A kind of high viscosity dye-type black neutral ink
Technical field
The invention belongs to technical field of ink, it is related to a kind of high viscosity dye-type black neutral ink.
Background technology
Between oiliness ball pen oil ink and aqueous ball point ink, viscosity is the neutral ink of influence to Neutral writing ink viscosity
The key factor of water quality, with fluent writing, writing is clear, and color and luster sense is good, and handwriting is water-fast, sun-proof, the holding time
Long the features such as, accepted extensively and used by consumer.
China is that gel pen produces the first big country, but up to the present ink used by gel pen it is most of according to
Rely import, though Neutral writing ink there are many enterprises developing, the quality of China-made Neutral ink is unsatisfactory, not only less varieties, and
And because ink set is unreasonable, ink pseudoplastic behavior is poor, occurs ink leak, refluence, Mao Shui when viscosity is low, then exist when viscosity is high
Ink amount less, poor lubricity, the shortcomings of write not enough smooth.Therefore the development of Neutral writing ink, developing target market prospect and economic benefit
It is very considerable.
The content of the invention
The present invention is directed to the above-mentioned problems in the prior art, there is provided a kind of high viscosity dye-type black neutral ink,
With typical thixotropy, the good fluent writing of lubricity, while the problems such as also completely solving ink leak, flow backwards, and with coloring
Firmly, the advantages of fluent writing, high temperature resistant.
Technical solution of the present invention is as follows:
A kind of high viscosity dye-type black neutral ink, parts by weight of raw materials constitutes and is:30~45 parts of black dyes, anionic water
Property 5~8 parts of polyurethane-acrylate composite emulsion, 5~8 parts of APEO, 8~10 parts of polyacrylamide, polyacrylic acid
15~20 parts of sodium, 10~15 parts of carboxymethyl chitosan, 6~10 parts of chondroitin sulfate, 6~8 parts of lecithin, superfine alumina silicate 5~8
Part, 3~5 parts of dicalcium powder, 15~17 parts of nano silicon, 6~8 parts of modified starch, 75~90 parts of deionized water.
Described black dyes is direct black, acid black, vat black etc..
Described superfine alumina silicate is 3000 mesh.
Described dicalcium powder is 2500 mesh.
The preferred modified manometer silicon dioxide of described nano silicon, method of modifying:Nanosized SiO_2 is 1 in mass ratio:5
~8 are added in ethylene glycol, and APTES is dropwise added dropwise after ultrasonic 20min, are heated to reflux 20~24h,
Suction filtration, filter cake absolute ethanol washing, drying is subsequently dispersed in deionized water, 15~20g/L of dispersion concentration, in indifferent gas
Under body protection, 0.2mol/L ammonium titanyl oxalates are added dropwise, and to ammonium titanyl oxalate, the concentration in system is 15~20mmol/L, then is added dropwise
It is 2~3 that the salpeter solution of 0.05mol/L adjusts PH, stirring, after 30~50 DEG C of 25~30h of reaction, suction filtration, and filter cake is successively with anhydrous
Ethanol, distillation water washing, vacuum drying.
The high viscosity dye-type black neutral ink preparation method is:First, deionized water is boiled, and adds modified starch
After dissolving, room temperature is down to, sequentially adds APEO, polyacrylamide, superfine alumina silicate, nano silicon, stirred,
20~25min of ultrasonic vibration, is subsequently adding carboxymethyl chitosan, chondroitin sulfate, lecithin, dicalcium powder, is quickly stirred after mixing
15min is mixed, Anion Waterbase Polyurethane-polyacrylate Hybrid Emulsion is then dropwise added dropwise under agitation, be eventually adding black
Dyestuff, Sodium Polyacrylate, 50~80 DEG C of stirring 30min are milled to slurry granularity for 950~1000nm, i.e., in feeding ball mill
.
High viscosity dye-type black neutral ink of the present invention is easily dried using aqueous solvent quick solidifying, in formula, anion
Type aqueous polyurethane-acrylate composite emulsion, is a kind of novel adhesive, with high surface, good ecological safety
Property and intermiscibility, film can be formed writing surface is dried, it is its water resistance, mechanical performance and heat endurance and adhesive force, anti-
Impact strength, hardness and pliability are good.The water absorbing capacity extra-heavies such as polyacrylamide, carboxymethyl chitosan, modified starch are added, is protected
Outlet capacity is high, can release repeatedly water, water suction, effectively prevent dehydration, increase viscosity, make writing adhesion-tight, can Exposure to Sunlight, high temperature and
Exist for a long time in water and do not fall off.Appropriate lecithin, superfine alumina silicate are added, increases waterproof and heat resistance.Nanometer titanium dioxide
Silicon, especially modified nano silicon is well dispersed in aqueous, and can be brought into other components in ink set
Ion it is compound trigger polymerization system, and carry out surface grafting polymerization, utilization space steric effect.Make high molecular moieties
Generation dissociate and it is powered, adsorb in inorganic particle surfaces.Increase system stability, the problems such as overcoming its precipitation, reunite.Add
Sodium Polyacrylate be a kind of thickener with various properties, the effect with fixing metal ions, and trip can be prevented
Negative consequence is produced from metal ion.Dicalcium powder is weather-proof, protect color, and chondroitin sulfate, APEO effectively improved and moisten when writing
Slip energy, the tough and tensile firm and nib of writing film forming is difficult dry and hard.
