CN104845448B - There is ageing-resistant function temperature sensing color changing Neutral writing ink mill base and preparation method thereof - Google Patents
There is ageing-resistant function temperature sensing color changing Neutral writing ink mill base and preparation method thereof Download PDFInfo
- Publication number
- CN104845448B CN104845448B CN201510253811.7A CN201510253811A CN104845448B CN 104845448 B CN104845448 B CN 104845448B CN 201510253811 A CN201510253811 A CN 201510253811A CN 104845448 B CN104845448 B CN 104845448B
- Authority
- CN
- China
- Prior art keywords
- temperature sensing
- color changing
- mill base
- ageing
- sensing color
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/17—Writing inks characterised by colouring agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses one and there is ageing-resistant function temperature sensing color changing Neutral writing ink mill base and preparation method thereof, the method mainly utilizes the modified melamine resin wall material as temperature sensing color changing microcapsule of amino and formaldehyde reaction generation, by introducing the absorption to ultraviolet of the BTA group with ageing-resistant and antibacterial action in wall material, can the ultraviolet destruction to core thermosensitive chromotropic paint, improve ageing-resistant performance and the anti-microbial property of mill base, avoid the migration problem produced time little molecule anti ultraviolet agent is applied in wall material simultaneously, substantially increase the light stability of temperature-sensitive reversible color mill base, there is higher concentration and preferable stability simultaneously, prepared by Neutral writing ink for the later stage there is the matching of excellence, it is applied to Neutral writing ink allotment have broad application prospects.
Description
Technical field
The present invention relates to a kind of extraordinary Neutral writing ink mill base and preparation method thereof, especially relate to
And one has ageing-resistant function temperature sensing color changing Neutral writing ink mill base and preparation method thereof,
It is applicable to the preparation of high concentration mill base and the Neutral writing ink of temperature sensing color changing Neutral writing ink
Preparation.
Background technology
Neutral writing ink is the important tool of office record, and it, mainly by dispersible pigment color paste, increases
The three major controls compositions such as thick dose and auxiliary agent, relative to traditional Neutral writing ink, temperature sensitive
Reversible neutral pen ink has Show Color at normal temperatures, and after ink is heated, fast
Speed variable color (colourless etc.), when by high-temperature reply to original room temperature, its ink is still simultaneously
For colourless, when temperature continues to be reduced to subzero about-20 DEG C, its color starts to recover
Characteristic to original colored state；Temperature-sensitive reversible color Neutral writing ink its mainly adopt
With having the mill base of temperature-sensitive reversible color, thickening and auxiliary agent is being coordinated to prepare,
Wherein in order to ensure reversible temperature sensitive reversible effect, temperature sensing color changing Neutral writing ink mill base uses
There is temperature induced color changing dyestuff (pigment) formed by the pseudo-pigment obtained after micro encapsulation,
Its technical barrier being primarily present is that the suitable temperature sensitive mill base microcapsule of discoloring temperature is equal
One changes technology of preparing.Temperature-sensitive reversible chromatic ink is mainly by happy, the Rhizoma Sparganii of Japan hundred at present
Deng managing performance, the domestic production for temperature-sensitive reversible chromatic ink is due to by research ink
The research institution of water is few, and at the lagging in development of temperature sensing color changing pigment (dyestuff), because of
This is for carrying out without large enterprise temporarily in the manufacturing country of temperature-sensitive Neutral writing ink and mill base thereof
Producing, only small part enterprise is being carried out compounding obtaining by external Leather Color Paste.
Temperature-sensitive reversible color Neutral writing ink its relative to conventional temperature-sensitive reversible color oil
For ink coating, it is interval that it has wide temperature sensing color changing, both its colour killing/secondary color temperature
Wide ranges (more than 60 DEG C), simultaneously for relatively conventional Neutral writing ink, its color
Slurry is microcapsule systems, has particles relatively big, and dispersible pigment color paste is polymer encapsulation
System, need to avoid the high-speed stirred destruction to microcapsule, therefore the preparation of its mill base with
Selecting increasingly complex, preparation technology is increasingly difficult, and current domestic rare enterprise can be big
Large-scale production.Kulcar Rahela et al. (Colorimetric properties of
Reversible thermochromic printing inks, Dyes and Pigments,
2010；Dynamic Colour Possibilities and Functional Properties of
Thermochromic Printing Inks, Acta Graphica, 2012) have studied spray
Ink its temperature sensing color changing mechanism of pad-ink and its colourshifting process affect it delayed
Factor, research finds its temperature sensing color changing process not only temperature influence, is also gone through by its heat
The impact of history, is the hysteresis effect of its variations in temperature, simultaneously pigment after micro encapsulation
Temperature sensing color changing stability more preferable, and after microcapsule destroys, its reversibility disappears.
Campbell Dean J. et al. (Demonstration of Thermodynamics and
Kinetics Using FriXion Erasable Pens, Journal of Chemical
Education, 2012) temperature-sensitive according to Pilot Pens company in 2006 exploitation can
Inversion color product P riXion erasable pens or highlighters is in DSC and change
Various performances in terms of color mechanism are described, it is indicated that the product of pilot Zhi Bi company
In the differential thermal analysis of product sample, show the pattern with energy gradient, i.e. at low temperature
Shi Moshui has color, and becomes colorless after crossing variable color energy level, is then turned by high temperature
When low temperature, it also needs to cross energy level and realizes colourless thinking coloured transformation, and it is corresponding simultaneously
Mechanism be also also exist by the developer of supplied for electronic and connect nucleophobic colour former with
And solvent three phase composition, the hysteresis of its temperature sensing color changing process.In addition there is file report
Road reversible thermal discoloration aqueous ink composition, the writing implement using it and writing implement
Group, it discloses a kind of reversible thermal discoloration aqueous ink composition, reversible thermochromic
Aqueous ink compositions comprises water, by (A) electron donating property coloring organic compound, (B)
Electronic acceptance compound and (C) determine the coloring reaction that above two compound occurs
The reversible thermochromic of the reversible thermochromic compositions of the reaction medium composition of temperature
Microcapsule pigment, high polymer coagulant, there is the combed high score point of carboxyl at side chain
Powder, organic nitrogen sulphur compound and water-soluble resin；Representative as this compositions
Example, utilizes electron donating property chromatic organic compound (electron donor) and electron acceptor
The electronics of compound (electron acceptor) give and accept reaction compositions.
