CN108795137A - Modified warming agent and reversible thermocoating and preparation method thereof and product - Google Patents
Modified warming agent and reversible thermocoating and preparation method thereof and product Download PDFInfo
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- CN108795137A CN108795137A CN201810743916.4A CN201810743916A CN108795137A CN 108795137 A CN108795137 A CN 108795137A CN 201810743916 A CN201810743916 A CN 201810743916A CN 108795137 A CN108795137 A CN 108795137A
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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
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
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- 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
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- 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
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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
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- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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Abstract
The present invention relates to thermo-color fields, specifically, providing a kind of modified warming agent and reversible thermocoating and preparation method thereof and product.Modified warming agent provided by the invention, including warming agent, carbon nanotube, silane coupling agent and polyurethane-modified macromolecule dispersing agent.Moisten processing carbon nanotube and warming agent by silane hot dipping so that carbon nanotube and warming agent generate chemical bond and interaction, stablize fixed warming agent using carbon nanotube.Reversible thermocoating provided by the invention, polyurethane-modified acrylic acid dispersion is the resin for having on plastics superpower adhesive force, in this, as major ingredient, aqueous polyurethane dispersion has the advantages that endurance and richness are high, as auxiliary film forming matter, in conjunction with the modification warming agent with well wear-resisting and endurance, with wetting agent, the reversible thermocoating that antifoaming agent, thixotropic agent and neutralizer can be had excellent performance under rational proportioning.
Description
Technical field
The present invention relates to thermo-color field, in particular to a kind of modified warming agent and reversible thermocoating and its
Preparation method and product.
Background technology
In the modern life, with the development of society, small household appliances occupy increasingly consequence in following consumption, such as
Hair dryer, electric cooker, poacher, wiring board etc..These small household appliances have plenty of itself and generate heat, have plenty of short circuit thermal, these heat
Amount can all live to people and produce serious influence, and current most products all do not do temperature indicating processing, and ten thousand in an unguarded moment, very
It is easy scald and fire either occurs.
On these small household electrical appliances coating can thermo-color can effectively prompt product and line temperature, people can be with
Take relevant measure.But current coating is essentially solvent based product, solvent based product has strong adhesive force, richness
High advantage, but it is seriously polluted, it is huge to worker's body harm.The a small amount of water paint having at present, richness and some
Resistance is unable to reach always requirement, can not large-scale application, therefore, solvent based coating is still dominant at present.Therefore exploitation one
Kind richness is high, and defoaming effect is good, has without the environment-friendly type aqueous reversible thermocoating of flowing down problems and rapid-curing cutback important
Industrial significance.
In view of this, special propose the present invention.
Invention content
The first object of the present invention is to provide a kind of modified warming agent and preparation method thereof, is answered in the prior art with alleviating
Modification warming agent for small household appliances surface is unstable, wear-resisting and endurance difference technical problem.
The second object of the present invention is to provide a kind of reversible thermocoating and preparation method thereof, to alleviate in the prior art
The problems such as water paint richness applied to small household appliances surface is low, and sagging is serious, and drying time is long.
The third object of the present invention is to provide a kind of product containing above-mentioned reversible thermocoating, the product to human body and
Environment is safe from harm, can accurate temperature indicating, improve the appearance of product, wear-resisting and endurance.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
The present invention provides a kind of modified warming agent, counts, is made of following raw material in parts by weight：9-11 parts of warming agent, carbon
1-3 parts of nanotube, 1-3 parts and polyurethane-modified macromolecule dispersing agent 1-3 parts of silane coupling agent.
Further, it counts, is made of following raw material in parts by weight：9.3-10.7 parts of warming agent, carbon nanotube 1.3-2.7
Part, 1.3-2.7 parts and polyurethane-modified macromolecule dispersing agent 1.3-2.7 parts of silane coupling agent；
Preferably, it counts, is made of following raw material in parts by weight：9.5-10.5 parts of warming agent, carbon nanotube 1.5-2.5
Part, 1.5-2.5 parts and polyurethane-modified macromolecule dispersing agent 1.5-2.5 parts of silane coupling agent.
