CN102241921A - Blue ink for roller ball pen and preparation method thereof - Google Patents
Blue ink for roller ball pen and preparation method thereof Download PDFInfo
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- CN102241921A CN102241921A CN2011101640622A CN201110164062A CN102241921A CN 102241921 A CN102241921 A CN 102241921A CN 2011101640622 A CN2011101640622 A CN 2011101640622A CN 201110164062 A CN201110164062 A CN 201110164062A CN 102241921 A CN102241921 A CN 102241921A
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Abstract
The invention discloses blue ink for a roller ball pen, consisting of the following components in percentage by weight: 15%-30% of blue pigment paste, 5%-30% of organic silicon modified acrylic resin emulsion, 10%-30% of solvent, 0.3%-0.8% of thickener, 1%-3% of pH regulator, 0.2%-2.0% of lubricating agent, 0.3%-2.0% of anti-rusting agent, 0.2%-2.0% of antiseptic agent, 0.02%-0.5% of defoaming agent and the balance of de-ionized water. The ink has the advantages of even dispersing efficiency, proper viscosity, high system stability, good high/low temperature resistance, and the like. The prepared roller ball pen is used for smooth writing without leaking, has a long cap-removing time, and can also be used for normally writing at a temperature of -20 DEG C to 60 DEG C. The invention also discloses a preparation method of the ink, which has the characteristics of easily-controlled process and convenience for adjustment.
Description
Technical field
The present invention relates to ink and preparation field thereof, be specifically related to a kind of gel ink pen blue ink and preparation method thereof.
Background technology
Fluent writing is lubricated, writing is clear, color and luster good because of it has for gel ink pen (being the Neutral writing ink pen), and rapid-curing cutback, is not stained with advantages such as not saturating, water-fast, sun-proof, long preservative period, becomes most popular in the world a kind of writing implement.The employed ink viscosity of gel ink pen between the viscosity of oiliness ball pen ink (1000～20000mPas) and aqueous ball point ink viscosity (＜10mPas) between, and has a good thixotropy, when gel ink pen is stored in the shaft of a writing brush with ink, ink is in high viscous state, prevents that ink from leaking by nib; When writing, when the ball in the nib slided, the shearing force of generation made the ink desaturation, and viscosity reduces, and writes thereby ink can flow through nib.
China produces first big country for the Neutral writing ink pen, but produces the almost whole dependence on import of the used ink of Neutral writing ink pen so far, mainly comes from Japan, Korea S, the U.S. and Germany.The home-made gel ink pen is being with ink because in stability, exist shortcoming aspect the fluency, and can't large-scale application.But the written matching of import ink and domestic production is relatively poor, and the domestic gel ink pen of producing uses ink owing to the technical elements reason, also there are some problems: one, poor stability, quality guaranteed period is short, through long time stored, layering, deposited phenomenon can be occurred, problems such as broken string, nib obstruction can be occurred when writing; Two, temperature tolerance is poor, and during temperature variation, it is inhomogeneous that ink is told China ink, and ink leak or broken string take place easily; Three, the time of raising one's hat lacks.
The nanometer dispersion technology of pigment is one of difficult problem of current international paint ink production, also is one of most critical technology of the high-quality ink of preparation, and can pigment disperse in the medium-term and long-term stabilized nano that keeps of ink, be the key that can the ink quality qualified.When the blue pigments particle can not be accomplished enough when thin, because gravity former thereby layering, precipitation that ink is produced, thereby the nib of resulting in blockage, and when particle during less than 500nm, the particle in water attracts each other, and can be inclined to reunion, again form macrobead, this moment, the form of China ink was extremely unstable, therefore, must it stably was scattered in the water by methods such as suitable surface treatment, surface grafting or use dispersion agents.In order to improve the dispersing of pigments performance, need carry out surface modification to pigment usually, or select suitable wetting agent, dispersion agent, be dispersed in the medium so that pigment can be stable.The conventional pigment process for treating surface mainly improves the surface properties of pigment by means such as acid, alkali, resin or oxidations, but these treating processess are loaded down with trivial details, and effect is also as one wishes not to the utmost.
A kind of Neutral writing ink is disclosed among the Chinese patent ZL200610024695.2, comprise following component: A: water-soluble dye 0.5～6 gram, B: polyacrylamide 1～8 gram of molecular weight＞200,000, C: organic water-soluble reductive agent 0.5～4 gram, D: nonyl phenol polyethoxye (5) ether 1～6mL, E: deionized water 100 grams; Wherein, water-soluble dye comprises: acid ink blue, acid ink are deceived; The organic water-soluble reductive agent comprises: xitix, oxalic acid, sodium oxalate.This Neutral writing ink can be used for recording of the Neutral writing ink pen sold in market, and writing quality is good, can stablize preservation; In addition, can not use liquid floating plug ester during this ink can, thereby simplify filling process.But its stability is still waiting further raising.
A kind of pigment carbon black gel ink pen ink and preparation method thereof is disclosed among the Chinese patent ZL200610028026.2.The component weight proportion of this gel ink pen ink is: carbon black color slurry 30%～40%, solvent 10～30%, thickening material 1%～5%, suppress volatilizer 0.5%～5%, pH regulator agent 1%～3%, lubricant 1%～2%, rust-preventive agent 0.5%～2%, sanitas 0.5%～2%, deionized water 30%～50%.It is simple, with low cost that this gel ink pen ink has technology, the writing quality that color and luster is vivid and good, but its stability is still waiting further raising.
Summary of the invention
The invention provides a kind of gel ink pen blue ink with good high low-temperature stability and sharpness.
The present invention also provides the preparation method of a kind of gel ink pen with blue ink, and this method is easy to control, is convenient to regulate.
Interaction according to pigment and solvent, in ink, introduce numerator self-assembly technique, by polyelectrolyte surface of pigments is carried out molecular level other places reason, make the pigment particles surface wrap up electrostatic double layer closely, suppress the further gathering of pigment primary particle, and can change the thickness and the electric charge intensity of electrostatic double layer as required, increase the stability of pigment in dispersion system.
A kind of gel ink pen blue ink, form by following raw materials by weight percent: blue pigments mill base 15%～30%, organosilicon modified crylic acid resin emulsion 5%～30%, solvent 10%～30%, thickening material 0.3%～0.8%, pH regulator agent 1%～3%, lubricant 0.2%～2.0%, rust-preventive agent 0.3%～2.0%, sanitas 0.2%～2.0%, defoamer 0.02%～0.5%, the deionized water surplus.
Blue pigments in the described blue pigments mill base can be selected this area blue series pigments commonly used for use, and as commercially available prod such as phthalocyanine blue 15:3 or C.I. pigment blue 60s, structural formula is as follows respectively:
The preparation method of described blue pigments mill base comprises step:
(1) anionic dispersing agents is dissolved in the deionized water, regulating the pH value with ammoniacal liquor is 7.5-9.5, obtain the anionic dispersing agents aqueous solution, add blue pigments again to the negatively charged ion aqueous dispersant, mix and made blue pigments fully wetting at least in 0.5 hour, add the polyquaternium positively charged ion then, mix obtaining product at least in 0.5 hour one time, finish an electrostatic double layer assembling;
(2) in a product of step (1), repeat alternately to add anionic dispersing agents and polyquaternium positively charged ion repeatedly, operate same step (1), obtain secondary product, finish a plurality of electrostatic double layer assemblings;
(3) in the repeatedly product of product of step (1) or step (2), add anionic polyacrylic grind resin and proper quantity of defoaming agent, mixed the back sand milling 4 hours～8 hours, make the blue pigments mill base;
In single electrostatic double layer assembling, the add-on of described anionic dispersing agents is 0.1%～3% of a blue pigments mill base quality, and the cationic add-on of described polyquaternium is 0.1%～3% of a blue pigments mill base quality;
The add-on of described blue pigments is 35%～45% of a blue pigments mill base quality;
The add-on of described anionic polyacrylic grind resin is 5%～12% of a blue pigments mill base quality.
According to the early-stage Study result, the cationic built-up time of described anionic dispersing agents and polyquaternium 0.5 hour is enough, can realize the adsorption equilibrium of polyelectrolyte.The concentration of polyelectrolyte can not be too high, because after each layer assembling fully, the process filtration step is not to remove the not unnecessary polyelectrolyte of absorption, if concentration is too high, the polyelectrolyte of absorption is not more so, cause slight precipitation easily behind the polyelectrolyte that adds opposite charges, the add-on of blue pigments is 35%～45% of a blue pigments mill base quality; In single electrostatic double layer assembling, the add-on of anionic dispersing agents is 0.1%～3% of a blue pigments mill base quality, the cationic add-on of polyquaternium is 0.1%～3% of a blue pigments mill base quality, enough assembled corresponding blue pigments specific surface area fully, in the case, not Xi Fu polyelectrolyte amount seldom, the polyelectrolyte that can not need filter direct adding opposite charges still can not cause precipitation.
The thickness of electrostatic double layer can be realized by the number of plies of assembling effectively regulating, and repeats alternately to add anionic dispersing agents and polyquaternium positively charged ion n time in a product of step (1), finishes the assembling film structure of n+1 electrostatic double layer.Owing to have bigger repulsive force between electrostatic double layer, 1-2 assembling double electrical layers is enough for effective dispersion of blue pigments, and more double electrical layers can not obviously increase dispersion effect, but but increases production cost, lowers efficiency; Wherein, n is a positive integer.
The mode that mixes is adopted in described mixing, and stirring velocity is preferably 400～1000 rev/mins.
Described anionic dispersing agents is selected a kind of in sodium polystyrene sulfonate, poly-Xylo-Mucine, polyoxyethylene alkyl ether sulfate salt, sodium alginate, the sodium polyacrylate for use.
Described polyquaternium cation chosen Poly Dimethyl Diallyl Ammonium Chloride, polymethyl acyl-oxygen ethyl alkyl dimethyl ammonium chloride, polymethyl acyl-oxygen ethyl n-benzyl, N, N-alkyl dimethyl ammonium chloride, polymethyl acyl-oxygen ethyl n-ethyl, N, N-dimethyl brometo de amonio, polymethyl acyl-oxygen ethyl n-butyl, N, N-dimethyl brometo de amonio, polymethyl acyl-oxygen ethyl n-hexadecyl, N, a kind of in the N-dimethyl brometo de amonio.
