CN1978558B - Black ink composition for aqueous ballpoint pen and aqueous ballpoint pen - Google Patents
Black ink composition for aqueous ballpoint pen and aqueous ballpoint pen Download PDFInfo
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- CN1978558B CN1978558B CN2005101289630A CN200510128963A CN1978558B CN 1978558 B CN1978558 B CN 1978558B CN 2005101289630 A CN2005101289630 A CN 2005101289630A CN 200510128963 A CN200510128963 A CN 200510128963A CN 1978558 B CN1978558 B CN 1978558B
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Abstract
To provide a black ink composition for an aqueous ballpoint pen and an aqueous ballpoint pen having a reduced wear of a ball receiving seat of a tip, a long writing distance, and having sufficient thickness. The black ink composition for an aqueous ballpoint pen is used in a ballpoint pen with a ball diameter of 0.38 mm or less and contains at least water, a color material and a water-soluble solvent, wherein it is characterized by using, as the above color material, a color material prepared black by mixing two or more pigments having different color indications of the C.I. Name (Colour Index Generic Name).
Description
Technical field
The present invention relates at ball diameter is 0.38mm or following thin word with employed used with water ball-point pens black ink composition in (superfine, super superfine) ballpoint pen and the ballpoint pen that uses water-base ink, more particularly, relate to used with water ball-point pens black ink composition that a kind of wearing and tearing that make the ball bearing seat of nib reduce and Writing distance is long, have sufficient concentration and the ballpoint pen that uses water-base ink.
Background technology
Usually, in ballpoint pen, ball produces rotation because of writing, thus with ink offset to by on the writing surface, and use the ballpoint pen of water-base ink, along with the rotation of ball, the ball bearing seat (clamper) of metal penpoint can be worn.
Problem like this is exactly known a long time ago, and can by add additives such as resin particle such as solid lubricant such as water-soluble machining oil or tensio-active agent, boron nitride or wax emulsion, perhaps in composition for ink, add new Mohs' hardness be 4 or particle diameters such as above aluminum oxide, silicon carbide, chromic oxide be that the particulate (for example the spy opens flat 2002-No. 206066 communiques) of 0.1 μ m～30 μ m is handled.
But, for the ballpoint pen that uses these inks, though can confirm suppressing wearing and tearing and writing to have certain effect aspect the sense, but when ball diameter is 0.5mm or when following, because the ink flow orifice is little, the load that causes per unit area to bear increases, and owing to the past holds the few permissible wear amount that causes of ball protuberance that is projected into the outside few, thereby wear problems becomes more remarkable.
Especially, when the mode by metal penpoint and superhard ball realizes that ball diameter is 0.38mm or following thin word with the water-base ink ballpoint pen of (ultra-fine, super superfine), if in black ink, use carbon black as the look material, even then containing under the situation that above-mentioned spy opens flat 2002-No. 206066 described particulates of communique, the ball bearing seat part of nib also can be worn, consequently cause the ink flow orifice to stop up, or keep the riveted part of ball to contact with paper, or the word that occurs writing exposes the style of calligraphy characterized by hollow strokes etc. and writes the bad problem that maybe can not write.This wearing and tearing by the supporting base that carbon black caused are along with ball diameter diminishes and acceleration.Therefore, for using ball diameter to be 0.38mm or following, particularly ball diameter is the ballpoint pen of thinner 0.28mm or following such super superfine ball, the treatable scope of various solutions that has exceeded above-mentioned prior art, and, also exist the wearing and tearing of the ball bearing seat of nib can not be suppressed the problem of effect fully for the ink that has used carbon black.
On the other hand, as the aqueous black ink, known a kind of aqueous black ink (for example the spy opens flat 11-No. 12525 communiques) that comprises water miscible orange, purple and green dyestuff; And a kind of composition for ink used with water ball-point pens, it comprises water soluble resin, water, water-miscible organic solvent, coloured material at least, and wherein, described coloured material comprises nigrosine (for example the spy opens flat 2002-No. 371219 communiques).