The Neutral writing ink of temperature-sensitive reversible color is all described by document above, but right
For Neutral writing ink, its temperature sensitive reversible pigment is often organic material, therefore to ultraviolet
The loss of properties on aging of light, irradiates under sunlight for a long time and easily makes temperature sensitive reversible face
The rotten inactivation of material, and Neutral writing ink is as the main tool of record at present, it is due to word
Mark is clear, and the writing holding time waits so long advantage, is widely used, preserves process simultaneously
In inevitably by the radiation effects of sunlight, light etc., therefore need exploitation to ultraviolet
Line has the aging resistance temperature-sensitive reversible color Neutral writing ink mill base of Absorption and has non-
The most important meaning, having document to disclose one at present can be reversible at-50 DEG C to 80 DEG C
Thermochromic compositions, reversible thermochromic compositions its mainly by microcapsule method,
Joined by electron donating property developer, electronic receipt colour former and solvent and light stabilizer
Close preparation and there is the Reversible temperature sensitive allochromatic material of light fastness, solve in use condition
Lower light resistance problem.But owing to light stabilizer is added on micro-with single function component
In capsule wall material, be easily heated, the impact of solvent etc. and migrate, thus cause light steady
Determine agent to be lost in core or the external world, cause temperature sensing color changing system light to be stably deteriorated,
Affect product quality.
Temperature induced color changing pigment can improve its resistance to oxidation, solvent resistant etc. property after micro encapsulation
Can, make developer, colour former and solvent carry out metachromasia in same system, because of
This has extraordinary stability；And at present colour former is mainly triarylmethane compound, glimmering
Alkanes, volution adjoin class etc. of muttering, and its ultra-violet resistance of this type of miscellaneous mutual ring Organic substance can be poor,
And at present for the ultra-violet resistance energy of developer Yu colour former, currently mainly at solvent body
Adding organic anti ultraviolet agent in system, this method is inevitably due to uvioresistant
Add the change of the environment to temperature sensing color changing, the especially uvioresistant under the conditions of ultraviolet
The living radical of agent is relatively big to electronics conduction effects, and therefore next step exploitation is novel
Microcapsule wall material, makes wall material itself have certain uvioresistant performance, thus reaches to protect
Protecting the purpose of core developer and colour former, the ultraviolet resistance improving temperature induced color changing is stable
Property is significant.And traditional method of modifying is in temperature sensing color changing pigment component
Add the reagent with anti-ultraviolet aging, to improve the aging resistance of temperature sensitive pigment
Performance, also can add the anti-purple with uvioresistant performance in the wall material of microcapsule simultaneously
Outer dose carries out being blended and obtains wall material and have the compositions of uvioresistant performance.The most how to make
Ageing-resistant function temperature sensing color changing Neutral writing ink mill base has good ultraviolet-resistent property and light
Stability and how to prepare the emphasis becoming current research.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides one
Having ageing-resistant function temperature sensing color changing Neutral writing ink mill base and preparation method thereof, it is main
It is to use that to have ageing-resistant and antibacterial action modified melamine resin be temperature sensing color changing
Microcapsule wall material, by having ageing-resistant and antibacterial action BTA in wall material
The group absorption to ultraviolet, reduces ultraviolet and breaks core thermosensitive chromotropic paint
Bad, improve the ageing-resistant performance of mill base, be applied to the highly concentrated of temperature sensing color changing Neutral writing ink
Degree mill base preparation has huge market prospect.
The present invention is to solve that its technical problem be the technical scheme is that
A kind of preparation method with ageing-resistant function temperature sensing color changing Neutral writing ink mill base,
Comprise the steps:
(1) preparation of temperature sensing color changing system: after adding cosolvent in a reservoir, at this
Cosolvent adds electron acceptor and the electronq donor of temperature-sensitive reversible color pigment
Fully dissolve, obtain uniform temperature sensing color changing system；Wherein said electronics accepts
Body: electronq donor: the mol ratio of cosolvent is 1:1.25～1.55:50～200, described
Cosolvent is 1 by water-fast unitary long-chain alkyl alcohol, ester and amine in molar ratio:
0.1～5.0:0.5～2.5 are mixed to form gained at 70～85 DEG C；Described electron acceptor
For the black TFBL of temperature-sensitive, crystal violet lactone, temperature-sensitive rhodo TF-R1In one；Institute
Stating electronq donor is that organic phenolic compound and carboxylic acid compound are according to mol ratio
It is mixed to form gained for 1:0.05～0.25；
(2) preparation of melamine resin pre-polymer solution: add trimerization in reaction vessel
Cyanamide, 1-amino BTA, formaldehyde and deionized water mix homogeneously, then adopt
With alkali compounds, the pH value of system is regulated to 8～9,1000～3000rpm
Mixing speed under be warming up to 65～85 DEG C after, continue stirring reaction 45～90min,
Obtain melamine resin pre-polymer solution；Wherein tripolycyanamide and 1-amino benzo three nitrogen
Amino total mole number in azoles: in formaldehyde, the molal quantity of aldehyde radical is 1:1.25～1.50,
And the mol ratio of tripolycyanamide and 1-amino BTA is 1:0.01～0.05, first
Aldehyde is 1:15～20 with the mol ratio of deionized water；
(3) preparation of ageing-resistant function temperature sensing color changing Neutral writing ink mill base: at room temperature
Gained temperature sensing color changing system adds in (1) water soluble surfactant active, and uses
High-speed stirred mulser, with the rotating speed emulsifying 45～75min of 8000～14000rpm, obtains
To stable O/W type emulsion, then in this O/W type emulsion, it is slowly added dropwise (2)
Middle gained melamine resin pre-polymer solution and water soluble dispersing agent, and regulation system pH
Being 6.0, under room temperature, mechanical agitation treats that melamine resin pre-polymer solution is molten in this system
After solving dispersion, again the pH value of system is adjusted to 4.5～5.5, and is warming up to
React 2.5～4.0h at 70～80 DEG C, obtain ageing-resistant function temperature sensing color changing Neutral writing ink
Mill base.
