CN102321408A - Red ink for neutral pen and preparation method thereof - Google Patents
Red ink for neutral pen and preparation method thereof Download PDFInfo
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- CN102321408A CN102321408A CN201110164680A CN201110164680A CN102321408A CN 102321408 A CN102321408 A CN 102321408A CN 201110164680 A CN201110164680 A CN 201110164680A CN 201110164680 A CN201110164680 A CN 201110164680A CN 102321408 A CN102321408 A CN 102321408A
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Abstract
The invention discloses red ink for a neutral pen, which comprises the following raw materials by weight percent: 20-30% of red pigment paste, 5-30% of organic silicone-modified acrylic resin emulsion, 10-30% of solvent, 0.3-0.8% of thickening agent, 1-3% of pH regulating agent, 0.2-2.0% of lubricating agent, 0.3-2.0% of antirusting agent, 0.2-2.0% of antiseptic agent, 0.02-0.5% of antifoaming agent, and deionized water for the rest. The red ink has advantages of uniform dispersion, proper viscosity, high system stability and excellent resistance to high and low temperature; the neutral pen writes smoothly without leakage, the uncapping time of the pen is long, and the pen can write normally in the environment of minus 20 to 60 DEG C. the invention also discloses a method for preparing the ink, which is characterized in that the process is easy to control and convenient to regulate.
Description
Technical field
The present invention relates to ink and preparation field thereof, be specifically related to a kind of gel ink pen with red 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, be not stained with do not pass through, advantages such as water-fast, sun-proof, long preservative period, become 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 passing through nib and leaking; 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 with ink owing to the technical elements reason; Also there are some problems: one, poor stability, the 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 be the key that can the ink quality qualified in the dispersion of the medium-term and long-term maintenance of ink stabilized nano.When red granules of pigments can not be accomplished enough when thin, because gravity former thereby layering, deposition 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 through 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-treated 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 through 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: SEPIGEL 305 1～8 gram of molecular weight＞200,000; C: organic water-soluble property reductive agent 0.5～4 gram, D: NP polyethoxye (5) ether 1～6mL, E: deionized water 100 grams; Wherein, water-soluble dye comprises: acid ink blue, acid ink are deceived; Organic water-soluble property reductive agent comprises: xitix, oxalic acid, sodium oxalate.This Neutral writing ink, the recording of the Neutral writing ink pen that can be used for selling in market, 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 ZL 200610028026.2.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 and use red 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 red 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; Through 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 is used red ink, is made up of following raw materials by weight percent: red pigment mill base 20%～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%; Skimmer 0.02%～0.5%, the deionized water surplus.
Red pigment in the described red pigment mill base can be selected this area red colour system pigment commonly used for use, is red pigment like the pyrrolopyrrole diketone, can be commercially available prod such as the Pigment red P.R.255 of Switzerland Ciba company (Ciba) or 254, and structural formula is distinguished as follows:
The preparation method of described red pigment mill base comprises step:
(1) anionic dispersing agents is dissolved in the deionized water; Use ammoniacal liquor to regulate the pH value and be 7.5-9.5, obtain the anionic dispersing agents aqueous solution, add again in red pigment to the negatively charged ion aqueous dispersant; Mix and made red pigment 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, accomplish 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 repeatedly product, accomplish 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 red pigment mill base;
In single electrostatic double layer assembling, the add-on of described anionic dispersing agents is 0.1%～3% of a red pigment mill base quality, and the cationic add-on of described polyquaternium is 0.1%～3% of a red pigment mill base quality;
The add-on of described red pigment is 35%～45% of a red pigment mill base quality;
The add-on of described anionic polyacrylic grind resin is 5%～12% of a red pigment 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 to remove the not unnecessary polyelectrolyte of absorption, if concentration is too high, the polyelectrolyte of absorption is not more so; Behind the polyelectrolyte that adds opposite charges, cause slight deposition easily, the add-on of red pigment is 35%～45% of a red pigment mill base quality; In single electrostatic double layer assembling; The add-on of anionic dispersing agents is 0.1%～3% of a red pigment mill base quality; The cationic add-on of polyquaternium is 0.1%～3% of a red pigment mill base quality, has enough assembled corresponding red pigment specific surface area fully, in the case; Not absorption the polyelectrolyte amount seldom, the polyelectrolyte that can not need filter direct adding opposite charges still can not cause deposition.
