JP2012233084A - Water-based ink composition for ball-point pen and ball-point pen housing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based ink composition for a ball-point pen, which satisfies both of dry-up resistance and dripping resistance even if it is a water-based ink using a shear-viscosity reduction imparting agent being applied to a ball-point pen having a simple structure and which exhibits long-term stable performance, and to provide a ball-point pen housing the composition.SOLUTION: The water-based ink composition for a ball-point pen includes a colorant, water, a shear-viscosity reduction imparting agent, and a polyoxypropylene methylglycoside. The ball-point pen houses the composition.

Description

  The present invention relates to a water-based ink composition for ballpoint pens. Furthermore, it is related with the water-based ink composition for ball-point pens which has the shear thinning viscosity which was excellent in the dry-up resistance in a nib point, and the dripping prevention performance.

Conventionally, an aqueous ballpoint pen ink composition containing a shear thinning agent such as xanthan gum or diutan gum has been disclosed (for example, see Patent Documents 1 and 2).
This type of ink has a high viscosity when it is left to stand without shear stress, and is stably held in the mechanism. When writing, the ink in the vicinity of the ball is low due to the high shear force of the ball rotating at high speed. As a result, the ink is discharged from the gap between the ball and the ball container and transferred onto the paper surface. Since the ink transferred onto the paper surface is released from the shearing force, it becomes a highly viscous state and does not cause handwriting blur, which is a defect of the conventional water-based ink composition. In addition, ink leakage does not occur due to the above-mentioned shear thinning and there is no need for a flow rate adjusting member (temporary ink retaining member such as a comb-like member) for adjusting the ink flow rate. It has been widely applied because it has many advantages such as obtaining writing instruments.
However, in the water-based ink, since the shear thinning agent may impair the dry-up resistance, leaving the pen tip exposed to the air for a long time may cause handwriting blurring or writing at the beginning of the handwriting. Problems such as disappearance may occur.

Therefore, a proposal has been made to improve the dry-up resistance performance by adding a water-soluble organic solvent, a wetting agent such as a polyhydric alcohol, urea, or a derivative thereof (for example, see Patent Document 3).
However, inks containing the above-mentioned wetting agents often have insufficient drying prevention effects or increase the ink viscosity and are liable to cause writing defects such as line skipping and blurring. For example, excessive addition of urea In this case, when water is evaporated from the nib and the concentration of the water-soluble organic solvent is increased, a solid content is deposited on the nib, which causes a so-called flower bloom phenomenon, which deteriorates the appearance and causes fading. In addition, urea and its derivatives generate ammonia due to decomposition, and have an adverse effect such as promoting the aggregation of the pigment due to the increase in the pH of the ink, and a satisfactory aqueous ink composition cannot be obtained. It was.
Further, when a large amount of the wetting agent is added, there are some problems such as drooping when the pen nib is left downward, particularly in a humid environment.

JP 59-74175 JP 2005-68363 A JP-A-8-127746

  The present invention is for a ballpoint pen that can satisfy both dry-up resistance and sagging property, and can exhibit stable performance in the long term, even with a water-based ink using a shear thinning agent that can be applied to a writing instrument with a simple structure. An aqueous ink composition and a ballpoint pen incorporating the same are provided.

The water-based ink composition for ballpoint pens of the present invention is required to contain a colorant, water, a shear thinning agent, and polyoxypropylene methyl glucoside.
Further, the polyoxypropylene methyl glucoside is added in an amount of 0.5 to 5% by weight based on the total amount of the ink composition, and the colorant is a microcapsule pigment containing a reversible thermochromic composition. And
Furthermore, a ballpoint pen incorporating any of the above-described water-based ink compositions for ballpoint pens is a requirement.

  According to the present invention, water-based ink for ballpoint pens that can form good handwriting over a long period of time, even with water-based ink using a shear thinning agent, because it has excellent dry-up resistance and drooping performance of the nib. An ink composition and a ballpoint pen incorporating the ink composition are provided.

