CN112659660A - Plastic-coated aluminum profile and preparation method thereof - Google Patents
Plastic-coated aluminum profile and preparation method thereof Download PDFInfo
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Abstract
The application relates to the field of co-extrusion profiles, and particularly discloses a plastic-coated aluminum profile and a preparation method thereof. The plastic-coated aluminum profile comprises an aluminum base material layer and a functional coating layer, and further comprises a bonding layer arranged between the aluminum base material layer and the functional coating layer, wherein the bonding layer is mainly prepared from the following components in parts by weight: polyethylene copolymer: 15-80 parts; maleic anhydride grafted polyolefin: 10-20 parts; antioxidant: 0.5-1 part; nylon resin: 7-13 parts; butyl rubber: 5-12 parts. The utility model provides a mould bonding strength between package aluminium alloy adhesive linkage and the aluminium base material layer is high, and bonding strength between adhesive linkage and the functional coating is high, and then makes functional coating peel off from the aluminium base material layer and drops, improves the composite quality who moulds the package aluminium alloy.
Description
Technical Field
The application relates to the technical field of co-extrusion profiles, in particular to a plastic-coated aluminum profile and a preparation method thereof.
Background
The plastic-coated aluminum profile is a composite profile, and is prepared by compounding a functional coating layer on the surface of an aluminum alloy base material in a melt extrusion mode. When the plastic-coated aluminum is compounded, coating layers with different functions can be selected for preparation, so that the composite section with excellent performance, rich functions and attractive appearance can be obtained, and various use requirements can be met.
In the plastic-coated aluminum profile in the related technology, the functional coating layer is obtained by compounding an adhesive, an anti-ultraviolet agent, a flame retardant and color master batches, and the functional coating layer and the base material are compounded by gluing the adhesive in the functional coating layer and the base material.
In view of the above-mentioned related technologies, the inventor believes that the functional coating layer of the manufactured plastic-coated aluminum profile is easy to fall off in practical application, which affects the beauty and use of the product, and the adhesive strength needs to be improved.
Content of application
In a first aspect, the application provides a plastic-coated aluminum profile, which adopts the following technical scheme:
the utility model provides a mould a packet of aluminium alloy, includes aluminium substrate layer and functional coating, mould a packet of aluminium alloy still including setting up the adhesive linkage between aluminium substrate layer and functional coating, the adhesive linkage is mainly made by the component of following parts by weight:
polyethylene copolymer: 15-80 parts;
maleic anhydride grafted polyolefin: 10-20 parts;
antioxidant: 0.5-1 part;
nylon resin: 7-13 parts;
butyl rubber: 5-12 parts.
By adopting the technical scheme, as the polyethylene copolymer, the nylon resin, the butyl rubber and the maleic anhydride grafted polyolefin are adopted, the raw materials are melted and blended to form an interpenetrating polymer network structure, so that the bonding strength of the bonding layer, the aluminum substrate layer and the functional coating layer is enhanced, and the falling probability of the functional coating layer of the plastic-coated aluminum profile is reduced.
The maleic anhydride grafted polyolefin can be used as an elastomer to improve the cracking resistance of the bonding layer; can also be used as a compatilizer for blending nylon resin and butyl rubber to promote the combination of the nylon resin and the butyl rubber. The three materials are blended to prepare the high-elasticity elastomer with a rubber phase, when an external force is applied to the bonding layer, shearing force is generated at the interface of the bonding layer and the aluminum substrate layer, so that interlayer separation is caused, and the high-elasticity elastomer can reduce the shearing force through elastic deformation and improve the peeling strength. Meanwhile, the elastic body can reduce the internal stress generated by shrinkage in the cooling and curing process of the bonding layer, and prevent the internal stress of the bonding layer from exceeding the adhesive force to cause the reduction of the bonding strength.
