CN110423514B - Ink accumulation-inhibiting ball-point pen ink composition - Google Patents
Ink accumulation-inhibiting ball-point pen ink composition Download PDFInfo
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Abstract
The present invention relates to an ink accumulation suppressing type ball point pen ink composition which may be a neutral ink or a W/O type emulsion ink. The modified xanthan gum is used as the system thickener, so that the viscosity of the system is ensured, the viscoelastic property with dominant elastic response is realized, and the modified xanthan gum has excellent ink accumulation inhibiting performance in the aspect of matching pen point application, particularly in the aspect of ink accumulation performance of a pen core. Compared with the existing ball-point pen ink composition which takes polyacrylic acid synthetic polymer as a thickening agent, the problem that the pen point accumulates ink in the vertical placement process of the pressing type neutral ball-point pen without a pen cap is solved, and the ink accumulation phenomenon in the writing process is avoided.
Description
Technical Field
The present invention relates to a ball-point pen ink composition, and more particularly, to a ball-point pen ink composition having excellent ink accumulation-suppressing properties.
Background
At present, writing tools in international markets are various, and ball pens become the most widely used writing tools in daily life. In recent years, the pen making industry in China is vigorously developed, and is ascending in the production and export major countries of the world pen making industry, wherein the output of ball pens is leaping the world first, but the ball pens in the market at present still have problems in application performance, particularly in pen point ink accumulation. For example, a push-type ball-point pen, without the protection of the cap, may have ink accumulation at the tip of the pen when it is placed vertically, and may be accompanied by ink dripping when it is severe. Even for a common plug-in ball-point pen, accumulated ink drop of the pen point also exists. Meanwhile, different systems of ink compositions such as neutrality, emulsification and the like can generate different degrees of writing ink accumulation problems in the using process, and the writing experience of consumers can be influenced.
The ink composition for the ball-point pen needs to have certain apparent viscosity, so that the ink composition does not flow out of a pen head under a static state, and meanwhile has certain shear thinning capability to meet the writing requirement.
Disclosure of Invention
Aiming at the problems of the ball-point pen ink composition in pen point ink accumulation, the invention provides a ball-point pen ink composition with excellent ink accumulation inhibiting performance, which mainly uses modified xanthan gum as a system thickening agent to replace polyacrylic acid thickening agent, so that the ball-point pen ink composition has a certain apparent viscosity and shear thinning capability and also has excellent ink accumulation inhibiting performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
an ink composition comprising a thickener which is a modified xanthan gum.
Further, the modified xanthan gum is carboxymethyl hydroxypropyl xanthan gum synthesized by adopting propylene oxide, sodium chloroacetate and xanthan gum to react, and the number average molecular weight of the carboxymethyl hydroxypropyl xanthan gum is 4 multiplied by 106～8×106The viscosity is 1100-2400 cP (the test method refers to GB 13886-2007).
Further, the modified xanthan gum is prepared from the following raw materials in parts by weight: 7.1-10.0 parts of xanthan gum, preferably 8.2-9.5 parts, more preferably 8.7-9.0 parts; 80.5 to 92.5 parts, preferably 85.3 to 90.1 parts, more preferably 86.7 to 89.1 parts of a lower monohydric alcohol aqueous solution of 60 to 80 wt.%; 0.5-1.8 parts of 15-25 wt.% NaOH aqueous solution, preferably 0.8-1.5 parts, more preferably 1.0-1.3 parts; modifier [ propylene oxide: sodium chloroacetate is 1.0 to 2.0 parts, preferably 1.4 to 1.9 parts, more preferably 1.6 to 1.8 parts, based on weight ratio 2:1 to 1: 2.
Further, the ink composition is a neutral ink composition or a W/O type emulsion ink composition.
The ink composition can be a neutral ink composition, and the neutral ink composition further comprises deionized water, a cosolvent, a preservative, a pH regulator, a pigment color paste and a thickening agent.
