JP6435173B2 - Ball pen refill with operating body and writing instrument containing it - Google Patents

Description

The present invention relates to a ballpoint pen refill with an operating body and a writing instrument containing the same. More specifically, the present invention relates to a ballpoint pen refill with an operating body formed by connecting operating bodies and a writing instrument containing the same.

Conventionally, writing instrument refills with ink compositions built into ink containing tubes with pen nibs have been widely used because they can be replaced after ink consumption. The writing instrument refill which connected the member was displayed with the empty writing instrument main body, and the customized writing instrument which a user can select and purchase a desired writing instrument main body and a writing instrument refill has appeared (for example, refer patent documents 1 thru | or 3).
In the writing instrument refill connected with the operating body and joint member, the operating body and joint member are colored in ink, so that the operation function and the original function as a connection part with the writing instrument body are displayed, as well as at the time of display alone and the writing instrument. Since the ink color contained in the refill in the accommodated state can be seen at a glance, it is a particularly useful configuration.

In addition, metals and resins are generally used as the material for the ink storage tube. However, when the metal is made of metal, the built-in ink cannot be visually recognized due to its high cost. While post-processing is required, resin-made ones are inexpensive and have built-in ink that can be visually recognized, and the operation body and joint members can be easily connected by fitting etc. It is useful.
However, when an ink containing tube made of a thermoplastic resin is used, deformation or shrinkage may occur due to environmental load such as aging or temperature change. At that time, since the connection force between the operating body or joint member and the ink storage tube is weakened, the operating body or joint member may be detached from the ink storage tube when the used refill is pulled out from the writing instrument body at the time of refill replacement. .

JP 2007-45139 A JP 2010-64365 A JP 2009-286018 A

Even if a thermoplastic resin is used as an ink storage tube for a writing instrument refill for connecting an operation body and a joint member, the operation body and the joint member are generated at the time of refill replacement due to environmental load such as aging and temperature change. The present invention provides a writing instrument refill excellent in stability over time and environmental resistance capable of reliably suppressing the separation of the ink and a writing instrument using the same.
In the present invention, “front” indicates the pen tip side, and “rear” indicates the opposite side of the pen tip in the axial direction.

The present invention comprises a ballpoint pen tip at the front end of an ink containing tube for containing the ink composition, and is connected by inserting and fitting the operating body at the rear end. A writing instrument refill withdrawn from an end, wherein the ink containing tube is made of a thermoplastic resin, and at least an end portion for connecting the operation body is formed of at least an inner layer, an outer layer, and an intermediate layer, and the intermediate layer is made of ethylene vinyl A ballpoint pen refill with an operating body, which is one of resins selected from alcohol copolymer resins, vinylidene chloride resins, acrylonitrile resins, and polyester resins, is a requirement.
Furthermore, it is a requirement that the inner layer, the outer layer, and the intermediate layer are formed by composite molding.
Furthermore, it is a requirement that a writing instrument containing one or more ball pen refills with an operating body described in any of the above, and that the writing instrument has a structure that grips the operating body and pulls out the refill when the refill is replaced. To do.

  According to the present invention, even when a thermoplastic resin is used as an ink storage tube of a writing instrument refill for connecting an operation body or a joint member, deformation or shrinkage that may occur due to environmental load such as aging or temperature change can be easily performed. Since it can suppress by a structure, the connection force of an operation body, a coupling member, and an ink storage pipe is maintained with an initial state. Therefore, even if it is pulled out from the writing instrument at the time of refill exchange, it becomes a writing instrument refill excellent in temporal stability and environmental resistance that can reliably suppress the operating body and the joint member from separating from the ink storage tube. Furthermore, it becomes a writing instrument with high refill exchangeability.

It is sectional drawing which shows an example of embodiment of the writing instrument refill of this invention. It is an external view which shows an example of the writing instrument which accommodated the writing instrument refill of FIG. 1 in the empty writing instrument main body. It is sectional drawing which shows an example of other embodiment of the writing instrument refill of this invention. It is an external view which shows an example of the writing instrument which accommodated the writing instrument refill of FIG. 3 in the empty writing instrument main body.

The writing instrument refill of the present invention contains an ink composition in an ink containing tube, and is provided with a pen tip (writing tip) communicating directly or via a connecting member with the tip of the ink containing tube. An operating body or a joint member is connected to the rear end portion.
As the pen tip, a marking pen tip such as a fiber tip, a felt tip, a plastic tip, or a ballpoint pen tip can be applied. The tip of the marking pen tip may be a shell type, a chisel type, a brush pen type, or the like.

The ballpoint pen tip has a structure in which a ball is held in a ball holding portion formed by pressing and deforming the vicinity of a tip of a metal pipe inward from the outer surface, and the ball holding portion by cutting a metal material with a drill or the like And a structure in which the ball is held in the ball holding portion, a structure in which the ball is urged forward by a spring body, or a structure in which a resin ball receiving seat is provided inside a metal or plastic chip Can be illustrated.
The ball may be about 0.1 to 1.5 mm in diameter, such as cemented carbide, stainless steel, ruby, ceramic, resin, rubber, etc., preferably 0.3 to 1.0 mm, more preferably 0. .3 to 0.7 mm is used.

  The ink containing tube is made of a thermoplastic resin, and a molded body made of polyolefin resin such as polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, nylon, etc. is preferably used in terms of productivity, and has moldability and solvent resistance. Polypropylene is particularly preferable because it is high and the resin coat layer and the inorganic vapor deposition layer are easily laminated.

