JP4223415B2 - Water-based ink composition for ballpoint pen and ballpoint pen incorporating the same - Google Patents

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 was excellent in lubrication performance, and the ball-point pen which incorporated the same.

〔Ｒ₂ は炭素数８〜２４のアルキル基又はアルキルフェニル基、Ｒ₃ はＲ₂ Ｏ（ＣＨ₂ ＣＨ₂ Ｏ）_p 、ｐは２〜２０の自然数〕
特公平６−７４３９５号公報 特公昭６１−３８２２６号公報 Conventionally, a water-based ballpoint pen that has a ball-holding part that holds a ball called a chip at the tip of the writing is likely to cause ink leakage due to wear of the ball-holding part due to rotation of the ball by writing. In addition, there was a drawback that it was difficult to obtain a smooth handwriting due to friction.
Accordingly, attempts have been made to add a lubricant to the water-based ink composition for ballpoint pens. Among them, it is disclosed that potassium oleate, polyoxyethylene alkyl ether represented by the following general formula (3) or phosphoric acid ester of polyoxyethylene alkylphenyl ether or the like is added to improve lubricity.

[R ₂ is an alkyl group or alkylphenyl group having 8 to 24 carbon atoms, R ₃ is R ₂ O (CH ₂ CH ₂ O) _p , p is a natural number of 2 to 20]
Japanese Examined Patent Publication No. 6-74395 Japanese Patent Publication No. 61-38226

Potassium oleate and phosphoric acid ester added to the water-based ink composition for ballpoint pens are effective lubricants exhibiting lubricity in an ink composition having severe chip wear.
However, although the above-mentioned potassium oleate can obtain a stable lubricity in the ink, it is difficult to obtain sufficient lubrication performance with a small amount of addition, so a large amount of addition is required, which may adversely affect the handwriting. There is.
In addition, although the phosphate ester represented by the general formula (3) has higher lubricity than potassium oleate, the one having high lubricity has low water solubility and the one having high water solubility is lubricity. However, it does not have both high water solubility and lubricity, and performance may deteriorate over time.

  The aqueous ink composition for ballpoint pens of the present invention is given by the general formula (1) and / or the general formula (2) in an aqueous ink composition comprising at least a colorant, a water-soluble organic solvent, and water. It is a requirement to comprise a phosphate ester. Furthermore, a ballpoint pen incorporating the water-based ink composition for ballpoint pens is a requirement.

  In the present invention, by adding the phosphoric acid ester having high water solubility to the water-based ink composition, it is possible to provide excellent lubrication performance stably for a long period of time. A water-based ink composition for a ballpoint pen that can be suppressed, has good ink ejection properties, has no handwriting blur or line breakage, and can provide a smooth writing feeling and good handwriting, and a ballpoint pen incorporating the same.

The phosphoric acid ester represented by the general formula (1) and the general formula (2) is a phosphoric acid ester of an alkylolamide ethylene oxide adduct, and has high stability in ink, a temperature difference and various It does not decompose due to the influence of additives, and has high water solubility and lubricating effect.
The phosphoric acid ester has an amide bond and a phosphoric acid group in the molecule, and is presumed to bring high lubricity due to these effects.

The substituent (R, R ₁ ) of the phosphoric ester is a straight chain of 7 to 21 carbon atoms or a side chain alkyl group, an alkenyl group, or an alkylphenyl group, preferably a straight chain of 9 to 17 carbon atoms or Either a side chain alkyl group, an alkenyl group or an alkylphenyl group is applied.

The phosphoric acid ester can be added in an amount of 0.01 to 10% by weight, preferably 0.05 to 10% by weight, in the ink composition.
If it is 0.01% by weight or less, it is difficult to obtain the desired effect, and if it is about 10% by weight or less, the desired effect can be sufficiently obtained, and no further addition is 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 are illustrated 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 finely and stably dispersed in an aqueous medium in advance using a surfactant or the like. Products are used, for example
C. I. Pigment Blue 15: 3B [Product Name: S.P. S. Blue GLL, pigment content 24%, manufactured by Sanyo Dye Co., Ltd.]
C. I. Pigment Red 146 [Product Name: S.P. S. Pink FBL, pigment content 21.5%, manufactured by Sanyo Color Co., Ltd.]
C. I. Pigment Yellow 81 [Product name: TC Yellow FG, pigment content about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.]
C. 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 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, luminous pigments, white pigments such as titanium dioxide used in correction pens, metal powders such as aluminum, fragrances, and fragrance capsule pigments.

  The colorant may be used alone or in combination of two or more, and is used in the range of 1 to 25% by weight, preferably 2 to 15% by weight in the ink composition.

As the water-soluble organic solvent, a conventional general-purpose solvent compatible with water can be used as appropriate, for example, 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 monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2 -Pyrrolidone etc. are mentioned.
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 to the paper surface or viscosity. 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 resins can be used alone or in combination of two or more, and are used in the range of 1 to 30% by weight in the ink composition.

  In addition, PH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite as necessary Rust prevention agent such as light, saponin, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetra Preservatives or antifungal agents such as chloro-4- (methylsulfonyl) pyridine, urea, nonionic surfactants, sorbitol, mannitol, sucrose, glucose, reduced starch hydrolysates, wetting agents such as sodium pyrophosphate, Improved defoamer and ink permeability The fluorine-based surfactants and nonionic surfactants may be used that.

  The lubricant used in the ink composition of the present invention is the phosphoric ester, but the derivative and metal soap, polyalkylene glycol, fatty acid ester, ethylene oxide addition type cationic activator, other phosphoric acid activator, etc. A lubricant can also be used in combination.

Further, a shear thinning agent can be added to the ink composition filled in the ballpoint ink storage tube.
As the shear thinning agent, a water-soluble or dispersible substance is effective, and xanthan gum, welan gum, and succinoglycan whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose (average molecular weight) About 1,000 to 8 million), guar gum, locust bean gum and derivatives thereof, hydroxyethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 based on alkyl esters of methacrylic acid, glycomannan, agar and carrageenan Carbohydrates having gelling ability extracted from seaweed such as benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymers, inorganic fine particles, nonionic surfactants having an HLB value of 8 to 12, dialkylsulfosuccinic acid Metal salts and nets Can be exemplified a salt, further, be added in combination in the ink composition N- alkyl-2-pyrrolidone and anionic surfactant can have stable shear thinning.

Furthermore, an ink backflow preventer (liquid stopper) can be disposed at the rear end 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 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 structure of the writing tip portion (tip) of the ballpoint pen filled with the water-based ink composition for ballpoint pens has a more effective general-purpose mechanism than before, and a ball in which the vicinity of the tip end of a metal pipe is pressed and deformed inward from the outer surface. A chip formed by holding a ball in the holding part, a chip formed by holding a ball in a ball holding part formed by cutting a metal material with a drill or the like, or a metal pipe or metal material A ball or the like held by a chip formed by cutting can be applied forward by a spring body.
The ball may be made of cemented carbide, stainless steel, ruby, ceramic or the like.

For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, or polyethylene terephthalate is preferably used as the shaft cylinder that accommodates the ink composition in terms of low ink evaporation and productivity.
In addition to directly connecting the tip to the shaft tube, the shaft tube and the chip may be connected via a connecting member.
When the ink composition is low in viscosity, the ink composition accommodated in the shaft cylinder includes a method of mounting an ink retaining member at the front of the shaft cylinder and storing the ink composition directly in the shaft cylinder, Examples of the method include impregnating the ink composition into a material body or a fiber processed body.
In addition, the said shaft cylinder may accommodate the said refill in a shaft cylinder as a form of the refill for ball-point pens.

Furthermore, 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, the ink storage tube may be configured to store the refill in a shaft cylinder as a form of a refill for a ballpoint pen, or the shaft cylinder itself having a tip attached to a tip is used as an ink storage body in the shaft cylinder. You may fill ink directly.

  The aqueous ink composition for ballpoint pens of the present invention and the ink composition of the comparative example are shown below. In addition, the number in a mixing | blending shows a weight part.

Example 1
Blue pigment dispersion 30.0
[Product name: SS BLUE GLL, manufactured by Sanyo Dye Co., Ltd.]
Ethylene glycol 15.0
Triethanolamine 0.5
Phosphate ester 0.5
[Product name: Amidette 51P, manufactured by Kawaken Fine Chemical Co., Ltd.]
Water 54.0
Total 100.0

  The said mixture was mixed, it stirred with the disper for 1 hour at room temperature, and the blue water-based ink composition was obtained by filtering.

Example 2
Red dye 5.0
[Product name: Phloxine, C.I. I. Acid Red92, C.I. I. 45410]
Dynamite Glycerin 15.0
Sodium carbonate 0.2
Xanthan gum 0.5
Phosphate ester 0.7
[Product name: Amidette P, manufactured by Kawaken Fine Chemical Co., Ltd.]
Water 78.6
Total 100.0

  The blend was mixed, stirred at room temperature with a disper for 1 hour, and filtered to obtain a red aqueous ink composition.

