CN102167935B - Ink composition, preparation method thereof, and pen point using ink composition - Google Patents
Ink composition, preparation method thereof, and pen point using ink composition Download PDFInfo
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- CN102167935B CN102167935B CN 201010115206 CN201010115206A CN102167935B CN 102167935 B CN102167935 B CN 102167935B CN 201010115206 CN201010115206 CN 201010115206 CN 201010115206 A CN201010115206 A CN 201010115206A CN 102167935 B CN102167935 B CN 102167935B
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Abstract
The invention provides an ink composition, a preparation method thereof, and a pen point using the ink composition. The ink composition comprises a coloring material, an additive, water and internal cross-linking water-soluble polyurethane emulsion. The pen point is used together with the ink composition. According to the technical scheme of the invention, writing ink marks can be erased within certain time and cannot be erased after the certain time.
Description
Technical field
The present invention relates to a kind of composition for ink of writing use, its preparation method and use the nib of this composition for ink, be specifically related to a kind of composition for the preparation of the erasable Neutral writing ink, the nib be used in conjunction with the erasable Neutral writing ink, and corresponding manufacture method.
Background technology
The major function of writing implement is to write, because wrongly write, just needs to revise, so the functional requirement of erasable has just been arranged, namely under the prerequisite of not destroying paper, with common eraser, writing can be wiped.
In the main class of writing implement, the topmost characteristics of pencil are exactly erasable performance, and pen and ballpoint pen are because its writing medium, the coloring material in (no matter oiliness or water-based) can be penetrated in the fiber of paper, so just can't with common eraser, writing be wiped under the prerequisite of not destroying paper.So, people just utilize redox reaction to fade, and principle and potential of hydrogen change and neutralization reaction metachromatic principle etc., invented the colour killing liquid that the color of the water-base inks such as pen can be eliminated, but, this erasing method is cumbersome, the instrument that other need to be arranged is coated in colour killing liquid on the writing that needs to eliminate, if also will write in the above must be in addition with the writing implement that pours into the writing medium that can not react with colour killing liquid.In addition, the water-base ink that can react with colour killing liquid, the potential of hydrogen of itself can be partially strong, can the phenomenon that variable color is even faded occur because of preservation environment and time, is unfavorable for the preservation of handwriting.
Afterwards, invent again the erasable ballpoint pen, contained the macromolecular materials such as rubber and resin in its oil-based ink, can form the book film around printing ink, be penetrated in the fiber of paper with the coloring material intercepted in printing ink, thereby reached the purpose of erasable.Due to macromolecular materials such as dissolving rubber and resins is a kind of volatile organic solvent, within the regular hour, can vapor away, before making, formed book film fades away, and the coloring material in printing ink can be penetrated in the fiber of paper again, and the writing of writing has like this been wiped to be fallen again.But, the ink viscosity of erasable ballpoint pen is very high, and mobility is poor, especially in printing ink, has volatile organic solvent to exist, must be placed under closed environment and just can preserve, therefore, from the erasable ballpoint pen is born, its pen core is all to adopt closed and structure internal pressurization power, so just greatly improved manufacturing cost, add the susceptibility of temperature and preservation problem etc., experienced the development of three more than ten years, the erasable ballpoint pen still fails to obtain applying more widely.
As the up-and-coming youngster in the large class of ballpoint pen, the Neutral writing ink ballpoint pen only just develops into very popular writing implement with time more than ten years.The principal feature of Neutral writing ink ballpoint pen is the medium viscosity gel water-base ink adopted between high viscosity oiliness printing ink and low viscosity aqueous ink.Usually Neutral writing ink is usingd pigment dyestuff as coloring material, and it is write stitching and has good keeping quality.So-called medium viscosity is not simple thickening, but adopt the gel thickening material with good stamp sex change and strong false contracting, this gel thickening material under static state, physics chemical action between its long chain molecule structure and particle, form similar reticulated structure, show as higher viscosity, homogeneity and the stability that both can keep granules of pigments to disperse, can prevent that again ink from oozing out or flowing backwards from ink storage pipe rear end from written gap location; Writing under state, increasing because written front end ball twirl makes shearing strain speed, this reticulated structure is destroyed, and the long chain molecule streamwise aligns, and resistance to flow is reduced, and shows as reduced viscosity, writes smoothness out of ink.
The distinguishing feature of Neutral writing ink ballpoint pen has brought up its good writing quality, also for development erasable Neutral writing ink, has increased technical difficulty simultaneously.At present, the so-called erasable Neutral writing ink that can see, or erasable performance is very poor, or stitching sticks with paste to fall even not had touching with hand, and erasable is within a certain period of time not yet arranged, crossed after the certain hour the not erasable Neutral writing ink of erasable.
Summary of the invention
Very poor in order to solve existing Neutral writing ink erasable performance, and can not realize erasable in certain hour, crossed after the certain hour the not technical problem of erasable, the present invention has been proposed.
According to an aspect of the present invention, its provide a kind of have good writing quality, within a certain period of time erasable, crossed after the certain hour the not erasable ink composition of erasable.The composition of described composition for ink comprises coloring material, additive and water, also comprise interior cross-linking aqueous polyaminoester emulsion, described interior cross-linking aqueous polyaminoester emulsion consists of one or more compositions that are selected from TDI (tolylene diisocyanate), MDI (diphenylmethanediisocyanate), DMPA (dimethylol propionic acid), (TODI) dimethyl diphenyl vulcabond, (HMDI) hexamethylene diisocyanate, the many alcohol of polyethylene glycol adipate, linking agent Ca, TMP.By introduce the monomer contain 3 or above functional group in polyurethane macromolecular, generate the urethane micelle with partial cross-linked or branched molecular structure, another kind method is to add the internal crosslinker that can coexist with emulsion-stabilizing in aqueous polyurethane emulsion, and the variation at emulsion system because of temperature or pH value, perhaps externally under the effect of energy, crosslinking reaction occurs with the functional group in urethane resin in, formation has cancellated cross-linking system and the film technique of film former, and utilize the time of film spontaneous curing, can realize within a certain period of time, be that film is write the ink marks erasable in the not yet curing time, and after certain hour, be to write the not effect of erasable of ink marks after film has solidified.It will be appreciated by those skilled in the art that, while adding the internal crosslinker that can coexist with emulsion-stabilizing in aqueous polyurethane emulsion, the ratio of described emulsion and internal crosslinker can be selected arbitrarily according to the needs of crosslinking reaction, usually, its ratio can be 3～9: 1.
