CN109486281B - Pen and gel ink - Google Patents
Pen and gel ink Download PDFInfo
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- CN109486281B CN109486281B CN201811488424.1A CN201811488424A CN109486281B CN 109486281 B CN109486281 B CN 109486281B CN 201811488424 A CN201811488424 A CN 201811488424A CN 109486281 B CN109486281 B CN 109486281B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
Abstract
The invention provides a pen and neutral ink, wherein the pen comprises a pen core, wherein the pen core is internally provided with ink, and the ink comprises a macromolecular dispersant, a thickening agent, water-based resin, a lubricant, a cosolvent, a humectant, a bactericide, a pH regulator and water. The neutral ink according to an embodiment of the present invention has excellent stability and writing lubricity.
Description
Technical Field
The invention relates to ink, in particular to neutral ink with excellent stability and writing lubricity.
Background
The gel-ink pen is a writing tool commonly used in the market at present, the number of the gel-ink pen and the refill manufactured and consumed by China as the gel-ink pen exceeds 80 hundred million every year, but the gel-ink for filling the gel-ink pen mostly depends on import, which is related to the technical difficulty of the development of the gel-ink. The neutral ink is divided into a pigment type and a dye type, and the pigment type neutral ink is suitable for long-term retention and has a leading position in the whole neutral ink consumption market.
Pigmented inks are complex multiphase dispersions that can include adjuvants such as wetting agents, lubricants, thickeners, and the like. The wetting agent is used for wetting a writing interface and assisting ink diffusion so as to be capable of normally writing on writing media with different surface properties; the lubricant is used for lubricating the ball seat body and the ball of the pen point in the writing process, so that the frictional resistance is reduced, and the writing is smooth; the thickening agent is used for thickening and endowing an ink system with shear thinning performance, the viscosity is reduced during writing, ink is smoothly discharged, and the viscosity is timely increased after the writing is stopped, so that ink leakage of a pen point is avoided.
Most of the prior neutral ink formulas only pay attention to the self functions of the auxiliary agents, so that the comprehensive application performance of the ink is not outstanding, the requirement on high quality is not met, and other performances are usually sacrificed for improving one performance. For example, shear thinning is an important feature of neutral inks, and wetting agents, lubricants, humectants, and other functional additives in the system can significantly affect or even impair the rheological properties of the ink.
Disclosure of Invention
One main object of the present invention is to provide a pen including a cartridge, in which an ink is disposed, the ink including a polymeric dispersant, a thickener, an aqueous resin, a lubricant, a cosolvent, a humectant, a bactericide, a pH adjuster, and water.
One embodiment of the invention provides neutral ink which comprises a high-molecular dispersing agent, a thickening agent, water-based resin, a lubricant, a cosolvent, a humectant, a bactericide, a pH regulator and water.
According to an embodiment of the invention, the neutral ink comprises carbon black.
According to an embodiment of the present invention, the neutral ink includes:
according to an embodiment of the present invention, the polymeric dispersant comprises a graft polymer comprising an acrylic backbone and pendant hydrophobic amine-based side chains, hydrophilic polyether side chains pendant from the acrylic backbone.
According to an embodiment of the present invention, the molar ratio of the hydrophilic polyether side chain to the hydrophobic amino side chain of the polymeric dispersant is 1/13-1/5.
According to one embodiment of the invention, the thickener is a linear alkyl or aryl modified acrylic emulsion.
According to an embodiment of the present invention, the aqueous resin is selected from a pure acrylic emulsion, a styrene-acrylic emulsion, or a tert-acrylic emulsion having a minimum film forming temperature higher than 50 ℃ and an acid value of 50 to 100.
According to an embodiment of the present invention, the lubricant comprises graphene oxide, and the graphene oxide contains one or more of sulfonic acid group, phosphoric acid group, carboxylic acid group, hydroxyl group and ester group, wherein the functional group accounts for 5% to 15% of the weight of the graphene oxide.
One embodiment of the present invention provides a method for preparing a neutral ink, including:
adding a cosolvent and a polymeric dispersant into deionized water;
adding carbon black into the system, then adding a pH regulator to enable the pH value of the system to be 8.0-9.0, and stirring for 1-2 hours to enable the carbon black to be completely wetted;
transferring the mixture in the system into a sand mill, circularly grinding the mixture by adopting 0.3-0.5 mm zirconium beads until the material particle size D50 is less than or equal to 150nm and D90 is less than or equal to 200nm, and filtering to obtain carbon black color paste; and
and sequentially adding the balance of pH regulator, thickener, humectant, lubricant, water-based resin, bactericide and the balance of water into the carbon black color paste, and filtering to obtain the neutral ink.
The neutral ink according to an embodiment of the present invention has excellent stability and writing lubricity.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below. It is to be understood that the invention is capable of other and different embodiments and its several details are capable of modification without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to be construed as limiting the invention.
The invention provides neutral ink which comprises a polymer dispersant, a thickening agent, water-based resin, a lubricant, a cosolvent, a humectant, a bactericide, a pH regulator and water, wherein the water can be deionized water.
According to the neutral ink disclosed by the embodiment of the invention, adverse factors are avoided through the synergistic effect among the auxiliaries, and the dispersion of an ink system, the long-term stability of viscosity and the smoothness of writing are realized.
In one embodiment, the neutral ink comprises carbon black.
In one embodiment, the carbon black is a surface treated medium pigment carbon black or a normal pigment carbon black, such as eurycor's teh black 5, teh black 4, Nerox 510, Nerox 600, mitsubishi's MA8, MA70, MA 100.
In one embodiment, the neutral ink comprises 6.0-10.0 parts by mass of carbon black, 1.5-4.0 parts by mass of a polymeric dispersant, 0.5-1.0 part by mass of a thickener, 5.0-10.0 parts by mass of a water-based resin, 0.01-0.1 part by mass of a lubricant, 5.0-10.0 parts by mass of a cosolvent, 10.0-20.0 parts by mass of a humectant, 0.1-0.3 part by mass of a bactericide, 0.5-2.0 parts by mass of a pH regulator, and 42.6-71.4 parts by mass of deionized water.
In one embodiment, the neutral ink includes 8.0 parts by mass of carbon black, 4.0 parts by mass of a polymeric dispersant, 1.0 part by mass of a thickener, 10 parts by mass of an aqueous resin, 0.05 part by mass of a lubricant, 7 parts by mass of a cosolvent, 15 parts by mass of a humectant, 0.2 part by mass of a bactericide, 1.0 part by mass of a pH adjuster, and 53.75 parts by mass of deionized water.
In one embodiment, the neutral ink includes 6.0 parts by mass of carbon black, 1.5 parts by mass of a polymeric dispersant, 0.5 parts by mass of a thickener, 5.0 parts by mass of an aqueous resin, 0.07 parts by mass of a lubricant, 7 parts by mass of a cosolvent, 18.0 parts by mass of a humectant, 0.2 parts by mass of a bactericide, 0.5 parts by mass of a pH adjuster, and 61.23 parts by mass of deionized water.
In one embodiment, the polymeric dispersant comprises a graft polymer having an acrylic backbone, and hydrophobic amino side chains and hydrophilic polyether side chains suspended from the backbone, wherein the weight average molecular weight of the graft polymer is 8000 to 12000, such as 9000, 10000, and the like.
In one embodiment, the graft polymer comprises the following structural units:
wherein:
R11、R12、R13each independently selected from methyl or ethyl; r21、R22Each independently selected from hydrogen atom, methyl, ethyl, propyl, butyl; m is1The average number of ethoxy groups may be 5 to 13, for example, 7, 8, 10, 11, 12, etc.
In one embodiment, the backbone of the graft polymer may be a block copolymer or a random copolymer.
In one embodiment, the graft polymer is prepared by copolymerizing polyethylene glycol monoacrylate, isooctyl acrylate, and dimethylaminoethyl acrylate.
In one embodiment, the mass ratio of polyethylene glycol 400 monoacrylate, isooctyl acrylate, dimethylaminoethyl acrylate is 7.6:25.4: 12.
In one embodiment, the mass ratio of polyethylene glycol 600 monoacrylate, isooctyl acrylate, dimethylaminoethyl acrylate is 8:28: 14.
In another embodiment, the graft polymer is prepared by copolymerizing polyethylene glycol monoacrylate, butyl acrylate and diethylaminoethyl acrylate.
In one embodiment, the mass ratio of polyethylene glycol 600 monoacrylate, butyl acrylate, and diethylaminoethyl acrylate is 5.3:31.7: 18.
In one embodiment, the mole ratio of the hydrophilic polyether side chain to the hydrophobic amine side chain of the graft polymer is 1/13-1/5, such as 1/12, 1/8, 1/6, and the like.
In one embodiment, the dispersant molecules are adsorbed on the carbon black surface through the interaction of nitrogen atoms on hydrophobic amino side chains on the acrylic polymer main chain and carboxyl, hydroxyl and ester groups on the surface of the carbon black particles, and hydrophilic polyether side chains extend in water to form steric hindrance, so that the carbon black particles are stably dispersed.
In one embodiment, the thickener is a linear alkyl or aromatic modified acrylic emulsion such as Coadd H-120, Coadd H-15, Rheovis HS1152, Rheovis HS 1162, which are commonly used (Shanghai) New materials.
In one embodiment, the linear alkyl or aryl modified acrylic emulsion has a mass concentration of 20% to 40%, for example, 25%, 30%, 35%, etc. Wherein the linear alkyl is C14-C18 linear alkyl, and the aromatic hydrocarbon is one or more of benzene ring and alkyl phenyl containing linear C4-C8 at para-position.
In one embodiment, in the swelling state, the straight-chain alkyl or aromatic hydrocarbon group on the thickener molecule and the carbon atom on the surface of the carbon black particle generate weak association to form a three-dimensional network structure, so that the viscosity building is realized and the dispersion stability of the carbon black particle is improved. Particularly, the association effect of straight-chain alkyl or aryl in the thickener molecules and the surface of the carbon black particles is weaker than the interaction between nitrogen atoms on a side chain of the acrylic acid graft polymer dispersant and the surface of the carbon black particles, so that the instability of a system caused by replacing dispersant molecules originally acting on the surface of the carbon black particles by competitive adsorption can be avoided.
In one embodiment, the aqueous resin may be acrylic, styrene-acrylic or acrylic emulsion with a minimum film forming temperature higher than 50 ℃ and an acid value of 50-100, such as joncryl 538 styrene-acrylic emulsion (minimum film forming temperature higher than 65 ℃ and acid value 53), joncryl 90 styrene-acrylic emulsion (minimum film forming temperature higher than 85 ℃ and acid value 76), EA2370 acrylic emulsion (minimum film forming temperature higher than 55 ℃ and acid value 88), PD-Hiqua2000 acrylic emulsion (minimum film forming temperature higher than 55 ℃ and acid value 50).
In one embodiment, the minimum film forming temperature of the aqueous resin may be greater than 55 ℃, greater than 65 ℃, greater than 85 ℃ and the like, and the acid value may be 53, 76, 88 and the like.
In one embodiment, the aqueous resin emulsion has a mass concentration of 20% to 60%, for example, 30%, 45%, 50%, or the like.
In one embodiment, on the one hand, the acrylic resin molecules of the water-based resin provide more association points for straight-chain alkyl or aryl modified acrylic emulsion thickener molecules, so that a viscosity system is more stable; on the other hand, the high film forming temperature can avoid that the ink outlet channel is blocked by dehydration and film forming in the uncapped state after the ink is filled into the pen, thereby damaging uncapped writing performance.
In one embodiment, the lubricant comprises graphene oxide containing one or more of sulfonic acid groups, phosphoric acid groups, carboxylic acid groups, hydroxyl groups, ester groups.
In one embodiment, the graphene oxide has a sheet diameter of 5 to 10 μm.
In one embodiment, the lubricant is graphene oxide aqueous dispersion, and the mass concentration may be 5% to 15%, such as graphene oxide dispersion FNG-B101 (5 to 10 microns in sheet diameter, 10% mass concentration) and FNG-B111 (5 to 10 microns in sheet diameter, 15% mass concentration) of a new suzhou high-pass material.
In one embodiment, graphene oxide having a carboxyl, sulfonic, or phosphoric acid functional group on the surface is used as a lubricant, and the association between the linear alkyl or aromatic modified acrylic emulsion and the hydrophobic group is less affected, and the thickening efficiency and stability are not substantially impaired. Carboxyl, sulfonic group or phosphoric group on the surface of the graphene oxide is adsorbed on the surfaces of the ball seat body and the ball bead through electrostatic attraction, chemical bonds and the like, and the flaky graphene is laminated between the ball seat body and the ball bead to play a role in boundary lubrication. Further, since graphene has a large sheet diameter and a very small thickness, a small amount of graphene added provides an excellent lubricating effect.
In one embodiment, the cosolvent may be one or more of ethylene glycol, glycerol, 1, 3-butanediol, tert-butanol, and isoprene glycol.
In one embodiment, the humectant may be one or more of propylene glycol, glycerin, polyethylene glycol, sorbitol, xylitol. Wherein the number average molecular weight of the polyethylene glycol is 200-6000, such as 500, 1000, 3000, 5000 and the like.
In one embodiment, the biocide may be one or more of an isothiazolinone, benzisothiazolinone, such as 1, 2-benzisothiazolinone.
In one embodiment, the pH adjusting agent may be one or more of dimethylethanolamine, triethanolamine, triethylamine, diisopropylethylamine, 2-amino-2-methyl-1-propanol.
According to the neutral ink provided by the embodiment of the invention, through the synergistic effect of multiple auxiliaries, the viscosity stability and the dispersion stability of pigment particles are high, writing is smooth, and the neutral ink has excellent comprehensive performance.
The use of the polymeric dispersant, particularly the graft polymer having an acrylic main chain and a hydrophobic amino side chain and a hydrophilic polyether side chain suspended from the main chain, contributes to the stable dispersion of carbon black particles in the system.
The neutral ink according to an embodiment of the present invention uses a linear alkyl or aryl modified acrylic emulsion as a thickener, and contributes to stable dispersion of carbon black particles and overall stability of an ink system.
The neutral ink provided by the embodiment of the invention adopts the water-based resin with high film-forming temperature, so that the damage of the blockage of an ink outlet channel caused by dehydration film-forming in a uncapped state after the ink is filled into a pen can be reduced to the writing performance.
One embodiment of the present invention provides a method for preparing a neutral ink, including:
1) adding cosolvent, high molecular dispersant and deionized water accounting for 40% of the formula according to the formula metering requirement, stirring uniformly, slowly adding carbon black, then adding pH regulator accounting for 60% of the formula to enable the pH value of the system to be 8.0-9.0, continuously stirring for 1-2 hours to enable the carbon black to be completely wetted, transferring the mixture into a sand mill, circularly grinding by adopting zirconium beads of 0.3-0.5 mm until the particle sizes of the materials are D50-200 nm, and D90-200 nm, and filtering to obtain the carbon black color paste.
2) And sequentially adding the balance of pH regulator, thickener, humectant, lubricant, water-based resin, bactericide and the balance of water into the obtained carbon black color paste, fully stirring, and filtering to obtain the pigment type black neutral ink.
In the preparation method of the neutral ink, the pH regulator is added in two steps, and 60% of the pH regulator is added into the color paste according to the formula in order to constantly neutralize the acid groups on the surfaces of new carbon black particles generated in the grinding process, so that the adsorption and dispersion stability of dispersant molecules are facilitated. The addition of a 40% by weight formulation of a pH adjusting agent during the subsequent ink preparation serves to neutralize the carboxylic acids in the linear or aromatic modified acrylic emulsion to form carboxylate ions which act as a thickening agent to form electrostatic repulsion.
Hereinafter, the gel ink and the method for preparing the same according to one embodiment of the present invention will be described in detail with reference to specific examples. Wherein, the parts are mass parts; the pigment carbon black extra black 5 in the Eupatorium is purchased from New Yirui material Co., Ltd, the thickener HS1152, the Joncryl 90 water-based styrene-acrylic emulsion and the film-forming water-based styrene-acrylic emulsion Joncryl 74-A are purchased from Pasf chemical engineering, Germany, the graphene oxide dispersion FNG-B111 is purchased from New Highuaku material science and technology Co., Ltd, the high molecular dispersant Solsperse 27000 is purchased from Highai Asia Pepper industry Co., Ltd, the xanthan gum Kelzan AP is purchased from Highai Yoghuai chemical industry Co., Ltd, and the fatty alcohol polyoxyethylene ether phosphate MOA-3P is purchased from Federal Fine chemical industry Co., Ltd, Guangdong.