Further, the warming agent is reversible temperature indicating material, preferably salicylidenedimine, 4- (4-
Anilino- benzeneazo) benzene sulfonic acid, polythiophene, polyaniline, polysilane, polybutadiene alkynes or NiCl2·2C6H12N4·10H2O；
Preferably, the silane coupling agent includes Degussa dynasylan hydrosil 1151, Degussa
Dynasylan hydrosil 2926, Degussa dynasylan hydrosil 2726 step figure MP200.
The present invention provides the preparation method of above-mentioned modified warming agent, includes the following steps：
By polyurethane-modified macromolecule dispersing agent, the warming agent of powdery and carbon nanotube are added in silane coupling agent,
75-85 DEG C of mixing 22-26h under vacuum condition, obtains modified warming agent.
The present invention provides a kind of reversible thermocoating containing above-mentioned modified warming agent again, counts in parts by weight, by following
Raw material forms：30-50 parts of polyurethane-modified acrylic acid dispersion, 5-40 parts of aqueous polyurethane dispersion, modified warming agent 0.5-
10 parts, 0.2-0.8 parts of wetting agent, 0.5-1 parts of antifoaming agent, 0.3-1 parts of thixotropic agent, 25-40 parts of neutralizer 0.1-0.5 and solvent.
Further, it counts, is made of following raw material in parts by weight：35-45 parts of polyurethane-modified acrylic acid dispersion, water
Property 10-35 parts of dispersions of polyurethanes, modified 1-9 parts of warming agent, 0.3-0.7 parts of wetting agent, 0.6-0.9 parts of antifoaming agent, thixotropic agent
0.4-0.9 parts, 27-37 parts of neutralizer 0.2-0.5 and solvent；
Preferably, it counts, is made of following raw material in parts by weight：37-43 parts of polyurethane-modified acrylic acid dispersion, it is aqueous
15-28 parts of dispersions of polyurethanes, modified 2-7 parts of warming agent, 0.4-0.6 parts of wetting agent, 0.6-0.8 parts of antifoaming agent, thixotropic agent
0.5-0.8 parts, 27-35 parts of neutralizer 0.2-0.4 and solvent；
Preferably, solvent is water.
The present invention provides the preparation method of above-mentioned reversible thermocoating, includes the following steps：Each raw material is uniformly mixed
To the reversible thermocoating.
The present invention finally provides a kind of product containing reversible thermocoating, is 30-70 by weight ratio:The reversible of 1-10 is shown
Thermo-paint is uniformly mixed with curing agent, and the product containing reversible thermocoating is obtained coated in product matrix surface.
Further, the curing agent includes HDI trimer curing agent, preferably polyether-type hydrophilic modifying HDI trimer
Curing agent and/or sulfonate hydrophilic modifying HDI trimer curing agent.
Further, the product is small household appliances, including hair dryer, poacher, wiring board or electric cooker.
Compared with prior art, beneficial effects of the present invention are：
The present invention provides a kind of modified warming agent, including warming agent, carbon nanotube, silane coupling agent and polyurethane-modified height
Dispersal agent molecule.Moisten processing carbon nanotube and warming agent by silane hot dipping so that carbon nanotube and warming agent generate chemical bond
And interaction, stablize fixed warming agent using carbon nanotube.On the one hand, carbon nanotube can improve the wear-resisting of warming agent and
Endurance, on the other hand, under the action of carbon nanotube is rich in electronics, the potential change of warming agent is rapider, can be rapid
Displays temperature variation.The modification warming agent expands the application range of warming agent, improves wear-resisting and resistance toization of warming agent
Property, it is suitble to industrialized production and application.
The present invention provides a kind of preparation method of above-mentioned modified warming agent, and this method is simple and easy to operate, can with commercial Application,
It is suitble to large-scale production.