The thickness of electrostatic double layer can be realized through the number of plies of assembling effectively regulating, and in a product of step (1), repeats alternately to add anionic dispersing agents and polyquaternium positively charged ion n time, accomplishes 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 red pigment, 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 Lewatit for use, is gathered Xylo-Mucine, a kind of in the polyoxyethylene alkyl ether sulfate salt, sodium-alginate, ZX-I.
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 red 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 red pigment particle and grind resin simultaneously, thus make grind completely the red pigment fine particle stable, be suspended in the whole mill base system equably; Can select a kind of in the commercially available prod such as anionic polyacrylic grind resin U.S.'s village minister (Johnson) J678, anionic polyacrylic grind resin ROHM AND HAAS (Rohm&Haas) M-101 for use.
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 the NS-651, R-170EM, FE-230N of Japanese Nissin company for use.
The multipolymer of the preferred XG 550 of described thickening material, Wei Lan glue, tragacanth, guar gum, Natvosol, acrylate or acrylic ester compound.The viscosity of ink can be regulated through 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, terepthaloyl moietie, glycol ether, triglycol, 1,3 butylene glycol, season pentanediol, Macrogol 200, PEG 400, USP Kosher, EGME, the propylene glycol monomethyl ether.
Gel ink pen uses ink to be mostly weakly alkaline, and its pH value is generally 7～9, can regulate the pH value of ink through the pH regulator agent.Organic amine is selected in described pH regulator agent for use, a kind of in preferred alcohol amine, diethylolamine, 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 said 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 GRANULAR WHITE, 1, a kind of in 2-benzisothia oxazolone-3 grade.
Described skimmer is a kind of in tributyl phosphate, organo-siloxane, toluylic acid bay alcohol ester, the polyethers etc.
Described gel ink pen may further comprise the steps with the preparation method of red 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 red pigment mill base, organosilicon modified crylic acid resin emulsion, the step b, lubricant, rust-preventive agent, sanitas, skimmer 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 the thick liquid nano gel ink pen and use red ink.
The consumption of deionized water does not have strict restriction in described thickener soln and the solvent mixture, to the performance not influence of gel ink pen with red 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 need not 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 red pigment stability of pigment paste and with the basis of ink set consistency on; Through replace negative and positive polyelectrolyte in the self-assembly in advance layer by layer on the red pigment surface; Realize the efficient dispersion of red pigment in the red pigment mill base, in anion pp acid balling resin, further disperse then, after grinding; The red pigment 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 red pigment particle diameter is stabilized in 100nm～300nm) to narrow diameter distribution, and system is stable, characteristics such as stable viscosity during temperature variation.Through 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 in the ink formulation and ink marks permeability problems, make gel ink pen with ink when guaranteeing fluent writing and not leaking, have good high low-temperature stability and 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 deposition 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 adaptable across various types of metallic ball nib, the gel ink pen fluent writing of processing but do not leak, the time of raising one's hat of pen is long, can in-20 ℃～60 ℃ environment, normally write.Ink does not contain the corrodibility composition, can not corrode metal nibs such as stainless steel, Alpaka, leaded brass.
Preparing method's process of the present invention is easy to control, is convenient to regulate.
Embodiment
Embodiment 1:
The preparation of red pigment mill base: (1) is with 0.1g Lewatit (Aldrich company; Molecular weight is～70000) be dissolved in the 59.3g deionized water, using ammoniacal liquor to regulate the pH value is 8, obtains the anionic dispersing agents aqueous solution; Add 35g red pigment P.R.254 again to the negatively charged ion aqueous dispersant; (rotating speed is 400 rev/mins) stirred and made red pigment fully wetting in 0.5 hour at a high speed, adds 0.1g Poly Dimethyl Diallyl Ammonium Chloride salt cation (Aldrich company, molecular weight is 100000～200000) then; (rotating speed is 400 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, accomplishes 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 skimmer (German Bi Ke company skimmer, BYK-019), after mixing; Sand milling 4 hours makes 100g red pigment mill base.
The Neutral writing ink preparation: a. is dissolved in XG 550 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 the solvent mixture 20g among 20g red pigment mill base, 5g organosilicon modified crylic acid resin emulsion NS-651 (Japanese Nissin company), the step b, phosphoesterase 30 .2g, benzotriazole 0.3g, Sodium Benzoate 0.2g, organo-siloxane skimmer (German Bi Ke company skimmer; 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 1g and the deionized water 37.98g that in the soup compound of step c, add step a stir after 30 minutes with the 1um filter element filtering, obtain the thick liquid nano gel ink pen and use red ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, the red pigment particle diameter is stabilized in 150nm～220nm in the Neutral writing ink.
