TW567148B - Ballpoint pen using water based 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

Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 567148 μ ________ B7 V. Description of the invention (d. Scope of the invention The invention relates to a ball pen using water-based ink. More specifically, the invention relates to a method using pseudoplastic water-based A ballpoint pen for ink. The previous technique used a ballpoint pen using water-based ink using the following ballpoint pen tip, in which the pen tip was placed in a thin metal tube and strongly deformed inwardly at a sticky point to form a ball receiver. It is made by protruding the seat inward, and then plugging the gap edge of the point inward; some proposals have been disclosed (Japanese Patent Laid-open Application No. 7-2 9 9 9 8, etc.). However, since these water-based ink ball pens using thin metal tubes use a grease-based backward leakage preventive agent, there are some problems, that is, the effect of preventing backward leakage is not safe, and when the pen tip is placed upward It will gradually cause backward leakage, even in the case of ordinary writing, that is, the pen tip is downward, which prevents the backward leakage of grease while the ink is consumed. Adheres and remains on the inner wall of the ink storage tube, thereby preventing the backward leakage of oil during writing and eventually causing the ink to leak backward. In addition, if a lot of grease is installed to prevent the backward leakage preventive agent When it is scarce, the outflow of ink will be greatly reduced, so it will cause water cut-off when writing at a speed that is more than twice as fast as normal. Also, if the ink with cutting-thinning characteristics is not used, if appropriate The viscosity 値 can be controlled so that when the ink does not drip from the pen end during unwriting, the splitting and water breakage caused by daylight are easy to occur. On the contrary, if the viscosity 墨水 of the ink is considered important when writing , Its paper size applies to Chinese National Standard (CNS) A4 specification (2) 0〆297 cm &quot;) when not writing ^ Decoration n Order II (please read the precautions on the back before filling this page) Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau 567148 A7 B7_ V. Description of the invention (2) The ink is easy to drip, so it will be very difficult to maintain a stable quality. Therefore, the applicant provided the ballpoint pen tip A joint with a check valve mechanism is used between the ink storage tubes, and the ink with cutting-thinning characteristics is provided to completely prevent the backward leakage of the ink when using a water-based ink ball pen as described above ((Japanese Patent License Published application No. 8-230374). However, according to the later research, there are some problems, that is, the general pen backward leakage of the ballpoint pen using this mechanism to prevent the backward leakage valve mechanism can effectively prevent, but When the ball pen is dropped, the ink from the rear end of the ink storage tube cannot be prevented from spreading out. Even if the conventional ink follower made of grease and the joint with a check valve mechanism are equipped on the rear part of the ink storage tube There is no improvement. Moreover, when using a known ink follower made of grease, the ink's followability is poor when writing quickly. Furthermore, for this type of ball-point pen using water-based ink, 尙 cannot successfully provide all the other requirements that the ball-point pen should have, such as the feel of writing, the amount of ink flowing out, splashing, and lined feathers. The stability of the edge, the amount of ink outflow, and the water cutoff from slight impact. It is well-known that Vostian stainless steel S U S 304 is used as a thin metal tube material to which a conventional nib belongs. The carbon content of the SUS304 material is set to 0.08% or less, and is typically greater than or equal to 0.03%. However, the present inventors have discovered that a ball receiving seat made of a material having a carbon content of 0.03% or more will be easily affected by the receiving seat when writing (if a pigment is used as a colorant). Worn and sink the ball. This paper size applies to China National Standard (CNS) A4 specifications (210X297) 1 ^ '~ L -------- 1¾ clothing ---- Ί--, 玎 ------ ^ (Please Read the notes on the back before filling in this page) Printed by the staff of the Intellectual Property Office of the Ministry of Economic Affairs and printed by the cooperative 567148 A7 B7 _ V. Description of the invention (3) The object of the present invention is to solve the above problems and provide a water-based ink The ballpoint pen can be written smoothly with a slight touch, and almost no splattering and splitting occur, and water will not break at a writing speed two or more times faster than the normal speed. Its stable ink flow can Continue to the end, even if the pen tip is upright and the cap is removed, the ink will not leak back at all. SUMMARY OF THE INVENTION The present invention provides the following ball pens to solve the above problems. (1) A ball pen using water-based ink, It includes: an atomic pen tip made by forming a ball house, which is deformed by pressing inward near the end of a thin metal tube to form an inwardly protruding portion of a ball receiving seat and cutting the finished product, and then Put a ball in the ball house so that it plugs inward An ink storage tube; a joint connecting the atomic pen tip and the ink storage tube, which has a mechanism for preventing ink from leaking backwards, including a plug and a receiving seat; a pseudoplastic water-based ink, its viscosity 20 to 600 mPa · sec at a shear rate of 38.4 sec-1, and 10 to i20mPa · sec at a shear rate of 384sec-1 (25t); and an ink follower , Which is the rear end of the ink contained in the ink storage tube, and the angular rate is in the entire range of 0.1 to 650 radians / second (rad / sec), and its tangent (5 (ta η (5) 値The modulus is 0.2 to 2.0 (25 1). This paper size is applicable to the Chinese National Standard (CNS) Α4 size (210X 297 mm) ~~ '

