CN110423514A - A kind of black ball point ink composition of inhibition product - Google Patents
A kind of black ball point ink composition of inhibition product Download PDFInfo
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- CN110423514A CN110423514A CN201910721609.0A CN201910721609A CN110423514A CN 110423514 A CN110423514 A CN 110423514A CN 201910721609 A CN201910721609 A CN 201910721609A CN 110423514 A CN110423514 A CN 110423514A
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- 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
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- C09D11/18—Writing inks specially adapted for ball-point writing instruments
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Abstract
The present invention relates to a kind of black type ball point ink composition of inhibition product, which can be Neutral writing ink or w/o type emulsion ink.The present invention uses modified xantham gum as system thickener, while guarantee system viscosity, has the prevailing viscoelasticity energy of elastic response, is matching written application aspect, especially in terms of pen core product performance of ink, with excellent inhibition product performance of ink.Compared with the existing ball point ink composition using polyacrylic synthesis macromolecule as thickener, solve the problems, such as that pressing neutral ball pen protects the product Mo Xianxiang occurred in the long-pending black and writing process of nib in vertical placement process without pen cap.
Description
Technical field
The present invention relates to a kind of ball point ink composition more particularly to a kind of balls with excellent inhibition product performance of ink
Pen and ink water composition.
Background technique
International market writing implement is many kinds of at present, and ball pen has been increasingly becoming the widest book of people's routine use
Write tool.In recent years, system industry in China's flourishes, and has ranked among the big producer and big export country of world's system industry,
The yield of middle ball pen has leapt to the first in the world, but existing market ball pen application performance especially in terms of nib product ink still
So it there are problems that.For example, protection of the pressing ball pen due to not no pen cap, can go out at nib in the case where vertical place
Now product ink, can also be with the black phenomenon of drop when serious.For common plug-in ball pen, written product drop ink is also
It equally exists.Meanwhile the different system composition for ink such as neutral, emulsification will appear different degrees of writing in use
Product Mo Wenti, these all will affect the writing experience of consumer.
Ball point ink composition needs to have certain apparent viscosity, guarantees not flow out while having from nib under static state
There is certain shear shinning ability to reach to write and require, a certain amount of thickener is added usually to meet the demand, and
The selection of thickener is often agent for polyacrylic acid thickening, and such thickener thickening effect is significant, but such composition for ink
Inhibit product performance of ink bad, nib product Mo Xianxiang easily occurs.
Summary of the invention
Above-mentioned ball point ink composition in terms of nib product ink there are aiming at the problem that, the present invention provides a kind of with excellent
The good ball point ink composition for inhibiting product performance of ink, mainly by preferred modified xantham gum as system thickener substitution poly- third
Alkene Acrylic associative thickener has excellent while making ball point ink composition have certain apparent viscosity and shear shinning ability
Inhibition product performance of ink.
To achieve the above object, present invention employs following technical solutions:
A kind of composition for ink includes thickener, and the thickener is modified xantham gum.
Further, the modified xantham gum is to be reacted using propylene oxide, sodium chloroacetate and xanthan gum, one kind of synthesis
Carboxy-methyl hydroxy propyl xanthan gum, number-average molecular weight are 4 × 106~8 × 106, viscosity is 1100~2400cP (test method ginseng
Examine GB13886-2007).
Further, by weight, the raw material for preparing of the modified xantham gum includes: 7.1~10.0 parts of xanthan gum, excellent
It is selected as 8.2~9.5 parts, more preferably 8.7~9.0 parts；80.5~92.5 parts of the low-grade monobasic alcohol aqueous solution of 60-80wt.%, preferably
It is 85.3~90.1 parts, more preferably 86.7~89.1 parts；0.5~1.8 part of the NaOH aqueous solution of 15~25wt.%, preferably 0.8
~1.5 parts, more preferably 1.0~1.3 parts；Modifying agent (propylene oxide: sodium chloroacetate=2:1~1:2 (weight ratio)) 1.0~2.0
Part, preferably 1.4~1.9 parts, more preferably 1.6~1.8 parts.
Further, the composition for ink is neutral ink composition or w/o type emulsion ink composition.
