CN103788939A - Thermochromic composition, thermochromic erasable neutral ink and pen core filled with the same - Google Patents
Thermochromic composition, thermochromic erasable neutral ink and pen core filled with the same Download PDFInfo
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- CN103788939A CN103788939A CN201210429205.2A CN201210429205A CN103788939A CN 103788939 A CN103788939 A CN 103788939A CN 201210429205 A CN201210429205 A CN 201210429205A CN 103788939 A CN103788939 A CN 103788939A
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Abstract
The invention provides a thermochromic composition, a thermochromic microcapsule prepared by the thermochromic composition, thermochromic erasable neutral ink prepared by the thermochromic microcapsule, and a pen core filled with the thermochromic erasable neutral ink. The thermochromic composition comprises (1) an electron donating compound; (2) an electron accepting compound; and (3) an organic solvent. The thermochromic composition is characterized in that the organic solvent is diester formed by benzene ring-containing carboxylic acid and dihydric alcohol, or diester formed by dicarboxylic acid and benzene ring-containing fatty alcohol. A pen core can be assembled by the thermochromic erasable neutral ink of the invention combined with a specially-prepared erasable pen nib, which can realize functions of complete erasure of handwriting and repeated writing.
Description
Technical field
The pen core of the thermochromism microcapsule that the present invention relates to thermochromic compositions, made by thermochromic compositions, the thermochromism erasable Neutral writing ink of being made by thermochromism microcapsule and assembling thermochromism erasable Neutral writing ink.
Background technology
Thermochromism is by heating up or lowering the temperature to change the color of system.Existing thermochromic systems, the change of its color is reversible mostly, raise (or reduce) change to a certain temperature hierarchy color, understand immediate recovery once the color that is reduced to this temperature (or rising higher than this temperature) system at temperature; Or the color change of system is completely irreversible, once change has occurred temperature variation system color, then cannot recover.Above-mentioned system all cannot directly apply to erasable ink system, because as erasable ink, once its handwriting color in the time that temperature raises does not wish after disappearing that temperature reduces just immediate recovery of color; Consider that in transportation, issuable high temperature makes ink colour killing simultaneously, need to make its secondary color and normally writing under a certain environment.
The machine reversible thermochromic systems of common are is the composite mixture of a class, and it is mainly by supplied for electronic colour developing organic compound with formed by electron compound.Wherein supplied for electronic colour developing organic compound mostly is triaryl methane, fluorane or volution series, and being subject to electron compound is a kind of Lewis acid, and it comprises lipid acid, phenols and metal-salt thereof.Both are of a great variety, can combine according to demand in actual applications.This composite mixture can reversibly change along with temperature change color.
In above-mentioned composite mixture, add a kind of organic solvent, can well dissolve composite mixture and affect its color shifting properties in its molten state.By the thermochromic compositions of this class organic solvent and composite compositions of mixtures, it is colored state at normal temperatures, be heated to and colour killing and heating stop temperature occur after a certain temperature reduce color and no longer recover, could again recover being placed in by the above-mentioned composition of colour killing lower than color under a certain temperature environment of colour killing temperature.U.S. Pat P5,879,443 have reported the ester generating by the lipid acid containing even carbon and containing the alcohol of odd number carbon can realize above-mentioned functions.U.S. Pat P7,708,913 have reported the compound that general formula is (e) also can realize above-mentioned functions.
In formula, R is expressed as alkyl, the alkylene containing 4 or above carbon atom.
Obviously, current the found organic compound that can realize above-mentioned functions is quite limited.Therefore need exploitation can realize the novel composition of above-mentioned functions.
Summary of the invention
First object of the present invention is to provide a kind of thermochromic compositions of novelty, wherein contained organic solvent is colored state with containing supplied for electronic colour developing organic compound and being subject to the thermochromic compositions that the composite mixture of electron compound forms at normal temperatures, be heated to a certain temperature or colour killing reaction occurs during higher than this temperature, composition color disappears and stops heating color and no longer recovers, and this temperature is defined as colour killing temperature; By be placed in by the thermochromic compositions of colour killing another temperature or this temperature when following color again recover, this temperature is defined as secondary color temperature.Secondary color temperature is lower than colour killing temperature, and said process can repeat.
Therefore, first aspect, the invention provides a kind of thermochromic compositions, and it contains (1) supplied for electronic compound; (2) be subject to electron compound; (3) organic solvent, is characterized in that, described organic solvent is the diester that contains the carboxylic acid of phenyl ring and diester or the di-carboxylic acid of dibasic alcohol formation and contain the fatty alcohol formation of phenyl ring.
According to the present invention one preferred embodiment, the general formula of described organic solvent is represented by following formula (a) or formula (b):
Wherein, R
1, R
2identical or different, represent separately the alkoxyl group that alkyl or phenyl that alkyl, alkoxyl group, phenyl replace replaces; Wherein the contained carbon atom number of alkyl or alkoxyl group is 1-6, preferably 2-4; N is selected from 6-20, preferably 8-16; M, p are identical or different, are selected from 0-6, preferably 2-4.
Such organic solvent with contain supplied for electronic colour developing organic compound and be subject to the original state of the composition that the composite mixture of electron compound forms to be: under normal temperature, be coloured solid state, when temperature is elevated to the fusing point of solvent, solvent is molten into liquid state and dissolves supplied for electronic colour developing organic compound and be subject to electron compound.Now, supplied for electronic when solid-state colour developing organic compound and blocked by solvent molecule by electron compound molecular interaction, composition color disappears.And due to supplied for electronic colour developing organic compound be subject to the dissolving of electron compound in solvent, the zero pour of system declines, thereby need to drop to a temperature lower than original solvent fusing point, supplied for electronic colour developing organic compound and to be subject to electron compound recrystallization be solid-state and recover intermolecular interaction and colour developing again.
Supplied for electronic compound of the present invention is triaryl methane or fluorane, and its general formula can be represented by following formula (c) and formula (d):
Wherein, X
1, X
2and X
3be independently of one another-NH
2,-NHR ,-N (CH
3)
2,-NHCOCH
3or-CH
3.
Wherein, R
1, R
2, R
3and R
4in have one to be selected from amino, all the other are independently from each other hydrogen, halogen, benzene, alkyl and alkoxyl group; R
5and R
6identical or different, represent separately the phenyl that alkyl, phenyl or alkyl replace.
The electron compound that is subject to of the present invention is acidic organic compound, comprises lipid acid, phenols and derivative thereof, preferably containing phenols and the derivative thereof of 2 and above phenolic hydroxyl group.
For guaranteeing the permanent stability of composition color, preferably containing phenols and the derivative thereof of 2 and above phenolic hydroxyl group.Being exemplified below of above-claimed cpd: 2, 2-bis-(4-hydroxy phenyl) propane (dihydroxyphenyl propane), two (4-hydroxyphenyl) ethane of 1-, 1, two (4-the hydroxyphenyl)-3-methylbutanes of 1-, 1, two (4-the hydroxyphenyl)-3-methylpropanes of 1-, 2, two [(2-hydroxy-5-methyl base phenyl) the methyl]-4-methylphenols of 6-, 4, 4 ', 4 "-methylene tri phenol, 2, two (4-hydroxyphenyl) HFC-236fa of 2-, α, α, α '-tri-(4-hydroxyphenyl)-1-ethyl-4-isopropyl benzene, 2, 2 '-methylene-bis [6-(2-hydroxy-5-methyl base phenmethyl)-4-methylphenol.
The ratio of above-mentioned three kinds of components in thermochromic compositions depends on the demand to depth of shade and discoloring temperature.Under normal circumstances, can effectively realize supplied for electronic compound described in the thermochromic compositions of above-mentioned colour change function: be subject to electron compound: the mass ratio of organic solvent is 1: 0.1-10: 10-100, preferably 1: 0.5-2: 20-60.
According to the present invention, one preferred embodiment, the mass percent that described supplied for electronic compound accounts for described thermochromic compositions is 1.5%-5.0%, described to be subject to the mass percent that electron compound accounts for described thermochromic compositions be 1%-9.0%, and the mass percent that described organic solvent accounts for described thermochromic compositions is 86%-97.5%.
Second object of the present invention is to provide a kind of thermochromism microcapsule, and it contains wall material and the capsule-core of sealing capsule-core, and described capsule-core is above-described thermochromic compositions.
Thermochromism microcapsule of the present invention, can select in-situ polymerization, interfacial polymerization, complex coacervation etc. to synthesize according to the difference of wall material.Applicable wall material has homopolymer or the multipolymer of monomers such as being selected from phenylethylene, oleic series, toxilic acid series and is selected from the complex coacervation product of the water-soluble colloid of the oppositely chargeds such as gum arabic, pectin, gelatin, xanthan gum.Wherein, the mass ratio of wall material and capsule-core is 6: 1-1: in 1 scope, and preferably 3: 1-1: 1.
The thermochromism microcapsule that the present invention obtains can be spheroidal or irregular polyhedrons, are generally spheroidal, as shown in Figure 1.Microcapsules Size within the scope of 0.5-20 μ m, preferably 1-5 μ m.These microcapsule have dispersion stabilization good in water-based system.
The 3rd object of the present invention is to provide a kind of thermochromism erasable Neutral writing ink, and it contains above-mentioned thermochromism microcapsule, additive and water.
Additive of the present invention can be selected from one or more following ingredients: water soluble resin, dispersion agent, viscosity modifier, defoamer, wetting Agent for Printing Inks and sanitas.Wherein, described water soluble resin can be vinylbenzene polyacrylic resin.Described dispersion agent can be selected from tween, polyoxyethylene alkyl phenyl ether, fatty monoethanol amide, polyoxyethylene alkyl amine; Anion surfactant: fatty sulfuric ester monoethanolamine salt, fatty alcohol sulfate monoethanolamine salt, polyethylene polyamines salt, hexadecyl pyridinium bromide; Cats product: one or more compositions in ethylene oxide adduct, the trimethylammonium stearylamide halogenide of polyoxyethylene carboxylate, polypropylene glycol.Described viscosity modifier can be selected from one or more compositions in sodium polyacrylate, Natvosol, polyvinylpyrrolidone, polyvinyl alcohol, xanthan gum, alkoxyl group urethane.Described defoamer can be selected from two or more compositions in silicone emulsion, higher alcohols fatty acid ester, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxypropylene etc.Described wetting Agent for Printing Inks can be selected from glycerol, butyleneglycol, polyoxyethylene glycol, 1,2-PD, two or more compositions in hexylene glycol, Sorbitol Powder, Xylitol etc.Described sanitas is two or more compositions that are selected from methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propylparaben, butyl p-hydroxybenzoate, Sorbic Acid, potassium sorbate, calcium sorbate, phenylformic acid, Sodium Benzoate etc.