But, above-mentioned aqueous black ink be for solve its in the so-called fibertip pen that with resinous nib is nib because of storage stability worsens the blocking problem caused, and use orange, purple and green water-soluble dye.
In addition, with regard to above-mentioned use nigrosine as with regard to the composition for ink used with water ball-point pens of coloured material, its present situation is: have certain effect though can confirm it at aspects such as suppressing wearing and tearing and Writing distance, but for ball diameter be 0.5mm or following, particularly ball diameter is that the wearing and tearing of 0.38mm or following ballpoint pen suppress also insufficient, and, also have the problem that can not demonstrate sufficient black.
Summary of the invention
The present invention is in view of above-mentioned prior art problems and present situation, and make in order to address the above problem, the object of the present invention is to provide a kind of used with water ball-point pens black ink composition, this composition for ink can be under 0.38mm or the situation following, particularly 0.28mm or following ballpoint pen being used for ball diameter, suppress the wearing and tearing of ball bearing seat, it is level and smooth and can write for a long time to write sense, has sufficient concentration simultaneously.
The present inventor carries out positive research at above-mentioned prior art problems, found that, be used for the composition for ink used with water ball-point pens that ball diameter is 0.38mm or following ballpoint pen, as the look material, use is by mixing the look material that two or more specific pigment are modulated into black, can obtain the used with water ball-point pens black ink composition and the water-base ink ballpoint pen of above-mentioned purpose, thereby finish the present invention.
That is, the present invention includes following (1)～(a 5) content.
(1) a kind of used with water ball-point pens black ink composition, it is 0.38mm or following ballpoint pen that said composition is used for ball diameter, and contain water, look material, water-soluble solvent at least, wherein, as described look material, use by mixing the look material that two or more pigment with the different form and aspect demonstration of C.I. title (colour index popular name (Colour Index Generic Name)) are modulated into black.
(2) as above-mentioned (1) described used with water ball-point pens black ink composition, wherein, the content of carbon black is 3 weight % or following.
(3), wherein in composition for ink, contain the aluminum oxide of 0.002～2 weight % and at least a kind particulate of titanium oxide as above-mentioned (1) or (2) described used with water ball-point pens black ink composition.
(4) as each described used with water ball-point pens black ink composition of above-mentioned (1)～(3), wherein, the median size of pigment is 150nm or following.
(5) a kind of ballpoint pen wherein, is each the described used with water ball-point pens black ink composition that is filled with in 0.38mm or the following ballpoint pen as above-mentioned (1)～(4) at ball diameter.
According to the present invention, a kind of used with water ball-point pens black ink composition and water-base ink ballpoint pen can be provided, this composition for ink can be under 0.38mm or the situation following, particularly 0.28mm or following ballpoint pen being used for ball diameter, suppress the wearing and tearing of ball bearing seat, it is level and smooth and can write for a long time to write sense, has sufficient concentration simultaneously.
Description of drawings
Fig. 1 (a) is the longitudinal profile synoptic diagram of the ballpoint tip of bullet cut structure, (b) is the horizontal section synoptic diagram of this ballpoint tip part.
Fig. 2 (a) is the longitudinal profile synoptic diagram of the ballpoint tip of pin type structure, (b) is the horizontal section synoptic diagram of this ballpoint tip part.
Embodiment
Below, embodiment of the present invention are described in detail one by one.
It is 0.38mm or following ballpoint pen that used with water ball-point pens black ink composition of the present invention is used for ball diameter, and contain water, look material, water-soluble solvent at least, wherein, as described look material, use by mixing the look material that two or more pigment with the different form and aspect demonstration of colour index title (colour index popular name) are modulated into black.