In addition, the high-elasticity elastomer can absorb impact energy, reduce the tendency of extension and diffusion of microcracks and improve the impact resistance and the cracking resistance of the plastic-coated aluminum profile;
the maleic anhydride grafted polyolefin has the function of a coupling agent, the organophilic group in the coupling agent can react with organic polymers such as polyethylene copolymer, nylon resin, butyl rubber and the like, the organophilic group in the coupling agent can react with the surface of the aluminum substrate layer to form a molecular bridge function, an interface layer is formed between the aluminum substrate layer and the bonding layer, and the interface layer can transfer stress, so that the bonding strength between the aluminum substrate layer and the bonding layer is enhanced; meanwhile, the method can prevent other media from permeating into the interface, improve the interface state and is beneficial to improving the aging resistance and the stress resistance of the product.
Preferably, the weight ratio of the polyethylene copolymer, the maleic anhydride branched polyolefin, the nylon resin and the butyl rubber is (1-5) to 1 to (0.5-1).
By adopting the technical scheme, the maleic anhydride branched polyolefin, the nylon resin and the butyl rubber form the high-elasticity elastomer of the rubber phase after the bonding layer is cured, and when the content of the high-elasticity elastomer is too high, a weak interface layer is generated between the bonding layer and the aluminum substrate layer, so that the bonding strength between the bonding layer and the aluminum substrate layer is reduced.
Preferably, the adhesive layer further comprises 4-6 parts by weight of styrene-acrylonitrile copolymer.
By adopting the technical scheme, the styrene-acrylonitrile copolymer can introduce strong electron-withdrawing groups into the bonding layer, so that a double-electron layer is formed between the interface of the bonding layer and the aluminum substrate layer, electrostatic attraction is generated, and the bonding strength of the bonding layer and the aluminum substrate layer is improved.
Preferably, the adhesive layer further comprises a leveling agent in 5-10 parts by weight, wherein the leveling agent is composed of sodium humate and polyacrylate in a weight ratio of 3: 2-7.
By adopting the technical scheme, the sodium humate and the polyacrylate contain more polar groups, which is beneficial to the dispersion of polymers and improves the leveling property of the bonding layer.
Preferably, the functional coating layer is mainly prepared from the following components in parts by weight:
adhesive: 20-70 parts of a solvent;
filling agent: 5-20 parts of a solvent;
flame retardant: 15-35 parts;
anti-ultraviolet agent: 0.2-1.3 parts;
antioxidant: 0.2-1 part;
lubricant: 0.2-1.5 parts;
mildew preventive: 0.1-1 part;
color master batch: 2-15 parts.
By adopting the technical scheme, functional auxiliaries such as the uvioresistant agent, the flame retardant, the color master batch and the like are bonded and molded under the action of the adhesive, so that the coating layer has different functional functions and appearances. In the functional coating co-extrusion process, the raw materials of part of the bonding layer are soaked into the functional coating, so that the adhesion of the bonding layer and the functional coating is improved, the composite effect of the functional coating of the plastic-coated aluminum profile is enhanced, and the plastic-coated aluminum profile is not easy to break and fall off.
Preferably, the adhesive is composed of PP resin and terpene resin in a weight ratio of (1-3) to 1 or HDPE resin and terpene resin in a weight ratio of (1-3) to 1.
By adopting the technical scheme, the terpene resin has a tackifying effect and can improve the adhesive strength of the adhesive; the terpene resin also has good compatibility, better binding capacity with other resins and compatibilization effect.
Preferably, the filler consists of talcum powder, modified carbon nano tubes and hydrated silicon dioxide in a mass ratio of (2-5) to (1-3) to 2.
By adopting the technical scheme, the talcum powder can increase the functional coating layer, so that the viscosity of the adhesive is improved; the surface of the hydrated silicon dioxide has adjacent hydroxyl groups, and the adjacent hydroxyl groups respectively generate adsorption with polar substances in the bonding layer and the functional coating layer. The maleic anhydride grafted polyolefin in the bonding layer has polarity, and the terpene resin in the functional coating layer has polarity, so that the hydrated silicon dioxide can generate adsorption with the maleic anhydride grafted polyolefin and the terpene resin, the bonding effect of the bonding layer and the functional coating layer is enhanced, and the composite quality of the plastic-coated aluminum profile is further improved. The carbon nano tube has excellent strength, elasticity and dispersibility, and can effectively enhance the strength and the aging resistance of the functional coating layer.
