, and drying for 3min to form a bonding layer on the surface of the organic silicon layer;
and 3, step 3: coating polyurethane acrylate glue on the surface of the bonding layer, wherein the thickness of wet glue is 100 mu m, carrying out UV curing at 50 ℃ for 5min, and forming a polyurethane layer on the surface of the bonding layer; and tearing off the release layer, baking the release layer at 125 ℃ for 10min to obtain a leather-like composite layer, and covering the first protective layer and the second protective layer on the two sides of the leather-like composite layer respectively to obtain the artificial leather-like film.
Example 2
Examples 2-3 differ from example 1 in that: the amount of the raw materials used is different, and is specifically shown in table 1;
TABLE 1 amounts (kg) of materials of examples 1-3
Examples 4 to 5
Examples 4-5 differ from example 1 in that: the coating humidity, curing temperature and time were varied and are shown in table 2;
table 2 humidity, curing temperature and time of the coatings of example 1, examples 4-5
Example 6
Example 6 differs from example 1 in that: the silane coupling agent is a silane complexing agent, and the silane complexing agent is prepared by the following steps:
step 1: 3kg of water white rosin resin, 1.38kg of isobutyl triethoxy silicon, 1.64kg of gamma-tert-butyl peroxy propyl trimethoxy silane and 1.78kg of methacryloxypropyl trimethoxy silane are weighed and dissolved in 55 percent by mass of ethanol, and then the mixture is put into a mixing kettle, the temperature is raised to 178 ℃ and the mixture is mixed for 1 hour to obtain a mixture A;
and 2, step: and (2) weighing 0.5kg of ethoxylated trimethylolpropane triacrylate and 1kg of silicone-acrylate emulsion, adding the mixture A obtained in the step (1), stirring for 15min, cooling to 95 ℃, and carrying out reduced pressure distillation for 30min to obtain the silane complexing agent.
Examples 7 to 8
Examples 7-8 differ from example 6 in that: the amounts of the raw materials used were varied and are specifically shown in table 3;
TABLE 3 raw material quantities (kg) of examples 6-8
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that: equal substitution of methacryloxypropyltrimethoxysilane by gamma-tert-butylperoxypropyltrimethoxysilane.
Comparative example 2
Comparative example 2 differs from example 1 in that: isobutyl triethoxy silicon and gamma-tert-butyl peroxy propyl trimethoxy silane are replaced by methacryloxy propyl trimethoxy silane in equal amount.
Comparative example 3
Comparative example 3 differs from example 1 in that: the wet glue thickness of the bonding glue is 1 μm.
Comparative example 4
Comparative example 4 differs from example 1 in that: the wet glue thickness of the organosilicon leather surface paste is 50 mu m.
Comparative example 5
Comparative example 5 differs from example 1 in that: the artificial leather-like film is prepared by the following method:
step 1: weighing 4.9kg of organic silicon epoxy resin and 4.9kg of ethyl acetate, uniformly stirring, adding 0.1kg of curing agent, stirring for 8min to obtain organic silicon leather surface paste, coating organic glue on a stripping layer, heating to 125 ℃ with the wet glue thickness of 100 mu m, curing for 40s, and forming an organic silicon layer on the surface of the stripping layer;
step 2: coating polyurethane acrylate glue on the surface of the organic silicon layer, wherein the thickness of wet glue is 103 mu m, carrying out UV curing at 50 ℃ for 5min, and forming a polyurethane layer on the surface of the organic silicon layer; and tearing off the release layer, baking the release layer at 125 ℃ for 10min to obtain a leather-like composite layer, and covering the first protective layer and the second protective layer on the two sides of the leather-like composite layer respectively to obtain the artificial leather-like film.
Comparative example 6
Comparative example 6 differs from example 1 in that: the water white rosin resin is replaced by ethanol with the mass fraction of 55% in an equivalent manner.
Comparative example 7
Comparative example 7 differs from example 1 in that: the ethoxylated trimethylolpropane triacrylate is equivalently replaced by 55% by mass of ethanol.
Performance test
After the first protective film and the second protective film were peeled off from the artificial leather-like films obtained in examples 1 to 8 and comparative examples 1 to 7, the leather-like composite layer was subjected to the following performance tests, and specific data are shown in Table 4.
Detection method/test method
1. Hardness of pencil
The test was carried out in reference to GB/T6739-1996, and the test was carried out on one side of the silicone layer of the artificial leather-like film, and the specific data are shown in Table 4.
2. Water resistance test
Boiling the leather-like composite layer in an electric heating pot with water at 80 deg.C, observing every 5min, and recording time when surface bubbles and fading occur on the surface; in addition, when the testing time is 100min, the experiment is stopped, and the recorded data is more than 100min, wherein the specific data is shown in table 4.
3. Hydrolysis test
Hydrolysis I: the leather-like composite layer is soaked in 10 percent sodium hydroxide solution at the temperature of 70 ℃, the observation is carried out once every 1 hour, and when the phenomena of shape change, cracking, pulverization and the like occur, the data is recorded. And when the time exceeds 15h, stopping the experiment, and recording data for more than 15h, wherein the specific data is shown in Table 4.
And (2) hydrolyzing: and (3) soaking the leather-like composite layer in 10% sodium hydroxide at normal temperature, observing once every 5h, recording data when the shape change, the cracking and the powdering occur, stopping the experiment when the test time of the test sample exceeds 90h, and recording the data for more than 90h, wherein the specific data are shown in Table 4.
4. Ultraviolet aging
Referring to the national standard GB/T23987, the leather-like composite layer is placed in an ultraviolet aging oven, the leather-like composite layer is observed once every 2 hours, and when cracks, crazing and the like appear on the surface, the aging time is recorded, and specific data are shown in Table 4.
5. Tear strength
With reference to the national standard GBT 529-2008, a XLW-L intelligent electronic tensile testing machine is adopted to detect the tear strength, and the specific data are shown in Table 4;
TABLE 4 Experimental data for examples 1-8 and comparative examples 1-7
The pencil hardness of the examples 1-8 reaches 1 grade, which shows that the artificial leather composite layer obtained by the application is softer, the ultraviolet aging time is more than 72 hours, and the ageing resistance of the artificial leather composite layer is better.
As can be seen from the comparison of example 1 and comparative examples 1-2, when methacryloxypropyltrimethoxysilane, gamma-t-butylperoxypropyltrimethoxysilane and isobutyltriethoxysilane are compounded, the obtained silane compound agent is used for adhesive glue to ensure that the organic silicon layer and the polyurethane layer are bonded stably, and the phenomena of delamination, foaming, cracking, moisture absorption, rotting and the like of the artificial leather compound layer are reduced.
It can be seen from the comparison of example 1 and comparative example 3 that when the wet thickness of the adhesive glue is less than the value in the range of the present application, the water resistance is reduced and it is easily hydrolyzed in alkali.
As can be seen by comparing example 1 and comparative example 4, when the wet thickness of the silicone leather paste is less than the value within the range of the present application, the tear strength decreases, indicating that the range of the present application is a preferable range.
As can be seen from comparison of example 1 and comparative example 5, the water resistance and alkali resistance were lowered when the adhesive layer was not contained, indicating that the adhesive layer was well joined to the polyurethane layer and the silicone layer, and the layer structure of the leather-like composite layer was stabilized.
As can be seen by comparing example 1 with comparative examples 6 to 7, water resistance is reduced when the white rosin resin or ethoxylated trimethylolpropane triacrylate is not added.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. An artificial leather-like membrane is sequentially provided with a first protective layer, a leather-like composite layer and a second protective layer from the upper surface to the lower surface, and is characterized in that the leather-like composite layer is sequentially provided with an organic silicon layer, an adhesive layer and a polyurethane layer from the inner surface to the outer surface; the laminating layer is obtained by curing adhesive glue, and the adhesive glue comprises the following raw materials in parts by weight:
48-100 parts of silane coupling agent
48-100 parts of ethyl acetate
2-5 parts of platinum catalyst
2-5 parts of a curing agent.
2. The artificial leather-like film according to claim 1, wherein: the wet glue thickness of the laminating layer is 3-8 mu m.
3. The artificial leather-like film according to claim 1, wherein: the wet glue thickness of the polyurethane layer is 100-120 mu m.
4. The artificial leather-like film according to claim 1, wherein: the polyurethane layer is obtained by photocuring polyurethane acrylate glue.
5. The artificial leather-like film according to claim 1, wherein: the organic silicon layer is obtained by curing organic silicon leather surface paste, and the organic silicon leather surface paste comprises the following raw materials in parts by weight:
49-100 parts of organic silicon epoxy resin
1-5 parts of curing agent
49-100 parts of ethyl acetate.
6. The artificial leather-like film according to claim 1, wherein: the wet glue thickness of the organic silicon layer is 100-120 mu m.
7. The artificial leather-like film according to claim 5, wherein: the silane coupling agent is a silane complexing agent, and the silane complexing agent comprises the following raw materials in parts by weight:
3-5 parts of water white rosin resin
4.8-10 parts of silane coupling agent
1-3 parts of silicone-acrylic emulsion
0.01 to 0.05 portion of catalyst
60-80 parts of 55-75% ethanol
0.5-1.5 parts of ethoxylated trimethylolpropane triacrylate.
8. The artificial leather-like film according to claim 7, wherein: the silane complexing agent is prepared by the following method:
step 1: weighing water white rosin resin and a silane coupling agent according to parts by weight, dissolving the water white rosin resin and the silane coupling agent in 55-75% of ethanol by mass, dropwise adding a catalyst, heating to 178-188 ℃, and mixing for 1-3 hours to obtain a mixture A;
and 2, step: and (2) weighing the ethoxylated trimethylolpropane triacrylate and the silicone-acrylate emulsion according to the parts by weight, adding the weighed ethoxylated trimethylolpropane triacrylate and the silicone-acrylate emulsion into the mixture A obtained in the step (1), stirring for 15-25min, cooling to 95-105 ℃, and carrying out reduced pressure distillation for 30-50min to obtain the silane complexing agent.
9. The artificial leather-like film according to any one of claims 1 to 8, wherein the silane coupling agent comprises isobutyltriethoxysilicane, γ -t-butylperoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, in a weight ratio of 1 (1.2-1.5) to 1.3-1.8.
10. A method for producing an artificial leather-like film according to any one of claims 1 to 9, comprising the steps of:
step 1: weighing 49-100 parts of organic silicon epoxy resin and 49-100 parts of ethyl acetate, uniformly stirring, adding 1-5 parts of curing agent, stirring for 8-15min to obtain organic silicon leather surface slurry, coating organic glue on a stripping layer, heating to 125-135 ℃ to cure for 40-60s, and forming an organic silicon layer on the surface of the stripping layer;
and 2, step: weighing 48-100 parts of silane coupling agent and 48-100 parts of ethyl acetate, stirring for 15-30min, adding 2-5 parts of curing agent, stirring for 10-20min, adding 2-5 parts of platinum catalyst, stirring for 10-20min to obtain adhesive glue, coating the adhesive glue on the surface of the organic silicon layer with the coating moisture content of 3-8 mu m, heating to 145-155 ℃, drying for 3-5min, and forming an adhesive layer on the surface of the organic silicon layer;
and step 3: coating polyurethane acrylate glue on the surface of the bonding layer, wherein the thickness of the wet glue is 100-120 mu m, carrying out UV curing at 50-80 ℃ for 5-6min, and forming a polyurethane layer on the surface of the bonding layer; and tearing off the release layer, baking the release layer at 125-135 ℃ for 10-20min to obtain a leather-like composite layer, and covering the first protective layer and the second protective layer on the two sides of the leather-like composite layer respectively to obtain the artificial leather-like film.
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