JPS58145771A - Ink for hollow pen - Google Patents

Abstract

PURPOSE:To provide ink for hollow pen best suited for film drawing, capable of giving stable touch without running even when the pen is allowed to stand in air for a long time, by blending a particular water-sol. dye, water-sol. org. solvent, and water. CONSTITUTION:Ink contg. a water-sol-dye of the formula (wherein X is H, a halogen atom, methyl, ethyl, methoxy, ethoxy), water-sol. org. solvent, and water. The content of said water-sol. dye is 5-20wt% based on the total amt. of ink; when the content is below 5wt% the touch is deficient in clearness for drawing, while when above 20wt% the change in concn. is caused by precipitation of the dye with the elapse of time. