CN116426161B - Quick-drying oil-based ball-point pen ink composition and ball-point pen refill - Google Patents

Quick-drying oil-based ball-point pen ink composition and ball-point pen refill Download PDF

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CN116426161B
CN116426161B CN202310271021.6A CN202310271021A CN116426161B CN 116426161 B CN116426161 B CN 116426161B CN 202310271021 A CN202310271021 A CN 202310271021A CN 116426161 B CN116426161 B CN 116426161B
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resin
disperse
solvent
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dye
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CN116426161A (en
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王勇
李剑飞
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Shandong Juese New Material Technology Co ltd
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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
    • C09D11/18—Writing inks specially adapted for ball-point writing instruments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids

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  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses a quick-drying oil-based ball-point pen ink composition and a ball-point pen refill, wherein the ink composition comprises 5-30% of dye, 20-80% of organic solvent, 2-25% of resin, 0.3-5% of wiredrawing agent, pH regulator and viscosity regulator, wherein the resin is modified alkyd resin or quick-drying resin, when the resin is modified alkyd resin, the dye is selected from modified disperse dye or metal complex dye, and when the resin is quick-drying resin, the dye is modified disperse dye. The invention provides an oil-based ball-point pen ink composition which is quick in handwriting drying speed and excellent in time stability and handwriting concentration. The invention overcomes the problems that the prior art cannot solve the slow dry speed of handwriting and various problems caused by the slow dry speed of handwriting by using the combination of the modified alkyd resin and the modified disperse dye, so that the ball-point pen ink has excellent quick-drying property, and the ink composition has excellent stability and water resistance with time and good writing feeling.

Description

Quick-drying oil-based ball-point pen ink composition and ball-point pen refill
Technical Field
The invention relates to the technical field of ink, in particular to a quick-drying oil-based ball-point pen ink composition and a ball-point pen refill.
Background
In the past, in oil-based ballpoint pen ink compositions, the ink was oily, and had good lubricity, and the ink was poorly soluble in water, hardly faded, and was hydrated. However, the oily ball-point pen has a relatively high viscosity, and the writing tends to fly during writing. Moreover, the written handwriting of the oily ball-point pen is not easy to dry, so that fingers, cuffs or other careless places where the handwriting is touched are easy to be stained by the ink of the ball-point pen, and the handwriting is stained or the fingers and cuffs are stained. On the other hand, since the oil-based ballpoint pen ink is hardly soluble in water and has a slow drying rate, it is very common that clothes are stained during use, and cleaning is not easy.
The publication "a method for preparing quick-drying ink" (application number: CN 201510455345.0) provides a method for preparing an ink composition comprising ketone-aldehyde resin, alkyd resin and acrylic resin, which can achieve a drying effect after being left for 1 hour.
The prior art does not have a quick-drying type ball-point pen ink, and the ball-point pen ink according to the above patent cannot solve various problems caused by slow drying speed of writing.
Disclosure of Invention
The object of the present invention is to obtain an oil-based ballpoint pen ink composition which is fast in handwriting drying speed and excellent in stability with time and handwriting concentration. The invention overcomes the problems that the prior art cannot solve the slow speed of handwriting drying and various problems caused by the slow speed of handwriting drying by using modified alkyd resin or the combination of quick-drying resin and modified disperse dye; the modified alkyd resin or the quick-drying resin provided by the invention can endow handwriting with excellent quick-drying property and water resistance, and the modified disperse dye has excellent time stability, so that the ball-point pen ink has excellent quick-drying property when being used together, and the ink composition has excellent time stability and water resistance and good writing feeling. In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
as a first aspect of the present invention, there is provided a quick-drying oil-based ballpoint pen ink composition comprising 5 to 30% of a dye, 20 to 80% of an organic solvent, 2 to 25% of a resin, 0.3 to 5% of a drawing agent, a pH adjuster and a viscosity adjuster, wherein the resin is a modified alkyd resin or a quick-drying resin, and when the resin is a modified alkyd resin, the dye is selected from a modified disperse dye or a metal complex dye, and when the resin is a quick-drying resin, the dye is a modified disperse dye; the ink composition preferably has a pH of 7 to 9; the quick-drying oil-based ball-point pen ink composition has a shear rate of 1.256s at 25 DEG C -1 The viscosity is 1000-3000 mPa.s.