Coloring material of the present invention is by the resin inclusion pigment, adopt that in-situ polymerization and microemulsion preparation method are synthetic to be obtained, wherein pigment comprises pigment dyestuff and mineral dye, such as charcoal blacks, phthalocyanine blue pigment etc., the resin of coating is generated by one or more polymerizations of the monomers such as phenylethylene, oleic series, toxilic acid series; The particle shape of the resin inclusion pigment obtained is spheroidal, sees Fig. 1, or irregular polyhedrons or shred, see Fig. 2, grain diameter is usually at 0.5～20 μ m, wherein more than 90% between 1～15 μ m, these colored particles have dispersion stabilization good in water-based system;
Additive of the present invention comprises one or more following ingredients: water soluble resin, dispersion agent, viscosity modifier, defoamer, anti-dry wetting Agent for Printing Inks, sanitas.Wherein, described water soluble resin is the vinylbenzene polyacrylic resin.Described dispersion agent is for being selected from tween, polyoxyethylene alkyl phenyl ether, fatty monoethanol amide, polyoxyethylene alkyl amine; The ethylene oxide adduct of anion surfactant fatty alcohol sulfate monoethanolamine salt, lipid acid sulfoalkyl ester, fatty alcohol sulfate monoethanolamine salt, polyethylene polyamines salt, hexadecyl pyridinium bromide, cats product polyoxyethylene carboxylate, polypropylene glycol, a kind of or more than one compositions in trimethylammonium stearylamide muriate.Described viscosity modifier is a kind of or more than one compositions that are selected from sodium polyacrylate, Polyanionic Cellulose, Natvosol, polyvinylpyrrolidone, polyvinyl alcohol, xanthan gum, oxyethyl group urethane.Described defoamer is by two or more combining such as silicone emulsion, the fatty acid ester compounded thing of higher alcohols, polyoxyethylene polyoxypropylene tetramethylolmethane ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxypropylenes.Described anti-dry wetting Agent for Printing Inks is by two or more combining such as glycerol, butyleneglycol, polyoxyethylene glycol, 1,2-PD, propylene glycol, hexylene glycol, Sorbitol Powder, Xylitols.Described sanitas is by two or more combining such as methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, P-hydroxybenzoic acid the third fat, parahydroxybenzoate butyl, Sorbic Acid, potassium sorbate, calcium sorbate, phenylformic acid, Sodium Benzoates.
Preferably, described composition for ink provided by the invention contains following component:
Interior cross-linking aqueous polyaminoester emulsion 0.5～2.5wt%
Coloring material 4～15wt%
Water soluble resin 10～30wt%
Dispersion agent 0.5～3wt%
Viscosity modifier 0.5～5wt%
Defoamer 0.5～2wt%
Anti-dry wetting Agent for Printing Inks 0.5～1.5wt%
Sanitas 0.1～0.5wt%
Deionized water 20～60wt%
Wherein, described coloring material comprises the pigment that accounts for its weight 50wt% and the resin that accounts for its weight 50%wt.
According to another aspect of the present invention, the preparation method that it also provides composition for ink of the present invention, comprise the following steps:
The mixture of resin raw material and pigment is added in the spirituous solution that contains stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; By the nitrogen protection atmosphere and in the situation that lasting the stirring adds the ethanolic soln that contains initiator, after completing, polyreaction can make the colored particles of resin-coated pigment simultaneously.Wherein, described initiator refers to that the easy decomposes of a class becomes free radical, be the compound of elementary free radical, can be used for causing radical polymerization and the copolymerization of alkene class, diene class monomer, also can be used for crosslinking curing and the polymer crosslinking reaction of unsaturated polyester.The kind of operational initiator is a lot, by its molecular structure, generally is divided into: peroxide initiator, as oil-soluble dibenzoyl peroxide, water miscible Potassium Persulphate etc.; The azo-compound initiator, i.e. azo initiator, as oil-soluble Diisopropyl azodicarboxylate, water miscible V-50 initiator etc.; The redox system initiator, as water-soluble hydrogen peroxide-ferrous salt.In preparation in accordance with the present invention, those skilled in the art can select the initiator of one or more mentioned kinds according to actual needs.
The colored particles of resin-coated pigment is added in pre-configured water soluble resin liquid, add again deionized water and stir, and then add a kind of, sanitas, the anti-dry wetting Agent for Printing Inks in dispersion agent, viscosity modifier, defoamer or BYK-073 or NOPC08034L and fully stir, and then add the auxiliary agent such as interior cross-linking aqueous polyaminoester emulsion and stir after obtain the erasable Neutral writing ink.
According to another aspect of the present invention, it also provides the nib be used in conjunction with described composition for ink, described nib comprises ball and ball seat body, described ball embeds in the rim of a bowl of described ball seat body, the ball seat bottom of this ball seat body is provided with the ink via hole, and be provided with the ink container that is radiated entends from the ink via hole, more specifically, the ball material of this nib is wolfram varbide, ball seat body material is stainless steel, its physical dimension is identical with the nib of common gel ink pen, but internal structure and size are not identical.Wherein: the diameter of described ball is 0.5mm～0.6mm; The quantity of described ink container is more than three or three; The sectional area of described ink container is 53800～95300 μ m
2; Radius clearance between described ball and the rim of a bowl is 18～32 μ m; End play between described ball and ball seat is 45～75 μ m.