Further, the neutral ink composition comprises the following components in parts by weight: 35.2-56.3 parts of deionized water, preferably 39.7-50.5 parts, more preferably 43.6-48.0 parts; 16.2-25.4 parts of cosolvent, preferably 16.8-20.0 parts, more preferably 17.5-19.5 parts; 0.1-0.4 part of preservative, preferably 0.15-0.35 part, more preferably 0.2-0.3 part; 1.0-2.6 parts of the pH regulator, preferably 1.0-2.3 parts, more preferably 1.0-1.6 parts; 27.2-40.5 parts of pigment color paste, preferably 28.0-38.5 parts, more preferably 29.5-35.7 parts; the thickener is 1.0 to 5.0 parts, preferably 1.5 to 4.5 parts, and more preferably 2.0 to 3.0 parts.
Further, in the neutral ink composition, the cosolvent is a polyalcohol substance; the preservative is an isothiazolinone substance; the pH regulator is organic amine substance.
On the other hand, the ink composition may also be a W/O type emulsion ink composition, which further includes deionized water, a dye, an organic solvent, an emulsifier, a thixotropic agent, and a thickener.
Further, the W/O type emulsion ink composition includes, by weight: 10.0-26.0 parts of deionized water, preferably 15.0-24.5 parts, and more preferably 18.0-23.0 parts; 20.0 to 30.0 parts of the dye, preferably 22.0 to 28.0 parts, more preferably 23.5 to 27.0 parts; 30.0-55.0 parts of the organic solvent, preferably 30.0-50.0 parts, more preferably 35.0-45.0 parts; 1.0-2.0 parts of emulsifier, preferably 1.0-1.8 parts, more preferably 1.2-1.6 parts; 0.4-0.7 part of thixotropic agent, preferably 0.4-0.6 part, more preferably 0.45-0.55 part; 10.0 to 15.0 parts of the thickener, preferably 11.0 to 15.0 parts, and more preferably 12.5 to 14.5 parts.
Further, in the W/O type emulsion ink composition, the organic solvent is an ether substance; the emulsifier is natural gum; the thixotropic agent is cellulose ether substance.
Meanwhile, the ink composition has a low frequency (omega ═ 0.1rad/s) loss factor tan delta of 0.5-5, a 5s shearing degree of 20-60%, and a recovery stage initial point slope of 10-35.
Wherein the neutral ink composition has a low frequency (ω ═ 0.1rad/s) loss factor tan δ of 0.5 to 5, a 5s shear level of 20% to 45%, and a recovery stage onset slope of 10 to 35.
The W/O type emulsion ink composition has a low frequency (omega ═ 0.1rad/s) loss factor tan delta of 0.5 to 3, a 5s shear degree of 20 to 60%, and a recovery stage initial point slope of 10 to 35.
In another aspect, the present invention provides a method for preparing the aforementioned neutral ink composition, comprising:
step (1): dissolving a cosolvent in deionized water at room temperature to obtain a mixed solution a;
step (2): adding a preservative and a pH regulator into the mixed solution a obtained in the step (1), and uniformly stirring to obtain a mixed solution b;
and (3): sequentially adding pigment color paste and a thickening agent into the mixed solution b obtained in the step (2), and stirring to obtain a mixture c;
and (4): and (4) filtering and defoaming the mixture c obtained in the step (3) to obtain the neutral ink composition.
Further, the stirring speed in the step (2) is 700-900 r/min, and the stirring time is 30-90 minutes; the stirring speed of the step (3) is 700-900 r/min, and the stirring time is 30-90 minutes;
in addition, the present invention provides a method for preparing the aforementioned W/O type emulsion ink composition, comprising:
step (1): adding the dye and a part of the emulsifier into a part of the organic solvent, heating and stirring until the dye and the part of the emulsifier are fully dissolved to obtain a mixed solution d;
step (2): mixing the thixotropic agent, the other part of the emulsifier, the other part of the organic solvent and deionized water, heating and stirring to form a water-in-oil emulsion to obtain a mixed solution e;
and (3): and (3) adding the mixed solution d obtained in the step (1) and the mixed solution e obtained in the step (2) into the same container, adding a thickening agent, and uniformly stirring and mixing to obtain the W/O type emulsified ink composition.
Further, the heating temperature in the step (1) is 40-50 ℃, the stirring speed is 300-500 r/min, and the stirring time is 30-60 minutes; the heating temperature in the step (2) is 40-50 ℃, the stirring speed is 300-500 r/min, and the stirring time is 30-60 minutes; and (3) carrying out the step (3) at normal temperature, wherein the stirring speed is 300-500 r/min, and the stirring time is 60-100 minutes.
In addition, the invention discloses a method for testing ink accumulation performance, which is characterized in that static ink accumulation and dripping performance of ink can be obtained by testing a low-frequency (omega is 0.1rad/s) loss factor tan delta of the ink; and testing the shearing degree for 5s and the initial point slope in the recovery stage to obtain the dynamic writing ink accumulation performance of the ink.
The ink accumulation inhibiting type ball-point pen ink composition preferably uses modified xanthan gum as a system thickener, ensures a certain viscosity of the system, and provides the system with viscoelastic performance with dominant elastic response at low frequency (omega ═ 0.1rad/s) at 25 ℃, and the ball-point pen ink composition has excellent ink accumulation inhibiting performance in the aspect of pen core application performance, particularly in the aspect of pen point ink accumulation after being prepared into a pen core, thereby greatly improving the writing experience of consumers.
Drawings
FIG. 1 shows the results of the oscillation frequency scans of the neutral ink examples 1 to 3, the neutral ink comparative example 4, the W/O type emulsion ink examples 5 to 7, and the W/O type emulsion ink comparative example 8.
FIG. 2 is a schematic diagram showing static ink droplets after the ink cartridges are manufactured according to the neutral ink examples 1 to 3, the neutral ink comparative example 4, the W/O emulsion ink examples 5 to 7, and the W/O emulsion ink comparative example 8.
FIG. 3 is a schematic diagram showing a thixotropic recovery test method of neutral ink examples 1 to 3, a neutral ink comparative example 4, W/O type emulsion ink examples 5 to 7, and a W/O type emulsion ink comparative example 8. The ratio of the difference between the complex viscosity corresponding to the dashed line 2 and the complex viscosity corresponding to the dashed line 1 to the complex viscosity corresponding to the dashed line 1 is referred to as the 5s shear degree, and the slope corresponding to the dashed line 3 is defined as the slope of the initial point of the recovery stage after the end of the shear.
FIG. 4 is a schematic diagram showing ink accumulation in the case where the pen cores are formed from the neutral inks of examples 1 to 3 and comparative neutral ink example 4, and the W/O type emulsion inks of examples 5 to 7 and comparative W/O type emulsion ink example 8, and then the pen cores are scribed with a writing and circling instrument.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The modified xanthan gum is used as the system thickener, so that the static drip ink and dynamic writing ink accumulation performance of the ink composition are ensured.
The preparation of the modified xanthan gum comprises the following components in parts by weight: 7.1-10.0 parts of xanthan gum, preferably 8.2-9.5 parts, more preferably 8.7-9.0 parts; 80.5 to 92.5 parts, preferably 85.3 to 90.1 parts, more preferably 86.7 to 89.1 parts of a 60 to 80 wt.% aqueous solution of a lower monohydric alcohol (monohydric alcohol having 1 to 5 carbon atoms); 0.5-1.8 parts of 15-25 wt.% NaOH aqueous solution, preferably 0.8-1.5 parts, more preferably 1.0-1.3 parts; modifier [ propylene oxide: sodium chloroacetate is 1.0 to 2.0 parts, preferably 1.4 to 1.9 parts, more preferably 1.6 to 1.8 parts, based on weight ratio 2:1 to 1: 2.
The modified xanthan gum can be prepared by the following steps:
step (1): fully dispersing xanthan gum in 60-80 wt.% lower monohydric alcohol aqueous solution at room temperature to obtain a mixed solution a;
step (2): adding 15-25 wt.% of NaOH aqueous solution into the mixed solution a, and alkalizing for 1-2 hours at room temperature to obtain a mixed solution b;
and (3): adding a modifier into the mixed solution b, heating to 60-100 ℃ for reaction for 2-4 h to obtain a product c;
and (4): and sequentially cleaning the product c with a high-concentration gradient ethanol solution, performing suction filtration, and drying at a high temperature of 60-80 ℃ for 8-10 h to obtain the modified xanthan gum.
The obtained modified xanthan gum has number average molecular weight of 4 × 106～8×106The viscosity is 1100-2400 cP (the test method refers to GB 13886-2007).
The ink composition comprises a neutral ink composition and a W/O type emulsion ink composition.
The neutral ink composition comprises the following components in parts by weight: 35.2 to 56.3 parts of deionized water, preferably 39.7 to 50.5 parts, more preferably 43.6 to 48.0 parts; 16.2-25.4 parts of cosolvent, preferably 16.8-20.0 parts, more preferably 17.5-19.5 parts; 0.1 to 0.4 part of preservative, preferably 0.15 to 0.35 part, more preferably 0.2 to 0.3 part; 1.0-2.6 parts of pH regulator, preferably 1.0-2.3 parts, more preferably 1.0-1.6 parts; 27.2-40.5 parts of pigment color paste, preferably 28.0-38.5 parts, more preferably 29.5-35.7 parts; 1.0 to 5.0 parts of thickener, preferably 1.5 to 4.5 parts, more preferably 2.0 to 3.0 parts.
The neutral ink composition is prepared by the following method:
step (1): dissolving a cosolvent in deionized water at room temperature to obtain a mixed solution a;
step (2): adding a preservative and a pH regulator into the mixed solution a, and uniformly stirring to obtain a mixed solution b;
and (3): adding the pigment color paste and the thickening agent into the mixed solution b in sequence, and stirring to obtain a mixture c;
and (4): and (c) filtering and defoaming the mixture c to obtain the neutral ink composition.
In addition, the W/O type emulsion ink composition includes, by weight: 10.0 to 26.0 parts of deionized water, preferably 15.0 to 24.5 parts, and more preferably 18.0 to 23.0 parts; 20.0 to 30.0 parts of dye, preferably 22.0 to 28.0 parts, more preferably 23.5 to 27.0 parts; 30.0 to 55.0 parts of organic solvent, preferably 30.0 to 50.0 parts, more preferably 35.0 to 45.0 parts; 1.0 to 2.0 parts of emulsifier, preferably 1.0 to 1.8 parts, more preferably 1.2 to 1.6 parts; 0.4 to 0.7 part of thixotropic agent, preferably 0.4 to 0.6 part, more preferably 0.45 to 0.55 part; 10.0 to 15.0 parts of thickener, preferably 11.0 to 15.0 parts, more preferably 12.5 to 14.5 parts.
The preparation method of the W/O type emulsified ink composition comprises the following steps:
step (1): adding a dye and an emulsifier into an organic solvent, heating and stirring until the dye and the emulsifier are fully dissolved to obtain a mixed solution d;
step (2): mixing a thixotropic agent, an emulsifier, an organic solvent and deionized water, heating and stirring to form a water-in-oil emulsion to obtain a mixed solution e;
and (3): and adding the mixed solution d and the mixed solution e into the same container, adding a thickening agent, and uniformly mixing to obtain the W/O type emulsified ink composition.
The present invention will be described in further detail with reference to examples.
Neutral ink example 1
(1) Preparing the following components in percentage by mass: 41.2 parts of deionized water, 18.4 parts of cosolvent (polyethylene glycol 400), 0.3 part of preservative (1,2 benzisothiazolin-3-one), 1.4 parts of pH regulator (ethanolamine), 37.1 parts of pigment paste (carbon black pigment BC4300) and 1.6 parts of thickener (modified xanthan gum);
(2) wherein, the modified xanthan gum comprises the following raw materials in parts by weight: 8.8 parts of xanthan gum, 87.5 parts of 70 wt.% ethanol aqueous solution, 1.1 parts of 20 wt.% NaOH aqueous solution and 1.6 parts of modifier (propylene oxide: sodium chloroacetate: 1), and is prepared by the following steps:
step I: fully dispersing xanthan gum in 70 wt.% ethanol solution at room temperature to obtain mixed solution a;
step II: adding 20 wt.% of NaOH aqueous solution into the mixed solution a, and alkalizing for 1.5h at room temperature to obtain a mixed solution b;
step III: adding a modifier into the mixed solution b, heating to 80 ℃ for reaction for 3 hours to obtain a product c;
step IV: and sequentially cleaning the product c by using high-concentration gradient ethanol solution, performing suction filtration, and drying at the high temperature of 70 ℃ for 9 hours to obtain the modified xanthan gum.
