CN116462865A - Composite material for bonding rubber and nickel-plated base material, preparation method thereof and automobile material - Google Patents
Composite material for bonding rubber and nickel-plated base material, preparation method thereof and automobile material Download PDFInfo
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- CN116462865A CN116462865A CN202310598401.0A CN202310598401A CN116462865A CN 116462865 A CN116462865 A CN 116462865A CN 202310598401 A CN202310598401 A CN 202310598401A CN 116462865 A CN116462865 A CN 116462865A
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920002050 silicone resin Polymers 0.000 claims abstract description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007822 coupling agent Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 238000007747 plating Methods 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims abstract 25
- 239000011247 coating layer Substances 0.000 claims abstract 4
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- -1 methyl siloxane Chemical class 0.000 claims description 6
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 24
- 238000005260 corrosion Methods 0.000 abstract description 24
- 239000002184 metal Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920001967 Metal rubber Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a composite material for bonding rubber and a nickel-plated base material, a preparation method thereof and an automobile material. The composite material comprises a nickel plating base material layer, a coupling agent layer, a first bottom coating layer, a second bottom coating layer and a rubber layer which are sequentially laminated from bottom to top; the material of the first primer layer comprises a combination of a titanate and a first silicone resin; the material of the second primer layer includes a combination of an acrylate and a second silicone resin. The composite material for bonding rubber and nickel plating base material provided by the invention has excellent bonding performance and corrosion resistance, and can be widely applied to the field of bonding rubber and nickel plating metal.
Description
Technical Field
The invention belongs to the technical field of rubber and nickel plating base material bonding materials, and particularly relates to a composite material for bonding rubber and nickel plating base material, a preparation method thereof and an automobile material.
Background
Adhesive materials of rubber and metal substrates are widely used in various fields, such as automobile manufacturing, mechanical manufacturing, building materials, and the like. The bond strength of rubber to metal substrates has a critical impact on the performance of the product. The life of a metal rubber part is largely dependent on the quality of the bond between the two materials. However, due to the large difference in the structure and chemical properties of the rubber and metal substrates, chemical bonds are difficult to form, and physical adsorption force is weak, so that the bonding performance between the rubber and metal substrates often has the problems of low bonding strength, poor corrosion resistance and the like.
Currently, researchers have mostly used the following ways to enhance the adhesion of two materials, such as increasing the surface area of the adhesion surface and electrostatic adsorption or increasing the chemical forces between the adhesion materials. CN104371629a discloses a rubber-metal adhesive, which has good adhesion, increases the shock absorption and wear resistance of rubber, and is convenient to use. However, the raw materials of the rubber and metal binder are complex and the preparation is complicated.
Accordingly, there is a need in the art to develop a rubber-to-metal substrate adhesive material that overcomes the above-described problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a composite material for bonding rubber and a nickel-plated base material, a preparation method thereof and an automobile material. The composite material for bonding rubber and nickel plating base material provided by the invention has excellent bonding performance and corrosion resistance, and can be widely applied to the field of bonding rubber and nickel plating metal.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a composite material for bonding rubber and a nickel-plated substrate, wherein the composite material comprises a nickel-plated substrate layer, a coupling agent layer, a first bottom coating, a second bottom coating and a rubber layer which are sequentially laminated from bottom to top;
the material of the first primer layer comprises a combination of a titanate and a first silicone resin;
the material of the second primer layer includes a combination of an acrylate and a second silicone resin.
The composite material for bonding the rubber and the nickel-plated base material has excellent bonding performance and corrosion resistance, and can effectively improve the bonding strength and durability of the rubber nickel-plated metal. On one hand, the coupling agent layer reacts with the first base coat to form the coupled first base coat, so that the coupling agent layer has good surface activity and weather resistance, and the performances of corrosion resistance, adhesive force and the like of the coupling agent layer can be improved. The coupled first primer layer and second primer layer undergo an addition reaction to provide a polymer containing hydroxyl groups and double bonds that can act as an adhesive. On the other hand, the coupling agent layer also undergoes a crosslinking reaction with the polymer containing hydroxyl groups and double bonds, which plays a role in improving the strength and heat resistance of the material.
Preferably, the titanate comprises any one or a combination of at least two of tetrapropyl titanate, tetraethyl titanate, or tetraisopropyl titanate.