Employed look material is to have the colour index title by mixing two or more among the present invention
The pigment that (colour index popular name) different form and aspect show and be modulated into the look material of black.By using synthetic like this look material, then composition for ink is being used under the situation that ball diameter is 0.38mm or following thin word (superfine, super superfine) ballpoint pen, the wearing and tearing of the ball bearing part of the metal penpoint in the time of can positively suppressing to write, simultaneously can reach sufficient concentration, avoid Writing distance too short.
The look material that can use so long as have the look material that pigment that the different form and aspect of C.I. title (colour index popular name) show are modulated into black and get final product by mixing two or more, does not limit especially.
As the pigment that can use, can list for example C.I. Pigment black 1,7; C.I. Pigment Yellow 73 1,2,3,12,13,14,16,17,20,24,34,35,42,53,55,65,73,74,75,81,83,86,93,94,95,97,98,99,100,101,104,108,109,110,114,117,120,125,128,129,137,138,139,147,148,150,151,153,154,155,166,167,168,173C, 174,180,185 etc.; C.I. Pigment red 1,2,3,5,7,8,9,10,12,16,17,19,22,38,41,43,48,48:2,48:3,49,50:1,52,53,53:1,57,57:1,58:2,60,63:1,63:2,64:1,86,88,90,9,112,122,123,127,146,149,166,168,170,175,176,177,179,180,181,184,185,189,190,192,194,198,202,206,207,209,215,216,217,220,223,224,226,227,228,238,240,245,254,225 etc.; C.I. pigment blue 1,2,3,15:1,15:2,15:3,15:4,15:6,16,17,22,25,60,64,66 etc.; C.I. pigment orange 5,10,13,16,36,40,43,48,49,51,55,59,61,71 etc.; C.I. pigment violet 1,3,5:1,16,19,23,29,30,31,33,36,37,38,40,42,50 etc.; C.I. pigment Green 7,10,36 etc.; C.I. pigment brown 23,25,26 etc.
Look material used in the present invention, be by above-mentioned various pigment are disperseed one by one, and, can list: 3, the black conditioned pigment that obtains of C.I. pigment violet 19 (β type) and C.I. pigment Yellow 14 for example by mixed C .I. pigment Blue 15 by mixing the look material that two or more these dispersed colors are modulated into black; By mixed C .I. pigment Blue 15: 3, the black conditioned pigment that obtains of C.I. pigment red 122 and C.I. pigment yellow 83; By mixed C .I. pigment Blue 15: 3, the black conditioned pigment that obtains of C.I. pigment Violet 23 and C.I. Pigment Yellow 73 10; By mixed C .I. pigment Blue 15: 6 and the black conditioned pigment that obtains of C.I. pigment orange 43; Black conditioned pigment that obtains by mixed C .I. pigment Green 7 and C.I. Pigment red 17 etc.
These pigment can pass through mixed dispersant, solvent, other additive kind and water, and use dispersion machines such as ball mill, ball mill to pulverize fully and disperse, carry out centrifugation then, remove thick composition, obtain the black pigment dispersion (toner) of small particle size.
In addition, employed look material is by mixing the look material that two or more pigment (Chromatic color) with the different form and aspect demonstration of C.I. title are modulated into black among the present invention, therefore, only use the situation of the pigment that a kind of form and aspect with C.I. title shows, for example, using nigrosine (C.I. title Pigment black 1) separately is not object of the present invention as the situation of look material.
In the present invention, in order further to reduce lightness and to be used for the little thin word of ink flowrate simultaneously with under the situation of ballpoint pen, also can access black and retouch line with sufficient concentration, the preferred median size of the pigment of the different form and aspect demonstration of the above-mentioned C.I. of having title of using is 150nm or following pigment, more preferably use median size to be 100nm or following pigment, especially preferably use the pigment of median size as 30nm～100nm.
If use median size to be 150nm or following pigment, promptly the median size of Chromatic color pigment is 150nm or following, more preferably 100nm or when following, scattering of light intensity can further reduce, thereby can access denseer black.
