WO2022206875A1 - 一种涂料组合物及其制备方法和应用 - Google Patents

一种涂料组合物及其制备方法和应用 Download PDF

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WO2022206875A1
WO2022206875A1 PCT/CN2022/084263 CN2022084263W WO2022206875A1 WO 2022206875 A1 WO2022206875 A1 WO 2022206875A1 CN 2022084263 W CN2022084263 W CN 2022084263W WO 2022206875 A1 WO2022206875 A1 WO 2022206875A1
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Prior art keywords
coating
heat
coating composition
resin
water
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PCT/CN2022/084263
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English (en)
French (fr)
Inventor
李志强
高明亮
于永江
周洪玉
周彬
王鹏飞
宿云婷
Original Assignee
烟台正海磁性材料股份有限公司
烟台高氏新材料科技有限公司
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Application filed by 烟台正海磁性材料股份有限公司, 烟台高氏新材料科技有限公司 filed Critical 烟台正海磁性材料股份有限公司
Priority to EP22779057.3A priority Critical patent/EP4317334A1/en
Priority to JP2023560389A priority patent/JP2024513033A/ja
Priority to KR1020237031801A priority patent/KR20230145469A/ko
Priority to US18/553,611 priority patent/US20240034892A1/en
Publication of WO2022206875A1 publication Critical patent/WO2022206875A1/zh

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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
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0085—Use of fibrous compounding ingredients
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
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    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Definitions

  • the invention belongs to the technical field of coating compositions, and in particular relates to a coating composition and a preparation method and application thereof.
  • epoxy powder resin coatings have been widely used in auto parts.
  • a powder composition of an organic foaming agent is added to the epoxy resin to obtain a cured material containing air bubbles in it, so that the coating has Better mechanical and thermal shock resistance.
  • Heat-expandable resin particles are thermoplastic hollow polymer microspheres composed of a thermoplastic shell and an enclosed liquid alkane gas. When heated, the gas pressure in the microsphere shell increases, the thermoplastic shell softens, and the expanded volume of the microsphere increases significantly.
  • the expanded microsphere coatings made of the above principles are widely used in plastics, wallpapers, adhesives, inks, printing and other fields. Among them, heat-curable powder coatings containing expanded microspheres are usually applied to the bottom of the car to slow down the impact of the rock suddenly bouncing off the bottom of the car during driving.
  • the patent document with publication number DE102014214381A1 provides a coating for the magnetic sheet by applying a heat-curable powder coating to the assembly process of the magnetic sheet of an automobile motor.
  • the coating consists of a heat-curable resin matrix, in which a For heat-expandable microspheres, the softening temperature of the matrix is lower than the reaction temperature of the heat-expandable microspheres, and under the influence of the reaction temperature of the heat-expandable microspheres, the volume of the microspheres increases irreversibly.
  • the resin matrix When the magnetic sheet coated with this coating is heated to a temperature higher than the reaction temperature of the expanded microspheres, the resin matrix first softens, and then the microspheres expand, the softened matrix has no resistance to expansion, and the total coating thickness of the magnetic sheet increases, Fill the gaps between the magnet pieces and the rotor slots so that the magnet pieces are fixed in the rotor slots.
  • heat-curable powder as a coating to solve the fixing of the rotor during the motor assembly process improves the assembly efficiency and processing accuracy.
  • the powder coating process of powder coating faces the problems of safe operation and environmental pollution in actual operation, and the working environment of the motor is harsh, and it needs to maintain the stability and adhesion of the magnetic sheet in an environment of high temperature, high humidity and high speed rotation. , and has high anti-corrosion properties.
  • the present invention provides a coating composition comprising at least 60% of the composition of heat-expandable microspheres with a thickness of the walls of the microspheres ⁇ 5 ⁇ m; for example, 60%, 70% , 75%, 80%; in another example, the thickness of the wall of the microsphere is ⁇ 5 ⁇ m, for example, the thickness of the wall of the microsphere is 5 ⁇ m, 4.5 ⁇ m, 3 ⁇ m, 2 ⁇ m, 1 ⁇ m, 0.5 ⁇ m.
  • the weight percentage of the composition of the heat-expandable microspheres is not more than 20%, exemplarily 15%, 10%, 8%, 6%.
  • the initial thermal expansion temperature T1 of the heat-expandable microspheres is 100 °C ⁇ T1 ⁇ 200°C, for example, T1 is 125 ° C ⁇ T1 ⁇ 180 °C, exemplarily 120°C, 130°C °C, 150°C, 160°C, 170°C, 190°C, or any value between the recited temperature points.
  • the maximum heat-resistant temperature T 2 of the heat - expandable microspheres is 145° C ⁇ T2 ⁇ 215 °C, for example, T2 is 150° C ⁇ T2 ⁇ 205 °C, exemplarily 155°C, 160°C, 165°C, 175°C, 185°C, 195°C, 200°C, or any value between the recited temperature points.
  • the weight proportion of the heat-expandable microspheres with a particle size of 8 ⁇ m ⁇ D ⁇ 20 ⁇ m is not less than 60% of the total weight of the heat-expandable microspheres, such as 60%, 65%, 70%, 80%, 90%, 100%;
  • the weight proportion of the heat-expandable microspheres with a particle size of 10 ⁇ m ⁇ D ⁇ 15 ⁇ m is not less than 50% of the total weight of the heat-expandable microspheres, for example, 55%, 60%, 70%.
  • the heat-expandable microspheres comprise a thermoplastic polymer shell and a liquid alkane enclosed by the thermoplastic polymer shell.
  • the thermoplastic polymer shell is made of a material that can be melted by heat or a material that can be split when heated and expanded.
  • the material of the thermoplastic polymer shell is selected from copolymers of vinylidene chloride and acrylonitrile, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride , polysulfone, vinylidene chloride homopolymer, random terpolymer of vinylidene chloride, acrylonitrile and divinylbenzene, polystyrene or polyvinyl chloride.
  • the liquid alkane may be selected from one, two or more of ethane, propane, isobutane, n-pentane, and isopentane.
  • the composition of the heat-expandable microspheres may also optionally contain a solvent, and the solvent contains at least one organic solvent with a boiling point above 220° C., for example, an organic solvent with a boiling point above 220° C.
  • the solvent may be selected from dodecyl alcohol esters.
  • the solvent in addition to at least one organic solvent with a boiling point above 220° C., the solvent may also contain one or both of ethylene glycol butyl ether and dipropylene glycol butyl ether.
