JP4952482B2 - Ballpoint pen tip - Google Patents

Description

  The present invention relates to a ballpoint pen tip that can determine the color of a handwriting.

Patent Document 1 discloses a tip-colored ballpoint pen in which the appearance color of a ball holder holding a ball for writing characters at the tip of the ballpoint pen is the same color as the color of a character drawn by the ball held by the ballholder. It is disclosed.
Japanese Utility Model Publication No. 4-47577

What is described in Patent Document 1 is to color a metal ballpoint pen tip. In general, a coloring component is difficult to fix on a metal surface, and it is necessary to perform baking or coating in order to give a color having fixing property, particularly fastness to rubbing.
In particular, when the ballpoint pen is a retractable ballpoint pen that appears and disappears from the front end opening of the exterior body by an operation, the ballpoint pen tip may be rubbed against other members such as the exterior body every time the refill appears and disappears, In some cases, the coloring that had been applied was removed.

The present invention comprises at least a pigment, an organic solvent, and a resin in a concave portion formed on the outer surface of the ball holder of a ball-point pen tip that includes at least a ball as a writing member and a ball holder that rotatably holds the ball , Summary of the ball-point pen tip in which the ratio of the pigment to the resin is in the range of 1: 1.0 to 1: 5.0, and the resin is colored to display the ink color with an ink that is a dibasic acid-modified rosin ester. And

In the present invention, since the concave portion formed on the outer surface of the ball holder is colored so as to display the ink color, the color is not easily lost even without special steps such as baking. In particular, color display can be maintained even when the ballpoint pen tip rubs against something.
Further, the rosin structure is obtained by performing the color display with an ink in which the ratio of the pigment to the resin is in the range of 1: 1.0 to 1: 5.0, and the resin is a dibasic acid-modified rosin ester. When the color display ink firmly adheres to the metal surface and is abraded by bonding the resin component with moderate elasticity due to the oxygen atom of the carboxylic acid in the molecule and the metal atom on the metal surface However, the effect of maintaining the color display can be achieved. Furthermore, by setting the acid value of the dibasic acid-modified rosin ester to 25 to 50 [mg (KOH) / g], it can be dissolved in a solvent such as water or alcohol, and it can be embrittled without becoming brittle. This is particularly preferable because it is possible to achieve the above-mentioned fixation.

  The ballpoint pen tip consists of at least a ball that serves as a writing member and a ball holder that rotatably holds the ball. The ball material is tungsten carbide, titanium, cobalt, chromium, nickel, etc. Materials and ceramics such as silicon carbide, silicon nitride, titanium nitride, alumina and zirconia can be used.

The ball holder has a ball as a writing member disposed in a through-hole as an ink passage, and has an inward protruding portion as a retraction restricting portion of the ball, for supplying ink around the ball to the inward protruding portion. A radial groove communicating with the central hole is formed. The tip opening portion has a ball-point pen tip shape in which, after the ball is placed, it is crimped to a diameter smaller than the diameter of the ball, and the ball is rotatably held with a part of the ball protruding.
As the material of the ball holder, a metal such as stainless steel, brass, or white can be used. Some are made from a coil wire, and some are made of pipe material having a medium hole in advance. Furthermore, it is also appropriate to provide a coil spring inside the ball holder that urges the ball forward to seal the gap between the ball and the ball holder. It is possible to prevent the rear part from slipping out, or to install a spring holder as a separate member. Further, an ink occlusion body such as a fiber bundling body that guides ink to the ball side may be interposed in the ball holder.

  A concave portion having a concave shape is formed on the outer surface of the ball holder on the axial center side from the outer surface of the ball holder. The concave portion may be formed in an annular shape over the entire circumference of the ball holder, may be spiral, or may be provided partially over the entire circumference. In addition, the depth and width of the recesses are appropriate, but ink may leak due to interference with the ink circulation holes inside the chip holder, and the ball holder may not be distorted or buckled due to a load due to cutting or pressing. It is essential. The width of the recess is not particularly limited as long as the ink color display is visible, but a width of about 0.5 mm to 2.0 mm is preferable. The method for forming such a recess can be performed by cutting or pressing the entire circumference or part of the ball holder with a cutting tool such as a cutting tool or a drill, or a pressing tool such as a punch. The concave portion is displayed with the same color as the ink contained in the refill.

