JPS58176281A - Emulsion ink composition for writing - Google Patents

Abstract

PURPOSE:To provide a highly light and water-resistant ink for ballpoint pen consisting of water or a mixture of water and organic solvent, water-soluble dye and/or water-dispersible pigment and carboxylated styrene/butadiene copolymer latex emulsion. CONSTITUTION:The ink compsn. contains (A) 30-60wt% water or a mixture of water and organic solvent, (B) 2-10wt% water-soluble dye and/or water-dispersible pigment and (C) 5-80wt% carboxylated styrene/butadiene copolymer latex and is so formulated that it may have a (B) content of 5 to 40wt%. Preferred emulsion (C) has a styrene bond content of 28-68%, a carboxyl group content of 0.5-10wt% a specific gravity of 1.05, a solid content of 25-70%, a pH of 11.5-8.5, a viscosity of 10 to 1,000cp and a particle diameter of 600- 5,000Angstrom .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a drawing ink that can be written using a conventionally known tip of a ballpoint pen.

The purpose of this is to have the same writing performance as a water-based ballpoint pen (, dark), and to have the same writing performance as an oil-based ballpoint pen (thin handwriting), excellent water resistance and light resistance, and a tip and ink storage tube. An object of the present invention is to provide an m-grip ink that allows a pen body to be easily and inexpensively created by simply joining the two.

Conventionally, ballpoint pens have generally used oil-based ink, but in recent years, ballpoint pens using water-based ink have also become available on the market. The reality is that ballpoint pens are divided into oil-based ballpoint pens and water-based ballpoint pens.

These oil-based and water-based ballpoint pens have their own advantages and disadvantages in terms of manufacturing methods and usability.
Alternatively, the advantages and disadvantages of both methods can be summarized as follows from the viewpoints of (2) physical properties of ink (5) handwriting and writing performance.

In other words, oil-based ballpoint pens have a very simple pen body (or core) that is simply joined to a hollow ink storage tube filled with ink. Ballpoint pens generally require an ink flow conductor component with porous or molded capillaries called a relay core for the nib tip, and a bellows-like component or ink flow conductor component to adjust the ink flow. (A component made of bundles of fibers called batting is essential.)

(2) Regarding the viscosity of ink, oil-based ballpoint pen inks are generally made with a relatively high viscosity such as OF2 at room temperature, whereas water-based ballpoint pen inks are generally made with a relatively high viscosity such as OF2. , P are prepared to have a low viscosity of about 2 to sops.

(5) Oil-based ballpoint pens do not bleed, have line widths that are thinner than the diameter of the ball used, and have excellent water resistance and light resistance, making them ideal for writing under high pressure, such as on slips. Yo (I can handle it, but compared to a water-based ballpoint pen? /
Tatami Hajime Gaya, which is said to be 1 meter long, is heavy and has a small amount of ink, resulting in thin handwriting, and the high viscosity of the ink tends to cause smudges and leaks, making the writing feel heavy and causing fatigue when writing for long periods of time. It is said to accompany The water-based ballpoint pen is
When writing for the first time, it is possible to write well from the beginning, and it is possible to produce dense handwriting without using too much pressure, but due to the low viscosity of the ink, there are many wrinkles that consume the ink, and the writing line is blurred, and the line width is It tends to be thicker than the diameter of the ball used. For high-pressure writing such as copying, the durability is inferior to oil-based ballpoint pens, and the water resistance and light resistance of the handwriting itself is also inferior to oil-based ones. By carefully examining the advantages and disadvantages of each, we have conducted research from the perspective of improving and developing ink, in order to develop a ballpoint pen that has the advantages of each and eliminates the disadvantages of each.As a result, the pace of ink is water-based. Although it has a composition similar to ballpoint pen ink, by dispersing styrene-butadiene latex emulsion in the ink at a suitable concentration, it has all the advantages of conventionally known water-based ballpoint pens and oil-based ballpoint pens, but on top of that. The inventors have discovered a new writing ink that can largely eliminate the drawbacks of the above, and have proposed the present invention.That is, according to the ink for making baskets of the present invention, Just like how to make an oil-based ballpoint pen, it can be easily made by simply joining the ballpoint pen tip to a hollow ink storage tube filled with ink, and does not require the tapping relay core, batting, or bellows-like parts of a water-based ballpoint pen. There is no such thing as

Therefore, it is expected that the pen body can be produced economically at low cost and in a simple and easy manufacturing process.