The present invention provides a kind of reversible thermocoating, and polyurethane-modified acrylic acid dispersion is to have superpower attachment on plastics
The resin of power, in this, as major ingredient, aqueous polyurethane dispersion has the advantages that endurance and richness are high, forms a film as auxiliary
Substance is being closed in conjunction with good wear-resisting and endurance modification warming agent with wetting agent, antifoaming agent, thixotropic agent and neutralizer
The reversible thermocoating that can be had excellent performance under the proportioning of reason.The reversible thermocoating rate of drying is fast, and richness is high, raw
Production is convenient, is safe from harm without flowing down problems, while to human body and environment.
The present invention provides a kind of preparation method of above-mentioned reversible thermocoating, and this method is simple to operation, and raw material is carried out
It is uniformly mixed, it is at low cost.
The present invention provides a kind of product containing above-mentioned reversible thermocoating, the product can accurate temperature indicating, temperature is made
Go out warning, while product appearance is beautiful, wear-resisting and endurance is high.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.
The present invention provides a kind of modified warming agent, counts, is made of following raw material in parts by weight：9-11 parts of warming agent, carbon
1-3 parts of nanotube, 1-3 parts and polyurethane-modified macromolecule dispersing agent 1-3 parts of silane coupling agent.
Moisten processing carbon nanotube and warming agent by silane hot dipping so that carbon nanotube and warming agent generate chemical bond and phase
Fixed warming agent is stablized in interaction using carbon nanotube.On the one hand, carbon nanotube can improve wear-resisting and resistance toization of warming agent
Property, on the other hand, under the action of carbon nanotube is rich in electronics, the potential change of warming agent is rapider, can rapidly show
The variation of temperature displaying function.The modification warming agent expands the application range of warming agent, improves the wear-resisting and endurance of warming agent, fits
Close industrialized production and application.
It should be noted that count in parts by weight, it is 9 parts that warming agent is typical but non-limiting, 9.5 parts, 10 parts, 10.5
Part or 11 parts；Typical but non-limiting carbon nanotube is 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts；Silane coupling agent it is typical but
Unrestricted is 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts；Polyurethane-modified macromolecule dispersing agent is typical but non-limiting to be
1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts.
It is preferably carried out in mode in one kind of the present invention, counts, be made of following raw material in parts by weight：Warming agent 9.3-
10.7 parts, 1.3-2.7 parts of carbon nanotube, 1.3-2.7 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent 1.3-2.7
Part.
It is preferably carried out in mode in one kind of the present invention, counts, be made of following raw material in parts by weight：Warming agent 9.5-
10.5 parts, 1.5-2.5 parts of carbon nanotube, 1.5-2.5 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent 1.5-2.5
Part.
The overall performance of modified warming agent can be improved by being advanced optimized to the proportioning of the raw material of modified warming agent, raw material profit
With rate height.
It is preferably carried out in mode in one kind of the present invention, warming agent is reversible temperature indicating material, preferably double salicylaldehyde contracting virtue
Aminated compounds, 4- (4- anilino-s benzeneazo) benzene sulfonic acid, polythiophene, polyaniline, polysilane, polybutadiene alkynes or NiCl2·
2C6H12N4·10H2O。
It is preferably carried out in mode in one kind of the present invention, silane coupling agent includes Degussa dynasylan hydrosil
1151, Degussa dynasylan hydrosil 2926, Degussa dynasylan hydrosil 2726 or advanced in years figure MP200.
The present invention provides a kind of preparation method of above-mentioned modified warming agent, includes the following steps：
By polyurethane-modified macromolecule dispersing agent, the warming agent of powdery and carbon nanotube are added in silane coupling agent,
75-85 DEG C of mixing 22-26h under vacuum condition, obtains modified warming agent.
This method is simple and easy to operate, can be suitble to large-scale production with commercial Application.Wherein vacuum condition is 0-0.02Pa,
Typical but non-limiting temperature is 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, typical but non-limiting incorporation time is 22,23,24,25 or 26h.