According to a particularly preferred embodiment of the present, in described thermochromism erasable Neutral writing ink, the shared mass percent of each component is as follows:
In addition, the present invention also provides the preparation method of described thermochromism erasable Neutral writing ink, and it comprises the following steps:
Take in proportion 3 components preparing thermochromic compositions: supplied for electronic colour developing organic compound, be subject to electron compound and organic solvent, be heated to melting and stir, the cooling thermochromic compositions solid that gets final product to obtain at room temperature after insulation 0.5-1h.
Wall material raw material and above-mentioned thermochromic compositions solid are added in the ethanolic soln that contains stablizer PVP, and ultrasonic dispersion the temperature by reaction system are controlled at 55-75 ℃; In nitrogen protection atmosphere and in the situation that continuing to stir, add the ethanolic soln that contains initiator, after completing, polyreaction can obtain the microcapsule granule of coated thermochromic compositions.Wherein, described initiator refers to that the easy decomposes of a class becomes free radical, i.e. the compound of elementary free radical, can be used for causing radical polymerization and the copolyreaction of alkene class, two vinyl monomers.The kind of operational initiator is a lot, is generally divided into by its molecular structure: peroxide initiator, and as oil-soluble Diisopropyl azodicarboxylate, water miscible V-50 initiator etc.; Redox system initiator, as water-soluble hydrogen peroxide-ferrous salt.Preparation in accordance with the present invention, those skilled in the art can select the initiator of one or more mentioned kinds according to actual needs.
In addition, according to the synthetic additive method that also can adopt invention technician to know of wall material of the present invention thermochromism microcapsule different from demand, herein without statement one by one.
The thermochromism microcapsule that make are added in pre-configured water soluble resin liquid, then add deionized water and stirring; Then add dispersion agent, viscosity modifier, defoamer, sanitas and wetting Agent for Printing Inks and stir and get final product to obtain thermochromism erasable Neutral writing ink of the present invention.
Thermochromism erasable Neutral writing ink of the present invention is characterised in that described thermochromism erasable Neutral writing ink is colored state at normal temperatures, be heated to colour killing temperature or colour killing reaction occurs during higher than colour killing temperature, ink color disappears and stops heating rear color and no longer recovers; By be placed in secondary color temperature by the thermochromism erasable Neutral writing ink of colour killing or during lower than secondary color temperature color again recover.Said process can repeat.Described colour killing temperature is higher than secondary color temperature.
According to the present invention another preferred embodiment, described colour killing temperature is higher than 45 ℃, described secondary color temperature is lower than 0 ℃.Select colour killing temperature higher than 45 ℃, secondary color temperature is lower than the thermochromic compositions of 0 ℃, is coated synthetic thermochromism microcapsule granule with wall material, makes thermochromism erasable Neutral writing ink by above-mentioned thermochromism microcapsule granule, additive and water.
The 4th object of the present invention is to provide a kind of pen core that assembles thermochromism erasable Neutral writing ink, and it is made up of above-mentioned thermochromism erasable Neutral writing ink, nib and other auxiliary accessories.
Therefore, the present invention also provides the special nib matching with described thermochromism erasable Neutral writing ink, comprise bullet shaped and needle tube shape nib, its ball diameter is 0.5-0.7mm, the quantity of nib ink container is more than 3 or 3, the radius clearance of ball and the rim of a bowl is within the scope of 15-30 μ m, and the end play of ball and ball seat is within the scope of 45-75 μ m.
Above-mentioned erasable Neutral writing ink is assembled into pen core, and its written handwriting is via in high rigidity plastic eraser wiping process, and most microcapsule granule is taken away by eraser chips on the one hand; Rubber and the fricative heat of writing medium are reacted microcapsule generation colour killing and are caused ink marks color to disappear on the other hand, thereby realize wiping completely and the function of repeated writing of person's handwriting.
The pen core being assembled into by auxiliary accessories such as nib provided by the invention, above-mentioned thermochromism erasable Neutral writing ink and oil pipe, connections can provide good writing quality: it is smooth to write smoothness out of ink, and amount out of ink and fluctuation thereof are controlled good.Handwriting, via the wiping of high rigidity plastic eraser, can be realized wiping completely and repeated writing of writing.
Accompanying drawing explanation
Fig. 1 is the microcapsule schematic diagram in the thermochromism erasable Neutral writing ink that makes of the embodiment of the present invention;
Fig. 2 is bullet shaped nib profile schematic diagram;
Fig. 3 is needle tube shape nib profile schematic diagram;
Fig. 4 is a kind of blue thermochromism erasable Neutral writing ink, bullet shaped nib with oil pipe, is linked and packed into the schematic diagram of pen core;
Fig. 5 is a kind of black thermochromism erasable Neutral writing ink, needle tube shape nib with oil pipe, is linked and packed into the schematic diagram of pen core.
Embodiment
Term in following examples " part " all refers to weight part.
Embodiment 1
Prepare a kind of black thermochromism erasable Neutral writing ink.
Take 1.0 parts of 2-phenylamino-3-methyl-6-dibutylamino fluoranes (production and sales of Long Sheng Chemical Co., Ltd. of Wenzhou City), 1.0 part 2,2-bis-(4-hydroxyphenyl) propane (sell by Nanjing Zhong Lian Chemical Co., Ltd., Bayer company of Germany produces) and 50.0 parts of undecane diacids two (4-benzyloxy) phenylethylester, be heated to melting and stir, the cooling thermochromic compositions solid that gets final product to obtain at room temperature after insulation 0.5-1h.