(2) Ink viscosity [several 100 from H1G several centimeters
It is unique in that it covers a viscosity range not found in conventional ballpoint pens because it can be arbitrarily adjusted up to centiboise.

(5) As for the liquid phase of the ink, the dispersion medium consists of an aqueous ink colored with a dye, and the dispersed phase consists of a solid content of 5 to 50% styrene-butadiene latex.
It is characterized by being a non-uniform (dispersed) system.

(The latex fine particles reduce the metal contact between the ball and the metal tip socket, so you can get a smooth writing feeling on the first stroke, and there is no smudge on the paper surface.)
Since there is no bleed, a thin line width smaller than the diameter of the ball can be obtained.

(SJ IE marks have a beautiful color tone due to the luster and luster caused by the formation of a latex film.

The latex used in the present invention has an extremely strong adhesion to the paper surface, and the water-based ink as a dispersion medium also penetrates the paper surface, so handwriting will not be erased by physical abrasion with an eraser or the like. do not have.

Because handwriting is coated with a hydrophobic film of latex, this writing product has extremely improved water resistance even when using water-bathed flF dyes, which are considered to have poor water resistance when used as conventional water-based inks. Ink can be created.

The ballpoint pen made using the emulsion ink composition for chicks of the present invention, as shown in Saue, suitably follows and combines the characteristics of conventional oil-based and water-based ballpoint pens, but has the negative characteristics attached to these. Since it is possible to improve the disadvantages of ballpoint pens, it is possible to make the ballpoint pen easier to use and to improve its performance.

Conventionally, a proposal to add a styrene-butadiene latex emulsion to a writing staff composition has been made, for example, in JP-A-5
There is 6-151679.

However, this proposal uses paper AII for the purpose of erasing handwriting.
In contrast, the present invention uses "carefully selected" non-penetrating styrene loop 1/diene latexes, especially carboxylated latexes, which have weak adhesion to paper surfaces. The idea differs in that it is based on the premise of solid adhesion and penetration of an aqueous medium into the paper surface.

Moreover, the patent publication does not have any idea of simplifying the manufacturing method of the pen body of the present invention and reducing the cost by using sterene-butage 15 tex emulsion, and furthermore, there is no idea that the method of producing the pen body of the present invention can be simplified and the cost can be reduced. Combined with
There is no idea that these shortcomings can be significantly improved.

Therefore, it is desirable to use a 2-text emulsion as a material for making an erasable handwriting film.

As described above, it is clear that the emulsion ink for markings of the present invention is different in concept from that of the precedent Japanese Patent Application Laid-Open No. 56-151679.

The purpose and effect of the use of the styrene-butadiene latex emulsion in the present invention and the points to be noted when creating a pen body using the ink are as follows.

(The aim is to modify the rheological properties of conventionally known aqueous ballpoint pen inks by utilizing the behavior of emulsion particles.

Through this modification, the disadvantages of iron water-based ballpoint pen inks are eliminated and the inks have the same advantages as oil-based ballpoint pens.

In other words, conventional ballpoint pen inks, whether water-based or oil-based, generally have a homogeneous phase. Creation shape M of the pen body like an oil-based ballpoint pen
(Construction method in which the pen tip of the tip of a pole pen tip is simply joined to a hollow ink storage tube filled with the ink) If the ink is used, it easily leaks from the tip of the pen tip due to its low viscosity, which is inconvenient. It is.

In the writing emulsion of the present invention, emulsion particles are dispersed in the ink at a suitable fIkWL, so the liquid phase of the ink becomes a non-uniformly dispersed system and exhibits a non-Newtonian tlL Nh as a rheological characteristic.

In other words, it has a yield value of one foot, and has thixotropic properties that allow it to flow as the pole rotates, so even if the viscosity (apparent viscosity) is low when flowing, there is no possibility of inconvenient leakage from the tip of the ballpoint pen tip. It disappears. □ (2) Furthermore, the tip of the pen tip is exposed to the outside air and is prone to drying, but a latex film will naturally form on the tip portion as it dries.