Preferably, the particle size of the talcum powder is less than 0.1 mu m.
By adopting the technical scheme, compared with the large-diameter particles, the talcum powder particles with the particle size of less than 0.1 mu m have fewer surface defects, more unpaired atoms and high possibility of physical or chemical combination with the polymer, and the interface bonding between the particles and the matrix is enhanced, so that a certain load can be borne, and the effect of enhancing and toughening is achieved.
In a second aspect, the application provides a preparation method of a plastic-coated aluminum profile, which adopts the following technical scheme:
the preparation method of the plastic-coated aluminum profile is prepared according to the following steps:
s1: mixing and granulating the components in the bonding layer to prepare a first premix, and mixing and granulating the components of the functional coating layer to prepare a second premix;
s2: heating the aluminum substrate layer to 90-180 ℃, then melting the first premix, co-extruding and coating the first premix on the surface of the aluminum substrate layer to form a bonding layer;
s3: and melting the second premix, co-extruding and coating the second premix on the surface of the bonding layer to form a functional coating layer, and cooling and solidifying to obtain a plastic-coated aluminum profile finished product.
Through adopting above-mentioned technical scheme, functional coating and adhesive linkage are crowded in-process altogether, and the raw materials of part adhesive linkage soaks functional coating, has improved the adhesion of adhesive linkage and functional coating, and then strengthens the bonding effect of functional coating and aluminium substrate layer, is difficult for peeling off the fracture.
In summary, the present application has the following beneficial effects:
1. in this application, adopt nylon resin, butyl rubber and maleic anhydride grafting polyolefin together to cooperate, obtain high-elastic elastomer, it is filled in the adhesive linkage, can reduce the trend of adhesive linkage microcrack extension, reduces the internal stress of adhesive linkage simultaneously, effectively improves the adhesive linkage and the adhesive strength of aluminium substrate layer for adhesive linkage and aluminium substrate layer's peel strength is showing and is improving.
2. The terpene resin and the hydrated silicon dioxide are preferably adopted in the functional coating layer, and the hydroxyl on the hydrated silicon dioxide can generate adsorption with the polar parts of the maleic anhydride grafted polyolefin and the terpene resin, so that the adhesive strength of the adhesive layer and the functional coating layer is enhanced, and the peeling strength of the adhesive layer and the functional coating layer is obviously improved.
Detailed Description
The present application will be described in further detail below with reference to examples.
Example 1, a plastic-coated aluminum profile, the specific selection of each component and the corresponding formulation thereof are shown in table 1 and prepared according to the following steps:
s1: sequentially adding the raw materials of the adhesive layer according to the sequence of maleic anhydride grafted polyolefin, nylon resin (nylon-66), butyl rubber, polyethylene copolymer and antioxidant, mixing and granulating to prepare a first premix; mixing and granulating the raw materials of the functional coating layer to prepare a second premix;
s2: heating the aluminum substrate layer to 160 ℃, melting the first premix through co-extrusion equipment, and coating the melted first premix on the surface of the aluminum substrate layer to form a bonding layer, thus obtaining a semi-finished product of the plastic-coated aluminum profile;
s3: and immediately melting the semi-finished product of the plastic-coated aluminum profile by using co-extrusion equipment, coating the second premix on the surface of the bonding layer to form a functional coating layer, and cooling and solidifying to obtain the finished product of the plastic-coated aluminum profile.
Wherein the maleic anhydride grafted polyolefin is maleic anhydride grafted PE; the polyethylene copolymer was an ethylene-vinyl acetate copolymer (EVA), and the content of vinyl acetate in the ethylene-vinyl acetate copolymer was 20%.