Disperse dyes have good chemical stability and therefore good stability over time. However, the ink has smaller molecules and no oil-soluble groups in the structure, and can be uniformly dispersed in the ink by the action of a dispersing agent, so that the ink has the defects of uneven dispersion, easy precipitation and blockage of a pen point. Through multiple experiments, the inventor successfully introduces the group with alkane into the disperse dye, the alkane group can enhance the solubility of the disperse dye in the organic solvent, the longer the alkyl group is, the stronger the lipophilicity is, and the better the solubility in the organic solvent after modification is. However, the longer the alkane group is, the better, the longer the alkane group is, the larger the steric hindrance is, and the reaction with the disperse dye is difficult.
The modified disperse dyes include disperse yellow 14, disperse yellow 16, disperse yellow 17, disperse yellow 185, disperse red 14, disperse red 53, disperse red 60, disperse orange 9, disperse orange 35, disperse violet 11, disperse violet 12, disperse blue 68, disperse blue 69, disperse blue 78, and the like, based on the disperse dye structure. Therefore, the above list is only a part of disperse dyes which can be modified by the pen after a plurality of experiments according to a part of commercial disperse dyes, and more precisely, the modified solvent yellow, the modified solvent red, the modified solvent orange, the modified solvent violet and the modified solvent blue should be named.
Examples of the metal complex dye include solvent yellow 21, solvent yellow 79, solvent brown 42, solvent brown 43, solvent red 8, solvent red 49, solvent red 100, solvent red 119, solvent red 122, solvent black 27, solvent black 29, solvent black 34, solvent black 35, solvent orange 45, solvent orange 54, solvent orange 62, solvent blue 5, and solvent blue 10.
The dyes listed above may be used singly or in combination of two or more.
Preferably, the modified disperse dye is prepared by the following method:
active substances containing long-chain alkane groups and double bonds and unmodified disperse dye are placed in the same container with a condensing tube, nitrogen is introduced, and water vapor is guaranteed to be discharged; adding carbon disulfide, vinyl sulfone sulfate and anhydrous aluminum chloride, and stirring for 20-30 minutes to fully dissolve the added substances; heating to 45-55 deg.c and reaction for 3-4 hr; cooling to 0-5 deg.c, vacuum filtering to eliminate insoluble aluminum chloride, vacuum distillation to eliminate solvent and obtain refined modified disperse dye.
Further, the weight of the unmodified disperse dye is 1, the addition amount of the active substance containing long-chain alkane and double bonds is 0.2-0.5, the addition amount of carbon disulfide is 0.3-0.6, the addition amount of vinyl sulfone sulfate is 0.2-0.4, and the addition amount of anhydrous aluminum chloride is 0.005-0.015.
The active substance containing long-chain alkane groups and double bonds can endow the disperse dye with excellent solubility, has active groups with double bonds, can generate electron pairs, reacts with the disperse dye, and is subjected to graft polymerization to prepare the modified disperse dye with one end containing long-chain alkane and the other end containing a disperse dye structure. On the other hand, if the alkane chain is too long, the space-time resistance in the reaction is too large and the reaction is insufficient.
Preferably, the active material containing long-chain alkane and double bond includes vinyltriethoxysilane, vinylhalohydrocarbon, octavinyloctasilsesquioxane, allylsiloxane, and the like.
Among them, octavinyl octasilsesquioxane is preferred because it has a double bond in the vinyl group, can generate electron pairs, has sufficient reactivity, has a strong silicone group and alkyl group lipophilicity, and enhances the solubility of the disperse dye in common solvents for ball point pens such as alcohols, esters, alcohol ethers, and the like.
The carbon disulfide can fully dissolve the above listed active substances, the reaction is complete, and the prepared modified disperse dye has good solubility.
Vinyl sulfone sulfate has stronger activity than octavinyl octasilsesquioxane, and vinyl sulfone groups are grafted with octavinyl octasilsesquioxane and ester groups on vinyl sulfone sulfate are grafted with disperse dye during reaction, so that octavinyl octasilsesquioxane and disperse dye are connected.
Further, the content of the dye is less than 5% relative to the ink composition, and writing is shallow or vivid, and if the content is more than 30%, the stability of the ink composition tends to be lowered with time. The dye content is therefore preferably 5 to 30%, more preferably 10 to 25%, most preferably 15 to 25% relative to the ink composition.
In the present invention, the organic solvent may be a solvent commonly used for ballpoint pen inks. Examples are: ether alcohol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol phenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, etc., alcohol solvents such as ethylene glycol, diethylene glycol, propanol, propylene glycol, glycerol, n-butanol, benzyl alcohol, etc., and ester solvents such as ethyl acetate, butyl acetate, etc. may be used. The above solvents may be used singly or in combination of two or more. But the use of more than four is not recommended.
Among these organic solvents, alcohol solvents having three or less carbon atoms such as ethylene glycol, diethylene glycol, propanol, propylene glycol, and glycerol are preferable in view of quick-drying property of handwriting.
If the content of the organic solvent is less than 30% relative to the ink composition, the amount of the dye to be dissolved is small, the writing density is poor, the lubricity is poor, and the writing feeling is poor. If the content is more than 80%, more dye may be dissolved, but quick-drying property may be deteriorated. The content of the organic solvent is therefore preferably from 20 to 80%, more preferably from 30 to 80%, particularly preferably from 50 to 70%.
In the invention, the resin is modified resin or quick-drying resin, and the modified resin is modified alkyd resin; preferably, the quick-drying resin is one or a combination of more of vinyl chloride-vinyl acetate resin, acrylic resin and styrene-acrylic resin. In the prior art, aldehyde ketone resin is generally selected, however, the experiment proves that the aldehyde ketone resin has a plurality of advantages, but the quick drying performance is general, and the problems of the pencil men cannot be solved. The inventor carries out a plurality of tests to modify alkyd resin, and connects active groups which can be oxidized and dried in air, such as allyl ether, because the active groups all contain double bonds, handwriting can react with oxygen to polymerize within two seconds, the polymerization result forms a three-dimensional network structure, so that written handwriting is quickly completely dried by liquid materials and becomes solid, and the prepared modified alkyd resin has excellent quick-drying property and does not influence the water resistance and yellowing resistance of the alkyd resin.
Meanwhile, the inventor finds that the modified alkyd resin is used together with various dyes, and the ink composition prepared by the modified alkyd resin and the dye have excellent quick-drying performance. The quick-drying resin is used together with the modified disperse dye, and is assisted with a proper solvent, so that the quick-drying resin also has excellent quick-drying performance. The quick-drying resin and the metal complex dye are used together, and the quick-drying performance is inferior to the two.
Further, if the content of the resin is less than 2% relative to the ink composition, the quick-drying property, water resistance and yellowing resistance are all deteriorated, and if the content is more than 20%, the viscosity of the ink composition becomes large and the writing feeling becomes poor. Therefore, the resin content is preferably 2 to 25%, more preferably 5 to 20%, still more preferably 10 to 20%.
Further, the modified alkyd resin is synthesized by the following method:
a. adding all glycerol and castor oil into a reaction kettle, starting a stirrer, heating to 115-125 ℃ within 30-40 minutes, suspending stirring, adding benzoyl peroxide accounting for 0.01% of the total amount of the glycerol and the castor oil as a catalyst, starting stirring, heating to 175-185 ℃ within 50-60 minutes, and reacting for 50-60 minutes;
b. cooling to 145-150deg.C, adding 4.5% of dimethylbenzene in total amount of phthalic anhydride, phthalic anhydride and glycerol, heating to 180-185 deg.C within 50-60 min, and condensing with water and dimethylbenzene in condenser; xylene in the upper layer and water in the lower layer;
c. adding trimethylolpropane trimethacrylate, controlling the temperature at 165-175 ℃ for reaction for 50-60 minutes, and carrying out reduced pressure distillation on the reaction product to thoroughly remove the dimethylbenzene.
The mass ratio range of the glycerol, the castor oil, the phthalic anhydride and the trimethylolpropane trimethacrylate is as follows: 20-30% of glycerol, 35-45% of castor oil, 25-35% of phthalic anhydride and 10-20% of trimethylolpropane trimethacrylate;
because the trimethylolpropane trimethacrylate has more double bonds and high activity and has high curing speed at normal temperature, the modified alkyd resin has high curing speed and can preserve the water resistance and yellowing resistance of the alkyd resin.
In the present invention, a drawing agent may be used. When many ball-point pen refill manufacturers purchase ink, the wire drawing length is often considered as a comprehensive index of the quality of the ink, and the ink with the wire drawing length can play a role in continuously discharging ink during writing, so that writing is smooth and continuous.
Preferably, the wiredrawing agent is one or more of polyvinyl alcohol, polyacrylamide, polyvinyl butyral, acrylic resin, butadiene polyvinylpyrrolidone or polyacrylamide resin, preferably polyvinylpyrrolidone or polyacrylamide resin.