Described anionic polyacrylic grind resin has more vinylformic acid negative charge, in process of lapping, can be on the blue granules of pigments of the dispersion of outermost layer positively charged active adsorption, further increased the repulsive force of electrostatic double layer, increased the consistency between blue pigments particle and grind resin simultaneously, thus make grind completely the blue pigments fine particle stable, be suspended in the whole mill base system equably; Can select anionic polyacrylic grind resin U.S.'s village minister (Johnson) J678, anionic polyacrylic grind resin ROHM AND HAAS (Rohm﹠amp for use; Haas) a kind of in the commercially available prod such as M-101.
Described organosilicon modified crylic acid resin emulsion is nonpolar organic-silicon-modified Emulsion acrylic resin.Described nonpolar organic-silicon-modified Emulsion acrylic resin can be selected a kind of in the commercially available prod such as NS-651, R-170EM, the FE-230N of Japanese Nissin company for use.
The multipolymer of the preferred xanthan gum of described thickening material, Wei Lan glue, tragacanth, guar gum, Natvosol, acrylate or acrylic ester compound.The viscosity of ink can be regulated by the consumption of regulating thickening material according to the demand of different nibs.
Described solvent is selected the water-soluble alcohol solvent for use, a kind of in preferred alcohol, 1-propyl alcohol, 2-propyl alcohol, ethylene glycol, glycol ether, triglycol, 1,3 butylene glycol, season pentanediol, Macrogol 200, poly(oxyethylene glycol) 400, glycerol, ethylene glycol monomethyl ether, the propylene glycol monomethyl ether.
Gel ink pen mostly is weakly alkaline with ink, and its pH value is generally 7～9, can regulate the pH value of ink by the pH regulator agent.Organic amine is selected in described pH regulator agent for use, a kind of in preferred alcohol amine, diethanolamine, trolamine, the 2-amino-2-methyl-1-propanol etc.
It is that tensio-active agent, phosphoric acid are a kind of in tensio-active agent, the polysiloxane series tensio-active agent etc. that described lubricant is selected higher fatty acid for use.Add lubricant and can use the wear resistance of nib when writing of described ink to improve greatly, write smoothness more, handwriting thickness is even, and the font color and luster is dense deeply, thoroughly waterproof; The not dried head of long-term placement is hung pen and is not leaked.
Described rust-preventive agent is benzotriazole or Methylbenzotriazole etc.
Described sanitas is Sodium Benzoate, potassium sorbate, 1, a kind of in 2-benzisothia oxazolone-3 grade.
Described defoamer is a kind of in tributyl phosphate, organo-siloxane, toluylic acid bay alcohol ester, the polyethers etc.
The described gel ink pen preparation method of blue ink may further comprise the steps:
A. thickening material is dissolved in the part deionized water, is dissolved to transparently fully, make thickener soln;
B. solvent and part deionized water are hybridly prepared into solvent mixture;
C. the solvent mixture among blue pigments mill base, organosilicon modified crylic acid resin emulsion, the step b, lubricant, rust-preventive agent, sanitas, defoamer and remaining deionized water are mixed,, obtain soup compound through emulsification and grinding;
D. in the soup compound of step c, add thickener soln and the pH regulator agent of step a, mix after-filtration, obtain thick liquid nano gel ink pen blue ink.
The not strict restriction of the consumption of deionized water in described thickener soln and the solvent mixture to the performance not influence of gel ink pen with blue ink, gets final product in right amount.
Among the step c, described emulsification times is preferably 15 minutes～and 30 minutes; The described sand milling time is preferably 30 minutes～and 60 minutes.Time is too short, and the sand milling effect is not enough, is longer than 60 minutes, and the particulate fineness has not obviously descended, and does not need to continue sand milling.
In the steps d, described mixing can be adopted the mode that mixes, preferred 15 minutes～30 minutes of the time of stirring.
Compared with prior art, the present invention has following advantage:
The present invention take into full account the blue pigments stability of pigment paste and with the basis of ink set consistency on, by replace negative and positive polyelectrolyte in the self-assembly in advance layer by layer on the blue pigments surface, realize the efficient dispersion of blue pigments mill base Smalt pigment, in anion pp acid balling resin, further disperse then, after grinding, the blue pigments particle fineness is little and even, and guarantees that mill base does not precipitate in ink, do not lump; It is even that the Neutral writing ink that obtains has colo(u)rant dispersion, and (the blue pigments particle diameter is stabilized in 100nm～300nm) to narrow diameter distribution, and system is stable, characteristics such as stable viscosity during temperature variation.By adopting nonpolar organic-silicon-modified Emulsion acrylic resin, can reduce the kapillary of ink in the faint polar micropore of paper surface band and expand the effect of oozing, write the phenomenon that back oozes, blurs thereby reduce paper, improve ink marks sharpness and resolving power.Solved gel ink pen with stability problem and ink marks permeability problems in the ink formulation, make gel ink pen with ink at the assurance fluent writing with when not leaking, have good high low-temperature stability and a sharpness.