Examples 2 to 8, a plastic-coated aluminum profile, which is different from example 1 in the specific selection of each component and the corresponding formulation thereof are shown in table 1.
TABLE 1 Components and amounts (kg) of examples 1 to 8
Among them, the particle size of talc referred to in table 1 was 0.05 μm, the particle size of carbon nanotubes was 10nm, and the particle size of hydrated silica was 2 μm.
Example 9, a plastic-coated aluminum profile, differs from example 1 in that hydrated silica is replaced with talc having an equivalent particle size of 0.01 μm.
Example 10, a plastic-coated aluminum profile, differs from example 1 in that the terpene resin is replaced with an equal amount of PP resin.
Example 11, a plastic-coated aluminum profile, differs from example 1 in that the terpene resin is replaced by an equal amount of PP resin in binder and the hydrated silica is replaced by an equal amount of talc having a particle size of 0.01 μm.
Example 12 is a plastic-coated aluminum profile different from example 1 in that the talc powder has a particle size of 1 μm.
Comparative example 1, a plastic-coated aluminum profile, differs from example 11 in that the polyethylene copolymer is replaced with an equal amount of maleic anhydride-grafted polyolefin.
Comparative example 2, a plastic-coated aluminum profile, was different from example 11 in that the nylon resin and the butyl rubber were replaced with the same amount of polyethylene copolymer.
Comparative example 3, a plastic-coated aluminum profile, was different from example 11 in that the same amount of polyethylene copolymer was used instead of the nylon resin, butyl rubber and maleic anhydride-grafted polyolefin.
Comparative example 4, a plastic-coated aluminum profile, differs from example 11 in that the maleic anhydride-grafted polyolefin is replaced with an equal amount of polyethylene copolymer.
Comparative example 5, a plastic steel profile, which adopts the following raw materials in parts by weight: 50 parts of PVC resin powder; 3 parts of fumed silica; 25 parts of calcium carbonate (calcareous filler); 3 parts of a calcium zinc stabilizer; 1 part of stearic acid (lubricant); 1 part of styrene is heated, mixed and cooled to the temperature of 50 ℃ to obtain premix; and heating the premix to 140 ℃ and then extruding and molding to obtain the plastic steel section.
Test 1: and (3) testing the peel strength of the bonding layer and the aluminum substrate layer and the peel strength of the bonding layer and the functional coating layer.
Test subjects: examples 1 to 12 and comparative examples 1 to 5.
The test method comprises the following steps: referring to the test standard in EN319, the test apparatus comprises a wood-plastic panel having an area of 5cm by 5cm and a height of 2cm, an aluminum block having an area of 5cm by 5cm and a height of 0.5cm, and a tie bar fixed to the center of the upper surface of the aluminum block. During testing, the sample is coated on the upper surface of the wood-plastic plate, and the aluminum block is bonded on the upper surface of the wood-plastic plate, so that the sample is bonded between the wood-plastic plate and the aluminum block.
Fixing the wood-plastic plate at the lower clamp of a universal tensile machine, fixing a pull rod with an upper clamp, applying a vertical upward pulling force to the pull rod until a sample layer of the sample is broken or degummed, recording a pulling force value N, dividing the pulling force value N by the area, and converting the pulling force value N into N/mm2I.e. the peel strength value.
TABLE 2 Peel Strength (N/mm) for examples 1 to 12 and comparative examples 1 to 52)
And (3) analyzing test results:
comparing examples 1-2 with comparative examples 1-5, the adhesive layers of examples 1-12 are all added with polyolefin instead of polyethylene copolymer, nylon resin, butyl rubber, maleic anhydride grafted polyolefin and other raw materials, and comparative examples 1-3 lack at least one of the four raw materials; as can be seen from table 2, the peel strength between the adhesion layer and the aluminum substrate layer of the plastic-coated aluminum profiles of examples 1 to 12 is higher than that of comparative examples 1 to 5, and therefore, the adhesion strength between the adhesion layer and the aluminum substrate layer can be improved by adding polyolefin instead of one or more of the polyethylene copolymer, the maleic anhydride grafted polyolefin, the nylon resin, the butyl rubber, and other raw materials to the plastic-coated aluminum raw material.
Comparing comparative example 3 with example 1, compared with comparative example 3, in example 1, nylon resin, butyl rubber and maleic anhydride grafted polyolefin are added, the nylon resin and the butyl rubber can be blended by taking the maleic anhydride grafted polyolefin as a compatilizer to obtain a high-elasticity elastomer in a rubber phase, so that the internal stress generated by shrinkage in the cooling and curing process of the bonding layer can be reduced, the generation of cracks in the shrinkage process can be reduced, and meanwhile, the internal stress of the bonding layer is prevented from exceeding the adhesive force to cause the reduction of the bonding strength. As can be seen from Table 2, the peel strength between the adhesive layer and the aluminum base material layer in example 1 was 6.5kN/mm2Much higher than 4.2N/mm of comparative example 32. Description of the inventionThe peeling strength of the bonding layer and the aluminum substrate layer is obviously improved by adopting nylon resin, butyl rubber and maleic anhydride grafted polyolefin.
Comparing examples 2-8, examples 9-11 with comparative example 4, examples 2-8, no hydrated silica was added in example 9, no terpene resin was added in example 10, no terpene resin and hydrated silica were added in example 11, and no maleic anhydride grafted polyolefin was added in comparative example 4. As can be seen from Table 2, the peel strength between the adhesive layer and the functional coating layer in examples 1 to 8 was 7.4 to 8.1N/mm2In examples 9 to 11, the peel strengths of the adhesive layer and the functional coating layer were 6.4N/mm in this order2、6.3N/mm2And 6.5N/mm2Comparative example 4 is 5.7N/mm2. Examples 9-11 and comparative example 4, which replace one or more of the terpene resin, hydrated silica and maleic anhydride grafted polyolefin, all have reduced peel strength and similar values, show that the use of the terpene resin and hydrated silica can improve the peel strength and adhesive strength of the functional coating layer and the adhesive layer, and the terpene resin and hydrated silica have synergistic effects, and both cooperate to improve the adhesive strength of the adhesive layer and the functional coating layer.
Comparative example 11 to comparative example 4, the adhesive layer of comparative example 4 was formed without the addition of maleic anhydride grafted polyolefin, as compared to example 11. As can be seen from Table 2, the peel strengths of the adhesive layer and the functional coating layer in example 11 and comparative example 4 were 6.5N/mm, respectively2And 5.7N/mm2The maleic anhydride grafted polyolefin added to the adhesive layer can generate a synergistic effect with the terpene resin and the hydrated silicon dioxide in the functional coating layer, and the adhesive strength between the adhesive layer and the functional coating layer can be enhanced.
Test 2: and (3) testing the aging resistance of the plastic-coated aluminum profile:
test subjects: examples 1 to 12 and comparative examples 1 to 5.
The test principle is as follows: ten samples were prepared from the same batch of the section bar in test 1, and after the sample was exposed to a xenon arc lamp for 2000 hours according to the laboratory light source exposure test method and standard in GB/T16422.2, the peel strength of the adhesive layer and the aluminum base material layer and the adhesive layer and the functional coating layer of the sample were measured by the sample method and standard in test 1, and the test results are shown in table 3.
TABLE 3 test results of aging resistance (N/mm) of plastic-coated aluminum profile2)
The analysis of test results in combination with examples 1 to 12 and comparative example 5 and in combination with table 3 shows that the peel strength of examples 1 to 12 of the present application is reduced by 5 to 10% after the aging resistance test, and still has a high peel strength. In particular, the plastic-coated aluminum profile prepared by adopting various antioxidants, uvioresistant agents and carbon nano tubes has better aging resistance.