In many prior arts, polyvinylpyrrolidone is often used as a film forming agent, and can also be used as a drawing agent, and in the research process, the inventor has unexpectedly found that when modified alkyd resin exists, the drawing length can be doubled by using polyvinylpyrrolidone as a drawing agent, and the satisfactory degree can be achieved. The modified alkyd resin has a poor drawing effect when the content of polyvinylpyrrolidone is less than 5%, and has a high viscosity and poor writing feeling when the content is more than 20%. The polyvinylpyrrolidone content is therefore preferably 5 to 20% relative to the modified alkyd resin.
Polyacrylamide is a high-quality drawing agent and can be used in ball-point pen ink to achieve satisfactory effect. The molecular weight of the polyacrylamide is preferably 500 to 2000 ten thousand, more preferably 500 to 900 ten thousand.
If the pH of the ink composition is too large or too small, the ink composition is easy to corrode production equipment, and also can corrode a ball-point pen point, so that the service life of the pen point is shortened. In the present invention, the pH of the ink composition is preferably 7 to 9.
In the present invention, commercially available pH adjusters such as diethanolamine, methyldiethanolamine, triethanolamine, triisopropanolamine and the like can be used.
Preferably, the quick-drying oil-based ballpoint pen ink composition has a shear rate of 1.256s at 25 DEG C -1 The viscosity is 1000-3000 mPa.s. If the viscosity is less than 500mpa·s, the handwriting is easy to bleed, the ink is easy to sag, leak ink and the like during writing, and if the viscosity is more than 5000mpa·s, the rotation resistance of the pen point of the ball-point pen during writing is large, the ink is not smooth, the writing is shallow, and the writing feeling is poor. The viscosity of the ink composition of the present invention is therefore preferably 500 to 5000 mPas, more preferably 500 to 4000 mPas, and particularly preferably 1000 to 3000 mPas, if further consideration is given to the depth of handwriting and good writing feeling.
Preferably, the viscosity modifier is at least one of hydroxypropyl methylcellulose, ethyl cellulose, cellulose series such as sodium carboxymethylcellulose, ethoxylated starch, polyvinylpyrrolidone, polyvinyl butyral, polyacrylic resin, polyacrylamide, hydrogenated castor oil and polyamide modified hydrogenated castor oil.
The ink composition of the present invention may further contain an antioxidant, a bactericide, a lubricant, and the like.
As a second aspect of the present invention, there is provided a ballpoint pen refill comprising a refill tube and an ink poured into the refill tube, the ink being the quick-drying oil-based ballpoint pen ink composition as the first aspect of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an oil-based ball-point pen ink composition which is quick in handwriting drying speed and excellent in time stability and handwriting concentration. The invention overcomes the problems that the prior art cannot solve the slow dry speed of handwriting and various problems caused by the slow dry speed of handwriting by using the combination of the modified alkyd resin and the modified disperse dye; the modified alkyd resin provided by the invention can endow writing with excellent quick-drying property and water resistance, and the modified disperse dye has excellent time stability, so that the ball-point pen ink has excellent quick-drying property when being used together, and the ink composition has excellent time stability and water resistance and good writing feeling.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
1. Preparation of modified disperse dye:
taking disperse red 60 as an example:
the active substance containing the alkane group and the double bond and the disperse red 60 are put into a three-neck flask with a condenser tube, and nitrogen is introduced to ensure that water vapor is discharged. 50ml of carbon disulphide, 10ml of vinyl sulphone sulphate, 0.18g of anhydrous aluminium chloride are rapidly added and stirred for 30 minutes. The temperature was raised to 50℃and the reaction was carried out for 4 hours. Rapidly cooling to 0-5deg.C, filtering under reduced pressure to remove insoluble aluminum chloride, distilling at 45deg.C under reduced pressure to remove solvent to obtain refined modified disperse dye.
The active substance containing long-chain alkane and double bond can endow the disperse dye with excellent solubility, has active groups with double bond, can generate electron pairs, reacts with the disperse dye, and is subjected to graft polymerization to prepare the modified disperse dye with one end containing long-chain alkane and the other end containing a disperse dye structure. On the other hand, if the alkane chain is too long, the space-time resistance in the reaction is too large and the reaction is insufficient. Examples thereof include vinyltriethoxysilane, vinylhalohydrocarbon, octavinyloctasilsesquioxane, and allylsiloxane.
Among them, octavinyl octasilsesquioxane is preferred because it has a double bond in the vinyl group, can generate electron pairs, has sufficient reactivity, has a strong silicone group and alkyl group lipophilicity, and enhances the solubility of the disperse dye in common solvents for ball point pens such as alcohols, esters, alcohol ethers, and the like.