Its further technical scheme is:
Described in step (1), the water-fast unitary long-chain alkyl alcohol in cosolvent is
N-heptanol, n-octyl alcohol, n-nonyl alcohol, Decanol, positive undecyl alcohol, lauryl alcohol, 14
At least one in alcohol, hexadecanol, octadecanol, docosanol and octacosanol.
Ester in cosolvent described in step (1) be butyl formate, Tetryl formate.,
Isoamyl formate, benzyl formate, ethyl acetoacetate, n-propyl acetate, acetic acid are just
Butyl ester, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoamyl acetate, second
Acid methyl pentyl ester, ethyl propionate, propyl propionate, n-butyl propionate, amyl propionate,
Methyl butyrate, ethyl n-butyrate., ethyl lactate, n-butyl lactate, diethyl carbonate,
At least one in ethyl benzoate, isopropyl benzoate and ethyl salicylate.
Described in step (1), the amine in cosolvent is ethylenediamine, oleyl amine and isopropanolamine
In at least one.
Described in step (1), the organic phenolic compound in electronq donor is to benzene two
At least one in phenol, paranitrophenol, bisphenol-A and alpha-Naphthol；Described electronics
Carboxylic acid compound in donor is phenylacetic acid, hydroxy carboxylic acid, hydroxyacetic acid, Portugal
At least one in grape saccharic acid and succinic acid.
Water soluble surfactant active described in step (3) be sodium lauryl sulphate, ten
At least one in dialkyl benzene sulfonic acids sodium and dodecyl sodium sulfate.
The invention also discloses a kind of above-mentioned preparation method prepare gained have resistance to always
Change function temperature sensing color changing Neutral writing ink mill base.
Its further technical scheme is:
This has ageing-resistant function temperature sensing color changing Neutral writing ink mill base by following resistance to by accounting for
Each component group of aging function temperature sensing color changing Neutral writing ink mill base gross mass percentages
Become: temperature sensing color changing system 15～35wt.%, melamine resin pre-polymer solution
10～30wt.%, water soluble surfactant active 0.5～2.0wt.% and balance deionized water.
The solid content of described ageing-resistant function temperature sensing color changing Neutral writing ink mill base is not less than
20wt.%, mill base grain diameter D90It is not more than 2.5 μm, mill base high speed settling speed
It is not more than 50 μm/min.
The solid content optimum of described ageing-resistant function temperature sensing color changing Neutral writing ink mill base is not
Less than 40wt.%, mill base grain diameter D90The optimum 250nm that is not more than, mill base height
Speed rate of settling optimum is not more than 50 μm/min, and color paste viscosity optimum is
70～200mPa s.
The method have the benefit that: present invention employing has ageing-resistant and anti-
The amino primary disease triazole of bacterium effect is modifying agent, and preparation has changing of uvioresistant effect
Property melamine resin be temperature sensing color changing microcapsule wall material, by wall material has ageing-resistant and
The absorption to ultraviolet of the BTA group of antibacterial action, reduces ultraviolet to core
The destruction of material thermosensitive chromotropic paint, improves the ageing-resistant performance of mill base, it is to avoid at present
Light stabilizer is added in microcapsule wall material with single function component, be easily heated,
The impact of solvent etc. and migrate, thus cause light stabilizer to be lost to core or the external world
In, cause temperature sensing color changing system light to be stably deteriorated, affect product quality.Often solve
Rule method uvioresistant, the problem such as migration loss of light stabilizer, the amino being simultaneously introduced
BTA has the phenyl ring of conjugation, is beneficial to carry out conjugation with dispersant molecule
And improving dispersion stability, BTA group itself has certain antibacterial
Effect, the most also can improve the anti-microbial property of system, and the present invention has ageing-resistant function
Temperature sensing color changing Neutral writing ink mill base and preparation method thereof, is applied to temperature sensing color changing neutrality ink
The high concentration mill base preparation of water has huge market prospect.
Detailed description of the invention
Specific embodiment below in conjunction with the application describes technical scheme in detail
The problem solved and the technique effect that can reach.
Embodiment 1
(1) preparation of temperature sensing color changing system: by electron acceptor and electronq donor
Cosolvent is prepared at 70 DEG C with the ratio that molar ratio is 1:1.25:50 of cosolvent,
Selecting alcohol, ester, the mixture of amine solvent is cosolvent, wherein in cosolvent alcohol with
The molar ratio of ester and amine is 1:0.1:0.5, and preferred alcohol is water-fast one
Unit long chain alkanol be n-heptanol, n-octyl alcohol, n-nonyl alcohol, Decanol, positive undecyl alcohol,
Lauryl alcohol, tetradecyl alchohol, hexadecanol, octadecanol, docosanol, octacosanol mixed
Compound；Preferably ester is the mixing of butyl formate, Tetryl formate. and ethyl salicylate
Thing；Preferably amine solvent is the mixture of ethylenediamine and isopropanolamine.It is subsequently adding
The temperature-sensitive reversible color pigment black TFBL of electron acceptor temperature-sensitive, carboxylic acids and phenols electricity
Sub-donor, carries out dissolving and prepares uniform temperature sensing color changing system；Described electricity
Sub-donor is carboxylic acid and phenols blend, and wherein phenols with the molar ratio of carboxylic acid is
1:0.05, preferred phenols is the mixture of hydroquinone and paranitrophenol, preferably
The mixture that carboxylic acid is phenylacetic acid and hydroxy carboxylic acid.