Example 1
Preparation of the dispersant
a. Adding 29g of water into a 250ml reaction kettle with a stirrer, then adding 1g of a nonionic surfactant of isomeric tridecanol polyoxyethylene ether (EO ═ 8) and 7.6g of reactive emulsifier polyethylene glycol 400 monoacrylate, stirring for 5min, then adding a mixture of 25.4g of isooctyl acrylate and 12g of dimethylaminoethyl acrylate under a stirring state, and stirring for 30min to prepare a pre-emulsion for later use;
b. in a separate 250ml four-necked flask equipped with a stirrer, a thermometer and a condenser were placed 19.04g of water, 0.5g of isotridecanol polyoxyethylene ether (EO-8) and NH4HCO30.3g, placing the mixture in a water bath kettle, heating the mixture to 80 ℃, adding 5g of pre-emulsion and 0.11g of aqueous solution of ammonium persulfate dissolved in 3g of water into a reaction kettle, stirring and preserving heat for 30 min;
c. dissolving 0.05g of ammonium persulfate in 2g of water, dripping the initiator solution and the rest of pre-emulsion into a reaction kettle within 3h, keeping stirring and constant temperature, keeping the temperature for reaction for 1h after finishing dripping, cooling, neutralizing with ammonia water until the pH value is 7.0 after the temperature is reduced to 25 ℃, pouring out the polymer in the reaction kettle, filtering for later use, and marking as a dispersant solution A (wherein the molar ratio of the hydrophilic polyether side chain and the hydrophobic amino side chain of the polymer is 1/5).
Measuring the molecular weight: the weight average molecular weight was 9000 by gel chromatography (GPC) using tetrahydrofuran as a mobile phase.
Preparation of the ink
Adding 5.0 parts of propylene glycol, 3.6 parts of the prepared dispersant solution A (effective concentration of 45%, weight average molecular weight 9000, molar ratio of hydrophilic polyether side chain to hydrophobic amino side chain of 1/5) and 0.3 part of 2-amino-2-methyl-1-propanol into 22.28 parts of deionized water, uniformly stirring, adding 6.0 parts of pigment carbon black extra black 5 in Eupatorium, continuously stirring for 2 hours after the addition is finished to fully wet the carbon black, transferring the mixture to a horizontal sand mill filled with zirconium beads with the diameter of 0.3mm, starting circular grinding, controlling the temperature of the material to be lower than 55 ℃ in the grinding process until the grinding is finished when the particle size D50 of the carbon black particles is not more than 150nm and the particle size D90 is not more than 200nm, and filtering to obtain the carbon black color paste.
Adding 0.2 part of 2-amino-2-methyl-1-propanol into the obtained carbon black color paste, adding 0.8 part of straight-chain alkyl modified acrylic emulsion thickener HS1152 (the effective concentration is 40%) under the stirring state, gradually opening the molecular chain segment of the thickener to increase the viscosity of the system, gradually increasing the stirring speed, after the system is uniformly mixed, under stirring, 10.0 parts of glycerol, 10.0 parts of polyethylene glycol 200, 0.2 part of graphene oxide dispersion FNG-B111 (15% of graphene mass concentration), 12.0 parts of Joncryl 90 aqueous styrene-acrylic emulsion (45% of effective concentration, minimum film-forming temperature greater than 85 ℃ and acid value 76), 0.2 part of 1, 2-benzisothiazolinone and 31.02 parts of deionized water are added, stirring is continued until all the materials are uniformly mixed, and the ink mixture is filtered by two stages of 1000 meshes and 1 micron to prepare the ink of example 1.
Examples 1 to 1
The same preparation method was used to replace 3.6 parts of the dispersant solution A (45% effective concentration) in example 1 with 1.62 parts of polyester-based polymeric dispersant Solsperse 27000 (100% effective concentration), the balance was made up with deionized water, and the types, amounts, etc. of other adjuvants were kept unchanged, thereby obtaining ink of example 1-1.
Examples 1 to 2
The ink of example 1-2 was prepared by the same preparation method except that 0.8 part of the straight-chain alkyl-modified acrylic emulsion thickener HS1152 (effective concentration 40%) in example 1 was replaced with 0.32 part of xanthan gum Kelzan AP (effective concentration 100%), the balance was made up with deionized water, and the kinds, amounts, etc. of the other adjuvants were kept unchanged.
Examples 1 to 3
Inks of examples 1 to 3 were obtained by the same production method except that 12.0 parts of Joncryl 90 aqueous styrene-acrylic emulsion (effective concentration: 45%) in example 1 was replaced with 10.8 parts of film-forming aqueous styrene-acrylic emulsion Joncryl 74-A (effective concentration: 50%, minimum film-forming temperature < 5 ℃), the balance was replaced with deionized water, and the kinds, amounts, etc. of other auxiliary agents were kept unchanged.
Examples 1 to 4
The ink of examples 1 to 4 was prepared by replacing 0.2 part of graphene oxide dispersion FNG-B111 (15% graphene mass fraction) of example 1 with 0.03 part of fatty alcohol-polyoxyethylene ether phosphate MOA-3P (effective concentration 100%), adding the balance with deionized water, and keeping the types, amounts, and the like of other additives unchanged by the same preparation method.