The carbon disulfide can fully dissolve the above listed active substances, the reaction is complete, and the prepared modified disperse dye has good solubility.
Vinyl sulfone sulfate has stronger activity than octavinyl octasilsesquioxane, and vinyl sulfone groups are grafted with octavinyl octasilsesquioxane and ester groups on vinyl sulfone sulfate are grafted with disperse dye during reaction, so that octavinyl octasilsesquioxane and disperse dye are connected.
Several examples of modified disperse dyes are given below
Example 1:
10g of vinyltriethoxysilane and 30g of disperse red 60 are placed in a three-neck flask with a condenser, nitrogen is introduced, and water vapor is guaranteed to be discharged. 70ml of carbon disulphide, 10ml of vinyl sulphone sulphate, 0.18g of anhydrous aluminium chloride are rapidly added and stirred for 30 minutes. The temperature was raised to 50℃and the reaction was carried out for 3 hours. Rapidly cooling to 0-5deg.C, filtering under reduced pressure to remove insoluble aluminum chloride, distilling at 45deg.C under reduced pressure to remove solvent to obtain refined modified disperse dye.
Example 2:
10g of vinyl chloride hydrocarbon and 30g of disperse red 60 are placed in a three-neck flask with a condenser, and nitrogen is introduced to ensure water vapor to be discharged. 70ml of carbon disulphide, 10ml of vinyl sulphone sulphate, 0.18g of anhydrous aluminium chloride are rapidly added and stirred for 30 minutes. The temperature was raised to 50℃and the reaction was carried out for 3 hours. Rapidly cooling to 0-5 ℃, filtering under reduced pressure to remove insoluble aluminum chloride, distilling under reduced pressure at 45 ℃ to remove carbon disulfide solvent, and obtaining the refined modified disperse dye.
Example 3:
10g of octavinyl octasilsesquioxane and 30g of disperse red 60 are placed in a three-neck flask with a condenser tube, and nitrogen is introduced to ensure water vapor to be discharged. 70ml of carbon disulphide, 10ml of vinyl sulphone sulphate, 0.18g of anhydrous aluminium chloride are rapidly added and stirred for 30 minutes. The temperature was raised to 50℃and the reaction was carried out for 3 hours. Rapidly cooling to 0-5 ℃, filtering under reduced pressure to remove insoluble aluminum chloride, distilling under reduced pressure at 45 ℃ to remove carbon disulfide solvent, and obtaining the refined modified disperse dye.
Comparative examples 1-3 solubility in solvents:
10g of the modified disperse dye prepared in examples 1 to 3 and 10g of the unmodified disperse dye were dissolved in 30g of benzyl alcohol respectively, stirred sufficiently for 30min, filtered with filter paper of the same specification, dried sufficiently at 60 ℃ to constant weight, and then weighed, the greater the weight of the filter paper, the more undissolved portions of the modified disperse dye were, and the poorer the modifying effect was. The weight of the filter paper is as follows from big to small in turn: the unmodified disperse dyes, example 2, example 1, example 3, i.e. the modified disperse dyes have a solubility of example 3, example 1, example 2, unmodified disperse dyes in order from the higher to the lower. Octavinyl octasilsesquioxane is therefore preferred.
2. Synthesis of modified alkyd resin: the following table shows the mass percentages of the raw materials
Raw materials ％
Glycerol 22
Castor oil 35
Phthalic anhydride 31
Trimethylolpropane trimethacrylate 12
a. Adding all the glycerol and the castor oil into a reaction kettle, starting a stirrer, heating to 120 ℃ within 40 minutes, suspending stirring, adding benzoyl peroxide accounting for 0.01% of the total amount of the glycerol and the castor oil as a catalyst, starting stirring, heating to 180 ℃ within 60 minutes, and reacting for 60 minutes.
b. Cooling to 150 ℃, adding dimethylbenzene accounting for 4.5% of the total amount of phthalic anhydride, phthalic anhydride and glycerin, and heating to 185 ℃ in 60 minutes, wherein water and dimethylbenzene are condensed in a condenser. Xylene in the upper layer and water in the lower layer.
c. Trimethylolpropane trimethacrylate is added, the temperature is controlled at 170 ℃, the reaction is carried out for 60 minutes, the reaction product is poured into a single-neck flask, and the xylene is thoroughly removed by reduced pressure distillation.
Because the trimethylolpropane trimethacrylate has more double bonds and high activity and has high curing speed at normal temperature, the modified alkyd resin has high curing speed and can preserve the water resistance and yellowing resistance of the alkyd resin.