  • the "initial particle size” refers to the median particle size D 50 of the heat-expandable microspheres before the heat-expansion
  • the "thickness” refers to the thickness of the shell wall of the heat-expandable microspheres before the heat-expansion.
  • the above particle size is the volume average diameter, the diameter of the unexpanded heat-expandable microspheres, and the thickness of the shell walls of the unexpanded heat-expandable microspheres can be determined by any method known in the art.
  • the weight ratio of the heat-expandable microspheres to the solvent is (4-40):1, preferably (5-20):1, exemplarily 4:1, 5:1, 6:1, 8:1.2, 7:1, 8:1, 9:1, 10:1, 15:1, 18:1.
  • the composition of heat-expandable microspheres may also optionally contain inorganic fibers.
  • the inorganic fibers are in the form of filaments or sheets (eg, flakes).
  • the inorganic fibers may be selected from one, two or more of nano-aluminosilicate fibers, carbon fibers, boron fibers, and the like.
  • the weight ratio of the inorganic fibers to the solvent is (0-2):1, such as (0.5-1.5):1, exemplarily 0.5:1, 3:5, 0.7:1 , 0.85:1, 0.9:1, 1:1, 1.2:1.
  • the expansion ratio of the composition of the heat-expandable microspheres is 150-300%, for example, 180-250%.
  • the composition of heat-expandable microspheres comprises heat-expandable microspheres, a solvent and inorganic fibers, wherein:
  • the proportion by weight of heat-expandable microspheres with a particle size of 8 ⁇ m ⁇ D ⁇ 20 ⁇ m is not less than 60% of the total weight of the heat-expandable microspheres, such as 60%, 65%, 70%, 80% %, 90%, 100%;
  • the weight proportion of the heat-expandable microspheres with a particle size of 10 ⁇ m ⁇ D ⁇ 15 ⁇ m is not less than 50% of the total weight of the heat-expandable microspheres, such as 55%, 60%, 70%;
  • the thickness of the walls of at least 60% of the heat-expandable microspheres is less than or equal to 3 ⁇ m;
  • the solvent contains at least dodecyl alcohol ester
  • the weight ratio of the heat-expandable microspheres to the solvent is (5-20): 1;
  • the inorganic fibers are nano-aluminosilicate fibers, and the weight ratio of the inorganic fibers to the solvent is (0.5-1.5):1.
  • the composition of heat-expandable microspheres is prepared by mixing raw materials comprising heat-expandable microspheres and a solvent, and optionally inorganic fibers with or without addition.
  • an aqueous thermoplastic resin is further included in the coating composition. Its glass transition temperature is -20°C-60°C.
  • the weight percentage of the water-based thermoplastic resin may be 10-30%, exemplarily 15%, 20%, 25%, 30%.
  • the water-based thermoplastic resin is selected from at least one of water-based acrylic resin and polyurethane resin.
  • an aqueous thermosetting resin is further included in the coating composition.
  • the weight percentage of the water-based thermosetting resin may be 10-40%, exemplarily 15%, 20%, 25%, 30%.
  • the water-based thermosetting resin is selected from at least one of water-based epoxy resin and hydroxyacrylic acid.
  • a hot melt filling resin is further included in the coating composition.
  • the weight percentage of the hot-melt filling resin may be 10-35%, exemplarily 10%, 15%, 20%, 25%, 30%.
  • the hot melt filling resin is selected from at least one of modified chlorinated polyvinyl chloride, polyester resin, polyurethane, polyamide, polyethersulfone, epoxy and polymethylmethacrylate.
  • the content of the water-based thermoplastic resin is lower than the content of the water-based thermosetting resin, and the dosage ratio of the water-based thermoplastic resin to the water-based thermosetting resin is preferably 1:1 to 1:2, Exemplary are 1:1, 1.5:1, 1:2.
  • the amount of the thermoplastic resin is too low, the expansion ratio of the coating composition will be insufficient, and the expansion effect cannot be achieved; but the amount of the thermoplastic resin is too high, and the intumescent coating will be cured, resulting in serious coating problems. shrinkage, and cannot meet the application requirements in motor assembly.
  • the glass transition temperature of the hot-melt filling resin is above 60°C, and preferably a translucent or transparent molten resin can be formed when heated at a high temperature above 130°C, so when the coating composition is used as an expansion binder, it can be used. The coating is bonded to the contact surface to provide support.
  • the ratio of the mass of the thermoplastic resin and the thermosetting resin to the mass of the hot-melt filling resin is 1.5:1 ⁇ 2.5:1, exemplarily 1.5:1, 2:1, 2.5:1 .
  • the coating composition may optionally contain other conventional coating additives.
  • the other conventional coating additives account for 0-15% of the total weight of the coating composition, more preferably 1-10% of the total weight of the coating composition, exemplarily 1%, 2%, 2.5% %, 3%, 4%, 5%.
  • the other conventional coating additives may be selected from curing agents, dispersants, defoaming agents, fillers, cross-linking agents, thickeners, colorants and the like, for example.
  • the coating composition may optionally contain 0.2-1.5% dispersant.
  • the dispersant may be selected from one of nonionic, anionic, and cationic dispersants, etc., to allow the coating composition to form a stable emulsion.
  • the dispersant may be selected from one, two or more of amine salts, quaternary ammonium salts, pyridinium salts, ethylene glycol, and acrylate polymer-type dispersants.
  • the coating composition may optionally contain 1-3% filler to improve the crystallization tendency and solubility of the coating composition, so as to increase the glass transition temperature and hardness of the intumescent coating, and to reduce the post-expansion Shrinkage of the coating.
  • the filler may be selected from one, two or more of insulating carbon black, calcium carbonate, and talc.
  • water is also included in the coating composition.
  • the sum of the weight percentages of the components in the coating composition is 100%.
  • the present invention also provides a method for preparing the above-mentioned coating composition, which comprises mixing the composition of heat-expandable microspheres, water-based thermoplastic resin, water-based thermosetting resin, hot-melt filling resin and optionally other conventional coating additives as described above. Proportional mix.
  • the present invention also provides a method for improving the stability of a heat-expandable coating, comprising applying the above coating composition on a base body, and then heating the base body to obtain a heat-expandable coating.
  • the base body is a magnetic material, such as a motor magnetic sheet used in the manufacture of an engine, preferably a NdFeB magnet.
  • the application may be selected from means known in the art, such as spraying, rolling, brushing, coating, electroplating, dipping, rolling, etc. to apply the coating composition to the substrate body surface method.
  • the method further comprises the step of drying or drying the body of the substrate to which the coating composition is applied.
  • the dry film thickness of the heat-expandable coating is 100-300 ⁇ m, exemplarily 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 300 ⁇ m.