The present invention provides a kind of reversible thermocoating containing above-mentioned modified warming agent, counts in parts by weight, by following original
Material composition：30-50 parts of polyurethane-modified acrylic acid dispersion, 5-40 parts of aqueous polyurethane dispersion, modified warming agent 0.5-10
25-40 parts of part, 0.2-0.8 parts of wetting agent, 0.5-1 parts of antifoaming agent, 0.3-1 parts of thixotropic agent, neutralizer 0.1-0.5 and solvent.
Polyurethane-modified acrylic acid dispersion is the resin for having on plastics superpower adhesive force, aqueous in this, as major ingredient
Dispersions of polyurethanes has the advantages that endurance and richness are high, as auxiliary film forming matter, in conjunction with good wear-resisting and resistance to
The modification warming agent for the property changed can be had excellent performance with wetting agent, antifoaming agent, thixotropic agent and neutralizer under rational proportioning
Reversible thermocoating.The reversible thermocoating rate of drying is fast, and richness is high, convenient for production, without flowing down problems, and meanwhile it is right
Human body and environment are safe from harm.
It should be noted that counting in parts by weight, typical but non-limiting polyurethane-modified acrylic acid dispersant is 30
Part, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts or 50 parts；Aqueous polyurethane dispersion it is typical but
Unrestricted is 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts；Modified warming agent is typical but non-limiting
It is 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts；It is 0.2 part that wetting agent is typical but non-limiting,
0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part or 0.8 part；It is 0.5 part that antifoaming agent is typical but non-limiting, 0.6 part, 0.7
Part, 0.8 part, 0.9 part or 1 part；It is 0.3 part that thixotropic agent is typical but non-limiting, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8
Part, 0.9 part or 1 part；Typical but non-limiting neutralizer is 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part；Solvent is typical
But unrestricted is 25 parts, 30 parts, 35 parts or 40 parts.
Polyurethane-modified acrylic acid dispersion is film forming matter, and wt is 50% or so, OH% 0.8-1.0.Aqueous poly- ammonia
Ester dispersion is film forming matter, and wt is 35% or so, OH% 3-5.Wetting agent is non-ionic wetting agent, preferably
BYK349, BYK348, BYK306 or BYK337.Antifoaming agent is mineral oil antifoam agent or organic silicon defoamer, is preferably first created
S8044, s2667 or ws2844, preferably s8044.Thixotropic agent is preferably BASF 1130.Neutralizer is preferably Angus AMP-
95.Solvent is water.
It is preferably carried out in mode in one kind of the present invention, counts, be made of following raw material in parts by weight：Polyurethane-modified third
35-45 parts of olefin(e) acid dispersion, 10-35 parts of aqueous polyurethane dispersion, modified 1-9 parts of warming agent, 0.3-0.7 parts of wetting agent disappear
27-37 parts of 0.6-0.9 parts of infusion, 0.4-0.9 parts of thixotropic agent, neutralizer 0.2-0.5 and solvent.
It is preferably carried out in mode in one kind of the present invention, counts in parts by weight, be made of following raw material material：It is polyurethane-modified
37-43 parts of acrylic acid dispersion, 15-28 parts of aqueous polyurethane dispersion, modified 2-7 parts of warming agent, 0.4-0.6 parts of wetting agent,
27-35 parts of 0.6-0.8 parts of antifoaming agent, 0.5-0.8 parts of thixotropic agent, neutralizer 0.2-0.4 and solvent.
The present invention provides a kind of preparation method of above-mentioned reversible thermocoating, includes the following steps：Each raw material is mixed equal
It is even to obtain the reversible thermocoating.This method is simple to operation, and raw material be uniformly mixed, at low cost.
The present invention finally provides a kind of product containing above-mentioned reversible thermocoating, is 30-70 by weight ratio:1-10's can
Inverse thermo-color is uniformly mixed with curing agent, and the product containing reversible thermocoating is obtained coated in product matrix surface.The production
Product can accurate temperature indicating, warning made to temperature, while product appearance is beautiful, wear-resisting and endurance is high.Reversible thermocoating allusion quotation
Type but it is unrestricted be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts or 70 parts；Curing agent is typical but non-
Restrictive is 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.