Embodiment 2:
The preparation of red pigment mill base: (1) is with 3g Lewatit (Sigma company; Molecular weight is～70000) be dissolved in the 36.5g deionized water, using ammoniacal liquor to regulate the pH value is 8, obtains the anionic dispersing agents aqueous solution; Add 45g red pigment P.R.254 again to the negatively charged ion aqueous dispersant; (rotating speed is 600 rev/mins) stirred and made red pigment fully wetting in 0.5 hour at a high speed, adds 3g Poly Dimethyl Diallyl Ammonium Chloride salt cation (Aldrich company, molecular weight is 100000～200000) then; (rotating speed is 600 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, accomplishes 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 skimmer (German Bi Ke company skimmer, BYK-019), after mixing; Sand milling 4 hours makes 100g red pigment mill base.
The Neutral writing ink preparation: a. is dissolved in XG 550 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 the solvent mixture 20g among 30g red pigment mill base, 10g organosilicon modified crylic acid resin emulsion NS-651 (Japanese Nissin company), the step b, phosphoesterase 30 .2g, benzotriazole 0.3g, Sodium Benzoate 0.2g, organo-siloxane skimmer (German Bi Ke company skimmer; 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 in the soup compound of step c, add step a stir after 30 minutes with the 1um filter element filtering, obtain the thick liquid nano gel ink pen and use red ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, the red pigment particle diameter is stabilized in 180nm～240nm in the Neutral writing ink.
Embodiment 3:
The preparation of red pigment mill base: (1) is dissolved in 0.5g polyoxyethylenated alcohol sodium sulfate (South Africa husky rope AES 270N) in the 55.5g deionized water; Using ammoniacal liquor to regulate the pH value is 9.5, obtains the anionic dispersing agents aqueous solution, adds 35g red pigment P.R.254 again to the negatively charged ion aqueous dispersant; (rotating speed is 1000 rev/mins) stirred and made red pigment 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, accomplishes an electrostatic double layer assembling;
(2) add 8g anionic polyacrylic grind resin ROHM AND HAAS (Rohm&Haas) M-101 in the product in step (1); And 0.5g organo-siloxane skimmer (German Bi Ke company skimmer; BYK-019); After mixing, sand milling 4 hours makes 100g red pigment 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 the solvent mixture 40g among 20g red pigment mill base, 10g organosilicon modified crylic acid resin emulsion FE-230N (Japanese Nissin company), the step b, SULPHOSUCCINIC ACID ESTER 2g, benzotriazole 2g, Sodium Benzoate 2g, organo-siloxane skimmer (German Bi Ke company skimmer; 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 in the soup compound of step c, add step a stir after 30 minutes with the 1um filter element filtering, obtain the thick liquid nano gel ink pen and use red ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, the red pigment particle diameter is stabilized in 120nm～180nm in the Neutral writing ink.
Embodiment 4:
The preparation of red pigment mill base: Xylo-Mucine (Aladdin chemical reagents corporation is gathered with 0.1g in (1); Molecular weight is 150000-250000) be dissolved in the 52.3g deionized water, using ammoniacal liquor to regulate the pH value is 8, obtains the anionic dispersing agents aqueous solution; Add 35g red pigment P.R.255 again to the negatively charged ion aqueous dispersant; (rotating speed is 800 rev/mins) stirred and made red pigment fully wetting in 0.5 hour at a high speed, adds 0.1g Poly Dimethyl Diallyl Ammonium Chloride salt cation (Aldrich company, molecular weight is 100000～200000) then; (rotating speed is 800 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, accomplishes 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 toluylic acid bay alcohol ester skimmer (Aldrich company); After mixing, sand milling 8 hours makes 100g red pigment 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, Triple Pressed Stearic Acid 0.5g, Methylbenzotriazole 0.5g, POTASSIUM SORBATE GRANULAR WHITE 0.5g, toluylic acid bay alcohol ester skimmer (Aldrich company) 0.1g and deionized water 20.9g among 25g red pigment 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 in the soup compound of step c, add step a stir after 30 minutes with the 1um filter element filtering, obtain the thick liquid nano gel ink pen and use red ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, the red pigment particle diameter is stabilized in 100nm～180nm in the Neutral writing ink.
Embodiment 5:
The preparation of red pigment 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, using ammoniacal liquor to regulate the pH value is 8, obtains the anionic dispersing agents aqueous solution; Add 35g red pigment P.R.255 again to the negatively charged ion aqueous dispersant; (rotating speed is 800 rev/mins) stirred and made red pigment fully wetting in 0.5 hour at a high speed, adds 0.1g poly dimethyl allyl chlorine (Aldrich company, molecular weight is 100000～200000) then; (rotating speed is 800 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, accomplishes an electrostatic double layer assembling;
(2) add the 0.2g Lewatit 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, accomplishes two electrostatic double layer assemblings;
(3) add 12g anionic polyacrylic grind resin U.S.'s village minister (Johnson) J678 in the secondary product in step (2); And 0.5g toluylic acid bay alcohol ester skimmer (Aldrich company); After mixing, sand milling 4 hours makes 100g red pigment 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, Triple Pressed Stearic Acid 0.5g, Methylbenzotriazole 0.5g, POTASSIUM SORBATE GRANULAR WHITE 0.5g, toluylic acid bay alcohol ester skimmer (Aldrich company) 0.1g and deionized water 15.9g among 20g red pigment 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 in the soup compound of step c, add step a stir after 15 minutes with the 1um filter element filtering, obtain the thick liquid nano gel ink pen and use red ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, the red pigment particle diameter is stabilized in 220nm～300nm in the Neutral writing ink.
Embodiment 6:
The preparation of red pigment mill base: (1) is with 0.1g Lewatit (Sigma company; Molecular weight is～70000) be dissolved in the 52.3g ionized water, using ammoniacal liquor to regulate the pH value is 8, obtains the anionic dispersing agents aqueous solution; Add 35g red pigment P.R.255 again to the negatively charged ion aqueous dispersant; (rotating speed is 800 rev/mins) stirred and made red pigment fully wetting in 0.5 hour at a high speed, adds 0.1g Poly Dimethyl Diallyl Ammonium Chloride salt cation (Aldrich company, molecular weight is 100000～200000) then; (rotating speed is 800 rev/mins) stirred and obtained product one time in 0.5 hour at a high speed, accomplishes 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 toluylic acid bay alcohol ester skimmer (Aldrich company); After mixing, sand milling 4 hours makes 100g red pigment mill base.
The Neutral writing ink preparation: a. is dissolved in ZX-I (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. USP Kosher solvent 15g and 10g deionized water are hybridly prepared into solvent mixture;
C. with solvent mixture 25g, Triple Pressed Stearic Acid 0.5g, benzotriazole 0.5g, POTASSIUM SORBATE GRANULAR WHITE 0.5g, toluylic acid bay alcohol ester skimmer (Aldrich company) 0.1g and deionized water 15.9g among 25g red pigment 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 in the soup compound of step c, add step a stir after 30 minutes with the 1um filter element filtering, obtain the thick liquid nano gel ink pen and use red ink; Packing is prepared into the Neutral writing ink finished product.In 18 months, the red pigment particle diameter is stabilized in 200nm～250nm in the Neutral writing ink.
Reference examples 1:
Utilize usual way to prepare the red pigment mill base: (1) uses ammoniacal liquor to regulate pH at 52.5g is in 8 the deionized water solution; Add 12g polyacrylic grind resin U.S.'s village minister (Johnson) J678, add 35g red pigment P.R.255 then, (rotating speed is 800 rev/mins) stirred and made red pigment fully wetting in 0.5 hour at a high speed; And add 0.5g toluylic acid bay alcohol ester skimmer (Aldrich company); After mixing, sand milling 4 hours can make 100g red pigment mill base.
The Neutral writing ink preparation: (1) at first is dissolved in ZX-I (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) USP Kosher solvent 15g and 10g deionized water are hybridly prepared into solvent mixture; (3) with red pigment mill base 25g, FE-230N emulsion (Japanese Nissin company) 20g, 25g solvent mixture, Triple Pressed Stearic Acid 0.5g; Benzotriazole 0.5g, POTASSIUM SORBATE GRANULAR WHITE 0.5g, toluylic acid bay alcohol ester skimmer (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 Neutral writing ink in 18 months, and the red pigment particle diameter increases to 2.2～4.5um in the Neutral writing ink.