Wherein, the composition for ink can be neutral ink composition, which further includes deionization
Water, cosolvent, preservative, pH adjusting agent, dispersible pigment color paste and thickener.
Further, by weight, the neutral ink composition includes: 35.2~56.3 parts of the deionized water,
Preferably 39.7~50.5 parts, more preferably 43.6~48.0 parts；16.2~25.4 parts of the cosolvent, preferably 16.8~20.0
Part, more preferably 17.5~19.5 parts；0.1~0.4 part of the preservative, preferably 0.15~0.35 part, more preferably 0.2~0.3
Part；1.0~2.6 parts of the pH adjusting agent, preferably 1.0~2.3 parts, more preferably 1.0~1.6 parts；The dispersible pigment color paste 27.2
~40.5 parts, preferably 28.0~38.5 parts, more preferably 29.5~35.7 parts；1.0~5.0 parts of the thickener, preferably 1.5~
4.5 parts, more preferably 2.0~3.0 parts.
Further, in neutral ink composition, the cosolvent is poly alcohols material；The preservative is isothiazole
Quinoline letones；The pH adjusting agent is organic amine substance.
On the other hand, the composition for ink may be w/o type emulsion ink composition, the w/o type emulsion ink group
Closing object further includes deionized water, dyestuff, organic solvent, emulsifier, thixotropic agent and thickener.
Further, by weight, the w/o type emulsion ink composition include: the deionized water 10.0~
26.0 parts, preferably 15.0~24.5 parts, more preferably 18.0~23.0 parts；20.0~30.0 parts of the dyestuff, preferably 22.0
~28.0 parts, more preferably 23.5~27.0 parts；30.0~55.0 parts of the organic solvent, preferably 30.0~50.0 parts, more preferably
It is 35.0~45.0 parts；1.0~2.0 parts of the emulsifier, preferably 1.0~1.8 parts, more preferably 1.2~1.6 parts；The touching
Become 0.4~0.7 part of agent, preferably 0.4~0.6 part, more preferably 0.45~0.55 part；10.0~15.0 parts of the thickener, it is excellent
It is selected as 11.0~15.0 parts, more preferably 12.5~14.5 parts.
Further, in w/o type emulsion ink composition, the organic solvent is ether material；The emulsifier is day
Right glue；The thixotropic agent is cellulose ether substance.
Meanwhile the composition for ink is with 0.5~5 low frequency (ω=0.1rad/s) fissipation factor tan δ, 20%~
60% 5s shear rate and 10~35 Restoration stage initial point slope.
Wherein, low frequency (ω=0.1rad/s) fissipation factor tan δ of the neutral ink composition with 0.5-5,20%
~45% 5s shear rate and 10~35 Restoration stage initial point slope.
The w/o type emulsion ink composition has 0.5~3 low frequency (ω=0.1rad/s) fissipation factor tan δ,
20%~60% 5s shear rate and 10~35 Restoration stage initial point slope.
On the other hand, the present invention provides the preparation method of aforementioned neutral ink composition, comprising:
Step (1): at room temperature, cosolvent being dissolved in deionized water, obtains mixed solution a；
Step (2): being added preservative, pH adjusting agent, and stir evenly in the mixed solution a that Xiang Suoshu step (1) obtains,
Obtain mixed solution b；
Step (3): will sequentially add dispersible pigment color paste, thickener in the mixed solution b that the step (2) obtains, and stir,
Obtain mixture c；
Step (4): mixture c filtering, the deaeration that the step (3) is obtained obtain neutral ink composition.
Further, the mixing speed of the step (2) is 700~900r/min, and mixing time is 30~90 minutes；Institute
The mixing speed of stirring for stating step (3) is 700~900r/min, and mixing time is 30~90 minutes；
In addition, the present invention also provides the preparation methods of aforementioned w/o type emulsion ink composition, comprising:
Step (1): dyestuff and a part of emulsifier are added in a part of organic solvent, and heating stirring is obtained to abundant dissolution
To mixed solution d；
Step (2): thixotropic agent, another part emulsifier, another part organic solvent and deionized water being mixed, heating stirring,
The emulsion for forming Water-In-Oil, obtains mixed solution e；
Step (3): by the mixed solution d that the step (1) the obtains and mixed solution e that the step (2) obtain
Same container is added, adds thickener and is uniformly mixed, obtains w/o type emulsion ink composition.