By methyl methacrylate, (the auspicious Chemical Co., Ltd. of upper Hypon sells, Germany's goldschmidt chemical corporation is produced) (Fu Tian Chemical Co., Ltd. of Jiaozhou City sells with styrene monomer, Daqing petrochemical company is produced) by 1: 9 mass ratio, amount to 5 parts, mix with 5 parts of the above-mentioned thermochromism solids making; Then this mixture is added in 30 parts of ethanolic solns that contain 0.2 part of stablizer PVP (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; In nitrogen protection and under lasting stirring state; add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), polyreaction makes the thermochromism microcapsule of resin parcel thermochromic compositions after 24 hours.
8 parts of above-mentioned thermochromism microcapsule granules that make are added in 25 parts of pre-configured water soluble resin liquid, add again 50 parts of deionized waters and stir, then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai Wen Pu chemical technology company limited sells for defoamer SPA-202 (production and sales of Shanghai Culture chemical color company limited) or BYK-073, BYK company of Germany produces) in 1 part, 1 part and 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.) of wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), carry out abundant stirring and obtain black thermochromism erasable Neutral writing ink (25 ℃ of system physical and chemical index control targets: viscosity 400～600cp, surface tension 25～35mN/m, pH value 7.0～8.5).
The colour killing temperature of above-mentioned black thermochromism Neutral writing ink is 55 ℃, and secondary color temperature is-10 ℃.
Embodiment 2
Prepare a kind of black thermochromism erasable Neutral writing ink.
Take 1.0 parts of 2-phenylamino-3-methyl-6-dibutylamino fluoranes (production and sales of Long Sheng Chemical Co., Ltd. of Wenzhou City), 2.0 part 2,2-bis-(4-hydroxyphenyl) propane (sell by Nanjing Zhong Lian Chemical Co., Ltd., Bayer company of Germany produces) and 40.0 parts of dodecanedioic acids two (4-benzyloxy) phenyl propyl ester, be heated to melting and stir, the cooling thermochromic compositions solid that gets final product to obtain at room temperature after insulation 0.5-1h.
By methyl methacrylate, (the auspicious Chemical Co., Ltd. of upper Hypon sells, Germany's goldschmidt chemical corporation is produced) (Fu Tian Chemical Co., Ltd. of Jiaozhou City sells with styrene monomer, Daqing petrochemical company is produced) by 1: 9 mass ratio, amount to 5 parts, mix with 5 parts of the above-mentioned thermochromism solids making; Then this mixture is added in 30 parts of ethanolic solns that contain 0.2 part of stablizer PVP (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; In nitrogen protection and under lasting stirring state; add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), polyreaction makes the thermochromism microcapsule of resin parcel thermochromic compositions after 24 hours.
8 parts of above-mentioned thermochromism microcapsule granules that make are added in 25 parts of pre-configured water soluble resin liquid, add again 50 parts of deionized waters and stir, then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, defoamer SPA-202 (production and sales of Shanghai Culture chemical color company limited) or BYK-073 (Shanghai Wen Pu chemical technology company limited production and sales, BYK company of Germany produces) in 1 part, 1 part and 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.) of wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), carry out abundant stirring and obtain black thermochromism erasable Neutral writing ink (25 ℃ of system physical and chemical index control targets: viscosity 400～600cp, surface tension 25～35mN/m, pH value 7.0～8.5).
The colour killing temperature of above-mentioned black thermochromism Neutral writing ink is 60 ℃, and secondary color temperature is-10 ℃.
Embodiment 3:
Prepare a kind of black thermochromism erasable Neutral writing ink.
Take 1.0 parts of 3-diethylin-7-(2 '-chloroaniline) fluorane (production and sales of Long Sheng Chemical Co., Ltd. of Wenzhou City), 0.5 part 4,4 '; 4 "-methylene tri phenol (sell by lark prestige Science and Technology Ltd., Tokyo HuaCheng Industry Co., Ltd produces) and 60.0 parts of eicosane diacids two (4-benzyloxy) phenylethylester, be heated to melting and stir, the cooling thermochromic compositions solid that gets final product to obtain at room temperature after insulation 0.5-1h.
By methyl methacrylate, (the auspicious Chemical Co., Ltd. of upper Hypon sells, Germany's goldschmidt chemical corporation is produced) (Fu Tian Chemical Co., Ltd. of Jiaozhou City sells with styrene monomer, Daqing petrochemical company is produced) by 1: 9 mass ratio, amount to 5 parts, mix with 5 parts of the above-mentioned thermochromism solids making; Then this mixture is added in 30 parts of ethanolic solns that contain 0.2 part of stablizer PVP (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; In nitrogen protection and under lasting stirring state; add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), polyreaction makes the thermochromism microcapsule of resin parcel thermochromic compositions after 24 hours.
8 parts of above-mentioned thermochromism microcapsule granules that make are added in 25 parts of pre-configured water soluble resin liquid, add again 50 parts of deionized waters and stir, then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai Wen Pu chemical technology company limited sells for defoamer SPA-202 (production and sales of Shanghai Culture chemical color company limited) or BYK-073, BYK company of Germany produces) in 1 part, 1 part and 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.) of wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), carry out abundant stirring and obtain black thermochromism erasable Neutral writing ink (25 ℃ of system physical and chemical index control targets: viscosity 400～600cp, surface tension 25～35mN/m, pH value 7.0～8.5).