3. Specific examples of ink compositions
Example 4: quick-drying red ball-point pen ink composition:
and (3) fully mixing and dissolving the modified alkyd resin, ethylene glycol and benzyl alcohol at 60 ℃, then adding modified disperse red 60 at the temperature to fully dissolve, then sequentially adding substances such as drawing agent polyvinylpyrrolidone, pH regulator triethanolamine, viscosity regulator polyvinyl butyral and the like to fully dissolve, and filtering to obtain the ink composition. The viscosity was determined to be 1350 mpa.s and the pH was determined to be 7.5.
The specific proportion is as follows:
example 5:
quick-drying red ball-point pen ink composition: an ink composition was prepared according to the procedure of example 1. The viscosity was measured to be 1580 mpa.s and the pH was 7.2.
The specific proportion is as follows:
example 6:
quick-drying red ball-point pen ink composition: an ink composition was prepared according to the procedure of example 1. The viscosity was determined to be 1550 mpa.s and the pH 7.8.
The specific proportion is as follows:
example 7:
quick-drying red ball-point pen ink composition: an ink composition was prepared according to the procedure of example 1. The viscosity was measured to be 1440 mpa.s and the pH was 7.9.
The specific proportion is as follows:
example 8:
quick-drying red ball-point pen ink composition: an ink composition was prepared according to the procedure of example 1. The measured viscosity was 1560 mpa.s and the pH was 8.0.
The specific proportion is as follows:
example 9:
quick-drying red ball-point pen ink composition: an ink composition was prepared according to the procedure of example 1. The viscosity was determined to be 1500 mpa.s and the pH was determined to be 8.0.
The specific proportion is as follows:
example 10:
quick-drying red ball-point pen ink composition: an ink composition was prepared according to the procedure of example 1. The viscosity was found to be 1590 mpa.s and the pH was found to be 7.2.
The specific proportion is as follows:
example 11:
quick-drying red ball-point pen ink composition: an ink composition was prepared according to the procedure of example 1. The viscosity was measured to be 1580 mpa.s and the pH was 7.3.
The specific proportion is as follows:
performance testing
1. Stability test
Referring to GB/T26714-2019 ink ball-point pen and pen refill, 7.8 shelf life experiments, the ink composition of 7 sets of examples was dispensed into 5 500ml ground bottles, placed in an incubator (60+ -2deg.C) for 10 days, taken out, naturally cooled, and placed in a refrigerator at-20deg.C for 3 days. Immediately after taking out, observing with a microscope, and judging whether caking, flocculation, oil slick and layering occur. And (5) immediately making a pen core after observation to see whether the ink is normal or not, and whether the writing is obviously broken or faded. And then testing the viscosity, wherein the difference between the viscosity and the viscosity without high and low temperature damage is within 5 percent.
2. Centrifugal test
Under natural conditions, 7 groups of ink compositions of the examples were prepared into cartridges and centrifuged at 3000r/min for 60min to see if they were layered. The non-delamination is excellent, the slight delamination is qualified, and the serious delamination is unqualified.
3. Quick-drying performance test
Referring to GB/T26714-2019 ink ball-point pen and pen core, 7.4 test dryness, preparing 7 groups of ink composition of the embodiment into pen cores respectively, preparing the pen cores into ball-point pen, sleeving a special weight of 60g at the lower end of the pen holder, enabling the test pen to form a dip angle of 65-70 degrees with the paper surface of the writing paper, manually drawing a straight line at a scribing speed of 60-80 mm/s, starting a stopwatch to count time to 20s, covering the writing paper with the same property on the line, pressing the special weight on the paper surface of the covering paper, re-counting time, separating the two papers after 1min, and checking whether the covering paper has ink marks. To compare the quick-drying performance of two ball-point pens, the two ball-point pens can be respectively timed to 20s, 15s, 10s, 5s and 2s after the stopwatch is started, writing paper with the same property is covered on the paper surface of the covering paper, the special weight is pressed on the paper surface of the covering paper, the two paper are separated after the timing is repeated for 1min, and whether the covering paper has ink marks is checked. In the invention, the method is limited by 2s, and if the hand-drawn linear ink marks of the lower paper are obviously visible on the upper paper, the paper is regarded as unqualified; if the test is visible but not obvious, the test is qualified; without ink, it is considered excellent.