In addition, in the present invention, reduce to specific amount by amount with carbon black, also can suppress wearing and tearing, therefore, with the content that can not wear and tear, the content that is about to carbon black is set at 3 weight % or following of composition for ink total amount, be preferably 1 weight % or following, can obtain sufficient concentration by black that this carbon black produced and the black (complementary color) that two or more coloured pigment dyestuffs are produced, even and be that 0.38mm or following thin word are with under the situation of ballpoint pen being used for ball diameter, the wearing and tearing of the ball bearing seat part of the metal penpoint in the time of also can positively suppressing to write avoid Writing distance too short simultaneously.
In addition, if the content of carbon black surpasses 3 weight % in composition for ink, then be difficult to bring into play fully effect of the present invention.
With respect to the total amount of composition for ink, the total content of these look materials (comprising the situation that contains 3 weight % or following carbon black) is preferably 1～15 weight %, more preferably 4～10 weight %.
If the look material contain quantity not sufficient 1 weight %, the concentration that then becomes deficiency can not obtain the black of target, on the other hand, if surpass 15 weight %, the time dependent stability of ink is not good enough, and the quality of pen worsens, so be not preferred.
Employed water-soluble solvent is in order to realize the various qualities of ink among the present invention, and for example the ink that prevents when low temperature freezes, prevents that the purposes such as ink dried of nib from using.Specifically, can be used alone or as a mixture glycolss such as ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, polyoxyethylene glycol, 1,3-butyleneglycol, thiodiglycol, glycerine; Or ethylene glycol monomethyl ether, diethylene glycol monomethyl ether.In ink was formed, its content was preferably 5～50 weight %, more preferably 10～30 weight %.
And then, in the present invention, even in order to be that 0.38mm or following thin word are with under the situation of ballpoint pen being used for ball diameter, also can positively be suppressed at the wearing and tearing of the ball bearing seat part of the metal penpoint when writing, preferably in composition for ink, contain at least a kind particulate of aluminum oxide and titanium oxide.
In order to obtain the good dispersion stabilization in composition for ink, the median size less than 0.1 μ m's of preferred employed particulate oxide aluminium and particulate titanium dioxide is fine, and writes sense in order to improve, and more preferably is shaped as spherical.
As the particulate oxide aluminium of preferred use, can list the aluminium C (primary particle size: 0.013 μ m, shape: spherical) that Japanese AEROSIL company makes and the NanoTek Al of C.I.KASEI (シ-ァ ィ changes into) company manufacturing
2O
3(primary particle size: 0.033 μ m, shape: spherical) etc.In addition, as particulate titanium dioxide, can list the titanium oxide P25 (primary particle size: 0.03 μ m that Japanese AEROSIL company makes, sphere), TTO-55A (primary particle size: 0.05 μ m of making of Ishihara Sangyo Kaisha, Ltd. shape:, shape: sphere) etc., these particulates can use separately, also 2 kinds can be used in combination.
Above-mentioned particulate oxide aluminium, particulate titanium dioxide also can use the same dispersion steps of process and above-mentioned pigment and the dispersive dispersion.
In composition for ink, the total content of these alumina particulates, titanium oxide microparticle is preferably 0.002～2 weight %, more preferably 0.05～1 weight %.
Particle diameter is 0.1 μ m or above aluminum oxide, titanium oxide for ball diameter is common ballpoint pen about 0.5mm, can confirm suppressing wearing and tearing and writing to have certain effect aspect the sense, and be that 0.38mm or following thin word are with in the ballpoint pen at ball diameter, write the sense variation, and, become and to write easily because of sedimentation produces obstruction.Therefore, be that preferred median size less than 0.1 μ m used in the ballpoint pen in 0.38mm or following thin word at ball diameter.In addition, when the total of alumina particulate and titanium oxide microparticle contains quantity not sufficient 0.002 weight %, can not obtain the effect of sufficient wearability, on the other hand, if content surpasses 2 weight %, then, write sense and worsen because the sedimentation of particle causes stopping up, the outflow reduction, wearability might variation on the contrary.