Preferably, described ball diameter is 0.5 millimeter, and ink container quantity is 3, and the sectional area of ink container is 54600～66800 μ m
2, the radius clearance between ball and the rim of a bowl is 19～28 μ m, the end play between ball and ball seat is 46～65 μ m.
Preferably, described ball diameter is 0.5 millimeter, and ink container quantity is 4, and the sectional area of ink container is 59700～77800 μ m
2, the radius clearance between ball and the rim of a bowl is 20～29 μ m, the end play between ball and ball seat is 49～68 μ m.
Preferably, described ball diameter is 0.55 millimeter, and ink container quantity is 3, and the sectional area of ink container is 56900～75300 μ m
2, the radius clearance between ball and the rim of a bowl is 20～30 μ m, the end play between ball and ball seat is 50～70 μ m.
Preferably, described ball diameter is 0.55 millimeter, and ink container quantity is 4, and the sectional area of ink container is 63700～85900 μ m
2, the radius clearance between ball and the rim of a bowl is 22～33 μ m, the end play between ball and ball seat is 52～70 μ m.
Preferably, described ball diameter is 0.6 millimeter, and ink container quantity is 4, and the sectional area of ink container is 75700～94500 μ m
2, the radius clearance between ball and the rim of a bowl is 23～35 μ m, the end play between ball and ball seat is 55～71 μ m.
Preferably, described ball diameter is 0.6 millimeter, and ink container quantity is 5, and the sectional area of ink container is 80900～94800 μ m
2, the radius clearance between ball and the rim of a bowl is 25～36 μ m, the end play between ball and ball seat is 57～72 μ m.
The present invention also provides pen or the pen core that uses above-mentioned nib to manufacture.
Ink provided by the invention and described nib can provide good writing quality: main manifestations is following three aspects:
First aspect, write smoothness out of ink lubricated, and namely under certain writing speed of writing pressure, certain limit, the stitching of writing can obviously not thicken, thin out, broken string, monolateral, hollow etc., writes feel lubricated.
Second aspect, amount out of ink is controlled good.Generally amount out of ink should not be too little, otherwise it is light to write stitching, and feel is dry and astringent; Amount out of ink also should not be too large, otherwise can write stitching overrich, difficult dry, long-pending China ink, and serious even can drip China ink.The factor that affects amount size out of ink is respectively: annular groove and the area of ink container, the surface appearance of ball etc. of the ball of the particle diameter of colored particles, nib and the end play between ball seat, ball seat body in the viscosity of ink and surface tension, ink.The size of the particle diameter of colored particles and the amount size out of ink relation that is inversely proportional in the viscosity of its ink inside and surface tension, ink; The ball of nib and the end play between ball seat and amount size out of ink are proportional; The annular groove of ball seat body and the area of ink container and amount size out of ink are nonlinear positive relationship; The roughness of ball surface and amount size out of ink are nonlinear positive relationship.Composition for ink provided by the invention and described nib are used in conjunction with down and are easy to control amount size out of ink.
The third aspect, the control of amount size fluctuating range out of ink is good.The factor that affects amount out of ink size fluctuating range is a lot, and the scope of its control is whole effective writing process, and the purpose of control is to wish that whole effective writing process remains good situation.Affect the factor of amount size fluctuating range out of ink except above-mentioned second aspect is described, also have the lubrication of ink between ball and ball seat; The material of ball seat body and hardness thereof; Radius clearance between ball and the rim of a bowl; Ink container quantity and the sectional area thereof of ball seat body; Ball seat body bowl drill diameter and anterior angle angle; The abrasion loss of ball seat bottom; Annular groove sectional area and the variation thereof of ball seat body; The perforation area of ink container and annular groove and variation thereof etc.
Composition for ink provided by the invention and the structure of choosing especially according to this composition for ink, size design are through a large amount of tests and checking repeatedly, and a series of theoretical analysis, the principal element that affects amount size out of ink and the analytical model of mutual relationship thereof have been set up, can change amount size out of ink by calculating, or determine that numerical quantity out of ink changes the performance perameter of written inner structure size and ink.
the accompanying drawing explanation
Fig. 1 is the spherical colored particles schematic diagram in the erasable Neutral writing ink;
Fig. 2 is the irregularly shaped colored particles schematic diagram in the erasable Neutral writing ink;
The written schematic diagram that Fig. 3 is three for the written China and Mexico tank quantity that coordinates with the erasable Neutral writing ink;
The written schematic diagram that Fig. 4 is four for the written China and Mexico tank quantity that coordinates with the erasable Neutral writing ink;
The written schematic diagram that Fig. 5 is five for the written China and Mexico tank quantity that coordinates with the erasable Neutral writing ink;
Fig. 6 is bullet type nib profile schematic diagram;
Fig. 7 is needle tube type pen point profile schematic diagram;
Fig. 8 is cucurbit head dummy nib profile schematic diagram.
embodiment
Embodiment 1:
Prepare black erasable Neutral writing ink.
Methyl methacrylate and styrene monomer are pressed to 1: 9 mass ratio, amount to 5 parts, be mixed together with 5 parts of charcoal blacks; Then aforementioned mixture is added in 30 parts of spirituous solutions that contain 0.2 part of stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; Simultaneously, with the nitrogen protection atmosphere and continue to stir in situation, add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile, polyreaction can make the colored particles of resin-coated pigment after 24 hours.8 parts of the colored particles of resin-coated pigment are added in 25 parts of pre-configured water soluble resin liquid, add again the deionized water of 50 parts and stir, and then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai is heard general chemical technology company limited and is sold for defoamer SPA-202 (production and sales of Shanghai Wenhua chemical color company limited) or BYK-073, Germany BYK company produces) in a kind of 1 part, 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.), 1 part and the fully stirring of anti-dry wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), and then add in 1 part the auxiliary agent such as cross-linking aqueous polyaminoester emulsion and stir after obtain black erasable Neutral writing ink.Wherein, described interior cross-linking aqueous polyaminoester emulsion is to add linking agent DesmodurN-330 (production and sales of German Bayer AG) by aqueous polyurethane emulsion MK-119 according to the ratio of 3: 1, by synthesizing in room temperature or higher than regulating pH under room temperature condition, usually to control finished product pH value 7.0～8.5, be advisable.
Embodiment 2:
Prepare black erasable Neutral writing ink.
Methyl methacrylate and styrene monomer are pressed to 1: 9 mass ratio, amount to 5 parts, be mixed together with 5 parts of charcoal blacks; Then aforementioned mixture is added in 30 parts of spirituous solutions that contain 0.2 part of stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; Simultaneously, with the nitrogen protection atmosphere and continue to stir in situation, add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile, polyreaction can make the colored particles of resin-coated pigment after 24 hours.8 parts of the colored particles of resin-coated pigment are added in 25 parts of pre-configured water soluble resin liquid, add again the deionized water of 50 parts and stir, and then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai is heard general chemical technology company limited and is sold for defoamer SPA-202 (production and sales of Shanghai Wenhua chemical color company limited) or BYK-073, Germany BYK company produces) in a kind of 1 part, 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.), 1 part and the fully stirring of anti-dry wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), and then add in 1 part the auxiliary agent such as cross-linking aqueous polyaminoester emulsion and stir after obtain black erasable Neutral writing ink.Wherein, described interior cross-linking aqueous polyaminoester emulsion is according to the ratios of 9: 1 and crosslinking aid S AC-100 (production and sales of Shanghai outstanding grace chemical industry company limited) by aqueous polyurethane emulsion MK-119 (Guangzhou is with the production and sales of letter chemical industry company limited), by synthesizing in room temperature or higher than regulating pH under room temperature condition, usually to control finished product pH value 7.0～8.5, be advisable.
Embodiment 3:
Prepare black erasable Neutral writing ink.
Methyl methacrylate and styrene monomer are pressed to 1: 9 mass ratio, amount to 5 parts, be mixed together with 5 parts of charcoal blacks; Then aforementioned mixture is added in 30 parts of spirituous solutions that contain 0.2 part of stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; Simultaneously, with the nitrogen protection atmosphere and continue to stir in situation, add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile, polyreaction can make the colored particles of resin-coated pigment after 24 hours.8 parts of the colored particles of resin-coated pigment are added in 25 parts of pre-configured water soluble resin liquid, add again the deionized water of 50 parts and stir, and then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai is heard general chemical technology company limited and is sold for defoamer SPA-202 (production and sales of Shanghai Wenhua chemical color company limited) or BYK-073, Germany BYK company produces) in a kind of 1 part, 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.), 1 part and the fully stirring of anti-dry wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), and then add in 1 part the auxiliary agent such as cross-linking aqueous polyaminoester emulsion and stir after obtain black erasable Neutral writing ink.Wherein, described interior cross-linking aqueous polyaminoester emulsion is to add linking agent F-0082 (production and sales of Shanghai You Wei trade Co., Ltd) by aqueous polyurethane emulsion MK-119 (Guangzhou is with the production and sales of letter chemical industry company limited) according to the ratios of 5: 1, by synthesizing in room temperature or higher than the adjusting pH under room temperature condition, usually to control finished product pH value 7.0～8.5, be advisable.
Embodiment 4:
Prepare black erasable Neutral writing ink.
Methyl methacrylate and styrene monomer are pressed to 1: 9 mass ratio, amount to 5 parts, be mixed together with 5 parts of charcoal blacks; Then aforementioned mixture is added in 30 parts of spirituous solutions that contain 0.2 part of stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; Simultaneously, with the nitrogen protection atmosphere and continue to stir in situation, add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile, polyreaction can make the colored particles of resin-coated pigment after 24 hours.8 parts of the colored particles of resin-coated pigment are added in 25 parts of pre-configured water soluble resin liquid, add again the deionized water of 50 parts and stir, and then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai is heard general chemical technology company limited and is sold for defoamer SPA-202 (production and sales of Shanghai Wenhua chemical color company limited) or BYK-073, Germany BYK company produces) in a kind of 1 part, 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.), 1 part and the fully stirring of anti-dry wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), and then add in 1 part the auxiliary agent such as cross-linking aqueous polyaminoester emulsion and stir after obtain black erasable Neutral writing ink.Wherein, described interior cross-linking aqueous polyaminoester emulsion is to add linking agent TMP by aqueous polyurethane emulsion MK-119 according to the ratio of 7: 1 (Mitsubishi gas is produced, PVG Hong Chi trade Co., Ltd sells), by synthesizing in room temperature or higher than the adjusting pH under room temperature condition, usually to control finished product pH value 7.0～8.5, be advisable.
Embodiment 5:
Prepare black erasable Neutral writing ink.
Methyl methacrylate and styrene monomer are pressed to 1: 9 mass ratio, amount to 5 parts, be mixed together with 5 parts of charcoal blacks; Then aforementioned mixture is added in 30 parts of spirituous solutions that contain 0.2 part of stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; Simultaneously, with the nitrogen protection atmosphere and continue to stir in situation, add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile, polyreaction can make the colored particles of resin-coated pigment after 24 hours.8 parts of the colored particles of resin-coated pigment are added in 25 parts of pre-configured water soluble resin liquid, add again the deionized water of 50 parts and stir, and then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai is heard general chemical technology company limited and is sold for defoamer SPA-202 (production and sales of Shanghai Wenhua chemical color company limited) or BYK-073, Germany BYK company produces) in a kind of 1 part, 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.), 1 part and the fully stirring of anti-dry wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), and then add in 1 part the auxiliary agent such as cross-linking aqueous polyaminoester emulsion and stir after obtain black erasable Neutral writing ink.Wherein, described interior cross-linking aqueous polyaminoester emulsion is to add linking agent Desmodur N-330 (production and sales of German Bayer AG) by aqueous polyurethane emulsion DISPERCOLL U54 (German Bayer AG produces, escape in Dongguan precious resin company limited sell) according to the ratios of 9: 1, by synthesizing in room temperature or higher than regulating pH under room temperature condition, usually to control finished product pH value 7.0～8.5, be advisable.
Embodiment 6:
Prepare black erasable Neutral writing ink.
Methyl methacrylate and styrene monomer are pressed to 1: 9 mass ratio, amount to 5 parts, be mixed together with 5 parts of charcoal blacks; Then aforementioned mixture is added in 30 parts of spirituous solutions that contain 0.2 part of stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; Simultaneously, with the nitrogen protection atmosphere and continue to stir in situation, add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile, polyreaction can make the colored particles of resin-coated pigment after 24 hours.8 parts of the colored particles of resin-coated pigment are added in 25 parts of pre-configured water soluble resin liquid, add again the deionized water of 50 parts and stir, and then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai is heard general chemical technology company limited and is sold for defoamer SPA-202 (production and sales of Shanghai Wenhua chemical color company limited) or BYK-073, Germany BYK company produces) in a kind of 1 part, 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.), 1 part and the fully stirring of anti-dry wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), and then add in 1 part the auxiliary agent such as cross-linking aqueous polyaminoester emulsion and stir after obtain black erasable Neutral writing ink.Wherein, described interior cross-linking aqueous polyaminoester emulsion is according to the ratios of 3: 1 and crosslinking aid S AC-100 (production and sales of Shanghai outstanding grace chemical industry company limited) by aqueous polyurethane emulsion DISPERCOLL U54 (German Bayer AG produces, escape in Dongguan precious resin company limited sell), by synthesizing in room temperature or higher than regulating pH under room temperature condition, usually to control finished product pH value 7.0～8.5, be advisable.
Embodiment 7:
Prepare black erasable Neutral writing ink.
Methyl methacrylate and styrene monomer are pressed to 1: 9 mass ratio, amount to 5 parts, be mixed together with 5 parts of charcoal blacks; Then aforementioned mixture is added in 30 parts of spirituous solutions that contain 0.2 part of stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; Simultaneously, with the nitrogen protection atmosphere and continue to stir in situation, add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile, polyreaction can make the colored particles of resin-coated pigment after 24 hours.8 parts of the colored particles of resin-coated pigment are added in 25 parts of pre-configured water soluble resin liquid, add again the deionized water of 50 parts and stir, and then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai is heard general chemical technology company limited and is sold for defoamer SPA-202 (production and sales of Shanghai Wenhua chemical color company limited) or BYK-073, Germany BYK company produces) in a kind of 1 part, 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.), 1 part and the fully stirring of anti-dry wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), and then add in 1 part the auxiliary agent such as cross-linking aqueous polyaminoester emulsion and stir after obtain black erasable Neutral writing ink.Wherein, described interior cross-linking aqueous polyaminoester emulsion is to add linking agent F-0082 (production and sales of Shanghai You Wei trade Co., Ltd) by aqueous polyurethane emulsion DISPERCOLL U54 (German Bayer AG produces, escape in Dongguan precious resin company limited sell) according to the ratios of 5: 1, by synthesizing in room temperature or higher than the adjusting pH under room temperature condition, usually to control finished product pH value 7.0～8.5, be advisable.
Embodiment 8:
Prepare black erasable Neutral writing ink.
Methyl methacrylate and styrene monomer are pressed to 1: 9 mass ratio, amount to 5 parts, be mixed together with 5 parts of charcoal blacks; Then aforementioned mixture is added in 30 parts of spirituous solutions that contain 0.2 part of stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; Simultaneously, with the nitrogen protection atmosphere and continue to stir in situation, add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile, polyreaction can make the colored particles of resin-coated pigment after 24 hours.8 parts of the colored particles of resin-coated pigment are added in 25 parts of pre-configured water soluble resin liquid, add again the deionized water of 50 parts and stir, and then add 2 parts of dispersion agents, 5 parts of viscosity modifiers, (Shanghai is heard general chemical technology company limited and is sold for defoamer SPA-202 (production and sales of Shanghai Wenhua chemical color company limited) or BYK-073, Germany BYK company produces) in a kind of 1 part, 0.1 part of sanitas SCJ-950 (production and sales of Beijing Jie Ershuan High Seience Technology Co., Ltd.), 1 part and the fully stirring of anti-dry wetting Agent for Printing Inks PDS-2 (production and sales of fine chemistry industry (Guangzhou) company limited are moistened in Qingdao for a long time), and then add in 1 part the auxiliary agent such as cross-linking aqueous polyaminoester emulsion and stir after obtain black erasable Neutral writing ink.Wherein, described interior cross-linking aqueous polyaminoester emulsion is that (Mitsubishi gas is produced to add linking agent TMP according to the ratios of 7: 1 by aqueous polyurethane emulsion DISPERCOLL U54 (German Bayer AG produces, escape in Dongguan precious resin company limited sell), PVG Hong Chi trade Co., Ltd sells), by synthesizing in room temperature or higher than the adjusting pH under room temperature condition, usually to control finished product pH value 7.0～8.5, be advisable.
The ink physicochemical property of embodiment 1-8 meets following performance after testing:
The colored particles particle diameter: 0.5～20 μ m, wherein more than 90% between 1～15 μ m;
Viscosity: 6 turn 2800～3200cp, 60 turns 400～600cp;
Surface tension: 25～35mN/m;
PH value: 7.0～8.5;
Erasable performance: in 24 hours, the handwriting erasing rate (is having slight vestige) more than 85%, and within 24 hours, outer handwriting erasing rate is below 55%;
First write performance: qualified;
Drying property: qualified;
Intermittently write: more than 24 hours;
Water tolerance: within 24 hours, stitching is normal;
Light permanency: within 24 hours, stitching is normal;
Lower temperature resistance: write normal in 24 hours;
Duplicating property: after duplicating, stitching is visible;
Perviousness: qualified;
Shelf stability: qualified.
Embodiment 9:
Prepare a kind of blue erasable Neutral writing ink.
Maleic anhydride and styrene monomer are pressed to 1: 1 mass ratio, amount to 5 parts, be mixed together with 5 parts of phthalocyanine blue pigments; Then aforementioned mixture is added in 30 parts of spirituous solutions that contain 0.2 part of stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; Simultaneously, with the nitrogen protection atmosphere and continue to stir in situation, add the ethanolic soln that contains 0.1 part of initiator azo isobutyronitrile, polyreaction can make the colored particles of resin-coated pigment after 24 hours.8 parts of the colored particles of resin-coated pigment are added in 25 parts of pre-configured water soluble resin liquid, add again the deionized water of 50 parts and stir, and then add in 2 parts of dispersion agents, 5 parts of viscosity modifiers, defoamer SPA-202 or BYK-073 or NOPC08034L a kind of 1 part, 0.1 part of sanitas SCJ-950,1 part of anti-dry wetting Agent for Printing Inks YZ-18 and fully stir, and then add 1 part be selected from the interior cross-linking aqueous polyaminoester emulsion auxiliary agent of embodiment 1-8 and stir after obtain blue erasable Neutral writing ink.
The physicochemical property of this ink is as follows after testing:
The colored particles particle diameter: 0.5～20 μ m, wherein more than 90% between 1～15 μ m;
Viscosity: 6 turn 2500～2900cp, 60 turns 350～550cp;
Surface tension 25～35mN/m;
PH value 7.0～8.5;
Erasable performance: in 24 hours, the handwriting erasing rate (is having slight vestige) more than 85%, and within 24 hours, outer handwriting erasing rate is below 50%;
First write performance: qualified;
Drying property: qualified;
Intermittently write: more than 24 hours;
Water tolerance: within 24 hours, stitching is normal;
Light permanency: within 24 hours, stitching is normal;
Lower temperature resistance: write normal in 24 hours;
Duplicating property: after duplicating, stitching is visible;
Perviousness: qualified;
Shelf stability: qualified.
Embodiment 10:
The nib coordinated with the erasable Neutral writing ink.
Nib of the present invention comprises ball and ball seat body, described ball embeds in the rim of a bowl of described ball seat body, the ball seat bottom of this ball seat body is provided with the ink via hole, and be provided with the ink container that is radiated entends from the ink via hole, the ball material of nib is wolfram varbide, and the ball specification is respectively Φ 0.5, Φ 0.55, Φ 0.6; Ball seat body material is free cutting stainless steel, and internal structure and size design are respectively three of ink container quantity, four, five three kinds of shapes, respectively as shown in Fig. 3～Fig. 5.For the ease of the ball seat body internal structure that shows that this is written, Fig. 3～Fig. 5 shows is to remove after ball along the structural representation of axially inwardly observing of described nib, and in figure, 3 mean the ball seat bodies, and 31 is ink container, and 32 is the ink via hole.The global shape of this nib can be designed to the profiles such as bullet shaped, needle tube shape or cucurbit capitiform, and concrete schematic diagram is respectively referring to Fig. 6, Fig. 7, Fig. 8, and the numeral 1 in figure means ball, and numeral 2 means ball seat.Perhaps, the profile of this nib also can be with reference to ripe prior art otherwise designed.
For choosing the scheme of optimum matching, made respectively following erasable gel ink pen head:
A. the ball diameter is 0.5 millimeter, ink container quantity is three, within the sectional area of ink container is controlled at the scope of 54600～66800 μ m2, within radius clearance between ball and the rim of a bowl is controlled at the scope of 19～28 μ m, within the end play between ball and ball seat is controlled at the scope of 46～65 μ m.
B. the ball diameter is 0.5 millimeter, ink container quantity is four, within the sectional area of ink container is controlled at the scope of 59700～77800 μ m2, within radius clearance between ball and the rim of a bowl is controlled at the scope of 20～29 μ m, within the end play between ball and ball seat is controlled at the scope of 49～68 μ m.
C. the ball diameter is 0.55 millimeter, ink container quantity is three, within the sectional area of ink container is controlled at the scope of 56900～75300 μ m2, within radius clearance between ball and the rim of a bowl is controlled at the scope of 20～30 μ m, within the end play between ball and ball seat is controlled at the scope of 50～70 μ m.
D. the ball diameter is 0.55 millimeter, ink container quantity is four, within the sectional area of ink container is controlled at the scope of 63700～85900 μ m2, within radius clearance between ball and the rim of a bowl is controlled at the scope of 22～33 μ m, within the end play between ball and ball seat is controlled at the scope of 52～70 μ m.
E. the ball diameter is 0.6 millimeter, ink container quantity is four, within the sectional area of ink container is controlled at the scope of 75700～94500 μ m2, within radius clearance between ball and the rim of a bowl is controlled at the scope of 23～35 μ m, within the end play between ball and ball seat is controlled at the scope of 55～711 μ m.
F. the ball diameter is 0.6 millimeter, ink container quantity is five, within the sectional area of ink container is controlled at the scope of 80900～94800 μ m2, within radius clearance between ball and the rim of a bowl is controlled at the scope of 25～36 μ m, within the end play between ball and ball seat is controlled at the scope of 57～72 μ m.