(2) preparation of melamine resin pre-polymer solution: add trimerization in the reactor
Cyanamide, 1-amino BTA and formalin and deionized water, use alkali to adjust
Joint system pH is 8～9, then in high-speed stirred, and temperature is increased to 65 DEG C of conditions
Under, control stir speed (S.S.) is 3000rpm, then proceedes to react 45min and obtains melamine
Resin prepolymer solution；In raw material, the molar ratio of amino with the molar ratio of aldehyde radical is
1:1.25, and the molar ratio of tripolycyanamide and 1-amino BTA is 1:0.01,
Formalin select mass fraction be the formalin of 37%, and formaldehyde with go from
The molar ratio of sub-water is 1:15.
(3) preparation of ageing-resistant function temperature sensing color changing Neutral writing ink mill base: in room temperature
Under with temperature sensing color changing system as oil phase, then add sodium lauryl sulphate water solublity
Surfactant, then control rotating speed is 8000rpm breast under high-speed stirred mulser
The change time is 75min, prepares stable O/W type emulsion.Then to O/W
System is slowly added dropwise melamine resin pre-polymer solution, and adds water soluble dispersing agent,
Regulation system pH is 6.0, and at room temperature mechanical agitation makes melamine resin prepolymer exist
System is dissolved dispersion, is 4.5 by system pH regulator the most again, and is warming up to 70 DEG C,
Keep reaction 4.0h, prepare and there is ageing-resistant function temperature sensing color changing Neutral writing ink color
Slurry.
The mass ratio of each component in this ageing-resistant function temperature sensing color changing Neutral writing ink mill base
Value is: heat-sensitive variable colour system 15wt%, melamine resin pre-polymer solution 10wt%,
Water soluble surfactant active 0.5wt%, balance deionized water.This is ageing-resistant after testing
The solid content of function temperature sensing color changing Neutral writing ink mill base is 22.5wt%, mill base particle
Footpath D90Being 2.1 μm, mill base high speed settling speed is 45 μm/min.
Embodiment 2
(1) preparation of temperature sensing color changing system: according to temperature sensing color changing system preparation process
Middle electron acceptor with the molar ratio of electronq donor and cosolvent is
1:1.55:200；It is 1:5.0:2.5 by the molar ratio of alcohol in cosolvent with ester and amine
Ratio prepare cosolvent at 85 DEG C, preferred alcohol is water-fast unitary long-chain
Alkanol n-heptanol and the mixture of lauryl alcohol, preferred ester is ethyl acetoacetate and second
The mixture of acid n-propyl；Preferably amine solvent is oleyl amine.Be subsequently adding temperature sensitive can
Inverse camouflage paint electron acceptor temperature-sensitive rhodo TF-R1, carboxylic acids and phenols electronics give
Give body, carry out dissolving and prepare uniform temperature sensing color changing system；Preferably electronics is given
Giving body is carboxylic acid and phenols blend, and wherein phenols with the molar ratio of carboxylic acid is
1:0.25, preferred phenols is bisphenol-A and alpha-Naphthol mixture, preferred carboxylic acid
For hydroxyacetic acid and the mixture of succinic acid.
(2) preparation of melamine resin pre-polymer solution: add trimerization in the reactor
Cyanamide, 1-amino BTA and formalin and deionized water, use alkali to adjust
Joint system pH is 8～9, then under the conditions of high-speed stirred and temperature are increased to 85 DEG C,
Control stir speed (S.S.) is 1000rpm, then proceedes to react 45min and obtains melamine resin
Pre-polymer solution；In raw material, the molar ratio of amino with the molar ratio of aldehyde radical is
1:1.50, and the molar ratio of tripolycyanamide and 1-amino BTA is 1:0.05,
Wherein formalin select mass fraction be the aqueous solution of 37%, and formaldehyde with go from
The molar ratio of sub-water is 1:20.
(3) preparation of ageing-resistant function temperature sensing color changing Neutral writing ink mill base: in room temperature
Under with temperature sensing color changing system as oil phase, then add dodecylbenzene sodium sulfonate water-soluble
Property surfactant, then under high-speed stirred mulser control rotating speed be 14000rpm
Emulsification times is 45min, prepares stable O/W type emulsion.Then to O/W
System is slowly added dropwise melamine resin pre-polymer solution, and adds water soluble dispersing agent,
Regulation system pH is 6.0, and at room temperature mechanical agitation makes melamine resin prepolymer exist
System is dissolved dispersion, is 5.5 by system pH regulator the most again, and is warming up to 80 DEG C,
Keep reaction 2.5h, prepare and there is ageing-resistant function temperature sensing color changing Neutral writing ink color
Slurry.
The mass ratio of each component in this ageing-resistant function temperature sensing color changing Neutral writing ink mill base
Value is: heat-sensitive variable colour system 35wt%, melamine resin pre-polymer solution 30wt%,
Water soluble surfactant active 2wt%, balance deionized water.This ageing-resistant merit after testing
The solid content of energy temperature sensing color changing Neutral writing ink mill base is in 37wt%, mill base particle
Footpath D90Being 2.45 μm, mill base high speed settling speed is 48 μm/min.
Embodiment 3
(1) preparation of temperature sensing color changing system: by temperature sensing color changing system preparation process
Electron acceptor is 1:1.50:100's with the molar ratio of electronq donor and cosolvent
Ratio, prepares cosolvent at 75 DEG C, and cosolvent is chosen as alcohol, ester, amine solvent
Mixture, wherein in cosolvent, the molar ratio of alcohol and ester and amine is
1:2.50:1.5, preferred alcohol is water-fast unitary long chain alkanol Decanol and positive ten
The mixture of one alcohol, preferred ester is the mixing of sec-butyl acetate and ethyl benzoate
Thing；Preferably amine solvent is the mixture of ethylenediamine, oleyl amine and isopropanolamine.So
Rear addition temperature-sensitive reversible color pigment electron acceptor crystal violet lactone, carboxylic acids and phenol
Electron-like donor, carries out dissolving and prepares uniform temperature sensing color changing system；Wherein
Electronq donor is carboxylic acid and phenols blend, wherein phenols and the molar ratio of carboxylic acid
For 1:0.20, preferred phenols is the mixing of hydroquinone, bisphenol-A and alpha-Naphthol
Thing, preferred carboxylic acid is the mixture of gluconic acid and succinic acid.
(2) preparation of melamine resin pre-polymer solution: add trimerization in the reactor
Cyanamide, 1-amino BTA and formalin and deionized water, use alkali to adjust
Under the conditions of joint system pH is 8.5, then in high-speed stirred, and temperature is increased to 75 DEG C,
Control stir speed (S.S.) is 3000rpm, then proceedes to react 90min and obtains melamine resin
Pre-polymer solution；In raw material, the molar ratio of amino with the molar ratio of aldehyde radical is
1:1.50, and the molar ratio of tripolycyanamide and 1-amino BTA is 1:0.05,
Raw material formalin select mass fraction be the aqueous solution of 37%, and formaldehyde with go from
The molar ratio of sub-water is 1:20.
(3) preparation of ageing-resistant function temperature sensing color changing Neutral writing ink mill base: in room temperature
Under with temperature sensing color changing system as oil phase, then add dodecyl sodium sulfate water solublity
Surfactant, then control rotating speed is 14000rpm breast under high-speed stirred mulser
The change time is 60min, prepares stable O/W type emulsion.Then to O/W
System is slowly added dropwise melamine resin pre-polymer solution, and adds water soluble dispersing agent,
Regulation system pH is 6.0, and at room temperature mechanical agitation makes melamine resin prepolymer exist
System is dissolved dispersion, is 5.5 by system pH regulator the most again, and is warming up to 80 DEG C,
Keep reaction 3.0h, prepare and there is ageing-resistant function temperature sensing color changing Neutral writing ink color
Slurry.
The mass ratio of each component in this ageing-resistant function temperature sensing color changing Neutral writing ink mill base
Value is: heat-sensitive variable colour system 20wt%, melamine resin pre-polymer solution 15wt%,
Water soluble surfactant active 1.5wt%, balance deionized water.This is ageing-resistant after testing
The solid content of function temperature sensing color changing Neutral writing ink mill base is in 29wt%, mill base granule
Particle diameter D90Being 1.90 μm, mill base high speed settling speed is 43 μm/min.
Embodiment 4
(1) preparation of temperature sensing color changing system: by temperature sensing color changing system preparation process
Electron acceptor is 1:1.45:150 with the molar ratio of electronq donor and cosolvent；
Under the conditions of 80 DEG C, it is chosen as alcohol, ester, the mixture of amine solvent are cosolvent,
It is that 1:0.1:0.5 prepares cosolvent, preferred alcohol by the molar ratio of alcohol with ester and amine
For water-fast unitary long chain alkanol hexadecanol, octadecanol and the mixing of docosanol
Thing, preferred ester is the mixture of isoamyl acetate and methyl amyl acetate；Preferably
Amine solvent is isopropanolamine.It is subsequently adding temperature-sensitive reversible color pigment electron acceptor
Crystal violet lactone, carboxylic acids and phenols electronq donor, carry out dissolving and prepare all
Even temperature sensing color changing system；Electronq donor is carboxylic acid and phenols blend, wherein phenol
Class is 1:0.15 with the molar ratio of carboxylic acid, and preferred phenols is hydroquinone, preferably
Carboxylic acid be hydroxyacetic acid.
(2) preparation of melamine resin pre-polymer solution: add trimerization in the reactor
Cyanamide, 1-amino BTA and formalin and deionized water, use alkali to adjust
Under the conditions of joint system pH is 9, then in high-speed stirred, and temperature is increased to 75 DEG C,
Control stir speed (S.S.) is 2500rpm, then proceedes to react 75min and obtains melamine resin
Pre-polymer solution；In raw material, the molar ratio of amino with the molar ratio of aldehyde radical is
1:1.50, and the molar ratio of tripolycyanamide and 1-amino BTA is 1:0.25,
Described formalin selects mass fraction to be the aqueous solution of 37%, described formaldehyde
It is 1:15 with the molar ratio of deionized water.
(3) preparation of ageing-resistant function temperature sensing color changing Neutral writing ink mill base: in room temperature
Under with temperature sensing color changing system as oil phase, then add dodecylbenzene sodium sulfonate water-soluble
Property surfactant, then under high-speed stirred mulser control rotating speed be 12000rpm
Emulsification times is 60min, prepares stable O/W type emulsion.Then to O/W
System is slowly added dropwise melamine resin pre-polymer solution, and adds water soluble dispersing agent,
Regulation system pH is 6.0, and at room temperature mechanical agitation makes melamine resin prepolymer exist
System is dissolved dispersion, is 4.5 by system pH regulator the most again, and is warming up to 80 DEG C,
Keep reaction 4.0h, prepare and there is ageing-resistant function temperature sensing color changing Neutral writing ink color
Slurry.
The mass ratio of each component in this ageing-resistant function temperature sensing color changing Neutral writing ink mill base
Value is: heat-sensitive variable colour system 25wt%, melamine resin pre-polymer solution 20wt%,
Water soluble surfactant active 2.0wt%, balance deionized water.This is ageing-resistant after testing
The solid content of function temperature sensing color changing Neutral writing ink mill base is in 33wt%, mill base granule
Particle diameter D90Being 2.30 μm, mill base high speed settling speed is 45 μm/min.
Embodiment 5
(1) preparation of temperature sensing color changing system: by temperature sensing color changing system preparation process
Electron acceptor is 1:1.25:75 with the molar ratio of electronq donor and cosolvent,
Be chosen as alcohol under the conditions of 75 DEG C, ester, the mixture of amine solvent are cosolvent, the most molten
In agent, alcohol is 1:2.5:1.5 with the molar ratio of ester and amine, and preferred alcohol is not for dissolving in
The unitary long chain alkanol docosanol of water and the mixture of octacosanol, preferred ester is
Isobutyl acetate and the mixture of ethyl salicylate；Preferably amine solvent is isopropanol
Amine.It is subsequently adding the temperature-sensitive reversible color pigment black TFBL of electron acceptor temperature-sensitive, carboxylic
Acids and phenols electronq donor, carry out dissolving and prepare uniform temperature sensing color changing body
System；Electronq donor is carboxylic acid and phenols blend, wherein phenols and carboxylic acid mole
Ratio is 1:0.10, and preferred phenols is the mixture of paranitrophenol and alpha-Naphthol,
Preferably carboxylic acid is hydroxy carboxylic acid.
(2) preparation of melamine resin pre-polymer solution: add trimerization in the reactor
Cyanamide, 1-amino BTA and formalin and deionized water, use alkali to adjust
Under the conditions of joint system pH is 9, then in high-speed stirred, and temperature is increased to 80 DEG C,
Control stir speed (S.S.) is 2500rpm, then proceedes to react 80min and obtains melamine resin
Pre-polymer solution；In raw material, the molar ratio of amino with the molar ratio of aldehyde radical is
1:1.50, and the molar ratio of tripolycyanamide and 1-amino BTA is 1:0.25,
Formalin selects mass fraction to be the aqueous solution of 37%, formaldehyde and deionized water
Molar ratio is 1:15.
(3) preparation of ageing-resistant function temperature sensing color changing Neutral writing ink mill base: in room temperature
Under with temperature sensing color changing system as oil phase, then add sodium lauryl sulphate water solublity
Surfactant, then under high-speed stirred mulser control rotating speed be 8000～
12000rpm emulsification times is 50min, prepares stable O/W type emulsion.
Then in O/W system, it is slowly added dropwise melamine resin pre-polymer solution, and adds water
Dissolubility dispersant, regulation system pH is 6.0, and at room temperature mechanical agitation makes melamine
Resin prepolymer dissolves dispersion in system, is 50 by system pH regulator the most again,
And it is warming up to 75 DEG C, keep reaction 3.5h, prepare and there is ageing-resistant function temperature
Quick variable color Neutral writing ink mill base.
The mass ratio of each component in this ageing-resistant function temperature sensing color changing Neutral writing ink mill base
Value is: heat-sensitive variable colour system 20wt%, melamine resin pre-polymer solution 15wt%,
Water soluble surfactant active 1.5wt%, balance deionized water.This is ageing-resistant after testing
The solid content of function temperature sensing color changing Neutral writing ink mill base is in 25wt%, mill base granule
Particle diameter D90Being 2.5 μm, mill base high speed settling speed is 50 μm/min.
The particle diameter of the mill base sample prepared by above-described embodiment 1 to embodiment 5 uses moral
The NANOPHOX type nano particle size instrument test sample particle diameter of Sympatec company of state
And distribution；Light source is He-Ne Lasers, wavelength 632.8nm, laser power 10mV,
Detection angles 90 °, tests temperature 25 DEG C, and required sample volume 4mL, in order to improve
Test accuracy, by diluted sample to scattered power higher than 0.5 before measuring.
Stability uses Germany LUMISIZER company LUMISIZER611 at a high speed
Centrifugal stabilometer is tested, and selection optical source wavelength is 865nm, and test temperature is
25 DEG C, rotating speed is 4000r/min, loop test 4000 times, each 90s.
Color fastness to daylight uses GB1710-79 pigment light resistance algoscopy, sample
It is coated on tinplate, is placed under sun-proof instrument and is exposed to the sun, be that standard card is graded
Contrast.
Anti-microbial property uses and adds 5mL mill base in 10cm surface plate, then at color
Slurry system adds staphylococcus glucose coccus, observes antibacterial bacterium colony in mill base raw
Product situation, observing time is 24,48,72,96h and the bacterium colony situation after 7 days.
Select on market conventional temperature sensing color changing Neutral writing ink mill base as a comparison case with reality
Executing example 1 to embodiment 5 and carry out implementation result contrast, comparing result sees table 1.
Table 1 implementation result explanation
Wherein it is provided without the modified colour paste system of amino BTA without anti-microbial property,
After 96h, area of colony is 1.5cm, and also 5 bacterium colonies, its 96h of embodiment 1
Its clump count rear is 1, and area of colony is 0.5cm.Embodiment 2 and embodiment 3
After its 24h, antibacterial has been wholly absent, and after its 72h of embodiment 4 and 5, clump count is
0.Owing to melamine resin itself is without anti-microbial property, therefore its anti-microbial property of mill base and body
The quality of the amino BTA added in system is relevant, adding of amino BTA
Enter amount its anti-microbial properties the most the best.Amino BTA has the anti-of excellence simultaneously
Ultraviolet performance, therefore its addition its uvioresistant performances the most are the best, therefore mill base
Color fastness to daylight is the highest, and therefore its color fastness to daylight of embodiment 2 and 3 is higher than unmodified
2-3 grade of mill base, simultaneously because aminophenyl triazole is beneficial to dividing of mill base
Dissipating, therefore have the performance of excellence for improving the stably dispersing of system, therefore it sinks
Reduction of speed rate is due to unmodified colour paste system.