Further, the heating temperature of the step (1) is 40~50 DEG C, and mixing speed is 300~500r/min, stirring
Time is 30~60 minutes；The heating temperature of the step (2) is 40~50 DEG C, and mixing speed is 300~500r/min, stirring
Time is 30~60 minutes；The step (3) carries out at normal temperature, and mixing speed is 300~500r/min, mixing time 60
~100 minutes.
In addition, the invention discloses a kind of methods of tested inks product performance of ink, which is characterized in that pass through tested inks
The static state product drop performance of ink of ink can be obtained in low frequency (ω=0.1rad/s) fissipation factor tan δ；Journey is sheared by test 5s
The dynamic text product performance of ink of ink can be obtained in degree and Restoration stage initial point slope.
The black type ball point ink composition of inhibition product according to the present invention, preferably modified xantham gum are thickened as system
Agent also provides while guarantee system has certain viscosity for system elastic under 25 DEG C of low frequencies (ω=0.1rad/s)
The prevailing viscoelasticity energy of response, the ball point ink composition are made after pen core in terms of pen core application performance, especially
It is that nib product ink aspect has excellent inhibition product performance of ink, greatly improves the writing experience of consumer.
Detailed description of the invention
Fig. 1 is Neutral writing ink Examples 1 to 3, Neutral writing ink comparative example 4 and w/o type emulsion ink embodiment 5~7, W/O
The oscillation frequency sweep result of type emulsion ink comparative example 8.
Fig. 2 is Neutral writing ink Examples 1 to 3, Neutral writing ink comparative example 4 and w/o type emulsion ink embodiment 5~7, W/O
The black schematic diagram of static state product drop after pen core is made in type emulsion ink comparative example 8.
Fig. 3 is Neutral writing ink Examples 1 to 3, Neutral writing ink comparative example 4 and w/o type emulsion ink embodiment 5~7, W/O
The thixotroping of type emulsion ink comparative example 8 restores test chart.The corresponding complex viscosity of dotted line 2 and the corresponding complex viscosity of dotted line 1
The ratio of difference complex viscosity corresponding with dotted line 1 is known as 5s shear rate, after the corresponding slope of dotted line 3 is defined as shearing
Restoration stage initial point slope.
Fig. 4 is Neutral writing ink Examples 1 to 3, Neutral writing ink comparative example 4 and w/o type emulsion ink embodiment 5~7, W/O
The black schematic diagram of product crossed after pen core using writing circle drawing instrument is made in type emulsion ink comparative example 8.
Specific embodiment
Below according to specific embodiment, technical scheme is described further.Protection scope of the present invention is unlimited
In following embodiment, these examples are enumerated merely for exemplary purpose without limiting the invention in any way.
The present invention uses modified xantham gum as system thickener, ensure that the static state product drop ink and dynamic of composition for ink
Write product performance of ink.
Preparing above-mentioned modified xantham gum component includes, 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；Low-grade monobasic alcohol (monohydric alcohol containing 1~5 carbon atom) aqueous solution of 60-80wt.%
80.5~92.5 parts, preferably 85.3~90.1 parts, more preferably 86.7~89.1 parts；The NaOH aqueous solution 0.5 of 15~25wt.%
~1.8 parts, preferably 0.8~1.5 part, more preferably 1.0~1.3 parts；Modifying agent (propylene oxide: sodium chloroacetate=2:1~1:2
(weight ratio)) 1.0~2.0 parts, preferably 1.4~1.9 parts, more preferably 1.6~1.8 parts.
The modified xantham gum can be made by the steps:
Step (1): at room temperature, xanthan gum is well-dispersed in the low-grade monobasic alcohol aqueous solution of 60~80wt.%, is mixed
Solution a；
Step (2): being added the NaOH aqueous solution of 15~25wt.% in Xiang Qianshu mixed solution a, and the 1~2h that alkalizes at room temperature,
Obtain mixed solution b；
Step (3): modifying agent is added in aforementioned mixed solution b, is warming up at 60~100 DEG C and is reacted, and the reaction time 2~
4h obtains product c；
Step (4): the ethanol solution of product c high concentration gradient successively cleans, and is filtered, 60~80 DEG C of high temperature dryings 8
~10h, obtains modified xantham gum.
