CN1816600A - Water-based ink composition for fine pointed ballpoint pen and fine pointed ballpoint pen - Google Patents
Water-based ink composition for fine pointed ballpoint pen and fine pointed ballpoint pen Download PDFInfo
- Publication number
- CN1816600A CN1816600A CN 200480019011 CN200480019011A CN1816600A CN 1816600 A CN1816600 A CN 1816600A CN 200480019011 CN200480019011 CN 200480019011 CN 200480019011 A CN200480019011 A CN 200480019011A CN 1816600 A CN1816600 A CN 1816600A
- Authority
- CN
- China
- Prior art keywords
- water
- ballpoint pen
- fine
- ink composition
- ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K1/00—Nibs; Writing-points
- B43K1/08—Nibs; Writing-points with ball points; Balls or ball beds
- B43K1/082—Balls
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pens And Brushes (AREA)
Abstract
Provided is a water-based ink composition for a fine pointed ballpoint pen characterized by blending an ink composition comprising at least water, a colorant and a water soluble solvent with at least one kind of ultra fine particles selected from the group consisting of alumina, titanium oxide, silica, silicon carbide and tungsten carbide each having an average particle diameter of less than 0.1 [mu]m, wherein a blending amount of the ultra fine particles is 0.002 to 2 % by weight based on the ink composition, particularly preferably an ink composition having a viscosity of 50 to 2000 mPa.s (25 DEG C) which is measured at 1 rpm by means of a corn and plate type rotational viscometer (1 DEG 34'R24 corn). Further, provided is a fine pointed ballpoint pen having a ball of a diameter of 0.4 mm or less, filled with the water-based ink composition described above.
Description
Technical field
The present invention relates to a kind of water-based ink composition that is used for ballpoint pen, in particular to a kind of when to be used for the ball diameter be 0.5 millimeter or littler, in the time of particularly in 0.4 millimeter or the littler fine pointed ballpoint pen, has the water-based ink composition of excellent ball mount pad wear resistance, line quality, venting characteristic and excellent time stability; And a kind of fine pointed ballpoint pen.
Background technology
When writing with ballpoint pen, ink is transported to writing position by the rotation of ball, and also have following problem so far: clamping ball and the parts (ball mount pad (ball-housing seat)) that contact with it in ball-point pen tip inside wear and tear along with the ball rotation, to such an extent as to discharging opening for permitting discharging of the toner stops up, perhaps the filleting of clamping ball part (caulking part) contacts with paper, causes to write bad (for example lack China ink and write failure).Therefore, attempted in ball pen ink, adding water-soluble machining oil and tensio-active agent, ink is mixed with for example solid lubricant of boron nitride, wax emulsion or resin particle as anti-wear agent.But, do not obtain satisfied effect for the wear resistance of ball-point pen tip mount pad.
In addition, advised that (for example Japan's special permission disclose No. 206066/2002) adds particle diameter is that 0.1 micron or bigger and 30 microns or littler fine particle (for example aluminum oxide), silicon carbide and chromic oxide (their new Mohs' hardness is 4 or bigger) are as the measure that prevents that the ball mount pad weares and teares in the ball-point pen tip in composition for ink.But, this brings writes the problem that sensation variation and line quality reduce, because the phenomenon (broken string (skipping)) that with the presentation direction difference inhomogenous phenomenon of venting amount (directivity defective (directional error)) and ball rotation stop to slide on bottom surface with ball the fracture of ruling occurred temporarily.Particularly in the ball diameter is 0.5 millimeter or littler fine pointed ballpoint pen, can not obtain the effect of satisfied inhibition mount pad wearing and tearing in some cases, thereby be difficult to the writing quality level that reaches specific.It is believed that the reasons for the above problems are as follows.In fine pointed ballpoint pen, to compare with conventional ball-point pen tip, the ball mount pad has littler area, so bears bigger load on the mount pad of unit surface, to such an extent as to it has high friction resistance and by noticeable wear.In addition, it has little discharging opening for permitting discharging of the toner and takes place easily and writes failure by what obstruction caused.In addition, little and the ball of the ball diameter of fine pointed ballpoint pen is little from the outstanding part of nib, so the wearing and tearing of mount pad make the ball protuberance littler, contacts with the paper surface to such an extent as to hold the filleting part of ball, cause tangible problem, for example comprise lack China ink and write writing of failure bad.Therefore, fine pointed ballpoint pen is under the state that wearing and tearing quicken, and the wear intensity of in addition keeping writing quality and being allowed is little.Therefore, cause the serious inconvenience that before ink is used up, can not write easily, and in the design of fine pointed ballpoint pen, have bigger problem.Particularly, be that friction resistance further increases, and therefore significantly causes the wearing and tearing of mount pad in the situation of 0.4 millimeter or littler fine pointed ballpoint pen at the ball diameter.Therefore in addition, make ball smoothly rotate difficulty, related to and write sensation variation and because directivity defective and broken string and serious problems that the quality of ruling reduces.