The above is only the preferred embodiment of the present invention, it is noted that for this
The those of ordinary skill of technical field, without departing from the inventive concept of the premise, also
Can make some improvements and modifications, these improvements and modifications also should be regarded as the present invention's
In protection domain.
Claims (10)
1. a preparation side with ageing-resistant function temperature sensing color changing Neutral writing ink mill base
Method, it is characterised in that: comprise the steps:
(1) preparation of temperature sensing color changing system: after adding cosolvent in a reservoir, at this
Cosolvent adds electron acceptor and the electronq donor of temperature-sensitive reversible color pigment
Fully dissolve, obtain uniform temperature sensing color changing system；Wherein said electronics accepts
Body: electronq donor: the mol ratio of cosolvent is 1:1.25～1.55:50～200, described
Cosolvent is 1 by water-fast unitary long-chain alkyl alcohol, ester and amine in molar ratio:
0.1～5.0:0.5～2.5 are mixed to form gained at 70～85 DEG C；Described electron acceptor
For the black TFBL of temperature-sensitive, crystal violet lactone, temperature-sensitive rhodo TF-R1In one；Institute
Stating electronq donor is that organic phenolic compound and carboxylic acid compound are according to mol ratio
It is mixed to form gained for 1:0.05～0.25；
(2) preparation of melamine resin pre-polymer solution: add trimerization in reaction vessel
Cyanamide, 1-amino BTA, formaldehyde and deionized water mix homogeneously, then adopt
With alkali compounds, the pH value of system is regulated to 8～9,1000～3000rpm
Mixing speed under be warming up to 65～85 DEG C after, continue stirring reaction 45～90min,
Obtain melamine resin pre-polymer solution；Wherein tripolycyanamide and 1-amino benzo three nitrogen
Amino total mole number in azoles: in formaldehyde, the molal quantity of aldehyde radical is 1:1.25～1.50,
And the mol ratio of tripolycyanamide and 1-amino BTA is 1:0.01～0.05, first
Aldehyde is 1:15～20 with the mol ratio of deionized water；
(3) preparation of ageing-resistant function temperature sensing color changing Neutral writing ink mill base: at room temperature
Gained temperature sensing color changing system adds in (1) water soluble surfactant active, and uses
High-speed stirred mulser, with the rotating speed emulsifying 45～75min of 8000～14000rpm, obtains
To stable O/W type emulsion, then in this O/W type emulsion, it is slowly added dropwise (2)
Middle gained melamine resin pre-polymer solution and water soluble dispersing agent, and regulation system pH
Being 6.0, under room temperature, mechanical agitation treats that melamine resin pre-polymer solution is molten in this system
After solving dispersion, again the pH value of system is adjusted to 4.5～5.5, and is warming up to
React 2.5～4.0h at 70～80 DEG C, obtain ageing-resistant function temperature sensing color changing Neutral writing ink
Mill base.
The most according to claim 1 have ageing-resistant function temperature sensing color changing neutrality
The preparation method of ink mill base, it is characterised in that: described in step (1) in cosolvent
Water-fast unitary long-chain alkyl alcohol be n-heptanol, n-octyl alcohol, n-nonyl alcohol, just
Decanol, positive undecyl alcohol, lauryl alcohol, tetradecyl alchohol, hexadecanol, octadecanol, 22
At least one in alcohol and octacosanol.
The most according to claim 1 have ageing-resistant function temperature sensing color changing neutrality
The preparation method of ink mill base, it is characterised in that: described in step (1) in cosolvent
Ester be butyl formate, Tetryl formate., isoamyl formate, benzyl formate, acetyl
Ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, acetic acid Zhong Ding
Ester, pentyl acetate, isoamyl acetate, methyl amyl acetate, ethyl propionate, propanoic acid
Propyl ester, n-butyl propionate, amyl propionate, methyl butyrate, ethyl n-butyrate., lactic acid second
Ester, n-butyl lactate, diethyl carbonate, ethyl benzoate, isopropyl benzoate and
At least one in ethyl salicylate.
The most according to claim 1 have ageing-resistant function temperature sensing color changing neutrality
The preparation method of ink mill base, it is characterised in that: described in step (1) in cosolvent
Amine be at least one in ethylenediamine, oleyl amine and isopropanolamine.
The most according to claim 1 have ageing-resistant function temperature sensing color changing neutrality
The preparation method of ink mill base, it is characterised in that: described in step (1), electronics gives
Organic phenolic compound in body be hydroquinone, paranitrophenol, bisphenol-A and α-
At least one in naphthols；Carboxylic acid compound in described electronq donor is benzene second
At least one in acid, hydroxy carboxylic acid, hydroxyacetic acid, gluconic acid and succinic acid.
The most according to claim 1 have ageing-resistant function temperature sensing color changing neutrality
The preparation method of ink mill base, it is characterised in that: water solublity table described in step (3)
Face activating agent is sodium lauryl sulphate, dodecylbenzene sodium sulfonate and dodecyl sulphur
At least one in acid sodium.
7. according to the preparation method described in any claim in claim 1 to 6
That prepares gained has ageing-resistant function temperature sensing color changing Neutral writing ink mill base.
The most according to claim 7 have ageing-resistant function temperature sensing color changing neutrality
Ink mill base, it is characterised in that: by following neutral by accounting for ageing-resistant function temperature sensing color changing
Each component composition of ink mill base gross mass percentages: temperature sensing color changing system
15～35wt.%, melamine resin pre-polymer solution 10～30wt.%, soluble surface live
Property agent 0.5～2.0wt.% and balance deionized water.