Gained modified xantham gum number-average molecular weight is 4 × 106~8 × 106, viscosity is 1100~2400cP (test method ginseng
Examine GB13886-2007).
The composition for ink includes two kinds of neutral ink composition and w/o type emulsion ink composition.
Wherein, neutral ink composition includes, 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；PH adjusting agent 1.0~2.6
Part, preferably 1.0~2.3 parts, more preferably 1.0~1.6 parts；27.2~40.5 parts of dispersible pigment color paste, preferably 28.0~38.5 parts,
More preferably 29.5~35.7 parts；1.0~5.0 parts of thickener, preferably 1.5~4.5 parts, more preferably 2.0~3.0 parts.
The neutral ink composition is prepared via a method which:
Step (1): at room temperature, cosolvent being dissolved in deionized water, obtains mixed solution a；
Step (2): preservative, pH adjusting agent are added in Xiang Qianshu mixed solution a, and stirs evenly, obtains mixed solution b；
Step (3): dispersible pigment color paste, thickener will be sequentially added in aforementioned mixed solution b, and stirred, obtain mixture c；
Step (4): by aforementioned mixture c filtering, deaeration, neutral ink composition is obtained.
In addition, w/o type emulsion ink composition includes, and by weight: 10.0~26.0 parts of deionized water, preferably 15.0
~24.5 parts, more preferably 18.0~23.0 parts；20.0~30.0 parts of dyestuff, preferably 22.0~28.0 parts, more preferably 23.5~
27.0 parts；30.0~55.0 parts of organic solvent, preferably 30.0~50.0 parts, more preferably 35.0~45.0 parts；Emulsifier 1.0~
2.0 parts, 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
It is well 0.45~0.55 part；10.0~15.0 parts of thickener, preferably 11.0~15.0 parts, more preferably 12.5~14.5 parts.
The preparation method of the w/o type emulsion ink composition, comprising:
Step (1): dyestuff and emulsifier are added in organic solvent, and heating stirring obtains mixed solution d to abundant dissolution；
Step (2): thixotropic agent, emulsifier, organic solvent and deionized water are mixed, and heating stirring forms the emulsus of Water-In-Oil
Liquid obtains mixed solution e；
Step (3): being added same container for aforementioned mixed solution d and mixed solution e, adds thickener and is uniformly mixed, obtains
W/o type emulsion ink composition.
The present invention is described in further detail by the following examples.
Neutral writing ink embodiment 1
(1) it stocks up according to following components and its mass percent:
41.2 parts of deionized water, 18.4 parts of cosolvent (polyethylene glycol 400), 0.3 part of preservative (1,2 benzisothiazole
Quinoline -3- ketone), 1.4 parts of pH adjusting agent (ethanol amine), 37.1 parts of dispersible pigment color paste (charcoal blacks BC4300), 1.6 parts of thickening
Agent (modified xantham gum)；
(2) wherein, modified xantham gum raw material includes, in parts by weight: the ethanol water 87.5 of 8.8 parts of xanthan gum, 70wt.%
Part, 1.1 parts of the NaOH aqueous solution of 20wt.%, 1.6 parts of modifying agent (propylene oxide: sodium chloroacetate=1:1), and as follows
Preparation:
Step I: at room temperature, xanthan gum being well-dispersed in the ethanol solution of 70wt.%, obtains mixed solution a；
The NaOH aqueous solution of 20wt.%, and the 1.5h that alkalizes at room temperature are added in II: Xiang Qianshu mixed solution a of step, is mixed
Close solution b；
Step III: modifying agent is added in aforementioned mixed solution b, is warming up at 80 DEG C and is reacted, and reaction time 3h is obtained
Product c；
The ethanol solution of step IV: product c high concentration gradient successively cleans, and is filtered, 70 DEG C of high temperature drying 9h, obtains
Modified xantham gum.
(3) prepared by neutral ink composition: 41.2 parts of deionized water and 18.4 parts of polyethylene glycol 400 being added to have and stirred
It mixes in the container of device and stirs, sufficiently dissolution obtains mixed solution a, and 0.3 part of 1,2 benzisoxas are then added under stirring
Thiazoline -3- ketone, 1.4 parts of triethanolamine, stir 1h under 800r/min speed, and get a uniform mixture b, then exist
37.1 parts of charcoal blacks BC4300 is first added under 800r/min speed, when system after mixing, under stirring again plus
Entering 1.6 parts of modified xantham gum, stir about 1h is uniformly mixed up to all the components, obtains mixed solution c, stop stirring later,
It is filtered, Neutral writing ink embodiment 1 is made after deaeration.
Neutral writing ink embodiment 2
Deionized water in Neutral writing ink embodiment 1 is changed to 45.0 parts, mill base (charcoal blacks BC4300) is changed to 32.3 parts, increases
Thick dose (modified xantham gum) is changed to 2.6 parts, remaining parameter (component, ratio), preparation method are all the same.
Neutral writing ink embodiment 3
Deionized water in Neutral writing ink embodiment 1 is changed to 49.0 parts, mill base (charcoal blacks BC4300) is changed to 27.3 parts, increases
Thick dose (modified xantham gum) is changed to 3.6 parts, remaining parameter (component, ratio), preparation method are all the same.
Neutral writing ink comparative example 4
The type of thickener in Neutral writing ink embodiment 1 is changed to agent for polyacrylic acid thickening VISCOLAM by modified xantham gum
330, remaining parameter (component, ratio), preparation method are all the same.
W/o type emulsion ink embodiment 5
(1) it stocks up according to following components and its mass percent:
18.6 parts of deionized water, 29.3 parts of dyestuff (nigrosine 63), 37.8 parts of organic solvent (ethylene glycol phenyl ether), 1.4
The emulsifier (Arabic gum) of part, 0.5 part of thixotropic agent (carboxymethyl cellulose), 12.4 parts of thickener (modified xantham gum).
(2) wherein, modified xantham gum raw material includes, in parts by weight: the ethanol water 87.5 of 8.8 parts of xanthan gum, 70wt.%
Part, 1.1 parts of the NaOH aqueous solution of 20wt.%, 1.6 parts of modifying agent (propylene oxide: sodium chloroacetate=1:1), and as follows
Preparation:
Step I: at room temperature, xanthan gum being well-dispersed in the ethanol solution of 70wt.%, obtains mixed solution a；
The NaOH aqueous solution of 20wt.%, and the 1.5h that alkalizes at room temperature are added in II: Xiang Qianshu mixed solution a of step, is mixed
Close solution b；
Step III: modifying agent is added in aforementioned mixed solution b, is warming up at 80 DEG C and is reacted, and reaction time 3h is obtained
Product c；
The ethanol solution of step IV: product c high concentration gradient successively cleans, and is filtered, 70 DEG C of high temperature drying 9h, obtains
Modified xantham gum.
(3) prepared by w/o type emulsion ink composition: the Arabic gum of 29.3 parts of nigrosine 63 and 0.7 part is added the first step
Into the container equipped with 18.9 parts of ethylene glycol phenyl ether, 45 DEG C are heated to, is stirred 45 minutes under 400r/min speed, formed and divided
Dissipate uniform mixed solution d；By 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 mixing, is heated to 45 DEG C, stirs 45 minutes under 400r/min speed, form the emulsus of Water-In-Oil
Liquid obtains mixed solution e.Mixed solution d and mixed solution e are added in same container second step, add 12.4 parts and change
Property xanthan gum, stirred under 400r/min speed 80 minutes until formed be uniformly mixed stable emulsion, obtain w/o type emulsification
Ink embodiment 3.
W/o type emulsion ink embodiment 6
Deionized water in w/o type emulsion ink embodiment 5 is changed to 21.6 parts, dyestuff (nigrosine 63) is changed to 25.3 parts, increases
Thick dose (modified xantham gum) is changed to 13.4 parts, remaining parameter (component, ratio), preparation method are all the same.
W/o type emulsion ink embodiment 7
Deionized water in w/o type emulsion ink embodiment 5 is changed to 24.6 parts, dyestuff (nigrosine 63) is changed to 21.3 parts, increases
Thick dose (modified xantham gum) is changed to 14.4 parts, remaining parameter (component, ratio), preparation method are all the same.