In addition, because the discharging opening for permitting discharging of the toner area is little, the venting characteristic of the fine pointed ballpoint pen that the ball diameter is little is variation often, to such an extent as to need to reduce the viscosity of ink usually.But, when mixing fine particle in ink, As time goes on the particle with big proportion settles down, and causes serious problem, therefore the obstruction of for example writing sensation variation, venting characteristic variation and being caused by sedimentation and writing of causing is bad need address this is that in early days.
Therefore, in the ball diameter for example is 0.5 millimeter or littler fine pointed ballpoint pen, only add particle diameter and be 0.1 micron or bigger and 30 microns or littler fine particle and can not suppress the wearing and tearing of mount pad satisfactorily, and the bad serious problems of writing that the line quality reduces, writes sensation variation, venting characteristic variation and the obstruction that causes owing to sedimentation causes occur.
An object of the present invention is to provide a kind of water-based ink composition that is used for fine pointed ballpoint pen, it can suppress the wearing and tearing of mount pad and be excellent aspect venting characteristic and the time stability, and has and level and smooth write sensation and can write for a long time; The present invention also provides a kind of fine pointed ballpoint pen.
Summary of the invention
In order to address the above problem, the inventor for the wear resistance of mount pad in the fine pointed ballpoint pen of minor diameter ball, line quality, write sensation, resist fine grain sedimentation and time stability to carry out research in detail and repeatedly, and draw: by in ink, adding the ultra-fine grain of specified quantitative as drawing a conclusion, described particle is selected from aluminum oxide, titanium dioxide, silicon-dioxide, silicon carbide and the wolfram varbide, every kind of particulate median size is less than 0.1 micron, and reduces ink viscosity to particular value or lowlyer can solve described problem.Thereby finished the present invention.
That is to say, the present invention relates to:
(1) a kind of water-based ink composition that is used for fine pointed ballpoint pen, it is characterized in that the composition for ink that will comprise water, tinting material and water-soluble solvent at least mixes with at least a ultra-fine grain, described particle is selected from aluminum oxide, titanium dioxide, silicon-dioxide, silicon carbide and the wolfram varbide, described every kind of particulate median size is less than 0.1 micron, wherein based on the total amount of described composition for ink, the combined amount of described ultra-fine grain is 0.002 to 2 weight %;
(2) as the described water-based ink composition that is used for fine pointed ballpoint pen of top project (1), it is 50 to 2000mPas (25 ℃) by the viscosity that cone-plate type rotational viscosimeter (1 ° 34 ' R24 awl) is measured under 1rpm; And
(3) a kind of ball diameter is 0.4 millimeter or littler fine pointed ballpoint pen, wherein is filled with top project (1) or (2) described water-based ink composition.
The water-based ink composition of the invention described above is used for fine pointed ballpoint pen has for example overcome that the line quality of directivity defective and broken string reduces, and avoided writing the infringement of sensation, venting characteristic and time stability.In addition, improved the wear-resisting effect at ball-point pen tip place and can prolong Writing distance.Described water-based ink composition is applicable to that the ball diameter is 0.4 millimeter or littler, and then 0.28 millimeter or littler fine pointed ballpoint pen, and shows special obvious effects therein.
Embodiment
To explain below and implement best mode of the present invention.
For the wearing and tearing that suppress mount pad and improve the dispersion stabilization of fine particle in composition for ink, at least the fine particle that comprises the aluminum oxide, titanium dioxide, silicon-dioxide, silicon carbide and the wolfram varbide that comprise in the composition for ink of the present invention of water, tinting material and water-soluble solvent must be very thin, and preferably median size is less than 0.1 micron ultra-fine grain, and write sensation in order to improve, preferably they are spheric.Being called ultra-fine grain herein, to mean particle diameter be 0.001 to the fine particle less than 0.1 micron.
The preferred ultra-fine grain aluminum oxide that uses comprises the Co. by Nippon Aerosil, aluminum oxide C (primary granule particle diameter: 0.013 micron), C.I.Kasel Co. that Ltd. produces, the Nano Tec Al that Ltd. produces
2O
3(primary granule particle diameter: 0.033 micron) and Taimei Chemical Co., the Taimicron TM 100J (primary granule particle diameter: 0.014 micron) that Ltd. produces.Ultra-fine grain titanium dioxide comprises Nippon Aerosil Co., the TTO-55A (primary granule particle diameter: 0.05 micron) that titanium dioxide P25 (primary granule particle diameter: 0.03 micron) that Ltd. produces and Ishihara Sangyo Kaisha Ltd. produce.
In the present invention, total amount based on composition for ink, the described every kind of particulate median size that is selected from aluminum oxide, titanium dioxide, silicon-dioxide, silicon carbide and the wolfram varbide is preferably 0.002 to 2 weight % less than the content of 0.1 micron ultra-fine grain, more preferably 0.05 to 1 weight %.Described ultra-fine grain can use separately in above-mentioned scope or two or more are used in combination.
At the ball diameter is in the situation of 0.5 millimeter or littler fine pointed ballpoint pen, the effect of the inhibition mount pad wearing and tearing that particle diameter is difficult for for 0.1 micron or bigger fine particle providing satisfied.In addition, in the ball diameter is 0.4 millimeter or littler fine pointed ballpoint pen, take place since writing of causing of the wearing and tearing of mount pad bad, write sensation variation, line quality and reduce and cause easily that the sedimentation of writing failure stops up.Particularly in the ball diameter is 0.28 millimeter or littler fine pointed ballpoint pen, discharging opening for permitting discharging of the toner reduce and the ball protuberance reduces and As time goes on the friction resistance increase has significantly reduced writing quality.Therefore, in fine pointed ballpoint pen, need to use median size less than 0.1 micron ultra-fine grain.If its content surpasses 2 weight %, write sensation and venting characteristic variation, and wear resistance variation in some cases.
The viscosity of measuring the composition for ink of the invention described above by cone-plate type rotational viscosimeter (1 ° of 34 ' R24 awl) under 1rpm is 50 to 2000mPas (25 ℃), is preferably 100 to 1000mPas (25 ℃).If above-mentioned viscosity is lower than 50mPas (25 ℃), As time goes on sedimentation takes place in described ultra-fine grain, and ink may cause seepage (bobbling) and cause in some cases and writes failure.On the other hand, if above-mentioned viscosity surpasses 2000mPas (25 ℃), venting characteristic variation is write the sensation variation thereby make in some cases, and therefore above-mentioned two scopes are not preferred.
For instance, the water-soluble solvent in the composition for ink of the present invention is used for preventing that ink from freezing to dry up at the nib place with ink at low temperatures.Particularly, it comprises glycol (for example ethylene glycol, glycol ether, triglycol, propylene glycol, polyoxyethylene glycol, 1,3-butyleneglycol, sulfo-glycol ether) and glycerine, and ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, and they can use or mix use separately.Its consumption is 5 to 50 weight % based on composition for ink, preferred 10 to 30 weight %.
Improve the stability of passing in time by adding dispersion agent, can suppress the reunion and the sedimentation of ultra-fine grain.Can use nonionic and anion surfactant and water soluble resin as dispersion agent.Water soluble resin comprises the synthetic water soluble resin, for example polyvinyl alcohol, polyacrylic acid, acrylic copolymer, maleic acid resin, polyvinylpyrrolidone, polyoxyethylene, water soluble acrylic resin and water-soluble phenylethene-acrylic resin; And the water-dispersion emulsion of acrylic resin, Synolac, ethenoid resin, vibrin, styrene resin, maleic acid resin and urethane resin.Preferably by dispersion agent they being changed into the material of water-dispersion in advance, again with its mixing.
The tinting material that is used for composition for ink of the present invention comprises pigment and/or water-soluble dye.Described pigment is not specifically limited, and can use and be selected from choosing any one kind of them at the inorganic and pigment dyestuff that conventionally has been used for water-based ink composition so far.
For instance, mineral dye comprises carbon black and metal powder.
In addition, for instance, pigment dyestuff comprises azo lake, insoluble azo pigment, chelating azo pigment, phthalocyanine pigment, perylene and Perinon pigment, anthraquinone pigment, quinacridone pigment, dyestuff color lake, nitropigments and nitroso pigments.Particularly, can use phthalocyanine blue (C.I.74160), phthalocyanine green (C.I.74260), hansa yellow 3G (C.I.11670), dual-azo yellow GR (C.I.21100), permanent red 4R (C.I.12335), brilliant carmine 6B (C.I.15850) and quinacridine red (C.I.46500).Also can use the plastic pigment that constitutes by vinylbenzene and acrylic resin particle.In addition, can use hollow resin particle that granule interior has a space to be used for the polychrome purposes as white pigment or as the false resin of dye coloring.
Any substantive dyestuff, matching stain, food dye and basic dyestuff may be used to water-soluble dye.
The case description of substantive dyestuff is as follows.Described dyestuff comprises that C.I. is directly black 17, C.I. is directly black 19, C.I. Direct black 22, C.I. are directly black 32, C.I. is directly black 38, C.I. directly black 51 and C.I. directly black 71; C.I. direct Huang 4, C.I. Direct Yellow 26, C.I. Direct Yellow 44 and C.I. Direct Yellow 50; Directly red 1, direct red 4, Direct Red 23, directly red 31, directly red 37, directly red 39, directly red 75, directly red 80, directly red 81, directly red 83, directly red 225, directly red 226 and directly red 227; And sun blue 1, sun blue 15, sun blue 71, sun blue 86, sun blue 106 and sun blue 119.