Example 3
Black dye solution 40.0
[Product name: Water Black 100-L, manufactured by Orient Chemical Co., Ltd.]
Diethylene glycol 15.0
Triethanolamine 0.5
Succinoglycan 0.4
(Organic acid-modified heteropolysaccharide consisting of glucose and galactose)
Phosphate ester 0.2
[Product name: Amidette 52P, manufactured by Kawaken Fine Chemical Co., Ltd.]
Water 43.9
Total 100.0

  The above blend was mixed, stirred at room temperature with a disper for 1 hour, and filtered to obtain a black aqueous ink composition.

Comparative Example 1
The phosphate ester used in Example 1 is represented by the general formula (3) [R ₂ : C ₁₂ H ₂₅ , R ₃ : R ₂ O (CH ₂ CH ₂ O) _p , p = 1] [trade name: Plysurf T205B. A water-based ink composition for ballpoint pens was obtained in the same manner except that the product was changed to “Daiichi Kogyo Seiyaku Co., Ltd.”.

Comparative Example 2
The phosphate ester used in Example 2 is represented by the general formula (3) [R ₂ : C ₁₂ H ₂₅ , R ₃ : R ₂ O (CH ₂ CH ₂ O) _p , p = 1] [trade name: Plysurf T205B. A water-based ink composition for ballpoint pens was obtained in the same manner except that the product was changed to “Daiichi Kogyo Seiyaku Co., Ltd.”.

Comparative Example 3
The phosphate ester used in Example 3 is represented by the general formula (3) [R ₂ : C ₁₂ H ₂₅ , R ₃ : R ₂ O (CH ₂ CH ₂ O) _p , p = 1] [trade name: Plysurf T205B A water-based ink composition for ballpoint pens was obtained in the same manner except that the product was changed to “Daiichi Kogyo Seiyaku Co., Ltd.”.

Comparative Example 4
A water-based ink composition for ballpoint pens was obtained in the same manner except that the phosphate ester used in Example 1 was replaced with water.

Comparative Example 5
A water-based ink composition for ballpoint pens was obtained in the same manner except that the phosphate ester used in Example 2 was replaced with water.

Comparative Example 6
A water-based ink composition for ballpoint pens was obtained in the same manner except that the phosphate ester used in Example 3 was replaced with water.

A ballpoint pen tip for holding a 0.5 mm diameter cemented carbide ball in a 0.53 mm diameter stainless steel pipe is provided at the writing tip portion of the ink of Example 1 and Comparative Examples 1 and 4; A ballpoint pen provided with a comb groove-shaped ink flow rate adjusting member (ink retaining member) at the rear end of the part was directly filled to obtain a ballpoint pen.
In addition, a ball-point pen tip that holds a 0.5 mm diameter cemented carbide ball in a 0.53 mm diameter stainless steel pipe is mounted with the inks of Examples 2 and 3 and Comparative Examples 2, 3, 5, and 6. After directly filling the ink containing tube made of polypropylene, the back end of the filled ink was filled with an ink backflow prevention body (liquid stopper) made of polybutene, and further subjected to centrifugal treatment to obtain a ballpoint pen.

  The ball pen was written 500 m on JIS P3201 writing paper A with a running tester, and then the ball sinking amount was measured and the handwriting was visually observed. Further, the ballpoint pens of Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to the same test with a running test machine after being allowed to elapse for 30 days in an environment of 50 ° C. The results are shown below.

The criteria in the table are as follows.
State of handwriting ○: A good handwriting was shown without blurring or jumping in the handwriting.
Δ: Slight blurring or line skipping occurs in the handwriting.
×: Blurred lines and line skipping are observed.

Claims (2)

For a ballpoint pen comprising a phosphate ester represented by the following general formula (1) and / or the following general formula (2) in a water-based ink composition comprising at least a colorant, a water-soluble organic solvent, and water. Water-based ink composition.

(N is an integer selected from 1 to 20, R is an alkyl group, alkenyl group or alkylphenyl group having 7 to 21 carbon atoms)

(M is an integer selected from 1 to 20, R ₁ is an alkyl group, alkenyl group or alkylphenyl group having 7 to 21 carbon atoms)   The ball-point pen which incorporated the water-based ink composition for ball-point pens of the said Claim 1.