Above-mentioned 6 kinds of erasable gel ink pen heads are coordinated with black erasable Neutral writing ink, blue erasable Neutral writing ink respectively, are made into pen core, by first write performance, writing quality, marking lengths, amount out of ink size, stitching width,
Intermittently write, the nib wearing and tearing, write the detection of the projects such as feel, and will detect data be divided into, in, differ from three kinds of situations, analyze the quality that judges its matched performance.Net result is that D, E are better; C is general; B is poor; A, F are poor.
Adopt black erasable Neutral writing ink and the above-mentioned nib coupling of embodiment 1 preparation, the results are shown in Table 1.
Table 1 zero represented in △ representative * representative is poor
Adopt blue erasable Neutral writing ink and the above-mentioned nib coupling of embodiment 2 preparations, the results are shown in Table 2.
Table 2 zero represented in △ representative * representative is poor
| Project | A | B | C | D | E | F |
| First write performance | ○ | △ | ○ | ○ | ○ | ○ |
| Writing quality | △ | × | △ | ○ | ○ | × |
| Marking lengths | ○ | ○ | ○ | △ | △ | × |
| Amount out of ink | × | △ | △ | △ | △ | △ |
| The stitching width | ○ | ○ | ○ | ○ | ○ | × |
| Intermittently write | △ | △ | △ | △ | △ | △ |
| The nib wearing and tearing | × | △ | △ | ○ | ○ | △ |
| Write feel | × | △ | ○ | ○ | ○ | ○ |
Embodiment 11:
The erasable Neutral ball-point for ball-point pen for preparing a kind of black.
Select the black erasable Neutral writing ink prepared and the erasable gel ink pen head matched, and other accessory comprises oil pipe, connection, lithium saponify (liquid floating plug), rubber protecting jacket etc.On the gel ink pen assembly machine, by following operation, assemble:
---load connects, and---dress nib---perfusion lithium saponify---is worn protective sleeve to pour into ink in oil pipe
Enter afterwards rotary process, get rid of the bubble that may exist in ink, just can obtain the erasable Neutral ball-point for ball-point pen of black.
The performance index of this pen core are as follows after testing:
First write performance: qualified;
Writing quality: normal;
Erasability (immediately): erasure rate (is having slight vestige) more than 85%;
Erasability (through time): erasure rate is below 55%;
Marking lengths: 200～250m;
Amount out of ink: 275～315mg/100m;
Intermittently write: more than 24 hours;
Stitching fastness: qualified;
Drying property: qualified;
Drip China ink: 24 hours without dripping China ink;
Water tolerance: within 24 hours, stitching is normal;
Light permanency: within 24 hours, stitching is normal;
Lower temperature resistance: write normal in 24 hours;
Duplicating property: after duplicating, stitching is visible;
Perviousness: qualified;
Keeping quality: qualified.
Embodiment 12:
The erasable Neutral ball-point for ball-point pen of preparation-kind of blueness.
Select the blue erasable Neutral writing ink prepared and the erasable gel ink pen head matched, and other accessory comprises oil pipe, connection, lithium saponify (liquid floating plug), rubber protecting jacket etc.On the gel ink pen assembly machine, by following operation, assemble:
---load connects, and---dress nib---perfusion lithium saponify---is worn protective sleeve to pour into ink in oil pipe
Enter afterwards rotary process, get rid of the bubble that may exist in ink, just can obtain blue erasable Neutral ball-point for ball-point pen.
The performance index of this pen core are as follows after testing:
First write performance: qualified;
Writing quality: normal;
Erasability (immediately): erasure rate (is having slight vestige) more than 85%;
Erasability (through time): erasure rate is below 50%;
Marking lengths: 190～240m;
Amount out of ink: 290～330mg/100m;
Intermittently write: more than 24 hours;
Stitching fastness: qualified;
Drying property: qualified;
Drip China ink: 24 hours without dripping China ink;
Water tolerance: within 24 hours, stitching is normal;
Light permanency: within 24 hours, stitching is normal;
Lower temperature resistance: write normal in 24 hours;
Duplicating property: after duplicating, stitching is visible;
Perviousness: qualified;
Keeping quality: qualified.
Claims (19)
1. a composition for ink is characterized in that containing following component:
Wherein, described coloring material comprises the pigment that accounts for its weight 50wt% and the resin that accounts for its weight 50%wt, and described interior cross-linking aqueous polyaminoester emulsion consists of one or more compositions that are selected from tolylene diisocyanate, diphenylmethanediisocyanate, dimethylol propionic acid, dimethyl diphenyl vulcabond, hexamethylene diisocyanate, the many alcohol of polyethylene glycol adipate, linking agent Ca, TMP.
2. composition according to claim 1, is characterized in that, described coloring material is the pigment by resin-coated, for the resin coated, by a kind of or more than one monomer polymerizations that are selected from vinylbenzene, vinylformic acid, toxilic acid or its derivative, formed.
3. composition according to claim 2, is characterized in that, the formed particle shape of the described pigment by resin-coated is spheroidal or irregular polyhedrons or shred.
4. composition according to claim 3, is characterized in that, the particle diameter of described particle is 0.5～20 μ m, and wherein the grain diameter more than 90% is 1～15 μ m.
5. composition according to claim 1, is characterized in that, described water soluble resin is the vinylbenzene polyacrylic resin.
6. composition according to claim 1, is characterized in that, described dispersion agent is for being selected from tween, polyoxyethylene alkyl phenyl ether, fatty monoethanol amide, polyoxyethylene alkyl amine; Anion surfactant fatty alcohol sulfate monoethanolamine salt, lipid acid sulfoalkyl ester, fatty alcohol sulfate monoethanolamine salt, polyethylene polyamines salt, hexadecyl pyridinium bromide; A kind of or more than one compositions in the ethylene oxide adduct of cats product polyoxyethylene carboxylate, polypropylene glycol, trimethylammonium stearylamide muriate.