Gel ink pen of the present invention has with ink and is uniformly dispersed, and viscosity is suitable, and system stability is high, and high low tempertaure storage long quality-guarantee period, high temperature can be stablized for 70 ℃ to deposit did not have precipitation in three months and advantage such as stable viscosity is constant and consistency is good, and resistant of high or low temperature is good; Can be widely used in various types of metallic ball nib, the gel ink pen fluent writing of making but do not leak, the time of raising one's hat of pen is long, can normally write in-20 ℃～60 ℃ environment.Ink does not contain the corrodibility composition, can not corrode metal nibs such as stainless steel, Alpaka, leaded brass.
Preparation method's process of the present invention is easy to control, is convenient to regulate.
Embodiment
Embodiment 1:
The preparation of blue pigments mill base: (1) is with 0.1g sodium polystyrene sulfonate (Aldrich company, molecular weight is～70000) be dissolved in the 59.3g deionized water, regulating the pH value with ammoniacal liquor is 8, obtain the anionic dispersing agents aqueous solution, add 35g blue pigments C.I. pigment blue 60 again to the negatively charged ion aqueous dispersant, (rotating speed is 400 rev/mins) stirred and made blue pigments fully wetting in 0.5 hour at a high speed, add 0.1g Poly Dimethyl Diallyl Ammonium Chloride salt cation (Aldrich company then, molecular weight is 100000～200000), (rotating speed is 400 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, finishes an electrostatic double layer assembling;
(2) add 5g anionic polyacrylic grind resin U.S.'s village minister (Johnson) J678 in the product in step (1), and 0.5g organo-siloxane defoamer (German Bi Ke company defoamer, BYK-019), after mixing, sand milling 4 hours makes 100g blue pigments mill base.
The Neutral writing ink preparation: a. is dissolved in xanthan gum 0.3g in the 10g deionized water, and it is transparent fully that stirring is dissolved to it, makes thickener soln;
B. 2-propyl alcohol solvent 10g and 10g deionized water are hybridly prepared into solvent mixture;
C. with solvent mixture 20g, phosphoesterase 30 .2g among 15g blue pigments mill base, 5g organosilicon modified crylic acid resin emulsion NS-651 (Japanese Nissin company), the step b, benzotriazole 0.3g, Sodium Benzoate 0.2g, organo-siloxane defoamer (German Bi Ke company defoamer, BYK-019) 0.02g and deionized water 10g, stir, the printing ink soup compound that obtains places mulser high speed (rotating speed is 1000 rev/mins) emulsification 15 minutes, place the sand mill sand milling then 60 minutes, and obtained soup compound;
D. the thickener soln, thanomin 1g and the deionized water 37.98g that add step a in the soup compound of step c stir after 30 minutes with the 1um filter element filtering, obtain thick liquid nano gel ink pen blue ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, Neutral writing ink Smalt pigment particle size is stabilized in 150nm～220nm.
Embodiment 2:
The preparation of blue pigments mill base: (1) is with 3g sodium polystyrene sulfonate (Sigma company, molecular weight is～70000) be dissolved in the 36.5g deionized water, regulating the pH value with ammoniacal liquor is 8, obtain the anionic dispersing agents aqueous solution, add 45g blue pigments C.I. pigment blue 60 again to the negatively charged ion aqueous dispersant, (rotating speed is 600 rev/mins) stirred and made blue pigments fully wetting in 0.5 hour at a high speed, add 3g Poly Dimethyl Diallyl Ammonium Chloride salt cation (Aldrich company then, molecular weight is 100000～200000), (rotating speed is 600 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, finishes an electrostatic double layer assembling;
(2) add 12g anionic polyacrylic grind resin U.S.'s village minister (Johnson) J678 in the product in step (1), and 0.5g organo-siloxane defoamer (German Bi Ke company defoamer, BYK-019), after mixing, sand milling 4 hours makes 100g blue pigments mill base.
The Neutral writing ink preparation: a. is dissolved in xanthan gum 0.8g in the 10g deionized water, and it is transparent fully that stirring is dissolved to it, makes thickener soln;
B. 2-propyl alcohol solvent 10g and 10g deionized water are hybridly prepared into solvent mixture;
C. with solvent mixture 20g, phosphoesterase 30 .2g among 30g blue pigments mill base, 10g organosilicon modified crylic acid resin emulsion NS-651 (Japanese Nissin company), the step b, benzotriazole 0.3g, Sodium Benzoate 0.2g, organo-siloxane defoamer (German Bi Ke company defoamer, BYK-019) 0.02g and deionized water 5g, stir, the printing ink soup compound that obtains places mulser high speed (rotating speed is 1000 rev/mins) emulsification 15 minutes, place the sand mill sand milling then 60 minutes, and obtained soup compound;
D. the thickener soln, thanomin 3g and the deionized water 20.48g that add step a in the soup compound of step c stir after 30 minutes with the 1um filter element filtering, obtain thick liquid nano gel ink pen blue ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, Neutral writing ink Smalt pigment particle size is stabilized in 180nm～250nm.