High viscosity dye-type black neutral ink of the present invention, be relative to prior art beneficial effect:Ink viscosity is high,
The problems such as completely solving ink leak, flow backwards, emit water, with typical thixotropy, the not stagnant pen of the good fluent writing of lubricity, while and also and
And with firm coloration, fluent writing the advantages of high temperature resistant, improves the coloring unfading of ink, good stability, for a long time
Storage is also not in precipitated and separated agglomeration, and fluent writing is durable, stable performance, will not block nib, can effectively prevent
Ink fades, and extends the writing holding time;Advantages of nontoxic raw materials is harmless, safety and environmental protection.
Specific embodiment
The present invention is further illustrated below by specific embodiment, it should be understood that the preparation side of the embodiment of the present invention
Method is only used for illustrating the present invention, rather than limitation of the present invention;On the premise of present inventive concept, prepared by the present invention
The simple modifications of method belong to the protection domain of application claims.
Embodiment 1
A kind of high viscosity dye-type black neutral ink, parts by weight of raw materials constitutes and is:42.7 parts of Vatdirectblack DB, anion
6 parts of type aqueous polyurethane-acrylate composite emulsion, 6.6 parts of APEO, 9 parts of polyacrylamide, Sodium Polyacrylate 18
Part, 13.6 parts of carboxymethyl chitosan, 8 parts of chondroitin sulfate, 7.5 parts of lecithin, 6 parts of superfine alumina silicate, 4 parts of dicalcium powder, nanometer
6 parts of silica 1,7.5 parts of modified starch, 85 parts of deionized water.
Preparation method is:First, deionized water is boiled, and after adding modified starch dissolving, is down to room temperature, is sequentially added poly-
Oxygen vinethene, polyacrylamide, superfine alumina silicate, nano silicon, stirring, ultrasonic vibration 25min are subsequently adding carboxymethyl
Shitosan, chondroitin sulfate, lecithin, dicalcium powder, quick stirring 15min after mixing, be then dropwise added dropwise under agitation it is cloudy from
Subtype aqueous polyurethane-acrylate composite emulsion, is eventually adding black dyes, Sodium Polyacrylate, 50~80 DEG C of stirrings
30min, is milled to slurry granularity for 950~1000nm in feeding ball mill, obtain final product.
Embodiment 2
A kind of high viscosity dye-type black neutral ink, parts by weight of raw materials constitutes and is:30 parts of vat direct black BCN, anionic
5.5 parts of aqueous polyurethane-acrylate composite emulsion, 5 parts of APEO, 8 parts of polyacrylamide, 15 parts of Sodium Polyacrylate,
12 parts of carboxymethyl chitosan, 6 parts of chondroitin sulfate, 6 parts of lecithin, 5.5 parts of superfine alumina silicate, 3 parts of dicalcium powder, nanometer titanium dioxide
15 parts of silicon, 6 parts of modified starch, 75 parts of deionized water.
Preparation method is with embodiment 1.
Embodiment 3
A kind of high viscosity dye-type black neutral ink, parts by weight of raw materials constitutes and is:45 parts of acid black 172, it is anion-type water-thinned
8 parts of polyurethane-acrylate composite emulsion, 8 parts of APEO, 10 parts of polyacrylamide, 20 parts of Sodium Polyacrylate, carboxylic first
14.5 parts of base enclosure glycan, 10 parts of chondroitin sulfate, 8 parts of lecithin, 8 parts of superfine alumina silicate, 5 parts of dicalcium powder, nano silicon
17 parts, 8 parts of modified starch, 90 parts of deionized water.
Preparation method is with embodiment 1.
Embodiment 4
Difference from Example 1 is that described nano silicon is modified manometer silicon dioxide, method of modifying:Nanometer
SiO2 is 1 in mass ratio:6 are added in ethylene glycol, and APTES is dropwise added dropwise after ultrasonic 20min, plus
Heat backflow 20h, suction filtration, filter cake absolute ethanol washing, drying is subsequently dispersed in deionized water, dispersion concentration 18g/L,
Under inert gas shielding, 0.2mol/L ammonium titanyl oxalates are added dropwise, and to ammonium titanyl oxalate, the concentration in system is 15~20mmol/L, then is dripped
Plus 0.05mol/L salpeter solution adjust PH be 2, stirring, 30~50 DEG C reaction 25h after, suction filtration, filter cake successively with absolute ethyl alcohol,
Distillation water washing, vacuum drying.
By Neutral writing ink obtained in above-described embodiment 1-4 and write and be shown in Table 1 in the test result after plain paper.
Table 1
It can also be seen that neutral black ink viscosity of the present invention is apparently higher than common Neutral writing ink from the data of contrast experiment, have
There is notable thixotropy, pseudoplastic behavior is good, and ink viscosity is larger when static, and ink viscosity diminishes under shearing force, writes stream
Freely, linear homogeneous stabilization, have stronger adhesive force, soaking-resistant, the solarization of resistance to daylight, high temperature resistant, it is difficult for drop-off, in colour-stable etc.
Feature, and the ink cured time of the present invention is fast, not fugitive color, lustrous surface is good..