7. composition according to claim 1, it is characterized in that, described viscosity modifier is a kind of or more than one compositions that are selected from sodium polyacrylate, Polyanionic Cellulose, Natvosol, polyvinylpyrrolidone, polyvinyl alcohol, xanthan gum, oxyethyl group urethane.
8. composition according to claim 1, it is characterized in that, described defoamer is by two or more combining such as silicone emulsion, the fatty acid ester compounded thing of higher alcohols, polyoxyethylene polyoxypropylene tetramethylolmethane ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxypropylenes.
9. composition according to claim 1, is characterized in that, described anti-dry wetting Agent for Printing Inks is by two or more combining such as glycerol, butyleneglycol, polyoxyethylene glycol, 1,2-PD, propylene glycol, hexylene glycol, Sorbitol Powder, Xylitols.
10. composition according to claim 1, it is characterized in that, described sanitas is by two or more combining such as methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, P-hydroxybenzoic acid the third fat, parahydroxybenzoate butyl, Sorbic Acid, potassium sorbate, calcium sorbate, phenylformic acid, Sodium Benzoates.
11. the preparation method according to the described composition for ink of any one in claim 1-10, comprise the following steps:
The mixture of resin raw material and pigment is added in the spirituous solution that contains stablizer PVP, carry out ultrasonic dispersion and the temperature of reaction system is controlled to 65-75 ℃; By the nitrogen protection atmosphere and in the situation that lasting the stirring adds the ethanolic soln that contains initiator, after completing, polyreaction can make the colored particles of resin-coated pigment simultaneously;
The colored particles of resin-coated pigment is added in pre-configured water soluble resin liquid, add again deionized water and stir, and then add dispersion agent, viscosity modifier, defoamer, sanitas, anti-dry wetting Agent for Printing Inks and fully stir, and then add the auxiliary agent such as interior cross-linking aqueous polyaminoester emulsion and stir after obtain the erasable Neutral writing ink.
12. right to use requires the nib of the described composition for ink of any one in 1-10, it comprises ball and ball seat body, described ball embeds in the rim of a bowl of described ball seat body, the ball seat bottom of this ball seat body is provided with the ink via hole, and be provided with the ink container that is radiated entends from the ink via hole, it is characterized in that:
The diameter of described ball is 0.5mm～0.6mm;
The quantity of described ink container is more than three or three;
The sectional area of described ink container is 53800～95300 μ m
2;
Radius clearance between described ball and the rim of a bowl is 18～32 μ m;
End play between described ball and ball seat is 45～75 μ m.
13. nib according to claim 12, is characterized in that, the ball diameter is 0.5 millimeter, and ink container quantity is 3, and the sectional area of ink container is 54600～66800 μ m
2, the radius clearance between ball and the rim of a bowl is 19～28 μ m, the end play between ball and ball seat is 46～65 μ m.
14. nib according to claim 12, is characterized in that, the ball diameter is 0.5 millimeter, and ink container quantity is 4, and the sectional area of ink container is 59700～77800 μ m
2, the radius clearance between ball and the rim of a bowl is 20～29 μ m, the end play between ball and ball seat is 49～68 μ m.
15. nib according to claim 12, is characterized in that, the ball diameter is 0.55 millimeter, and ink container quantity is 3, and the sectional area of ink container is 56900～75300 μ m
2, the radius clearance between ball and the rim of a bowl is 20～30 μ m, the end play between ball and ball seat is 50～70 μ m.
16. nib according to claim 12, is characterized in that, the ball diameter is 0.55 millimeter, and ink container quantity is 4, and the sectional area of ink container is 63700～85900 μ m
2, the radius clearance between ball and the rim of a bowl is 22～32 μ m, the end play between ball and ball seat is 52～70 μ m.
17. nib according to claim 12, is characterized in that, the ball diameter is 0.6 millimeter, and ink container quantity is 4, and the sectional area of ink container is 75700～94500 μ m
2, the radius clearance between ball and the rim of a bowl is 23～32 μ m, the end play between ball and ball seat is 55～71 μ m.
18. nib according to claim 12, is characterized in that, the ball diameter is 0.6 millimeter, and ink container quantity is 5, and the sectional area of ink container is 80900～94800 μ m
2, the radius clearance between ball and the rim of a bowl is 25～32 μ m, the end play between ball and ball seat is 57～72 μ m.
19. right to use requires pen or pen core that in 13～18, the described nib of any one is manufactured.
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| CN102490520B (en) * | 2011-12-23 | 2014-03-26 | 上海好顺笔业有限公司 | Lead-free pen point and preparation method thereof |
| CN103788939A (en) * | 2012-10-31 | 2014-05-14 | 上海晨光文具股份有限公司 | Thermochromic composition, thermochromic erasable neutral ink and pen core filled with the same |
| WO2015065796A1 (en) * | 2013-10-31 | 2015-05-07 | E. I. Du Pont De Nemours And Company | Aqueous ink-jet inks containing two or more binders |
| CN105017807B (en) * | 2015-07-30 | 2017-03-29 | 苏州雄鹰笔墨科技有限公司 | A kind of reversible temperature sensitive chromotropic dye, preparation method and applications |
| EP4053229A4 (en) * | 2019-10-30 | 2023-11-22 | Kabushiki Kaisha Pilot Corporation (also trading as Pilot Corporation) | Ink composition for oil-based ballpoint pen and oil-based ballpoint pen using same |
| CN113150618B (en) * | 2021-02-26 | 2022-12-16 | 烟台好前程文具有限公司 | Colored pencil lead and preparation method thereof |
| CN113248658B (en) * | 2021-06-17 | 2022-04-19 | 韶关盛怡文具有限公司 | High-viscoelasticity resin special for space pen ink, preparation method and ink using resin |
| CN114517422A (en) * | 2022-03-08 | 2022-05-20 | 湖南翠上环保科技有限公司 | Coating for paper products and preparation method thereof |
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