Embodiment 3:
The preparation of blue pigments mill base: (1) is dissolved in 0.5g polyoxyethylenated alcohol sodium sulfate (South Africa husky rope AES 270N) in the 55.5g deionized water, regulating the pH value with ammoniacal liquor is 9.5, obtain the anionic dispersing agents aqueous solution, add 35g blue pigments C.I. pigment blue 60 again to the negatively charged ion aqueous dispersant, (rotating speed is 1000 rev/mins) stirred and made blue pigments fully wetting in 0.5 hour at a high speed, add 0.5g polymethyl acyl-oxygen ethyl n-butyl then, N, N-dimethyl brometo de amonio positively charged ion (molecular weight 10000-50000), (rotating speed is 1000 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, finishes an electrostatic double layer assembling;
(2) add 8g anionic polyacrylic grind resin U.S.'s village minister (Johnson) J678 in the product in step (1), and 0.5g organo-siloxane defoamer (German Bi Ke company defoamer, BYK-019), after mixing, sand milling 4 hours makes 100g blue pigments mill base.
The Neutral writing ink preparation: a. is dissolved in guar gum 0.5g in the 10g deionized water, and it is transparent fully that stirring is dissolved to it, makes thickener soln;
B. 2-propyl alcohol solvent 30g and 10g deionized water are hybridly prepared into solvent mixture;
C. with solvent mixture 40g, phosphoric acid ester 2g among 20g blue pigments mill base, 10g organosilicon modified crylic acid resin emulsion FE-230N (Japanese Nissin company), the step b, benzotriazole 2g, Sodium Benzoate 2g, organo-siloxane defoamer (German Bi Ke company defoamer, BYK-019) 0.5g and deionized water 12g, stir, the printing ink soup compound that obtains places mulser high speed (rotating speed is 1000 rev/mins) emulsification 15 minutes, place the sand mill sand milling then 60 minutes, and obtained soup compound;
D. the thickener soln and the trolamine 1g that add step a in the soup compound of step c stir after 30 minutes with the 1um filter element filtering, obtain thick liquid nano gel ink pen blue ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, Neutral writing ink Smalt pigment particle size is stabilized in 120nm～200nm.
Embodiment 4:
The preparation of blue pigments mill base: (1) is with poly-Xylo-Mucine (the Aladdin chemical reagents corporation of 0.1g, molecular weight is 150000-250000) be dissolved in the 52.3g deionized water, regulating the pH value with ammoniacal liquor is 8, obtain the anionic dispersing agents aqueous solution, add 35g blue pigments phthalocyanine blue 15:3 again to the negatively charged ion aqueous dispersant, (rotating speed is 800 rev/mins) stirred and made blue pigments fully wetting in 0.5 hour at a high speed, add 0.1g Poly Dimethyl Diallyl Ammonium Chloride salt cation (Aldrich company then, molecular weight is 100000～200000), (rotating speed is 800 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, finishes an electrostatic double layer assembling;
(2) add 12g anionic polyacrylic grind resin ROHM AND HAAS (Rohm﹠amp in the product in step (1); Haas) M-101, and 0.5g toluylic acid bay alcohol ester defoamer (Aldrich company), after mixing, sand milling 8 hours makes 100g blue pigments mill base.
The Neutral writing ink preparation: a. is dissolved in Natvosol 0.5g in the 10g deionized water, and it is transparent fully that stirring is dissolved to it, makes thickener soln;
B. alcohol solvent 15g and 10g deionized water are hybridly prepared into solvent mixture;
C. with solvent mixture 25g, stearic acid 0.5g, Methylbenzotriazole 0.5g, potassium sorbate 0.5g, toluylic acid bay alcohol ester defoamer (Aldrich company) 0.1g and deionized water 20.9g among 25g blue pigments mill base, 15g organosilicon modified crylic acid resin emulsion FE-230N (Japanese Nissin company), the step b, stir, the printing ink soup compound that obtains places mulser high speed (rotating speed is 1000 rev/mins) emulsification 30 minutes, place the sand mill sand milling then 30 minutes, and obtained soup compound;
D. the thickener soln and the trolamine 2g that add step a in the soup compound of step c stir after 30 minutes with the 1um filter element filtering, obtain thick liquid nano gel ink pen blue ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, Neutral writing ink Smalt pigment particle size is stabilized in 100nm～180nm.
Embodiment 5:
The preparation of blue pigments mill base: (1) is with 0.1g sodium alginate (Aladdin chemical reagents corporation, molecular weight is 32000-250000) be dissolved in the 51.9g deionized water, regulating the pH value with ammoniacal liquor is 8, obtain the anionic dispersing agents aqueous solution, add 35g blue pigments phthalocyanine blue 15:3 again to the negatively charged ion aqueous dispersant, (rotating speed is 800 rev/mins) stirred and made blue pigments fully wetting in 0.5 hour at a high speed, add 0.1g Poly Dimethyl Diallyl Ammonium Chloride salt cation (Aldrich company then, molecular weight is 100000～200000), (rotating speed is 800 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, finishes an electrostatic double layer assembling;
(2) add the 0.2g sodium polystyrene sulfonate again in the product in step (1), (rotating speed is 800 rev/mins) stirred and it fully disperseed in 0.5 hour at a high speed, add 0.2g Poly Dimethyl Diallyl Ammonium Chloride salt cation then, (rotating speed is 800 rev/mins) stirred and obtained secondary product in 0.5 hour at a high speed, finishes two electrostatic double layer assemblings;
(3) add 12g anionic polyacrylic grind resin ROHM AND HAAS (Rohm﹠amp in the secondary product in step (2); Haas) M-101, and 0.5g toluylic acid bay alcohol ester defoamer (Aldrich company), after mixing, sand milling 4 hours makes 100g blue pigments mill base.