Hr n I, n I 1— nn 1 mmmn !! I— T Hi --- n ——I ----------- 1 (Please read the notes on the back before filling this page} Economy Printed by the Employees' Cooperative of the Ministry of Intellectual Property Bureau 567148 A7 _ B7 V. Description of the invention (4) (2) The ball-point pen using water-based ink as described in item (1), wherein the surface of the pseudoplastic water-based ink is The tension is 3 2 m N / m or less (2 5 ° C). (3) A ball pen using water-based ink as described in item (1) or (2), wherein the viscosity of the ink follower 500 to 8, 000 mPa · sec at a shear rate of 2000 sec-1 and 25 ° C (4) Atoms using water-based inks as described in any one of items (1) to (3) Pen, wherein the thin metal tube of the atomic pen tip is made of Vostian stainless steel with a carbon content of less than 0.33%. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is one of the embodiments of the present invention. A longitudinal cross-sectional view of the main part of the ball pen, this figure shows a state where the pen tip is downward. FIG. 2 is a longitudinal cross-sectional view of the main part of the ball-point pen using water-based ink as one of the embodiments of the present invention. Shows the state of the pen tip upwards. Fig. 3 is a longitudinal sectional view of a main part of a ball pen using water-based ink as one of the embodiments of the present invention. Fig. 4 is a cross-sectional view of Fig. 3AA. Component comparison table A: A — A: 1: Paper size of ballpoint pen tip is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) IT III ϋ IIL / Ki-—i II 1 · _ T n _ _ _ n _ Good 0¾. TP winding (please read the precautions on the back before filling this page) 567148 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) Receiving seat 2 5 The mechanism for preventing backward leakage. In this method, although the joint has a plug to prevent backward leakage, preferably the mechanism for preventing backward leakage should include a metal ball and a receiving seat, so that the ink leaks from the rear end of the ink storage tube in the direction of the bolt 31. It can prevent even the backward leakage caused by the pen body standing upright and the cap removed when writing. In the connector 2 2 of the embodiment shown in the figure, the ballpoint pen tip 1 is tightly pressed into the front end of the connector. And the receiving element 21 is pressed It is embedded in the rear end of the joint, and the ink storage tube 10 is tightly embedded in the outside of the side of the rear end of the joint. The main body of the joint 22 and the receiving element 21 may be made of a synthetic resin having elastic deformation. Further, the valve The chamber 23 is placed in the middle part of the joint 22, and the plug 20 for preventing backward leakage is loosely engaged in the valve chamber. The stopper 20 is composed of a removable stopper having a larger specific gravity than the ink 1 1. Preferably, the metal ball is a stainless steel ball. Since the protrusion 24 is formed on the front side of the valve chamber 23, when the side of the pen tip is downward, the ball plug 20 will lock the protrusion 24, and the ink can flow into the ballpoint 1 from between the protrusions. In the ink feed path 6, writing is possible. In addition, since the conical or spherical receiving seat 2 5 is provided at the front side of the receiving element 2 1 which is tightly fitted into the rear end of the joint 2 2; when the pen tip side is upward, the plug 20 will be tight with the receiving seat Touch the ground to seal the ink so that the ink does not leak backwards, even when writing up, the ink under the ball 2 runs out. (Ink) --------- ^ 卜 装-(Please read the precautions on the back before filling this page), 11-line paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) ); 10: 567148 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (8) Ballpoint pen used for water-based ink as in the present invention, the ink is a pseudoplastic water-based ink, its viscosity 20 to 600 mPa · sec at a shear rate of 38.4 sec-1, and 10 to 120 mPa · sec at a shear rate of 384 sec-1 (25 ° C), preferably at At a shear rate of 38 · 4 sec-1, it is 50 to 350 mPa · sec, and at a shear rate of 384 sec-1), it is 15 to 8 OmPa · sec. By using a pseudo-plastic water-based ink as specified above, the shearing force will be applied to the ink to reduce the viscosity of the ink by writing the ballpoint pen (where the nib is made of metal) to the ink to reduce the viscosity of the ink. It is possible to write smoothly with water-based ink like a general ballpoint pen, and then produce excellent fonts on paper. In addition, because the ink has a high viscosity when not writing, the ink splashing from the pen end point can be prevented. In this way, the ink can be directly filled into the ink storage tube, the structure of the pen can be simplified, and the remaining amount of ink can be borrowed. Observed by the transparent substance used in the ink storage tube. If the viscosity exceeds 600 m Pa · sec at a shear rate of 38.4 sec · 1 or 1 20 mPa · sec at a shear rate of 384 se c_1, the ink is written at a writing speed two or more times faster than usual. The follow-up will deteriorate. In addition, line-splitting (split into multiple lines when scribing) and splashing are also more likely to be caused. On the other hand, if the viscosity is less than 20 mPa · sec at a shear rate of 38 · 4 sec — 1 or less than 10 m P a · sec at a shear rate of 384 sec-1, ink from the end of the pen will stain. It is easy to cause, and it is easier to be smudged without being confused when scribing. Moreover, by limiting the surface tension of the pseudoplastic water-based ink to 3 2 this paper size applies the Chinese National Standard (CNS) A4 specification (2) 0 × 297 male H * (Please read the precautions on the back before filling this page) -Packing- Thread 567148 A7 B7 V. Description of the invention (d-based cellulose, sodium methyl cellulose, acacia, alkali salt of shellac, polyethylene oxide, sodium alginate, tragacanth, Guar gum, sycamore gum, etc. The colorants for the water-based inks used in the present invention include all dyes that are soluble or dispersible in water, titanium dioxide and all known inorganic and organic pigments, borrowed dyes And white plastic pigments are fake pigments prepared by dyeing resin emulsions. As a specific example, dyes include acid dyes such as eosin, flame red, and water yellow # 6-C, acid red and water blue # 1 〇05, bright Blue FCF, Niger NB, direct dyes such as direct black 154, direct sky blue 5B, violet BB, basic dyes such as rhodamine and methyl violet. For example, inorganic pigments include carbon black and metal powder. Organic pigments include azo lake Insoluble azo pigment , Chelating azo pigments, phthalocyanine pigments, perylene pigments, orange pigments, anthracene pigments, quinacridone pigments, dye lakes, nitro pigments, and nitroso pigments. In particular, they also include inorganic pigments such as Carbon black, titanium black, zinc oxide, red iron oxide, chromium trioxide, black iron oxide, cobalt blue, yellow iron oxide, chrome green, zinc sulfide, zinc barium white, cadmium yellow, silver vermillion, cadmium red, chrome yellow, Molybdate orange, zinc chromate, europium chromate, white carbon, clay, talc, ultramarine, precipitated barium sulfate, barite powder, calcium carbonate, white lead, Prussian blue, manganese purple, bromide powder, brass powder , C · I · Pigment Blue 1, c _ I · Pigment Blue 1 5, C · I. Pigment Blue 17, C · I · Pigment Blue 27, C · I · Pigment Red 5, C · I · Pigment Red 2 2 , C · I · Pigment Red 3 8, C · I. Pigment Red 4 8, C. I · Pigment Red 4 9, C. I · Pigment Red 5 3, C · I · Pigment Red 5 7, C · I · Pigment Red 8 1, C · I · Pigment Red 1 〇4, C · I · Pigment Red 1 4 6, L ----------- ^ Pack-(Please read the precautions on the back first (Fill in this page)