〔式中のａ，ｂ，ｃ，ｄの和（ａ＋ｂ＋ｃ＋ｄ）はプロピレンオキサイド付加モル数を表し、１０又は２０である〕 The polyoxypropylene methyl glucoside is a monosaccharide to which a plurality of propylene oxides are added, and in particular, a structure represented by the following general formula (1) is preferably used. Examples of commercially available products include NOF Corporation's Cubiobride MG-10P and MG-20P (both are trade names).
Shear thinning agents such as gums and water-soluble polymers added to the ink are easy to form a very strong dry film when moisture evaporates at the nib. However, in the configuration of the present invention, since the polyoxypropylene methyl glucoside first forms a film and coats the pen tip, the dry film of the dry film is not allowed to stand. It is thought that formation is prevented and dry-up resistance is imparted.

[The sum of a, b, c and d in the formula (a + b + c + d) represents the number of moles of propylene oxide added and is 10 or 20]

The polyoxypropylene methylglucoside can be added in an amount of 0.5 to 5% by weight, preferably 0.5 to 3% by weight, based on the total amount of the ink composition.
If it is less than 0.5% by weight, it is difficult to provide sufficient dry-up resistance, and even if added in excess of 5% by weight, no improvement in dry-up resistance beyond a certain level is observed. The above addition is not required.

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.
In addition, pearl pigments, gold and silver metallic pigments, luminous pigments, white pigments such as titanium dioxide used in correction pens, metal powders such as aluminum, thermochromic compositions, photochromic compositions, and fragrances Examples thereof include capsule pigments directly or microencapsulated.

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 encapsulated in microcapsules 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, large hysteresis characteristics (ΔH _B = 8 to 50 ° C.) described in JP- _B -4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ), That is, when the shape of the curve plotting the change in the color density due to the temperature change is lowering the temperature from the lower temperature side than the color changing temperature range, as opposed to increasing the temperature from the lower temperature side. Reversible heat with color memory in a specific temperature range when the color changes in a low temperature range below the complete color development temperature or in a high temperature range above the complete color erase temperature. A heat-decolorable microcapsule pigment in which the color-changing composition is encapsulated in microcapsules is also applicable.
Specifically, as the reversible thermochromic composition having color memory, a complete color development temperature can be obtained only in a freezing room, a cold district, etc., that is, −50 to 0 ° C., preferably −40 to − 5 ° C., more preferably −30 to −10 ° C., and 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, by specifying the range of 60 to 80 ° C. and specifying the ΔH value of 40 to 100 ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily life temperature range).

The colorant can be used singly or in combination of two or more, and is used in the range of 1 to 30% by weight, preferably 2 to 25% by weight in the ink composition.

Further, if necessary, a conventional general-purpose water-soluble organic solvent compatible with water can be used. Specifically, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono Examples include ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, and N-methyl-2-pyrrolidone.
In addition, the said water-soluble organic solvent can be used 1 type or in combination of 2 or more types, and is used in 2 to 60 weight%, Preferably it is 5 to 35 weight%.

  Furthermore, a water-soluble resin can be added in order to impart adhesion and viscosity to the paper surface. Examples of the water-soluble resin include alkyd resins, acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin. The water-soluble resin can be used alone or in combination of two or more, and is used in the range of 1 to 30% by weight in the ink composition.

  As the shear thinning agent, a substance that is soluble or dispersible in water is effective, and xanthan gum, welan gum, zetasy gum, dieutan gum, macrohomopsis gum, and a constituent monosaccharide is an 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 Examples include inorganic fine particles, nonionic surfactants having an HLB value of 8 to 12, metal salts and amine salts of dialkylsulfosuccinic acid, and further, N-alkyl-2-pyrrolidone and anionic surfactant in the ink composition An agent may be added in combination.

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) A preservative or antifungal agent such as pyridine, an antifoaming agent, a fluorine-based surfactant or a nonionic surfactant that improves ink permeability may be used. In addition, other wetting agents such as sorbitol, mannitol, sucrose, glucose, reduced starch hydrolyzate, urea, sodium pyrophosphate can be used in combination.
Furthermore, a lubricant can be added, such as metal soap, polyalkylene glycol fatty acid ester, ethylene oxide addition type cationic surfactant, phosphate ester 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, dimethyldithiocarbamate, N-acyl-L -A condensate of glutamic acid and L-lysine or a salt thereof is used.
Ascorbic acids, erythorbic acids, α-tocopherol, catechins, synthetic polyphenols, kojic acid, alkylhydroxylamine, oxime derivatives, α-glucosylrutin, α-lipoic acid, phosphonate, phosphinate, sulfite, sulfoxylate It is also possible to chemically remove bubbles by adding dithionite, thiosulfate, thiourea dioxide or the like.
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.

The water-based ink composition is filled in a ballpoint pen with a ballpoint tip attached to the writing tip.
The structure and shape of the ballpoint pen itself are not particularly limited, and a conventional one can be applied. For example, the ballpoint pen has an ink containing tube filled with an ink composition, and the ink containing tube has a ball. An example is a ballpoint pen that communicates with a tip attached to the tip and further has an ink backflow prevention body in close contact with the ink end face.

The ballpoint pen tip will be described in more detail. A tip formed by holding a ball in a ball holding portion obtained by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, or a metal material is cut by a drill or the like A chip formed by holding the ball in the ball holding part formed by the above, or a ball held in a chip formed by cutting a metal pipe or metal material, and the like that is urged forward by a spring body, etc. Can be applied.
Moreover, a cemented carbide, stainless steel, a ruby, a ceramic, etc. can be applied to the said ball | bowl, and the thing of the range of diameter 0.1mm-2.0mm is used suitably.

For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, or polyethylene terephthalate is preferably used as the ink storage tube for storing the water-based ink composition in terms of low ink evaporation and productivity. Further, by using a transparent, colored transparent, or translucent molded body as the ink containing tube, the ink color, the remaining amount of ink, and the like can be confirmed.
In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member.
The ink storage tube may be a refill type in which the refill is stored in a shaft tube, or the shaft tube itself having a tip attached to a tip is used as an ink container, and ink is directly applied to the shaft tube. It may be filled.

Further, an ink backflow preventer (liquid stopper) is filled in the rear end portion of the ink composition filled in the ink containing tube.
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 co-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 ballpoint pen may be either a cap-type or a retractable type, and the retractable ballpoint pen is placed in the shaft cylinder (outer shaft) with the writing tip provided on the ballpoint pen refill exposed to the outside air. Any structure can be used as long as it is housed and the writing tip protrudes from the opening of the shaft cylinder by the operation of the retracting mechanism.
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 tube and the side surface of the shaft tube, and by pressing the knock portion, the writing tip portion of the ballpoint pen refill is projected and retracted from the front end opening portion of the shaft tube, or on the shaft tube. The structure which makes the writing tip part of a ball-point pen refill appear and disappear from the axial cylinder front-end opening part by pressing the provided clip part can be illustrated.
The rotary type has a rotating part at the rear part of the shaft cylinder, and can be exemplified by a configuration in which the writing tip part of the ballpoint pen refill is projected and retracted from the front end part of the shaft cylinder by turning the rotating part.
The slide type has a slide part on the side surface of the shaft cylinder, and the sliding tip of the writing point of the ballpoint pen refill is projected and retracted from the front end opening of the shaft cylinder by operating the slide, or the clip part provided on the shaft cylinder is slid. By doing so, it is possible to exemplify a configuration in which the writing tip portion of the ballpoint pen refill is projected and retracted from the opening at the front end of the shaft cylinder.
The retractable ballpoint pen may be a composite retractable ballpoint pen (refill exchange type) in which a plurality of ballpoint pen refills are accommodated in a shaft cylinder.