The colour killing temperature of above-mentioned black thermochromism Neutral writing ink is 55 ℃, and secondary color temperature is-10 ℃.
Embodiment 4:
Prepare a kind of black thermochromism erasable Neutral writing ink.
Take 1.0 parts of 2-phenylamino-3-methyl-6-diethylin fluoranes (production and sales of Long Sheng Chemical Co., Ltd. of Wenzhou City), 0.5 part 4,4 '; 4 "-methylene tri phenol (sell by lark prestige Science and Technology Ltd., Tokyo HuaCheng Industry Co., Ltd produces) and 20.0 parts of undecane dicarboxylic acids two (4-benzyloxy) phenyl butyl ester, be heated to melting and stir, the cooling thermochromic compositions solid that gets final product to obtain at room temperature after insulation 0.5-1h.
By methyl methacrylate, (the auspicious Chemical Co., Ltd. of upper Hypon sells, Germany's goldschmidt chemical corporation is produced) (Fu Tian Chemical Co., Ltd. of Jiaozhou City sells with styrene monomer, Daqing petrochemical company is produced) by 1: 9 mass ratio, amount to 5 parts, mix with 5 parts of the above-mentioned thermochromism solids making; Then this mixture is added in 30 parts of ethanolic solns that contain 0.2 part of stablizer PVP (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; In nitrogen protection and under lasting stirring state; add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), polyreaction makes the thermochromism microcapsule of resin parcel thermochromic compositions after 24 hours.
8 parts of above-mentioned thermochromism microcapsule granules that make are added in 25 parts of pre-configured water soluble resin liquid, add again 50 parts of deionized waters and stir, then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai Wen Pu chemical technology company limited sells for defoamer SPA-202 (production and sales of Shanghai Culture chemical color company limited) or BYK-073, BYK company of Germany produces) in 1 part, 1 part and 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.) of wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), carry out abundant stirring and obtain black thermochromism erasable Neutral writing ink (25 ℃ of system physical and chemical index control targets: viscosity 400～600cp, surface tension 25～35mN/m, pH value 7.0～8.5).
The colour killing temperature of above-mentioned black thermochromism Neutral writing ink is 60 ℃, and secondary color temperature is-10 ℃.
Embodiment 5:
Prepare a kind of blue thermochromism erasable Neutral writing ink.
Take 1.0 part 3, two (4-the dimethylamino phenyl)-6-Dimethylaminobenzene peptides (production and sales of Long Sheng Chemical Co., Ltd. of Wenzhou City) of 3-, 1.0 part 2,2-bis-(4-hydroxyphenyl) propane (sell by Nanjing Zhong Lian Chemical Co., Ltd., Bayer company of Germany produces) and 50.0 part of 11 carbon glycol dibenzyloxy benzene yl acetate, be heated to melting and stir, the cooling thermochromic compositions solid that gets final product to obtain at room temperature after insulation 0.5-1h.
By methyl methacrylate, (the auspicious Chemical Co., Ltd. of upper Hypon sells, Germany's goldschmidt chemical corporation is produced) (Fu Tian Chemical Co., Ltd. of Jiaozhou City sells with styrene monomer, Daqing petrochemical company is produced) by 1: 9 mass ratio, amount to 5 parts, mix with 5 parts of the above-mentioned thermochromism solids making; Then this mixture is added in 30 parts of ethanolic solns that contain 0.2 part of stablizer PVP (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; In nitrogen protection and under lasting stirring state; add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), polyreaction makes the thermochromism microcapsule of resin parcel thermochromic compositions after 24 hours.
8 parts of above-mentioned thermochromism microcapsule granules that make are added in 25 parts of pre-configured water soluble resin liquid, add again 50 parts of deionized waters and stir, then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, defoamer SPA-202 (production and sales of Shanghai Culture chemical color company limited) or BYK-073 (Shanghai Wen Pu chemical technology company limited production and sales, BYK company of Germany produces) in 1 part, 1 part and 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.) of wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), carry out abundant stirring and obtain blue thermochromism erasable Neutral writing ink (25 ℃ of system physical and chemical index control targets: viscosity 400～600cp, surface tension 25～35mN/m, pH value 7.0～8.5).
The colour killing temperature of above-mentioned blue thermochromism Neutral writing ink is 55 ℃, and secondary color temperature is-10 ℃.
Embodiment: 6:
Prepare a kind of blue thermochromism erasable Neutral writing ink.
Take 1.0 part 3, two (4-the dimethylamino phenyl)-6-Dimethylaminobenzene peptides (production and sales of Long Sheng Chemical Co., Ltd. of Wenzhou City) of 3-, 2.0 part 2,2-bis-(4-hydroxyphenyl) propane (sell by Nanjing Zhong Lian Chemical Co., Ltd., Bayer company of Germany produces) and 40.0 part of 12 carbon glycol benzyloxy phenenyl propionic ester, be heated to melting and stir, the cooling thermochromic compositions solid that gets final product to obtain at room temperature after insulation 0.5-1h.
By methyl methacrylate, (the auspicious Chemical Co., Ltd. of upper Hypon sells, Germany's goldschmidt chemical corporation is produced) (Fu Tian Chemical Co., Ltd. of Jiaozhou City sells with styrene monomer, Daqing petrochemical company is produced) by 1: 9 mass ratio, amount to 5 parts, mix with 5 parts of the above-mentioned thermochromism solids making; Then this mixture is added in 30 parts of ethanolic solns that contain 0.2 part of stablizer PVP (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; In nitrogen protection and under lasting stirring state; add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), polyreaction makes the thermochromism microcapsule of resin parcel thermochromic compositions after 24 hours.
8 parts of above-mentioned thermochromism microcapsule granules that make are added in 25 parts of pre-configured water soluble resin liquid, add again 50 parts of deionized waters and stir, then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, defoamer SPA-202 (production and sales of Shanghai Culture chemical color company limited) or BYK-073 (Shanghai Wen Pu chemical technology company limited production and sales, BYK company of Germany produces) in 1 part, 1 part and 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.) of wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), carry out abundant stirring and obtain blue thermochromism erasable Neutral writing ink (25 ℃ of system physical and chemical index control targets: viscosity 400～600cp, surface tension 25～35mN/m, pH value 7.0～8.5).
The colour killing temperature of above-mentioned blue thermochromism Neutral writing ink is 60 ℃, and secondary color temperature is-10 ℃.
Embodiment 7:
Prepare a kind of blue thermochromism erasable Neutral writing ink.
Take 1.0 part 3, two (4-the dimethylamino phenyl)-6-Dimethylaminobenzene peptides (production and sales of Long Sheng Chemical Co., Ltd. of Wenzhou City) of 3-, 0.5 part 4,4 '; 4 "-methylene tri phenol (sell by lark prestige Science and Technology Ltd., Tokyo HuaCheng Industry Co., Ltd produces) and 60.0 part of ten carbon glycol dibenzyloxy benzene yl acetate, be heated to melting and stir, the cooling thermochromic compositions solid that gets final product to obtain at room temperature after insulation 0.5-1h.
By methyl methacrylate, (the auspicious Chemical Co., Ltd. of upper Hypon sells, Germany's goldschmidt chemical corporation is produced) (Fu Tian Chemical Co., Ltd. of Jiaozhou City sells with styrene monomer, Daqing petrochemical company is produced) by 1: 9 mass ratio, amount to 5 parts, mix with 5 parts of the above-mentioned thermochromism solids making; Then this mixture is added in 30 parts of ethanolic solns that contain 0.2 part of stablizer PVP (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; In nitrogen protection and under lasting stirring state; add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), polyreaction makes the thermochromism microcapsule of resin parcel thermochromic compositions after 24 hours.
8 parts of above-mentioned thermochromism microcapsule granules that make are added in 25 parts of pre-configured water soluble resin liquid, add again 50 parts of deionized waters and stir, then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, defoamer SPA-202 (production and sales of Shanghai Culture chemical color company limited) or BYK-073 (Shanghai Wen Pu chemical technology company limited production and sales, BYK company of Germany produces) in 1 part, 1 part and 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.) of wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), carry out abundant stirring and obtain blue thermochromism erasable Neutral writing ink (25 ℃ of system physical and chemical index control targets: viscosity 400～600cp, surface tension 25～35mN/m, pH value 7.0～8.5).
The colour killing temperature of above-mentioned blue thermochromism Neutral writing ink is 55 ℃, and secondary color temperature is-10 ℃.
Embodiment 8:
Prepare a kind of blue thermochromism erasable Neutral writing ink.
Take 1.0 part 3, two (4-the dimethylamino phenyl)-6-Dimethylaminobenzene peptides (production and sales of Long Sheng Chemical Co., Ltd. of Wenzhou City) of 3-, 0.5 part 4,4 '; 4 " (lark becomes Science and Technology Ltd. to sell to-methylene tri phenol, Tokyo HuaCheng Industry Co., Ltd produces) and 20.0 part of 13 carbon glycol benzyloxy phenenyl butyric ester, be heated to melting and stir, the cooling thermochromic compositions solid that gets final product to obtain at room temperature after insulation 0.5-1h.
By methyl methacrylate, (the auspicious Chemical Co., Ltd. of upper Hypon sells, Germany's goldschmidt chemical corporation is produced) (Fu Tian Chemical Co., Ltd. of Jiaozhou City sells with styrene monomer, Daqing petrochemical company is produced) by 1: 9 mass ratio, amount to 5 parts, mix with 5 parts of the above-mentioned thermochromism solids making; Then this mixture is added in 30 parts of ethanolic solns that contain 0.2 part of stablizer PVP (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; In nitrogen protection and under lasting stirring state; add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile (production and sales of Shanghai Jing Chun Industrial Co., Ltd.), polyreaction makes the thermochromism microcapsule of resin parcel thermochromic compositions after 24 hours.
8 parts of above-mentioned thermochromism microcapsule granules that make are added in 25 parts of pre-configured water soluble resin liquid, add again 50 parts of deionized waters and stir, then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, defoamer SPA-202 (production and sales of Shanghai Culture chemical color company limited) or BYK-073 (Shanghai Wen Pu chemical technology company limited production and sales, BYK company of Germany produces) in 1 part, 1 part and 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.) of wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), carry out abundant stirring and obtain blue thermochromism erasable Neutral writing ink (25 ℃ of system physical and chemical index control targets: viscosity 400～600cp, surface tension 25～35mN/m, pH value 7.0～8.5).