The case description of matching stain is as follows.Described dyestuff comprises C.I. Acid Black 1, C.I. acid black 2, C.I. acid black 24, C.I. acid black 26, C.I. erie black 31, C.I. erie black 52, C.I. Acid Black 1 07, C.I. Acid Black 1 09, C.I. Acid Black 1 10, C.I. Acid Black 1 19 and C.I. Acid Black 1 54; C.I. turmeric yellow 7, C.I. turmeric yellow 17, C.I. turmeric yellow 19, C.I. acid yellow 23, C.I. turmeric yellow 25, C.I. turmeric yellow 29, C.I. quinoline yellow 8, C.I. turmeric yellow 42, C.I. turmeric yellow 49, C.I. turmeric yellow 61, C.I. turmeric yellow 72, C.I. turmeric yellow 78, C.I. acid yellow 11 0, C.I. turmeric yellow 127, C.I. turmeric yellow 135, C.I. turmeric yellow 141 and C.I. turmeric yellow 142; C.I. Xylene Red 8, C.I. Xylene Red 9, C.I. azogeramine 4, C.I. acid red 18, C.I. Xylene Red 26, C.I. Xylene Red 27, C.I. acid red 35, C.I. Xylene Red 37, C.I. Xylene Red 51, C.I. Xylene Red 52, C.I. Xylene Red 57, C.I. Xylene Red 82, C.I. acid red 87, C.I. acid red 92, C.I. Xylene Red 94, C.I. azogeramine 15, C.I. azogeramine 29, C.I. azogeramine 31, C.I. acid red 18 6, C.I. Acid Red 249, C.I. Xylene Red 254, C.I. Xylene Red 265 and C.I. Xylene Red 279; C.I. acid violet 18 and C.I. acid violet 17; C.I. Blue VRS, C.I. Acid Blue 7, C.I. acid blue 9, C.I. acid blue 22, C.I. acid blue 23, C.I. acid blue 25, C.I. Acid Blue 40, C.I. acid blue 41, C.I. acid blue 43, C.I. acid blue 62, C.I. Acid Blue 78, C.I. acid blue 83, C.I. acid blue 90, C.I. acid blue 93, C.I. Blue VRS 03, C.I. Blue VRS 12, C.I. Acid blue 113 and C.I. Blue VRS 58; And C.I. acid green 3, C.I. acid green 9, C.I. acid green 16, C.I. ACID GREEN 25 and C.I. acid green 27.
In substantive dyestuff or matching stain, comprise a large amount of food dyes, but wherein do not comprise C.I. edible yellow 3 as an example of food dye.
The example of basic dyestuff will be described below.It comprises C.I. basic yellow 1, C.I. basic yellow 2 and C.I. basic yellow 21; C.I. Basic Orange 2, C.I. 2, ba,sic, or,ang,e 2 14 and C.I. 2, ba,sic, or,ang,e 2 32; C.I. red 2, C.I. alkalescence red 9 of alkali red 1:1, C.I. alkalescence and C.I. alkali red 1:1 4; C.I. vesuvine 12; And C.I. basic black 2 and C.I. basic black 8.
Above-mentioned every kind of tinting material can use separately or be used in combination with its two or more mixture.Based on the total amount of composition for ink, colorant content is usually at 0.5 to 30 weight %, in the scope of preferred 1 to 15 weight %.If store the composition for ink that colorant content surpasses 30 weight % for a long time, pigment can be reunited or deposition of dye, thereby stops up nib, to such an extent as to cause and write failure.If content is lower than 0.5 weight %, therefore painted die down or the tone of lines is uncertain be not preferred.
When using pigment, must use dispersion agent as tinting material.Described dispersion agent has on the surface of pigments of being adsorbed on, and improve the avidity of pigment and water and pigment stably is dispersed in effect in the water, and use nonionic and anion surfactant is as dispersion agent.The preferred water-soluble polymers that uses.
Especially, in order to suppress the sedimentation of ultra-fine grain, in water-based ink composition of the present invention, add viscosity that a small amount of thickening material improves ink and be effectively and preferred.In order to control the venting characteristic and to suppress SEDIMENTATION FOR FINE PARTICLE, the thickening material that can add preferably can provide pseudoplastic shear-thinning reagent, and can use known compound.For instance, the preferred at least a compound that is selected from synthetic polymer, natural rubber, Mierocrystalline cellulose and the polysaccharide that uses.
Particularly, described for instance thickening material comprises Sudan Gum-arabic, succinoglycan (succinoglycan), welan gum (welan gum), tragacanth gum, guar gum, Viscogum BE, Lalgine, carrageenin, gelatin, casein, xanthan gum, dextran, methylcellulose gum, ethyl cellulose, Natvosol, carboxymethyl cellulose, hydroxyethanoic acid sodium starch, propanediol alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, poly-(sodium acrylate), carboxyvinyl polymer, polyoxyethylene, the multipolymer of vinyl acetate and polyvinylpyrrolidone, the salt of cross-linking type acrylate copolymer and styrene-propene acid copolymer.Based on the total amount of composition for ink, the content of described thickening material represents to be preferably 0.1 to 0.6 weight % with solids content, more preferably 0.1 to 0.4 weight %.
In composition for ink of the present invention, can add pH control agent, rust-preventive agent, anticorrosion and bactericidal agent and lubricant if desired.Lubricant comprises non-ionic compound, for example high-grade aliphatic ester, polyoxy alkylidene high-grade aliphatic ester and the alkyl phosphate of the fatty acid ester of polyhydroxy-alcohol, sugar; Anionic compound, for example alkylsulfonate of higher fatty acid amides and alkylaryl sulphonate, all these compounds can also be as the surface treatment agent of pigment; The derivative of polyalkylene glycol, fluorine based surfactant and polyether-modified silicone.Rust-preventive agent comprises benzotriazole, tolyl-triazole, cyclohexyl ammonium nitrite and Saponin/TSM, and the pH control agent comprises ammonia, urea, trolamine, aminomethyl propanol and sodium hydroxide.Sanitas or sterilant comprise phenol, sodium omadine (Sodium Omadine), Sodium Benzoate and benzoglyoxaline based compound.
Can adopt traditionally known method to produce water-based ink composition of the present invention, and above-mentioned various components by mix predetermined quantities for instance, and for example utilize the agitator of homogenizer and decollator to stir and mix these components to obtain described composition.In addition, if desired, can remove the coarse particles that comprises in the composition for ink by filtration or centrifugation.
Also unclear for the mechanism that the described ultra-fine grain that is selected from aluminum oxide, titanium dioxide, silicon-dioxide, silicon carbide and the wolfram varbide suppresses the wearing and tearing of ball mount pad, and it is believed that in fine pointed ballpoint pen, by being embedded in the ball mount pad less than 0.1 micron ultra-fine grain at the produced simultaneously big pressure of venting along with ball rotation in writing, to such an extent as to the surface hardness of mount pad increases, the wearing and tearing that ball rotates the mount pad that causes have been suppressed.Because ultra-fine grain evenly is present in when writing in the ink between ball and the mount pad, so above-mentioned effect can not disturbed the rotation of ball.Therefore, it is believed that water-based ink composition of the present invention has stably suppressed the wearing and tearing of ball mount pad, and good writing sensation and can not damage the line quality is provided.
Embodiment
Below with reference to the more specifically bright the present invention of embodiment, but the present invention is not limited to these embodiment.
Embodiment 1 to 9 and comparing embodiment 1 to 9
According to the amount (weight %) of appropriate combination as shown in table 1, mix following component 1 to 13 by agitator, thereby obtain water-based ink composition corresponding to embodiment 1 to 9 and comparing embodiment 1 to 9 with the form of homogeneous solution.
1-a. tinting material (pigment): carbon black
1-b. tinting material (dyestuff): red No. 105
2-a. provide the reagent of shear-thinning property: xanthan gum
2-b. the reagent of shear-thinning property is provided: the cross-linking type polyacrylic acid
3-a. water-miscible organic solvent: glycerine
3-b. water-miscible organic solvent: propylene glycol
4. lubricant: phosphoric acid ester alkyl oxide
5. rust-preventive agent: benzotriazole
6. sanitas: 1, the 2-benzisothiazole-3-ketone
7.pH control agent: trolamine
8-a. aluminum oxide: 0.033 micron of primary granule particle diameter
8-b. aluminum oxide: 0.013 micron of primary granule particle diameter
8-c. aluminum oxide: 0.7 micron of primary granule particle diameter
9-a. titanium dioxide: 0.05 micron of primary granule particle diameter
9-b. titanium dioxide: 0.03 micron of primary granule particle diameter
9-c. titanium dioxide: 0.27 micron of primary granule particle diameter
10. silicon carbide: 0.04 micron of primary granule particle diameter
11. wolfram varbide: 0.06 micron of primary granule particle diameter
12. water soluble resin: styrene-propene hydrochlorate multipolymer
12. Purified Water (refined water)
As for by cone-plate type rotary viscosity measuring viscosity, use the cone-plate type rotational viscosimeter EMD of Tokimec Inc. production to measure viscosity number down with ST motor rotary speed 1rpm (1 ° of 34 ' R24) at 25 ℃.
Ball-point pen tip with various ball diameters is installed in the transom that the shaft of a writing brush (internal diameter is the shaft of a writing brush that 3.4 millimeters PP makes) and polypropylene are made, the described shaft of a writing brush and transom all are installed in Mitsubishi Pencil Co., Ltd. among the UM-151 of Sheng Chaning, and fill with water-based ink composition that obtains in embodiment and the comparing embodiment and ink follower, and accept centrifugal treating (500G, 5 minutes) and come froth breaking.Then, they are packed in the ballpoint pen and the various handwriting tests shown in below accepting.
Implement handwriting test according to following mode, and every kind is used five ballpoint pens to come the implementation evaluation test.
1) wear-resistant test: implement 1000 meters spirals by the machine handwriting test and write (writing end), and according to following standard evaluation:
Write condition: 100gf, write angle 75 degree, writing speed 4.5 mm/min
◎: no problem and can write in all samples
Zero: observe some and lack China ink, but can write end
△: observe scarce China ink, but can write end
▲: at least one pen has thin write line and can not write because the venting amount reduces
*: because noticeable wear all pens in writing all can not be write
2) write sensory testing: write to estimate by circle and write sensation sensuously, and according to following standard evaluation:
◎: very level and smooth
Zero: level and smooth
△: feel the scraping sensation
*: relatively poor
3) quality of write line: the write line of writing acquisition according to following standard evaluation by 200 meters spirals in the machine handwriting test.
Write condition: 100gf, write angle 75 degree, writing speed 4.5 mm/min
◎: good
Zero: observe that some is light, but good
△: observe some broken string
▲: break and observe some directivity defective
*: in whole line, observe the directivity defective
4) anti-centrifugal property: make described ballpoint pen accept the centrifugal of separating centrifuge (800G, 10 minutes), estimate its lettering feature according to following standard by the frequency (frequency) of the about 1.5 centimetres circle of diameter then:
◎: just can write and without any problem from beginning
Zero: observe the slight China ink that lacks during beginning, still when the picture circular frequency is in 5 times, recover
△: when drawing circular frequency, observe scarce China ink, but recover afterwards at 5 to 10 times
*: when drawing circular frequency at 10 times or observe when above and lack China ink
5) lettering feature as time passes: described ballpoint tip was kept for 2 weeks down at 50 ℃ downwards, estimate the lettering feature of passing in time according to following standard by picture circle (writing rounds) and frequency thereof then:
◎: just can write and without any problem from beginning
Zero: observe the slight China ink that lacks during beginning, still when the picture circular frequency is in 5 times, recover
△: when drawing circular frequency, observe scarce China ink, but recover afterwards at 5 to 20 times
*: when drawing circular frequency at 20 times or observe when above and lack China ink and maybe can't write
The evaluation result of embodiment 1 to 9 is illustrated in the table 1 together, and the evaluation result of comparing embodiment 1 to 9 is illustrated in 2 together.
Table 1
| Particle diameter (micron) | Embodiment | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | |||
| Tinting material | 1-a 1-b | 5 | 6 | 5 | 5 | 5 | 5 | 6 | 5 | 5 | |
| Thickening material | 2-a 2-b | 0.2 | 0.15 | 0.4 | 0.3 | 0.3 | 0.3 | 0.25 | 0.4 | 0.05 | |
| Water-soluble solvent | 3-a 3-b | 20 | 10 10 | 20 | 10 10 | 10 10 | 20 | 10 10 | 10 10 | 10 10 | |
| Lubricant rust-preventive agent sanitas pH control agent | 4 5 6 7 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.6 0.3 0.1 2 | 0.6 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | |
| The aluminum oxide fine particle | 8-a 8-b 8-c | 0.033 0.013 0.7 | 0.05 | 0.3 | 0.8 | 0.1 | 0.4 | ||||
| The titanium dioxide fine particle | 9-a 9-b 9-c | 0.05 0.03 0.27 | 0.6 | 0.2 | |||||||
| The silicon carbide fine particle | 10 | 0.04 | 0.3 | ||||||||
| The wolfram varbide fine particle | 11 | 0.06 | 0.3 | ||||||||
| The water soluble resin Purified Water | 12 13 | 0.5 all the other | 0.3 all the other | 0.5 all the other | 0.5 all the other | 0.5 all the other | 0.5 all the other | 0.3 all the other | 0.5 all the other | 0.5 all the other | |
| Viscosity (mPas) | 1rpm | 256 | 858 | 1340 | 678 | 755 | 576 | 2125 | 3251 | 38 | |
| Wear resistance is write the lettering feature that the centrifugal property of sensation write line mass reactance is passed in time | ◎ ◎ ◎ ◎ ◎ | ◎ ◎ ○ ◎ ◎ | ◎ △ ◎ ◎ ◎ | ◎ ◎ ○ ◎ ◎ | ◎ ◎ ◎ ◎ ◎ | ○ ◎ ◎ ◎ ◎ | ◎ △ ○ ◎ ◎ | ◎ △ △ ◎ ◎ | ○ ○ ◎ △ ○ | ||
| Ball diameter (millimeter) | 0.28 | 0.18 | 0.4 | 0.2 | 0.28 | 0.5 | 0.28 | 0.28 | 0.28 | ||
Table 2
| Particle diameter (micron) | Comparing embodiment | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | |||
| Tinting material | 1-a 1-b | 5 | 6 | 6 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Thickening material | 2-a 2-b | 0.22 | 0.15 | 0.15 | 0.3 | 0.22 | 0.22 | 0.22 | 0.3 | 0.3 | |
| Water-soluble solvent | 3-a 3-b | 20 | 10 10 | 10 10 | 20 | 20 | 20 | 20 | 20 | 20 | |
| Lubricant rust-preventive agent sanitas pH control agent | 4 5 6 7 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | 0.8 0.3 0.1 2 | |
| The aluminum oxide fine particle | 8-a 8-b 8-c | 0.033 0.013 0.7 | 0.5 | 0.001 | 3 | ||||||
| The titanium dioxide fine particle | 9-a 9-b 9-c | 0.05 0.03 0.27 | 0.6 | 0.6 | 0.6 | ||||||
| The silicon carbide fine particle | 10 | 0.04 | |||||||||
| The wolfram varbide fine particle | 11 | 0.06 | |||||||||
| The water soluble resin Purified Water | 12 13 | 0.3 all the other | 0.2 all the other | 0.2 all the other | 0.5 all the other | 0.5 all the other | 0.5 all the other | 0.5 all the other | 0.3 all the other | 0.3 all the other | |
| Viscosity (mPas) | 1rpm | 320 | 652 | 550 | 538 | 332 | 332 | 332 | 794 | 794 | |