The film exhibits a self-sealing effect, preventing ink from leaking from inside, preventing outside air from entering, and preventing deterioration and gelation of the ink itself due to drying.

Therefore, a completely sealed structure at the tip, as in the case of a water-based ballpoint pen, is not necessarily required.

Although it does not interfere with the present invention to add a suitable anti-drying agent into the ink to prevent drying, the anti-drying ability does not need to be very strong for the reasons mentioned above.

It is sufficient to use a small amount of glycols such as ethylene glycol, phrobin glycol, diethylene glycol, or glycerin.

However, in the pen body, the open part of the ink storage tube (on the opposite side of the pen tip) tends to have a dry film that obstructs the flow of ink, so a non-volatile viscous fluid or grease is used to connect it to the outside air. You should make a decision.

This non-volatile viscous fluid such as grease also has the function of preventing backflow of ink when the inner diameter of the ink storage tube is larger than the ink can be retained by the surface tension of the ink.

(5) The latex dispersed in the ink is generally 5
Since the solid content is in the range of 50% to 50%, it is possible to obtain handwriting that is thinner than the diameter of the ball used, without excessive penetration into the paper surface, etc. during writing, and without bleeding.

In addition, this solid content forms a film after drying, so it can give the print a gloss and luster that could not be expected with conventional water-based inks that contain almost no resin, making it a beautiful basket. You will get traces.

For such purposes, styrene-butadiene latex emulsion plays an extremely important role in preparing the ink of the present invention, but there is a wide range of options when it comes to obtaining the latex emulsion as a material. Also, the material cost is extremely low.

The styrene binder/latex emulsion used in the present invention contains styrene bonds ranging from 2a% to 6%.
9% range, and its specific gravity is tOS ~ (19511
i11 form content is 26% to zO%, PH is 1t5 to 115,
Viscosity is 10CP~1 o o o CPS particle size is 600, A~50. : Something in the range of 0 to 2 people is good.

Examples of these products are rJ manufactured by Japan Synthetic Rubber Co., Ltd.
sPos6+, 0650. o660J etc., Nippon Zeon's 1N1yOL" aaso, "Hiker 201" etc. 1. [Dow Latex L-14 made by Dow Company]
011, L-1855, L-2001J, etc. manufactured by Sumitomo Chemical Co., Ltd. [Naugatac, 2000, 2105.2711J, etc.] can be used.

The ink of the present invention can be easily prepared by appropriately selecting these styrene-butadiene latex emulsions and adding them to the ink.

The water or organic solvent used in the ink of the present invention should be suitably selected as a dye bath cleavage agent for the ink, a viscosity modifier, an anti-drying agent for the ink, and an anti-agglomeration agent for latex emulsions.

The water may be tap water or ion-exchanged water, but in the case of a ballpoint pen that uses Renki Tetsu 7', which is the main object of the present invention, 4
From the viewpoint of rust prevention, distilled water is particularly desirable.

In addition, examples of organic solvents include ethylene glycol,
Propylene glycol, phthalate/+7: l -k dietele 7 f IJ col, triete V glycol weighing Glycols such as ethylene glycol 1 ethylene glycol monomethyl ether, ethylene glycol monoethyl needle, ethylene glycol monopterether, 5 methyl- Glycol ethers such as methoxybutanol, ethylene glycol monomethyl acetate, glycerin, 1°5.5-pentatriol, triethanolamine, and thiodiethylene glycol can be used.

The water-soluble dye used in the present invention refers to water or
! Any substance that can be dissolved or uniformly dispersed in the aqueous medium of the i-agent can be suitably used.

Fine particles. Pigments, ah, also interfere with the present invention.

An example is naphthol yellow 8 (C, I, + 0
516], Tartrazine (0, I, 19140) Sunscent Yellow (C, 1, + 5985) *Eosin GH (C.

1.45580), Newcoccin (0,I, 1625
5).

Annodo 70xin PB (C, 1, asala), Acid Rhodamine BH (0, 1, 42b 4S, Acid Aiolet 5B (0, I, 42640), Soluble Blue Be (C, I, 42755), Brilliant Blue 0, Eng.42090), Cyanine Green 5G
(C.1.6 2 560), and Nigrosine BR
(c, 1.50420); Scarlet GSH (0, 1.2 9 1 6 5), Direct Sky Blue sB (0, I, z4aoo), Guaiolette BB (C, 1.27905), Black G (0, I, 55255), black o (0.1
．． ssa ss) and deep black EX (C
．． Direct dyes such as Flavin 8 (0.1.49005J, Methylguaiolesotho (C,I,42555), Crystal Guaiole);
(Cjj2555), Majienta (C, 1.4251
Basic dyes such as rhodamine (C, I, 45160) can be used. In addition to this, there is also a rust preventive agent for the gold nib tip VJ, a lubricant for smooth writing performance, and a surface tension agent for the FJ4a to improve the surface tension of the ink.
Addition of anti-piping agent, etc. to prevent corrosion of the active ink.
Rokoto also does not inhibit misfire 8A.

[11!] of the writing emulsion ink of the present invention! As a guideline for 1% water or organic solvent, 10%
~90 wt%, preferably Fis o ~60 wc
yb, water bath dye at α1-20 wt%, preferably 2-1.

wt%, styrene-butadiene latex 2-9O
It is suitably prepared in a range of wt%, preferably 5 to ao wt%.

The solid content of latex in the ink is 5 to 50 wt%
, preferably 10 to 40 Wu%.

Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited to this.

In addition, all the compounding amounts in the compounding examples are parts by weight.

Example 1 40.1 ml of distilled water was placed in a Mitsuro flask (500+nl volume) equipped with a dropping funnel and a stirring blade at a temperature of 1 tt.
/ Glycerin 1011 benzotriazole (rust inhibitor) (
L2J/ was weighed and stirred at 40°C for 50 minutes to mix and dissolve the materials.

Then the dye Newcoxin (0,1.1 6 2 5
5) 1.9 and eosin uH (0, I, 4ssao
)7: Add J, heat the solution to 50°C, and stir for 50 minutes.

'f&〃・Check that it becomes uniform, then add styrene-butadiene latex emulsion (Asahi Dow Latex L-2).
001 Styrene bond 45% Solid content 48% Viscosity 2 0 0
0PS) 1 0 0, +7 is dripped from the dropping funnel.

At this time, stirring was carried out at 20 to 50 rpm. ]), m. Stir gently and allow the latex to be added little by little over a period of 15 to 20 minutes.

During this time, the liquid temperature is kept at 50° to 40°C.

After dropping all the latex, at a liquid temperature of 40°C, the stirring speed [2
0 r, p, m ~ 5 0 r, p, m,
After stirring for 2 hours, the liquid phase takes on a glossy, bright red color.

The liquid mixture was refrigerated at 5° C. overnight and filtered through a filter press to obtain a red writing emulsion ink.

The viscosity WIL was +0000PS at 20°C.

Add this ink to the α5y ink storage tube made of polypropylene.
It can be stored and the tip has a metal ballpoint pen tip 5611 (α
A 5% ball, a 17% ball e1x ball node were joined together, and grease was injected into the tip to create a ballpoint pen core.

When I applied a mosquito core to a drawing tester, I found that the horizontal lines did not bleed into blood donations, etc., and did not leak.

#IiA of each handwriting line is α71 with a 1% diameter ball,
14S% with α7% diameter pole, 125t with ASZ diameter ball
As shown in the figure, all of them gave a basket trace that was thinner than the diameter of the ball used.

In addition, as a storage test, no ink leaked from the tip of the pen even when the pen tip was left facing downward (at room temperature) for one month.

The first basket after being left for one month was also good.

Water resistance was also extremely good.

Implementation M2 Distilled water 809, propylene glycol aOal, and 2 g of thiodiethylene glyco rust agent pen/thiazole were mixed and dissolved at 40°C in the same container as in Example-1.

Deep black B X (Q I, 50
255) Add 16ft, stir further, and heat to 50°C to solubilize.

After that, a styrene-butadiene latex emulsion (J8RO561 styrene ratio SO%
, total solids content 69%, viscosity 4800 PSJ589 was added dropwise, thoroughly dispersed, and then refrigerated at 5° C. overnight, followed by filter press filtration to obtain a black emulsion ink composition for basket finishing.

The viscosity was 1500P3 at 20°C.