(3) Preparation of a neutral ink composition: 41.2 parts of deionized water and 18.4 parts of polyethylene glycol 400 are added into a container with a stirring device and stirred to be fully dissolved to obtain a mixed solution a, then 0.3 part of 1,2 benzisothiazolin-3-one and 1.4 parts of triethanolamine are added under the stirring state, the mixture is stirred for 1h at the speed of 800r/min to obtain a uniform mixed solution b, 37.1 parts of carbon black pigment BC4300 is added under the speed of 800r/min, after the system is uniformly mixed, 1.6 parts of modified xanthan gum is added under the stirring state, the mixture is stirred for about 1h until all components are uniformly mixed to obtain a mixed solution c, then the stirring is stopped, and the neutral ink of example 1 is prepared after filtering and defoaming.
Neutral ink example 2
The deionized water in the neutral ink example 1 is changed to 45.0 parts, the color paste (carbon black pigment BC4300) is changed to 32.3 parts, the thickening agent (modified xanthan gum) is changed to 2.6 parts, and the rest parameters (components and proportion) and the preparation method are the same.
Neutral ink example 3
The deionized water in the neutral ink example 1 is changed to 49.0 parts, the color paste (carbon black pigment BC4300) is changed to 27.3 parts, the thickening agent (modified xanthan gum) is changed to 3.6 parts, and the rest parameters (components and proportion) and the preparation method are the same.
Comparative neutral ink example 4
The thickener in the neutral ink example 1 is changed from modified xanthan gum to polyacrylic thickener VISCOLAM 330, and the rest parameters (components and proportion) and the preparation method are the same.
W/O emulsion ink example 5
(1) Preparing the following components in percentage by mass: 18.6 parts of deionized water, 29.3 parts of a dye (oil-soluble black 63), 37.8 parts of an organic solvent (ethylene glycol phenyl ether), 1.4 parts of an emulsifier (gum arabic), 0.5 part of a thixotropic agent (carboxymethyl cellulose), and 12.4 parts of a thickener (modified xanthan gum).
(2) Wherein, the modified xanthan gum comprises the following raw materials in parts by weight: 8.8 parts of xanthan gum, 87.5 parts of 70 wt.% ethanol aqueous solution, 1.1 parts of 20 wt.% NaOH aqueous solution and 1.6 parts of modifier (propylene oxide: sodium chloroacetate: 1), and is prepared by the following steps:
step I: fully dispersing xanthan gum in 70 wt.% ethanol solution at room temperature to obtain mixed solution a;
step II: adding 20 wt.% of NaOH aqueous solution into the mixed solution a, and alkalizing for 1.5h at room temperature to obtain a mixed solution b;
step III: adding a modifier into the mixed solution b, heating to 80 ℃ for reaction for 3 hours to obtain a product c;
step IV: and sequentially cleaning the product c by using high-concentration gradient ethanol solution, performing suction filtration, and drying at the high temperature of 70 ℃ for 9 hours to obtain the modified xanthan gum.
(3) Preparation of W/O type emulsion ink composition: firstly, adding 29.3 parts of oil-soluble black 63 and 0.7 part of Arabic gum into a container filled with 18.9 parts of ethylene glycol phenyl ether, heating to 45 ℃, and stirring for 45 minutes at the speed of 400r/min to form a uniformly dispersed mixed solution d; mixing 0.5 part of carboxymethyl cellulose, 0.7 part of Arabic gum, 18.9 parts of ethylene glycol phenyl ether and 18.6 parts of deionized water, heating to 45 ℃, and stirring at the speed of 400r/min for 45 minutes to form a water-in-oil emulsion to obtain a mixed solution e. And secondly, adding the mixed solution d and the mixed solution e into the same container, adding 12.4 parts of modified xanthan gum, and stirring at the speed of 400r/min for 80 minutes until an emulsion with uniform and stable mixing is formed to obtain the W/O type emulsion ink example 3.
W/O emulsion ink EXAMPLE 6
The deionized water in W/O type emulsified ink example 5 is changed into 21.6 parts, the dye (oil-soluble black 63) is changed into 25.3 parts, the thickening agent (modified xanthan gum) is changed into 13.4 parts, and the rest parameters (components and proportion) and the preparation method are the same.
W/O emulsion ink EXAMPLE 7
The deionized water in W/O type emulsified ink example 5 was changed to 24.6 parts, the dye (oil-soluble black 63) was changed to 21.3 parts, the thickener (modified xanthan gum) was changed to 14.4 parts, and the other parameters (components, proportions) and preparation methods were the same.
