CN1247386C - Ball pen using with water-base ink - Google Patents

Abstract

A ballpoint pen having a ballpoint pen tip using a metal tube, an ink reservoir, a joint which connects the ballpoint pen tip and the ink reservoir and has an ink back leaking-preventing mechanism having a metal ball and a receiving seat, wherein the ballpoint pen is filled with a pseudo-plastic water based ink whose viscosity is 20 to 600 mPa.sec at a shear rate of 38.4 sec<-1> and is 10 to 120 mPa.sec at a shear rate of 384 sec<-1> (25 DEG C) and an ink follower which is filled at the rear end of the ink in the ink reservoir and whose value of tan delta of modulus is 0.2 to 2.0 (25 DEG C) in the whole range of angular frequency of 0.1 to 650 rad/sec, and the ballpoint pen causes almost no blobbing and starving and produces stable ink discharge and further causes no back leaking of the ink even if the pen is left standing upward with a cap off.

Description

Use the ball pen of water-based inks

Technical field

The present invention relates to a kind of ball pen that uses water-based inks.More specifically, the present invention relates to a kind of water-base ballpoint that uses Pseudoplastic water-base printing ink.

Background technology

About using water-based inks and adopting the ball pen at ball pen tip, some of the recommendations (the unsettled open No.7-299988 of Japanese patent application etc.) were disclosed, make in the following way at this ball pen tip: near the summit, be used as the inside protrusion that receives ball base by inside extrusion deformable metal tubule to form, in metal thin tube, put into ball and inwardly clog the edge of opening on summit then.

Yet, because these use water-based inks and adopt the ball pen of metal thin tube to use the leakage agent backward that prevents that grease makes, the problem that exists is to prevent that the effect of leaking backward is also unreliable, leak with when pen is placed with point upward, causing gradually backward, with in addition under the situation of writing usually, promptly wherein the tip is downward, be used to prevent that the grease that leaks backward is bonding and along with the consumption of printing ink, be retained on the inwall of ink cavity, therefore during writing, be used to finally prevent that the grease that printing ink leaks backward from reducing, cause the leakage backward of printing ink.In addition, when filling many greases so that preventing that leakage agent has no lack of backward, greatly reduce the discharge rate of printing ink, therefore, when under speed, writing fast, can cause the situation of pause greater than common speed twice.

In addition, do not use therein under the situation of printing ink,, division and pause take place easily in the line of describing when the suitable viscosity number of control makes that printing ink does not ooze from pen tip with the form of drop when not writing with shear thinning performance.On the contrary, have at printing ink under the situation of such viscosity number, think that wherein writing quality is a weight, when not writing, printing ink is easy to ooze with the form of drop, therefore is difficult to keep the quality of balance.

Then, the inventor has advised using the joint that contains check valve mechanism between ball pen tip and ink cavity, the printing ink that has the shear thinning performance with use, with in the ball pen of above-mentioned use water-based inks, prevent the leakage backward (the unsettled open No.8-230374 of Japanese patent application) of printing ink perfectly.

Yet according to research subsequently, the problem of existence is in adopting this ball pen that prevents leak valve mechanism backward, can prevent effectively that the common of printing ink from leaking backward, but in the falling of ball pen, can not prevent the scattering of printing ink from the ink cavity rear end.Even contain the conventional ink follower of forming by grease (follower) in the rear end of ink cavity, and contain joint, can not change this situation with check valve mechanism.In addition, when using the conventional ink follower of being made up of grease, have such problem, promptly the servo-actuated of printing ink (followability) is relatively poor in writing fast.In addition, in the ball pen of this use water-based inks, such ball pen is not provided, they satisfy all nonnegotiable demands for ball pen, as attenuate (feathering), the stability and because the light pause of impacting that printing ink is discharged of the discharge rate of the feel of writing, printing ink, bespatter, delineation lines.

Known use austenitic stainless steel SUS304 is as the material as the most advanced and sophisticated metal thin tube of routine.The carbon content of SUS304 material is defined as 0.08% or littler and typically be 0.03% or bigger.Yet the inventor finds, problem is when pigment during as colouring agent, along with wearing and tearing owing to the received block of writing, by carbon content be 0.03% or the ball received block made of bigger material be easy to cause the sinking of ball.

The objective of the invention is to address the above problem and provide the ball pen that uses water-based inks, this ball pen can be write smoothly when touching, wherein be difficult to take place bespatter and division, when under with common speed twice or bigger speed, writing fast, the situation that can occur pausing not, even the stable discharge of printing ink can last till last and upwards place pen is static when the cap for brush is closed, printing ink can not leak backward yet.

Summary of the invention

The invention provides following ball pen to address the above problem.

(1) a kind of ball pen that uses water-based inks comprises:

The ball pen tip, it is made in the following way: form the ball chamber, this ball chamber is by near the summit of metal thin tube, be used as the inside protrusion of ball received block with formation by inside extrusion distortion, thereon cut workpiece and make and then ball put into the ball chamber with the filling summit edge of opening;

Ink cavity;

Joint, this joint connects ball pen tip and ink cavity, and contains the mechanism that prevents that printing ink from leaking backward, and this mechanism comprises block piece and received block;

Pseudoplastic water-base printing ink was at 38.4 seconds ^-1Shear rate under, its viscosity is 20-600mPa second and at 384 seconds ^-1Shear rate under, its viscosity is 10-20mPa second (25 ℃); With

Ink follower, it is filled in the rear end of printing ink in the ink cavity and wherein in the gamut of 0.1-650rad/ angular frequency second, the tan δ of modulus is 0.2-2.0 (25 ℃).

(2) ball pen of the use water-based inks of project (1), wherein the surface tension of Pseudoplastic water-base printing ink is 32mN/m or littler (25 ℃).

(3) ball pen of the use water-based inks of project (1) or (2) is wherein under 25 ℃, at 200 seconds ^-1Shear rate under, the viscosity of ink follower is 500-8,000mPa second.

(4) ball pen of any one use water-based inks in project (1)-(3), wherein the metal thin tube at ball pen tip is made up of less than 0.03% austenitic stainless steel carbon content.

Description of drawings

Fig. 1 be one embodiment of the invention the use water-based inks ball pen major part longitudinal sectional view and show the wherein state of pointed end.

Fig. 2 be one embodiment of the invention the use water-based inks ball pen major part longitudinal sectional view and show the wherein state of point upward.

Fig. 3 is the longitudinal sectional view of major part of ball pen of the use water-based inks of one embodiment of the invention.

Fig. 4 is the cross-sectional view of Fig. 3 along the A-A direction.

The specific embodiment

Below with reference to the accompanying drawings, explain the embodiment of the ball pen of water-based inks used according to the invention.

In ball pen of the present invention, recharge (refill) and comprise by joint 22 ball pen most advanced and sophisticated 1 is connected with the ink cavity 10 that is filled with printing ink 11 and ink follower 12 that joint 22 contains the mechanism that printing ink leaks backward that prevents that is installed in the cylinder.

(ball pen tip)

Being used for the present invention uses the tip of the ball pen of water-based inks to make in the following way: form the ball chamber, this ball chamber is by near the summit of metal thin tube, be used as the inside protrusion of ball received block with formation by inside extrusion distortion, thereon cut workpiece and make and then ball put into the ball chamber with the filling summit edge of opening.Referring to Fig. 3 and 4, this ball pen tip comprises ball 2 and is used for the anchor clamps 3 of clamping ball 2, makes in the following way: by near three points terminal, from excircle direction extrusion deformable metal tubule, form ball received block 4 and ink tank 5, put into ball then with filling.

Ball 2 is made up of hard metal, hardened steel or pottery etc.Use austenitic stainless steel, typically SUS304 is used for anchor clamps 3, but especially when pigment is used as colouring agent, and preferably wherein carbon content is defined as 0.03% or littler SUS316 or SUS304L.Generally, will be the metal thin tube that the austenitic stainless steel of 0.03-0.08% is made by carbon content, as the metal thin tube 3 that constitutes ball pen tip with this structure.Yet, the problem that the inventor notices is in the common metal tubule, wearing and tearing along with the ball received block, ball is easy to, and discovery, be 0.03 or the metal thin tube made of littler austenitic stainless steel by using by carbon content, such ball pen tip is provided, even wherein use the printing ink of pigment as colouring agent, ball also sinks hardly.

Such ball pen tip is characterised in that they constitute the ball pen with following advantage: ball pen can be made under low cost and write smoothly under touching, with be easy to make the ball pen that is used to write small character and pen tip and can see and can easily navigate to scale.

(joint)

In the present invention, joint is characterised in that it makes that ball pen is most advanced and sophisticated to be connected with ink cavity, and contains and prevent printing ink leakage mechanism backward, and this mechanism comprises block piece and the received block in the ink flow passage.In embodiment as illustrated in fig. 1 and 2, the receiving element 21 that constitutes received block 25 is inserted in the joint 22, prevent leakage mechanism backward with formation, this mechanism is included in block piece 20 and the received block 25 that is used to prevent the printing ink leakage in the ink flow passage.In this way, because joint contains block piece, as the block piece that is used to prevent that printing ink from leaking, prevent that preferably leakage mechanism comprises metal balls and received block backward, even when a main body makes progress, write and work as the cap for brush when closing with the static placement of pen, also can prevent leakage phenomenon backward, promptly printing ink leaks from the rear end of ink cavity in the direction of embolism 31.

In the joint 22 of embodiment as shown in the figure,,, insert ball pen most advanced and sophisticated 1 inner at the joint front end in the mode of extrusion, with mode, in its back-end, insert receiving element 21 inner with extrusion, with mode,, ink cavity 10 is inserted the outside in its distal side with extrusion.The such joint 22 and the main body of receiving element 21 can be made by elastically deformable synthetic resin.

In addition, provide valve chamber 23 and block piece 20 looselys that will be used for preventing leaking backward are bonded on valve chamber at the mid portion of joint 22.Block piece 20 is higher than the movable blocking member of printing ink 11 by proportion, and preferable alloy ball, particularly stainless steel ball are formed.Owing to form protrusion 24 in the front side of valve chamber 23, when the following time of most advanced and sophisticated side direction of a main body, ball block piece 20 locks onto on the protrusion 24 and printing ink flow between protrusion in the ink feed paths 6 the ball pen tip 1, therefore can write.

In addition,, provide taper or spherical received block 25,, receiving element 21 is inserted in the rear end of joint 22 in the mode of extrusion in the front side of receiving element 21.Therefore, when on the most advanced and sophisticated side direction of a main body, block piece 20 and received block 25 closely contacts to seal printing ink, and when upwards writing, even used up the printing ink of ball below 2, printing ink can not leak backward like this.

(printing ink)

It was Pseudoplastic water-base printing ink that the present invention is used to use the printing ink of water-based inks ball pen, at 38.4 seconds ^-1Shear rate under, its viscosity is 20-600mPa second and at 384 seconds ^-1Shear rate under, its viscosity is 10-120mPa second (25 ℃), and was preferred, at 38.4 seconds ^-1Shear rate under, its viscosity is 50-350mPa second and at 384 seconds ^-1Shear rate under, its viscosity is 15-80mPa second (25 ℃).By using above-mentioned Pseudoplastic water-base printing ink, in writing with ball pen, by rotation at tip place ball, shearing force is applied on the printing ink, wherein the tip is made to reduce the viscosity of printing ink by metal tube, ball pen as the use water-based inks is the same like this, can smoothly write to obtain excellent person's handwriting on paper.In addition, because the viscosity of printing ink is higher when not writing, and can prevent the bespatter of printing ink from pen tip, can directly printing ink be filled in the ink cavity like this, therefore the structure of pen can be simplified and remaining printing ink can be observed by the transparent material that use is used for ink cavity.If at 38.4 seconds ^-1Viscosity under the shear rate is above 600mPa second or at 384 seconds ^-1Viscosity under the shear rate surpasses 120mPa second, when writing fast with the twice of common speed or more times, and printing ink servo-actuated deterioration.In addition, also cause the division (wherein delineation lines splits into the phenomenon of a plurality of lines) and the bespatter of delineation lines easily.On the other hand, if at 38.4 seconds ^-1Viscosity under the shear rate is less than 20mPa second or at 384 seconds ^-1Viscosity under the shear rate is less than 10mPa second, causes that from pen tip the bespatter of printing ink and delineation lines are easier to defile and become unclear easily.

In addition, owing to be that 32mN/m or littler (25 ℃) strengthen the wetability of printing ink to the tip by the surface tension of controlling above-mentioned Pseudoplastic water-base printing ink, the intensity of delineation lines or width can scatterings, and this has guaranteed stable printing ink discharge rate.Particularly, because the diameter of ball pen ink feeding-passage that contains the tip of using metal tube is much smaller than the diameter at shelly tip, the mobility of printing ink becomes slow.Therefore, shortcoming be when impact be applied on the main body and printing ink leave ball around the time, be easy to cause the pause of delineation lines.When the high relatively capillary conventional printing ink of having of adopt filling, such pause (below be called because the light pause of impacting) takes place, require attempting writing the quality of some words up to the recovery delineation lines.Yet, owing to when the surface tension of the printing ink of filling is 32mN/m or littler (25 ℃), strengthened the wetability of printing ink, even take place because the light pause of impacting to most advanced and sophisticated inwall, the recovery of delineation lines quality is also very fast, has therefore greatly reduced the material injury to the user.

On the other hand, when surface tension surpassed 32mN/m (25 ℃), printing ink reduced the wetability at tip.Particularly, in the ball pen that its tip is made by metal thin tube, when writing, air is incorporated into the inside of pen tip by the summit from pen tip, therefore reduced the stability (being called the effect of Fluid Pulsation phenomenon) of flow in writing, so such scope is not preferred.

In the adjusting of the viscosity that is used for water-based inks of the present invention, as needs, can be with the viscosity-control additive blend.Viscosity-control additive comprises, for example the alkali salt of the sodium salt of the derivative of the copolymer of the alkali salt of the alkali salt of alkali salt, styrene and the maleic acid of the alkali salt of polyacrylic acid or polymethylacrylic acid, acrylic or methacrylic acid copolymer, vinylacetate and crotonic acid copolymer, the modified polyvinylalcohol that contains vinyl alcohol, methyl vinyl ether and maleic acid, polyalkylene oxide, methylcellulose, hydroxy ethyl cellulose, carboxymethyl cellulose, gum arabic, shellac, PEO, mosanom, bassora gum, guar gum, Karaya Gum etc.

The colouring agent that is used for water-based inks of the present invention comprises all pigment at water dissolving or the dyestuff that disperses, titanium oxide and conventional inorganic and organic pigment, passes through the false pigment with dyestuff and the preparation of white plastic pigments coloured resinemulsion.As concrete example, dyestuff comprises acid dyes,, water blue #105 red as the yellow #6-C of Eosine, Phloxine, water, acid, Brilliant Blue FCF, Nigrosine NB, direct dyes, as directly black 154, direct sky blue 5B, purple BB, basic-dyeable fibre such as rhodamine and crystal violet.Inorganic pigment comprises, for example carbon black, metal dust.Organic pigment comprises, for example azo lake, insoluble azo colour, chelate AZOpigments, phthalocyanine pigments, perylene pigment, perinone pigment, anthraquinone pigment, quinacridone pigment, dyestuff color lake, nitropigments, nitroso pigments.Particularly, they comprise inorganic pigment, as carbon black, titanium is black, zinc oxide, red ferric oxide, chromium oxide, Black Rouge, cobalt blue, yellow ferric oxide, chrome green, zinc sulphide, lithopone, cadmium yellow, bright red, cadmium red, chrome yellow, the molybdate orange, zinc chromate, strontium chromate, white carbon, clay, talcum powder, ultramarine, blanc fixe, blanc fixe, calcium carbonate, white lead, Prussian blue, manganese violet, aluminium powder, brass powder, C.I. pigment blue 1, C.I. pigment blue 15, C.I. pigment blue 17, C.I. pigment blue 27, C.I. paratonere 5, C.I. paratonere 22, C.I. pigment red 38, C.I. pigment red 48, C.I. pigment red 49, C.I. paratonere 53, C.I. paratonere 57, C.I. pigment red 81, C.I. paratonere 104, C.I. pigment red 146, C.I. paratonere 245, C.I. pigment yellow 1, C.I. pigment yellow 3, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 17, C.I. pigment yellow 34, C.I. pigment yellow 55, C.I. pigment yellow 74, C.I. pigment yellow 83, C.I. pigment yellow 95, C.I. pigment yellow 166, C.I. pigment yellow 167, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 16, C.I. pigment violet 1, C.I. pigment violet 3, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 50, C.I. pigment Green 7.

In addition, the use amount of colouring agent depends on the intensity of delineation lines suitably and changes, and is preferably 0.1-40wt%, based on total ink.

In addition, the water-soluble liquid medium that is used to improve the stability of writing sense of touch and passing in time of blend comprises polyalcohol such as propane diols, glycerine, polyethylene glycol, the alkylene oxide adduct of glycerine and alkylene oxide adduct of trihydroxy propane and composition thereof.

In addition, comprise polyoxyethylene as lubricant and the surfactant that is used for control surface tension force and improves the blend of the wetting agent write sense of touch, the derivative of polyoxyethylene-polyoxypropylene such as polyoxyethylene lauryl ether, glycerine, the derivative of diglycerol or polyglycereol such as distearyl acid four glyceride, the derivative of carbohydrate such as single oleic acid Isosorbide Dinitrate, the surfactant that contains fluorinated alkyl is as perfluoralkyl phosphate, the polyether-modified siloxanes such as the polyethylene glycol adducts of dimethyl polysiloxane, hardened castor oil, the phosphate base surfactant, fluorine based surfactant, soft soap etc.

In addition, about other additive, what use is water-soluble polymer as pigment dispersing agent, as the ammonium salt of the ammonium salt of styrene-maleic acid copolymer, styrene-propene acid copolymer with as preventing the reduced sugar that mainly contains maltitol of volatile material, mainly containing the reduced sugar, reduction compound sugar, reduction maltose-compound sugar, reduction dextrin, reduction maltodextrin, alpha-cyclodextrin, beta-schardinger dextrin-, malt-base cyclodextrin etc. of D-sorbite.

As needs, use respectively BTA, saponarin etc. as antirust agent and potassium hydroxide, calcium phosphate, amino methyl propyl alcohol etc. as pH conditioning agent and sodium omadine, 1,2-[4-morpholinodithio quinolines etc. are as anticorrisive agent.

Can as needs, mix, stir and filter mentioned component, and obtain to be used for the water-based inks of ball pen of the present invention easily by dissolving and heating.In addition, compare with other method of preparation ball pen water-based inks, if it is aspect that does not pay particular attention to and the condition such as the temperature that is used to stir with filter process are in the actual range of ball pen water-based inks, also no problem.

(ink follower)

The present invention is used to use the ink follower of water-based inks ball pen to be limited to such material, and wherein in the gamut of 0.1-650rad/ angular frequency second, tan δ value (it is the ratio of loss modulus to storage modulus) is 0.2-2.0 (25 ℃).Ink follower with specific like this tan δ value has stable servo-actuated, be independent of the ink flow speed and the writing rate of the ball pen that is used for wherein using metal thin tube, with can wipe printing ink from the ink cavity inwall well, during writing, a part of servo-actuated agent does not adhere on the wall and is retained on the wall simultaneously.In addition, ink follower can't the position of scattering and printing ink and ink follower can not be put upside down owing to being applied to the impact on the main body.In addition, the servo-actuated agent also can have Elementary Function, promptly prevents the printing ink volatilization by cutting off printing ink and outside atmosphere.

In addition, use therein in the ball pen of metal thin tube, the diameter of ink feed paths is much smaller than the diameter at shelly tip, so the mobility of printing ink becomes slow, when with common speed twice or more when speed is doubly write, cause the jump of delineation lines easily like this.In addition, use routine to prevent to leak backward in the ball pen of grease therein, the servo-actuated of grease self is relatively poor, and therefore the jump of delineation lines often takes place.On the other hand, such ball pen does not have negative effect to the servo-actuated of printing ink, therefore servo-actuated does not reduce in writing fast, do not produce the jump of delineation lines, this ball pen uses the leakage mechanism backward that prevents that comprises block piece and received block, with the use ink follower, wherein in the gamut of 0.1-650rad/ angular frequency second, the tan δ value of modulus is 0.2-2.0 (25 ℃).

If in the particular range of 0.1-650rad/ angular frequency second or in its gamut, the tan δ value of modulus is less than 0.2 (25 ℃), the elasticity of ink follower becomes quite by force and therefore is difficult to printing ink is packed in the ink cavity, causes carrying out actual use.

In addition, if in the particular range of 0.1-650rad/ angular frequency second or in its gamut, tan δ value surpasses 2 (25 ℃), and ink follower is when impact being applied on the main body to the consumption response problem relatively poor and that exist of printing ink in the ink cavity, is easy to scattering.

In addition, if under 25 ℃, at 200 seconds ^-1Shear rate under, preferably the viscosity with ink follower is set at 500-8,000mPa second, more preferably 1,000-6,000mPa second, ink follower can guarantee that printing ink has excellent servo-actuated, with can prevent scattering, wherein, be easy to produce this scattering when impacting when being applied on the main body.If under 25 ℃, at 200 seconds ^-1Shear rate under, the viscosity of ink follower is less than 500mPa second, the situation that may occur is when impacting when being applied on the main body, ink follower is easy to scattering, thereby causes that printing ink leaks out a main body, therefore pollutes surround such as clothes.In addition, if under these conditions, the viscosity of ink follower surpasses 8, and 000mPa second, the servo-actuated agent is difficult to ink flow during writing, so may cause the pause of delineation lines.

Ink follower of the present invention is characterised in that in the gamut of 0.1-650rad/ angular frequency second the tan δ value of modulus is 0.2-2.0 (25 ℃), and is preferred, it is characterized in that in above-mentioned scope, and tan δ value is 0.2-2.0 (25 ℃) and under 25 ℃, at 200 seconds ^-1Shear rate under, the viscosity of ink follower is 500-8,000mPa second.Can by select suitably base oil and as the kind of the thickener of ink follower and blending amount and as needs, by selecting as described below creating conditions suitably, obtain the such feature of ink follower of the present invention.

Preferably use under 25 ℃, in 1-400 second ^-1Shear rate under, viscosity is 5Pa second or littler water-insoluble organic solvent, as the base oil of ink follower of the present invention.The performance that is used as the base oil of ink follower of the present invention is insoluble naturally or indissoluble in water, yet viscosity number is to prevent the greatest factor of printing ink from the base oil of rear end leakage effect for obtaining, and this is a feature of the present invention.Almost show Newtonian viscosity (its medium viscosity is constant, and is irrelevant with shear rate) as the solvent of base oil, like this can be in 1-400 second ^-1Any shear rate under, measure viscosity and use such solvent, under 25 ℃, the viscosity of this solvent is 5Pa second or still less, preferred 2Pa second or littler, more preferably 0.5-1.5Pa second.In the high-rate of shear scope, comprise the ink follower that viscosity surpasses the base oil of 5Pa second and have high viscosity, it almost can not be filled in the ink cavity like this.In addition, when writing, use the printing ink servo-actuated reduction of the ball pen of such ink follower, therefore the problem that produces is to be easy to cause pause.

When mixing the base oil of some kinds, the control viscosity number is in above-mentioned scope.Specific solvent as base oil comprises polybutene (its molecular weight is about 600 or bigger), mineral oil, silicone oil etc.Consider the long-term behaviour of ball pen, the solvent that evaporate into a few wt% degree in two or three years is not preferred, as number-average molecular weight less than 600 polybutene.Preferably be about 1wt% or littler solvent at following condition devolatilization: single or mixed base oil that will about 10g is placed in that diameter is about in the Petri culture dish neutralization in the open of 40mm in the atmosphere, under 50 ℃, leaves standstill 14 days.In addition, the solvent that preferably owing to oxidation viscosity is not increased is not preferred.

Trade name), polybutene HV-15 (Nippon PetrochemicalsCo. the concrete industrial products of polybutene comprise Nissan polybutene 200N, polybutene 30N (NOFCorporation:, Ltd.: trade name), polybutene 35R (Idemitsu Kosan Co., Ltd.: trade name).

The concrete industrial products of mineral oil comprise Diana technical oil MC-32S, MC-W90 (Idemitsu Kosan Co., Ltd.: trade name).

The concrete industrial products of silicone oil comprise TFS451 series, TFS456 series, TFS458 series (TOSHIBA Silicone Co., Ltd.: trade name).

About ink follower of the present invention, preferably use for example calcium salt of phosphate of thickener, fine particle silica, polystyrene-poly ethylene butene-polystyrene block copolymer, polystyrene-poly ethylene, propylene-polystyrene block copolymer, the hydrogenation styrene butadiene ribber, polystyrene-poly ethylene butene-polyolefin crystal block copolymer, polyolefin crystal-polyvinylidene-polyolefin crystal block copolymer, polystyrene-butadiene rubber-polystyrene block copolymer, styrene-isoprene rubber-polystyrene block copolymer, dialkyl group acetyl aluminum alkoxide.In them two or more can be used in combination.

These thickeners generally can be divided into polymer base and inorganic (or non-polymer) base; Polymer base thickener is divided into polystyrene-poly ethylene butene-polystyrene block copolymer, polystyrene-poly ethylene, propylene-polystyrene block copolymer, the hydrogenation styrene butadiene ribber, polystyrene-poly ethylene butene-polyolefin crystal block copolymer, polyolefin crystal-polyvinylidene-polyolefin crystal block copolymer, polystyrene-butene rubber-polystyrene block copolymer, styrene-isoprene rubber-polystyrene block copolymer and inorganic (non-polymer) basic thickener are divided into the calcium salt of phosphate, fine particle silica and dialkyl group acetyl aluminum alkoxide.

The concrete industrial products of the calcium salt of phosphate comprise Crodax DP-301LA (CRODA JAPANK.K./trade name).

Fine particle silica is divided into hydrophily fine particle silica and hydrophobicity fine particle silica, the concrete industrial products of hydrophily fine particle silica comprise AEROSIL-300, AEROSIL-380 (Nippon Aerosil Co.Ltd./trade name), and the concrete industrial products of hydrophobicity fine particle silica comprise AEROSIL-974D, AEROSIL-972 (NipponAerosil Co. Ltd./trade name).

The concrete industrial products of polystyrene-poly ethylene butene-polystyrene block copolymer comprise kraton FG-1901X, kraton G-1650, kraton G-1651, kraton G-1652, kraton G-1654X, kraton G-1657X, kraton G-1726X, kratonFG-1092X (Shell Japan Ltd./trade name), SEPTON 8007, SEPTON 8004, SEPTON 8006 (Kuraray Co., Ltd./and trade name), Tuftec M-1943, TuftecM-1911, Tuftec M-1913 (Asahi Kasei Corporation/ trade name).

The concrete industrial products of polystyrene-poly ethylene, propylene-polystyrene block copolymer comprise kraton G-1730 (Shell Japan Ltd./trade name), SEPTON 2002, SEPTON2005, SEPTON 2006, SEPTON 2007, SEPTON 2043, SEPTON 2063, SEPTON2104, SEPTON 4033, SEPTON 4055, SEPTON 4077 (Kuraray Co., Ltd./trade name).

The concrete industrial products of hydrogenation styrene butadiene ribber comprise DYNARON 1320P, DYNARON 1321P (JSR Corporation/ trade name), Tuftec H1062, TuftecH1052, TuftecH1141, Tuftec H1041, Tuftec H1053, TuftecH1043, Tuftec H1272 (Asahi Kasei Corporation/ trade name).

The concrete industrial products of polystyrene-poly ethylene butene-polyolefin crystal block copolymer comprise DYNARON 4600P (JSR Corporation/ trade name).

The concrete industrial products of polyolefin crystal-polyvinylidene-polyolefin crystal block copolymer comprise DYNARON 1321P (JSR Corporation/ trade name).

The concrete industrial products of polystyrene-butadiene rubber-polystyrene block copolymer comprise kraton D-1101, kraton D-1102, kraton D-1155, kraton D-KX405, kraton D-KX408, kraton KX-410, kraton D-KX414, kraton D-KX65S, kraton D-KX403P, kraton D-KX139S, kraton D-KX155P, kratonD-1118, kraton D-1116, kraton D-1188X, kraton D-1122X, kratonD-1300X, Cariflex TR-1101S, Cariflex TR-1184, Cariflex TR-1186, Cariflex TR-4113P, Cariflex TR-4122P, Cariflex TR-4260P (ShellJapan Ltd./trade name), Tufprene-A, Tufprene-125, Tufprene-126, Tufprene-315, Solprene-T-411, Solprene-T-414, Solprene-T-416, Solprene-T-406, Solprene-T-475, Asaprene-T-475, Asaprene-T-420, Asaprene-T-430, Asaprene-T-431, Asaprene-T-432, Asaprene-T-436 (Asahi Kasei Corporation/ trade name), JSR-TR-1000, JSR-TR-2000, JSR-TR-2003, JSR-TR-2250, JSR-TR-2601, JSR-TR-2606, JSR-TR-2787, JSR-TR-2827, JSR-TR-2600, JSR-TR-1086, JSR-TR-1600 (JSR Corporation/ trade name), Europrene SOLT-161 (Tosoh Corporation/ trade name).

The concrete industrial products of styrene-isoprene rubber-polystyrene block copolymer comprise kraton D-KX-400P, kraton D-1113X, kraton D-1114X, kratonD-1125X, kraton D-1320X, kraton D-1107, kraton D-1112, kratonD-1113, kraton D-1117, kraton D-1119, kraton D-1124, kratonD-1161, kraton D-1111, kraton D-KX406, kraton D-KX603, CariflexTR-1107 (Shell Japan, Ltd./trade name), Solprene-418 (Asahi KaseiCorporation/ trade name), JSR-SIS-5000 (JSR Corporation/ trade name), Quintac-3421, Quintac-3422, Quintac-3435, Quintac-3530, Quintac-3450 (Nippon Zeon Co.Ltd./trade name).

The concrete industrial products of dialkyl group acetyl aluminum alkoxide comprise PLENACTAL-M (Ajinomoto Fine-Techno Co., Inc.).

These thickeners of appropriate amount produce the effect that elasticity or structural viscosity are provided and pass through the control blending amount, can control tan δ value and be 0.2-2.0 (25 ℃).In addition, as needs, clay thickener or metallic soap can be used with above-mentioned thickener.Use amount about these thickeners, when they use separately, the preferred respectively calcium salt that uses the phosphate of 2-25wt%, the fine particle silica of 3-12wt%, polystyrene-poly ethylene butene-polystyrene block copolymer of 0.3-10wt% and/or polystyrene-poly ethylene, propylene-polystyrene block copolymer, the hydrogenation styrene butadiene ribber of 1.0-20wt%, polystyrene-poly ethylene butene-polyolefin crystal block copolymer of 1.0-25wt% or polyolefin crystal-polyvinylidene-polyolefin crystal block copolymer, 1.0-20wt% (more preferably, polystyrene-butene rubber 1.0-5wt%)-polystyrene block copolymer, 1.0-25wt% (more preferably, the dialkyl group acetyl aluminum alkoxide of styrene-isoprene rubber-polystyrene block copolymer 2.0-20wt%) and 2.0-20wt%.

If the blending amount of every kind of composition is less than above-mentioned quantity, the servo-actuated agent can not have enough viscoplasticity and therefore only owing to lighter impact, ink follower generation scattering causes that also printing ink leaks backward in a main body.In addition, only by a main body is placed in the mode that a summit makes progress, because the variation of environment temperature, the viscosity of servo-actuated agent reduces, and causes that printing ink leaks backward.On the other hand, if blending amount surpasses above-mentioned quantity, in suitable scope, the servo-actuated agent has higher viscoplasticity, and ink follower hardening and the therefore relatively poor servo-actuated of printing ink owing to writing cause the pause of delineation lines like this.

In addition, as needs, thickener auxiliary agent (clay thickener, metallic soap etc.), the servo-actuated improver (surfactant etc.) and the antioxidant that are used for ink follower can blend.Yet some antioxidant have increased tan δ value widely.Therefore, if when not needing blend, even with scheduled volume blend thickener, tan δ value can surpass 2, should be noted blend like this.

In the present invention, being used to use the manufacture method of ink follower of the ball pen of water-based inks can be simple method, wherein when using inorganic thickening agent such as hydrophobic silica, at room temperature, all the components such as base oil, the surfactant that is used for ink follower are mediated in advance, adopted distributor then, mediate as mill and kneader.In addition, when using the polymer that at room temperature dissolves hardly and disperse,, can under the condition of heating, they be stirred and mediate as needs.In addition, also can adopt distributor,,, will be controlled to be 0.2-2.0 (25 ℃) in the tan δ value of 0.1-650rad/ under second by further heating and kneading as mill and kneader.

Particularly, when the tan δ value of the ink follower that uses polymer base thickener and manufacturing during less than desired value, can the employing distributor, as mill and kneader,, make the structural collapse of thickening and improve tan δ value by kneading again.On the other hand, when tan δ value was higher than desired value, by being heated to the glass transition temperature greater than thickener (polymer) again, therefore the thickening mechanism of improving polymer reduced tan δ value to strengthen the thickening structure.In addition, when the tan δ value of the ink follower that uses inorganic thickening agent to make during less than desired value, with base oil dilution ink follower with adjusting viscosity.When tan δ value is higher than desired value, adopt kneader or agitator to disperse thickener again to improve the thickening structure, can reduce tan δ value.

Embodiment

Reference example and Comparative Examples are explained the present invention in detail, but the present invention is not limited to these these embodiment.

Be used for the prescription of embodiment and Comparative Examples and physical property and see Table 1 and table 2.

Following two kinds of joints are used for embodiment and Comparative Examples.

(joint 1): contain by what metal balls was made and prevent the joint of leakage barriers and receiving element backward

(joint 2): do not contain by what metal balls was made and prevent the joint of leakage barriers backward

Following two kinds of ball pen tips are used for embodiment and Comparative Examples.

(most advanced and sophisticated 1): the tip of Zhi Zaoing in the following way: formation ball chamber, this ball chamber is by near the summit of metal thin tube, be used as the inside protrusion of ball received block with formation by inside extrusion distortion, cut workpiece and making thereon, wherein metal thin tube is that 0.016% austenitic stainless steel (SUS316L) is made by carbon content.

(most advanced and sophisticated 2): the tip of Zhi Zaoing in the following way: formation ball chamber, this ball chamber is by near the summit of metal thin tube, be used as the inside protrusion of ball received block with formation by inside extrusion distortion, cut workpiece and making thereon, wherein metal thin tube is that 0.053% austenitic stainless steel (SUS304) is made by carbon content.

The evaluation result of a main body sees Table 3 and table 4 in embodiment and the Comparative Examples.

(evaluation method of a main body and standard)

The measurement of Pseudoplastic water-base ink viscosity value

(1) measurement of viscosity number

Measurement device:

E type rotation viscometer

Viscosimeter model RE100

(by TOKISANGYO CO., LTD. makes)

Measuring condition (frequency dependence):

Cone: 1 ° 34 ' ^*R24

Shear rate: 38.4 seconds ^-1, 384 seconds ^-1

Measuring Time: 600 seconds

Measure temperature: 25 ℃

The measurement of ink follower physical property

(1) measurement of modulus tan δ value

Measurement device:

Dynamic spectrometer RDS-II

(Rheometric Scientific Co.，Ltd.)

Measuring condition (frequency dependence):

Geometry: parallel-plate 50mm  kinetic measurement

Scan type: frequency scanning

Frequency range: 0.06-650rad/ second

Measure at interval: 5 point/decades

Distortion: 100%

Measure temperature: 25 ℃

Atmosphere: in nitrogen

(2) measurement of viscosity number

Measurement device:

E type rotation viscometer

Digital Viscometer DUV-E

(by Tokyo Keiki CO., LTD. makes)

Measuring condition (frequency dependence):

Cone: 3 ° ^*R14

Shear rate: 200 seconds ^-1

Measuring Time: 600 seconds

Measure temperature: 25 ℃

The evaluation of main body

(1) writes sense of touch

Adopt following standard, write sense of touch by writing to estimate with ball pen spiral on paper, the ball diameter of each ball pen is 0.5mm and according to every kind of specification manufacturing.

Zero: the level and smooth and stable sense of touch of writing

△: the coarse and difficult slightly sense of touch of writing

*: coarse and difficult writes sense of touch and chattering and deflection error is arranged

(2) printing ink discharge rate

Adopt following standard, estimate the printing ink discharge rate by writing with ball pen spiral on paper, the ball diameter of each ball pen is 0.5mm and according to every kind of specification manufacturing.

Zero: enough printing ink discharge rates and can clearly observe delineation lines

△: the printing ink discharge rate is less relatively, but can observe delineation lines

*: the printing ink discharge rate is obviously less, is difficult to observe delineation lines

(3) evaluation of bespatter

Adopt following standard, by writing the bespatter situation of estimating with ball pen spiral on paper, the ball diameter of each ball pen is 0.5mm and according to every kind of specification manufacturing.

Zero: almost do not have bespatter

△: less bespatter is arranged, but in the limit that allows

*: bespatter is serious and delineation lines is unclear

(4) evaluation that attenuates of delineation lines

Adopt following standard, by writing the situation of attenuating of estimating with ball pen spiral on paper, the ball diameter of each ball pen is 0.5mm and according to every kind of specification manufacturing.

Zero: phenomenon does not almost attenuate

*: attenuate serious and delineation lines unclear

(5) write fast in the evaluation of servo-actuated

Adopt following standard, under normal speed and under twice speed, estimate delineation lines by arbitrarily writing on based on the paper of iso standard with ball pen, the ball diameter of each ball pen is 0.5mm and according to every kind of specification manufacturing.

Zero: can smoothly and stably write

△: under twice speed, division is arranged when writing

*: under normal speed, division is arranged

(6) stability of printing ink discharge

Adopt following standard, by the tester of writing under the following conditions, write to the end with ball pen spiral on based on the paper of iso standard, and estimate the variation of every 100m discharge rate and the condition of delineation lines, the ball diameter of each ball pen is 0.5mm and according to every kind of specification manufacturing.

Write condition:

Writing speed: 4.5m/min

Write angle: 60 °

Write load: 100g

Zero: discharge rate is stable and to the last pause and intensity are not inhomogeneous

●: the discharge rate varied slightly, but to the last pause and intensity are not inhomogeneous

△: discharge rate irregular slightly and have pause and intensity inhomogeneous

*: discharge rate clearly changes and has more pause and intensity inhomogeneous

(7) because the light pause of impacting

Use and contain diameter and be the ball of 0.5mm and the ball pen of making according to every kind of specification, write and then a summit is upwards dropped on the Japanese cedar plate from the eminence of 5cm at spiral on the paper and (apply gently and impact on the pen), and then write (diameter is about 3cm) with the ball pen spiral.Adopt following standard, estimate the quality of delineation lines in writing again.

Zero: can write again, when spiral is write, not pause within taking turns one

△: can write again, when spiral is write, within three-wheel, not pause

*: when spiral is write, within three-wheel, can not write again

(8) owing to impact the scattering of the printing ink that causes

The ball pen summit that to contain ball that diameter is 0.5mm and make according to every kind of specification upwards drops to the Japanese cedar plate last time that thickness is 2cm from the 1.5m eminence, the main body that range estimation falls.

Adopt following standard, estimate printing ink and scatter to ink cavity degree in addition.

Zero: the interface between not scattering of printing ink and printing ink and the ink follower is clear.

*: clearly observe the scattering of printing ink.

(9) anti-leaks backward

Use and contain diameter and be the ball of 0.5mm and the ball pen of making according to every kind of specification, the summit spiral that makes progress is write up to not writing, static placement then makes progress a summit.After one hour, the leakage situation backward of range estimation printing ink.

Zero: do not observe backward and leak.

*: observe backward and leak.

(10) Jian Duan wearability

Under the following conditions, by writing tester, with containing ball that diameter is 0.5mm and the ball pen of making according to every kind of specification, spiral is write 700m on based on the paper of iso standard, after writing, observe the state of wear of most advanced and sophisticated ball received block by light microscope.

Adopt following standard, estimate the state of wear of most advanced and sophisticated ball received block and the terminal point of writing.

Write condition:

Writing speed: 4.5m/min

Write angle: 60 °

Write load: 100g

Zero: almost do not observe the wearing and tearing of most advanced and sophisticated ball received block and can write 700m.

△: observe the wearing and tearing of most advanced and sophisticated ball received block and can write 500m.

The prescription and the performance of table 1 embodiment printing ink

		Printing ink

1	Printing ink 2	Printing ink 3	Printing ink 4
					Embodiment	Embodiment	Embodiment	Embodiment
Ink colors	Black	Blue	Black						Black
				Colorant pigment	Carbon black Printex25 (trade name of Degussa) pigment	7.00				7.00
Phthalocyanine blue Chromofine indigo plant 4965 (Dainichiseika Color﹠Chemicals Mfg.Co., the trade name of Ltd.) pigment		7.50
					The colouring agent dyestuff	Water is deceived R455 (Orient Chemical Industries, the trade name of Ltd.) dyestuff				7.00
Yellow 6C (Orient Chemical Industries, the trade name of the Ltd.) dyestuff of water			1.00
						The dispersing of pigments agent	Styrene maleic acid resin ammonium salt	2.00			2.00
The styrene acrylic resin ammonium salt		2.30
					Liquid medium		Propane diols	18.00	15.00	15.00
Glycerine		10.00		10.00
						The expoxy propane 4mol adduct of diglycerol				10.00
The volatilization prevention material	Maltitol	5.00	5.00	5.00							5.00
					Surfactant (lubricant)	Soft soap	0.50	0.40		0.50
Ricinoleic acid potassium		0.20	0.40
						Perfluoralkyl phosphate	0.20	0.10
Fluorine-based Arrcostab			0.30	0.20
						Antiseptic	Sodium omadine	0.10	0.10	0.10	0.10
Antirust agent	Saponarin	0.10	0.10	0.10	0.10
						The pH conditioning agent	Nitrogen ylmethyl propyl alcohol	0.30	0.30	0.30	0.20
Viscosity-control additive	Xanthans KELXZAN HP (SANSHO Co., the trade name of Ltd.)	0.30	0.30	0.40	0.20
						Cross-linking type polyacrylic acid Hiviswako 105 (trade name of Wako Pure Chemical Industries Ltd.)		0.10		0.20
	PVP PVP-K90 (GAF Co., the trade name of Ltd.)				5.00
							Ion exchange water	66.50	58.60	70.40	59.50
	Amount to	100.00	100.00	100.00	100.00
						At 25 ℃, 38.4 seconds -1Under ink viscosity (mPa second)	130	200	320	400
At 25 ℃, 384 seconds -1Under ink viscosity (mPa second)	25	40	30	80
					Ink surface tension under 25 ℃ (mN/m)	28.0	30.5	23.5	25.4
Remarks	Printing ink of the present invention	Printing ink of the present invention	Printing ink of the present invention	Printing ink of the present invention

The prescription and the performance of table 2 Comparative Examples printing ink

		Printing ink 5	Printing ink 6	Printing ink 7	Printing ink 8
								Comparative Examples	Comparative Examples	Comparative Examples	Comparative Examples
Ink colors		Black	Blue	Black	Black
						Colorant pigment	Carbon black Printex25 (trade name of Degussa) pigment	7.00		7.00	7.00
Phthalocyanine blue Chromofine indigo plant 4965 (Dainichiseika Color﹠Chemicals Mfg.Co., the trade name of Ltd.) pigment		7.50
					The colouring agent dyestuff		Water is deceived R455 (Orient Chemical Industries, the trade name of Ltd.) dyestuff
Yellow 6C (Orient Chemical Industries, the trade name of the Ltd.) dyestuff of water
						The dispersing of pigments agent	Styrene maleic acid resin ammonium salt	2.00		2.00	2.00
The styrene acrylic resin ammonium salt		2.30
					Liquid medium		Propane diols		15.00	18.00
Glycerine	10.00	10.00		10.00
						The expoxy propane 4mol adduct of diglycerol	10.00			10.00
The volatilization prevention material	Maltitol	5.00	5.00	5.00							5.00
					Surfactant (lubricant)	Soft soap		0.40	0.50	0.50
Ricinoleic acid potassium		0.20
						Perfluoralkyl phosphate		0.10	0.20
Fluorine-based Arrcostab	0.20			0.20
						Antiseptic	Sodium omadine	0.10	0.10	0.10	0.10
Antirust agent	Saponarin	0.10	0.10	0.10	0.10
						The pH conditioning agent	The amino methyl propyl alcohol	0.20	0.30	0.30	0.20
Viscosity-control additive	Xanthans KELXZAN HP (SANSHO Co., the trade name of Ltd.)	0.60			0.10
						Cross-linking type polyacrylic acid Hiviswako 105 (trade name of Wako Pure Chemical Industries Ltd.)	0.10	0.02	0.20
	PVP PVP-K90 (GAF Co., the trade name of Ltd.)	8.00		15.00
							Ion exchange water	56.70	58.98	51.60	64.80
	Amount to	100.00	100.00	100.00	100.00
						At 25 ℃, 38.4 seconds -1Under ink viscosity (mPa second)		650	18	350	30
At 25 ℃, 384 seconds -1Under ink viscosity (mPa second)		80	7	200	8
						Ink surface tension under 25 ℃ (mN/m)		28.6	29.7	30.9	25.5
Remarks		38.4 second -1Following viscosity ↑	38.4 second -1Following viscosity ↓ 384 seconds -1Following viscosity ↓	384 seconds -1Following viscosity ↑	384 seconds -1Following viscosity ↓

↑ be higher than the scope of the invention

↓ be lower than the scope of the invention

The prescription and the performance of table 3 embodiment ink follower

		Servo-actuated agent A	Servo-actuated agent B	Servo-actuated agent C	Servo-actuated agent D
								Embodiment	Embodiment	Embodiment	Embodiment
The ink follower prescription	Base oil: polybutene mean molecule quantity 1350 notes 1				50.0
						Base oil: mineral oil mean molecule quantity 740 notes 2	96.5	92.0	94.0	44.0
	Base oil: polybutene mean molecule quantity 580 notes 3
						Thickener: the calcium salt note 4 of phosphate			3.5
	Thickener: fine particle silica note 5
						Thickener: polystyrene-poly ethylene butene-polystyrene block copolymer note 6	3.0
	Thickener: hydrogenation styrene butadiene ribber note 7			2.5
						Thickener: polystyrene-poly ethylene butene-polyolefin crystal block copolymer note 8				5.0
	Thickener: polyolefin crystal-polyvinylidene-polyolefin crystal block copolymer note 9				1.0
						Thickener: polystyrene-butene rubber-polystyrene block copolymer note 10		7.5
	Thickener: styrene-isoprene rubber-polystyrene block copolymer note 11
						Thickener: dimethyl dioctadecyl ammonium bentonite note 12
	Additive: fluorine based surfactant note 13	0.5	0.5
						The ink follower performance	Tan δ value (25 ℃), 0.06rad/ second	0.86	0.86	0.94	0.55
Tan δ value (25 ℃), 0.25rad/ second	1.08	0.87	0.95	0.58
					Tan δ value (25 ℃), 0.63rad/ second		0.98	0.91	0.90	0.72
Tan δ value (25 ℃), 1.0rad/ second	0.87	0.91	0.89	0.85
					Tan δ value (25 ℃), 4.0rad/ second		0.92	0.94	0.88	1.09
Tan δ value (25 ℃), 6.3rad/ second	0.91	0.96	0.85	1.61
					Tan δ value (25 ℃), 10rad/ second		0.78	1.01	0.81	1.24
Tan δ value (25 ℃), 40rad/ second	0.67	1.05	0.78	1.02
					Tan δ value (25 ℃), 63rad/ second		0.65	1.22	0.81	0.97
Tan δ value (25 ℃), 100rad/ second	0.69	1.42	0.81	0.98
					Tan δ value (25 ℃), 400rad/ second		0.75	1.50	0.83	1.03
Tan δ value (25 ℃), 600rad/ second	0.82	1.55	1.14	0.90
					Tan δ value (25 ℃), 650rad/ second		0.83	1.58	1.15	0.92
200 seconds -1Under viscosity number (mPa second)	5050	3970	3240	6020

The prescription and the performance of table 4 Comparative Examples ink follower

		Servo-actuated agent E	Servo-actuated agent F	Servo-actuated agent G	Servo-actuated agent H
								Comparative Examples	Comparative Examples	Comparative Examples	Comparative Examples
The ink follower prescription	Base oil: polybutene mean molecule quantity 1350 notes 1		99.1		50.0
						Base oil: mineral oil mean molecule quantity 740 notes 2			99.2	19.5
	Base oil: polybutene mean molecule quantity 580 notes 3	97.5
						Thickener: the calcium salt note 4 of phosphate			0.3
	Thickener: fine particle silica note 5	2.5
						Thickener: polystyrene-poly ethylene butene-polystyrene block copolymer note 6
	Thickener: hydrogenation styrene butadiene ribber note 7		0.9	0.4
						Thickener: polystyrene-poly ethylene butene-polyolefin crystal block copolymer note 8
	Thickener: polyolefin crystal-polyvinylidene-polyolefin crystal block copolymer note 9
						Thickener: polystyrene-butene rubber-polystyrene block copolymer note 10				27.0
	Thickener: styrene-isoprene rubber-polystyrene block copolymer note 11				3.0
						Thickener: dimethyl dioctadecyl ammonium bentonite note 12
	Additive: fluorine based surfactant note 13				0.5
						The ink follower performance	Tan δ value (25 ℃), 0.06rad/ second	22.52	0.84	1.51	0.08
Tan δ value (25 ℃), 0.25rad/ second	22.54	0.86	1.53	0.09
					Tan δ value (25 ℃), 0.63rad/ second		24.92	0.92	1.40	0.09
Tan δ value (25 ℃), 1.0rad/ second	27.16	0.99	1.34	0.12
					Tan δ value (25 ℃), 4.0rad/ second		31.85	1.06	1.27	0.13
Tan δ value (25 ℃), 6.3rad/ second	28.49	1.20	1.21	0.24
					Tan δ value (25 ℃), 10rad/ second		25.03	1.28	1.15	0.39
Tan δ value (25 ℃), 40rad/ second	23.99	1.39	1.00	0.41
					Tan δ value (25 ℃), 63rad/ second		22.14	1.63	0.96	0.48
Tan δ value (25 ℃), 100rad/ second	30.39	2.04	1.02	0.53
					Tan δ value (25 ℃), 400rad/ second		31.43	2.99	1.61	0.62
Tan δ value (25 ℃), 600rad/ second	32.64	2.50	2.56	0.74
					Tan δ value (25 ℃), 650rad/ second		32.55	2.50	2.57	0.89
200 seconds -1Under viscosity number (mPa second)	2000	2800	490	12500

Table 3 and 4 note are as follows.

Note 1: polybutene 30N (NOF Corporation: trade name)

Note 2:Diana technical oil PW-380 (Idemitsu Kosan Co., Ltd.: trade name)

Note 3:Nissan polybutene 015N (NOF Corporation: trade name)

Note 4:Crodax DP-30 (CRODA JAPAN K.K.: trade name)

Note 5:AEROSIL-974D (Nippon Aerosil Co.Ltd.: trade name)

Note 6:SEPTON 8007 (Kuraray Co., Ltd.: trade name)

Note 7:Tuftec H1141 (Asahi Kasei Corporation: trade name)

Note 8:DYNARON 4600P (JSR Co., Ltd.: trade name)

Note 9:DYNARON 6200P (JSR Co., Ltd.: trade name)

Note 10:AsapreneT-431 (Asahi Kasei Corporation: trade name)

Note 11:Solprene-418 (Asahi Kasei Corporation: trade name)

Note 12:Benton 34 (Wilbur-ellis CO.LTD.: trade name)

Note 13:FFtop EF-801 (MITUBISHI MATERIALS CORPORATION: trade name)

[table 5] embodiment

	Embodiment

		1	2	3	4	5	6	7	8	9	10
Printing ink												(1)	(2)	(3)	(1)	(1)	(2)	(4)	(4)	(1)	(4)
	Ink follower	A	A	A	B	C	C	B	D	A	B
Joint												(1)	(1)	(1)	(1)	(1)	(1)	(1)	(1)	(2)	(2)
	Most advanced and sophisticated	(1)	(1)	(1)	(1)	(1)	(1)	(1)	(1)	(1)	(1)
(1) writes sense of touch												○	○	○	○	○	○	○	○	○	○
	(2) printing ink discharge rate	○	○	○	○	○	○	○	○	○	○
(3) evaluation of bespatter												○	○	○	○	○	○	○	○	○	○
	(4) delineation lines attenuates	○	○	○	○	○	○	○	○	○	○
(5) servo-actuated in writing fast												○	○	○	○	○	○	○	○	○	○
	(6) stability of printing ink discharge	○	○	○	○	○	○	●	●	●	●
(7) because the light pause of impacting												○	○	○	○	○	○	○	○	○	○
	(8) owing to impact the scattering that causes printing ink	○	○	○	○	○	○	○	○	○	○
(9) anti-leaks backward												○	○	○	○	○	○	○	○	×	×
	(10) Jian Duan wearability	○	○	○	○	○	○	○	○	○	○

[table 6] Comparative Examples

	Comparative Examples
															11	12	13	14	15	16	17	18	19	20	21	22	23
Printing ink	(5)	(6)	(7)	(8)	(1)	(1)	(1)	(3)	(1)	(1)	(2)	(3)	(6)
														Ink follower	A	A	A	A	E	F	G	H	E	A	C	H	F
Joint	(1)	(1)	(1)	(1)	(1)	(1)	(1)	(1)	(2)	(1)	(1)	(1)	(2)
														Most advanced and sophisticated	(1)	(1)	(1)	(1)	(1)	(1)	(1)	(1)	(1)	(2)	(2)	(2)	(2)
(1) writes sense of touch	×	○	×	○	○	○	○	△	○	×	×	△	×
														(2) printing ink discharge rate	×	○	×	○	○	○	○	×	○	△	△	×	△
(3) evaluation of bespatter	○	△	○	△	○	○	△	○	○	○	○	×	△
														(4) delineation lines attenuates	○	×	○	×	○	○	○	○	○	○	○	○	×
(5) servo-actuated in writing fast	×	○	×	○	△	○	○	△	△	○	○	×	○
														(6) stability of printing ink discharge	○	○	○	○	○	○	○	○	○	△	△	○	△
(7) because the light pause of impacting	○	△	△	△	○	○	○	○	○	○	○	△	△
														(8) owing to impact the scattering that causes printing ink	○	○	○	○	×	×	×	○	×	○	○	○	○
(9) anti-leaks backward	○	○	○	○	○	○	○	○	×	○	○	○	×
														(10) Jian Duan wearability	○	○	○	○	○	○	○	○	○	△	△	○	△

According to the present invention, use the ball pen of water-based inks can under low cost, produce and under touching, write smoothly and the wherein bespatter and the division generation hardly of delineation lines.In addition, when under speed, writing fast,, do not cause the leakage backward of printing ink even it does not cause pause and the static placement that when the cap for brush is closed pen made progress with common speed twice or many times yet.The preferred embodiment according to the present invention can obtain wherein to the last can both stablize ball pen discharge printing ink, that use water-based inks.

Claims (5)

1. ball pen that uses water-based inks comprises:

The ball pen tip, it is made in the following way: form the ball chamber, this ball chamber is by near the summit of metal thin tube, be used as the inside protrusion of ball received block with formation by inside extrusion distortion, cut workpiece and making is put into ball the edge of opening of ball chamber with the filling summit then thereon;

Ink cavity;

Joint, this joint connects ball pen tip and ink cavity, and contains the mechanism that prevents that printing ink from leaking backward, and this mechanism comprises block piece and received block;

Pseudoplastic water-base printing ink is at 25 ℃ and 38.4 seconds ^-1Shear rate under, its viscosity is 20-600mPa second and 25 ℃ and 384 seconds ^-1Shear rate under, its viscosity is 10-20mPa second; With

Ink follower, it is filled in the rear end of printing ink in the ink cavity, and this ink follower is 0.2-2.0 in the tan of 25 ℃ of following modulus δ value in the gamut of 0.1-650rad/ angular frequency second.

2. the ball pen of the use water-based inks of claim 1, wherein the surface tension at 25 ℃ of following Pseudoplastic water-base printing ink is 32mN/m or littler.

3. the ball pen of the use water-based inks of claim 1, wherein under 25 ℃, under 200 seconds-1 shear rate, the viscosity of ink follower is 500-8,000mPa second.

4. the ball pen of the use water-based inks of claim 2, wherein under 25 ℃, under 200 seconds-1 shear rate, the viscosity of ink follower is 500-8,000mPa second.

5. the ball pen of any one use water-based inks among the claim 1-4, wherein the metal thin tube at ball pen tip is made less than 0.03% austenitic stainless steel by carbon content.

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