， 1T line Ministry of Economics Intellectual Property Bureau Employees' Cooperative Cooperatives Print this paper scale to apply Chinese National Standard (CNS) A4 specification (21 〇χ 297mm)-Ιό 567148 Ministry of Economic Affairs Intellectual Property Bureau 8 Industry Consumer Cooperatives print this paper scale Applicable to China National Standard (CNS) A4 specification (2.0 × 297 mm) A7 B7 V. Description of invention (yc · I · Pigment Red 2 4 5, C · I · Pigment Yellow; [, c ·; [.Pigment Page 3. C_I · Pigment Yellow 12, c · 丨 · Pigment Yellow 13, cI, Pigment Page i4, cI · Pigment Yellow 17, c · I · Pigment Page 34, CI · Pigment Yellow 55, C · I · Pigment Yellow 74 , C · I · Pigment Yellow 83, c · I · Pigment Yellow 95, c ··· Pigment Page 166, C.I · Pigment Yellow 167, C · I.Pigment Orange 5, C · 1 · Pigment Orange I3, c · I · Pigment Orange 16, c ,; [, Pigment Violet 1, C · I · Pigment Violet 3, c · I · Pigment Violet; [9, C_ I · Pigment Violet 23, C. I _ Pigment Violet 5〇, c .; [Pigment Green 7. Moreover, the amount of the colorant may be appropriately changed depending on the strength of the scribing line, 'preferably from 0.1 to 40% by weight relative to the total amount of ink. Furthermore, may be Incorporate to improve writing touch and for a while Later stable water-soluble liquid media include polyhydric alcohols such as propylene glycol, glycoside oil, polyethylene glycol, alkylene oxide adducts of glycoside oils, and alkylene oxide adducts of trihydroxypropane, and mixtures thereof. In addition, surfactants that can be incorporated as lubricants and wetting agents to control surface tension and improve writing touch include polyethylene oxide, ethylene oxide-propylene oxide derivatives such as ethylene oxide lauryl ether, Glycoside derivatives, diglycoside oils or polyglycoside oils such as tetraglycoside distearate, sugar derivatives such as sorbitan monooleate, surfactants with fluorinated alkyl groups such as perfluoroalkyl groups Phosphate esters, polyether-unmodified silicones, such as polyethylene glycol adducts of dimethylpolysiloxane, hardened castor oil, phosphate-based surfactants, fluorine-based surfactants, potassium soap, and the like. -I -------------- Ί--1T ------ (Please read the precautions on the back before filling in this page) 567148 Α7 Β7 Ministry of Economic Affairs 1 Industrial and Consumer Cooperatives Co., Ltd. V. Invention Description (d In addition, related to other additives, it can be used as a pigment dispersant Water-soluble polymers such as ammonium salts of styrene-maleic acid copolymers, ammonium salts of styrene-acrylic acid copolymers, and reducing sugars mainly containing maltitol as reduction substances, mainly reducing sugars containing sorbitol Sugar, reduced oligosaccharide, reduced malto-oligosaccharide, reduced dextrin, reduced malto-dextrin, α-cyclodextrin, ^ -cyclodextrin, maltosylcyclodextrin, etc., if required Separate use of benzotriazole and saponin as rust inhibitors, and potassium hydroxide, calcium phosphate, amine methylpropanol, etc. as ρ 剂 regulators, and sodium pyridinium, phenyl isothiazoline Wait as a preservative. The water-based ink used in the ballpoint pen of the present invention can be prepared by dissolving the above ingredients while heating (required to the right to mix, scramble, and pass), and if necessary, can be mixed, stirred and filtered. In addition, compared to other water-based ink preparation methods used for ballpoint pens, no special care is required, and as long as the conditions of the stirring temperature and filtration process are within the actual range of water-based inks for ballpoint pens, There is no problem. (Ink follower) The ink follower which can be used in the ball-point pen using water-based ink according to the present invention is limited to an angular rate in the entire range of 0.1 to 650 radians / second (rad / sec) The modulus of ta η 5 値 (expressed as the ratio of the loss modulus to the storage modulus) is 0 · 2 to 2 · 0 (2 5 ° C). For the ball-point pen using a thin metal tube, the ink follower with this specific ta η 5 ， has stable followability without relying on the ink flow rate and writing speed, and can wipe off the ink on the inner wall of the ink tube. , While writing and (Please read the notes on the back before filling this page)

-5 _ n ΙΓ 111 jf -----!-SI I 1, VI The size of this paper is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm). The paper is printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. The scale applies to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 567148 A7 ___B7 V. Description of the invention (d. There will be no part of the follower sticking to the wall. In addition, the ink follower will not be caused by application. The position of the ink and the ink follower will not be reversed due to the collision of the pen body. In addition, the original function of the follower is to prevent the ink from blocking the external atmosphere. Ink volatilization becomes feasible. In addition, in the ball-point pen using a thin metal tube, the diameter of the ink feed path is smaller than the tip of the tube-like pen, so the fluidity of the ink becomes slow, so that It is easy to cause jumpers when writing underlines at two or more times the speed. In addition, in the use of ball pens that are known to prevent backward leakage of grease, the grease itself has poor fluidity, so the underlined jumpers It often happens. Another Surface, using a mechanism for preventing ink from leaking backwards including a stopper and a receiving seat, and using an angular rate of the entire range from 0 · 1 to 6 50 radians / second, the modulus of ta η 5 値 is 0.2 to 2 · The ball-point pen of the ink follower of 0 has no adverse effect on the fluidity of the ink, so the fluidity will not be reduced during fast writing, and the jumper will not be generated when the line is drawn. If the angular rate is within a specific range or In the entire range of 0 · 1 to 6 50 radians / second, the ta η δ 値 modulus of the follower is less than 0.2 (2 5 ° C), and the elasticity of the ink follower becomes quite strong. So that it is difficult to fill the ink into the ink storage tube, so it becomes useless. Furthermore, if the angular rate is within a specific range or the entire range of 0.1 to 650 radians / second, its When the ta η 5 値 modulus exceeds 2.0, the ink follower's response to the ink consumption in the ink storage tube will become worse, and there will be a problem of easy spreading when the pen body is impacted. In addition, if Ink follower viscosity at 25 ° C and shear rate -16-— — i- I- I II— II —---n D nm 111 j— j II Ding. --- m I. n! (Please read the notes on the back before filling in this page) Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printing Purple 567148 A7 B7

V. Description of the invention (U SOOsec — 1 is preferably in the range of 500 to 8,000 m Pa · sec, more preferably 1000 to 6,000 m Pa · sec. The moving parts can ensure the excellent fluidity of the ink, and can prevent the dispersion that is easy to occur when the impact is applied to the pen body. If the viscosity of the ink follower is low at 25 ° C and the shear rate is 2 0 0 sec-1 At 500 m Pa · sec, there is a possibility that the ink follower will spread easily and cause the ink to leak out of the pen body. When the collision is applied to the pen body, it will stain the surrounding environment such as clothes. If the viscosity of the ink follower exceeds 8,000 mPa · sec under the same conditions as described above, the follower can hardly follow the ink when writing, so water breakage may occur during scribing. Ink of the present invention The follower is characterized in that the modulus of ta η 5 値 is 0.2 to 2 _ 0 (2 5 ° C) in the entire range of 0.1 to 6 50 radians / second, preferably , Ta η 5 値 is 0 · 2 to 2 · 0 (25 ° C) in the above range, and the viscosity of the ink follower is 25 t: and the shear rate is 2 00 sec-1 The lower line is 500 to 8,000 m Pa · sec. Such characteristics of the ink follower of the present invention can be selected by appropriately selecting the type of base oil and thickener used for the ink follower and The blending amount is obtained, and if necessary, it can be obtained by appropriately selecting manufacturing conditions as described below. It is preferable to use the viscosity at 25 ° C and the shear rate of 1 to 4 0 0 sec-1 A water-insoluble organic solvent of 5 Pa · sec is used as the base oil of the ink follower of the present invention. The characteristics of the base oil used in the ink follower of the present invention are originally insoluble or almost insoluble. However, Applies Chinese National Standard (CNS) A4 specifications (210X 297 male-17 two '— ί-II-III ^ _ 士 1 ^ ---- II 丁 _ I I___ —good. Read the precautions on the back before filling this page) 567148 A7 B7 V. Description of the invention (4 (Please read the precautions on the back before filling in this page) To prevent the ink from leaking from the back end, the viscosity is 値The most important factor of base oil, which is also a feature of the present invention, can be used as a base oil Almost all exhibited Newtonian viscosity (viscosity is not related to shear force, a constant), so that viscosity can be measured at any shear rate in the range of 1 to 4 0 0 sec-1, so viscosity should be used at 2 5 Pa · sec or less, preferably 2 Pa · sec or less, more preferably 0.5 to 1.5 Pa · sec at 5 ° C. Ink followers that contain base oils with a viscosity exceeding 5 Pa · s e c will have high viscosity at high shear rate ranges, making it almost impossible to fit them into the ink tank. Furthermore, ball pens that use such ink followers will reduce the ink's followability during writing, which will increase the problem of water breakage. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When mixing certain types of base oils, the viscosity 値 should be controlled within the range described above. Specific solvents that can be used as base oils include polybutene (whose molecular weight is about 600 or more), mineral oil, silicone oil, and the like. Solvents that can be volatile up to several weight percent in two or three years, such as polybutene with a number average molecular weight of less than 600 are not considered to be good performance after a long period of time. Preferably, the solvent whose volatilization loss is about 1% by weight or less is measured by placing about 10 g of a single or mixed base oil at a pressure of about 40 mm in a spare at atmospheric pressure. On a petri dish and left in open air at 50 ° C for 14 days. Furthermore, solvents whose viscosity increases due to oxidation are also less desirable. Specific products of polybutene include Nissan polybutene 200N, polybutene 3 0 N (N 0 F Corporation: trade name), polybutene Η V — 1 5 (Nippon Petrochemicals Co., Ltd: trade name), The size of the polybutadiene paper is in accordance with the Chinese National Standard (CNS) A4 (210X 297 mm). The printed paper is in accordance with the Chinese National Standard (CNS) A4 (21〇X: 297 mm). 567148 A7 _B7 __ 5. Description of the invention (讫 3 5 R (Idemitsu kosan Co., Ltd: trade name) ° Specific products of mineral oil include Diana treatment oil MC-32S, MC — W 9 0 (Idemitsu kosan Co , Ltd: trade name). Specific products of silicone oil include TFS 4 5 1 · series, TSF 456 series, TSF458 series (TOSHIBA Silicone Co · Ltd: trade name). Regarding the ink follower of the present invention, the preferred The following materials are used as thickeners, for example, calcium salts of phosphate esters, fine-grained silica, polystyrene-polyvinylbutene-polystyrene block copolymers, polystyrene-polyethylene propylene- Polystyrene block copolymer, Polystyrene butadiene rubber, polystyrene-polyethylene butene-polyolefin crystal block copolymer, polyolefin crystal-polyethylene butene-polyolefin crystal block copolymer, polystyrene-butadiene Rubber-polystyrene block copolymer, polystyrene-isoprene rubber-polystyrene block copolymer, dialkylated ethenyl alkoxy aluminum. They can be combined in two or more kinds In general, these thickeners can be summarized as polymer-based and inorganic (non-polymer) -based; polymer-based thickeners can be individually classified as polystyrene-polyethylene butyl Olefin-polystyrene block copolymer, polystyrene-polyethylene propylene-polystyrene block copolymer, hydrogenated polystyrene butene rubber, polystyrene-polyethylene butene-polyolefin crystalline block copolymer Polyolefin crystalline-polyethylene butene-polyolefin crystalline block copolymer, polystyrene-butene rubber-polystyrene block copolymer, and polystyrene-isoprene rubber-polystyrene block Copolymers, while inorganic (non-polymer) thickeners can be individually classified as phosphate esters Salt, fine-grained dioxide dioxide '' L ------------- batch coat Γ--1T ------- ^ (Please read the precautions on the back first (Fill in this page again) 567148 A7 B7 V. Description of the invention (0 and dialkylated ethynyl aluminum alkoxide. (Please read the notes on the back before filling out this page) Specific products of calcium salts of phosphate esters include Crodax DP_301LA (CRODA JAPAN KK · KK · Company name) Fine-grained silica can be further classified into hydrophilic fine-grained silica and hydrophobic fine-grained silica, and specific products of hydrophilic fine-grained silica Including AEROSIL-300'AEROSIL-380 (Nippon Aerosil Co., Ltd company / trade name), specific products of hydrophobic fine-grained silica include AEROS IL-9 74D, AEROSIL— 9 7 2 (Nippon Aerosil Co., Ltd. Company / Product Name) ο Specific products of polystyrene-polyvinylbutene-polystyrene block copolymers include Kraton FG—190 × L, Krato G -1 6 5 0 'Kraton G — 1 6 5 1. Kraton G-1 6 5 2, Kraton G — 1 6 5 4 X 'Kraton G — 1 6 5 7 X'

Kraton G-1 7 2 6 X, Kraton FG-1092X (

Shell Japan Ltd. / company name), SEPTON 8 0 0 7, SEPTON 8 0 0 4, SEPTON 8 0 0 (Printed by Kuraray Co., Employees ’Cooperative of Intellectual Property Office, Ministry of Economic Affairs

Ltd. company / trade name), Tuftec M — 1 9 4 3. Tuftec M -19 11 'Tuftec M-1 9 1 3 (Asahi Kasei 〇011011 〖011 company / trade name).

Specific products of polystyrene-polyethylene propylene-polystyrene block copolymers include Kraton G-1 7 3 0 (Shell Japan Ltd./company name), SEPTON 2002, SEPTON 2005, SEPTON 2006 'SEPTON 2007' SEPTON -20-This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 gong) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 567148 A7 __ B7 V. Description of the invention (4 2043, SEPTON 2063, SEPTON 2104, SEPTON 4033 'SEPTON 4055' SEPTON 4 0 7 7 (Kuraray Co., Ltd. / company name). Specific products of hydrogenated polystyrene butadiene rubber include DYNARON 1 320P, DYNARON 1 321 P (JSR Corporation / product name) , Tuftec Η 1 〇6, Tuftec Η 1 〇5, Tuftec Η 1 1 4 1, Tuftec Η 1 〇4 1, Tuftec Η 1 〇3, Tuftec Η 1 〇4 3 'Tuftec Η 1 2 7 2 ( Asahi Kasei

Corporation). Specific products of the polystyrene-polyvinylbutene-polyolefin crystalline block copolymer include DYNARON 4 600 (JSR Corp./trade name). Specific products of polyolefin crystalline-polyethylene butene-polyolefin crystalline block copolymers include DYNARON 1 3 2 1 P (; fSR Col.pol.ation &amp; Division / Trade Name). Specific products of polystyrene-butadiene rubber-styrene block copolymers include Kraton D-1 1 0 1, Kraton D-1 1 0 2, Kraton D-1 1 5 5 ^ Kraton D-KX 4 0 5 'Kraton D-KX 4 0 8, Kraton DKX 4 i 〇. Kraton D-KX 4 1 4' Kraton D-κ X 6 5 s, Kraton D -KX 4 0 3 P, Kraton D ^ K χ χ 3 gs Kraton D-KXl55P, Kl.atC) nD—ll8, KmOnD-1116 ^ Kraton D-1 1 8 8 X, Kraton D -1 1 2 2 X 'Kraton D ~ 1 3 〇〇χ. Cariflex TR- In this paper, the national standard (CNS) A4 specification (210 x2 ^^-r2T =-, ------------ τ——IT ------ 0 (please read the back first) Please note this page before filling in this page) Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 567148 A7 __B7_ V. Description of the invention (4 1 1 0 1 S, Cariflex TR — 1 1 8 4, Cariflex TR- 1 1 8 6, Cariflex TR — 4113P, Cariflex TR- 4 1 2 2 P, Cariflex TR-4 2 6 0 P (Shell Japan

Ltd./company name), Tufprene-A, Tufprene — 1 2 5, Tufprene — 1 2 6, Tufprene — 3 1 5, Tufprene — T — 4 1 1, Tufprene — T — 4 1 4, Tufprene — T — 4 1 6, Tufprene— T-4 0 6, Tufprene— T — 4 7 5, Asaprene — Ding 4 7 5, Asaprene— T — 4 2 0, Asaprene—T — 4 3 0, Asaprene— T — 4 3 1. Asaprene— T-4 3 2.

Asaprene-Ding — 4 3 6 (Asahi Kasei Corporation / trade name), JSR — TR-100, JSR — TR-2000, JSR-TR-2003, JSR-TR-2250, JSR-TR-2601, JSR-TR ~ 2606, J SR-TR-2787, JSR-TR -2827, J SR-TR-2600, JSR-TR -1 0 8 6, J SR — TR — 1 6 0 0 (JSR Corporation / Products Name), Europrene SOLT-161 (Tosoh Corporation / trade name). Specific products of polystyrene-isoprene rubber-polystyrene block copolymer include Kraton D-KX-400P 'Kraton D — 1 1 1 3 X, Kraton D-1 1 1 4 χ &gt; Kraton D -1 1 2 5 X 'Kraton D-1 3 2 0 X, Kraton D- 110 7' Kraton D-1 1 1 2, Kraton D-1 1 l 3, Kraton ϋ-1 1 1 7, Kraton D-1 1 1 9. Kraton This paper size applies to China; (CNS) A4 regulations (210x 2S) 7 Gongchu;) ~ 22-一 &quot; '------------ 1¾ clothing- --Ί--IT ------ ^ (Please read the notes on the back before filling out this page) Printed by the Industrial Property Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 567148 Μ B7 V. Description of the invention (2b D-1 1 2 4 'Kraton D-1 1 6 1, Kraton D — 1 1 1 1, Kraton D — KX 4 0 6, Kraton D-KX 6 0 3' Cariflex TR-1 1 0 7 (Shell Japan, Ltd. company / Trade name) 'Solprene — 4 1 8 (Asahi Kasei (!! 〇1-? 〇111 ^ 〇11 company // trade name)'] 311 — 8 18 — 5 0 0 0 (JSR Corporation / trade name), Quintac — 3 4 2 1, Quintac — 3 4 2 2, Quintac — 3 4 3 5, Quintac — 3 5 3 0, Quintac 3 4 5 0 (Nippon Zeon Co., Ltd./trade name). Specific products of the dialkylated ethynyl aluminum alkoxide include PLENACT AL-M (Aj inomoto Fine-Techno Co., Inc.). These If the amount of thickener is appropriate, it can provide the effect of elasticity or structural viscosity, and it is also feasible to control ta η 5 0 at 0 · 2-2 · 0 (25 ° C) by controlling the blending amount. Furthermore, if necessary, clay thickeners or metal soaps can also be used together with the aforementioned thickeners. As for the amount of these thickeners, when they are used alone, it is preferable to use 2 to 2 respectively. 5% by weight of calcium phosphate salt, 3 to 12% by weight of polystyrene-polyvinylbutene-polystyrene block copolymer and / or 0.3 to 10% by weight of polystyrene-polyethylene propylene -Polystyrene block copolymer, 1.0 to 20% by weight of hydrogenated polystyrene butadiene rubber} · 0 to 25% by weight of polystyrene-polyethylene butene-polyolefin crystal block copolymerization Polymer or sintered hydrocarbon crystals-polyethylene terephthalate is a polycrystalline hydrocarbon crystalline block copolymer, 1 · 0 to 20% by weight of polystyrene monobutylene rubber — Polystyrene block copolymer (more preferably, 1.0 to 15% by weight), 1.0 to this paper size Applies to Chinese National Standard (CNS) A4 specification (210X297 mm) H — I 1 ^. Order II line (please read the notes on the back before filling this page) 567148 A7 ____ B7__ V. Description of the invention (2) | 2 55% by weight of polystyrene-isoprene rubber-polystyrene block copolymerization (More preferably, 2.0 to 20% by weight) and 2.0 to 20% by weight of a dialkylated ethenyl aluminum alkoxide. If each component is blended in a lower amount than the aforementioned amount, the follower will not provide sufficient viscoelasticity, so the ink follower will spread out, and the ink in the pen body will be caused only by slight collision. Leaked backwards. Furthermore, the ink follower will reduce the viscosity by changing the normal temperature, and the ink will leak backward only because the pen end point is upward. On the other hand, if the blending amount exceeds the aforementioned amount, the follower will have a higher viscoelasticity than the appropriate range, so that the ink follower will harden, and will be caused by the poor followability of the ink when writing. Water cut off when marking. In addition, if necessary, thickener auxiliary agents (clay thickeners, metal soaps, etc.), follower enhancers (surfactants, etc.) for ink followers, and Oxidant. However, some antioxidants greatly increase t a η 5 値. If these substances are added unnecessarily, even if the thickener is added in a prescribed amount, t a η 5 値 may exceed 2; therefore, it is necessary to pay attention to such blending. The manufacturing method of the ink follower for the ball-point pen using water-based ink according to the present invention is simple. It is to knead all ingredients such as base oil and surfactant for the ink follower in advance at room temperature, and then, if When an inorganic thickener such as hydrophobic silica is also used, it can be kneaded by a dispenser such as a rolling machine and a kneader. Furthermore, when using a polymer that hardly dissolves or disperses at room temperature, it can be kneaded while being heated, if necessary. In addition to this, it is possible, by further heating and by means of dispensers such as rolling mills and kneading-

In I-! Ί--^ ir I 1-- I (Please read the notes on the back before filling this page),-| 1 Intellectual Property Bureau of the Ministry of Economic Affairs g; Industry and consumer cooperatives print this paper to apply the standard Chinese National Standard (CNS) A4 specification (210X297 mm) 567148 A7 B7 V. Invention description (2j (Please read the precautions on the back before filling this page)

Shear rate: 38 · 4sec-384sec — Measuring time: 6 〇 0 sec Measuring temperature: 2 5 ° C • Measurement of the physical characteristics of the ink follower (1) ta η 5 値 Modulus measurement measuring equipment: dynamic spectrometry RDS — II (Rheo metric Scientific Co., Ltd) Measurement conditions (frequency-dependent) Geometry: Parallel plate 50 mm Φ Dynamic measurement Sweep shape: Cycle sweep Video rate range: 0 · 06-650 radians / second measurement Interval: 5 degrees / decane distortion: 100% Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Measurement temperature: 25 ° C Atmospheric: (2) viscosity in nitrogen Nitrogen measurement equipment:

E-type Rotary Viscometer DIGITAL VISCOMETER DUV-E This paper size applies to Chinese National Standard (CNS) A4 specifications (2) OX 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 567148 A7 __B7 _ V. Description of the invention (2 Including (manufactured by Tokyo Keiki Co., Ltd.) Measurement conditions (frequency dependent properties) Cone: 1 ° * R 1 4 Shear rate: 200 sec—1 Measurement time: 60 0 0 sec Measurement temperature: 2 5 ° C • The evaluation of the pen body was performed by spirally writing on the paper with ball-point pens and evaluating the writing touch by the following criteria. Each ball-point pen has a ball of 0.5 mm in diameter and is prepared according to each specification. 0: Smooth And stable writing feel. △: Slight rough and hard writing feel. X: Rough and hard writing feel, with jumper and direction error (2) Spiral ink writing on paper via ballpoint pen The following criteria are used to evaluate the ink outflow. Each ball pen has a ball with a diameter of 0.5 mm and is prepared according to each specification. 〇: sufficient ink outflow, and the strokes can be clearly seen The line. △: The water outflow is relatively small, but the line drawn is still visible. X: The ink outflow is significantly less, and the line drawn is difficult to see. (3) Evaluation of splashes The paper dimensions are subject to Chinese national standards (CNS ) Λ4 specification (210X 297 mm) Binding __. I line (Please read the notes on the back before filling out this page) Printed on the paper standard of the China National Standards (CNS) Λ4 specification (210 X 297 mm) 567148 A7 B7 V. Description of the invention (Writing spirally on a paper with a ball pen and using the following criteria to evaluate the splash, each ball pen has a 0.5 mm diameter ball , And prepared according to each specification. 〇: There is almost no splashing. △: Slight splashing, but within the allowable limit. X: Severe splashing, and the line drawn is not clear. (4) Scoring The feather edges are evaluated by writing on the paper spirally with a ball pen and the following criteria are used to evaluate the feather edges. Each ball pen has a ball with a diameter of 0.5 mm and is prepared according to each specification. 〇: There are hardly any feather edges. X: Serious feather edges And the line drawn is not clear. (5) Evaluation of follow-up during fast writing According to the ISO standard method, a freehand line is drawn on the paper at a normal speed and twice the speed by a ball pen, and evaluated by the following criteria Scribing, each ball pen has a ball with a diameter of 0.5 mm, and is prepared according to each specification. 00: Can write smoothly and securely. △: At double speed, it will split when scribing. X : At normal speed, it will split when scribing. (6) Stability of ink outflow -29------------- Load ---- Ί--1T ------ line (Please read the notes on the back before filling out this page) The paper size printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) Α4 specification (210X 297mm) 567148 A7 ____B7 _ V. Description of the invention (2 >> 〇: In a spiral writing round, you can write again without water cut. △: Within three rounds of spiral writing, you can write again without stopping the water. X: Within three rounds of spiral writing, no more writing. (8) Each ink ball with a diameter of 0.5 mm is scattered due to the light collision of the ink, and the ballpoint pens prepared according to each specification are dropped from a height of 1,5 meters to one with a pen tip length of 2. The thickness of the cedar board is about a centimeter thick, and then the pen body that falls down is observed visually. The extent to which the ink spreads out of the ink tank can be evaluated by the following criteria. 〇: The ink did not spread, and the interface between the ink and the ink follower was clear. X: Dispersion of the ink was clearly observed. (9) Anti-backward leakage characteristics Use ball pens each with a diameter of 0.5mm, prepared according to each specification, and write spirally with the pen end point upwards until writing is impossible, and then use the pen end point Keep the pen upright. After 1 hour, the backward leakage of the ink was visually observed. ○: No backward leakage was observed. X: Backward leakage was observed. (10) Abrasion resistance of nib-Κ -------- ^ — 1 ^ ----- 1--1Τ ------ ^ (Please read the precautions on the back before filling in this page ) 567148 A7 __ B7 V. Description of the invention (with the help of a writing tester under the following conditions and according to the IS0 standard method let ball pens (each with a 0.5 mm diameter ball, and prepared according to each ~ ^ grid ) Write 700 meters in a spiral shape on the paper, and then observe the wear state of the ball receiving seat of the pen tip after writing with a $ _ microscope. Writing conditions: Writing speed: 4.5 meters / minute Writing angle: 6 0 ° Writing load · 100g 0: Observe that the ball receiving seat is almost free of wear, and can be written to 7000 meters. △: Observe that the ball receiving seat is worn, and can write up to 500 meters,- ---------- Ί--IT ------ 0 (Please read the notes on the back before filling out this page) Printed by the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies to China National Standard (CNS) A4 specification (210X 297 mm) 567148 \ Ί Β7 V. Description of the invention (^ Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ Table 1 Ink Preparation of the Examples Special Ink 1 Ink 2 Ink 3 Ink 4 Example Example Example Example Ink Color Black Blue Black Black Colorant Carbon Black Printex 25 (trade name of Dequssa Company) Pigment Pigment 7.00 7.00 Chromofine Blue 4965 (Dainichiseika Color &amp; Chemicals Mfg. Co., Ltd.'s trade name_) Pigment 7.50 Colorant Water Black R455 (trade name of Orient Chemical Industries, Ltd.) dye 7.00 Water Yellow 6C (Orient Chemical Industries, Ltd . The product name of the public W) dye 1.00 pigment styrene maleic acid resin ammonium salt 2.00 2.00 Zhuzhu agent styrene acrylic resin ammonium salt 2.30 liquid propylene glycol 18.00 15.00 15.00 ^ glycoside oil 10.00 10.00 propylene oxide of diglycoside oil 4 mol Additives 10.00 Prevent maltitol volatile substances 5.00 5.00 5.00 5.00 Surface active potassium soap 0.50 0.40 0.50 (moisturizing) noodles 0.20 0.40 full gas alkyl phosphate 0.20 0.10 _ gas-based courtyard vinegar 0.30 0.20 antiseptic Sodium pyridinate 0.10 0.10 0.10 0.10 Enzyme saponin 0.10 0.10 0.10 0.10 PH Amine Methyl Propanol Monomer 0.30 0.30 .030 0.20 Viscosity Chinese rubber KELXZAN HP (trade name of Sansho Co., Ltd. Public Control Agent Division) 0.30 0.30 0.40 0.20 Polyacrylic acid Hiviswako 105 (Wake Pure Chemical) in crosslinked form Trade name of Industries Ltd.) 0.10 0.20 Polyvinylpyrrolidone PVP-K90 (trade name of GAFCo., Ltd.) 5.00 Ion exchange water 66.50 58.60 70.40 59.50 Total 100.00 100.00 100.00 100.00 In 25 ^, 38.4 86 (^ Ink viscosity at mPa.sec 130 200 320 400 to 25 ° C, 384 sec · 1 Ink viscosity at mPa.sec 25 40 30 80 Ink surface tension at 25 ° C (mN / m) 28.0 30.5 23.5 25.4 Remarks Ink of the present invention Ink of the present invention Ink of the present invention Ink of the present invention II—i I I -..... = II »L · 士 ^ —II n =------- 1 ^ 1 n ϋ— ^ i knot (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 567148

AB V. Description of the invention (Table 2 Ink formulation and characteristics of the comparative examples Ink printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed ink 5 Ink 6 Ink 7 Ink 8 Comparison 1 Example Comparative Example Comparative Example Comparative Example Example Ink Color Black Blue Black Black Coloring Agent Carbon Black Piintex 25 (trade name of Dequssa Company) Pigment Pigment 7.00 7.00 7.00 Chromofine Blue 4965 (Dainichiseika Color &amp; Chemicals Mfg. Co., Ltd. company trade name ) Pigment 7.50 Colorant Water Black R455 (trade name of Orient Chemical Industries, Ltd. dye company) dye water yellow 6C (trade name of Orient Chemical Industries, Ltd. company) dye pigment styrene maleic acid ammonium salt 2.00 2.00 2.00 Dispersant Styrene acrylic resin ammonium salt 2.30 Liquid propylene glycol, 15.00 18.00 Medium glycoside oil 10.00 10.00 10.00 Dipropylene oil propylene oxide 4 mol adduct 10.00 10.00 Prevent maltitol volatile substances 5.00 5.00 5.00 5.00 Surface active potassium soap pulls 0.40 0.50 0.50 (fitting agent) Potassium 0.20 Perfluoroalkyl phosphate 0.10 0.20 Gas based vinegar 0.20 0.20 Preservative sodium pyridinium 0.10 0.10 0.10 0.10 Rust inhibitor saponin 0.10 0.10 0.10 0.10 pH adjuster methyl propanol monoblock 0.30 0.30 0.30 0.20 Viscosity KELXZAN HP (trade name of Sansho Co., Ltd. control agent company) 0.60 0.10 Polyisopropionate Hiviswako 105 (trade name of Wake Pure Chemical Industries Ltd.) 0.10 0.02 0.20 polyvinyl based Pyrrolidone PVP-K90 (trade name of GAF Co., Ltd.) 8.00 15.00 Ion-exchanged water 56.70 58.98 51.60 64.80 Total 100.00 100.00 100.00 100.00 Ink viscosity (mPa.sec) at SStWjsec · 1 650 18 350 30 at 25 Ink viscosity (mPa.sec) at ° C, 384 sec · 1 80 7 200 8 Ink surface tension (mN / m) at 25 ° C 28.6 29.7 30.9 25.5 Remarks 38.4 sec'1 viscosityΐ 38.4 sec'1 viscosity i 384 sec · 1 viscosity1 38.4 sec · 1 viscosity 丨 384 sec "viscosity i means higher than the range of the present invention, 丨 means lower than the range of the present invention. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) (please read the precautions on the back before filling this page).---Mouth silk 567148 A7 B7 V. Description of the invention (3 full table 3 Examples) Preparation and characteristics of the ink follower Printed follower A Follower B Follower C Follower D Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics Example Example Example Example Ink Prepared Material Base oil: Polybutene average molecular weight 1350 Note 1 50.0 Base oil: Mineral oil average molecular weight 740 Note 2 96.5 92.0 94.0 44.0 Base oil: Polybutene average molecular weight 580 Note 3 Thickener: Phosphate calcium salt Note 4 3.5 Thickener: Fine-grained silica Note 5 Thickener: Polystyrene-polyvinylbutene-polystyrene block copolymer Note 6 3.0 Thickener: Hydrogenated styrene butadiene rubber Note 7 2.5 Thickening Agent: Polystyrene-Polybutylene-Polymer crystalline block copolymers Note 8 5.0 Thickener: Polyolefin crystalline · Polybutylene-Polyolefin crystalline block copolymers Note 9 1.0 Thickener: Poly Acetophenone Notes on rubber-polystyrene block copolymers 10 7.5 Thickener: Polystyrene-isoprene rubber-polystyrene block copolymers Note 11 Thickener: Di-methyldi-octadecane Annotation of ammonium ammonium bentonite 12 Additive: Annotation of surfactant based on fluorine 13 0.5 0.5 Characteristics of ink follower Tαηδ 値 (25 ° C) 0.06 radians / second 086 0,86 0.94 0.55 Tan6 値 (25 ° C) 0.25 radians / less 1.08 0.87 0.95 0.58 Tan6 値 (25 ° C) 0.63 radians per second 0.98 0.91 0.90 0.72 TaW 値 (25.1.0 radians 0.87 0.91 0.89 0.85 Tan6 値 (25 ° C) 4.0 radians 0.92 0.94 0.88 1.09 Tan5 値 (25.〇6.3 radians proud 0.91 0.96 0.85 1.61 Tan6 値 (25 ° C) 10 radians /? 0.77 1.01 0.81 1.24 Tan5 値 (25 ° C) 40 radians / 1 less 0.67 1.05 0.78 1.02 Tan5 値 (25 〇C) 63 radians / second 0.65 1.22 0.81 0.97 Tηηδ 値 (25 ° C) 100 radians less 0.69 1.42 I 0.81 0.98 Tan5 値 (25 ° C) 400 radians / second 0.75 1.50 1 0.83 1.03 Tan5 値 (25 ° C) 600 Radius 0.82 1.55 1.14 丨 0.90 Tan525 (25 ° C) 650 radians / second 丨 0.83 1.58 1.15 丨 0.92 at 20 (^ (^ 下 之 之Viscosity (such as 3 meanings) 5050 3970 3240 '6020 -------- ί 丨 ---------- Order ------ (Please read the precautions on the back before filling in this Page) This paper size is applicable to Chinese National Standard (CNS) Λ ^ 4 specification (21〇X 297 mm) 567148

A

7 B V. Description of the invention (3 Tables 4) Preparation and characteristics of the ink follower of the comparative example Printed follower E Follower F Follower G Follower G Comparative Example Comparative Example Comparative Example Comparative Example Ink Follower Preparation Base Oil: Polybutene Average Molecular Weight 1350 Note 1 99.1 50.0 Base Oil: Mineral Oil Average Molecular Weight 740 Note 2 99.2 19.5 Base Oil : Polybutene average molecular weight 580 Note 3 97.5 Thickener: Phosphate calcium salt Note 4 0.3 Thickener: Fine-grained silica Note 5 2.5 Thickener: Polystyrene like polyethylene butadiene-polystyrene Notes to block copolymers 6 Thickener: Hydrogenated styrene butadiene rubber Note 7 0.9 0.4 Thickener: Polystyrene styrene Polybutylene polyisocyanate Crystal block copolymer Note 8 Thickener: Polyolefin Crystalline-polyvinylbutene-polyolefin crystalline block copolymer Note 9 Thickener: Polystyrene butadiene rubber-polystyrene block copolymer Note 10 27.0 Thickener: Polystyrene-isoprene Ene rubber-poly Ethylene Block Copolymer Note 11 3.0 Thickener: Di-methyldi · octadecyl Supentonite Note 12 Additive: Fluorine-based Surfactant Note 13 0.5 Ink Follower Characteristics Tan5 値 (25 ° C) 0.06 radians 22.52 0.84 1.51 0.08 Tan6 値 (25 ° C) 0.25 radians 22.54 0.86 1.53 0.09 Tan5 値 (25 ° C) 0.63 radians / second 24.92 0.92 1.40 0.09 ταηδ 値 (25t) 1.0 radians / second 27.16 0.99 1.34 0.12 Tan5 値 (25 ° C) 4.0 radians less 31.85 1.06 1.27 0.13 ΤΣίηδ 値 (25t) 6.3 radians /? 28.49 1.20 1.21 0.24 Tan5 値 (25 ° C) 10 radians per second 25.03 1.28 1.15 0.39 Tan5 値 (25 ° C) 40 radians / second 23.99 1.39 1.00 0.41 Tan5 値 (25 ° C) 63 radians / second 22.14 1.63 0.96 0.48 ταηδ 値 (25 ° C) 100 radians 30.39 2.04 1.02 0.53 Tan5 値 (25 ° C) 400 radians 31.43 2.99 1.61 0.62 Tan5 値 (25 ° C) 600 radians / second 32.64 2.50 2.56 0.74-Tan5 値 (25 ° C) 650 radians / less less 32.55 2.50 2.57 0.89 Viscosity below 20 (^ (: * 丨 the viscosity 値 (11 ^ parent ( :) 2000 2800 490 12500 (Please read the precautions on the back before filling this page) This paper ruler Applicable to China National Standard (CNS) A4 specifications (210X297 mm) Printed by the Employees ’Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs 567148 A7 B7 V. Description of the invention (Notes to Tables 3 and 4 are listed below: Note 1: Polybutadiene 30N (NOFC〇RP〇RATION company: trade name) Note 2: Diana treatment oil PW-38 (Idemitsu Kosan Co. Ltd .: trade name) Note 3: Nissan polybutene 015N (N〇F Corporation: Trade name) Note 4: Crodax DP-30 (CRODA JAPAN KK: trade name) Note 5: AER〇SIL-974D (Nippon Aerosil Co., Ltd .: trade name) Note Army 6: DEPT〇N 8007 (KURARAY C〇.LTD. Company: Shangkou mouth name) Note 7: Tuftec H1141 (ASAHI KASEI Corporation: trade name) Note 8: DYNARON 4600P (JSR C〇.LTD. Company: trade name) Note 9: DYNARON 6200P (JSR CO. LTD. Company: trade name) Note 10: Asaprene T-431 (ASAHI KASEI Corporation: trade name) Note ll: Solprene-418 (ASAHI KASEI Corporation: trade name) Note 12: Ben ton 34 ( Wilbur-ellis Co., Ltd .: Trade name) Note 13 : EFtop. EF-801 (MITUBISHI MATERIALS (: 〇1 ^? 〇1 ^ 八 丁 1〇1 ^ company: trade name) This paper size applies to Chinese National Standard (CNS) Λ4 specifications (210X 297 mm) IIII n batch订-Order I line (please read the precautions on the back before filling this page) 567148 A7 B7 (8) The ink spread due to slight collision 5. Description of the invention (3 &amp; Table 5 Example ink ink follower connector nib (1 ) Writing feel (2) Amount of ink outflow (3) Evaluation of splattering (4) Feather edge of scribing (5) Follow-up of fast writing (6) Stability of ink outflow (7) Break due to slight collision Water (9) Backward Leakage Resistance (10) Wear Resistance of Pen Tips Example

HI ί im— n «n tmri.n In If (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs

567148 V. Description of the invention (^ Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economy (Table 6) Comparative Example Comparative Example 11 12 13 14 15 16 17 18 19 20 21 22 23 Ink (5) ⑹ ⑺ ⑻ ⑴ ⑴ ⑶ ⑶ ⑶ ⑴ ⑶ ⑶ ⑹ Ink follower AAAAEFG Η AC AC Η F connector Writing touch X 〇X 〇〇〇〇〇 △ 〇XX Δ X ⑵Ink efflux X 〇 'X 〇〇〇〇〇X 〇 △ Δ X Δ (3) Evaluation of staining 〇Δ 〇Δ 〇〇Δ 〇〇〇 〇X Δ ⑷Frayed feather edge 〇X 〇X 〇〇〇〇〇〇〇〇〇X ⑶ follow-up fast writing X 〇X 〇Δ 〇〇Δ △ 〇〇X 〇⑹ stability of ink out 〇〇 〇〇〇〇〇〇〇〇 △ △ 〇Δ 断 water due to slight collision △ Δ Δ 〇〇〇〇〇〇〇〇〇 △ △ ⑻ due to light collision ink spread out XXXXXX 〇X 〇〇〇〇〇〇⑼ Anti-backward leakage characteristics 〇〇〇 〇〇〇〇〇〇〇〇〇〇〇 (10) Wear resistance of the pen tip 0 〇〇〇〇〇〇〇〇〇Δ △ 〇 △!-1---is----ϋ- ί —1 ·- ϋ (Please read the notes on the back before filling this page) ·-Silk i This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210x 297 mm) 567148 A7 ______B7_ 5. Description of the invention (d According to the present invention, use Water-based ink ball pens can be produced at low cost. 'Slight contact makes writing smooth and there is almost no splatter and splitting when scribing. Moreover, it does not cause breaks when writing two or more times faster than usual. Water will not leak back even if the pen end is upright and the cap is removed. According to a more preferred embodiment of the present invention, a stable ink outflow can be obtained in the end using a water-based ink ball pen. (Please (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs ^ 4 0-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

567148 A8 B8 C8 D8 VI. Patent Application No. 91 104178 Patent Application Chinese Patent Application Amendment June 23, 1992 Amendment 1. A ball pen using water-based ink, which includes:-forming a ball by The atomic pen tip made by the house is near the end of the thin metal tube and is deformed by inward extrusion to form the inwardly protruding part of the ball receiving seat, and the finished product is cut off and then placed in the ball house. Put a ball into the ball and make it inwardly plug the gap edge of the end point to combine it; an ink storage tube; a joint connecting the atomic pen tip and the ink storage tube, this joint has a mechanism to prevent ink from leaking backwards, It includes a stopper and a receptacle; a pseudoplastic water-based ink with a viscosity of 20 to 600 mPa · sec at a shear rate of 38.4 se c-1, and a shear rate of 384sec-1 (25 ° C) 10 to 120 mPa · sec; and an ink follower, which is the rear end of the ink contained in the ink storage tube, and the angular rate is in the entire range of 0.1 to 650 radians / second (rad / sec) , Whose tangent 5 (tan5) 値 has a modulus of 0.2 to 2.0 (25 ° C)2. The ballpoint pen using water-based ink as described in the first item of the scope of application, wherein the surface tension of the pseudo-plastic water-based ink is 32 mN / m or less (25 ° C). 3 · If you apply water-based ink for ballpoint pens in the scope of the first case of the application, the paper size of the ballot pen is applicable to China National Standard (CNS) A4 (210X297 mm) --------- ^-(Please Please read the notes on the back before filling this page.) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Printed 567148 A8 B8 C8 D8. 6. The scope of patent application, in which the viscosity of the ink follower is at a shear rate of 200 sec — 500 to 8,000 mPa.sec at 1 and 25 ° C. 4 · Ballpoint pen using water-based ink as in item 2 of the scope of the application, where the viscosity of the ink follower is 500 to 8,000 mPa at a shear rate of 2 0 se 〇_1 and 25 ° C. sec. 5. The ballpoint pen using water-based ink as described in any one of items 1 to 4 of the scope of the application, wherein the thin metal tube of the ballpoint pen is made of Vostian stainless steel with a carbon content of less than 0.03% to make. Coupons-(Please read the notes on the reverse side before filling out this page), language printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standards (CNS) A4 (210X297 mm) -2-