Comparative example 8 of W/O emulsion ink
The thickening agent in the W/O type emulsified ink in example 5 is changed from modified xanthan gum to polyacrylic acid thickening agent VISCOLAM 330, and the rest parameters (components and proportion) and the preparation method are the same.
The samples of the neutral ink examples 1 to 3, the neutral ink comparative example 4, the W/O type emulsion ink examples 5 to 7, and the W/O type emulsion ink comparative example 8 were subjected to the ink build-up suppressing performance verification test.
The ink accumulation inhibiting performance verification test is divided into a static part and a dynamic part, wherein static ink accumulation is verified in the static state, and writing ink accumulation is verified in the dynamic state.
The static drip ink performance detection is generally to manufacture a certain number of pen cores from the ball-point pen ink composition, remove caps of the pen cores, suspend the pen cores in the air and vertically place the pen cores for a certain time, and observe the static drip ink degree of the pen cores. The dynamic writing ink accumulation detection is to prepare a certain amount of pen cores from the ball pen ink composition, perform scribing test on the pen cores by using a writing and rounding instrument, and observe the condition of writing ink accumulation.
The degree of difficulty of static ink dripping of the ball-point pen ink composition is characterized by the value of the loss factor tan delta at a low frequency (omega is 0.1rad/s) at 25 ℃; and (3) representing the difficulty degree of the dynamic writing pen stopping ink accumulation of the ball-point pen ink composition by using the 5s shearing degree and the initial point slope of the recovery stage after the shearing is finished.
The static drip ink performance verification test includes an oscillating strain sweep and an oscillating frequency sweep. The specific test steps of the oscillatory strain sweep test are as follows.
Using HAAKE RS6000 rotary rheometer, adopting CD (controlled strain) mode, selecting 60/1 DEG TiL conical plate, testing temperature is 25 ℃, frequency is 1HZThe strain is gradually increased from 0 to 10 in the oscillation mode, and the curves of the elastic modulus G ', the viscous modulus G' and the loss factor tan delta of the sample along with the change of the strain gamma are obtained, and the strain area where the tan delta does not change along with the change of the strain is called a linear viscoelastic area.
The material property constants are only obtained from tests in the linear viscoelastic region, so the linear viscoelastic region of the ball-point pen ink composition must first be determined to select the appropriate strain for the dynamic oscillation frequency sweep experiment to be performed in the linear viscoelastic region and to produce a sufficiently large response.
The specific test steps of the oscillation frequency scanning test are as follows.
Selecting proper strain in a linear visco-elastic area, using a HAAKE RS6000 rotational rheometer, selecting a 60/1-degree TiL conical plate, measuring the temperature at 25 ℃, gradually increasing the angular velocity omega from 0 to 100, scanning the oscillation frequency of a sample to obtain a change curve of tan delta with the angular velocity omega, and using the value of tan delta at the time of smaller omega, namely low frequency, to represent the difficulty degree of static drip ink of neutral ink.
The loss factor tan delta is the ratio of viscous modulus G 'to elastic modulus G', when the tan delta value is larger than 1, the system has viscoelasticity performance with viscous response being dominant, the larger the tan delta value is, the better the fluidity of the pigment type neutral ink system is, and the more easily the static ink dripping phenomenon occurs.
The data of the static drip test results after the lead was formed for the neutral ink examples 1 to 3, the neutral ink comparative example 4, the W/O type emulsion ink examples 5 to 7, and the W/O type emulsion ink comparative example 8 are shown in Table 1.
TABLE 1 static ink drip test results
It can be seen that the neutral ink examples 1 to 3 and the W/O type emulsion ink examples 5 to 7 using the modified xanthan gum have lower low frequency tan δ values and lower static ink drop ratios than the neutral ink comparative example 4 and the W/O type emulsion ink comparative example 8 using the polyacrylic thickener, respectively.
The dynamic writing ink accumulation detection comprises a thixotropic recovery test, and the specific test steps are as follows.