The Neutral writing ink preparation: a. is dissolved in Wei Lan glue 0.5g in the 10g deionized water, and it is transparent fully that stirring is dissolved to it, makes thickener soln;
B. Macrogol 200 solvent 10g and 10g deionized water are hybridly prepared into solvent mixture;
C. with solvent mixture 20g, stearic acid 0.5g, Methylbenzotriazole 0.5g, potassium sorbate 0.5g, toluylic acid bay alcohol ester defoamer (Aldrich company) 0.1g and deionized water 15.9g among 20g blue pigments mill base, 30g organosilicon modified crylic acid resin emulsion FE-230N (Japanese Nissin company), the step b, stir, the printing ink soup compound that obtains places mulser high speed (rotating speed is 1000 rev/mins) emulsification 20 minutes, place the sand mill sand milling then 45 minutes, and obtained soup compound;
D. the thickener soln and the trolamine 2g that add step a in the soup compound of step c stir after 15 minutes with the 1um filter element filtering, obtain thick liquid nano gel ink pen blue ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, Neutral writing ink Smalt pigment particle size is stabilized in 220nm～300nm.
Embodiment 6:
The preparation of blue pigments mill base: (1) is with 0.1g sodium polystyrene sulfonate (Sigma company, molecular weight is～70000) be dissolved in the 52.3g ionized water, regulating the pH value with ammoniacal liquor is 8, obtain the anionic dispersing agents aqueous solution, add 35g blue pigments phthalocyanine blue 15:3 again to the negatively charged ion aqueous dispersant, (rotating speed is 800 rev/mins) stirred and made blue pigments fully wetting in 0.5 hour at a high speed, add 0.1g Poly Dimethyl Diallyl Ammonium Chloride salt cation (Aldrich company then, molecular weight is 100000～200000), (rotating speed is 800 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, finishes an electrostatic double layer assembling;
(2) add 12g anionic polyacrylic grind resin ROHM AND HAAS (Rohm﹠amp in the product in step (1); Haas) M-101, and 0.5g toluylic acid bay alcohol ester defoamer (Aldrich company), after mixing, sand milling 4 hours makes 100g blue pigments mill base.
The Neutral writing ink preparation: a. is dissolved in sodium polyacrylate (Aladdin reagent company, molecular weight～2000) 0.5g in the 10g deionized water, and it is transparent fully that stirring is dissolved to it, makes thickener soln;
B. glycerol solvent 15g and 10g deionized water are hybridly prepared into solvent mixture;
C. with solvent mixture 25g, stearic acid 0.5g, benzotriazole 0.5g, potassium sorbate 0.5g, toluylic acid bay alcohol ester defoamer (Aldrich company) 0.1g and deionized water 15.9g among 25g blue pigments mill base, 20g organosilicon modified crylic acid resin emulsion FE-230N (Japanese Nissin company), the step b, stir, the printing ink soup compound that obtains places mulser high speed (rotating speed is 1000 rev/mins) emulsification 15 minutes, place the sand mill sand milling then 60 minutes, and obtained soup compound;
D. the thickener soln and the trolamine 2g that add step a in the soup compound of step c stir after 30 minutes with the 1um filter element filtering, obtain thick liquid nano gel ink pen blue ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, Neutral writing ink Smalt pigment particle size is stabilized in 200nm～250nm.
Reference examples 1:
Utilize usual way to prepare the blue pigments mill base: (1) regulates pH at 52.5g with ammoniacal liquor be in 8 the deionized water solution, adds 12g polyacrylic grind resin ROHM AND HAAS (Rohm﹠amp; Haas) M-101, add 35g blue pigments phthalocyanine blue 15:3 then, (rotating speed is 800 rev/mins) stirred and made blue pigments fully wetting in 0.5 hour at a high speed, and add 0.5g toluylic acid bay alcohol ester defoamer (Aldrich company), after mixing, sand milling 4 hours can make 100g blue pigments mill base.
The Neutral writing ink preparation: (1) at first is dissolved in sodium polyacrylate (Aladdin reagent company, molecular weight～2000) 0.5g in the 10g deionized water, and it is transparent fully that stirring is dissolved to it, prepares thickener soln; (2) glycerol solvent 15g and 10g deionized water are hybridly prepared into solvent mixture; (3) with blue pigments mill base 25g, FE-230N emulsion (Japanese Nissin company) 20g, 25g solvent mixture, stearic acid 0.5g, benzotriazole 0.5g, potassium sorbate 0.5g, toluylic acid bay alcohol ester defoamer (Aldrich company) 0.1g, deionized water 15.9g stirs; (4) prepared printing ink soup compound is placed mulser high speed (rotating speed is 1000 rev/mins) emulsification 15 minutes, placed the sand mill sand milling then 60 minutes.(5) add the thickening material that (1) step prepared behind the sand milling, trolamine 2g stirred after 30 minutes, and the gained thick liquid with 1um filter element filtering, packing, is prepared into the Neutral writing ink finished product.In 18 months, Neutral writing ink Smalt pigment particle size increases to 2～7um.
Reference examples 2:
Adopt the blue pigments mill base of embodiment 6 preparations.