In addition, in order further to improve the time dependent stability of ink, in aqueous ink composition of the present invention, also can contain dispersion agent.
As spendable dispersion agent, can list the tensio-active agent of for example nonionic class, anionic species or water soluble resin etc.As water soluble resin, for example can list water-dispersible emulsions such as synthesizing water-solubility polymer such as polyvinyl alcohol, polyacrylic acid, acrylic copolymer, maleic acid resin, Polyvinylpyrolidone (PVP), polyethylene oxide, water soluble acrylic resin, water-soluble phenylethene-acrylic resin or acrylic resin, Synolac, Vinylite, vibrin, styrene resin, maleic acid resin, urethane resin etc.
In ink was formed, the content of these dispersion agents was preferably 0.3～4.5 weight %, more preferably 1.2～3 weight %.
In addition, in order to suppress the sedimentation of particulate, it is effectively that aqueous ink composition of the present invention contains tackifier, thereby is preferred especially.As the tackifier that can use, good and can suppress the aspects such as sedimentation of particulate from the outflow of ink, be preferably and give pseudoplastic shearing visbreaking imparting agent, and can use known tackifier.Be preferably selected from for example synthetic macromolecule, natural rubber, Mierocrystalline cellulose and polyose at least a kind.Specifically, can list for example Sudan Gum-arabic, tragacanth gum, guar gum, Viscogum BE, Lalgine, carrageenin, gelatin, casein, xanthan gum, dextran, methylcellulose gum, ethyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, starch glycolic acid and salt thereof, propylene glycol alginate, polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyvinyl methyl ether, polyacrylic acid and salt thereof, carboxyvinyl polymer, polyethylene oxide, the multipolymer of vinyl acetate and Polyvinylpyrolidone (PVP), cross-linking type acrylate copolymer and salt thereof, non-crosslinked type acrylate copolymer and salt thereof, styrene acrylic copolymer and salt etc. thereof.In ink composition, its content is preferably 0.1～0.6 weight % with solid component meter, more preferably 0.1～0.4 weight %.
In composition for ink of the present invention, remainder is water (Purified Water, ion exchanged water, distilled water, pure water, a ultrapure water etc.), and then, as required, can also contain pH value conditioning agent, rust-preventive agent, anticorrosion and antiseptic-germicide, the lubricant etc. of appropriate amount.
As lubricant, can list the fatty acid ester of the polyvalent alcohol of the surface treatment agent that also can be used for pigment, the nonionic classes such as high-grade aliphatic ester, polyoxyalkylene high-grade aliphatic ester, alkyl phosphate of sugar; And anionic species such as alkylsulfonate of higher fatty acid amides, alkylallyl sulfonate; The derivative of polyalkylene glycol and fluorine are tensio-active agent, polyether-modified polysiloxane etc.In addition, as rust-preventive agent, can list benzotriazole, tolyl-triazole, dicyclohexyl ammonium nitrite, Chinese honey locust glycoside etc., as the pH regulator agent, can list ammoniacal liquor, urea, trolamine, amino methyl propyl alcohol, sodium hydroxide etc., as sanitas or antiseptic-germicide, can list phenol, pyrithione sodium (Sodium Omadine), sodium benzoate, benzimidazoles compound etc.
In order to make aqueous black composition for ink of the present invention, can adopt existing known method, for example quantitative above-mentioned each composition of hybrid regulatory, and stirrers such as employing homogenizing mixing tank or dispersion machine mixes and obtains aqueous black composition for ink of the present invention.And then, as required, also can be by filtering and oversize particle in the composition for ink is removed in centrifugation.