When we made a core of the cough ink in the same manner as in Example-1 and conducted a drawing test, we were able to obtain fine, suitable marks without bleeding, and we were able to obtain beautiful black handwriting with a glossy finish. Ta.

The ml mark has extremely good water resistance and light resistance, and can be stored for a period of time without ink leaking from the nib.

Also, even after leaving it for one month, the tip did not dry out and the first basket was very good.

Procedural amendment (voluntary) July 8, 1980 Director-General of the Patent Office Kazuo Wakasugi 1. Indication of the case 1982 Patent Application No. 59147 2. Emulsion ink composition for displaying the title of the invention 3. Amendments made Relationship with the Nagisa Case Patent Applicant Address: 6-10-12-4 Toshima, Kita-ku, Tokyo, Agent: 107 As attached, (1) Full text of the scope of the patent claims (page 1, line 5 of the specification) - page 3, line 17) are corrected as shown in Attachment A.

(2) On page 4, line 4 of the specification, the phrase "water-resistant needle" is corrected to "water-resistant, resistant."

(3) On page 4, line 14, after "manufacturing method", rl
” to join.

(4) On page 4, line 15, the phrase ``there is,'' is corrected to ``rgameshi.''

(5) From the last line of page 4 to the first line of page 5, it says, ``How to make the body (or core) of an oil-based ballpoint pen?''
The body (or core) of an oil-based ballpoint pen is corrected.

(6) On page 7, line 3, the statement "According to K." is corrected as follows.

It reached r.

Thus, according to the invention: 0) water or a mixture of water and a water-miscible organic solvent 30-6
0% by weight, (1) water-soluble dye and/or water-dispersible pigment 2~1O
% by weight, and (1) carboxylated styrene-butadiene copolymer latex emulsion comprising 5 to 80% by weight;
and the content of the carboxylated styrene-butadiene copolymer in the ink composition is 5 to 40% by weight, preferably 1% by weight.
There is provided a writing ink composition suitable for use in a ballpoint pen using a metal ballpoint tip tip having a weight of 0 to 40%.

The writing ink composition provided by the present invention has the following characteristics and advantages. ” (7) Add “11” after “created” in line 7 on page 7 of the same document.

(8) On page 7, line 14, after the words “to be done”, “
, j.

(9) In the third line from the bottom of page 7, the text "5 to 50 inches" is corrected to "5 to 40 weight -."

(10) The statement "There is" on page 9, line 9 is made in Publication No. 1. Correct it as j.

(11) In the 4th line from the bottom of No. 9, the text ``Isao Tokukaisho'' is corrected to ``r''.

(12) In the same page, page 1O, line 7, the text ``What is 131679'' has been corrected to read ``What is 131679?''.

(13) On page 12, line 7 of the same document, the phrase "does not impede the present invention" should be corrected to j, although r is also possible.

(14) On page 12, line 10, add "r" before the "ethylene glycol," and add "j" as an anti-drying agent.

(15) On page 13, line 3 of the same page, read “so-” j4
Correct it to 0%J.

(16) In the last line of page 13 of the same page, after the phrase ``within a range of'', add ``the content of r-carboxyl group is 0.5 to 10% by weight''.

(1 copy) On page 34, line 1: ``Add r and j after o and ssJ.''

(18) On page 14, line 2, [1OCP~1.000
(P5 grain particles and 6ru tr 10CP5~1.0000
F5. "Particles," he corrected.

(19) Add rDL-636, L-2301, and J after [1-1835J] in the 8th line of 141X.

(20) On the last line of page 14 of the same page, ``Kima'' should be stopped.''
I am corrected.

(21) Paragraph 1sJ [The third line from the bottom says, "Even if covered with a pigment, the present invention will not be impaired." R Pigments can be used in the ink composition of the present invention. Correct it with J.

(22) On page 17, lines 3 to 11, “The present invention...
...suitable. ” will be deleted.

(23) On page 18, line 10 of the same page, the phrase "dropping all the latex" is corrected to "once the latex addition is complete."

(24) No. 21j [Embodiment 3 shown in Attachment B is added on a new line after the first line.