Utilize ordinary emulsion to prepare Neutral writing ink: (1) at first is dissolved in sodium polyacrylate (Aladdin reagent company, molecular weight～2000) 0.5g in the 10g deionized water, and it is transparent fully that stirring is dissolved to it, prepares thickener soln; (2) glycerol solvent 15g and 10g deionized water are hybridly prepared into solvent mixture; (3) with blue pigments mill base 25g, common unmodified polypropylene yogurt liquid (Zhuan Chen J77) 20g, 25g solvent mixture, stearic acid 0.5g, benzotriazole 0.5g, potassium sorbate 0.5g, toluylic acid bay alcohol ester defoamer (Aldrich company) 0.1g, deionized water 15.9g stirs; (4) prepared printing ink soup compound is placed mulser high speed (rotating speed is 1000 rev/mins) emulsification 15 minutes, placed the sand mill sand milling then 60 minutes.(5) add the thickening material that (1) step prepared behind the sand milling, trolamine 2g stirred after 30 minutes, and the gained thick liquid with 1um filter element filtering, packing, is prepared into the Neutral writing ink finished product.In 18 months, Neutral writing ink Smalt pigment particle size increases to 4～15um.
Embodiment 1-6 and reference examples 1-2 product performance index are compared as follows:
Annotate: viscosity is measured with reference to standard GB/T14624.5-93 " the ink viscosity method of inspection ".
The pH value adopts Accurate pH instrumentation fixed (25 ℃);
Write situation, high low temperature stability test method detects with reference to People's Republic of China's light industry standard QB/T2625-2003 " Neutral writing ink pen and pen core ".
The above results shows, uses gel ink pen of the present invention with the gel ink pen fluent writing of ink but do not leak, and the time of raising one's hat of pen is long, and resistant of high or low temperature is good, can normally write in-20 ℃～60 ℃ environment.
Claims (10)
1. gel ink pen blue ink, form by following raw materials by weight percent: blue pigments mill base 15%～30%, organosilicon modified crylic acid resin emulsion 5%～30%, solvent 10%～30%, thickening material 0.3%～0.8%, pH regulator agent 1%～3%, lubricant 0.2%～2.0%, rust-preventive agent 0.3%～2.0%, sanitas 0.2%～2.0%, defoamer 0.02%～0.5%, the deionized water surplus.
2. gel ink pen blue ink according to claim 1 is characterized in that, the blue pigments in the described blue pigments mill base is phthalocyanine blue 15:3 or C.I. pigment blue 60.
3. gel ink pen blue ink according to claim 1 and 2 is characterized in that, the preparation method of described blue pigments mill base comprises step:
(1) anionic dispersing agents is dissolved in the deionized water, regulating the pH value with ammoniacal liquor is 7.5～9.5, obtain the anionic dispersing agents aqueous solution, add blue pigments again to the negatively charged ion aqueous dispersant, mix and made blue pigments fully wetting at least in 0.5 hour, add the polyquaternium positively charged ion then, mix obtaining product at least in 0.5 hour one time, finish an electrostatic double layer assembling;
(2) in a product of step (1), repeat alternately to add anionic dispersing agents and polyquaternium positively charged ion repeatedly, obtain repeatedly product, finish a plurality of electrostatic double layer assemblings;
(3) in the repeatedly product of product of step (1) or step (2), add anionic polyacrylic grind resin and proper quantity of defoaming agent, mixed the back sand milling 4 hours～8 hours, make the blue pigments mill base;
In single electrostatic double layer assembling, the add-on of described anionic dispersing agents is 0.1%～3% of a blue pigments mill base quality, and the cationic add-on of described polyquaternium is 0.1%～3% of a blue pigments mill base quality;
The add-on of described blue pigments is 35%～45% of a blue pigments mill base quality;
The add-on of described anionic polyacrylic grind resin is 5%～12% of a blue pigments mill base quality.
4. gel ink pen blue ink according to claim 3 is characterized in that, in the step (2), repeats alternately to add anionic dispersing agents and polyquaternium positively charged ion 1 time in a product of step (1), finishes 2 electrostatic double layer assemblings.
5. gel ink pen blue ink according to claim 3 is characterized in that, the mode that mixes is adopted in described mixing, and stirring velocity is 400 rev/mins～1000 rev/mins.
6. gel ink pen blue ink according to claim 3 is characterized in that, described anionic dispersing agents is a kind of in sodium polystyrene sulfonate, poly-Xylo-Mucine, polyoxyethylene alkyl ether sulfate salt, sodium alginate, the sodium polyacrylate;
Perhaps, described polyquaternium positively charged ion is Poly Dimethyl Diallyl Ammonium Chloride, polymethyl acyl-oxygen ethyl alkyl dimethyl ammonium chloride, polymethyl acyl-oxygen ethyl n-benzyl, N, N-alkyl dimethyl ammonium chloride, polymethyl acyl-oxygen ethyl n-ethyl, N, N-dimethyl brometo de amonio, polymethyl acyl-oxygen ethyl n-butyl, N, N-dimethyl brometo de amonio, polymethyl acyl-oxygen ethyl n-hexadecyl, N, a kind of in the N-dimethyl brometo de amonio.