A resin coat layer or an inorganic vapor deposition layer is laminated | stacked on the edge part to which an operation body and a coupling member are connected at least among the said ink storage pipes, and it becomes a laminated body of two or more layers.
As the resin coating layer, ethylene vinyl alcohol copolymer resin, vinylidene chloride resin, acrylonitrile resin, polyester resin and the like are preferable from the viewpoint of high deterioration resistance, and at least one of them is used for the thermoplastic resin of the ink containing tube. It is formed by laminating at least one layer (any number of layers of two or more layers).
Examples of the ethylene vinyl alcohol copolymer resin include Kuraray Co., Ltd., trade name: EVAL. The vinylidene chloride resin may be a vinylidene chloride copolymer resin, such as vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-methacrylic acid copolymer, vinylidene chloride-acrylate copolymer, vinylidene chloride-methacrylate copolymer. And vinylidene chloride-vinyl acetate copolymer.

The position where the resin coat layer is formed is not particularly specified, such as the innermost layer (inner surface layer), the outermost layer (outer surface layer), or an intermediate layer, but is not particularly specified in the middle of the thermoplastic resin constituting the ink containing tube. A layer (that is, a layer excluding the inner layer and the outer layer) is preferable. Supporting from the inside as an intermediate layer of thermoplastic resin such as polypropylene (ie, three or more resin layers), it acts as the core of the thermoplastic resin layer, so deformation such as bending of the laminated portion, shrinkage with time, etc. Can be more reliably suppressed.
In addition, as a method of forming the resin coat layer on the ink containing tube, the resin coat layer is directly formed on the molded body molded with a thermoplastic resin by means of composite molding such as two-color molding, coating, printing, or the like. It may be formed or may be a method in which an adhesive layer is indirectly provided. An adhesive can be used between the resin coat layer and the thermoplastic resin, and a resin material is particularly preferable.

The inorganic vapor deposition layer is preferably a layer using a metal oxide, and specific examples include aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, tin oxide and the like.
The inorganic vapor-deposited layer can be provided as an intermediate layer (that is, a state where a portion where the metal oxide is exposed is further coated with a thermoplastic resin) in addition to the outer surface and the inner surface of the ink containing tube. Preferably, since it is excellent in workability and the inorganic vapor deposition layer can be reliably adhered to the thermoplastic resin, a plasma film forming method using plasma, a chemical vapor deposition method (CVD method), a vacuum vapor deposition method, molecules in the evaporation source An ion plating method or a sputtering method is used in which a film is formed by irradiating an electron beam to heat and evaporate. Therefore, what was formed in the innermost side (inner surface layer) and outermost side (outer surface layer) of the ink storage tube is preferable. In addition, when setting it as an intermediate | middle layer, after forming an inorganic vapor deposition layer by the said method on the resin film surface, the method of sticking to the thermoplastic resin surface is preferable. When this method is adopted, the inorganic vapor deposition layer may be attached to the inner surface, or may be attached to the outer surface. In addition, a general purpose thing can be applied as an adhesive material for sticking.

The resin coat layer and the inorganic vapor deposition layer are laminated at least on the end portion of the ink storage tube to which the operating body and the joint member are connected, in order to eliminate the directionality of the ink storage tube and improve the assemblability. It is preferable to form at both ends, and further, it is preferable to laminate the entire ink containing tube in consideration of the moldability and vapor deposition of the laminate. When laminated on the whole, productivity is improved and the ink containing tube is not easily deformed by stress. Therefore, even if the refill with the operating body as in Patent Document 1 is inserted from the rear end portion of the writing instrument body, deformation at the time of insertion or withdrawal can be suppressed, which may cause a catch in a sliding operation. And the pen tip can appear and disappear smoothly.
Moreover, since oxygen permeation can be reduced as compared with the case where a thermoplastic resin is used alone, it is possible to impart poor oxygen permeability from the outside into the ink containing tube (ink side).

The wall thickness of the ink containing tube is not particularly limited, but the outer diameter of the ink containing tube constituting the writing instrument refill is roughly determined. If each layer is thickened, the inner diameter of the ink containing tube is reduced and built-in. Therefore, the thickness of the ink containing tube is preferably 0.1 to 1.5 mm, preferably 0.3 to 1.0 mm, and more preferably 0.5 to 0.8 mm.
In particular, in the case of a composite writing instrument in which a plurality of writing instrument refills are accommodated in the shaft cylinder, and the writing tip part of any writing instrument refill is projected and retracted from the front end opening of the shaft cylinder by the operation of the retracting mechanism, the outer diameter of the shaft cylinder is reduced. In order to facilitate gripping, it is necessary to design the outer diameter of the ink containing tube to be small. Furthermore, in order to prevent the amount of ink from being reduced, it is necessary to make the thickness of the ink containing tube as thin as possible, so that it becomes easy to deform. Also from this point, the application of the ink containing tube provided with the entire laminated portion of the present invention is a particularly useful requirement.
In addition, since it is preferable that the said ink accommodating tube has transparency so that the ink remaining amount can be visually recognized, what has the transparency as the above-mentioned resin coat layer and inorganic vapor deposition layer is suitable.