Three-stage measurements of complex viscosity | η | were performed on pigmented gel inks using a HAAKE RS6000 rotational rheometer. The test is divided into three phases:
the first stage is an oscillation time scanning mode, the stage simulates a static state, a proper strain is selected from a linear viscous elastic area, the scanning frequency is set to be low, and the temperature is kept for 120s at 25 ℃;
the second stage is a shear mode, which aims to simulate the shear process of the pigment type neutral ink carried out by the ball during writing and set the shear rate to be 1000s-1The shearing time is 5 s;
the third stage is an oscillation time scanning mode, which is a recovery stage after shearing is finished, a proper strain is selected from a linear viscous elastic area, the scanning frequency is set to be low, and the temperature is kept for 120s at 25 ℃;
the degree of change in complex viscosity | η |, within 5s of shear from the initial value was defined as the degree of 5s shear, which is different for different systems of ball-point pen ink compositions, and also represents the magnitude of thixotropy of the different systems of ball-point pen ink compositions.
Under the condition that the shearing degree of 5s is similar, the larger the slope of the initial point in the recovery stage is, the faster the viscosity system is constructed after shearing is stopped, and the more difficult the ink accumulation occurs after pen stopping.
The results of scribing with a writing and circling instrument after preparing the lead from the neutral ink examples 1 to 3, the neutral ink comparative example 4, the W/O type emulsion ink examples 5 to 7, and the W/O type emulsion ink comparative example 8 are shown in Table 2.
TABLE 2 results of the scribes
It can be seen that the gel ink examples 1 to 3 and the W/O type emulsion ink examples 5 to 7 using the modified xanthan gum have higher initial point slopes at the recovery stage and fewer ink dots per hundred meters of machine drawn lines than the gel ink comparative example 4 and the W/O type emulsion ink comparative example 8 using the polyacrylic thickener, respectively.
Therefore, the modified xanthan gum is preferably used as the system thickener, the viscosity of the system is ensured, the viscoelastic property with dominant elastic response is realized, and the ink accumulation inhibiting performance is excellent in the aspect of matching pen point application, particularly in the aspect of ink accumulation performance of a pen core. Compared with the existing ball-point pen ink composition which takes polyacrylic acid synthetic polymer as a thickening agent, the problem that the pen point accumulates ink in the vertical placement process of the pressing type neutral ball-point pen without a pen cap is solved, and the ink accumulation phenomenon in the writing process is avoided.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (17)
1. The ball-point pen ink composition comprises a thickening agent, and is characterized in that the thickening agent is modified xanthan gum, the modified xanthan gum is carboxymethyl hydroxypropyl xanthan gum synthesized by reacting propylene oxide, sodium chloroacetate and xanthan gum, and the number average molecular weight of the carboxymethyl hydroxypropyl xanthan gum is 4 x 106～8×106The viscosity is 1100-2400 cP; the test method of the viscosity refers to GB 13886-2007.
2. The ink composition of claim 1, wherein the modified xanthan gum is prepared from the following raw materials in parts by weight: 7.1-10.0 parts of xanthan gum; 80.5-92.5 parts of 60-80 wt.% lower monohydric alcohol aqueous solution; 0.5-1.8 parts of 15-25 wt.% NaOH aqueous solution; 1.0-2.0 parts of a modifier; the modifier is a mixture of propylene oxide and sodium chloroacetate in a weight ratio of 2: 1-1: 2.
3. The ink composition according to any one of claims 1 to 2, wherein the ink composition is a neutral ink composition or a W/O type emulsion ink composition.
4. The ink composition of claim 3, wherein the ink composition is a neutral ink composition, and the neutral ink composition further comprises deionized water, a cosolvent, a preservative, a pH adjuster, and a pigment paste.
5. The ink composition of claim 4, wherein the neutral ink composition comprises, in parts by weight: 35.2-56.3 parts of deionized water; 16.2-25.4 parts of a cosolvent; 0.1-0.4 part of preservative; 1.0-2.6 parts of the pH regulator; 27.2-40.5 parts of pigment color paste; 1.0-5.0 parts of a thickening agent.
6. The ink composition of claim 5, wherein the co-solvent in the neutral ink composition is a polyalcohol; the preservative is an isothiazolinone substance; the pH regulator is organic amine substance.
7. The ink composition of claim 3, wherein the ink composition is a W/O type emulsified ink composition further comprising deionized water, a dye, an organic solvent, an emulsifier, and a thixotropic agent.
8. The ink composition of claim 7, wherein the W/O type emulsified ink composition comprises, in parts by weight: 10.0-26.0 parts of deionized water; 20.0-30.0 parts of dye; 30.0-55.0 parts of the organic solvent; 1.0-2.0 parts of an emulsifier; 0.4-0.7 part of thixotropic agent; 10.0-15.0 parts of a thickening agent.