It is preferably carried out in mode in one kind of the present invention, curing agent includes HDI trimer curing agent, preferably polyether-type parent
Water is modified HDI trimer curing agent and/or sulfonate hydrophilic modifying HDI trimer curing agent.Polyether-type modified firming agent wt%
For 100, NCO% 20-22；Sulfonate modified curing agent wt% is 100, NCO% 17-19.
Be preferably carried out in mode in one kind of the present invention, product is small household appliances, including hair dryer, poacher, wiring board or
Electric cooker.
The technical solution provided to facilitate the understanding of the present invention, with reference to embodiment to technical solution provided by the invention
It is further described.
Embodiment 1
The present embodiment provides a kind of modified warming agent, and meter includes following raw material in parts by weight：Double salicylaldehyde contracting arylamine class
3 parts of 9 parts of compound, 3 parts of carbon nanotube, 1 part of silane coupling agent and polyurethane-modified macromolecule dispersing agent.
Embodiment 2
The present embodiment provides a kind of modified warming agent, and meter includes following raw material in parts by weight：NiCl2·2C6H12N4·
10H21 part of 11 parts of O, 1 part of carbon nanotube, 3 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent.
Embodiment 3
The present embodiment provides a kind of modified warming agent, and meter includes following raw material in parts by weight：9.3 parts of polysilane, carbon is received
2.7 parts of 2.7 parts of mitron, 1.3 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent.
Embodiment 4
The present embodiment provides a kind of modified warming agent, and meter includes following raw material in parts by weight：10.7 parts of polythiophene, carbon is received
1.3 parts of 1.3 parts of mitron, 2.7 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent.
Embodiment 5
The present embodiment provides a kind of modified warming agent, and meter includes following raw material in parts by weight：9.5 parts of polybutadiene alkynes, carbon
2.5 parts of 2.5 parts of nanotube, 1.5 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent.
Embodiment 6
The present embodiment provides a kind of modified warming agent, and meter includes following raw material in parts by weight：N-salicylideneaniline class
Close 1.5 parts of 10.5 parts of object, 1.5 parts of carbon nanotube, 2.5 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent.
Embodiment 7
The present embodiment provides a kind of modified warming agent, and meter includes following raw material in parts by weight：(4- anilino-s benzene is even by 4-
Nitrogen) 2 parts of 10 parts of benzene sulfonic acid, 2 parts of carbon nanotube, 2 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent.
Embodiment 8
The present embodiment provides a kind of preparation methods of modified warming agent, are raw material with embodiment 7, include the following steps：It will
Polyurethane-modified macromolecule dispersing agent, the warming agent that crushed and carbon nanotube are added in silane coupling agent, vacuum condition
The lower 80 DEG C of mixing of 0.01Pa for 24 hours, obtain modified warming agent.
Comparative example 1
This comparative example provides a kind of modified warming agent, and meter includes following raw material in parts by weight：(4- anilino-s benzene is even by 4-
Nitrogen) 5 parts of 5 parts of benzene sulfonic acid, 5 parts of carbon nanotube, 0.5 part of silane coupling agent and polyurethane-modified macromolecule dispersing agent.
Compared with Example 7, proportioning is different.
Comparative example 2
This comparative example provides a kind of modified warming agent, and meter includes following raw material in parts by weight：(4- anilino-s benzene is even by 4-
Nitrogen) 2 parts of 10 parts of benzene sulfonic acid, 2 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent.
Compared with Example 7, lack carbon nanotube.
Comparative example 3
This comparative example provides a kind of modified warming agent, and meter includes following raw material in parts by weight：(4- anilino-s benzene is even by 4-
Nitrogen) 2 parts of 10 parts of benzene sulfonic acid, 2 parts of carbon nanotube and polyurethane-modified macromolecule dispersing agent.
Compared with Example 7, lack silane coupling agent.
Comparative example 4
This comparative example provides a kind of preparation method of modified warming agent, by the polyurethane-modified high score of raw material in embodiment 7
Sub- dispersant, the warming agent that crushed and carbon nanotube are added in silane coupling agent, and the lower 100 DEG C of mixing 12h of normal pressure is changed
Warm-natured sense agent.
Test example 1
The modification warming agent raw material of embodiment 1-7 and comparative example 1-3 is prepared according to the preparation method in embodiment 8
Modified warming agent, performance test is carried out at the same time with the modification warming agent in comparative example 4, as a result such as following table：
| Reversible color performance | |
| Embodiment 1 | Reversible, high sensitivity, discoloration is apparent in the short time |
| Embodiment 2 | Reversible, high sensitivity, discoloration is apparent in the short time |
| Embodiment 3 | Reversible, high sensitivity, discoloration is apparent in the short time |
| Embodiment 4 | Reversible, high sensitivity, discoloration is apparent in the short time |
| Embodiment 5 | Reversible, high sensitivity, discoloration is apparent in the short time |
| Embodiment 6 | Reversible, high sensitivity, discoloration is apparent in the short time |
| Embodiment 7 | Reversible, high sensitivity, discoloration is apparent in the short time |
| Comparative example 1 | Reversible, sensitivity is slightly worse, and Coloring Time is slightly long |
| Comparative example 2 | Reversible, poor sensitivity, Coloring Time is long |
| Comparative example 3 | Reversible, sensitivity is slightly worse, and Coloring Time is slightly long |
| Comparative example 4 | Reversible, high sensitivity, Coloring Time is slightly grown |
Embodiment 9
The present embodiment provides modified warming agent in a kind of reversible thermocoating, including embodiment 7, in parts by weight meter packet
It includes：30 parts of polyurethane-modified acrylic acid dispersion, 40 parts of aqueous polyurethane dispersion, modified 0.5 part of warming agent, BYK349 0.8
Part, first create 25 parts of 0.5 part of s8044,1,130 1 parts of BASF, Angus AMP-95 0.1-0.5 and water.
Embodiment 10
The present embodiment provides modified warming agent in a kind of reversible thermocoating, including embodiment 7, in parts by weight meter packet
It includes：50 parts of polyurethane-modified acrylic acid dispersion, 5 parts of aqueous polyurethane dispersion, modified 10 parts of warming agent, BYK348 0.2
Part, first create s26671 parts, 1,130 0.3 parts of BASF, 40 parts of Angus AMP-95 0.5 and water.
Embodiment 11
The present embodiment provides modified warming agent in a kind of reversible thermocoating, including embodiment 7, in parts by weight meter packet
It includes：35 parts of polyurethane-modified acrylic acid dispersion, 35 parts of aqueous polyurethane dispersion, modified 1 part of warming agent, BYK306 0.7
Part, first create 37 parts of 0.6 part of ws2844,1,130 0.9 parts of BASF, Angus AMP-95 0.2 and water.
Embodiment 12
The present embodiment provides modified warming agent in a kind of reversible thermocoating, including embodiment 7, in parts by weight meter packet
It includes：45 parts of polyurethane-modified acrylic acid dispersion, 10 parts of aqueous polyurethane dispersion, modified 9 parts of warming agent, BYK337 0.3
Part, first create 27 parts of 0.9 part of s8044,1,130 0.4 parts of BASF, Angus AMP-95 0.5 and water.
Embodiment 13
The present embodiment provides modified warming agent in a kind of reversible thermocoating, including embodiment 7, in parts by weight meter packet
It includes：37 parts of polyurethane-modified acrylic acid dispersion, 28 parts of aqueous polyurethane dispersion, modified 2 parts of warming agent, BYK349 0.6
Part, first create 35 parts of 0.6 part of s2667,1,130 0.8 parts of BASF, Angus AMP-95 0.2 and water.
Embodiment 14
The present embodiment provides modified warming agent in a kind of reversible thermocoating, including embodiment 7, in parts by weight meter packet
It includes：43 parts of polyurethane-modified acrylic acid dispersion, 15 parts of aqueous polyurethane dispersion, modified 7 parts of warming agent, BYK349 0.4
Part, first create ws28440.8 parts, 1,130 0.5 parts of BASF, 35 parts of Angus AMP-95 0.2-0.4 and water.
Embodiment 15
The present embodiment provides modified warming agent in a kind of reversible thermocoating, including embodiment 7, in parts by weight meter packet
It includes：40 parts of polyurethane-modified acrylic acid dispersion, 25 parts of aqueous polyurethane dispersion, modified 6 parts of warming agent, BYK349 0.5
Part, first create 32 parts of 0.7 part of s8044,1,130 0.6 parts of BASF, Angus AMP-95 0.3 and water.
Comparative example 5
This comparative example provides a kind of reversible thermocoating, including modified warming agent in embodiment 7, in parts by weight meter packet
It includes：20 parts of polyurethane-modified acrylic acid dispersion, 45 parts of aqueous polyurethane dispersion, modified 1 part, 1 part of BYK349 of warming agent,
First create 50 parts of 0.1 part of s8044,1,130 2 parts of BASF, Angus AMP-95 0.1 and water.
Compared with embodiment 15, proportioning is different.
Comparative example 6
This comparative example provides a kind of reversible thermocoating, including modified warming agent in embodiment 7, in parts by weight meter packet
It includes：40 parts of polyurethane-modified acrylic acid dispersion, modified 6 parts of warming agent, first creates 0.7 part of s8044, Bath by BYK3490.5 parts
32 parts of 1,130 0.6 parts of husband, Angus AMP-95 0.3 and water.
Compared with embodiment 15, lack aqueous urethane dispersants.
Comparative example 7
This comparative example provides a kind of reversible thermocoating, including modified warming agent in embodiment 7, in parts by weight meter packet
It includes：40 parts of polyurethane-modified acrylic acid dispersion, 25 parts of aqueous polyurethane dispersion, modified 6 parts of warming agent, BYK349 0.5
Part, 32 parts of 1,130 0.6 parts of BASF and water.
Compared with embodiment 15, lack antifoaming agent and neutralizer.
Comparative example 8
This comparative example provides a kind of reversible thermocoating, including modified warming agent in embodiment 7, in parts by weight meter packet
It includes：25 parts of aqueous polyurethane dispersion, modified 6 parts, 0.5 part of BYK349 of warming agent, first creates 0.7 part of s8044, BASF 1130
0.6 part, 32 parts of Angus AMP-95 0.3 and water.
Compared with embodiment 15, lack polyurethane-modified acrylic acid dispersion.
Embodiment 16
The present embodiment provides a kind of products containing reversible thermocoating, are prepared by the following method：Reversible temperature indicating is applied
Material is uniformly mixed with curing agent, is coated in product surface.Curing agent is polyether-type modified firming agent.
Embodiment 17
The present embodiment provides a kind of products containing reversible thermocoating, are prepared by the following method：Reversible temperature indicating is applied
Material is uniformly mixed with curing agent, is coated in product surface.Curing agent is that mass ratio is 1:1 polyether-type modified firming agent and sulfonic acid
Salt hydrophilic modifying HDI trimer curing agent.
Test example 2
Reversible thermocoating in embodiment 9-15 and comparative example 5-8 is applied according to the preparation method of the product in embodiment 16
Frosting is overlayed on, is tested for the property, as a result such as following table：
Test example 3
Reversible thermocoating in embodiment 15 is prepared into production according to the preparation method of the product in embodiment 16-17
Product make product coated in auxiliary material surface as a comparison case using curing agent as aziridine, test wearability and binding force, find real
Apply a 16-17 it is with obvious effects be better than comparative example, it is best with the properties of product in embodiment 17, illustrate solidification provided by the invention
Agent can improve the raw material chemical crosslinking of coating so that coating has higher durability.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of modified warming agent, which is characterized in that count, be made of following raw material in parts by weight：9-11 parts of warming agent, carbon is received
1-3 parts of mitron, 1-3 parts and polyurethane-modified macromolecule dispersing agent 1-3 parts of silane coupling agent.