  Pigments used as colorants for inks used for color display include carbon blacks such as Pigment Black 6 and 7; metal complex pigments such as Pigment Blue 27 and 9; Pigment Violet 15 and Pigment Red 259; 6. Pigment Yellow 42, Pigment Black 11, Pigment Red 101, and other metal oxide pigments, Pigment Yellow 53, Pigment Brown 24, and other complex oxide pigments, Pigment White 21, 22, 27, 28, 19, 24 1, 14 Inorganic pigments such as pearlescent pigments such as titanium dioxide and coated mica, Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 82, 83, 84, 90 90: 1, 151, 169, 172, 173, 174, 191, Pigment Orange 39, Pigment Yellow 18, 100, 104, 115, 117, Pigment Blue 1, 1 : 2, 2, 2, 3, 8, 10, 10, 11, 12, 14, 53, 62, 63, Pigment Violet 1, 2, 2: 2, 3 3: 1, 3: 3, 4, 5, 5, 5: 1, 6: 1, 7: 1, 9, 12, 20, 26, 27, 39, Pigment Green 1, 2, 3, 4, 8, 9, 10, 12, 12, 45, Pigment Rake pigments such as Brown 3, Pigment Red 1, 3, 21, 21, 112, 114, 146, 170, 187, 150, 185, 38, 41, Pigment Orange 5, 38, 36, 16, 13, 13, 34, Pigment Yellow 1, 3, 97, 167, 154, 12, 13, 13, 17, 17, 55, 83, 81 10, insoluble azo pigments such as Pigment Brown 25, condensed azo pigments such as Pigment Red 144 and 166, Pigment Red 53, 53: 1, 53: 3, 50, 50: 1, 49, 49: 1, 49: 2, 49: 3, 57: 1, 48: 1, 48: 2, 48: 3, 48: 4, 52: 1, 63: 1, 63: 2, 58: 2, 58: 4, 51, 60 : 1, 64: 1, Pigment Orange 17, 18, 18, 19 Pigment Yellow 61, 62, etc. Azo lake pigments, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, Pigment Green 7, 36, 37 and the like phthalocyanine pigments, Pigment Red 122, 202, 206, 207, 209, quinacridone pigments such as Pigment Orange 48 and Pigment Violet 19, anthraquinone pigments such as Pigment Red 168 and 177, Pigment Orange 51, Pigment Yellow 24 and 108, and Pigment Blue 60, Pigment Red 123 and 149, 178, 179, 190, 224, Pigment Violet 29, Perylene pigments such as CI pigment black 31 and 32, perinone pigments such as pigment red 194 and pigment orange 43, indigo pigments such as pigment red 88 and 181, pigment brown 27, pigment blue 66 and 63, and pigment violet. 23, 37, etc. Dioxazine pigments, Pigment Yellow 138, etc., quinophthalone pigments, Pigment Orange 61, Pigment Yellow 109, 110, 173, etc. Isoindolinone pigments, Pigment Red 260, Pigment Orange 66, 69 Pigment Yellow 139, 185, etc. Isoindoline pigments, Pigment Yellow 150, Pigment Green 8, Pigment Green 10 and other azo metal complex pigments, Pigment Red 257, Pigment Ole Di68, azomethine metal complex pigments such as Pigment Yellow 129, 153 and 65, diketopyrrolopyrrole pigments such as Pigment Red 254, 255, 264, 270 and 272, Pigment Orange 71 and 73 Color display from among organic blue pigments such as CI pigment blue 18, 19, 56, 57, 61, 56: 1, 61: 1, etc., alkali blue pigments, pigment black 1, aniline black, etc. One or two or more kinds that can be dispersed as fine particles in the ink for use can be appropriately selected and used. It is also effective to use a so-called color chip that has been subjected to pigment dispersion treatment and formed into a flake shape together with a resin or plasticizer. For example, NC Black (Pigment Black 7: 45%, Nitrocellulose: 45%, Acetyl Tributyl Citrate: 10%), L1 / 8 Red F3RT-70AT (Pigment Red 170: 45%, Nitrocellulose: 45%, Citric Acid Acetyltributyl: 10%), L1 / 8 Nonphthal Blue A (Pigment Blue 15: 40%, Nitrocellulose: 42%, Acetyltributyl Citrate: 18%), Yellow NIF (Pigment Yellow 83: 45%, Nitrocellulose: 45) %, Acetyltributyl citrate: 10%) (above, manufactured by Taihei Chemicals Co., Ltd.) and the like can be appropriately selected and used. The amount of the above pigment used varies depending on the type of pigment, but is 1 to 30% by weight, preferably 3 to 10% by weight, based on the total amount of the color display ink.

  The resin used as the fixing agent for the color display ink is a dibasic acid-modified rosin ester. Specific examples thereof include pentalin 255 (acid value 180 to 200), 261 (acid value 190 to 210), and 269. (Acid value 200), 830 (acid value 73-78) (above, manufactured by Rika Hercules Co., Ltd.), Harrier Star MT (acid value 25-35), MSR-4 (acid value 120-140), Harimac 135G (acid value 32-38), T-80 (acid value 170-200), FX-25 (acid value 155-175), AS-5 (acid value 185-210), (above, Harima Chemical Co., Ltd.), Ester Gum H (acid value of 10 or less) (Arakawa Chemical Industries, Ltd.), Beccasite 1111 (acid value 33-39), 1110 (acid value 25-35), 1120 (acid) (Value 25-35) This Ink and Chemicals Co., Ltd.), and the like. These resins can be used singly or in combination, and are added to impart fixability to the pen tip, so the amount used is in the range of 3.0 to 15.0% by weight with respect to the total amount of the ink composition. Is preferred. Further, the ratio of the resin to the pigment is 1: 1.0 to 1: 5.0 further improves the fixability of color display. Furthermore, by setting the acid value of the dibasic acid-modified rosin ester to 25 to 50 [mg (KOH) / g], it can be dissolved in a solvent such as water or alcohol, and it can be embrittled without becoming brittle. This is particularly preferable because it is possible to achieve the above-mentioned fixation.

  As the solvent for the color display ink, it is preferable to use an organic solvent having a boiling point of 170 ° C. or less in order to speed up drying of the color display portion and prevent the undried color display portion from flowing or disturbing in the ballpoint refill manufacturing process. . For example, lower alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and tertiary butyl alcohol, aromatic hydrocarbons such as xylene and toluene, and lower aliphatics such as methyl ethyl ketone and methyl isobutyl ketone Lower alcohol esters of lower fatty acids such as ketones, ethyl acetate and butyl acetate, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane, propylene glycol monomethyl ether, ethylene And glycol ethers such as glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. These can be used alone or as a mixture of two or more thereof, and the amount used is 50 to 90% by weight, preferably 70 to 85% by weight, based on the total amount of the color display ink.

The method of applying the color display ink to the recess is preferably applied with a marking pen because of its simplicity and productivity. Here, the form of the marking pen is not particularly limited, and a commercially available marking pen filled with a desired ink can also be used. It can be applied by contacting the tip of the marking pen while rotating the ballpoint pen tip. When applying with a marking pen, the viscosity of the ink is preferably 7 to 50 mPa · s.

  A ball-point pen body is formed by combining a ball-point pen tip with an ink-holding member that contains ink. When this ball-point pen body is accommodated in the exterior body, it becomes what is called a “refill”. For example, it can be a retractable ball-point pen that appears and disappears from the front end opening of the exterior body.

  The ink storage member may include an ink occlusion member such as a fiber bundling body inside, or may not include a member that holds such ink but may store ink in a free state. When the ink is accommodated in a free state, a high-viscosity fluid may be disposed at the ink interface as a backflow preventer. Further, the discharge may be supported by pressing the ink by, for example, enclosing compressed air in the ink containing portion. The materials constituting the ink storage member are polyamide resin, vinyl chloride resin, ethylene vinyl alcohol copolymer, polyacrylonitrile, fluororesin, polyacetal resin, polyethylene, polypropylene, polyethylene terephthalate, polycarbonate resin, polystyrene resin, ABS resin. Various materials such as resin such as polybutylene terephthalate, polybutylene naphthalate, polyethylene naphthalate, and metals such as stainless steel can be used, but it is necessary to consider the ease of manufacturing, ink color visibility, vapor permeability, etc. There is. It is also appropriate to color this extruded pipe or to add pigments or extenders.

  As the ink contained in the ink containing member and used for writing, either water-based ink using water as a main medium or oil-based ink using an organic solvent such as alcohol as a main medium can be used. Certain pigments and / or dyes, high-boiling organic solvents for preventing freezing, resin components that impart fixability to the writing surface, surfactants and polysaccharides that adjust surface tension, viscoelasticity, lubricity, etc. A rust preventive / antifungal agent or the like is blended, and a white concealing component such as titanium oxide may be blended for the purpose of correcting typographical errors.

Hereinafter, an example will be described based on the drawings.
The one shown in FIG. 1 assumes what is called a refill, and a ball-point pen tip 2 is press-fitted and connected to the tip of the ink containing tube 1.
The ink containing tube 1 is obtained by cutting an extruded pipe made of polypropylene resin into an appropriate length. A ballpoint pen tip 2 is press-fitted at one end and the other end is opened. Inside the ink storage tube 1, an ink 3 and a backflow preventing body composition 4 which is in contact with the ink interface and thickened with polybutene as a base material are disposed.

  The ball-point pen tip 2 partially protrudes a ball 5 as a writing member from the tip and holds the ball 5 in a freely rotatable manner, and a rear end portion is press-fitted into the tip of the ink containing tube 1. In order to provide visibility of the tip portion of the ball-point pen tip 2, the tip side portion is an inclined wall 2a, and a recess 2b is formed in this portion. The recess 2b is formed in a band shape by cutting. The recess 2b is colored with the same color as the handwriting color.

FIG. 2 shows a vertical sectional view of another example.
The ball-point pen tip 2 is provided with a large-diameter portion 2c and a small-diameter portion 2d, and a step portion formed therebetween is a recess 2b. A ball 5 protrudes from the tip of the small diameter portion 2d. That is, the linear inner side connecting the tip of the small diameter portion and the large diameter portion is a portion corresponding to the recess 2b. Ink is applied to the side wall of the small-diameter portion 2d in a strip shape to display the same color as the writing color.

  FIG. 3 shows a half sectional view of another example. This is an example in which a metal pipe is deformed to form a ballpoint pen tip 2. An inward projecting portion serving as a rearward movement restricting portion of the ball 5 is formed by rolling from the outside (by a punch or the like), and ink is applied to a partial concave portion 2b formed on the outside to display a color. Yes.

The color display ink will be described.
(Color display ink formulation example 1 “Black”)
Butyl acetate 40.0 parts Cellosolve acetate 19.0 parts Isopropyl alcohol 19.0 parts NC black (black color chip, 45% pigment, manufactured by Taihei Chemicals Co., Ltd.) 8.0 parts ester gum H (hydrogenated rosin ester 7.0 parts Harimac 135G (rosin-modified maleic acid resin, Harima Chemicals Co., Ltd.) 7.0 parts The above components were stirred at room temperature (25 ° C.) with a propeller stirrer for 5 hours, A black color display ink was obtained. The ratio of “pigment” to “hydrogenated rosin ester” and “rosin-modified maleic resin” is 1: 3.89. (The result of viscosity measurement with a B-type viscometer was 14.0 mPa · s.)

(Color display ink formulation example 2 “red”)
Propylene glycol monomethyl ether acetate 71.0 parts Ethylcyclohexane 15.0 parts L1 / 8 Red F3RT-70AT (red color chip, pigment content 45%, manufactured by Taihei Chemicals Co., Ltd.) 8.0 parts Beccasite 1111 (natural resin Modified maleic resin, manufactured by Dainippon Ink & Chemicals, Inc.)
6.0 parts The above ingredients were stirred with a propeller stirrer at room temperature (25 ° C.) for 5 hours to obtain a red color display ink. The ratio of “pigment” to “natural resin-modified maleic resin” is 1: 1.67. (The result of the viscosity measurement with a B-type viscometer was 15.4 mPa · s.)

(Color display ink combination example 3 “Blue”)
Propylene glycol monomethyl ether acetate 72.0 parts Ethylcyclohexane 15.0 parts L1 / 8 non-phthal blue A (blue color chip, pigment content 40%, Taihei Chemicals Co., Ltd.)
(Manufactured) 8.0 parts Beccasite 1111 5.0 parts The above components were stirred at room temperature (25 ° C) with a propeller stirrer for 5 hours to obtain a blue color display ink. The ratio of “pigment” to “natural resin-modified maleic resin” is 1: 1.56. (The result of the viscosity measurement with a B-type viscometer was 17.0 mPa · s.)

(Color display ink formulation example 4 “Green”)
Propylene glycol monomethyl ether acetate 70.0 parts Ethylcyclohexane 15.0 parts L1 / 8 non-phthal blue A (blue color chip, pigment content 40%, Taihei Chemicals Co., Ltd.)
5.0 parts Yellow NIF (yellow color chip, pigment content 45%, manufactured by Taihei Chemical Products Co., Ltd.) 5.0 parts Becacsite 1111 5.0 parts The above components were mixed with a propeller stirrer at room temperature (25 ° C). The mixture was stirred for a time to obtain a green color display ink. The ratio of “pigment” to “natural resin-modified maleic resin” is 1: 1.5. (The result of viscosity measurement with a B-type viscometer was 18.6 mPa · s.)