  The operation body and the joint member connected to the rear end of the ink containing tube are made of resin or metal. In particular, by coloring at least a portion of the ink hue accommodated in the refill, the writing instrument refill alone can exhibit decoration and a color display function. In the ballpoint pen refill, the ball diameter can also be displayed. As a connection method with these ink storage tubes, any method such as covering, insertion, etc., fitting, locking, clamping, screwing, etc. may be used, but since the connection strength and assemblability are high. The fitting is suitable, and in particular, a structure in which the end of the operation body or the joint member is inserted and fitted into the ink containing tube is preferred.

The operation body is connected to the rear end of the ink storage tube, and protrudes from the side wall of the shaft tube when it is housed in the shaft tube of the writing instrument body. By sliding the projecting operation body, the writing tip portion appears and disappears from the opening at the tip of the shaft tube.
The joint member is connected to the rear end of the ink storage tube. When the joint member is received in the shaft cylinder of the writing instrument body, the joint member is connected and held by a method such as fitting to the rear end of the shaft cylinder, the rotating slide body, the slide lever, Is done. At this time, the connecting force on the writing instrument main body side is set to be smaller than the coupling force between the joint member and the ink storage tube, and the joint member is also removed together when the ink storage tube is pulled out during refill replacement.

  In addition to directly storing the ink composition, the ink storage tube includes an ink occlusion body made of a fiber bundle impregnated with ink, a comb groove-shaped ink flow rate adjustment member, and an ink flow rate adjustment member made of a fiber bundle. Or a valve mechanism may be used.

  The ink composition accommodated in the ink accommodating tube can be applied without being limited to general-purpose water-based inks, oil-based inks, emulsion inks and the like according to the type of the nib and the refill structure. In particular, since the water-based ink easily absorbs oxygen from the outside of the refill into the solvent, the ink stability is likely to be lost with time, and air generation due to water evaporation is likely to occur. Therefore, the refill configuration of the present invention is useful. This is because in the writing instrument refill in which the resin coat layer or the inorganic vapor deposition layer is formed on the ink containing tube, it is difficult for oxygen to enter from the laminated portion, and also from this point, it is more preferably laminated on the entire ink containing tube. Things are effective.

The water-based ink composition is composed of water, a colorant, a water-soluble organic solvent, an additive such as a resin, and the like.
As the colorant, all dyes and pigments that can be dissolved or dispersed in an aqueous medium can be used, and specific examples thereof will be exemplified below.
As the dye, an acid dye, a basic dye, a direct dye, or the like can be used.
Examples of the acid dye include New Coxin (CI. 16255), Tartrazine (CI. 19140), Acid Blue Black 10B (CI. 20470), Guinea Green (CI. 42085), Brilliant Blue FCF. (CI.42090), Acid Violet 6B (C.I.42640), Soluble Blue (C.I.42755), Naphthalene Green (C.I.44025), Eosin (C.I.45380), Phloxin (C.I. 45410), erythrosine (C.I. 45430), nigrosine (C.I. 50420), acid flavin (C.I. 56205) and the like are used.
Examples of basic dyes include chrysoidine (C.I. 11270), methyl violet FN (C.I. 42535), crystal violet (C.I. 42555), malachite green (C.I. 42000), Victoria blue FB ( CI 44045), rhodamine B (C.I. 45170), acridine orange NS (C.I. 46005), methylene blue B (C.I. 52015) and the like are used.
As direct dyes, Congo Red (C.I. 22120), Direct Sky Blue 5B (C.I. 24400), Violet BB (C.I. 27905), Direct Deep Black EX (C.I. 30235), Kaya Las Black G Conch (C.I. 35225), Direct Fast Black G (C.I. 35255), Phthalocyanine Blue (C.I. 74180) and the like are used.

Examples of the pigment include inorganic pigments such as carbon black and ultramarine blue, and organic pigments such as copper phthalocyanine blue and benzidine yellow, as well as water-dispersed pigments that are finely and stably dispersed in an aqueous medium in advance using a surfactant or the like. For example, C.I. I. Pigment Blue 15: 3B [Product Name: S.P. S. Blue GLL, pigment content 22%, manufactured by Sanyo Color Co., Ltd.], C.I. I. Pigment Red 146 [Product Name: S.P. S. Pink FBL, pigment content 21.5%, manufactured by Sanyo Dye Co., Ltd.], C.I. I. Pigment Yellow 81 [Product name: TC Yellow FG, pigment content about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.], C.I. I. Pigment Red220 / 166 [Product name: TC Red FG, pigment content: about 35%, manufactured by Dainichi Seika Kogyo Co., Ltd.]. As the fluorescent pigment, a fluorescent pigment in the form of fine particles of a synthetic resin in which various fluorescent dyes are formed into a solid solution in a resin matrix can be used.
Other examples include pearl pigments, gold and silver metallic pigments, phosphorescent pigments, white pigments such as titanium dioxide used in correction pens, and metal powders such as aluminum.
Furthermore, a thermochromic composition, a photochromic composition, a fragrance and the like, capsule pigments in which these are encapsulated, and the like can be exemplified.