Use the ballpoint pen of water-base ink of the present invention to be characterised in that, at ball diameter is to be filled with the aqueous black composition for ink with above-mentioned formation in 0.38mm or following (superfine) ballpoint pen, preferably be filled into 0.28mm or following (super superfine), more preferably 0.2mm or following, be preferably in 0.18mm or the following ballpoint pen especially.
The structure of ballpoint pen of using this water-base ink is so long as ball diameter is 0.38mm or following getting final product, not special restriction, for example can list Fig. 1 (a) and (b) shown in the ballpoint tip with bullet cut structure 1 ballpoint pen, Fig. 2 (a) and (b) shown in the ballpoint pen of ballpoint tip 2 with pin type structure.In addition, Reference numeral 1a, the 2a among the figure is ball, and 1b, 2b are clamper, and 1c, 2c are ball bearing seat part, and 1d, 2d are ink port.
The present invention according to such formation, be used for the aqueous ink composition that ball diameter is 0.38mm or following ballpoint pen, as the look material, use is by mixing the look material that two or more pigment with the different form and aspect demonstration of C.I. title are modulated into black, thereby can obtain when being used for ball diameter is 0.38mm or following, particularly when 0.28mm or following ballpoint pen, can suppress the wearing and tearing of ball bearing seat, it is level and smooth and can write for a long time to write sense, can form the used with water ball-point pens black ink composition of retouching line and the water-base ink ballpoint pen of full concentration simultaneously.
Embodiment
The present invention will be described in more detail below by embodiment and comparative example, but the present invention is not limited to following embodiment etc.
Use the look material that stirrer forms modulation as shown in table 1 below (by mix two or more have pigment that the different form and aspect of C.I. title show obtain black modulation look material A～E) and each ink composition according to as the combined group one-tenth of following table 2 and table 3 (mixing unit: weight %, total amount 100 weight %) be uniformly dispersed.Obtain aqueous ink composition corresponding to embodiment 1～14, comparative example 1～6, reference example 1.
At resulting each aqueous ink composition, the pH meter F-24 that uses the hole field to make manufacturing measures ink pH value (25 ℃).
In addition, at resulting various aqueous ink compositions, use the axis body of the UM-151 of Mitsubishi's pencil manufacturing, resulting aqueous ink composition and ink are followed (the ball material: ballpoint tip supersteel) (bullet cut or aciculiform that body is filled into the various ball diameters that are equipped with shown in table 2 and table 3, nib material: in ink barrel stainless steel) (pipe of the PP system of internal diameter: 3.4mm and the joint component of receiving the PP system on the ball-point pen tip), by centrifugal treating (500G, 5 minutes) deaeration, be then assembled in the ballpoint pen, retouch line concentration by following evaluation method, wearability, write sense, various handwriting tests such as time dependent writing property.
In various handwriting tests, 10 (5 of bullet cuts, 5 on pin type) ballpoint pens are estimated.
In addition, the Writing method of retouching in the evaluation method of line concentration, wearability adopts mechanical handwriting test to carry out, and the condition of writing is:
When ball diameter is not 0.18mm, with 100gf, write angle 60 degree, writing speed 4.5mm/min the condition of writing,
When ball diameter is 0.18mm, with 50gf, write angle 70 degree, writing speed 4.5mm/min the condition of writing,
Carrying out spiral writes.
Its result is shown in following table 2 and table 3.
Retouch the evaluation method of line concentration
Adopt mechanical handwriting test to write, resulting concentration of writing the black of retouching line is compared with the line of retouching of ballpoint pen under the same book write condition that uses the benchmark ink that has cooperated following composition, and estimate according to following benchmark.
The ballpoint pen that cooperates the benchmark ink:
With reference example 1 (cooperate with benchmark ink, carbon black content 7%) synthetic ink be filled into the ballpoint pen that obtains in the handwriting identical with the employed handwriting pattern of comparative example with embodiment.
Metewand:
◎: compare with the line of retouching of benchmark ink, the concentration of black is equal or denseer,
Zero: compare with the line of retouching of benchmark ink, the concentration of black is low slightly, but have sufficient concentration,
△: compare with the line of retouching of benchmark ink, the concentration of black is low, sufficient a little inadequately,
*: compare with the line of retouching of benchmark ink, the concentration of black is low, and is impracticable.
The evaluation method of wearability
Adopt mechanical handwriting test to write, measure average Writing distance, and estimate according to following metewand.
Metewand:
◎: can write fully no problemly.
Zero: the word of writing has the style of calligraphy characterized by hollow strokes slightly, can write and stop pen.
△: the word of writing has the style of calligraphy characterized by hollow strokes, can write and stop pen.
△ △: at least 1 or many flow decline occurs, and it is thin out to retouch line, can not write.
*: wearing and tearing significantly occur, all promptly can not write halfway.
Write the evaluation method of sense
By drawing a circle, and write sense according to following metewand evaluation.
Metewand:
◎: very level and smooth,
Zero: level and smooth,
△: have hang the paper sense,
*: poor.
The evaluation method of time dependent writing property
Resulting each ballpoint pen after placing for 2 weeks upside down under 50 ℃, is confirmed by drawing a circle, and estimated according to following metewand.
Metewand:
◎: can write from the beginning no problemly.
Zero: the style of calligraphy characterized by hollow strokes is arranged during beginning slightly, but within the number of times 2 times of drawing a circle, recover normal.
△: the number of times of drawing a circle has the style of calligraphy characterized by hollow strokes about 10 times, recovers normal then.
*: draw a circle number of times 20 times or more times have the style of calligraphy characterized by hollow strokes.
Table 1
In last table 2 and table 3,
*1～
*14 is as described below.
*1:MCF-88 (Mitsubishi Chemical Ind's manufacturing)
*2: propylene glycol
*3: Diethylene Glycol
*4: ヶ Le ザ Application (three brilliant companies make)
*5: ジ ュ Application ロ Application PW-111 (Japanese pure medicine company make)
*6: Off ォ ス Off ァ ノ-Le RD-510Y (manufacturing of Dong Bang chemical company)
*7: Off ォ ス Off ァ ノ-Le RS-610 (manufacturing of Dong Bang chemical company)
*8:Chemitech (ヶ ミ テ ッ Network) BT-G (manufacturing of Chemipro company)
*9: バ ィ ォ デ Application S (big and chemical industrial company makes)
*10:Aluminum C (Japanese AEROSIL company make)
*11:TTO-55A (the former industry corporate system of stone is made)
*12: trolamine
*13: the amino methyl propyl alcohol
*14:N4PLUS (manufacturing of Beckman Coltar company)
By the result of last table 1～table 3 as can be known, the aqueous black composition for ink that satisfies the embodiment 1～14 of condition of the present invention promptly be used in ball diameter be the thin word of 0.38mm or following (ball diameter is 0.38mm, 0.28mm, 0.18mm specifically) with in the ballpoint pen, also have and good retouch line concentration, wearability, write sense and time dependent writing property.
On the other hand, it is 0.38mm or following thin word when using ballpoint pen that the black water composition for ink of the comparative example 1～6 of the condition of discontented unabridged version invention is used for ball diameter, retouches line concentration, wearability, writes sense, time dependent writing property is all relatively poor.In addition, reference example 1 is that ball diameter is the non-thin word ballpoint pen of 0.5mm, at this moment, because ball diameter is big, thereby retouches the evaluation of line concentration and wearability etc. and unsatisfactory.
Claims (5)
1. used with water ball-point pens black ink composition, it is used for ball diameter is the following ballpoint pen of 0.38mm, and contain water, look material, water-soluble solvent at least, wherein, as described look material, use by mixing carbon black below the 3 weight % and two or more to have the look material that pigment dyestuff that the different form and aspect of colour index popular name show is modulated into black.