7. gel ink pen blue ink according to claim 1 is characterized in that, described organosilicon modified crylic acid resin emulsion is nonpolar organic-silicon-modified Emulsion acrylic resin;
Perhaps, described thickening material is the multipolymer of xanthan gum, Wei Lan glue, tragacanth, guar gum, Natvosol, acrylate or acrylic ester compound.
8. gel ink pen blue ink according to claim 1, it is characterized in that, described solvent is a kind of in ethanol, 1-propyl alcohol, 2-propyl alcohol, ethylene glycol, glycol ether, triglycol, 1,3 butylene glycol, season pentanediol, Macrogol 200, poly(oxyethylene glycol) 400, glycerol, ethylene glycol monomethyl ether, the propylene glycol monomethyl ether;
Described pH regulator agent is a kind of in thanomin, diethanolamine, trolamine, the 2-amino-2-methyl-1-propanol;
Described lubricant is that higher fatty acid is that tensio-active agent, phosphoric acid are a kind of in tensio-active agent, the polysiloxane series tensio-active agent;
Described rust-preventive agent is benzotriazole or Methylbenzotriazole;
Described sanitas is Sodium Benzoate, potassium sorbate, 1, a kind of in the 2-benzisothia oxazolone-3;
Described defoamer is a kind of in tributyl phosphate, organo-siloxane, toluylic acid bay alcohol ester, the polyethers.
9. according to the preparation method of each described gel ink pen of claim 1～8, may further comprise the steps with blue ink:
A. thickening material is dissolved in the part deionized water, is dissolved to transparently fully, make thickener soln;
B. solvent and part deionized water are hybridly prepared into solvent mixture;
C. the solvent mixture among blue pigments mill base, organosilicon modified crylic acid resin emulsion, the step b, lubricant, rust-preventive agent, sanitas, defoamer and remaining deionized water are mixed,, obtain soup compound through emulsification and grinding;
D. in the soup compound of step c, add thickener soln and the pH regulator agent of step a, mix after-filtration, obtain thick liquid nano gel ink pen blue ink.
10. according to the preparation method of claim 9 a described gel ink pen, it is characterized in that among the step c, described emulsification times is 15 minutes～30 minutes with blue ink; The described sand milling time is 30 minutes～60 minutes.
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| CN103374263A (en) * | 2013-07-30 | 2013-10-30 | 大连理工大学 | Dye-type neutral ink and preparation method thereof |
| CN104672987A (en) * | 2015-02-14 | 2015-06-03 | 力嘉包装(深圳)有限公司 | Water-based environment-friendly multi-purpose ink |
| CN108359311A (en) * | 2018-05-25 | 2018-08-03 | 上海晨光文具股份有限公司 | Aqueous anti-dizzy dye ink |
| CN109135420A (en) * | 2018-06-25 | 2019-01-04 | 太原理工大学 | A kind of rapid-curing cutback direct-liquid type water-based ink |
| CN114005574A (en) * | 2021-11-11 | 2022-02-01 | 中国有色桂林矿产地质研究院有限公司 | High-temperature electronic paste doped with ammonium alginate biphenyl paste and preparation method thereof |
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| JP2006028371A (en) * | 2004-07-16 | 2006-02-02 | Mitsubishi Pencil Co Ltd | Ink composition for writing tool |
| CN101245206A (en) * | 2008-03-12 | 2008-08-20 | 武汉大学 | Erasable neutral pen and ink water and manufacture method thereof |
| CN101805542A (en) * | 2010-05-13 | 2010-08-18 | 鲁继烈 | Water-based dye ink and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006028371A (en) * | 2004-07-16 | 2006-02-02 | Mitsubishi Pencil Co Ltd | Ink composition for writing tool |
| CN101245206A (en) * | 2008-03-12 | 2008-08-20 | 武汉大学 | Erasable neutral pen and ink water and manufacture method thereof |
| CN101805542A (en) * | 2010-05-13 | 2010-08-18 | 鲁继烈 | Water-based dye ink and application thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374263A (en) * | 2013-07-30 | 2013-10-30 | 大连理工大学 | Dye-type neutral ink and preparation method thereof |
| CN103374263B (en) * | 2013-07-30 | 2015-08-19 | 大连理工大学 | A kind of dye type gel ink and preparation method thereof |
| CN104672987A (en) * | 2015-02-14 | 2015-06-03 | 力嘉包装(深圳)有限公司 | Water-based environment-friendly multi-purpose ink |
| CN108359311A (en) * | 2018-05-25 | 2018-08-03 | 上海晨光文具股份有限公司 | Aqueous anti-dizzy dye ink |
| CN109135420A (en) * | 2018-06-25 | 2019-01-04 | 太原理工大学 | A kind of rapid-curing cutback direct-liquid type water-based ink |
| CN109135420B (en) * | 2018-06-25 | 2021-11-19 | 太原理工大学 | Quick-drying direct-liquid type water-based ink |
| CN114005574A (en) * | 2021-11-11 | 2022-02-01 | 中国有色桂林矿产地质研究院有限公司 | High-temperature electronic paste doped with ammonium alginate biphenyl paste and preparation method thereof |
| CN114005574B (en) * | 2021-11-11 | 2023-09-26 | 中国有色桂林矿产地质研究院有限公司 | High-temperature electronic paste doped with ammonium alginate biphenyl paste and preparation method thereof |
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