Example 2
Preparation of the dispersant
a. Adding 24g of water into a 250ml reaction kettle with a stirrer, then adding 1g of a nonionic surfactant of isomeric tridecanol polyoxyethylene ether (EO-8) and 8g of reactive emulsifier polyethylene glycol 600 monoacrylate, stirring for 5 minutes, then adding a mixture of 28g of isooctyl acrylate and 14g of dimethylaminoethyl acrylate under a stirring state, and stirring for 30 minutes to prepare a pre-emulsion for later use;
b. in a separate 250ml four-necked flask equipped with a stirrer, a thermometer and a condenser were placed 19.06g of water, 0.5g of isotridecanol polyoxyethylene ether (EO-8) and NH4HCO30.3g, placing the mixture in a water bath kettle, heating the mixture to 80 ℃, adding 5g of pre-emulsion and 0.1g of aqueous solution of ammonium persulfate dissolved in 3g of water into a reaction kettle, stirring and preserving heat for 30 min;
c. dissolving 0.04g of ammonium persulfate in 2g of water, dripping the initiator solution and the rest of pre-emulsion into a reaction kettle within 3 hours, keeping stirring and constant temperature, keeping the temperature for reaction for 1 hour after finishing dripping, cooling, neutralizing with ammonia water until the pH value is 7 after the temperature is reduced to 25 ℃, pouring out the polymer in the reaction kettle, filtering for later use, and marking as a dispersant solution B (wherein the molar ratio of the hydrophilic polyether side chain and the hydrophobic amino side chain of the polymer is 1/8).
Measuring the molecular weight: the weight average molecular weight was 10000 as measured by gel chromatography (GPC) using tetrahydrofuran as a mobile phase.
Preparation of the ink
Adding 7.5 parts of 1, 3-butanediol, 4.5 parts of the prepared dispersant solution B (the effective concentration of 50 percent, the weight-average molecular weight of the graft polymer is 10000, the molar ratio of the hydrophilic polyether side chain to the hydrophobic amino side chain is 1/8) and 0.6 part of triethanolamine into 17.64 parts of deionized water, stirring uniformly, adding 8.0 parts of Mitsubishi MA8 carbon black, continuing to stir for 2 hours after the addition is finished to fully wet the carbon black, transferring the mixture into a horizontal sand mill filled with zirconium beads with the diameter of 0.3mm, starting circular grinding, controlling the temperature of the material to be lower than 55 ℃ in the grinding process until the particle size D50 of the carbon black particles is less than or equal to 150nm and the D90 is less than or equal to 200nm, finishing grinding, and filtering to obtain the carbon black color paste.
Adding 0.4 part of triethanolamine into the obtained carbon black color paste, adding 1.0 part of straight-chain alkyl modified acrylic emulsion thickener Coadd H-120 (the effective concentration is 30%) under the stirring state, gradually opening the molecular chain segment of the thickener, increasing the viscosity of the system, gradually increasing the stirring speed, continuously adding 10.0 parts of polyethylene glycol 200, 8.0 parts of polyethylene glycol 600, 0.6 part of graphene oxide dispersion FNG-B101 (the mass concentration of 10%) and 15.0 parts of EA370 pure acrylic emulsion (the effective concentration is 40%, the lowest film forming temperature is higher than 60 ℃, the acid value is 88), 0.3 part of 1, 2-benzisothiazolinone and 26.46 parts of deionized water under the stirring state, continuously stirring until all the materials are uniformly mixed, and filtering the prepared ink mixture by two stages of 1000 meshes and 1 micron to prepare the ink of the embodiment 2.
Example 2-1
Preparation of the dispersant
The graft polymer was prepared using the same raw materials and methods as in example 2 except that the amounts of polyethylene glycol 600 monoacrylate and dimethylaminoethyl acrylate were different, the weight average molecular weight of the graft polymer in the prepared dispersant solution B1 was 10000, and the molar ratio of the polyether side chain to the amine side chain was 1/5.
Preparation of the ink
Example 2-1 ink was obtained by the same preparation method except that 4.5 parts of the dispersant solution B (polymer weight average molecular weight: 10000, molar ratio of polyether side chain to amino side chain: 1/8) in example 2 was replaced with 4.5 parts of the dispersant solution B1 (polymer weight average molecular weight: 10000, molar ratio of polyether side chain to amino side chain: 1/5), and the kind, amount, etc. of other auxiliary agents were kept unchanged.
Examples 2 to 2
Preparation of the dispersant
The graft polymer was prepared using the same raw materials and methods as in example 2 except that the amounts of polyethylene glycol 600 monoacrylate and dimethylaminoethyl acrylate were different, the weight average molecular weight of the graft polymer in the prepared dispersant solution B2 was 10000, and the molar ratio of the polyether side chain to the amine side chain was 1/13.
Preparation of the ink
Example 2-2 ink was obtained by the same preparation method except that 4.5 parts of the dispersant solution B (polymer weight average molecular weight: 10000, molar ratio of polyether side chain to amino side chain: 1/8) in example 2 was replaced with 4.5 parts of the dispersant solution B2 (polymer weight average molecular weight: 10000, molar ratio of polyether side chain to amino side chain: 1/13), and the kind, amount, etc. of other auxiliary agents were kept unchanged.
Examples 2 to 3
Preparation of the dispersant
The graft polymer was prepared using the same raw materials and methods as in example 2 except that the amounts of polyethylene glycol 600 monoacrylate and dimethylaminoethyl acrylate were different, the weight average molecular weight of the graft polymer in the prepared dispersant solution B3 was 10000, and the molar ratio of the polyether side chain to the amine side chain was 1/4.
Preparation of the ink
The same preparation method was used to obtain inks of examples 2 to 3 by replacing 4.5 parts of the dispersant solution B (polymer weight average molecular weight: 10000, molar ratio of polyether side chain to amino side chain: 1/8) in example 2 with 4.5 parts of the dispersant solution B3 (polymer weight average molecular weight: 10000, molar ratio of polyether side chain to amino side chain: 1/4), while keeping the kinds, amounts, etc. of other additives unchanged.
Examples 2 to 4
Preparation of the dispersant
The graft polymer was prepared using the same raw materials and methods as in example 2 except that the amounts of polyethylene glycol 600 monoacrylate and dimethylaminoethyl acrylate were different, the weight average molecular weight of the graft polymer in the prepared dispersant solution B4 was 10000, and the molar ratio of the polyether side chain to the amine side chain was 1/15.
Preparation of the ink
The same preparation method was used to obtain inks of examples 2 to 4 by replacing 4.5 parts of the dispersant solution B (polymer weight average molecular weight: 10000, molar ratio of polyether side chain to amino side chain: 1/8) in example 2 with 4.5 parts of the dispersant solution B4 (polymer weight average molecular weight: 10000, molar ratio of polyether side chain to amino side chain: 1/15), while keeping the kinds, amounts, etc. of other additives unchanged.
Example 3
Preparation of the dispersant
a. Adding 19g of water into a 250ml reaction kettle with a stirrer, then adding 1g of non-ionic surfactant of isomeric tridecanol polyoxyethylene ether (EO ═ 8) and 5.3g of reactive emulsifier polyethylene glycol 600 monoacrylate, stirring for 5 minutes, then adding a mixture of 31.7g of butyl acrylate and 18g of diethylaminoethyl acrylate under the stirring state, stirring for 30 minutes, and preparing a pre-emulsion for later use;
b. in a separate 250ml four-necked flask equipped with a stirrer, a thermometer and a condenser were placed 19.09g of water, 0.5g of isotridecanol polyoxyethylene ether (EO-8) and NH4HCO30.3g, placing the mixture in a water bath kettle, heating the mixture to 80 ℃, adding 5g of pre-emulsion and 0.08g of aqueous solution of ammonium persulfate dissolved in 3g of water into a reaction kettle, stirring and preserving heat for 30 min;
c. dissolving 0.03g of ammonium persulfate in 2g of water, dripping the initiator solution and the rest of pre-emulsion into a reaction kettle within 3 hours, keeping stirring and constant temperature, keeping the temperature for reaction for 1 hour after finishing dripping, cooling, neutralizing with ammonia water until the pH value is 7 after the temperature is reduced to 25 ℃, pouring out the polymer in the reaction kettle, filtering for later use, and marking as a dispersant solution C (wherein the molar ratio of the hydrophilic polyether side chain to the hydrophobic amino side chain is 1/13).
Measuring the molecular weight: the weight average molecular weight was 12000, as determined by gel chromatography (GPC) using tetrahydrofuran as the mobile phase.
Preparation of the ink
Adding 4.0 parts of ethylene glycol, 4.0 parts of isoprene glycol, 6.0 parts of the prepared dispersant solution C (55% effective concentration, the weight average molecular weight of a graft polymer is 12000, the molar ratio of a hydrophilic polyether side chain to a hydrophobic amino side chain is 1/13) and 0.9 part of diisopropylethylamine into 16.84 parts of deionized water, stirring uniformly, adding 10.0 parts of Eupatorium terra black 4 carbon black, stirring for 2 hours after the addition is finished to fully wet the carbon black, transferring the mixture into a horizontal sand mill filled with zirconium beads with the diameter of 0.3mm, starting circular grinding, controlling the material temperature to be lower than 55 ℃ in the grinding process until the grinding is finished when the particle size D50 of the carbon black particles is not more than 150nm and the D90 is not more than 200nm, and filtering to obtain the carbon black color paste.
0.6 part of diisopropylethylamine is added into the obtained carbon black color paste, 1.5 parts of straight-chain alkyl modified acrylic emulsion thickener Coadd H-15 (the effective concentration is 30%) is added under the stirring state, the viscosity of the system is increased along with the gradual opening of the molecular chain segment of the thickener, the stirring speed is gradually increased, after the system is uniformly mixed, 5.0 parts of sorbitol, 10.0 parts of polyethylene glycol 600, 0.8 part of graphene oxide dispersion FNG-B101 (the mass concentration of 10% of graphene), 15.0 parts of Joncryl 538 styrene-acrylic emulsion (the lowest film forming temperature is more than 65 ℃, the acid value is 53, the effective concentration is 45%), 0.1 part of 1, 2-benzisothiazolinone and 25.26 parts of deionized water are continuously stirred until all the materials are uniformly mixed, and the prepared ink mixture is filtered by a two-stage of 1000 meshes and 1 micron to prepare the ink of the embodiment 3.
Example 3-1
Preparation of the dispersant
The graft polymer was prepared using the same raw materials and methods as in example 3, except that the amounts of polyethylene glycol 600 monoacrylate and diethylaminoethyl acrylate were different, the weight average molecular weight of the graft polymer in the prepared dispersant solution C1 was 12000, and the molar ratio of the polyether side chain to the amine side chain was 1/8.
Preparation of the ink
Example 3-1 ink was obtained by the same preparation method except that 5.0 parts of the dispersant solution C (polymer weight average molecular weight 12000, molar ratio of polyether side chain to amino side chain 1/13) in example 3 was replaced with 5.0 parts of the dispersant solution C1 (polymer weight average molecular weight 12000, molar ratio of polyether side chain to amino side chain 1/8), and the kind, amount, etc. of other auxiliary agents were kept unchanged.
Examples 3 to 2
Preparation of the dispersant
The graft polymer was prepared using the same raw materials and methods as in example 3, except that the amounts of polyethylene glycol 600 monoacrylate and diethylaminoethyl acrylate were different, the weight average molecular weight of the graft polymer in the prepared dispersant solution C2 was 12000, and the molar ratio of the polyether side chain to the amine side chain was 1/4.
Preparation of the ink
Example 3-2 ink was obtained by the same preparation method except that 5.0 parts of the dispersant solution C (polymer weight average molecular weight 12000, molar ratio of polyether side chain to amino side chain 1/13) in example 3 was replaced with 5.0 parts of the dispersant solution C2 (polymer weight average molecular weight 12000, molar ratio of polyether side chain to amino side chain 1/4), and the kind, amount, etc. of other auxiliary agents were kept unchanged.
Examples 3 to 3
Preparation of the dispersant
The graft polymer was prepared using the same raw materials and methods as in example 3, except that the amounts of polyethylene glycol 600 monoacrylate and diethylaminoethyl acrylate were different, the weight average molecular weight of the graft polymer in the prepared dispersant solution C3 was 12000, and the molar ratio of the polyether side chain to the amine side chain was 1/15.
Preparation of the ink
Ink of example 3-3 was obtained by the same preparation method except that 5.0 parts of dispersant solution C (polymer weight average molecular weight 12000, molar ratio of polyether side chain to amino side chain 1/13) in example 3 was replaced with 5.0 parts of dispersant solution C3 (polymer weight average molecular weight 12000, molar ratio of polyether side chain to amino side chain 1/15), and the kind, amount, and the like of other auxiliary agents were kept unchanged.
Comparative example
Comparative ink was obtained by the same production method except that 12.0 parts of the Joncryl 90 aqueous styrene-acrylic emulsion 12.0 parts in example 1 was replaced with deionized water, and the kinds, amounts and the like of other auxiliary agents were kept unchanged.
Evaluation of associative thickening Effect of straight-chain alkyl Or aromatic modified acrylic emulsion thickeners
The apparent viscosity of the carbon black paste of example 1, the ink of example 1 and the ink of example 1-2 was measured by a rotational rheometer using a mixed solution of the thickener, the aqueous resin, the lubricant, the humectant, the bactericide, the pH adjuster and the deionized water to which the carbon black paste of example 1 was not added, a mixed solution of the thickener, the aqueous resin, the lubricant, the humectant, the bactericide, the pH adjuster and the deionized water to which the paste of example 1-2 was not added, and the results are shown in table 1.
TABLE 1 viscosity data of the mixtures, pastes and inks of examples 1 and 1-2
| Numbering | 1.256s-1Shear viscosity (cp) | 12.56s-1Shear viscosity (cp) |
| Example 1 liquid mixture | 123 | 118 |
| Example 1-2 Mixed solution | 2824 | 480 |
| Example 1 carbon Black paste | 79 | 65 |
| Practice ofExample 1 ink | 1498 | 554 |
| Examples 1-2 inks | 1465 | 361 |
The inks of examples 1-2 used xanthan gum, which is a non-associative thickener, as the thickener in example 1, with the other adjuvants. The viscosity of the mixed liquid in the embodiment 1-2 is obviously higher than that of the mixed liquid in the embodiment 1, which shows that the mixed liquid plays a thickening role in the system, and the carbon black color paste is added to prepare the ink in the embodiment 1-2, because the concentration of the thickening agent is reduced due to the introduction of water in the color paste, the whole viscosity is reduced.
The viscosity of the mixed liquid in the embodiment 1 is obviously lower than that of the mixed liquid in the embodiment 1-2, and the viscosity of the ink in the embodiment 1 prepared by adding the same carbon black color paste is obviously increased, which shows that the molecules of the linear alkyl modified acrylic emulsion thickener in the mixed liquid in the embodiment 1 are associated with the carbon black particles in the color paste to construct a three-dimensional network structure, so that the viscosity is obviously improved. This viscosity system, which is built up by association with the pigment particles, is beneficial for the long-term stability of the ink.
The inks of the examples and the comparative examples are matched with the ball-point diameter bullet type pen point with 0.5mm in the market mainstream to be made into a pen core for evaluating the application performance and the long-term stability.
1. Writing lubricity evaluation
The pen core is placed on a writing lubricity detector to perform circle marking under the load of 1N, so that the artificial writing is simulated, the size of the frictional resistance borne by the pen head in the circle marking process is given by the instrument, and the frictional coefficient of the pen core is obtained by dividing the size of the frictional resistance by the load. 10 samples are tested, the average value of the samples is used as an evaluation index of the writing lubricity of the pen core, the ink lubricity is better when the friction coefficient is smaller, and the test result is shown in table 2.
2. Off-cap writing performance evaluation
Taking 25 pen cores which are in normal writing at the beginning, placing the pen cores in a uncapping horizontal mode for 3, 7, 10, 15 and 30 days under a test environment with the ambient temperature of 20-25 ℃ and the relative humidity of 50-60%, taking 5 pen cores at each time node, enabling 5 pen core traces within 100mm before pen opening to be qualified normally until unqualified pen cores are formed, enabling the former time node to be the uncapping writing days of the pen cores and serve as an evaluation index of uncapping writing performance, and enabling test results to be shown in table 2.
3. Long term stability evaluation
The physical and chemical properties and the service performance of the refill after being stored at normal temperature still meet the maximum storage time specified by QB/T2626-2011 standards of neutral ink ball-point pens and refills, the refill is used as an evaluation index of long-term stability, and the test result is shown in Table 2.
Table 2 test results of application properties of ink-filled cartridges in examples and comparative examples
| Ink numbering | Long term stability | Uncapped writing performance | Lubricating performance |
| Example 1 | 22 months | 30 days | 0.21 |
| Examples 1 to 1 | 12 months old | 10 days | 0.25 |
| Examples 1 to 2 | 12 months old | 15 days | 0.25 |
| Examples 1 to 3 | 15 months old | 5 days | 0.28 |
| Examples 1 to 4 | 18 months old | 30 days | 0.35 |
| Example 2 | 24 months | 25 days | 0.22 |
| Example 2-1 | 25 months old | 25 days | 0.18 |
| Examples 2 to 2 | 24 months | 25 days | 0.18 |
| Examples 2 to 3 | 16 months old | 20 days | 0.22 |
| Examples 2 to 4 | 16 months old | 20 days | 0.22 |
| Example 3 | 23 months old | 25 days | 0.2 |
| Example 3-1 | 24 months | 30 days | 0.19 |
| Examples 3 to 2 | 17 months old | 30 days | 0.21 |
| Examples 3 to 3 | 17 months old | 30 days | 0.23 |
| Comparative example | 15 months old | 15 days | 0.25 |
The adsorption effect of the polyester polymer dispersant adopted in example 1-1 on carbon black particles is similar to that of straight-chain alkyl modified acrylic emulsion thickener molecules, and the dispersant molecules are smaller than the molecular weight of the thickener molecules and are easy to replace, so that the long-term stability of the system is poorer than that of example 1. The xanthan gum thickener used in examples 1-2 thickened only by hydration, occupying the space available for the carbon black particles and also detrimental to the long term stability of the system.
From the above, it can be seen that, the acrylic polymer dispersant containing the hydrophobic amino side chain and the hydrophilic polyether side chain is adsorbed on the surface of the carbon black through the interaction of the nitrogen atom on the hydrophobic amino side chain and the carboxyl, hydroxyl and ester groups on the surface of the carbon black particles, and the hydrophilic polyether side chain extends in water to form steric hindrance, so that a good stable dispersion effect of the carbon black particles is achieved.
The acrylic emulsion modified by straight-chain alkyl or aryl is used as a thickening agent, weak association is generated with carbon atoms on the surface of carbon black particles in a swelling state, a three-dimensional network structure is formed, and the dispersion stability of the carbon black particles is improved while the viscosity construction is realized. Particularly, the association effect of straight-chain alkyl or aryl in the thickener molecules and the surface of the carbon black particles is weaker than the interaction between nitrogen atoms on a side chain of an acrylic polymer dispersant and the surface of the carbon black particles, so that the instability of a system caused by replacing dispersant molecules originally acting on the surface of the carbon black particles by competitive adsorption is avoided.
The aqueous acrylic resin emulsion with high film forming temperature is adopted to provide more association points for the thickener molecules so as to further enhance the stability of the system. The water-based acrylic resin emulsion with high film-forming temperature can prevent the ink from losing water to form a film and blocking an ink outlet channel in a uncapped state after the ink is filled into a pen to damage uncapped writing performance. Graphene oxide serves as a lubricant, plays an excellent lubricating role in the friction process of the ball seat body and the ball, and simultaneously avoids the damage to the thickening efficiency and stability of the linear alkyl or aryl modified acrylic emulsion.
By reasonably selecting the functional additives, the synergistic effect among the additives is exerted, adverse effects are avoided, the pigment type neutral ink which is stable for a long time and is smooth in writing is obtained, and the filled pen core has an ultra-long quality guarantee period and excellent writing performance.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (9)
1. A neutral ink comprises carbon black, a polymeric dispersant, a thickening agent, water-based resin, a lubricant, a cosolvent, a humectant, a bactericide, a pH regulator and water;
the high molecular dispersing agent comprises a graft polymer, wherein the graft polymer comprises an acrylic acid main chain, a hydrophobic amino side chain and a hydrophilic polyether side chain, the hydrophobic amino side chain and the hydrophilic polyether side chain are suspended from the acrylic acid main chain, and the molar ratio of the hydrophilic polyether side chain to the hydrophobic amino side chain of the high molecular dispersing agent is 1/13-1/5;
the thickening agent is a straight-chain alkyl or aryl modified acrylic emulsion;
the water-based resin is selected from pure acrylic emulsion, styrene-acrylic emulsion or tertiary acrylic emulsion with the lowest film forming temperature higher than 50 ℃ and the acid value of 50-100;
the lubricant comprises graphene oxide containing one or more of sulfonic acid groups, phosphoric acid groups, carboxylic acid groups, hydroxyl groups and ester groups.
2. The neutral ink of claim 1, comprising:
3. the neutral ink of claim 1, wherein the graft polymer comprises the following side chains:
R12、R13each independently selected fromMethyl or ethyl; r21、R22Each independently selected from hydrogen atom, methyl, ethyl, propyl, butyl; m is1Represents the average number of ethoxy groups.
4. The neutral ink according to claim 3, wherein m is1Is between 5 and 13.
5. The neutral ink according to claim 1, wherein the graft polymer has a weight average molecular weight of 8000 to 12000.
6. The neutral ink according to claim 1, wherein the graft polymer is prepared by copolymerizing polyethylene glycol monoacrylate, isooctyl acrylate, and dimethylaminoethyl acrylate; or the graft polymer is prepared by copolymerizing polyethylene glycol monoacrylate, butyl acrylate and diethylaminoethyl acrylate.
7. The neutral ink according to claim 1, wherein the linear alkyl group is a C14-C18 linear alkyl group, and the aromatic hydrocarbon group is one or more of a benzene ring, and an alkylphenyl group having a linear C4-C8 at the para-position.
8. A pen comprising a cartridge in which the neutral ink according to any one of claims 1 to 7 is provided.
9. A method of preparing a neutral ink of any one of claims 1 to 7, comprising:
adding a cosolvent and a polymeric dispersant into deionized water;
adding carbon black into the system, then adding a pH regulator to enable the pH value of the system to be 8.0-9.0, and stirring for 1-2 hours to enable the carbon black to be completely wetted;
transferring the mixture in the system into a sand mill, circularly grinding the mixture by adopting 0.3-0.5 mm zirconium beads until the material particle size D50 is less than or equal to 150nm and D90 is less than or equal to 200nm, and filtering to obtain carbon black color paste;
and sequentially adding the balance of pH regulator, thickener, humectant, lubricant, water-based resin, bactericide and the balance of water into the carbon black color paste, and filtering to obtain the neutral ink.
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| CN201811488424.1A CN109486281B (en) | 2018-12-06 | 2018-12-06 | Pen and gel ink |
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