  • the present invention also provides a substrate comprising a coating layer and a substrate body, wherein the coating layer is prepared from the above coating composition.
  • the thickness of the coating is 100-300 ⁇ m, exemplarily 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 300 ⁇ m.
  • the coating is located on the surface of the base body.
  • the base body has the meaning as described above.
  • the coating composition has the meaning as described above.
  • the coating composition of the present invention will rapidly soften and destroy the thin shell sphere in a short time during the heating and expansion process, and with the volatilization of the organic solvent, it will interact with the resin matrix in the coating on the surface and inside of the coating. After the expansion, part of the polymer material wraps the airbag and hardens to form a stable hollow structure. Therefore, the expanded coating has a stable structure, high resistance to thermal shrinkage, high mechanical strength and adhesion, and can be used for fixing high temperature resistant parts, and it can be placed in a high temperature environment for a long time (140-180 °C) can maintain the bonding stability.
  • the high boiling point solvent in the coating composition of the present invention can also reduce the softening and film-forming temperature of the resin in the coating composition, so as to improve the compatibility of the resin.
  • the thermal expansion coating thus obtained has high thermal shrinkage resistance, high mechanical strength and cohesive force after thermal expansion, and can be applied to the fixation of high temperature resistant parts, and can be used for a long time in a high temperature environment (140- 180°C) to maintain the bonding stability.
  • the water-based high-temperature-resistant thermal expansion adhesive coating of the present invention can reduce VOC emissions and environmental hazards caused by solvent-based adhesives.
  • the emulsion or dispersion (liquid with fluidity) of the water-based thermoplastic resin with a glass transition temperature of -20 to 60° C. is used, which is beneficial to improve the film-forming property of the coating at medium and low temperature, so that the coating can be formed at room temperature at room temperature.
  • (15-35°C) can form a complete coating under the conditions of self-drying or medium-low temperature (35-90°C) baking. And can be baked at 150 °C for 96 hours without yellowing or slightly yellowing, and resistant to artificial aging for more than 360 hours.
  • the coating powder is above grade 1.
  • the present invention can form a translucent or transparent molten state with a certain fluidity and cohesive force by adding a small amount of particle size above 800 mesh, glass transition temperature above 60 ° C, and high temperature heating above 130 ° C.
  • Melt-filling resin the resin can improve the compatibility between components at high temperature, so that the prepared coating has sufficient fineness and uniform density after drying at medium and low temperature.
  • baking at a high temperature above 150 ° C for more than 96 hours the color of the coating will basically not change yellow, so the high temperature resistance and service life of the coating can be improved.
  • the paint film can be expanded after the paint film is expanded. , infiltrate with resin, play the role of skeleton support and increase strength in the coating, thereby improving the strength and shrinkage resistance of the intumescent coating.
  • FIG. 1 is a photograph of the unswelled state of the coating of Example 7 (scale 100 ⁇ m, magnified 500 times).
  • FIG. 2 is a photograph of the expanded state of the coating of Example 7 (scale 100 ⁇ m, magnified 500 times).
  • Figure 3 is the state in which the magnet with the expansion coating is assembled to the motor rotor tooling
  • FIG. 4 is a comparison of the infrared spectrum results of the intumescent coating of Example 7 before foaming and after foaming.
  • the heat-expandable microspheres used in the present invention can be purchased from the market, for example, two or more compositions selected from 920DU80, 920DU20, 909DU80, 920DU40, and 461DU40 in the Expancel series of AKZO-Nobel.
  • the weight ratio of expanded microspheres, dodecyl alcohol ester and inorganic fibers in the composition of heat-expandable microspheres is 8:1.2:0.8, that is, the weight percentage of each component is as follows: expanded microspheres 8wt%, dodecyl alcohol Ester 1.2wt%, inorganic fiber 0.8wt%.
  • AKZO-Nobel's Expancel series uses different combinations of heat-expandable microspheres.
  • the microspheres of type 920DU80 and 461DU40 are uniformly mixed according to the weight ratio of 1:2, and the heat-expandable microspheres are obtained by BFS-MAGIC test of German sympatec company.
  • the preparation method of the described coating composition of embodiment 1-5 comprises the steps:
  • the composition of heat-expandable microspheres is prepared by mixing the expanded microspheres, dodecyl alcohol ester and nano-aluminosilicate fibers, and then the composition of heat-expandable microspheres and other coating additives ( Filler insulating carbon black, dispersant ethylene glycol) are added to the water-based coating resin.
  • the coating composition samples 1-5 were formulated according to the proportions in the table below.
  • the content, particle size, wall thickness of the expanded microspheres and the composition and content of the high boiling point solvent in the composition of the heat-expandable microspheres of the present invention will affect the performance of the expanded coating, and the expanded microspheres, solvents, inorganic fibers
  • the amount thereof will also affect the properties of the coating composition, thereby affecting the properties of the intumescent coating made from the coating composition.
  • Coating composition samples 6-11 were prepared by adjusting the composition of the heat-expandable microsphere composition.
  • AKZO-Nobel's Expancel series uses different combinations of heat-expandable microspheres.
  • Microspheres of type 920DU80 and 461DU40 are mixed in a weight ratio of 1:2 to obtain heat-expandable microspheres with an initial particle size of 15.50 ⁇ m.
  • Combination (Example 6);
  • microspheres of models 920DU80, 920DU20 and 920DU40 were mixed according to a weight ratio of 1:1:1 to obtain a combination of microspheres with an initial particle size of 13.10 ⁇ m of heat-expandable microspheres (Examples 7, 8, 9, 10);
  • microspheres of models 920DU80, 909DU80 and 920DU40 were mixed according to a weight ratio of 1:1:1 to obtain a combination of microspheres with an initial particle size of 17.30 ⁇ m of heat-expandable microspheres (Example 11);
  • the waterborne polyurethane resin is 25wt%
  • the waterborne epoxy resin is 35wt%
  • the polyurethane resin is 15wt%
  • the polymethyl methacrylate is 10wt%
  • the water-based silicone resin is 1wt%
  • the dispersant glycol content is 1wt% %
  • filler insulating carbon black 2 wt % thickener acrylic acid 0.5 wt %
  • defoamer polydimethylsiloxane 0.5 wt %
  • the difference is: the composition of the heat-expandable microsphere composition is as follows Table 2 shown in.
  • the preparation method of the coating composition comprises the steps:
  • the average wall thickness of the heat-expandable microspheres is obtained by the scanning electron microscope (SEM) S-4700 of Hitachi, Japan, and is the average value of the wall thicknesses of all microspheres ( ⁇ 20) at the visible interface.