9. The ink composition according to claim 8, wherein in the W/O type emulsion ink composition, the organic solvent is an ether substance; the emulsifier is natural gum; the thixotropic agent is cellulose ether substance.
10. The ink composition of claim 3, wherein the ink composition has a low frequency loss factor tan δ of 0.5 to 5, a 5s shear of 20% to 60%, and a recovery stage onset slope of 10 to 35; wherein, the low-frequency condition of the low-frequency loss factor is ω 0.1 rad/s.
11. The ink composition of claim 10, wherein the neutral ink composition has a low frequency loss factor tan δ of 0.5 to 5, a 5s shear of 20% to 45%, and a recovery stage onset slope of 10 to 35; wherein, the low-frequency condition of the low-frequency loss factor is ω 0.1 rad/s.
12. The ink composition of claim 10, wherein the W/O type emulsion ink composition has a low frequency loss factor tan δ of 0.5 to 3, a 5s shear level of 20 to 60%, and a recovery stage onset slope of 10 to 35; wherein, the low-frequency condition of the low-frequency loss factor is ω 0.1 rad/s.
13. A method of making a neutral ink composition, comprising:
step (1): dissolving a cosolvent in deionized water at room temperature to obtain a mixed solution a;
step (2): adding a preservative and a pH regulator into the mixed solution a obtained in the step (1), and uniformly stirring to obtain a mixed solution b;
and (3): sequentially adding pigment color paste and a thickening agent into the mixed solution b obtained in the step (2), and stirring to obtain a mixture c;
and (4): filtering and defoaming the mixture c obtained in the step (3) to obtain a neutral ink composition;
wherein the thickening agent is modified xanthan gum, the modified xanthan gum is carboxymethyl hydroxypropyl xanthan gum synthesized by adopting propylene oxide, sodium chloroacetate and xanthan gum to react, and the number average molecular weight of the carboxymethyl hydroxypropyl xanthan gum is 4 multiplied by 106～8×106The viscosity is 1100-2400 cP; the test method of the viscosity refers to GB 13886-2007.
14. The method according to claim 13, wherein the reaction mixture,
the stirring speed of the step (2) is 700-900 r/min, and the stirring time is 30-90 minutes;
the stirring speed of the step (3) is 700-900 r/min, and the stirring time is 30-90 minutes.
15. A method for preparing a W/O type ball point pen emulsion ink composition, comprising:
step (1): adding the dye and a part of the emulsifier into a part of the organic solvent, heating and stirring until the dye and the part of the emulsifier are fully dissolved to obtain a mixed solution d;
step (2): mixing the thixotropic agent, the other part of the emulsifier, the other part of the organic solvent and deionized water, heating and stirring to form a water-in-oil emulsion to obtain a mixed solution e;
and (3): adding the mixed solution d obtained in the step (1) and the mixed solution e obtained in the step (2) into the same container, adding a thickening agent, and uniformly stirring and mixing to obtain a W/O type ball-point pen emulsified ink composition;
wherein the thickening agent is modified xanthan gum, the modified xanthan gum is carboxymethyl hydroxypropyl xanthan gum synthesized by adopting propylene oxide, sodium chloroacetate and xanthan gum to react, and the number average molecular weight of the carboxymethyl hydroxypropyl xanthan gum is 4 multiplied by 106～8×106The viscosity is 1100-2400 cP; the test method of the viscosity refers to GB 13886-2007.
16. The method according to claim 15,
the heating temperature in the step (1) is 40-50 ℃, the stirring speed is 300-500 r/min, and the stirring time is 30-60 minutes;
the heating temperature in the step (2) is 40-50 ℃, the stirring speed is 300-500 r/min, and the stirring time is 30-60 minutes;
and (3) carrying out the step (3) at normal temperature, wherein the stirring speed is 300-500 r/min, and the stirring time is 60-100 minutes.
17. The method for testing the ink accumulation performance of the ink is characterized in that the static ink accumulation and dripping performance of the ink can be obtained by testing a low-frequency loss factor tan delta of the ink; the dynamic writing ink accumulation performance of the ink can be obtained by testing the 5s shearing degree and the initial point slope in the recovery stage; wherein, the low-frequency condition of the low-frequency loss factor is ω 0.1 rad/s.
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