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 (9)
1. The utility model provides a mould a packet of aluminium alloy, includes aluminium substrate layer and functional coating, its characterized in that, mould a packet of aluminium alloy still including setting up the adhesive linkage between aluminium substrate layer and functional coating, the adhesive linkage is mainly made by the component of following part by weight:
polyethylene copolymer: 15-80 parts;
maleic anhydride grafted polyolefin: 10-20 parts;
antioxidant: 0.5-1 part;
nylon resin: 7-13 parts;
butyl rubber: 5-12 parts.
2. The plastic-covered aluminum profile according to claim 1, characterized in that: the weight ratio of the polyethylene copolymer, the maleic anhydride grafted polyolefin, the nylon resin and the butyl rubber is (1-5): 1, (0.5-1): 0.5-1.
3. The plastic-covered aluminum profile according to claim 1, characterized in that: the adhesive layer further comprises 4-6 parts by weight of styrene-acrylonitrile copolymer.
4. The plastic-covered aluminum profile according to claim 1, characterized in that: the adhesive layer further comprises 5-10 parts by weight of a leveling agent, and the leveling agent consists of sodium humate and polyacrylate in a weight ratio of 3 (2-7).
5. The plastic-covered aluminum profile according to claim 1, characterized in that: the functional coating layer is mainly prepared from the following components in parts by weight:
adhesive: 20-70 parts of a solvent;
filling agent: 5-20 parts of a solvent;
flame retardant: 15-35 parts;
anti-ultraviolet agent: 0.2-1.3 parts;
antioxidant: 0.2-1 part;
lubricant: 0.2-1.5 parts;
mildew preventive: 0.1-1 part;
color master batch: 2-15 parts.
6. The plastic-covered aluminum profile according to claim 5, characterized in that: the adhesive is composed of PP resin and terpene resin in a weight ratio of (1-3): 1 or HDPE resin and terpene resin in a weight ratio of (1-3): 1.
7. The plastic-covered aluminum profile according to claim 5, characterized in that: the filler consists of talcum powder, modified carbon nano tubes and hydrated silicon dioxide in a weight ratio of (2-5) - (1-3) - (2).
8. The plastic-covered aluminum profile according to claim 5, characterized in that: the particle size of the talcum powder is less than 0.1 mu m.
9. The preparation method of the plastic-coated aluminum profile of any one of claims 1 to 8, which is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, mixing and granulating the components in the bonding layer to prepare a first premix, and mixing and granulating the components of the functional coating layer to prepare a second premix;
s2, heating the aluminum substrate layer to 90-180 ℃, melting the first premix, co-extruding and coating the first premix on the surface of the aluminum substrate layer to form a bonding layer;
and S3, melting the second premix, co-extruding and coating the second premix on the surface of the bonding layer to form a functional coating layer, and cooling and solidifying to obtain a plastic-coated aluminum profile finished product.
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CN1662367A (en) * | 2002-06-14 | 2005-08-31 | 陶氏环球技术公司 | Thermoplastic elastomer bonded directly to metal substrate |
CN109111617A (en) * | 2018-06-11 | 2019-01-01 | 台州市港泰铝塑板有限公司 | The fire-retardant sandwich layer of aluminium-plastic panel and aluminium-plastic panel |
CN112920597A (en) * | 2021-01-30 | 2021-06-08 | 上海优泰装饰材料有限公司 | High-stability nylon heat insulation strip for aluminum alloy door and window and preparation method thereof |
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2020
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WO1998050465A1 (en) * | 1997-05-02 | 1998-11-12 | Dsm N.V. | Thermoplastic elastomer composition adapted for adhesion to polar materials |
ATE251989T1 (en) * | 1998-07-31 | 2003-11-15 | Hutchinson | COMPOSITE PRODUCT MADE OF THERMOPLASTIC AND ELASTOMER |
CN1662367A (en) * | 2002-06-14 | 2005-08-31 | 陶氏环球技术公司 | Thermoplastic elastomer bonded directly to metal substrate |
CN109111617A (en) * | 2018-06-11 | 2019-01-01 | 台州市港泰铝塑板有限公司 | The fire-retardant sandwich layer of aluminium-plastic panel and aluminium-plastic panel |
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