The thermochromic composition includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible thermochromic composition comprising a reaction medium that determines the temperature at which the color reaction occurs. The composition is suitable, and is preferably encapsulated in a microcapsule and applied as a reversible thermochromic microcapsule pigment.
Examples of the reversible thermochromic composition include those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., at a predetermined temperature (discoloration point). Discolored before and after, decolored state in the temperature range above the high temperature side discoloration point, color development state in the temperature range below the low temperature side discoloration point, only one specific state exists in the normal temperature range among the two states, The other state is maintained as long as the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. A heat decolorable microcapsule pigment in which a reversible thermochromic composition having relatively small characteristics (ΔH = 1 to 7 ° C.) is encapsulated in a microcapsule can be applied.
Furthermore, comparatively large hysteresis characteristics (ΔH = 8 to 50) described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ° C), and exhibit large hysteresis characteristics described in JP-A-2006-137886, JP-A-2006-188660, JP-A-2008-45062, JP-A-2008-280523, In other words, the shape of the curve plotting the change in color density due to temperature change differs greatly between when the temperature is raised from the lower temperature side than the color change temperature range and when the temperature is lowered from the higher temperature side than the color change temperature range. The color changes following the path, and the color development state in the low temperature range below the complete color development temperature, or the color erase state in the high temperature range above the complete color erase temperature is in the specific temperature range. Microcapsule pigment was contained a reversible thermochromic composition heated decolorizable having chroma memory property can be applied.
In addition, as the reversible thermochromic composition having color memory, which is applied to writing instrument inks, specifically, a complete coloring temperature is a temperature that can be obtained only in a freezing room, a cold region or the like, that is, −50 to 0 ° C. , Preferably −40 to −5 ° C., more preferably −30 to −10 ° C., and a complete decoloring temperature obtained from a frictional heat generated by a friction body, a heating body such as a hair dryer, that is, 50 to 95 ° C. , Preferably 50 to 90 ° C., more preferably 60 to 80 ° C., and by specifying ΔH value 40 to 100 ° C., effective in maintaining colors exhibited in normal conditions (daily living temperature range) Can function.

  In addition, a conventional general-purpose water-soluble organic solvent compatible with water can be used, for example, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol. , Hexylene glycol, 1,3-butanediol, neoprene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether, propylene glycol Monoethyl ether, 2-pyrrolidone, N- methyl-2-pyrrolidone.

In addition, if necessary, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, rust preventives such as benzotriazole, tolyltriazole and saponin , Carboxylic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) Preservatives or antifungal agents such as pyridine, urea, sorbit, mannitol, sucrose, glucose, reduced starch hydrolysates, wetting agents such as sodium pyrophosphate, antifoaming agents, fluorine-based interfaces that improve ink permeability An activator or a nonionic surfactant may be used.
Further, a lubricant can be added, such as metal soap, polyalkylene glycol fatty acid ester, ethylene oxide addition type cationic surfactant, phosphate ester type surfactant, N-acyl amino acid type surfactant, dicarboxylic acid type surfactant. , Β-alanine type surfactant, 2,5-dimercapto-1,3,4-thiadiazole and its salts and oligomers, 3-amino-5-mercapto-1,2,4-triazole, thiocarbamate, dimethyl A dithiocarbamate, α-lipoic acid, a condensate of N-acyl-L-glutamic acid and L-lysine, a salt thereof, or the like is used.
Further, oligomers of N-vinyl-2-pyrrolidone, oligomers of N-vinyl-2-piperidone, N-vinyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, ε-caprolactam, N-vinyl-ε-caprolactam By adding a thickening inhibitor such as an oligomer, it is possible to enhance the function in the intruding form.
Further, one or more wetting agents such as urea, nonionic surfactant, sorbit, mannitol, sucrose, glucose, reduced starch hydrolyzate, sodium pyrophosphate and the like can be added.

  In addition, one or more water-soluble resins such as alkyd resins, acrylic resins, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin can be added within a range that does not impair drying resistance.

A shear thinning agent can be added to the water-based ink.
As the shear thinning agent, water-soluble or dispersible substances are effective, and xanthan gum, welan gum, zetasy gum, dieutan gum, macrohomopsis gum, and the constituent monosaccharides are organic acid-modified heterogeneous of glucose and galactose. Succinoglycan, which is a polysaccharide (average molecular weight: about 100 to 8 million), guar gum, locust bean gum and its derivatives, hydroxyethyl cellulose, alkyl alginate, alkyl ester of methacrylic acid, molecular weight 100,000 to 150,000 Polymers, glucomannan, carbohydrates having gelling ability extracted from seaweed such as agar and carrageenan, cross-linked poly N-vinyl-carboxylic acid amide, benzylidene sorbitol and benzylidene xylitol or their derivatives, cross-linkable acrylic acid Coalescence Inorganic fine particles, nonionic surfactants having an HLB value of 8 to 12, can be exemplified metal salts and amine salts of dialkyl sulfosuccinate. Furthermore, N-alkyl-2-pyrrolidone and an anionic surfactant may be used in combination in the ink composition.

The oil-based ink composition includes a colorant, an organic solvent, and an additive such as a resin.
As the colorant, all dyes and pigments that can be dissolved or dispersed in an organic solvent can be used, and specific examples thereof are illustrated below.
As the dye, a conventionally known oil-soluble dye can be used. Specifically, rhodamine B base (CI 45170B, Taoka Dye Manufacturing Co., Ltd.), Soldan Red 3R (CI 21260, Chugai) Kasei Co., Ltd.), methyl violet 2B base (C.I. 42535B, USA, National Aniline Div.), Victoria Blue F4R (C.I. 42563B), nigrosine base LK (C.I. 50415) (above) , BASF, Germany), Bali First Yellow # 3104 (C.I. 13900A), Bali First Yellow # 3105 (C.I. 18690A), Orient Spirit Black AB (C.I. 50415), Bali First Black # 3804 (C.I. 12195), Bali First Yellow # 1109, Bali First Orange # 2210, Bali First Red # 1320, Bali First Blue # 1605, Bali First Violet # 1701 (manufactured by Orient Chemical Co., Ltd.), Spiron Black GMH Special, Spiron Yellow C- 2GH, spirone yellow C-GNH, spirone red C-GH, spirone red C-BH, spirone blue C-RH, spirone violet C-RH, S. P. T.A. Orange 6, S. P. T.A. Examples include Blue 111 (manufactured by Hodogaya Chemical Co., Ltd.). Furthermore, C.I. I. Basic Blue 1, 7, 7, 8, C.I. I. Basic violet 1, 3 and C.I. I. Basic dyes such as Basic Red 1 and C.I. I. Examples thereof include salt-forming dyes with acid dyes selected from Acid Yellow 23, 36 and the like.

As the pigment, a conventionally known pigment can be used. I. PIGMENT RED2, 3, 5, 8, 17, 17, 22, 31, 38, 41, C.I. I. PIGMENT ORANGE 5, 10, 13, 16, 36, 40, 43, 61, 64, 71, 73, C.I. I. PIGMENT VIOLET 19, 23, 31, 33, 36, 37, 38, 50, C.I. I. PIGMENT BLUE 2, 9, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 17, 17, 22, 25, 28, 29, 36 60, 68, 76, C.I. I. PIGMENT BROWN 23, 25, 26, C.I. I. PIGMENT YELLOW 1, 3, 12, 13, 24, 83, 93, 94, 95, 97, 99, 128, 139, 153, 173, C.I. I. PIGMENT GREEN 7, 10, 36, C.I. I. Organic pigments such as PIGMENT BLACK 7, carbon black such as black iron oxide, furnace black, channel black, thermal black, acetylene black, yellow iron oxide, red iron oxide, ultramarine, bitumen, cobalt blue, titanium yellow, turquoise, Examples thereof include inorganic pigments such as molybdate orange and titanium oxide.
Furthermore, as other pigments, fluorescent pigments, pearl pigments, phosphorescent pigments, metal pigments, composite metal pigments, metal oxide pigments, thermochromic pigments, and the like can be used.

  As the organic solvent, conventionally known ballpoint pen solvents can be used. For example, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl glycol, propylene glycol normal butyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene group Glycol ether solvents such as coal normal propyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether, ethylene glycol, diethylene glycol, Glycol solvents such as propylene glycol, dipropylene glycol, hexylene glycol, glycerin and polyethylene glycol, ester solvents such as 2-ethylhexyl acetate, isobutyl isobutyrate, ethyl lactate, butyl lactate, benzyl alcohol, β- Phenylethyl alcohol, α-methylbenzyl alcohol, lauryl alcohol, tridecyl alcohol, iso Decyl alcohol, iso-tri dodecyl alcohol, alcohol solvents such like.

  As the resin, a resin usually used as a fixing agent or a dispersing agent in a writing instrument ink composition is appropriately used. For example, a ketone resin, a sulfonamide resin, an acrylic resin, a maleic acid resin, a styrene and a maleic acid ester Polymer, copolymer of styrene and acrylic acid or ester thereof, ester gum, xylene resin, urea resin, polyamide resin, alkyd resin, phenol resin, alkylphenol resin, terpene phenol resin, rosin resin or hydrogenated compound thereof, Examples thereof include polyvinyl butyral, polyvinyl acetal, polyvinyl alkyl ether, polyvinyl pyrrolidone, and polyethylene oxide.

  Furthermore, viscosity modifiers such as bentonite, synthetic fine powder silica, hydrogenated castor oil, fatty acid amide wax, antiseptics, rust preventives, antifoaming agents, lubricants, dispersants, anti-scratch agents, leak-proofing agents, surfactants Various additives such as these can also be added to the oil-based ink.

As the emulsion ink, either a W / O type or an O / W type in which a water-based component and an oil-based component are dispersed based on any of them can be used.
For example, as the W / O type, an aqueous component containing water, a polyhydric alcohol, a shear thinning agent, and a colorant is dispersed in an oily component containing a polar solvent and a spinnability imparting agent such as polyvinylpyrrolidone. Examples of the O / W type include those obtained by emulsifying and dispersing an oil component containing a colorant, an organic solvent, a sucrose fatty acid ester, and sodium acyl lactate in water.
In addition, the composition which comprises the said emulsion ink can be applied combining suitably from the composition illustrated with the above-mentioned water-based ink and oil-based ink.

Furthermore, when the ink composition is filled in the ink containing tube, an ink backflow prevention body (liquid stopper) can be disposed at the rear end of the ink composition.
As the ink backflow preventer, either liquid or solid can be used, and examples of the liquid ink backflow preventer include non-volatile media such as polybutene, α-olefin oligomer, silicone oil, and refined mineral oil. If desired, silica, aluminum silicate, swellable mica, fatty acid amide and the like can be added to the medium. Moreover, a resin molding is mentioned as a solid ink backflow prevention body. The liquid and solid ink backflow preventers can be used in combination.

The writing instrument refill is housed in a writing instrument main body (shaft tube) serving as an exterior of the writing tool, and a writing tool or a cap-type writing tool in which the writing tip end portion of the refill appears and disappears from the shaft tube tip opening portion by the operation of the retracting mechanism. Moreover, what can be applied as general-purpose writing instrument exteriors, such as resin, metal, and ceramics, is mentioned as said axial cylinder. Further, an opening / closing lid may be provided at the rear end of the shaft tube for exchanging the refill with operating body.
The writing instrument may be a composite type penetrating writing instrument that accommodates a plurality of writing instrument refills in addition to the one that accommodates one writing instrument refill in the shaft tube. In that case, a unit in which an operating body and a joint member are connected to the rear end of each refill, such as a mechanical pencil unit, an eraser unit, a touch pen unit, and a friction body unit, can be used in combination.

Examples of the operation method of the retracting mechanism include a knock type, a rotary type, and a slide type.
The knock type has a knock portion on the rear end portion of the shaft cylinder and the side surface of the shaft tube, and the writing tip portion of the writing instrument refill is projected and retracted from the front end opening portion of the shaft tube by pressing the knock portion, or on the shaft tube. The structure which makes the writing front-end | tip part of a writing instrument refill protrude and retract from the axial cylinder front-end opening part by pressing the provided clip part can be illustrated.
The rotary type can be exemplified by a configuration in which the shaft cylinder has a rotating portion (rear shaft or the like), and the writing tip of the writing instrument refill is caused to appear and disappear from the front end opening portion of the writing tube by turning the rotating portion.
The slide type has a slide portion on the side surface of the shaft cylinder, and the slide tip of the writing instrument refill is projected and retracted from the front end opening portion of the shaft cylinder by operating the slide, or the clip portion provided on the shaft cylinder is slid. By doing so, a configuration in which the writing tip portion of the writing instrument refill is caused to appear and disappear from the shaft front end opening portion can be exemplified. When the refill with operating body is used, the slide portion functions as a refill operating body.

Examples of the present invention are shown below, but the present invention is not limited thereto.
In addition, the part in an Example is a mass part, and the melt flow rate (MFR) of resin is the value measured according to JISK6921-2.
Example 1
Preparation of black water-based ink composition 5.0 parts of black dye, 0.5 part of xanthan gum, 10.0 parts of N-vinyl-2-pyrrolidone oligomer, 0.3 part of antifungal agent, 0.5 part of lubricant, triethanol A black aqueous ink composition 6 comprising 1.0 part of amine and 82.7 parts of water was prepared.

Preparation of ink containing tube As first layer (inner layer), polypropylene [MFR: 1 to 10] as thermoplastic resin portion 41, and ethylene vinyl alcohol copolymer resin as resin coat layer 42 as second layer (intermediate layer), Polypropylene [MFR: 1 to 10] is used as the third layer (outer layer) and is cylindrical with an inner diameter of 1.7 mm and an outer diameter of 3.1 mm by an extrusion molding machine (multi-layer extrusion die, three layers of three layers). The ink containing tube 4 was manufactured by extruding to a length of 85 mm.
The thickness of the first layer of the ink containing tube 4 was 0.48 mm, the thickness of the second layer was 0.05 mm, and the thickness of the third layer was 0.17 mm.

Ballpoint refill fabrication (see Figure 1)
After fixing the ball-point pen tip 2 holding a 0.3 mm carbide ball to the tip of the ink containing tube 4 by pressing and deforming the vicinity of the tip of the metal pipe via the connecting member 3, The aqueous ink composition 6 was filled, and then an ink follower (liquid stopper 61) mainly composed of polybutene was filled so as to come into contact with the ink 6. Further, the front end of the operation body 5 made of a black opaque resin molding was inserted and fitted inside the rear end portion of the ink containing tube 4 to obtain a ball pen refill with an operation body (writing instrument refill 1). Although not shown in the drawings, the pen tip has a built-in spring for pressing the ball forward.

  Further, in the configuration of the ballpoint pen refill 1 with the operation body, an operation having the aqueous ink composition 6 and the operation body 5 of three colors of red, blue, and green, respectively, by changing the color of the ink and the hue of the operation body. A body-mounted ballpoint pen refill 1 was obtained.

Ballpoint pen production (see Figure 2)
A writing instrument body 8 with a clip 97 having a lid 95 that can be freely opened and closed at the rear end opening, and four window holes 94 provided at equal intervals in the side wall of the shaft tube 9 so as to be connected in the axial direction from the rear end. On the other hand, a spring is disposed in the front of each window hole 94 in the axial direction. Each refill 1 extends from the rear end opening of the shaft tube 9 so that the operating body 5 protrudes from the window hole 94. Was inserted, and the lid 95 was closed to obtain a composite ballpoint pen (writing instrument 7) in which the writing tip portion 2 of each refill 1 was selectively projected and retracted by the sliding operation of the operating body 5. Each refill 1 can be easily taken out by opening the lid 95 and holding the operating body 5 and then pulling it out rearward in the axial direction.

Comparative Example 1
A composite ballpoint pen 7 was obtained in the same manner as in the ballpoint pen of Example 1 except that the ink containing tube 4 was made of polypropylene alone.
The obtained ball-point pen and the ball-point pen produced in Example 1 were left in a horizontal state for 90 days in an environment of 50 ° C., and then the operation tool 5 was grasped from the writing tool body 8 of each composite ball-point pen and the refill 1 was pulled out. When the operation of storing again was repeated, the ballpoint pen refill 1 with the operating body of the example could be repeated without any problem. On the other hand, in the ball pen refill 1 with the operation body of the comparative example, there are those in which the operation body 5 is detached from the ink storage tube 4, the connection portion is bent, or the ink storage tube 4 is curved. It was.
In addition, while there is no change in the ballpoint pen refill 1 with the operating body of the embodiment, the air is generated in the ballpoint pen refill 1 with the operating body of the comparative example. The interface was separated.
A spiral circle was continuously written on the JIS P3201 writing paper A at room temperature using each of the writing tools 7. At that time, the ballpoint pen refill 1 with the operating body of the example could completely write out the ink 6, whereas the ballpoint refill 1 with the operating body of the comparative example cannot be written or cannot be written on the way. there were.

Example 2
Preparation of ink containing tube As the first layer (inner layer), polypropylene (MFR: 1 to 10), which is a thermoplastic resin, polyolefin adhesive resin as the second layer, and ethylene vinyl alcohol copolymer as the resin coating layer as the third layer Resin, polyolefin adhesive resin as the fourth layer, polypropylene [MFR: 1 to 10] as the fifth layer (outer layer), an inner diameter of 1.7 mm by an extrusion molding machine (multilayer extrusion mold, 5 layers of 5 types), It was extruded into a cylindrical shape with an outer diameter of 3.1 mm, and the length was cut to 85 mm to produce an ink containing tube.
The thickness of the first layer of the ink containing tube is 0.45 mm, the thickness of the second layer is 0.03 mm, the thickness of the third layer is 0.05 mm, and the thickness of the fourth layer is 0 mm. 0.03 mm and the thickness of the fifth layer was 0.14 mm.

A black pen refill 1 with a black operation body was obtained in the same manner as in Example 1 except that the ink containing tube was used.
Further, in the same manner as in Example 1, a ballpoint pen refill with an operation body having an aqueous ink composition of three colors, red, blue and green, and an operation body was obtained.

Ballpoint pen production (see Figure 2)
Further, each refill 1 was inserted into the writing instrument main body 8 used in Example 1 from the rear end opening of the shaft tube 9 and the lid body 95 was closed to obtain a composite ballpoint pen (writing instrument 7).

Comparative Example 2
Among the ballpoint pens of Example 2, a composite ballpoint pen was obtained in the same manner except that the ink containing tube was made of polypropylene alone.
The obtained ball-point pen and the ball-point pen produced in Example 2 were left for 90 days in a horizontally placed environment at 50 ° C., then the operation tool was grasped from the writing instrument body of each composite ball-point pen, and the refill was pulled out and stored again. When the operation of repeating was repeated, the ballpoint pen refill with the operating body of the example could be repeated without any problem. On the other hand, in the ballpoint pen refill with the operation body of the comparative example, there are the case where the operation body is detached from the ink storage tube, the connection portion is bent, or the ink storage tube is curved.
In addition, while there is no change in the ballpoint pen refill with the operation body of the example, the air is generated in the ballpoint pen refill with the operation body of the comparative example, and the interface between the ink and the liquid stopper is separated. It was.
A spiral circle was continuously written on JIS P3201 writing paper A at room temperature using each of the writing tools. At that time, the ballpoint pen refill with the operating body of the example could completely write the ink, whereas the ballpoint pen refill with the operating body of the comparative example could not be written halfway or could not be written.

Example 3
Preparation of ink containing tube Using polypropylene (MFR: 1 to 10), which is a thermoplastic resin, it is extruded into a cylindrical shape with an inner diameter of 1.7 mm and an outer diameter of 3.1 mm using an extrusion molding machine, and the length is adjusted. An ink containing tube was prepared by cutting to 85 mm.
Further, an inorganic vapor deposition layer was formed on the outside of the ink containing tube by laminating a 0.1 μm SiOx film layer by a plasma CVD film forming method to obtain an ink containing tube.

A black pen refill 1 with a black operation body was obtained in the same manner as in Example 1 except that the ink containing tube was used.
Further, in the same manner as in Example 1, a ballpoint pen refill 1 with an operating body having an aqueous ink composition of three colors, red, blue and green and an operating body was obtained.

Ballpoint pen production (see Figure 2)
Further, each refill 1 was inserted into the writing instrument main body 8 used in Example 1 from the rear end opening of the shaft tube 9 and the lid body 95 was closed to obtain a composite ballpoint pen (writing instrument 7).

Comparative Example 3
Among the ballpoint pens of Example 3, a composite ballpoint pen was obtained in the same manner except that the ink containing tube was made of polypropylene alone.
The obtained ballpoint pen and the ballpoint pen produced in Example 3 were left for 90 days in a horizontally placed environment at 50 ° C., then the operation tool was grasped from the writing instrument body of each composite ballpoint pen, and the refill was pulled out and stored again. When the operation of repeating was repeated, the ballpoint pen refill with the operating body of the example could be repeated without any problem. On the other hand, in the ballpoint pen refill with the operation body of the comparative example, there are the case where the operation body is detached from the ink storage tube, the connection portion is bent, or the ink storage tube is curved.
In addition, while there is no change in the ballpoint pen refill with the operation body of the example, the air is generated in the ballpoint pen refill with the operation body of the comparative example, and the interface between the ink and the liquid stopper is separated. It was.
A spiral circle was continuously written on JIS P3201 writing paper A at room temperature using each of the writing tools. At that time, the ballpoint pen refill with the operating body of the example could completely write the ink, whereas the ballpoint pen refill with the operating body of the comparative example could not be written halfway or could not be written.

Example 4
Production of Ink Housing Tube On the outer surface of the polypropylene ink housing tube 41 produced in Example 3, a GL-AU film made by Toppan Printing Co., Ltd. (Al ₂ O ₃ layer of 1 μm thickness using PET with a thickness of 10 μm as a base material) The ink containing tube 4 having a structure in which the inorganic vapor-deposited layer 43 is laminated on the outer surface of the thermoplastic resin portion 41 is obtained by joining and welding the layer 43) and the multilayer composite film having the hot-melt adhesive layer.

Ballpoint refill production (see Figure 3)
After fixing the ball-point pen tip 2 holding a 0.5 mm carbide ball to a ball holding portion formed by cutting a metal column at the tip of the ink containing tube 4 via a connecting member 3, the first embodiment is performed. The aqueous ink composition 6 was filled, and then an ink follower (liquid stopper 61) mainly composed of polybutene was filled so as to come into contact with the ink. Further, a ballpoint pen refill 1 with a joint member was obtained by inserting and fitting the front end of a joint member 5 ′ made of a black opaque resin molded body inside the rear end portion of the ink containing tube 4.

  Further, in the configuration of the ballpoint pen refill 1 with a joint member, the colorant of the ink 6 and the hue of the joint member 5 'are changed, so that the water-based ink composition 6 and the joint member 5' of two colors of red and blue are respectively changed. A ballpoint refill 1 with a joint member was obtained.

Making a ballpoint pen (see Figure 4)
Three window holes 94 are provided at equal intervals on the rear shaft side wall of the writing instrument main body screwed so as to be separable in the front-rear direction, and a slide lever 96 projects from the window hole 94. In addition, the writing instrument body 8 in which a spring is disposed in front of each slide lever 96 in the axial direction is used as an exterior. The slide lever 96 is made of a transparent resin, and a hole portion through which the rear end of the joint member 5 'can be inserted and fitted is provided at the front end thereof. Therefore, at the time of fitting, the fitting part exhibits a color display function. One of the slide levers 96 is formed into a clip 97 shape.
After dividing the shaft tube 9 of the writing instrument main body 8, each refill 1 is inserted into the front end of the slide lever 96 and the front shaft 91 is screwed, so that the writing tip portion 2 of each refill 1 is operated by operating the slide lever 96. A compound ballpoint pen (writing instrument 7) was obtained. Each refill 1 is highly replaceable because it can be easily removed by dividing the shaft tube 9 and gripping the ink containing tube 4 and then pulling it forward in the axial direction.

Comparative Example 4
Among the ballpoint pens 7 of Example 4, a composite ballpoint pen was obtained in the same manner except that the ink containing tube 4 was made of polypropylene alone.
The obtained ballpoint pen and the ballpoint pen 7 produced in Example 4 were left for 90 days in an environment of 50 ° C. in a horizontally placed state, and then the ink containing tube 4 was grasped from the writing instrument body 8 of each composite ballpoint pen 7 to refill. When the operation of pulling out 1 and storing it again was repeated, the ballpoint pen refill 1 with a joint member of the example could be repeated without any problem. On the other hand, in the ballpoint pen refill with the joint member of the comparative example, the joint member 5 ′ is detached from the ink containing tube 4 and remains fitted to the slide lever 96.
Further, while the inside of the ballpoint pen refill 1 with the joint member of the embodiment is not changed from the initial state, air is generated in the ballpoint pen refill with the joint member of the comparative example, and the interface between the ink 6 and the liquid stopper 61 is generated. Was separated.

DESCRIPTION OF SYMBOLS 1 Writing instrument refill 2 Ball-point pen tip 3 Connection member 4 Ink storage pipe 41 Thermoplastic resin part 42 Resin coat layer 43 Inorganic vapor deposition layer 5 Operation body 5 'Joint member 6 Ink 61 Liquid stopper 7 Writing instrument (composite ball-point pen)
8 Writing instrument body 9 Shaft tube 91 Front shaft 92 Rear shaft 93 Tip opening 94 Window hole 95 Cover body 96 Slide lever 97 Clip

Claims (4)

A ballpoint pen tip is provided at the front end of the ink containing tube for containing the ink composition, and the operation body is connected to the rear end by inserting and fitting it. When the refill is replaced, the operation body is grasped and pulled out from the rear end of the writing instrument body. Writing instrument refill,
The ink containing tube is made of a thermoplastic resin, and at least an end connecting the operating body is formed of at least three layers of an inner layer, an outer layer, and an intermediate layer, and the intermediate layer is an ethylene vinyl alcohol copolymer resin, vinylidene chloride resin, acrylonitrile. Ball pen refill with operating body, which is either resin or resin selected from polyester resin . The ballpoint pen refill with operation body according to claim 1, wherein the inner layer, the outer layer, and the intermediate layer are formed by composite molding. A writing instrument containing one or more ballpoint pen refills with an operating body according to claim 1 or 2. The writing instrument according to claim 3, wherein the writing instrument has a structure in which the refill is pulled out by gripping the operating body during refill replacement.

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