(Color display ink formulation example 5 “Black”)
Except for Ester Gum H and Harimac 135G from Color Display Ink Formulation Example 1, except that the amount of Harimac T-80 (rosin-modified maleic acid resin, acid value 170-200, manufactured by Harima Chemical Co., Ltd.) was added. A black color display ink was obtained in the same manner as in Display Ink Formulation Example 1. The ratio of “pigment” to “rosin-modified maleic resin” is 1: 3.89. (The result of the viscosity measurement with a B-type viscometer was 14.6 mPa · s.)

(Color display ink formulation example 6 “red”)
In the same manner as in Color Display Ink Formulation Example 2 except that the addition amount of Becacite 1111 in Color Display Ink Formulation Example 2 is 3.0 parts and the addition amount of propylene glycol monomethyl ether acetate is 74.0 parts. A color indicating ink was obtained. The ratio of “pigment” to “natural resin (rosin) -modified maleic resin” is 1: 0.83. (The result of the viscosity measurement with a B-type viscometer was 11.8 mPa · s.)

(Color display ink formulation example 7 “Blue”)
Except for becacite 1111 of color display ink blending example 3, the same amount as that of color display ink blending example 3 except that Harrier Star L (rosin-modified glycerin ester, oxidation degree 4-8, Harima Kasei Co., Ltd.) was added. As a result, a blue color display ink was obtained. The ratio of “pigment” to “rosin-modified glycerin ester” is 1: 1.56. (The result of the viscosity measurement with a B-type viscometer was 20.4 mPa · s.)

(Color display ink formulation example 8 “Green”)
Except for Becacite 1111 in Color Display Ink Formulation Example 4, except that Hilac 111 (Ketone Resin, manufactured by Hitachi Chemical Co., Ltd.) is added in the same amount, Green Display is performed in the same manner as Color Display Ink Formulation Example 4. An ink was obtained. The ratio of “pigment” to “ketone acid resin” is 1: 1.5. (The result of the viscosity measurement with a B-type viscometer was 17.0 mPa · s.)

(Test 1)
Ballpoint pen tip shown in FIGS. 1 to 3 in the ink storage tube used for the refill (product code: BKSS7-A2) for Pentel Co., Ltd. multicolor (4 colors) ballpoint ROLLY C4 (product code: BPC47T) A test sample was prepared. As a comparative sample, ink was applied to the side wall of the ballpoint pen tip of ROLLY C4 refill (product code: BKSS7-A2).
Each test sample is incorporated into the exterior body of the multicolored ballpoint pen ROLLY C4 (product code: BPC47T), the pen tip is inserted and removed 1000 times, and the ink color display ink adhering to the inner surface near the front end of the exterior body The presence or absence of adhesion was visually determined. The results are shown in Table 1.

(Test 2)
Also, using a commercially available cutter on a stainless steel plate, scratches were made so that 10 mm squares and 10 horizontal squares were lined up to form 100 squares, on which color display ink formulation examples 1 to 8 5 minutes after applying each ink, put a high quality paper on the application surface, and put a weight of a cylinder with a diameter of 50 mm and a weight of 500 g on the high quality paper, and the distance between the paper and the weight is 5 mm from side to side. After 10 reciprocations, the number of peeled pieces was counted. The results are shown in Table 2.

The figure of the refill in which the ball-point pen tip of the present invention is connected to the tip of the ink storage tube. The longitudinal cross-sectional view of another example. The half sectional view of another example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ink receiving tube 2 Ball-point pen tip 2a Inclined wall 2b Recessed part 2c Large diameter part 2d Small diameter part 3 Ink 4 Backflow prevention body composition 5 Ball

Claims (3)

The concave portion formed on the outer surface of the ball-point pen tip composed of at least a ball as a writing member and a ball holder that rotatably holds the ball comprises at least a pigment, an organic solvent, and a resin. The ball-point pen tip which gave the color which displays an ink color with the ink whose ratio is in the range of 1: 1.0-1: 5.0 and the said resin is a dibasic acid modified rosin ester . The ballpoint pen tip according to claim 1 whose acid value of said resin is the range of 25-50 [mg (KOH) / g] . The ball-point pen tip according to claim 1 or 2, wherein the ball-point pen tip is attached to a tip of a refill mounted in a retractable ball-point pen that protrudes and protrudes from a tip opening of an exterior body by an operation.