Examples will be described below, but the present invention is not limited to these examples.
The composition of the water-based ink for ballpoint pens of Examples and Comparative Examples is shown in the following table. In addition, the numerical value of a composition in a table | surface shows a weight part.

The contents of the raw materials in the table will be described along the note numbers.
(1) Product name: Special Yellow NS, manufactured by LANXESS
(2) Product name: Water Orange 18 manufactured by Orient Chemical Industry Co., Ltd.
(3) 4.5 parts of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (a) and 1,1-bis (4'-hydroxyphenyl) n- as component (b) Reversible thermochromic composition comprising 4.5 parts of decane, 7.5 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as the component (c) Microcapsule pigment encapsulating a product (T ₁ : −20 ° C., T ₂ : −9 ° C., T ₃ : 40 ° C., T ₄ : 57 ° C., ΔH: 63 ° C., average particle size: 2.5 μm, reversible thermal discoloration Composition / wall film = 2.6 / 1.0, color changes from black to colorless)
(4) Daiwa Kasei Co., Ltd., trade name: Food Red No. 3 (5) Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf AL
(6) Product name: Proxel XL-2, manufactured by Zeneca Corporation
(7) NOF Co., Ltd., trade name: Macbiobride MG-10P, compound with a + b + c + d = 10 in the general formula (1) (8) Sanki Co., Ltd., trade name: Kelzan

Preparation of Ink Components other than the thickener were added to the water, mixed and stirred, then the thickener was added, stirred at 400 rpm for 1 hour with a disper at 20 ° C., and filtered to prepare each ink.

Preparation of Ink Backflow Preventing Body After adding 1.5 parts of fatty acid amide as a thickener to 98.5 parts of polybutene as a base oil, the mixture was kneaded with three rolls to obtain an ink backflow preventing body.

Preparation of Ballpoint Pen The ink composition of the above examples and comparative examples was filled into a ballpoint pen refill fitted with one end of a polypropylene pipe with a stainless steel tip holding a cemented carbide ball having a diameter of 0.4 mm, and the rear end After the ink backflow preventive body was disposed on, the ballpoint pen refill was incorporated into a shaft cylinder (cap type) to prepare a sample ballpoint pen.
The following tests were conducted using the sample ballpoint pen.

Cap-off test Each sample ballpoint pen that was confirmed to be writable was exposed to the air in the air, left in a 20 ° C environment for 7 days in the horizontal position, and then written at the old JIS P3201 at room temperature. Three lines of 12 spiral circles were handwritten on line A by handwriting. The handwriting state at that time was confirmed visually.

Sagging test Using each sample ballpoint pen that has been confirmed to be writable, with the pen tip exposed to the air at 20 ° C and 95 RH for 2 hours in the pen tip downward position, the tip of the pen tip was visually observed. Was observed.
The results of the test are shown in the following table.

The evaluation of the test results is as follows.
Cap-off test ○: No blurring or recovery with writing within one line.
Δ: Scratching occurred on the first line, but recovered with writing within three lines.
X: It does not recover by writing within 3 lines, or writing is impossible.
Sag test ○: No abnormality.
×: Drops or dripping occurred at the tip of the pen tip.

Claims (4)

  A water-based ink composition for ballpoint pens containing a colorant, water, a shear thinning agent, and polyoxypropylene methylglucoside.   The aqueous ink composition for ballpoint pens according to claim 1, wherein the polyoxypropylene methyl glucoside is added in an amount of 0.5 to 5% by weight based on the total amount of the ink composition.   The water-based ink composition for ballpoint pens according to claim 1 or 2, wherein the colorant is a microcapsule pigment containing a reversible thermochromic composition.   The ball-point pen which incorporated the water-based ink composition for ball-point pens in any one of the said Claim 1 thru | or 3.