  • the coating composition samples of Examples 1-11 were respectively coated on the surface of the magnetic sheet by means of roller brushing, and the surface coating was dried and hardened under normal temperature conditions.
  • the hardened coating has certain anti-corrosion properties, which facilitates the transportation and protection of the magnetic sheet.
  • After transporting the magnetic sheet to the workplace such as: transporting the magnetic sheet to the motor rotor assembly site, inserting the magnetic sheet assembly into the slot of the motor rotor, placing the motor rotor with the expandable coating in a high temperature oven, Make the temperature in the high-temperature oven reach 180 °C, and heat for 10 minutes.
  • the surface of the magnet is coated with a thermally expandable coating. After being heated, the coating softens and then expands.
  • the expanded microspheres are first heated to expand, and then the microspheres are expanded due to the action of the high-boiling point solvent.
  • the shell softens and cracks, cross-linking with the resin matrix in the coating to form a coating structure with stable support.
  • 1 is the expansion coating
  • 2 is the sintered magnet
  • 3 is the reserved clearance for the motor assembly
  • 4 is the motor tooling.
  • the gap reserved for the motor assembly is 250 ⁇ m
  • the thickness of the intumescent coating is 110 ⁇ m on one side. Assembly at expansion temperature.
  • the coating expands due to heat, fills the reserved gap of the motor, and tightly fixes the magnet in the motor tooling. In this state, the bonding thrust of the magnet in the motor tooling at room temperature and high temperature at 170°C is detected.
  • Fig. 4 is the infrared spectroscopic characterization results of the coating of Example 7 before and after expansion and foaming. It can be seen from the figure that: after the coating is expanded, its wavelength is 1016.36 cm -1 and the wavelength is 725.74 cm -1 The peak intensity of the characteristic peaks at 100°C is significantly enhanced, which may be due to the re-reaction of the resin in the coating during the high-temperature expansion process to form a cross-linked coating structure, so that the coating structure has a stable support.
  • the present invention By rationally optimizing the dosage ratio of the above resins, it was unexpectedly found that when the dosage ratio of water-based thermoplastic resin and water-based thermosetting resin is 1:1 to 1:2, and the total amount of water-based thermoplastic resin and water-based thermosetting resin
  • the dosage ratio of the hot-melt resin is 1.5: When it is within the range of 1 to 2.5:1, the normal temperature bonding thrust of the coating can be improved, especially the bonding thrust of the coating after high temperature expansion, so it can meet the needs of the motor under high temperature working conditions.

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Abstract

本发明公开一种涂料组合物制备方法和应用，所述涂料组合物包含至少60％的微球的壁的厚度≤5μm的可加热膨胀微球的组合物、水性热塑性树脂、水性热固性树脂和热熔填充树脂。本发明的涂料组合物在加热膨胀过程中的短时间内，会迅速软化破坏薄壳球体，随着有机溶剂的挥发，使之在涂层表面及内部与涂层中的树脂基质交联，生成相互交联的网状结构，从而加强涂层空隙支撑，使涂层实现阶梯型膨胀，并且膨胀后部分高分子材料包裹气囊并硬化形成稳定空心结构。从而使膨胀后的涂层具有稳定的结构，较高的抗热收缩性，较高的机械强度和粘结力，可以应用于耐高温零件的固定，且长期置于高温环境下(140-180℃)能够保持粘结稳定性。

Description

一种涂料组合物及其制备方法和应用
本申请要求享有2021年4月2日向中国国家知识产权局提交的，专利申请号为202110362416.8，发明名称为“一种涂料组合物及其制备方法和应用”的在先申请的优先权权益。所述在先申请的全文通过引用的方式结合于本申请中。
技术领域
本发明属于涂料组合物技术领域，尤其涉及一种涂料组合物及其制备方法和应用。
背景技术
随着汽车工业的发展，耐高温胶黏剂被广泛应用于发动机的制造，但大多采用特种溶剂型胶黏剂，并采用注胶、点胶方式施工，用以粘结、固定发动机零件。然而上述方法材料成本高，且对设备工艺要求高，同时还存在加工精度低，容易出现溢胶、污染工件和施胶不匀等缺陷。
近年来，随着新能源汽车工业的快速发展，电机磁片装配作为发动机生产的主要工艺之一，各大汽车制造商除了继续使用传统注胶方式外，都在寻求新能源汽车发动机装配中磁材固定的高效解决方案。
目前，环氧型粉末树脂涂料已经被广泛应用于汽车零部件中。如，公开号为JP1993148429A的专利文献，为了提高膜的耐冲击性，通过在环氧树脂中添加有机发泡剂的粉末组合物，以获得在其内部含有气泡的固化材料，以使涂层具有更好的耐机械冲击性和热冲击性。
又如公开号为US20090270533A1的专利文献，公开了一种可热固化的粉末涂料组合物，该组合物使用具有可交联官能团的树脂、热膨胀性树脂颗粒、固 化剂、纤维状填料，以此获得优异的长期耐腐蚀性以及优异的耐崩裂性、挠性和粘附性的涂膜，以解决成膜过程中固化材料和基材接触面上大量气泡的形成，致使涂层的耐崩裂性和耐腐蚀性差的问题。
热膨胀性树脂颗粒即膨胀微球，是一种热塑性空心聚合物微球，由热塑性外壳和封入的液态烷烃气体组成。当加热时，微球壳内气体压力增加，热塑性外壳软化，微球膨胀体积显著增加。利用上述原理制成的膨胀微球涂料，被广泛应用于塑胶、壁纸、粘合剂、油墨、印花等领域。其中，含有膨胀微球的可热固化粉末涂料通常被应用在汽车底部，以减缓行驶过程中突然弹起的岩石对汽车底部的影响。
如公开号为DE102014214381A1的专利文献，通过将可热固化粉末涂料应用于汽车电机磁片的装配工序，为磁片提供涂层，该涂层由可热固化的树脂基体组成，在基体中嵌入了可热膨胀微球，基质的软化温度低于可热膨胀微球的反应温度，在高于微球反应温度的影响下，微球体积不可逆地增加。将涂覆有该涂层的磁片加热到高于膨胀微球的反应温度时，树脂基质先软化，然后微球膨胀，软化的基质对膨胀没有抵抗力，磁片总的涂层厚度增加，将磁片和转子槽内的空隙填满，致使磁片固定在转子槽内。使用可热固化粉末作为涂层来解决电机装配过程中转子的固定，提高了装配效率和加工精度。但粉末涂料的喷粉工艺在实际操作中面临安全操作及环境污染的问题，且电机的工作环境严苛，需要高温、高湿、高速旋转的环境下，保持磁片的稳固性及粘结性，并具有较高的防腐性能。
发明内容
为了改善上述技术问题，本发明提供一种涂料组合物，所述涂料组合物包含至少60％的微球的壁的厚度≤5μm的可加热膨胀微球的组合物；例如，60％、70％、75％、80％；又如所述微球的壁的厚度≤5μm，比如所述微球的壁的厚度为5μm、4.5μm、3μm、2μm、1μm、0.5μm。
根据本发明的实施方案，所述组合物中，所述可加热膨胀微球的组合物的重量百分比不超过20％，示例性为15％、10％、8％、6％。
根据本发明的实施方案，所述可加热膨胀微球的初始热膨胀温度T 1为100℃≤T 1≤200℃，例如T 1为125℃≤T 1≤180℃，示例性为120℃、130℃、150℃、160℃、170℃、190℃或所列举的温度点之间的任意值。
根据本发明的实施方案，所述可加热膨胀微球的最高耐热温度T 2为145℃≤T 2≤215℃，例如T 2为150℃≤T 2≤205℃，示例性为155℃、160℃、165℃、175℃、185℃、195℃、200℃或所列举的温度点之间的任意值。
本领域技术人员能够理解，所述初始热膨胀温度T 1≤最高耐热温度T 2。
根据本发明的实施方案，粒径为8μm≤D≤20μm的可加热膨胀微球的重量占比不低于所述可加热膨胀微球的总重量的60％，例如为60％、65％、70％、80％、90％、100％；
优选地，粒径为10μm≤D≤15μm的可加热膨胀微球的重量占比不低于所述可加热膨胀微球的总重量的50％，例如为55％、60％、70％。
根据本发明的实施方案，所述可加热膨胀微球包括热塑性聚合物外壳和由所述热塑性聚合物外壳封入的液态烷烃。
例如，所述热塑性聚合物外壳的材质为可热熔的物质或经加热膨胀会裂开的物质制得。比如，所述热塑性聚合物外壳的材质选自偏二氯乙烯和丙烯腈的共聚物，聚乙烯醇，聚乙烯醇缩丁醛，聚甲基丙烯酸甲酯，聚丙烯腈，聚偏二氯乙烯，聚砜，偏二氯乙烯均聚物，偏二氯乙烯、丙烯腈和二乙烯基苯的无规三元共聚物，聚苯乙烯或聚氯乙烯。
根据本发明的实施方案，所述液态烷烃可以选自乙烷、丙烷、异丁烷、正戊烷、异戊烷中的一种、两种或更多种。
根据本发明的实施方案，所述可加热膨胀微球的组合物还可以任选含有溶剂，所述溶剂至少含有一种沸点在220℃以上的有机溶剂，例如所述沸点在220℃以上的有机溶剂可以选自十二碳醇酯。
根据本发明的实施方案，所述溶剂除含有至少一种沸点在220℃以上的有机溶剂外，还可以含有乙二醇丁醚和二丙二醇丁醚中的一种或两种。
本发明中，所述“初始粒径”指可加热膨胀微球在加热膨胀前的中值粒径D 50，所述“厚度”指可加热膨胀微球的壳壁在加热膨胀前的厚度。
上述粒径为体积平均直径，未膨胀可加热膨胀微球的直径、以及未膨胀可加热膨胀微球的壳壁的厚度可通过本领域已知的任何方法来测定。
根据本发明的实施方案，所述可加热膨胀微球与所述溶剂的重量比为(4-40):1，优选(5-20):1，示例性为4:1、5:1、6:1、8:1.2、7:1、8:1、9:1、10:1、15:1、18:1。
根据本发明的实施方案，所述可加热膨胀微球的组合物还可以任选含有无机纤维。例如，所述无机纤维呈纤维丝状或片状(例如薄片状)。比如，所述无机纤维可以选自纳米硅酸铝纤维、碳纤维和硼纤维等中的一种、两种或更多种。无机纤维在所述可加热膨胀微球的组合物膨胀后，可以与下述涂层中的树脂相互浸润，在下述涂层中起骨架支撑和增加强度的作用，以提高膨胀涂层的强度和抗收缩性。
根据本发明的实施方案，所述无机纤维与所述溶剂的重量比为(0-2):1，例如(0.5-1.5):1，示例性为0.5:1、3:5、0.7:1、0.85:1、0.9:1、1:1、1.2:1。
根据本发明的实施方案，所述可加热膨胀微球的组合物的膨胀倍率为150-300％，例如为180-250％。
根据本发明示例性的方案，所述可加热膨胀微球的组合物包含可加热膨胀微球、溶剂和无机纤维，其中：
(1)粒径为8μm≤D≤20μm的可加热膨胀微球的重量占比不低于所述可加热膨胀微球的总重量的60％，例如为60％、65％、70％、80％、90％、100％；
粒径为10μm≤D≤15μm的可加热膨胀微球的重量占比不低于所述可加热膨胀微球的总重量的50％，例如为55％、60％、70％；
(2)所述可加热膨胀微球中至少60％微球的壁的厚度≤3μm；
(3)所述溶剂至少含有十二碳醇酯；
所述可加热膨胀微球与所述溶剂的重量比为(5-20):1；
(4)所述无机纤维为纳米硅酸铝纤维，所述无机纤维与所述溶剂的重量比为(0.5-1.5):1。
根据本发明的实施方案，所述可加热膨胀微球的组合物由包括可加热膨胀微球和溶剂，以及任选加入或不加入的无机纤维的原料混合后制备得到。
根据本发明的实施方案，所述涂料组合物中还包含水性热塑性树脂。其玻璃化温度为-20℃-60℃。例如，所述组合物中，所述水性热塑性树脂的重量百分比可以为10-30％，示例性为15％、20％、25％、30％。
优选地，所述水性热塑性树脂选自水性丙烯酸树脂、聚氨酯树脂中的至少一种。
根据本发明的实施方案，所述涂料组合物中还包含水性热固性树脂。例如，所述组合物中，所述水性热固性树脂的重量百分比可以为10-40％，示例性为15％、20％、25％、30％。
优选地，所述水性热固性树脂选自水性环氧树脂、羟基丙烯酸中的至少一种。
根据本发明的实施方案，所述涂料组合物中还包含热熔填充树脂。例如，所述组合物中，所述热熔填充树脂的重量百分比可以为10-35％，示例性为10％、15％、20％、25％、30％。
优选地，所述热熔填充树脂选自改性氯化聚氯乙烯、聚酯树脂、聚氨酯、聚酰胺、聚醚砜、环氧和聚甲基丙烯酸甲酯中的至少一种。
本发明的涂料组合物中，所述水性热塑性树脂的含量要低于所述水性热固性树脂的含量，优选所述水性热塑性树脂与所述水性热固性树脂的用量比为1:1～1:2，示例性为1:1、1.5:1、1:2。
本发明中，所述热塑性树脂用量过低，会导致涂料组合物的膨胀倍率不足，达不到膨胀效果；但所述热塑性树脂用量过高，又会使膨胀涂层固化后，出现 涂层严重收缩的情况，而无法满足电机装配中的应用需求。所述热熔填充树脂的玻璃化温度在60℃以上，优选在130℃以上高温加热时能形成半透明或透明的熔融态的树脂，因而在涂料组合物作为膨胀粘结剂应用时，可以使涂层与接触面粘结在一起，以提供支撑力。
优选地，所述热塑性树脂和所述热固性树脂的质量之和与所述热熔填充树脂的质量之比为1.5:1～2.5:1，示例性为1.5:1、2:1、2.5:1。
根据本发明的实施方案，所述涂料组合物中，任选的还可以含有其他常规的涂料添加剂。优选地，所述其他常规的涂料添加剂占所述涂料组合物总重量的0-15％，更优选占所述涂料组合物总重量的1-10％，示例性为1％、2％、2.5％、3％、4％、5％。
根据本发明的一个实施方案，所述其他常规的涂料添加剂例如可以选自固化剂、分散剂、消泡剂、填充剂、交联剂、增稠剂、着色剂等。
例如，所述涂料组合物中，任选的可以含有0.2-1.5％的分散剂。例如，所述分散剂可以选自非离子、阴离子及阳离子分散剂等中的一种，以使涂料组合物形成稳定的乳浊液。优选地，所述分散剂可以选自胺盐、季胺盐、吡啶鎓盐、乙二醇、丙烯酸酯高分子型分散剂中的一种、两种或更多种。
例如，所述涂料组合物中，任选的可以含有1-3％的填充剂，用以改善涂料组合物的结晶倾向和溶解度，以提高膨胀涂层的玻璃化温度和硬度，并降低膨胀后涂层的收缩率。优选地，所述填充剂可以选自绝缘炭黑、碳酸钙、滑石粉中的一种、两种或更多种。
根据本发明的实施方案，所述涂料组合物中还包含水。
根据本发明的实施方案，所述涂料组合物中各组分的重量百分比之和为100％。
本发明还提供上述涂料组合物的制备方法，包括将可加热膨胀微球的组合物、水性热塑性树脂、水性热固性树脂、热熔填充树脂及任选的还可以含有的 其他常规的涂料添加剂按上述配比混合。
本发明还提供一种用于提升可加热膨胀涂层稳定性的方法，包括将上述涂料组合物施用在基体本体上，再通过加热基体本体，得到可加热膨胀涂层。
根据本发明的实施方案，所述基体本体为磁材，例如用于发动机制造生产中的电机磁片，优选为钕铁硼磁体。
根据本发明的实施方案，所述施用可以选自本领域已知手段，例如喷涂、滚涂、刷涂、涂覆、电镀、浸蘸、辊涂等将所述涂料组合物施用在所述基体本体表面的方法。
根据本发明的实施方案，所述方法还包括对施用涂料组合物的基体本体进行干燥或使其干燥的步骤。
根据本发明的实施方案，所述可加热膨胀涂层的干膜厚度为100-300μm，示例性为100μm、150μm、200μm、300μm。
本发明还提供一种基体，所述基体包括涂层和基体本体，其中所述涂层由上述涂料组合物制备得到。
根据本发明的实施方案，所述涂层的厚度为100-300μm，示例性为100μm、150μm、200μm、300μm。
根据本发明的实施方案，所述涂层位于所述基体本体的表面。
优选地，所述基体本体具有如上文所述的含义。
优选地，所述涂料组合物具有如上文所述的含义。
本发明的有益效果:
(1)本发明的涂料组合物在加热膨胀过程中的短时间内，会迅速软化破坏薄壳球体，随着有机溶剂的挥发，使之在涂层表面及内部与涂层中的树脂基质交联，生成相互交联的网状结构，从而加强涂层空隙支撑，使涂层实现阶梯型膨胀，并且膨胀后部分高分子材料包裹气囊并硬化形成稳定空心结构。从而使 膨胀后的涂层具有稳定的结构，较高的抗热收缩性，较高的机械强度和粘结力，可以应用于耐高温零件的固定，且长期置于高温环境下(140-180℃)能够保持粘结稳定性。
(2)本发明的涂料组合物中的高沸点溶剂还可以降低涂料组合物中树脂的软化成膜温度，以提高树脂的相容性。且由此制得的热膨胀涂层在热膨胀以后，具有较高的抗热收缩性、较高的机械强度和粘结力，可以应用于耐高温零件的固定，并长期在高温环境下(140-180℃)保持粘结稳定性。
(3)本发明的水性的耐高温热膨胀粘结涂料，能够减少因溶剂型粘结剂造成的VOC排放及环境危害问题。
(4)本发明通过采用玻璃化温度为-20～60℃的水性热塑性树脂的乳液或分散体(具有流动性的液体)，有利于提高涂层的中低温成膜性，使涂层在常温(15-35℃)可自干或中低温(35-90℃)烘烤条件下，能够形成完整的涂层。且能够在150℃下烘烤96h后不黄变或轻微黄变，并耐人工老化超过360h涂层粉化在1级以上。
(5)本发明通过添加少量的粒径在800目以上、玻璃化温度在60℃以上，在130℃以上高温加热下能形成半透明或透明的熔融态的具有一定流动性和粘结力热熔填充树脂，该树脂在高温下能够提高组分之间的相容性，从而使制得的涂层在中低温干燥后，具有足够的细度，均匀致密性。并在150℃以上高温烘烤96h以上，涂层颜色基本不变黄，因此可以提高涂层的耐高温性和使用寿命。
(6)本发明通过采用具有纤维状或薄片状结构的无机物(纳米硅酸路纤维、超细煅烧云母粉)或高硬度的耐高温有机硅类树脂补强剂，能够使漆膜膨胀后，与树脂相互浸润，在涂层中起骨架支撑和增加强度的作用，从而提高膨胀涂层的强度和抗收缩性。
附图说明
图1为实施例7的涂层未膨胀状态的照片(标尺100μm，放大500倍)。
图2为实施例7的涂层膨胀后状态的照片(标尺100μm，放大500倍)。
图3为带有膨胀涂层的磁体装配到电机转子工装的状态；
图中：1、膨胀涂层；2、烧结磁体；3、预留间隙；4、电机工装。
图4为实施例7的涂层膨胀涂层发泡前、发泡后的红外光谱结果对比。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。
本发明采用的可加热膨胀微球可通过市场购买获得，例如选自AKZO-Nobel公司的Expancel系列中920DU80、920DU20、909DU80、920DU40、461DU40的两种及以上组合物。
下表示出了AKZO-Nobel公司的Expancel系列中五种可加热膨胀微球的主要参数。
型号 直径(±1)/μm 初始膨胀温度T 1/℃ 最高耐热温度T 2/℃
920DU80 18-24 123-133 185-195
920DU20 5-9 120-145 155-175
909DU80 18-24 120-130 175-190
920DU40 10-16 123-133 185-195
461DU40 9-15 100-107 145-152
实施例1-5
可加热膨胀微球的组合物中膨胀微球、十二碳醇酯和无机纤维的重量比为8:1.2:0.8，即各组分的重量百分比如下：膨胀微球8wt％，十二碳醇酯1.2wt％， 无机纤维0.8wt％。
如表1所示的可加热膨胀微球的组合物，含有可加热膨胀微球：
AKZO-Nobel公司的Expancel系列中采用不同的可加热膨胀微球的组合，将型号920DU80与461DU40的微球按照重量比1:2均匀混合，德国sympatec公司的BFS-MAGIC测试得到可加热膨胀微球的初始粒径为15.50μm，平均壁厚为2μm，其中90％的微球的壁的厚度≤5μm的可加热膨胀微球的组合物(实施例1-5)；
实施例1-5所述涂料组合物的制备方法，包括如下步骤：
先将膨胀微球、十二碳醇酯和纳米硅酸铝纤维混合制得可加热膨胀微球的组合物，然后在低剪切搅拌下将可加热膨胀微球的组合物和其他涂料添加剂(填充剂绝缘炭黑、分散剂乙二醇)加入到水性涂料树脂中。
按照下表比例，配置所述涂料组合物样品1-5。
表1涂料组成成分表
组分 样品1 样品2 样品3 样品4 样品5
水性丙烯酸树脂(wt％) 20 25 15 35 8
水性环氧树脂(wt％) 30 25 30 10 26
聚酯树脂(wt％) 25 30 30 30 44
绝缘炭黑(wt％) 2 2 2 2 2
乙二醇(wt％) 0.5 0.5 0.5 0.5 0.5
可膨胀组合物(wt％) 10 10 10 10 10
水性有机硅树脂(wt％) 2 1 5 5 4.5
水(wt％) 10.5 6.5 7.5 7.5 9.5
实施例6-11
本发明中可加热膨胀微球的组合物中膨胀微球的含量、粒径、壁厚及高沸点溶剂的成分、含量会对膨胀涂层的性能产生影响，且膨胀微球、溶剂、无机纤维作为可加热膨胀微球的组合物，其用量也会对涂料组合物的性能产生影响，进而影响由该涂料组合物制成的膨胀涂层的性能。
实施例6-11通过调节可加热膨胀微球的组合物的组成，来制备涂料组合物样品6-11。
AKZO-Nobel公司的Expancel系列中采用不同的可加热膨胀微球的组合，将型号920DU80与461DU40的微球按照重量比1:2混合得到可加热膨胀微球的初始粒径为15.50μm的微球组合(实施例6)；
将型号920DU80、920DU20和920DU40的微球按照重量比1:1:1混合得到可加热膨胀微球的初始粒径为13.10μm的微球组合(实施例7、8、9、10)；
将型号920DU80、909DU80和920DU40的微球按照重量比1:1:1混合得到可加热膨胀微球的初始粒径为17.30μm的微球组合(实施例11)；
涂料组合物样品6-11中，水性聚氨酯树脂25wt％，水性环氧树脂35wt％，聚氨酯树脂15wt％，聚甲基丙烯酸甲酯10wt％，水性有机硅树脂1wt％，分散剂乙二醇含量1wt％，填充剂绝缘炭黑2wt％，增稠剂丙烯酸0.5wt％，消泡剂聚二甲基硅氧烷0.5wt％，不同之处在于：可加热膨胀微球的组合物的组成如下表2中所示。
所述涂料组合物的制备方法，包括如下步骤：
先将膨胀微球、十二碳醇酯和纳米硅酸铝纤维混合制得可加热膨胀微球的组合物，然后在低剪切搅拌下将可加热膨胀微球的组合物和其他涂料添加剂(填充剂绝缘炭黑、增稠剂丙烯酸、消泡剂聚二甲基硅氧烷、分散剂乙二醇)加入到水性涂料树脂中。
表2可加热膨胀微球的组合物的组分成分表
Figure PCTCN2022084263-appb-000001
Figure PCTCN2022084263-appb-000002
注：[1]可加热膨胀微球的平均壁厚由日本日立公司扫描电子显微镜(SEM)S-4700测试得到，为可视界面所有微球(≥20个)的壁厚的平均值。
将实施例1-11的涂料组合物样品，采用滚筒刷涂的方式，分别涂覆到磁片表面，在常温条件下，使表面涂层干燥硬化。硬化后的涂层具有一定的防腐性能，便于磁片的运输和保护。将磁片运输到工作场所后，如：将磁片运输到电机转子装配现场，将磁片组建安插到电机转子的卡槽中，将装配有可膨胀涂层的电机转子放置在高温烘箱中，使高温烘箱内的温度达到180℃，加热10min，磁体表面因涂覆可热膨胀涂层，受热后，涂层软化后膨胀，膨胀微球先受热膨胀，后因高沸点溶剂的作用，膨胀微球外壳软化破裂，与涂层中的树脂基质交联，形成具有稳定支撑的涂层结构。
由图1、图2可知，将实施例7的涂料组合物涂覆于烧结钕铁硼磁体表面，经过常温固化后，得到涂覆有膨胀涂层的磁体，结果如图1所示。进一步将涂覆有膨胀涂层的磁体于190℃下进行高温加热10min，涂层膨胀，得到相互交联的涂层结构(见图2)。
如图3所示：1为膨胀涂层，2为烧结磁体，3为电机装配预留间隙，4为电机工装。将带有膨胀涂层1的烧结磁体2(其中：烧结磁体尺寸为40mm*15mm*5mm)装配到电机工装4中，电机装配预留的间隙为250μm，膨胀涂层单面厚度为110μm，在膨胀温度下进行装配。涂层受热膨胀，填充电机预留间隙，将磁体紧密固定在电机工装中。检测该状态下，磁体在电机工装中常温及170℃下高温的粘结推力。
图4为实施例7的涂层膨胀发泡前、发泡后的红外光谱表征结果，从图中可以看出：涂层膨胀后，其在波长为1016.36cm -1处和波长725.74cm -1处的特征峰的峰强度显著增强，这可能是由于涂层在高温膨胀过程中涂层内的树脂再次 发生反应，形成了交联状的涂层结构，从而使得涂层结构具有稳定的支撑。
表3膨胀条件及测试条件
Figure PCTCN2022084263-appb-000003
由表3中结果可知：改变水性热塑性树脂与水性热固性树脂和/或水性热塑性树脂和水性热固性树脂总质量与热熔树脂的用量比，会对涂层固化后的粘结推力产生影响，本发明通过合理优化上述树脂的用量比意外发现当水性热塑性树脂与水性热固性树脂的用量比为1:1～1:2、水性热塑性树脂和水性热固性树脂的总量与热熔树脂的用量比为1.5:1～2.5:1范围内时，可以提高涂层的常温粘结推力，特别是高温膨胀后涂层的粘结推力，因而可以满足电机在高温工作条件下的使用需求。
样品6-11的性能测试结果表明：改变可加热膨胀微球的组合物中膨胀微球、溶剂和无机纤维的用量比，会对高温膨胀后涂层的粘结推力产生影响。
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种涂料组合物，其特征在于，所述涂料组合物包含至少60％的微球的壁的厚度≤5μm的可加热膨胀微球的组合物。
    优选地，所述组合物中，所述可加热膨胀微球的组合物的重量百分比不超过20％。
    优选地，所述可加热膨胀微球的初始热膨胀温度T 1为100℃≤T 1≤200℃。
    优选地，所述可加热膨胀微球的最高耐热温度T 2为145℃≤T 2≤215℃。
    优选地，粒径为8μm≤D≤20μm的可加热膨胀微球的重量占比不低于所述可加热膨胀微球的总重量的60％。
    优选地，粒径为10μm≤D≤15μm的可加热膨胀微球的重量占比不低于所述可加热膨胀微球的总重量的50％。
    优选地，所述可加热膨胀微球包括热塑性聚合物外壳和由所述热塑性聚合物外壳封入的液态烷烃。
    优选地，所述液态烷烃可以选自乙烷、丙烷、异丁烷、正戊烷、异戊烷中的一种、两种或更多种。
  2. 如权利要求1所述的涂料组合物，其特征在于，所述可加热膨胀微球的组合物还可以任选含有溶剂，所述溶剂至少含有一种沸点在220℃以上的有机溶剂，例如所述沸点在220℃以上的有机溶剂可以选自十二碳醇酯。
    优选地，所述可加热膨胀微球与所述溶剂的重量比为(4-40):1。
    优选地，所述可加热膨胀微球的组合物还可以任选含有无机纤维。优选地，所述无机纤维可以选自纳米硅酸铝纤维、碳纤维和硼纤维等中的一种、两种或更多种。
    优选地，所述无机纤维与所述溶剂的重量比为(0-2):1。
    优选地，所述可加热膨胀微球的组合物的膨胀倍率为150-300％。
  3. 如权利要求1或2所述的涂料组合物，其特征在于，所述涂料组合物中还包含水性热塑性树脂。优选地，所述组合物中，所述水性热塑性树脂的重量百分比可以为10-30％。
    优选地，所述水性热塑性树脂选自水性丙烯酸树脂、聚氨酯树脂中的至少一种。
  4. 如权利要求1-3任一项所述的涂料组合物，其特征在于，所述涂料组合物中还包含水性热固性树脂。
    优选地，所述组合物中，所述水性热固性树脂的重量百分比可以为10-40％。
    优选地，所述水性热固性树脂选自水性环氧树脂、羟基丙烯酸树脂中的至少一种。
  5. 如权利要求1-4任一项所述的涂料组合物，其特征在于，所述涂料组合物中还包含热熔填充树脂。
    优选地，所述组合物中，所述热熔填充树脂的重量百分比可以为10-35％。
    优选地，所述热熔填充树脂选自改性氯化聚氯乙烯、聚酯树脂、聚氨酯、聚酰胺、聚醚砜、环氧和聚甲基丙烯酸甲酯中的至少一种。
  6. 如权利要求1-5任一项所述的涂料组合物，其特征在于，所述水性热塑性树脂与所述水性热固性树脂的用量比为1:1～1:2。
    优选地，所述热塑性树脂和所述热固性树脂的质量之和与所述热熔填充树脂的质量之比为1.5:1～2.5:1。
  7. 如权利要求1-6任一项所述的涂料组合物，其特征在于，所述涂料组合物中任选的还可以含有其他常规的涂料添加剂。
    优选地，所述其他常规的涂料添加剂占所述涂料组合物总重量的0-15％。
    优选地，所述其他常规的涂料添加剂例如可以选自固化剂、分散剂、消泡剂、填充剂、交联剂、增稠剂、着色剂等。
    优选地，所述涂料组合物中还包含水。
    优选地，所述涂料组合物中各组分的重量百分比之和为100％。
  8. 权利要求1-7任一项所述的涂料组合物的制备方法，其特征在于，包括将可加热膨胀微球的组合物、水性热塑性树脂、水性热固性树脂、热熔填充树脂及任选的还可以含有的其他常规的涂料添加剂按上述配比混合。
  9. 一种用于提升可加热膨胀涂层稳定性的方法，包括将权利要求1-7任一项所述的涂料组合物和/或权利要求8所述制备方法制得的涂料组合物施用在基体本体上，再通过加热基体本体，得到可加热膨胀涂层。
    优选地，所述基体本体为磁材。
    优选地，所述可加热膨胀涂层的干膜厚度为100-300μm。
  10. 一种基体，所述基体包括涂层和基体本体，其中所述涂层由权利要求1-7任一项所述的涂料组合物和/或权利要求8所述制备方法制得的涂料组合物制备得到。
    优选地，所述涂层的厚度为100-300μm，示例性为100μm、150μm、200μm、300μm。
    优选地，所述涂层位于所述基体本体的表面。
PCT/CN2022/084263 2021-04-02 2022-03-31 一种涂料组合物及其制备方法和应用 WO2022206875A1 (zh)

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CN113764150B (zh) * 2021-06-11 2023-01-10 烟台正海磁性材料股份有限公司 一种可膨胀烧结钕铁硼磁体及其制备方法和应用
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