2. modified warming agent according to claim 1, which is characterized in that count, be made of following raw material in parts by weight：Temperature
Feel 9.3-10.7 parts of agent, 1.3-2.7 parts of carbon nanotube, 1.3-2.7 parts of silane coupling agent and polyurethane-modified macromolecule dispersing agent
1.3-2.7 part；
Preferably, it counts, is made of following raw material in parts by weight：9.5-10.5 parts of warming agent, 1.5-2.5 parts of carbon nanotube, silicon
1.5-2.5 parts and polyurethane-modified macromolecule dispersing agent 1.5-2.5 parts of alkane coupling agent.
3. modified warming agent according to claim 1 or 2, which is characterized in that the warming agent is reversible temperature indicating material, excellent
It is selected as salicylidenedimine, 4- (4- anilino-s benzeneazo) benzene sulfonic acid, polythiophene, polyaniline, polysilane, poly- fourth
Diine or NiCl2·2C6H12N4·10H2O；
Preferably, the silane coupling agent includes Degussa dynasylan hydrosil 1151, Degussa dynasylan
Hydrosil 2926, Degussa dynasylan hydrosil 2726 step figure MP200.
4. being modified the preparation method of warming agent according to claim 1-3 any one of them, which is characterized in that including following step
Suddenly：
By polyurethane-modified macromolecule dispersing agent, the warming agent of powdery and carbon nanotube are added in silane coupling agent, vacuum
Under the conditions of 75-85 DEG C of mixing 22-26h, obtain modified warming agent.
5. a kind of reversible thermocoating being modified warming agent containing claim 1-3 any one of them, which is characterized in that by weight
Number meter is measured, is made of following raw material：30-50 parts of polyurethane-modified acrylic acid dispersion, 5-40 parts of aqueous polyurethane dispersion,
Modified 0.5-10 parts of warming agent, 0.2-0.8 parts of wetting agent, 0.5-1 parts of antifoaming agent, 0.3-1 parts of thixotropic agent, neutralizer 0.1-0.5
With 25-40 parts of solvent.
6. reversible thermocoating according to claim 5, which is characterized in that count, be made of following raw material in parts by weight：
35-45 parts of polyurethane-modified acrylic acid dispersion, 10-35 parts of aqueous polyurethane dispersion, modified 1-9 parts of warming agent, wetting agent
0.3-0.7 parts, 0.6-0.9 parts of antifoaming agent, 0.4-0.9 parts of thixotropic agent, 27-37 parts of neutralizer 0.2-0.5 and solvent；
Preferably, it counts, is made of following raw material in parts by weight：37-43 parts of polyurethane-modified acrylic acid dispersion, aqueous poly- ammonia
15-28 parts of ester dispersion, modified 2-7 parts of warming agent, 0.4-0.6 parts of wetting agent, 0.6-0.8 parts of antifoaming agent, thixotropic agent 0.5-0.8
Part, 27-35 parts of neutralizer 0.2-0.4 and solvent；
Preferably, solvent is water.
7. the preparation method of reversible thermocoating described in claim 5 or 6, which is characterized in that include the following steps：By each original
Material is uniformly mixed and obtains the reversible thermocoating.
8. a kind of product containing reversible thermocoating described in claim 5 or 6, which is characterized in that by weight ratio be 30-
70：The reversible thermocoating of 1-10 is uniformly mixed with curing agent, is obtained containing reversible thermocoating coated in product matrix surface
Product.
9. product according to claim 8, which is characterized in that the curing agent includes HDI trimer curing agent, preferably
Polyether-type hydrophilic modifying HDI trimer curing agent and/or sulfonate hydrophilic modifying HDI trimer curing agent.
10. product according to claim 8 or claim 9, which is characterized in that the product is small household appliances, including hair dryer, boiled egg
Device, wiring board or electric cooker.
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