W/o type emulsion ink comparative example 8
The type of thickener in w/o type emulsion ink embodiment 5 is changed to agent for polyacrylic acid thickening by modified xantham gum
VISCOLAM 330, remaining parameter (component, ratio), preparation method are all the same.
To aforementioned Neutral writing ink Examples 1 to 3, Neutral writing ink comparative example 4 and w/o type emulsion ink embodiment 5~7, W/O
8 sample of type emulsion ink comparative example carries out inhibiting long-pending performance of ink verification test.
The inhibition product performance of ink verification test is divided into static and dynamic two parts, and static product drop ink is verified when static, is moved
Product ink is write in verifying when state.
The static product drop performance of ink detection is usually that ball point ink composition is fabricated to a certain number of pen cores, will
Pen core hanging vertical placement regular hour after raising one's hat, the static state product for observing pen core drip black degree.Dynamic text product ink detects
Ball point ink composition is made into a certain number of pen cores, carries out scribing line test to it using writing circle drawing instrument, observation is write
The situation of product ink.
Characterization ball point ink composition is removed with the size of fissipation factor tan δ value under 25 DEG C of low frequencies (ω=0.1rad/s)
The complexity of static state product drop ink；With 5s shear rate and after shearing, Restoration stage initial point slope removes characterization ball pen and ink
Water composition dynamic text stops the complexity of pen product ink.
Static state product drop performance of ink verification test includes oscillation strain sweep and oscillation frequency sweep.The oscillation strain is swept
It is as follows to retouch the specific testing procedure of test.
The cone-plate of 60/1 ° of TiL is selected using CD (controlled strain) mode using HAAKE RS6000 rotational rheometer, is surveyed
Trying temperature is 25 DEG C, frequency 1HZ, strain gradually increase to 10 by 0 in oscillation mode, obtain sample elastic modulus G', stickiness
The curve that modulus G " and fissipation factor tan δ changes with strain γ, tan δ be not referred to as linear with changed strain region is strained
The area Nian Dan.
Test only in the linear area Nian Dan could obtain the characteristic constant of substance, it is therefore necessary to determine ball pen first
The linear area Nian Dan of composition for ink makes dynamic oscillation frequency scanning experiment in the linear area Nian Dan to select suitable strain
It carries out and the response generated is sufficiently large.
It is as follows that the oscillation frequency sweep tests specific testing procedure.
Suitable strain is selected in the linear area Nian Dan, using HAAKE RS6000 rotational rheometer, selects 60/1 ° of TiL
Cone-plate, test temperature be 25 DEG C, angular velocity omega gradually increases to 100 from 0, to sample carry out oscillation frequency sweep, obtain tan δ
With the change curve of angular velocity omega, the size of the tan δ value in the smaller i.e. low frequency of ω is used to characterize Neutral writing ink static state product drop ink
Complexity.
Fissipation factor tan δ be loss moduli G " and elastic modulus G ' ratio show that system has when tan δ value is greater than 1
The prevailing viscoelasticity energy of stickiness response, tan δ value is bigger, and the mobility of Pigment type neutral ink system is better, static
The black phenomenon of product drop gets over Yi Fasheng.
Neutral writing ink Examples 1 to 3, Neutral writing ink comparative example 4 and w/o type emulsion ink embodiment 5~7, w/o type emulsify
The static state product after pen core is made in ink comparative example 8, and to drip black test result data as shown in table 1.
The static product of table 1 drips black test result
As can be seen that using Neutral writing ink Examples 1 to 3,5~7 points of the w/o type emulsion ink embodiment of modified xantham gum
Xiang Bi not be had using Neutral writing ink comparative example 4, the w/o type emulsion ink comparative example 8 of agent for polyacrylic acid thickening lower low
Frequency tan δ value and less static product drip black rate.
Dynamic text product ink detection includes that thixotroping restores test, and specific testing procedure is as follows.
Compound viscosity is carried out to Pigment type neutral ink using HAAKE RS6000 rotational rheometer | η * | three-stage survey
Examination.The test is divided into three phases:
First stage is duration of oscillation scan pattern, this step simulations is static, chooses suitable strain, scanning frequency from the linear area Nian Dan
Rate is set as low frequency, keeps the temperature 120s under the conditions of 25 DEG C；
Second stage is shear mode, it is intended to the shear history that Pigment type neutral ink is taken out of by ball in simulation writing, setting
Shear rate is 1000s-1, shear time 5s；
Phase III is duration of oscillation scan pattern, this stage is the Restoration stage after shearing, is chosen from the linear area Nian Dan
Suitable strain, scan frequency are set as low frequency, keep the temperature 120s under the conditions of 25 DEG C；
By complex viscosity in shearing 5s | η * | the variation degree compared to initial value is defined as 5s shear rate, different systems
Ball point ink composition 5s shear rate is different, and it is thixotropic that it can further represent different system ball point ink compositions
Size.
In the similar situation of 5s shear rate, Restoration stage initial point slope is bigger, viscosity system structure after shearing stops
Build it is faster, stop pen product ink be more not susceptible to.
Neutral writing ink Examples 1 to 3, Neutral writing ink comparative example 4 and w/o type emulsion ink embodiment 5~7, w/o type emulsify
Ink comparative example 8 uses the scribing results of writing circle drawing instrument as shown in table 2 after pen core is made.
Table 2 writes scribing results
As can be seen that using Neutral writing ink Examples 1 to 3,5~7 points of the w/o type emulsion ink embodiment of modified xantham gum
Xiang Bi not be had using Neutral writing ink comparative example 4, the w/o type emulsion ink comparative example 8 of agent for polyacrylic acid thickening higher extensive
Multiple stage initial point slope and less machine every hundred meters of long-pending ink dot numbers of scribing line.
It can be seen that the preferred modified xantham gum of the present invention has while guarantee system viscosity as system thickener
The elastic prevailing viscoelasticity energy of response is matching written application aspect, especially in terms of pen core product performance of ink, has excellent
Good inhibition product performance of ink.Macromolecule is synthesized as the ball point ink composition phase of thickener using polyacrylic with existing
Than solving the problems, such as that pressing neutral ball pen protects nib product ink and writing process in vertical placement process without pen cap
The product Mo Xianxiang of middle appearance.
Those skilled in the art should be noted that embodiment described in the invention is only exemplary, can be
Various other replacements, changes and improvements are made in the scope of the present invention.Thus, the present invention is not limited to the above embodiments, and only
It is defined by the claims.
Claims (18)
1. a kind of composition for ink includes thickener, which is characterized in that the thickener is modified xantham gum.
2. composition for ink as described in claim 1, which is characterized in that the modified xantham gum is using propylene oxide, chlorine
Sodium acetate and xanthan gum reaction, a kind of carboxy-methyl hydroxy propyl xanthan gum of synthesis, number-average molecular weight are 4 × 106~8 × 106,
Viscosity is 1100~2400cP.
3. composition for ink as described in claim 1, which is characterized in that by weight, the preparation of the modified xantham gum
Raw material includes: 7.1~10.0 parts of xanthan gum；80.5~92.5 parts of the low-grade monobasic alcohol aqueous solution of 60-80wt.%；15~
0.5~1.8 part of the NaOH aqueous solution of 25wt.%；Modifying agent (propylene oxide: sodium chloroacetate=2:1~1:2 (weight ratio)) 1.0
~2.0 parts.
4. composition for ink as described in any one of claims 1-3, which is characterized in that the composition for ink is Neutral writing ink
Composition or w/o type emulsion ink composition.
5. composition for ink as claimed in claim 4, which is characterized in that the composition for ink is neutral ink composition,
The neutral ink composition further includes deionized water, cosolvent, preservative, pH adjusting agent and dispersible pigment color paste.
6. composition for ink as claimed in claim 5, which is characterized in that by weight, the neutral ink composition packet
It includes: 35.2~56.3 parts of the deionized water；16.2~25.4 parts of the cosolvent；0.1~0.4 part of the preservative；It is described
1.0~2.6 parts of pH adjusting agent；27.2~40.5 parts of the dispersible pigment color paste；1.0~5.0 parts of the thickener.