| Wear resistance is write the lettering feature that the centrifugal property of sensation write line mass reactance is passed in time | × △ △ ◎ ◎ | ▲ × ▲ × × | ▲ △ ○ ○ ○ | △ × △ △ △ | ▲ × ▲ × × | ▲ ▲ ▲ △ × | △ ▲ ▲ △ △ | × ○ ○ ◎ ◎ | ▲ ○ ○ ◎ ◎ | ||
| Ball diameter (millimeter) | 0.18 | 0.18 | 0.2 | 0.28 | 0.28 | 0.4 | 0.5 | 0.38 | 0.5 | ||
In the ball diameter was 0.5 millimeter or littler fine pointed ballpoint pen, the water-based ink composition that satisfies condition of the present invention had been excellent aspect lettering feature and the wear resistance to evaluation result from table 1 and table 2 as can be seen.On the other hand, obviously as seen in the ball diameter was 0.5 millimeter or littler fine pointed ballpoint pen, the water-based ink composition of discontented unabridged version invention condition had been relatively poor aspect lettering feature and the wear resistance.Particularly, in comparing embodiment 1, comparing embodiment 8 and the comparing embodiment 9 of not adding according to ultra-fine grain of the present invention, with and the comparing embodiment 3 of addition outside lower limit of the present invention in, wear resistance is non-constant.As seen be in 0.1 micron or bigger fine grain comparing embodiment 2, comparing embodiment 5, comparing embodiment 6 and the comparing embodiment 7 having added the primary granule particle diameter, wear resistance does not reach satisfied level, and various performances, it all is relatively poor for example writing sensation, anti-centrifugal property and lettering feature as time passes, and this trend is more obvious in having the ballpoint pen of littler ball.In addition, in the comparing embodiment 4 of fine particle addition outside the upper limit of the present invention, write and feel remarkable variation.Therefore, obviously visible water-based ink composition outside the scope of the invention can not solve problem of the present invention.
Industrial applicability
Water-based ink composition of the present invention is applicable to fine pointed ballpoint pen, and particularly the ball diameter is 0.5 millimeter or less fine pointed ballpoint pen.
Claims (3)
1. water-based ink composition that is used for fine pointed ballpoint pen; it is characterized in that the composition for ink that will comprise water, tinting material and water-soluble solvent at least mixes with at least a ultra-fine grain; described particle is selected from aluminum oxide, titanium dioxide, silicon-dioxide, silicon carbide and the wolfram varbide; described every kind of particulate median size is less than 0.1 micron; wherein based on the total amount of described composition for ink, the combined amount of described ultra-fine grain is 0.002 to 2 weight %.
2. the described water-based ink composition that is used for fine pointed ballpoint pen of claim 1, it is 50 to 2000mPas (25 ℃) by the viscosity that cone-plate type rotational viscosimeter (1 ° of 34 ' R24 awl) is measured under 1rpm.
3. a ball diameter is 0.4 millimeter or littler fine pointed ballpoint pen, wherein is filled with claim 1 or 2 described water-based ink compositions.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP292277/2003 | 2003-08-12 | ||
| JP2003292277 | 2003-08-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1816600A true CN1816600A (en) | 2006-08-09 |
| CN100462411C CN100462411C (en) | 2009-02-18 |
Family
ID=34131711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800190119A Active CN100462411C (en) | 2003-08-12 | 2004-08-06 | Water-based ink composition for fine pointed ballpoint pen and fine pointed ballpoint pen |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4671958B2 (en) |
| CN (1) | CN100462411C (en) |
| TW (1) | TWI328027B (en) |
| WO (1) | WO2005014736A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8511926B2 (en) | 2008-03-17 | 2013-08-20 | The Pilot Ink Co., Ltd. | Water-based ballpoint pen |
| CN104073059A (en) * | 2014-01-26 | 2014-10-01 | 王勇 | Thermal disappearing ink |
| CN106243830A (en) * | 2016-07-31 | 2016-12-21 | 梁枭 | The gel ink pen ink that writing can be eliminated |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006016476A (en) * | 2004-06-30 | 2006-01-19 | Pentel Corp | Oily ink composition for ballpoint pen |
| JP5441238B2 (en) * | 2008-01-07 | 2014-03-12 | 株式会社パイロットコーポレーション | Water-based ballpoint pen ink composition |