2. used with water ball-point pens black ink composition as claimed in claim 1 wherein, contains the aluminum oxide of 0.002～2 weight % and at least a kind particulate of titanium oxide in composition for ink.
3. used with water ball-point pens black ink composition as claimed in claim 1, wherein, the median size of pigment is below the 150nm.
4. used with water ball-point pens black ink composition as claimed in claim 2, wherein, the median size of pigment is below the 150nm.
5. water-base ink ballpoint pen wherein, is filled with each described used with water ball-point pens black ink composition of claim 1～4 in ball diameter is ballpoint pen below the 0.38mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP350151/2004 | 2004-12-02 | ||
| JP2004350151A JP2006160793A (en) | 2004-12-02 | 2004-12-02 | Black ink composition for water-based ballpoint pen and water-based ballpoint pen |
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| Publication Number | Publication Date |
|---|---|
| CN1978558A CN1978558A (en) | 2007-06-13 |
| CN1978558B true CN1978558B (en) | 2010-12-01 |
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| JP (1) | JP2006160793A (en) |
| CN (1) | CN1978558B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008231410A (en) * | 2007-02-20 | 2008-10-02 | Fujifilm Corp | Ink composition for stationery, water-based gel ink and water-based marking pen ink using the same |
| JP5557427B2 (en) * | 2008-03-19 | 2014-07-23 | 株式会社パイロットコーポレーション | Ballpoint pen refills placed on the same cylinder type |
| JP5651296B2 (en) * | 2008-09-30 | 2015-01-07 | 株式会社サクラクレパス | Ballpoint pen |
| CN102558968B (en) * | 2011-12-29 | 2013-11-20 | 苏州世名科技股份有限公司 | Ink composition for ball-point pen of which ball diameter is less than 0.5 millimeter |
| CN104592810A (en) * | 2015-02-04 | 2015-05-06 | 韦棋 | Anti-fade environment-friendly black ink |
| JP2016221691A (en) * | 2015-05-27 | 2016-12-28 | 株式会社パイロットコーポレーション | Ball point pen refill group arranged in the same model of barrels |
| JPWO2021131899A1 (en) * | 2019-12-24 | 2021-07-01 | ||
| JP2021181515A (en) * | 2020-05-18 | 2021-11-25 | 三菱鉛筆株式会社 | Ink composition for water-based ballpoint pens |
| JP7854269B2 (en) * | 2021-04-20 | 2026-05-01 | 三菱鉛筆株式会社 | Water-based ballpoint pen ink composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384859A (en) * | 1999-11-05 | 2002-12-11 | 樱花彩色产品株式会社 | Water-based ink for ballpoint pens |
| CN1470576A (en) * | 2002-07-25 | 2004-01-28 | 明基电通股份有限公司 | Pigment-based black ink |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2593968B2 (en) * | 1991-02-08 | 1997-03-26 | 新日鐵化学株式会社 | Solar heat shielding black paint composition and coated structure |
| JPH10166780A (en) * | 1996-12-12 | 1998-06-23 | Mitsubishi Pencil Co Ltd | Aqueous gel ink ballpoint pen |
| JP2002020647A (en) * | 2000-07-05 | 2002-01-23 | Dainippon Ink & Chem Inc | Black pigment composition |
| 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 |
| JP2004291632A (en) * | 2003-03-07 | 2004-10-21 | Mitsubishi Pencil Co Ltd | Aqueous ballpoint pen |
-
2004
- 2004-12-02 JP JP2004350151A patent/JP2006160793A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384859A (en) * | 1999-11-05 | 2002-12-11 | 樱花彩色产品株式会社 | Water-based ink for ballpoint pens |
| CN1470576A (en) * | 2002-07-25 | 2004-01-28 | 明基电通股份有限公司 | Pigment-based black ink |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1978558A (en) | 2007-06-13 |
| JP2006160793A (en) | 2006-06-22 |
| TW200626684A (en) | 2006-08-01 |
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