4. Water resistance test
After writing the ink composition of example 7 sets of pen cores in spiral form on writing paper, immersing the writing paper in water for 60 minutes, taking out, naturally drying, then visually confirming the state of the handwriting, and if the state of the handwriting is not the blurring or blurring of the handwriting, if not, the pen cores are considered to be excellent, and if the state of the handwriting is slightly blurring or blurring, the pen cores are considered to be qualified, and if the state of the handwriting is not the blurring or blurring of the handwriting, the pen cores are considered to be unqualified.
5. Writing feeling
The cartridge prepared from the ink composition of example 7 was subjected to sensory evaluation by handwriting under natural conditions.
6. Scribing on machine
Under natural conditions, the pencil leads prepared from 7 groups of ink compositions of examples were subjected to scribing test on a scribing machine, and scribing effects were recorded.
Table 1 below shows the performance test tables of examples 4-11 of the present invention
The above-mentioned comparison result shows that,
1. tests of all properties of the modified alkyd resin in the embodiment 4-7 of the invention show that the quick-drying property of the modified alkyd resin is greatly improved on the basis of keeping the original water resistance and stability, because after the active group is connected into the alkyd resin, the active group contains double bonds, and the handwriting can be polymerized with oxygen in two seconds to enable the handwriting to be quickly and completely dried from a liquid material to become solid, so that the prepared modified alkyd resin has excellent quick-drying property besides keeping the excellent water resistance and stability of the alkyd resin.
2. Comparing inventive examples 4 and 6, example 4 used modified alkyd resin and modified disperse dye, example 6 used quick-drying resin and modified disperse dye, and example 4 using modified alkyd resin had an improvement in quick-drying performance over example 6 using conventional quick-drying resin.
3. Comparing inventive examples 5 and 7, example 5 uses a modified alkyd resin and a metal complex dye, example 7 uses a quick-drying resin and a metal complex dye, and example 5 using a modified alkyd resin has an improvement in quick-drying performance over example 7 using a conventional quick-drying resin.
4. Comparing examples 4 and 6 of the present invention with examples 8 and 9, example 4 uses a modified alkyd resin and a modified disperse dye, example 6 uses a quick-drying resin and a modified disperse dye, example 5 uses a modified alkyd resin and an unmodified disperse dye, example 9 uses a quick-drying resin and an unmodified disperse dye, and examples 8 and 9 using an unmodified disperse dye were found to be inferior in stability, centrifugation, writing feeling, and scribing effect because the unmodified disperse dye cannot be dissolved in the solvent used in the present invention, can only be dispersed therein, has poor dispersing effect, has a large particle size, is easily agglomerated, and is poor in stability, centrifugation, writing feeling, and scribing effect. After modification, long-chain alkane endows the disperse dye with excellent solubility, and after dissolution, the particle size is small, and the stability, the centrifugation, the writing feeling and the scribing effects are good.
5. In comparison between examples 4 and 6 of the present invention and examples 10 and 11, the proportion of polyvinylpyrrolidone in the modified alkyd resin in example 10 was large, but the viscosity index was clearly unacceptable with less thickener, but the proportion of polyvinylpyrrolidone in the modified alkyd resin in example 11 was small, and the viscosity index was acceptable with more thickener, but the stability, writing feeling and scribing effect were also unacceptable.
In summary, the ink composition of the invention has better quick-drying property than the prior art, solves the problems of easy line flying and slow drying speed of oily ball-point pen writing, easy pollution of other articles touching or difficult recognition of writing, and has excellent time stability, water resistance and good writing feeling.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. The quick-drying oil-based ball-point pen ink composition is characterized by comprising 5-30% of dye, 20-80% of organic solvent, 2-25% of resin, 0.3-5% of wiredrawing agent, pH regulator and viscosity regulator, wherein the resin is modified alkyd resin or quick-drying resin, when the resin is modified alkyd resin, the dye is selected from modified disperse dye or metal complex dye, and when the resin is quick-drying resin, the dye is modified disperse dye; the pH value of the ink composition ranges from 7 to 9; the quick-drying oil-based ball-point pen ink composition has a shear rate of 1.256s at 25 DEG C -1 The viscosity is 1000-3000 mPa.s;
the modified disperse dye is prepared by the following method:
active substances containing long-chain alkane groups and double bonds and unmodified disperse dye are placed in the same container with a condensing tube, nitrogen is introduced, and water vapor is guaranteed to be discharged; adding carbon disulfide, vinyl sulfone sulfate and anhydrous aluminum chloride, and stirring to dissolve; then heating to 45-55 ℃ and reacting for 3-4 hours; after the reaction is finished, cooling to 0-5 ℃, filtering under reduced pressure, removing insoluble aluminum chloride, distilling under reduced pressure, and removing the solvent to obtain the refined modified disperse dye;
the modified alkyd resin is synthesized by the following steps:
a. adding all glycerol and castor oil into a reaction kettle, starting a stirrer, heating to 115-125 ℃ within 30-40 minutes, suspending stirring, adding benzoyl peroxide accounting for 0.01% of the total amount of the glycerol and the castor oil as a catalyst, starting stirring, heating to 175-185 ℃ within 50-60 minutes, and reacting for 50-60 minutes;
b. cooling to 145-150deg.C, adding 4.5% of dimethylbenzene in total amount of phthalic anhydride, phthalic anhydride and glycerol, heating to 180-185 deg.C within 50-60 min, and condensing with water and dimethylbenzene in condenser; xylene in the upper layer and water in the lower layer;
c. adding trimethylolpropane trimethacrylate, controlling the temperature at 165-175 ℃ for reaction for 50-60 minutes, and carrying out reduced pressure distillation on the reaction product;
the mass percentage ranges of the glycerol, the castor oil, the phthalic anhydride and the trimethylolpropane trimethacrylate are as follows: 20-30% of glycerol, 35-45% of castor oil, 25-35% of phthalic anhydride and 10-20% of trimethylolpropane trimethacrylate;
the mass ratio of the active substance containing long-chain alkane groups and double bonds, the unmodified disperse dye, the carbon disulfide, the vinyl sulfone sulfate and the anhydrous aluminum chloride is 0.2-0.5:1:0.3-0.6:0.2-0.4:0.005-0.015;
the active substance containing long-chain alkane and double bond is selected from vinyl triethoxysilane, vinyl halohydrocarbon, octavinyl octasilsesquioxane or allyl siloxane;
the modified disperse dye is based on a disperse dye structure, and the disperse dye is one or a combination of more of disperse yellow 14, disperse yellow 16, disperse yellow 17, disperse yellow 185, disperse red 14, disperse red 53, disperse red 60, disperse orange 9, disperse orange 35, disperse violet 11, disperse violet 12, disperse blue 68, disperse blue 69 and disperse blue 78;
the metal complex dye is selected from one or a combination of a plurality of solvent yellow 21, solvent yellow 79, solvent brown 42, solvent brown 43, solvent red 8, solvent red 49, solvent red 100, solvent red 119, solvent red 122, solvent black 27, solvent black 29, solvent black 34, solvent black 35, solvent orange 45, solvent orange 54, solvent orange 62, solvent blue 5 and solvent blue 10;
the quick-drying resin is one or a combination of more of vinyl chloride-vinyl acetate resin, acrylic resin and styrene-acrylic resin.
2. The quick-drying oil-based ballpoint pen ink composition according to claim 1, wherein said organic solvent is selected from the group consisting of ether alcohol solvents, and ester solvents.
3. The quick-drying oil-based ballpoint pen ink composition according to claim 1, wherein the drawing agent is one or more of polyvinyl alcohol, polyacrylamide, polyvinyl butyral, acrylic resin, butadiene, polyvinylpyrrolidone or polyacrylamide resin.
4. A ballpoint pen refill comprising a refill tube and ink poured into the refill tube, characterized in that the ink is the quick-drying oil-based ballpoint pen ink composition according to any one of claims 1 to 3.
CN202310271021.6A 2023-03-20 2023-03-20 Quick-drying oil-based ball-point pen ink composition and ball-point pen refill Active CN116426161B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106634370A (en) * 2016-10-11 2017-05-10 淄博职业学院 Environment-friendly scrubbing-resistant automobile heat-preservation color-retention heat-insulation paint and preparation method thereof
JP2017094629A (en) * 2015-11-26 2017-06-01 株式会社パイロットコーポレーション Oil-based ball point pen refill and oil-based ball point pen using the same
JP2021021011A (en) * 2019-07-27 2021-02-18 株式会社パイロットコーポレーション Aqueous ink composition for writing instruments and writing instrument including the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017094629A (en) * 2015-11-26 2017-06-01 株式会社パイロットコーポレーション Oil-based ball point pen refill and oil-based ball point pen using the same
CN106634370A (en) * 2016-10-11 2017-05-10 淄博职业学院 Environment-friendly scrubbing-resistant automobile heat-preservation color-retention heat-insulation paint and preparation method thereof
JP2021021011A (en) * 2019-07-27 2021-02-18 株式会社パイロットコーポレーション Aqueous ink composition for writing instruments and writing instrument including the same

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