7. composition for ink as claimed in claim 6, which is characterized in that in the neutral ink composition, the cosolvent
For poly alcohols material；The preservative is isothiazolinone substance；The pH adjusting agent is organic amine substance.
8. composition for ink as claimed in claim 4, which is characterized in that the composition for ink is w/o type emulsion ink group
Object is closed, which further includes deionized water, dyestuff, organic solvent, emulsifier and thixotropic agent.
9. composition for ink as claimed in claim 8, which is characterized in that by weight, the w/o type emulsion ink combination
Object includes: 10.0~26.0 parts of the deionized water；20.0~30.0 parts of the dyestuff；The organic solvent 30.0~55.0
Part；1.0~2.0 parts of the emulsifier；0.4~0.7 part of the thixotropic agent；10.0~15.0 parts of the thickener.
10. composition for ink as claimed in claim 9, which is characterized in that described in the w/o type emulsion ink composition
Organic solvent is ether material；The emulsifier is natural gum；The thixotropic agent is cellulose ether substance.
11. composition for ink as claimed in claim 4, which is characterized in that the composition for ink has 0.5~5 low frequency
(ω=0.1rad/s) fissipation factor tan δ, 20%~60% 5s shear rate and 10~35 Restoration stage initial point
Slope.
12. composition for ink as claimed in claim 11, which is characterized in that the neutral ink composition is with 0.5~5
Low frequency (ω=0.1rad/s) fissipation factor tan δ, at the beginning of 20%~45% 5s shear rate and 10~35 Restoration stage
Starting slope.
13. composition for ink as claimed in claim 11, which is characterized in that the w/o type emulsion ink composition has 0.5
~3 low frequency (ω=0.1rad/s) fissipation factor tan δ, 20%~60% 5s shear rate and 10~35 recovery rank
Section initial point slope.
14. a kind of preparation method of neutral ink composition, comprising:
Step (1): at room temperature, cosolvent being dissolved in deionized water, obtains mixed solution a；
Step (2): being added preservative, pH adjusting agent, and stir evenly in the mixed solution a that Xiang Suoshu step (1) obtains,
Obtain mixed solution b；
Step (3): will sequentially add dispersible pigment color paste, thickener in the mixed solution b that the step (2) obtains, and stir,
Obtain mixture c；
Step (4): mixture c filtering, the deaeration that the step (3) is obtained obtain neutral ink composition.
15. preparation method as claimed in claim 14, which is characterized in that
The mixing speed of the step (2) is 700~900r/min, and mixing time is 30~90 minutes；
The mixing speed of the step (3) is 700~900r/min, and mixing time is 30~90 minutes.
16. a kind of preparation method of w/o type emulsion ink composition, comprising:
Step (1): dyestuff and a part of emulsifier are added in a part of organic solvent, and heating stirring is obtained to abundant dissolution
To mixed solution d；
Step (2): thixotropic agent, another part emulsifier, another part organic solvent and deionized water being mixed, heating stirring,
The emulsion for forming Water-In-Oil, obtains mixed solution e；
Step (3): by the mixed solution d that the step (1) the obtains and mixed solution e that the step (2) obtain
Same container is added, adds thickener and is uniformly mixed, obtains w/o type emulsion ink composition.
17. preparation method as claimed in claim 16, which is characterized in that
The heating temperature of the step (1) is 40~50 DEG C, and mixing speed is 300~500r/min, and mixing time is 30~60
Minute；
The heating temperature of the step (2) is 40~50 DEG C, and mixing speed is 300~500r/min, and mixing time is 30~60
Minute；
The step (3) carries out at normal temperature, and mixing speed is 300~500r/min, and mixing time is 60~100 minutes.
18. a kind of method of tested inks product performance of ink, which is characterized in that pass through the low frequency (ω=0.1rad/s) of tested inks
The static state product drop performance of ink of ink can be obtained in fissipation factor tan δ；It is initial by test 5s shear rate and Restoration stage
The dynamic text product performance of ink of ink can be obtained in point slope.
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| CN111551697A (en) * | 2020-05-27 | 2020-08-18 | 上海应用技术大学 | Method for rapidly evaluating long-term stability of ball-point pen ink composition containing thickening system |
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