The colour killing temperature of above-mentioned blue thermochromism Neutral writing ink is 60 ℃, and secondary color temperature is-10 ℃.
Embodiment 9:
Prepare a kind of thermochromism erasable Neutral ball-point for ball-point pen of black.
By the black thermochromism erasable Neutral writing ink coupling bullet shaped nib of preparation in embodiment 1, ball diameter is 0.6mm, ink container quantity is 3, within the radius clearance of ball and the rim of a bowl is controlled at 20-28 μ m scope, within the end play between ball and ball seat is controlled at 50-70 μ m scope.Other accessory comprises oil pipe, connection, lithium saponify (liquid floating plug), rubber protecting jacket etc.Assemble by following operation:
In oil pipe, pour into ink-load and connect-fill nib-perfusion lithium saponify-Dai protective sleeve-centrifugal, get final product to obtain the thermochromism erasable Neutral ball-point for ball-point pen of black.
The performance index of this pen core are as follows after testing:
Just write performance: qualified;
Writing quality: write formation black handwriting on paper, this person's handwriting can completely dissolve via high rigidity plastic eraser wiping black; Above-mentioned black handwriting is placed in to minute black completely dissolve of 60 ℃ of baking oven numbers, from baking oven, take out and be placed in black under room temperature and no longer recover, person's handwriting after colour killing is placed in to the refrigerator and cooled of-10 ℃ after several minutes, color reverts to original black again, takes out to be placed in this person's handwriting under room temperature and still to remain black from refrigerator.Above-mentioned variable color behavior can repeat.
Marking lengths: 200-250m;
Amount out of ink: 250-350mg/100m;
Intermittently write: more than 24 hours;
Stitching fastness: qualified;
Drip China ink: 24 hours without dripping China ink;
Water tolerance: stitching was normal in 24 hours;
Light permanency: stitching was normal in 24 hours;
Perviousness: qualified;
Keeping quality: qualified.
Embodiment 10
Prepare a kind of thermochromism erasable Neutral ball-point for ball-point pen of blueness.
By the blue thermochromism erasable Neutral writing ink coupling needle tube shape nib of preparation in embodiment 3, ball diameter is 0.5mm, ink container quantity is 3, within the radius clearance of ball and the rim of a bowl is controlled at the scope of 20-28 μ m, within the end play between ball and ball seat is controlled at the scope of 50-70 μ m.Other accessory comprises oil pipe, connection, lithium saponify (liquid floating plug), rubber protecting jacket etc.Assemble by following operation:
In oil pipe, pour into ink-load and connect-fill nib-perfusion lithium saponify-Dai protective sleeve-centrifugal, get final product to obtain the thermochromism erasable Neutral ball-point for ball-point pen of black.
The performance index of this pen core are as follows after testing:
Just write performance: qualified;
Writing quality: write on paper and form blue person's handwriting, this person's handwriting can completely dissolve via high rigidity plastic eraser wiping blueness; Above-mentioned blue person's handwriting is placed in to minute blue completely dissolve of 60 ℃ of baking oven numbers, from baking oven, take out and be placed in blueness under room temperature and no longer recover, person's handwriting after colour killing is placed in to the refrigerator and cooled of-10 ℃ after several minutes, color reverts to original blueness again, takes out to be placed in this person's handwriting under room temperature and still to remain blueness from refrigerator.Above-mentioned variable color behavior can repeat.
Marking lengths: 200-250m;
Amount out of ink: 250-350mg/100m;
Intermittently write: more than 24 hours;
Stitching fastness: qualified;
Drip China ink: 24 hours without dripping China ink;
Water tolerance: stitching was normal in 24 hours;
Light permanency: stitching was normal in 24 hours;
Perviousness: qualified;
Keeping quality: qualified.
Claims (27)
1. thermochromic compositions, it contains (1) supplied for electronic compound; (2) be subject to electron compound; (3) organic solvent, is characterized in that, described organic solvent is the diester that contains the carboxylic acid of phenyl ring and diester or the di-carboxylic acid of dibasic alcohol formation and contain the fatty alcohol formation of phenyl ring.
2. thermochromic compositions according to claim 1, is characterized in that the general formula of described organic solvent is represented by following formula (a) or formula (b):
Wherein, R
1, R
2identical or different, represent separately the alkoxyl group that alkyl or phenyl that alkyl, alkoxyl group, phenyl replace replaces, wherein the contained carbon atom number of alkyl or alkoxyl group is 1-6, preferably 2-4; N is selected from 6-20, preferably 8-16; M, p are identical or different, are 0-6, preferably 2-4.
3. thermochromic compositions according to claim 1 and 2, is characterized in that described supplied for electronic compound: be subject to electron compound: the mass ratio of organic solvent is 1: 0.1-10: 10-100, preferably 1: 0.5-2: 20-60.
4. thermochromic compositions according to claim 1 and 2, it is characterized in that the mass percent that described supplied for electronic compound accounts for described thermochromic compositions is 1.5%-5.0%, described to be subject to the mass percent that electron compound accounts for described thermochromic compositions be 1%-9.0%, and the mass percent that described organic solvent accounts for described thermochromic compositions is 86%-97.5%.
5. thermochromic compositions according to claim 1, is characterized in that described supplied for electronic compound is triaryl methane or fluorane.
6. thermochromic compositions according to claim 5, is characterized in that the general formula of described triaryl methane is represented by following formula (c):
Wherein, X
1, X
2and X
3be independently of one another-NH
2,-NHR ,-N (CH
3)
2,-NHCOCH
3or-CH
3.
7. thermochromic compositions according to claim 5, is characterized in that the general formula of described fluorane is represented by following formula (d):
Wherein, R
1, R
2, R
3and R
4in have one to be selected from amino, all the other are independently from each other hydrogen, halogen, benzene, alkyl and alkoxyl group; R
5and R
6identical or different, represent separately the phenyl that alkyl, phenyl or alkyl replace.
8. thermochromic compositions according to claim 1, described in it is characterized in that, being subject to electron compound is acidic organic compound, comprises lipid acid, phenols and derivative thereof, preferably containing phenols and the derivative thereof of 2 and above phenolic hydroxyl group.
9. thermochromism microcapsule, it contains wall material and the capsule-core of sealing capsule-core, it is characterized in that described capsule-core is the thermochromic compositions described in claim 1-8 any one.
10. thermochromism microcapsule according to claim 9, what it is characterized in that described microcapsule is shaped as spheroidal or irregular polyhedrons.
11. thermochromism microcapsule according to claim 9, the particle diameter that it is characterized in that described microcapsule is 0.5-20 μ m, preferably 1-5 μ m.
12. thermochromism microcapsule according to claim 9, it is characterized in that the monomer polymerization that described wall material is selected from vinylbenzene, vinylformic acid, toxilic acid or derivatives thereof by one or more forms, or be selected from the complex coacervation product of oppositely charged lyophilic colloid, as gum arabic, pectin, gelatin or xanthan gum.
13. thermochromism microcapsule according to claim 9, the mass ratio that it is characterized in that described wall material and capsule-core is 6: 1-1: 1, preferably 3: 1-1: 1.
14. thermochromism erasable Neutral writing inks, it contains thermochromism microcapsule described in claim 9-13 any one, additive and water.
15. thermochromism erasable Neutral writing inks according to claim 14, is characterized in that described additive is selected from one or more following ingredients: water soluble resin, dispersion agent, viscosity modifier, defoamer, wetting Agent for Printing Inks and sanitas.
16. thermochromism erasable Neutral writing inks according to claim 15, is characterized in that described water soluble resin is vinylbenzene polyacrylic resin.
17. thermochromism erasable Neutral writing inks according to claim 15, is characterized in that described dispersion agent is selected from tween; Polyoxyethylene alkyl phenyl ether; Fatty monoethanol amide; Polyoxyethylene alkyl amine; Anion surfactant: fatty sulfuric ester monoethanolamine salt, fatty alcohol sulfate monoethanolamine salt, polyethylene polyamines salt, hexadecyl pyridinium bromide; Cats product: one or more compositions in ethylene oxide adduct, the trimethylammonium stearylamide halogenide of polyoxyethylene carboxylate, polypropylene glycol.
18. thermochromism erasable Neutral writing inks according to claim 15, is characterized in that described viscosity modifier is selected from one or more compositions in sodium polyacrylate, Natvosol, polyvinylpyrrolidone, polyvinyl alcohol, xanthan gum and alkoxyl group urethane.
19. thermochromism erasable Neutral writing inks according to claim 15, is characterized in that described defoamer is selected from two or more compositions in silicone emulsion, higher alcohols fatty acid ester, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxypropylene.
20. thermochromism erasable Neutral writing inks according to claim 15, is characterized in that described wetting Agent for Printing Inks is selected from glycerol, butyleneglycol, polyoxyethylene glycol, 1,2-PD, two or more compositions in hexylene glycol, Sorbitol Powder or Xylitol.
21. thermochromism erasable Neutral writing inks according to claim 15, is characterized in that described sanitas is selected from two or more compositions in methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propylparaben, butyl p-hydroxybenzoate, Sorbic Acid, potassium sorbate, calcium sorbate, phenylformic acid and Sodium Benzoate.
22. according to the thermochromism erasable Neutral writing ink described in any one in claim 14-21, it is characterized in that the shared mass percent of each component is as follows:
23. according to the thermochromism erasable Neutral writing ink described in any one in claim 14-22, it is characterized in that described thermochromism erasable Neutral writing ink is colored state at normal temperatures, be heated to colour killing temperature or colour killing reaction occurs during higher than colour killing temperature, ink color disappears and stops heating rear color and no longer recovers; By be placed in secondary color temperature by the thermochromism erasable Neutral writing ink of colour killing or during lower than secondary color temperature color again recover.
24. thermochromism erasable Neutral writing inks according to claim 23, is characterized in that described colour killing temperature is higher than secondary color temperature.
25. thermochromism erasable Neutral writing inks according to claim 23, is characterized in that described colour killing temperature is higher than 45 ℃, and described secondary color temperature is lower than 0 ℃.
The pen core of 26. assembling thermochromism erasable Neutral writing inks, it is made up of thermochromism erasable Neutral writing ink, nib and other auxiliary accessories described in any one in claim 14-25.
27. pen cores according to claim 26, it is characterized in that described nib is selected from bullet shaped or needle tube shape nib, its ball diameter is 0.5-0.7mm, the quantity of nib ink container is more than 3 or 3, the radius clearance of ball and the rim of a bowl is within the scope of 15-30 μ m, and the end play of ball and ball seat is within the scope of 45-75 μ m.
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Application publication date: 20140514 |