Preferably, the first silicone resin comprises any one or a combination of at least two of methyl silicone resin, methyl siloxane resin, methyl vinyl silicone resin, methyl phenyl silicone vinyl resin, methyl phenyl silicone ether resin or methyl phenyl silane resin.
Preferably, the refractive index of the first silicone resin is 1.3 to 1.7, and may be, for example, 1.3, 1.4, 1.5, 1.6, 1.7, or the like.
In the invention, the refractive index of the first organic silicon resin is adjusted, so that the material is more compact and has high strength.
Preferably, the weight average molecular weight of the first silicone resin is 1000-10 ten thousand, for example, 1000, 2000, 3000, 5000, 8000, 1 ten thousand, 2 ten thousand, 3 ten thousand, 4 ten thousand, 5 ten thousand, 6 ten thousand, 7 ten thousand, 8 ten thousand, 9 ten thousand, 10 ten thousand, etc.
In the invention, the viscosity of the material is moderate, the chemical property is stable by adjusting the weight average molecular weight of the first organic silicon resin, the chemical stability and corrosion resistance are reduced if the molecular weight is too low, otherwise, the processing is difficult, air bubbles are generated in the curing process, and the property is influenced.
Preferably, the mass ratio of the titanate to the first silicone resin in the first primer layer is (1-3): (1-3), and for example, may be 1:1, 1:2, 1:3, 2:1, 1:1, 2:3, 3:1, 3:2, etc.
In the invention, the material has good strength, temperature resistance and corrosion resistance by regulating and controlling the mass ratio of the titanate to the first organic silicon resin, and if the mass ratio is too low, the strength and corrosion resistance are reduced, otherwise, the material becomes brittle, the processability is affected, and the material is difficult to mold or process.
Preferably, the acrylate comprises any one or a combination of at least two of methyl acrylate, ethyl acrylate or butyl acrylate.
Preferably, the second silicone resin comprises any one or a combination of at least two of methyl silicone resin, methyl siloxane resin, methyl vinyl silicone resin, methyl phenyl silicone vinyl resin, methyl phenyl silicone ether resin, or methyl phenyl silane resin.
Preferably, the refractive index of the second silicone resin is 1.3 to 1.7, and may be, for example, 1.3, 1.4, 1.5, 1.6, 1.7, or the like.
In the invention, the refractive index of the second organic silicon resin is adjusted, so that the material is more compact and has high strength.
Preferably, the weight average molecular weight of the second silicone resin is 1000-10 ten thousand, for example, 1000, 2000, 3000, 5000, 8000, 1 ten thousand, 2 ten thousand, 3 ten thousand, 4 ten thousand, 5 ten thousand, 6 ten thousand, 7 ten thousand, 8 ten thousand, 9 ten thousand, 10 ten thousand, etc.
In the invention, the viscosity of the material is moderate, the chemical property is stable by adjusting the weight average molecular weight of the second organic silicon resin, the chemical stability and corrosion resistance are reduced if the molecular weight is too low, otherwise, the processing is difficult, air bubbles are generated in the curing process, and the property is influenced.
Preferably, the mass ratio of the acrylic ester to the second silicone resin in the second primer layer is (1-3): (1-3), and for example, may be 1:1, 1:2, 1:3, 2:1, 1:1, 2:3, 3:1, 3:2, etc.
According to the invention, the mass ratio of the acrylic ester to the second organic silicon resin is regulated, so that the material is fully reacted, the obtained composite material has good strength and corrosion resistance, the strength and hardness of the material can be influenced and the material becomes brittle if the mass ratio is too low, otherwise, the corrosion resistance of the material can be reduced, and the processing performance is influenced, so that the material is difficult to form or process.
Preferably, the coupling agent layer is a silane coupling agent layer.
The thickness of the nickel plating base layer is preferably 0.5mm to 10mm, and may be, for example, 0.5mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, or the like.
The thickness of the coupling agent layer is preferably 2 μm to 10. Mu.m, and may be, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or the like.
Preferably, the thickness of the first primer layer is 20 μm to 50 μm, and may be, for example, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, or the like.
Preferably, the thickness of the second primer layer is 20 μm to 50 μm, and may be, for example, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, or the like.
In the invention, the thickness of the first bottom coating and the second bottom coating is regulated, so that the adhesion and corrosion resistance of the material have optimal performance, and the problems of falling off, low adhesion strength, poor corrosion resistance and the like can occur when the thickness is too low, and otherwise, the problems of uneven surface, bubbles and the like can occur.
The rubber layer preferably has a thickness of 0.1mm to 10mm, and may be, for example, 0.1mm, 0.5mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, or the like.
In a second aspect, the present invention provides a method of preparing a composite of rubber according to the first aspect bonded to a nickel-plated substrate, the method comprising the steps of:
coating a coupling agent solution on the surface of the nickel-plated substrate layer to form a coupling agent layer;
coating a first primer solution on the surface of the coupling agent layer to form a first primer layer;
coating a second primer solution on the surface of the first primer layer to form a second primer layer;
and bonding and vulcanizing the second primer layer and rubber to obtain the composite material bonded by the rubber and the nickel-plated substrate.
Preferably, the first primer solution includes a titanate, a first silicone resin, and a first solvent.
Preferably, the first solvent comprises any one or a combination of at least two of toluene, acetone or ethyl acetate.
Preferably, the solid content of the first primer solution is 15 to 30%, for example, 15%, 18%, 20%, 22%, 25%, 28%, 30%, or the like.
According to the invention, the solid content of the first primer solution is regulated, so that the first primer solution is convenient to coat, the prepared composite material has good bonding strength and corrosion resistance, the coating thickness of the material is insufficient if the solid content is too low, the using effect is affected, otherwise, the viscosity of the material is increased, the coating is difficult to coat, the curing speed of the coating is also affected, and the production efficiency is affected.
Preferably, the second primer solution comprises an acrylate, a second silicone resin, and a second solvent;
preferably, the second solvent comprises any one or a combination of at least two of toluene, acetone or ethyl acetate;
preferably, the solid content of the second primer solution is 15 to 30%, for example, 15%, 18%, 20%, 22%, 25%, 28%, 30%, or the like.
In the invention, the solid content of the second primer solution is regulated, so that the second primer solution is convenient to coat, the prepared composite material has good bonding strength and corrosion resistance, the coating thickness of the material is insufficient if the solid content is too low, the using effect is affected, otherwise, the viscosity of the material is increased, the coating is difficult to coat, the curing speed of the coating is also affected, and the production efficiency is affected.
Preferably, the temperature of the vulcanization is 100 ℃ to 180 ℃, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ and the like; the time is 5min to 20min, for example, 5min, 10min, 15min, 20min, etc.
In a third aspect, the present invention provides an automotive material comprising a composite of rubber according to the first aspect bonded to a nickel-plated substrate.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a composite material for bonding rubber and a nickel-plated base material, which has excellent bonding performance and corrosion resistance, and can effectively improve the bonding strength and durability of rubber nickel-plated metal. On one hand, the coupling agent layer reacts with the first base coat to form the coupled first base coat, so that the coupling agent layer has good surface activity and weather resistance, and the performances of corrosion resistance, adhesive force and the like of the coupling agent layer can be improved. The coupled first primer layer and second primer layer undergo an addition reaction to provide a polymer containing hydroxyl groups and double bonds that can act as an adhesive. On the other hand, the coupling agent layer also undergoes a crosslinking reaction with the polymer containing hydroxyl groups and double bonds, which plays a role in improving the strength and heat resistance of the material.
The preparation method of the composite material for bonding the rubber and the nickel-plated base material provided by the invention not only can meet the stability and convenience in mass production, but also can improve the production efficiency.
Drawings
Fig. 1 is a schematic structural diagram of a composite material obtained by bonding rubber and a nickel-plated substrate according to example 1.
Detailed Description
The technical scheme of the invention is further described below by combining the attached drawings and the specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present example provides a composite material in which rubber and a nickel plating substrate are bonded, as shown in fig. 1, the composite material comprising, in order from bottom to top, a nickel plating substrate layer having a thickness of 5mm, a silane coupling agent layer having a thickness of 6 μm, a first primer layer having a thickness of 35 μm, a second primer layer having a thickness of 35 μm, and a rubber layer having a thickness of 5 mm.
The material of the first base coat comprises a combination of titanate (purchased from Nanjing Netherd materials technology Co., ltd.) and methyl phenyl silicone resin (purchased from Jilin Donghu silicone Co., ltd.), wherein the mass ratio of the titanate to the methyl phenyl silicone resin in the first base coat is 1:1; the material of the second primer layer comprises a combination of methyl acrylate and methyl phenyl silicone, wherein the mass ratio of methyl acrylate (available from Langma chemical Co., ltd. In Zhongshan) to methyl phenyl silicone (available from Jilin Donghu silicone Co., ltd.) in the second primer layer is 1:1.
The embodiment also provides a preparation method of the composite material formed by bonding the rubber and the nickel-plated base material, which comprises the following steps:
coating a silane coupling agent solution on the surface of the nickel-plated substrate layer to form a silane coupling agent layer;
mixing titanate, methyl phenyl silicone resin and ethyl acetate to obtain a first primer solution with the solid content of 22%, and coating the surface of the coupling agent layer with the first primer solution to form a first primer layer;
mixing methyl acrylate, methyl phenyl silicone resin and ethyl acetate to obtain a second primer solution with the solid content of 22%, and coating the second primer solution on the surface of the first primer layer to form a second primer layer;
and (3) bonding the second primer layer with rubber and vulcanizing for 15min at 150 ℃ to obtain the composite material bonded by the rubber and the nickel-plated base material.
Example 2
The present example provides a composite material in which rubber and a nickel plating substrate are bonded, the composite material comprising, in order from bottom to top, a nickel plating substrate layer having a thickness of 1mm, a silane coupling agent layer having a thickness of 2 μm, a first primer layer having a thickness of 20 μm, a second primer layer having a thickness of 20 μm, and a rubber layer having a thickness of 1 mm.
The material of the first base coat comprises a combination of titanate (purchased from Nanjing Netherd materials technology Co., ltd.) and methyl phenyl silicone resin (purchased from Jilin Donghu silicone Co., ltd.), wherein the mass ratio of the titanate to the methyl phenyl silicone resin in the first base coat is 1:1; the material of the second primer layer comprises a combination of methyl acrylate (available from the company of Langma chemical industry Co., ltd. In Zhongshan) and methyl phenyl silicone (available from the company of organosilicon Co., ltd. In Jilin Donghu), wherein the mass ratio of methyl acrylate to methyl phenyl silicone in the second primer layer is 1:1.
The embodiment also provides a preparation method of the composite material formed by bonding the rubber and the nickel-plated base material, which comprises the following steps:
coating a silane coupling agent solution on the surface of the nickel-plated substrate layer to form a silane coupling agent layer;
mixing titanate, methyl phenyl silicone resin and ethyl acetate to obtain a first primer solution with a solid content of 15%, and coating the surface of the coupling agent layer with the first primer solution to form a first primer layer;
mixing methyl acrylate, methyl phenyl silicone resin and ethyl acetate to obtain a second primer solution with the solid content of 15%, and coating the second primer solution on the surface of the first primer layer to form a second primer layer;
and (3) bonding the second primer layer with rubber and vulcanizing for 20min at 100 ℃ to obtain the composite material bonded by the rubber and the nickel-plated substrate.
Example 3
The present embodiment provides a composite material in which rubber and a nickel plating substrate are bonded, the composite material comprising, in order from bottom to top, a nickel plating substrate layer having a thickness of 10mm, a silane coupling agent layer having a thickness of 10 μm, a first primer layer having a thickness of 50 μm, a second primer layer having a thickness of 50 μm, and a rubber layer having a thickness of 10mm.
The material of the first base coat comprises a combination of titanate (purchased from Nanjing Netherd materials technology Co., ltd.) and methyl phenyl silicone resin (purchased from Jilin Donghu silicone Co., ltd.), wherein the mass ratio of the titanate to the methyl phenyl silicone resin in the first base coat is 1:1; the material of the second primer layer comprises a combination of methyl acrylate (available from the company of Langma chemical industry Co., ltd. In Zhongshan) and methyl phenyl silicone (available from the company of organosilicon Co., ltd. In Jilin Donghu), wherein the mass ratio of methyl acrylate to methyl phenyl silicone in the second primer layer is 1:1.
The embodiment also provides a preparation method of the composite material formed by bonding the rubber and the nickel-plated base material, which comprises the following steps:
coating a silane coupling agent solution on the surface of the nickel-plated substrate layer to form a silane coupling agent layer;
mixing titanate, methyl phenyl silicone resin and ethyl acetate to obtain a first primer solution with the solid content of 30%, and coating the surface of the coupling agent layer with the first primer solution to form a first primer layer;
mixing methyl acrylate, methyl phenyl silicone resin and ethyl acetate to obtain a second primer solution with the solid content of 30%, and coating the second primer solution on the surface of the first primer layer to form a second primer layer;
and (3) bonding the second primer layer with rubber and vulcanizing for 5min at 180 ℃ to obtain the composite material bonded by the rubber and the nickel-plated base material.