Reference examples 2:
Adopt the red pigment mill base of embodiment 6 preparations.
Utilize ordinary emulsion to prepare Neutral writing ink: (1) at first is dissolved in ZX-I (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) USP Kosher solvent 15g and 10g deionized water are hybridly prepared into solvent mixture; (3) with red pigment mill base 25g, common unmodified polypropylene yogurt liquid (Zhuan Chen J77) 20g, 25g solvent mixture, Triple Pressed Stearic Acid 0.5g; Benzotriazole 0.5g, POTASSIUM SORBATE GRANULAR WHITE 0.5g, toluylic acid bay alcohol ester skimmer (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, the red pigment particle diameter increases to 3～11um in the Neutral writing ink.
Embodiment 1-6 and reference examples 1-2 product performance index are following:
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 the 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 in-20 ℃～60 ℃ environment, normally write.
Claims (10)
1. a gel ink pen is used red ink, is made up of following raw materials by weight percent: red pigment mill base 20%～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%; Skimmer 0.02%～0.5%, the deionized water surplus.
2. gel ink pen according to claim 1 is used red ink, it is characterized in that, the red pigment in the described red pigment mill base is a red pigment for the pyrrolopyrrole diketone.
3. gel ink pen according to claim 1 and 2 is used red ink, it is characterized in that, the preparation method of described red pigment mill base comprises step:
(1) anionic dispersing agents is dissolved in the deionized water; Using ammoniacal liquor to regulate the pH value is 7.5～9.5, obtains the anionic dispersing agents aqueous solution, adds in red pigment to the negatively charged ion aqueous dispersant again; Mix and made red pigment 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, accomplish 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, accomplish 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 red pigment mill base;
In single electrostatic double layer assembling, the add-on of described anionic dispersing agents is 0.1%～3% of a red pigment mill base quality, and the cationic add-on of described polyquaternium is 0.1%～3% of a red pigment mill base quality;
The add-on of described red pigment is 35%～45% of a red pigment mill base quality;
The add-on of described anionic polyacrylic grind resin is 5%～12% of a red pigment mill base quality.
4. gel ink pen according to claim 3 is used red ink, it is characterized in that, in the step (2), in a product of step (1), repeats alternately to add anionic dispersing agents and polyquaternium positively charged ion 1 time, accomplishes 2 electrostatic double layer assemblings.
5. gel ink pen according to claim 3 is used red ink, it 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 according to claim 3 is used red ink, it is characterized in that, described anionic dispersing agents is Lewatit, gather a kind of in Xylo-Mucine, polyoxyethylene alkyl ether sulfate salt, sodium-alginate, the ZX-I;
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 according to claim 1 is used red ink, it 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 XG 550, Wei Lan glue, tragacanth, guar gum, Natvosol, acrylate or acrylic ester compound.
8. gel ink pen according to claim 1 is used red ink; It is characterized in that; Described solvent is a kind of in ethanol, 1-propyl alcohol, 2-propyl alcohol, terepthaloyl moietie, glycol ether, triglycol, 1,3 butylene glycol, season pentanediol, Macrogol 200, PEG 400, USP Kosher, EGME, the propylene glycol monomethyl ether;
Described pH regulator agent is a kind of in thanomin, diethylolamine, 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 GRANULAR WHITE, 1, a kind of in the 2-benzisothia oxazolone-3;
Described skimmer 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 red 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 red pigment mill base, organosilicon modified crylic acid resin emulsion, the step b, lubricant, rust-preventive agent, sanitas, skimmer 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 the thick liquid nano gel ink pen and use red 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 red ink; The described sand milling time is 30 minutes～60 minutes.
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| 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 |
| CN104937048A (en) * | 2012-11-27 | 2015-09-23 | 株式会社樱花彩色笔 | Ink composition |
| CN109694618A (en) * | 2019-02-01 | 2019-04-30 | 常熟美克尼化工有限公司 | Gel ink pen neutral ink composition and preparation method thereof and gel ink pen |
| CN110628271A (en) * | 2019-10-12 | 2019-12-31 | 义乌市梦成玩具有限公司 | Novel red raw material |
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| 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 |
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| CN110628271A (en) * | 2019-10-12 | 2019-12-31 | 义乌市梦成玩具有限公司 | Novel red raw material |
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| CN102321408B (en) | 2013-08-07 |
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