Above (Attachment A) [Claims] 10% by weight of mosquito carboxylic acid in the ink composition (Attachment B) "Example 3 Dissolving device equipped with a thermometer, a dropping funnel and a stirring blade" In a 500-volume Mitsuro flask, add 2511 parts of distilled water, 251 parts of diethylene glycol, and 0 benzotriazole (rust inhibitor).
．． Charge 2N and stir at 40°C for 30 minutes.

This was then coated with Dye C, I, Direct Black 19.
(t', 1.asss) sII is added, the liquid temperature is raised to 50°C, and the mixture is stirred for 30 minutes. After confirming that the liquid is homogeneous, add a styrene-butadiene latex emulsion (Asahi Dow Latex Z-2ooiH styrene bond ratio 45-;
Solid content 48-; viscosity 200 Cps) 5211 was dropped from the dropping funnel.

At this time, stirring was carried out for 20 to 30 days, p, 'I11. The latex is added dropwise, taking 15 to 20 minutes to complete.

During this time, the liquid temperature is maintained at 30° to 40°C.

After dropping all the latex, the liquid temperature was 40°C and the stirring speed was 2O.
f,% to ~30 de,p, milk and stir for 2 hours.

The mixture was chilled at 5° C. overnight and passed through a filter press to obtain a glossy black writing emulsion ink.

The viscosity is 28 CPS at 20°C.

Pour this ink into a polypropylene ink storage tube with 0.5
g, and 3 types of metal ballpoint pen tips (0,
5tn/m ball, α7m/ty* ball.

1m/tn ball) were joined, grease was injected into the tail end, and a ballpoint pen core was created.

When we conducted a drawing line test using a drawing tester using the cores, we found that each of them drew beautiful lines, did not bleed onto the paper surface, and did not cause any blemishes. The width of each handwritten line is approximately 0.7 gl/g for a l inertia/'FIL diameter ball, approximately Q for a 6.7 tn/' diameter ball,
4 tn/m, αs tn/m diameter ball approximately o
, 2sm/Jin, and the diameter and width of the balls used in both cases gave small and narrow cage marks.

In addition, as a storage test, no ink leaked from the tip of the pen even when the pen tip was left facing downward (at room temperature) for one month. Furthermore, the first basket was also good after being left for one month.

The water resistance of handwriting was also extremely good. "563-

Claims (1)

[Scope of Claims] (A writing ink composition suitable for use in a ballpoint pen using a ballpoint pen tip tip, the composition of which is (1) water or EI and a comb solvent (water bathing dye); (2) A writing emulsion ink composition characterized by comprising a water-dispersible pigment (11υ styrene-butadiene latex emulsion) A styrene-butadiene latex emulsion is used as a thickener, and the latex is It has the property of firmly adhering to the writing surface and penetrating it.
The styrene bond ratio of the latex is in the range of 20% to 69%, the skeleton specific gravity is tOS ~ (L95. Solid content is 25% to 70%, the PH range is 115 to IIL5°, the viscosity range is 10CP8 to 1 oao OPS (zs°C) The writing emulsion ink composition according to claim 1, characterized in that it contains a sterene-butadiene latex emulsion in which the particle size of the emulsion is in the range of 600A to 5OOOA. (5) A writing emulsion ink composition used in a ballpoint pen that is simply constructed by joining a menggen tip tip nib to a hollow ink storage tube, the viscosity of which is +Ocps at room temperature. ~s o o
1 to be adjusted to the cps range! ! The ink has thixotropic properties, and the metal-tip nib allows it to be stored without excessive leakage, and while it has sufficient density, it does not smear in your handwriting. The Fudeogawa emulsion ink composition according to claim 1 TA, which is capable of imparting shine and luster to handwriting and is not erased by physical abrasion with an eraser or the like. 4) It is hydrophilic when the handwriting is wet, but when the handwriting is dry 11
fJEi is a writing emulsion ink composition according to claim 1, characterized in that the styrene-butadiene latex emulsion forms a hydrophobic film to improve the water resistance of handwriting. (5) The writing emulsion ink composition according to claim 1, wherein the solid content of the styrene-butadiene latex emulsion is dispersed as fine particles in a range of 5% to 50%. (6) The emulsion ink composition for bride printing according to claim 1, characterized in that at least one of water-soluble acid dyes, direct dyes, basic dyes, or water-dispersible fine particle pigments is used as the pigment. thing.