Example 4
This example differs from example 1 in that the mass ratio of titanate to methylphenyl silicone resin in the first primer layer is 1:9, and the other is the same as in example 1.
Example 5
This example differs from example 1 in that the mass ratio of titanate to methylphenyl silicone in the first primer layer is 9:1, and the other is the same as in example 1.
Example 6
This example differs from example 1 in that the mass ratio of methyl acrylate to methyl phenyl silicone in the second primer layer is 1:9, and the other is the same as example 1.
Example 7
This example differs from example 1 in that the mass ratio of methyl acrylate to methyl phenyl silicone in the second primer layer is 9:1, all other things being equal to example 1.
Example 8
This example differs from example 1 in that the thickness of each of the first primer layer and the second primer layer is 10 μm, and the other is the same as example 1.
Example 9
This example differs from example 1 in that the thickness of each of the first primer layer and the second primer layer is 60 μm, and the other is the same as example 1.
Comparative example 1
This comparative example is different from example 1 in that the composite material includes a nickel plating base material layer, a first primer layer, a second primer layer, and a rubber layer, that is, does not contain a silane coupling agent layer, which are laminated in this order from bottom to top, and is otherwise identical to example 1.
Comparative example 2
This comparative example is different from example 1 in that the composite material includes a nickel plating base material layer, a silane coupling agent layer, a second primer layer, and a rubber layer, that is, does not contain a first primer layer, which are laminated in this order from bottom to top, and is otherwise identical to example 1.
Comparative example 3
This comparative example is different from example 1 in that the composite material includes a nickel plating base material layer, a silane coupling agent layer, a first primer layer, and a rubber layer, that is, does not contain a second primer layer, which are laminated in this order from bottom to top, and is otherwise identical to example 1.
Comparative example 4
This comparative example is different from example 1 in that the composite material includes a nickel plating base material layer, a second primer layer, and a rubber layer, that is, a silane coupling agent-free layer and a first primer layer, which are laminated in this order from bottom to top, and the other is the same as example 1.
Comparative example 5
This comparative example is different from example 1 in that the composite material includes a nickel plating base material layer, a first primer layer, and a rubber layer, that is, a silane coupling agent-free layer and a second primer layer, which are laminated in this order from bottom to top, and the other is the same as example 1.
Comparative example 6
This comparative example differs from example 1 in that the titanate in the first primer layer was replaced with an equal amount of methyl phenyl silicone, all other things being equal to example 1.
Comparative example 7
This comparative example differs from example 1 in that methyl acrylate in the second primer layer was replaced with an equal amount of methyl phenyl silicone resin, all other things being equal to example 1.
Test conditions
The rubber-nickel plated substrate bonded composites provided in examples 1 to 9 and comparative examples 1 to 7 were tested as follows:
(1) Corrosion resistance (adhesive strength after corrosion resistance): and (3) carrying out a salt spray test on the finished product for 168 hours, wherein the salt spray standard is referred to GB/T2423.17. Performing an adhesive strength test after the test, and referring to a standard GB/T11211-2009;
(2) Bond strength: reference standard GB/T11211-2009.
The test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the composite material for bonding rubber and nickel plating base material provided by the invention has excellent bonding performance and corrosion resistance, and the preparation method provided by the invention can effectively improve the bonding strength and durability of rubber and nickel plating base material, and particularly when the preferred range of the application is adopted, the corrosion resistance can reach more than 10.2MPa, and the bonding strength can reach more than 11.3MPa as can be seen from examples 1-3.
Examples 4-5 are cases where the mass ratio of titanate to methylphenyl silicone is outside the preferred range of the present application ((1-3): (1-3)), indicating that a composite material having both good strength, temperature resistance and corrosion resistance could not be obtained; examples 6-7 are cases where the mass ratio of methyl acrylate to methyl phenyl silicone is outside the preferred range of the present application ((1-3): (1-3)), indicating poor overall properties of the resulting composite; examples 8-9 are cases where the thickness of the primer layer is outside the preferred range (20 μm to 50 μm) in this application, indicating that it results in a decrease in the adhesive strength and corrosion resistance of the material.
Comparative examples 1-5 demonstrate that the resulting composite has poor overall properties; comparative examples 6 and 7 show that the primer layer prepared from a single methylphenyl silicone resin is less effective than the specific type of resin composition provided by the present invention because the acrylate has good adhesion, can bond rubber and nickel substrates well, and has good temperature resistance. The titanate has good corrosion resistance, and the application range of the material is improved.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The composite material is characterized by comprising a nickel plating substrate layer, a coupling agent layer, a first bottom coating layer, a second bottom coating layer and a rubber layer which are sequentially laminated from bottom to top;
the material of the first primer layer comprises a combination of a titanate and a first silicone resin;
the material of the second primer layer includes a combination of an acrylate and a second silicone resin.
2. The composite material of claim 1, wherein the titanate comprises any one or a combination of at least two of tetrapropyl titanate, tetraethyl titanate, or tetraisopropyl titanate;
preferably, the first silicone resin comprises any one or a combination of at least two of methyl silicone resin, methyl siloxane resin, methyl vinyl silicone resin, methyl phenyl silicone vinyl resin, methyl phenyl silicone ether resin or methyl phenyl silane resin;
preferably, the refractive index of the first silicone resin is 1.3-1.7;
preferably, the weight average molecular weight of the first silicone resin is 1000 to 10 ten thousand;
preferably, the mass ratio of the titanate to the first silicone resin in the first primer layer is (1-3): 1-3.
3. The composite material of claim 1 or 2, wherein the acrylate comprises any one or a combination of at least two of methyl acrylate, ethyl acrylate, or butyl acrylate;
preferably, the second silicone resin comprises any one or a combination of at least two of methyl silicone resin, methyl siloxane resin, methyl vinyl silicone resin, methyl phenyl silicone vinyl resin, methyl phenyl silicone ether resin or methyl phenyl silane resin;
preferably, the refractive index of the second silicone resin is 1.3-1.7;
preferably, the weight average molecular weight of the second silicone resin is 1000 to 10 ten thousand;
preferably, the mass ratio of the acrylic acid ester and the second organic silicon resin in the second base coat is (1-3): 1-3.
4. A composite material according to any one of claims 1 to 3, wherein the coupling agent layer is a silane coupling agent layer.
5. The composite material according to any one of claims 1 to 4, wherein the nickel-plated substrate layer has a thickness of 0.5mm to 10mm;
preferably, the coupling agent layer has a thickness of 2 μm to 10 μm;
preferably, the thickness of the first primer layer is 20 μm to 50 μm;
preferably, the thickness of the second primer layer is 20 μm to 50 μm;
preferably, the thickness of the rubber layer is 0.1 mm-10 mm.
6. A method of preparing a composite of rubber according to any one of claims 1-5 bonded to a nickel-plated substrate, comprising the steps of:
coating a coupling agent solution on the surface of the nickel-plated substrate layer to form a coupling agent layer;
coating a first primer solution on the surface of the coupling agent layer to form a first primer layer;
coating a second primer solution on the surface of the first primer layer to form a second primer layer;
and bonding and vulcanizing the second primer layer and rubber to obtain the composite material bonded by the rubber and the nickel-plated substrate.
7. The method of claim 6, wherein the first primer solution comprises a titanate, a first silicone resin, and a first solvent;
preferably, the first solvent comprises any one or a combination of at least two of toluene, acetone or ethyl acetate;
preferably, the solid content of the first primer solution is 15 to 30%.
8. The method according to claim 6 or 7, wherein the second primer solution comprises an acrylate, a second silicone resin, and a second solvent;
preferably, the second solvent comprises any one or a combination of at least two of toluene, acetone or ethyl acetate;
preferably, the second primer solution has a solids content of 15 to 30%.
9. The method according to any one of claims 6 to 8, wherein the temperature of the vulcanization is 100 ℃ to 180 ℃ for 5min to 20min.
10. An automotive material comprising a composite of a rubber according to any one of claims 1-5 bonded to a nickel-plated substrate.
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| CN202310598401.0A CN116462865A (en) | 2023-05-25 | 2023-05-25 | Composite material for bonding rubber and nickel-plated base material, preparation method thereof and automobile material |
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