The most according to claim 7 have ageing-resistant function temperature sensing color changing neutrality
Ink mill base, it is characterised in that: described ageing-resistant function temperature sensing color changing Neutral writing ink color
The solid content of slurry is not less than 20wt.%, mill base grain diameter D90It is not more than 2.5 μm,
Mill base high speed settling speed is not more than 50 μm/min.
The most according to claim 7 have ageing-resistant function temperature sensing color changing neutrality
Ink mill base, it is characterised in that: described ageing-resistant function temperature sensing color changing Neutral writing ink color
The solid content of slurry is not less than 40wt.%, mill base grain diameter D90It is not more than 250nm,
Mill base high speed settling speed is not more than 50 μm/min, and color paste viscosity is
70～200mPa s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510253811.7A CN104845448B (en) | 2015-05-18 | 2015-05-18 | There is ageing-resistant function temperature sensing color changing Neutral writing ink mill base and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510253811.7A CN104845448B (en) | 2015-05-18 | 2015-05-18 | There is ageing-resistant function temperature sensing color changing Neutral writing ink mill base and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104845448A CN104845448A (en) | 2015-08-19 |
| CN104845448B true CN104845448B (en) | 2016-10-05 |
Family
ID=53845456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510253811.7A Active CN104845448B (en) | 2015-05-18 | 2015-05-18 | There is ageing-resistant function temperature sensing color changing Neutral writing ink mill base and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104845448B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106442388A (en) * | 2016-09-07 | 2017-02-22 | 无限极（中国）有限公司 | Method for rapidly detecting stability of emulsion type daily chemical products |
| CN108841250A (en) * | 2018-05-24 | 2018-11-20 | 真彩文具股份有限公司 | Environment-friendly type fluorescence temperature sensing color changing water-based ink mill base and preparation method thereof |
| CN110143017A (en) * | 2019-03-01 | 2019-08-20 | 苏州盛风文化创意发展有限公司 | A kind of mounting face method of heat discoloration folding fan |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5646203A (en) * | 1994-03-31 | 1997-07-08 | Toppan Moore Co., Ltd. | Microcapsule-containing oil-based coating liquid, ink, coated sheet, and method of preparing the same |
| CN101970603A (en) * | 2007-07-10 | 2011-02-09 | 株式会社樱花彩色笔 | Thermochromic composition and thermochromic microcapsules |
| CN102191032A (en) * | 2010-03-19 | 2011-09-21 | 陈铨荣 | Reversible thermochromic organic material microcapsule |
| CN102477290A (en) * | 2010-11-30 | 2012-05-30 | 北京华纺高新技术有限公司 | Thermo-sensitive discoloration material microcapsule and preparation method thereof |
-
2015
- 2015-05-18 CN CN201510253811.7A patent/CN104845448B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5646203A (en) * | 1994-03-31 | 1997-07-08 | Toppan Moore Co., Ltd. | Microcapsule-containing oil-based coating liquid, ink, coated sheet, and method of preparing the same |
| CN101970603A (en) * | 2007-07-10 | 2011-02-09 | 株式会社樱花彩色笔 | Thermochromic composition and thermochromic microcapsules |
| CN102191032A (en) * | 2010-03-19 | 2011-09-21 | 陈铨荣 | Reversible thermochromic organic material microcapsule |
| CN102477290A (en) * | 2010-11-30 | 2012-05-30 | 北京华纺高新技术有限公司 | Thermo-sensitive discoloration material microcapsule and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104845448A (en) | 2015-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020200218A1 (en) | Microcapsule-type temperature change pigment, preparation method therefor and use thereof, and temperature change ink and use thereof | |
| CN104845448B (en) | There is ageing-resistant function temperature sensing color changing Neutral writing ink mill base and preparation method thereof | |
| Zhu et al. | Thermochromic microcapsules with highly transparent shells obtained through in-situ polymerization of urea formaldehyde around thermochromic cores for smart wood coatings | |
| DK2183328T3 (en) | Aqueous pigment preparations with non-ionic additives based on allyl and vinyl ethers | |
| CN101955708B (en) | Method for preparing nano microcapsule water-based color paste | |
| EP2772517B1 (en) | Colorant, microcapsule pigment prepared by using same, and ink composition for writing instrument | |
| CN105170041A (en) | Reversible thermochromic microcapsule pigment preparation method | |
| CN105860581B (en) | A kind of disperse dye composition and preparation method thereof | |
| JP7394929B2 (en) | water-based ballpoint pen | |
| CN102227253A (en) | Process, dispersions and use | |
| CN103205139B (en) | Polymerizable dye monomers, color polymer emulsion and preparation methods thereof | |
| Majeed et al. | Novel approach to water-efficient bulk industrial textile printing production of cotton fabric | |
| CN108559018B (en) | Nano-scale water Narrow Molecular Weight Distribution acrylic acid copolymer ester and preparation method thereof | |
| CN104877065A (en) | Organic reversible thermochromic microcapsule with long service life and large color difference and preparation method thereof | |
| CN101597446A (en) | A kind of stable-type yellow nanometer water-type pigment dispersion | |
| CN1974694B (en) | Water-base writing ink composition | |
| CN107653704A (en) | A kind of fiber stoste mill base and preparation method thereof | |
| CN108841250A (en) | Environment-friendly type fluorescence temperature sensing color changing water-based ink mill base and preparation method thereof | |
| CN104448933A (en) | Red liquid disperse dye and preparation method and usage thereof | |
| CN102532943B (en) | Preparation method for reverse phase microemulsion of dye solution | |
| JP2019203223A (en) | Method for dyeing polypropylene fiber and colored polypropylene fiber | |
| Zhou et al. | Study on preparation, characterization and application of mixed-colorants thermochromic microcapsules | |
| CN102504071B (en) | Preparation method of polymethylmethacrylate with high molecular weight and narrow molecular weight distribution | |
| CN102875822B (en) | Preparation method of photochromic latex emulsion | |
| CN104497631A (en) | Blue liquid disperse dye and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |