CN108795137B - Modified temperature sensing agent and reversible temperature indicating coating as well as preparation method and product thereof - Google Patents

Modified temperature sensing agent and reversible temperature indicating coating as well as preparation method and product thereof Download PDF

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CN108795137B
CN108795137B CN201810743916.4A CN201810743916A CN108795137B CN 108795137 B CN108795137 B CN 108795137B CN 201810743916 A CN201810743916 A CN 201810743916A CN 108795137 B CN108795137 B CN 108795137B
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parts
agent
modified
temperature
reversible
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CN108795137A (en
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钟伟杰
李洪武
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Guangzhou Haoyi New Material Technology Co ltd
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Guangzhou Nuowei Chemical Co ltd
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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/26—Thermosensitive paints
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to the field of temperature indicating coatings, and particularly provides a modified temperature sensing agent, a reversible temperature indicating coating, a preparation method of the reversible temperature indicating coating and a product of the reversible temperature indicating coating. The modified temperature sensing agent provided by the invention comprises a temperature sensing agent, a carbon nano tube, a silane coupling agent and a polyurethane modified high-molecular dispersing agent. The carbon nano tube and the temperature sensing agent are subjected to silane heat infiltration treatment, so that the carbon nano tube and the temperature sensing agent generate chemical bonds and interaction, and the temperature sensing agent is stably fixed by the carbon nano tube. According to the reversible temperature indicating coating provided by the invention, the polyurethane modified acrylic acid dispersoid is resin with super-strong adhesive force on plastics, and is used as a main material, the aqueous polyurethane dispersoid has the advantages of high chemical resistance and fullness, and can be used as an auxiliary film forming substance, combined with a modified temperature sensing agent with good wear resistance and chemical resistance, and a wetting agent, a defoaming agent, a thixotropic agent and a neutralizing agent in a reasonable proportion to obtain the reversible temperature indicating coating with excellent performance.

Description

Modified temperature sensing agent and reversible temperature indicating coating as well as preparation method and product thereof
Technical Field
The invention relates to the field of temperature indicating coatings, in particular to a modified temperature sensing agent, a reversible temperature indicating coating, a preparation method and a product thereof.
Background
In modern life, with the development of society, small household appliances occupy more and more important positions in future consumption, such as electric hair dryers, electric rice cookers, egg cookers, patch boards and the like. Some of the small household appliances generate heat, some of the small household appliances generate heat in a short circuit mode, the heat can seriously affect the life of people, most of the existing products are not subjected to temperature display treatment, and the small household appliances are easy to scald or have a fire hazard because the heat is not kept in the world.
The temperature indicating paint is coated on the small household electrical appliance products, so that the temperature of the products and lines can be effectively indicated, and people can take related measures. However, the existing coating is basically a solvent type product, which has the advantages of strong adhesion and high fullness, but is seriously polluted and has great harm to the body of workers. At present, the fullness and some resistances of a small amount of water-based paint can not meet the requirements all the time, and the water-based paint can not be applied on a large scale, so the solvent-based paint is still dominant at present. Therefore, the development of the environment-friendly water-based reversible temperature indicating coating which has high fullness, good defoaming effect, no sagging problem and quick drying has important industrial significance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a modified temperature sensing agent and a preparation method thereof, so as to solve the technical problems of instability, poor wear resistance and poor chemical resistance of the modified temperature sensing agent applied to the surface of a small household appliance in the prior art.
The second purpose of the invention is to provide a reversible temperature indicating coating and a preparation method thereof, so as to solve the problems of low fullness, severe sagging, long drying time and the like of a water-based coating applied to the surface of a small household appliance in the prior art.
The third purpose of the invention is to provide a product containing the reversible temperature indicating coating, which has no harm to human bodies and environment, can accurately indicate temperature, and improves the appearance, wear resistance and chemical resistance of the product.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a modified temperature sensing agent which is prepared from the following raw materials in parts by weight: 9-11 parts of temperature sensing agent, 1-3 parts of carbon nano tube, 1-3 parts of silane coupling agent and 1-3 parts of polyurethane modified polymer dispersing agent.
Further, the feed additive comprises the following raw materials in parts by weight: 9.3-10.7 parts of temperature sensing agent, 1.3-2.7 parts of carbon nano tube, 1.3-2.7 parts of silane coupling agent and 1.3-2.7 parts of polyurethane modified polymer dispersing agent;
preferably, the feed consists of the following raw materials in parts by weight: 9.5-10.5 parts of temperature sensing agent, 1.5-2.5 parts of carbon nano tube, 1.5-2.5 parts of silane coupling agent and 1.5-2.5 parts of polyurethane modified polymer dispersing agent.
Further, the temperature sensing agent is a reversible temperature indicating material, preferably a bisaldehyde condensed arylamine compound, 4- (4-anilinobenzeneazo) benzenesulfonic acid, polythiophene, polyaniline, polysilane, polydiacetylene or NiCl2·2C6H12N4·10H2O；
Preferably, the silane coupling agent comprises dynasylan hydrosil1151, dynasylan hydrosil 2926, or mezzanine MP 200.
The invention provides a preparation method of the modified temperature-sensing agent, which comprises the following steps:
adding the polyurethane modified high-molecular dispersing agent, the powdery temperature-sensing agent and the carbon nano tube into the silane coupling agent, and mixing for 22-26h at 75-85 ℃ under a vacuum condition to obtain the modified temperature-sensing agent.
The invention also provides a reversible temperature indicating coating containing the modified temperature sensing agent, which comprises the following raw materials in parts by weight: 30-50 parts of polyurethane modified acrylic acid dispersoid, 5-40 parts of aqueous polyurethane dispersoid, 0.5-10 parts of modified temperature-sensitive agent, 0.2-0.8 part of wetting agent, 0.5-1 part of defoaming agent, 0.3-1 part of thixotropic agent, 0.1-0.5 part of neutralizing agent and 25-40 parts of solvent.
Further, the feed additive comprises the following raw materials in parts by weight: 35-45 parts of polyurethane modified acrylic acid dispersoid, 10-35 parts of aqueous polyurethane dispersoid, 1-9 parts of modified temperature-sensing agent, 0.3-0.7 part of wetting agent, 0.6-0.9 part of defoaming agent, 0.4-0.9 part of thixotropic agent, 0.2-0.5 part of neutralizing agent and 27-37 parts of solvent;
preferably, the feed consists of the following raw materials in parts by weight: 37-43 parts of polyurethane modified acrylic acid dispersoid, 15-28 parts of aqueous polyurethane dispersoid, 2-7 parts of modified temperature-sensitive agent, 0.4-0.6 part of wetting agent, 0.6-0.8 part of defoaming agent, 0.5-0.8 part of thixotropic agent, 0.2-0.4 part of neutralizing agent and 27-35 parts of solvent;
preferably, the solvent is water.
The invention provides a preparation method of the reversible temperature indicating coating, which comprises the following steps: and uniformly mixing the raw materials to obtain the reversible temperature indicating coating.
The invention finally provides a product containing the reversible temperature indicating coating, wherein the reversible temperature indicating coating and the curing agent in the weight ratio of 30-70:1-10 are uniformly mixed and coated on the surface of a product matrix to obtain the product containing the reversible temperature indicating coating.
Further, the curing agent comprises an HDI trimer curing agent, preferably a polyether type hydrophilic modified HDI trimer curing agent and/or a sulfonate hydrophilic modified HDI trimer curing agent.
Furthermore, the product is a small household appliance, and comprises an electric hair drier, an egg boiler, a patch board or an electric cooker.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a modified temperature sensing agent, which comprises a temperature sensing agent, a carbon nano tube, a silane coupling agent and a polyurethane modified high-molecular dispersing agent. The carbon nano tube and the temperature sensing agent are subjected to silane heat infiltration treatment, so that the carbon nano tube and the temperature sensing agent generate chemical bonds and interaction, and the temperature sensing agent is stably fixed by the carbon nano tube. On one hand, the carbon nano tube can improve the wear resistance and the chemical resistance of the temperature-sensing agent, and on the other hand, under the action of rich electrons of the carbon nano tube, the potential of the temperature-sensing agent changes more rapidly, and the temperature change can be displayed rapidly. The modified temperature sensing agent enlarges the application range of the temperature sensing agent, improves the wear resistance and the chemical resistance of the temperature sensing agent, and is suitable for industrial production and application.
The invention provides a preparation method of the modified temperature sensing agent, which is simple and easy to operate, can be applied industrially and is suitable for large-scale production.
The invention provides a reversible temperature indicating coating, wherein a polyurethane modified acrylic acid dispersoid is resin with super-strong adhesive force on plastics, and the resin is used as a main material, the aqueous polyurethane dispersoid has the advantages of high chemical resistance and fullness, and the polyurethane modified acrylic acid dispersoid is used as an auxiliary film forming substance, is combined with a modified temperature sensing agent with good wear resistance and chemical resistance, and can be mixed with a wetting agent, a defoaming agent, a thixotropic agent and a neutralizing agent in a reasonable proportion to obtain the reversible temperature indicating coating with excellent performance. The reversible temperature indicating coating has the advantages of high drying speed, high fullness, convenient production, no sagging problem and no harm to human bodies and environment.
The invention provides a preparation method of the reversible temperature indicating coating, which is simple and easy to operate, and has low cost because the raw materials are uniformly mixed.
The invention provides a product containing the reversible temperature indicating coating, which can accurately indicate the temperature, warn the temperature, and meanwhile, the product has beautiful appearance, high wear resistance and high chemical resistance.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
The invention provides a modified temperature sensing agent which is prepared from the following raw materials in parts by weight: 9-11 parts of temperature sensing agent, 1-3 parts of carbon nano tube, 1-3 parts of silane coupling agent and 1-3 parts of polyurethane modified polymer dispersing agent.
The carbon nano tube and the temperature sensing agent are subjected to silane heat infiltration treatment, so that the carbon nano tube and the temperature sensing agent generate chemical bonds and interaction, and the temperature sensing agent is stably fixed by the carbon nano tube. On one hand, the carbon nano tube can improve the wear resistance and the chemical resistance of the temperature-sensing agent, and on the other hand, under the action of rich electrons of the carbon nano tube, the potential of the temperature-sensing agent changes more rapidly, and the temperature change can be displayed rapidly. The modified temperature sensing agent enlarges the application range of the temperature sensing agent, improves the wear resistance and the chemical resistance of the temperature sensing agent, and is suitable for industrial production and application.
It should be noted that, by weight, the temperature sensitive agent is typically, but not limited to, 9 parts, 9.5 parts, 10 parts, 10.5 parts or 11 parts; carbon nanotubes are typically, but not limited to, 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts; silane coupling agents are typically, but not limited to, 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts; typically, but not by way of limitation, the polyurethane-modified polymeric dispersant is 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts.
In a preferred embodiment of the invention, the composition consists of the following raw materials in parts by weight: 9.3-10.7 parts of temperature sensing agent, 1.3-2.7 parts of carbon nano tube, 1.3-2.7 parts of silane coupling agent and 1.3-2.7 parts of polyurethane modified polymer dispersing agent.
In a preferred embodiment of the invention, the composition consists of the following raw materials in parts by weight: 9.5-10.5 parts of temperature sensing agent, 1.5-2.5 parts of carbon nano tube, 1.5-2.5 parts of silane coupling agent and 1.5-2.5 parts of polyurethane modified polymer dispersing agent.
The proportion of the raw materials of the modified temperature-sensing agent is further optimized, so that the overall performance of the modified temperature-sensing agent can be improved, and the utilization rate of the raw materials is high.
In a preferred embodiment of the invention, the temperature sensing agent is a reversible temperature indicating material, preferably a bisalicylaldehyde condensed arylamine compound, 4- (4-anilinobenzoylazo) benzenesulfonic acid, polythiophene, polyaniline, polysilane, polydiacetylene or NiCl2·2C6H12N4·10H2O。
In a preferred embodiment of the present invention, the silane coupling agent comprises dynasylan hydrate 1151, dynasylan hydrate 2926, or mezzanine MP 200.
The invention provides a preparation method of the modified temperature sensing agent, which comprises the following steps:
adding the polyurethane modified high-molecular dispersing agent, the powdery temperature-sensing agent and the carbon nano tube into the silane coupling agent, and mixing for 22-26h at 75-85 ℃ under a vacuum condition to obtain the modified temperature-sensing agent.
The method is simple and easy to operate, can be applied to industry, and is suitable for large-scale production. Wherein the vacuum is 0-0.02Pa, the temperature is typically, but not limited to, 75 deg.C, 76 deg.C, 77 deg.C, 78 deg.C, 79 deg.C, 80 deg.C, 81 deg.C, 82 deg.C, 83 deg.C, 84 deg.C or 85 deg.C, and the mixing time is typically, but not limited to, 22, 23, 24, 25 or 26 h.
The invention provides a reversible temperature indicating coating containing the modified temperature sensing agent, which comprises the following raw materials in parts by weight: 30-50 parts of polyurethane modified acrylic acid dispersoid, 5-40 parts of aqueous polyurethane dispersoid, 0.5-10 parts of modified temperature-sensitive agent, 0.2-0.8 part of wetting agent, 0.5-1 part of defoaming agent, 0.3-1 part of thixotropic agent, 0.1-0.5 part of neutralizing agent and 25-40 parts of solvent.
The polyurethane modified acrylic acid dispersoid is resin with super-strong adhesive force on plastics, and is used as a main material, the aqueous polyurethane dispersoid has the advantages of high chemical resistance and fullness, and the reversible temperature indicating coating with excellent performance can be obtained by combining a modified temperature sensing agent with good wear resistance and chemical resistance, a wetting agent, a defoaming agent, a thixotropic agent and a neutralizing agent in a reasonable proportion as an auxiliary film forming substance. The reversible temperature indicating coating has the advantages of high drying speed, high fullness, convenient production, no sagging problem and no harm to human bodies and environment.
It should be noted that, by weight, the polyurethane modified acrylic dispersant is typically, but not limited to, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts or 50 parts; the aqueous polyurethane dispersion is typically, but not limited to, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, or 40 parts; typical but not limiting examples of modifying temperature sensitive agents are 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or 9 parts; wetting agents are typically, but not limited to, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, or 0.8 parts; defoamers are typically, but not limited to, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1 part; thixotropic agents are typically, but not limited to, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1 part; typical but not limiting examples of neutralizing agents are 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, or 0.5 parts; the solvent is typically, but not limited to, 25 parts, 30 parts, 35 parts, or 40 parts.
The polyurethane modified acrylic acid dispersoid is a film-forming substance, the weight is about 50 percent, and the OH percent is 0.8-1.0. The aqueous polyurethane dispersoid is a film-forming substance, the weight is about 35 percent, and the OH percent is 3-5. The wetting agent is a non-ionic wetting agent, preferably BYK349, BYK348, BYK306 or BYK 337. The defoaming agent is mineral oil defoaming agent or organic silicon defoaming agent, preferably s8044, s2667 or ws2844, preferably s 8044. The thixotropic agent is preferably basf 1130. The neutralizing agent is preferably Angus AMP-95. The solvent is water.
In a preferred embodiment of the invention, the composition consists of the following raw materials in parts by weight: 35-45 parts of polyurethane modified acrylic acid dispersoid, 10-35 parts of aqueous polyurethane dispersoid, 1-9 parts of modified temperature-sensing agent, 0.3-0.7 part of wetting agent, 0.6-0.9 part of defoaming agent, 0.4-0.9 part of thixotropic agent, 0.2-0.5 part of neutralizing agent and 27-37 parts of solvent.
In a preferred embodiment of the invention, the material consists of the following raw materials in parts by weight: 37-43 parts of polyurethane modified acrylic acid dispersoid, 15-28 parts of aqueous polyurethane dispersoid, 2-7 parts of modified temperature-sensitive agent, 0.4-0.6 part of wetting agent, 0.6-0.8 part of defoaming agent, 0.5-0.8 part of thixotropic agent, 0.2-0.4 part of neutralizing agent and 27-35 parts of solvent.
The invention provides a preparation method of the reversible temperature indicating coating, which comprises the following steps: and uniformly mixing the raw materials to obtain the reversible temperature indicating coating. The method is simple and easy to operate, and the raw materials are uniformly mixed, so that the cost is low.
The invention finally provides a product containing the reversible temperature indicating coating, wherein the reversible temperature indicating coating and the curing agent in a weight ratio of 30-70:1-10 are uniformly mixed and coated on the surface of a product matrix to obtain the product containing the reversible temperature indicating coating. The product can accurately show temperature, warn the temperature, and meanwhile, the product has attractive appearance and high wear resistance and chemical resistance. The reversible temperature indicating coating is typically, but not limited to, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, or 70 parts; the curing agent is typically, but not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts.
In a preferred embodiment of the invention, the curing agent comprises an HDI trimer curing agent, preferably a polyether type hydrophilic modified HDI trimer curing agent and/or a sulfonate hydrophilic modified HDI trimer curing agent. The weight percent of the polyether modified curing agent is 100, and the NCO percent is 20-22; the weight percent of the sulfonate modified curing agent is 100, and the NCO percent is 17-19.
In a preferred embodiment of the invention, the product is a small household appliance, including a hair dryer, an egg boiler, a patch board or a rice cooker.
In order to facilitate understanding of the technical solutions provided by the present invention, the technical solutions provided by the present invention are further described below with reference to the embodiments.
Example 1
The embodiment provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: 9 parts of disalicylaldehyde arylamine compound, 3 parts of carbon nano tube, 1 part of silane coupling agent and 3 parts of polyurethane modified polymer dispersing agent.
Example 2
The embodiment provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: NiCl2·2C6H12N4·10H2O11 part, carbon nanotube 13 parts of silane coupling agent and 1 part of polyurethane modified polymer dispersant.
Example 3
The embodiment provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: 9.3 parts of polysilane, 2.7 parts of carbon nano tube, 1.3 parts of silane coupling agent and 2.7 parts of polyurethane modified polymer dispersant.
Example 4
The embodiment provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: 10.7 parts of polythiophene, 1.3 parts of carbon nano tubes, 2.7 parts of silane coupling agent and 1.3 parts of polyurethane modified polymer dispersing agent.
Example 5
The embodiment provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: 9.5 parts of polydiacetylene, 2.5 parts of carbon nano tubes, 1.5 parts of silane coupling agent and 2.5 parts of polyurethane modified polymer dispersing agent.
Example 6
The embodiment provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: 10.5 parts of salicylaldehyde arylamine compounds, 1.5 parts of carbon nano tubes, 2.5 parts of silane coupling agents and 1.5 parts of polyurethane modified polymeric dispersants.
Example 7
The embodiment provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: 10 parts of 4- (4-anilinobenzene azo) benzenesulfonic acid, 2 parts of carbon nano tube, 2 parts of silane coupling agent and 2 parts of polyurethane modified high-molecular dispersing agent.
Example 8
The embodiment provides a preparation method of a modified temperature sensing agent, which takes the embodiment 7 as a raw material and comprises the following steps: adding the polyurethane modified high-molecular dispersing agent, the crushed temperature-sensing agent and the carbon nano tube into a silane coupling agent, and mixing for 24 hours at 80 ℃ under the vacuum condition of 0.01Pa to obtain the modified temperature-sensing agent.
Comparative example 1
The comparative example provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: 5 parts of 4- (4-anilinobenzene azo) benzenesulfonic acid, 5 parts of carbon nano tubes, 0.5 part of silane coupling agent and 5 parts of polyurethane modified high-molecular dispersing agent.
The formulation was different from that of example 7.
Comparative example 2
The comparative example provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: 10 parts of 4- (4-anilinobenzene azo) benzenesulfonic acid, 2 parts of silane coupling agent and 2 parts of polyurethane modified high-molecular dispersing agent.
In contrast to example 7, carbon nanotubes were absent.
Comparative example 3
The comparative example provides a modified temperature sensing agent, which comprises the following raw materials in parts by weight: 10 parts of 4- (4-anilinobenzene azo) benzenesulfonic acid, 2 parts of carbon nano tube and 2 parts of polyurethane modified high-molecular dispersing agent.
In contrast to example 7, the silane coupling agent was absent.
Comparative example 4
The comparative example provides a preparation method of a modified temperature-sensitive agent, which comprises the steps of adding the polyurethane modified polymer dispersant in example 7, the crushed temperature-sensitive agent and the carbon nano tube into a silane coupling agent, and mixing for 12 hours at 100 ℃ under normal pressure to obtain the modified temperature-sensitive agent.
Test example 1
Modified temperature sensing agents prepared by the modified temperature sensing agent raw materials of examples 1-7 and comparative examples 1-3 according to the preparation method of example 8 and simultaneously tested with the modified temperature sensing agent of comparative example 4, and the results are as follows:
reversible color change properties
Example 1 Reversibility, high sensitivity, obvious color change in short time
Example 2 Reversibility, high sensitivity, obvious color change in short time
Example 3 Reversibility, high sensitivity, obvious color change in short time
Example 4 Reversibility, high sensitivity, obvious color change in short time
Example 5 Reversibility, high sensitivity, obvious color change in short time
Example 6 Reversibility, high sensitivity, obvious color change in short time
Example 7 Reversibility, high sensitivity, obvious color change in short time
Comparative example 1 Reversibility, slightly poor sensitivity and slightly long color change time
Comparative example 2 Reversibility, poor sensitivity, long time of color change
Comparative example 3 Reversibility, slightly poor sensitivity and slightly long color change time
Comparative example 4 Reversibility, high sensitivity, slightly long color-changing time
Example 9
The embodiment provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in the embodiment 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 30 parts of polyurethane modified acrylic dispersion, 40 parts of aqueous polyurethane dispersion, 0.5 part of modified temperature-sensing agent, 0.5 part of BYK 3490.8 part of pioneer s 80440.5 part of BASF 11301 part of Angus AMP-950.1-0.5 part of water 25 part of the modified temperature-sensing agent.
Example 10
The embodiment provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in the embodiment 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 50 parts of polyurethane modified acrylic acid dispersion, 5 parts of aqueous polyurethane dispersion, 10 parts of modified temperature-sensing agent, BYK 3480.2 parts, firstly 26671 parts, basf 11300.3 parts, Angus AMP-950.5 and 40 parts of water.
Example 11
The embodiment provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in the embodiment 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 35 parts of polyurethane modified acrylic dispersion, 35 parts of aqueous polyurethane dispersion, 1 part of modified temperature-sensing agent, BYK 3060.7 parts, piowss 28440.6 parts, BASF 11300.9 parts, Angus AMP-950.2 parts and 37 parts of water.
Example 12
The embodiment provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in the embodiment 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 45 parts of polyurethane modified acrylic dispersion, 10 parts of aqueous polyurethane dispersion, 9 parts of modified temperature-sensing agent, BYK 3370.3 parts, pioneer s 80440.9 parts, basf 11300.4 parts, Angus AMP-950.5 parts and 27 parts of water.
Example 13
The embodiment provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in the embodiment 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 37 parts of polyurethane modified acrylic dispersion, 28 parts of aqueous polyurethane dispersion, 2 parts of modified temperature-sensing agent, BYK 3490.6 parts, 26670.6 parts of pioneer, 11300.8 parts of BASF, Angus AMP-950.2 and 35 parts of water.
Example 14
The embodiment provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in the embodiment 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 43 parts of polyurethane modified acrylic acid dispersion, 15 parts of aqueous polyurethane dispersion, 7 parts of modified temperature-sensing agent, BYK 3490.4 parts, pioneer ws28440.8 parts, basf 11300.5 parts, Angus AMP-950.2-0.4 parts and 35 parts of water.
Example 15
The embodiment provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in the embodiment 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 40 parts of polyurethane modified acrylic dispersion, 25 parts of aqueous polyurethane dispersion, 6 parts of modified temperature-sensing agent, BYK3490.5 parts, pioneer s 80440.7 parts, basf 11300.6 parts, Angus AMP-950.3 parts and water 32 parts.
Comparative example 5
The comparative example provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in example 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 20 parts of polyurethane modified acrylic acid dispersion, 45 parts of aqueous polyurethane dispersion, 1 part of modified temperature-sensing agent, 3491 parts of BYK, 80440.1 parts of pioneer, 11302 parts of basf, AMP-950.1 parts of Angus and 50 parts of water.
The mixture ratio was different from that in example 15.
Comparative example 6
The comparative example provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in example 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 40 parts of polyurethane modified acrylic acid dispersion, 6 parts of modified temperature sensing agent, BYK3490.5 parts, pioneer s 80440.7 parts, basf 11300.6 parts, Angus AMP-950.3 parts and 32 parts of water.
In comparison with example 15, the aqueous polyurethane dispersant was absent.
Comparative example 7
The comparative example provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in example 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 40 parts of polyurethane modified acrylic dispersion, 25 parts of aqueous polyurethane dispersion, 6 parts of modified temperature-sensing agent, BYK3490.5 parts, 11300.6 parts of basf and 32 parts of water.
In contrast to example 15, the defoamer and neutralizer were absent.
Comparative example 8
The comparative example provides a reversible temperature indicating coating, which comprises the modified temperature sensing agent in example 7, and the reversible temperature indicating coating comprises the following components in parts by weight: 25 parts of aqueous polyurethane dispersion, 6 parts of modified temperature-sensing agent, BYK3490.5 parts, pioneer s 80440.7 parts, basf 11300.6 parts, Angus AMP-950.3 parts and 32 parts of water.
In contrast to example 15, the polyurethane modified acrylic dispersion was absent.
Example 16
This example provides a product containing a reversible thermochromic coating prepared by the following method: the reversible temperature indicating coating and the curing agent are mixed evenly and coated on the surface of the product. The curing agent is polyether modified curing agent.
Example 17
This example provides a product containing a reversible thermochromic coating prepared by the following method: the reversible temperature indicating coating and the curing agent are mixed evenly and coated on the surface of the product. The curing agent is polyether modified curing agent and sulfonate hydrophilic modified HDI tripolymer curing agent with the mass ratio of 1: 1.
Test example 2
The reversible temperature indicating coatings of examples 9 to 15 and comparative examples 5 to 8 were applied to the surface of plastic according to the preparation method of the product of example 16, and were subjected to the performance test, and the results are shown in the following table:
Figure GDA0002436963800000131
Figure GDA0002436963800000141
test example 3
The reversible temperature indicating coating in the embodiment 15 is prepared into a product according to the preparation method of the product in the embodiment 16-17, the curing agent is aziridine as a comparative example and is coated on the surface of auxiliary materials to prepare the product, and the wear resistance and the bonding force are tested, so that the effect of the embodiment 16-17 is obviously better than that of the comparative example, and the best product performance in the embodiment 17 shows that the curing agent provided by the invention can improve the chemical crosslinking of the raw materials of the coating, so that the coating has higher durability.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (14)

1. The modified temperature-sensing agent is characterized by comprising the following raw materials in parts by weight: 9-11 parts of a temperature sensing agent, 1-3 parts of a carbon nano tube, 1-3 parts of a silane coupling agent and 1-3 parts of a polyurethane modified polymer dispersing agent;
the preparation method of the modified temperature sensing agent comprises the following steps:
adding a polyurethane modified high-molecular dispersing agent, a powdery temperature-sensing agent and a carbon nano tube into a silane coupling agent, mixing for 22-26h at 75-85 ℃ under a vacuum condition, carrying out hot-dip wetting treatment on the carbon nano tube and the temperature-sensing agent through the silane coupling agent to enable the carbon nano tube and the temperature-sensing agent to generate chemical bonds and interaction, and stably fixing the temperature-sensing agent by using the carbon nano tube to obtain the modified temperature-sensing agent;
the temperature-sensing agent is a disalicylaldehyde condensed arylamine compound, 4- (4-anilinobenzeneazo) benzenesulfonic acid, polythiophene, polyaniline, polysilane, polydiacetylene or NiCl2·2C6H12N4·10H2O。
2. The modified temperature sensing agent of claim 1, which is prepared from the following raw materials in parts by weight: 9.3-10.7 parts of temperature sensing agent, 1.3-2.7 parts of carbon nano tube, 1.3-2.7 parts of silane coupling agent and 1.3-2.7 parts of polyurethane modified polymer dispersing agent.
3. The modified temperature sensing agent of claim 2, which is characterized by comprising the following raw materials in parts by weight: 9.5-10.5 parts of temperature sensing agent, 1.5-2.5 parts of carbon nano tube, 1.5-2.5 parts of silane coupling agent and 1.5-2.5 parts of polyurethane modified polymer dispersing agent.
4. The modified temperature-sensitive agent according to claim 1 or 2, wherein the silane coupling agent comprises dynasylan hydrosil1151, dynasylan hydrosil 2926 or mezzanine MP 200.
5. A reversible temperature indicating coating containing the modified temperature sensing agent of any one of claims 1-4, which is characterized by comprising the following raw materials in parts by weight: 30-50 parts of polyurethane modified acrylic acid dispersoid, 5-40 parts of aqueous polyurethane dispersoid, 0.5-10 parts of modified temperature-sensitive agent, 0.2-0.8 part of wetting agent, 0.5-1 part of defoaming agent, 0.3-1 part of thixotropic agent, 0.1-0.5 part of neutralizing agent and 25-40 parts of solvent.
6. A reversible temperature indicating coating according to claim 5, characterized by consisting of the following raw materials in parts by weight: 35-45 parts of polyurethane modified acrylic acid dispersoid, 10-35 parts of aqueous polyurethane dispersoid, 1-9 parts of modified temperature-sensing agent, 0.3-0.7 part of wetting agent, 0.6-0.9 part of defoaming agent, 0.4-0.9 part of thixotropic agent, 0.2-0.5 part of neutralizing agent and 27-37 parts of solvent.
7. A reversible temperature indicating coating according to claim 6, characterized by consisting of the following raw materials in parts by weight: 37-43 parts of polyurethane modified acrylic acid dispersoid, 15-28 parts of aqueous polyurethane dispersoid, 2-7 parts of modified temperature-sensitive agent, 0.4-0.6 part of wetting agent, 0.6-0.8 part of defoaming agent, 0.5-0.8 part of thixotropic agent, 0.2-0.4 part of neutralizing agent and 27-35 parts of solvent.
8. A reversible thermochromic paint according to claim 5, characterized in that the solvent is water.
9. The method for preparing the reversible temperature indicating paint according to any one of claims 5 to 8, characterized in that the reversible temperature indicating paint is obtained by uniformly mixing the raw materials.
10. A product containing a reversible thermochromic coating as claimed in any of claims 5 to 8, characterized in that the weight ratio of 30 to 70:1-10 parts of reversible temperature indicating paint and a curing agent are uniformly mixed and coated on the surface of a product matrix to obtain a product containing the reversible temperature indicating paint.
11. The product of claim 10, wherein the curing agent comprises an HDI trimer curing agent.
12. The product of claim 10, wherein the curing agent is a polyether hydrophilic modified HDI trimer curing agent and/or a sulfonate hydrophilic modified HDI trimer curing agent.
13. The product according to any one of claims 10 to 12, wherein the product is a small household appliance.
14. The product of claim 13, wherein the small appliance comprises a hair dryer, an egg boiler, a patch panel, or a rice cooker.
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