| US8303699B2 (en) * | 2008-04-15 | 2012-11-06 | Xerox Corporation | Photo-erasable ink for full color printing |
| JP7451383B2 (en) * | 2016-05-31 | 2024-03-18 | 三菱鉛筆株式会社 | ballpoint pen |
| JP6804875B2 (en) * | 2016-05-31 | 2020-12-23 | 三菱鉛筆株式会社 | Ballpoint pen |
| JP7290430B2 (en) | 2019-02-25 | 2023-06-13 | 三菱鉛筆株式会社 | Ink composition for water-based ballpoint pen |
| JP2022165774A (en) * | 2021-04-20 | 2022-11-01 | 三菱鉛筆株式会社 | Aqueous ball-point pen ink composition |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0776665A (en) * | 1993-09-08 | 1995-03-20 | Pilot Corp:The | Ink for water-based ball-point pen |
| JPH10195365A (en) * | 1997-01-07 | 1998-07-28 | Mitsubishi Pencil Co Ltd | Oil-base ink for ballpoint |
| JP3753490B2 (en) * | 1997-01-28 | 2006-03-08 | 三菱鉛筆株式会社 | Oil-based ink for ballpoint pens |
| JPH10329477A (en) * | 1997-04-04 | 1998-12-15 | Pilot Ink Co Ltd | Ballpoint pen tip |
| JPH1180628A (en) * | 1997-09-04 | 1999-03-26 | Kao Corp | Water-base ink |
| JP3879479B2 (en) * | 2000-11-08 | 2007-02-14 | ぺんてる株式会社 | Ballpoint pen ink and ballpoint pen using the same |
| JP2003073587A (en) * | 2001-08-30 | 2003-03-12 | Sakura Color Prod Corp | Ink composition erasable by light irradiation |
| JP2004292757A (en) * | 2003-03-28 | 2004-10-21 | Pentel Corp | Ink for ball-point pen and ball-point pen using the same |
-
2004
- 2004-08-06 WO PCT/JP2004/011653 patent/WO2005014736A1/en active Application Filing
- 2004-08-06 CN CNB2004800190119A patent/CN100462411C/en active Active
- 2004-08-06 JP JP2006519263A patent/JP4671958B2/en active Active
- 2004-08-09 TW TW93123814D patent/TWI328027B/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8511926B2 (en) | 2008-03-17 | 2013-08-20 | The Pilot Ink Co., Ltd. | Water-based ballpoint pen |
| CN101978003B (en) * | 2008-03-17 | 2014-03-12 | 百乐墨水株式会社 | Water-based ballpoint pen |
| CN104073059A (en) * | 2014-01-26 | 2014-10-01 | 王勇 | Thermal disappearing ink |
| CN106243830A (en) * | 2016-07-31 | 2016-12-21 | 梁枭 | The gel ink pen ink that writing can be eliminated |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005014736A1 (en) | 2005-02-17 |
| CN100462411C (en) | 2009-02-18 |
| JP2007518838A (en) | 2007-07-12 |
| JP4671958B2 (en) | 2011-04-20 |
| TWI328027B (en) | 2010-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1125152C (en) | Aqueous pigment-based ball-point ink having white color tone | |
| CN1239979A (en) | Water-based ballpoint ink having metallic glossy color | |
| CN1993435A (en) | Water-based ink composition | |
| CN1816600A (en) | Water-based ink composition for fine pointed ballpoint pen and fine pointed ballpoint pen | |
| CN1079103C (en) | Aqueous pigment dispersion, water-soluble resin, production process of resin, and equipment suitable for use with dispersion | |
| CN1313544C (en) | Aluminum flake pigment comprising aluminum flake as basic particle, method for producing the same, and coating and ink using the same | |
| CN102167941A (en) | Aqueous plastic coating paint | |
| CN1267689A (en) | Bright water printing ink composition | |
| CN1756805A (en) | Pigment preparation and method for producing the same | |
| CN1144849C (en) | Direct filling type water-base ball-point ink having metallic sheen | |
| CN102597135A (en) | Aqueous dispersion for inkjet printing | |
| CN101037571A (en) | Low-luster polishing agent combination and preparation method thereof | |
| JP5062875B2 (en) | Water-based ballpoint pen | |
| CN1978558B (en) | Black ink composition for aqueous ballpoint pen and aqueous ballpoint pen | |
| CN101466801A (en) | Water-base double-color developing ink composition and writing utensils using the same | |
| CN1821321A (en) | Water paint ink for ink jet printer | |
| CN1139642C (en) | Water-base ballpoint ink composition | |
| CN1746228A (en) | Manufacture of pigment | |
| CN101033353A (en) | Color type water-based ink compositions and preparation method thereof | |
| CN1384859A (en) | Water-based ink ball pen | |
| CN1122692C (en) | Aqueous ink composition for writing utensils | |
| CN1303420A (en) | Double-color ink and writing utensil containing same | |
| CN1831044A (en) | Nonionic associative thickener containing vinyl addition polymer backbone | |
| CN1101840C (en) | Dye additive containing diazo compounds and dyeing compositions | |
| CN1254515C (en) | Brightening aqueous ink composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |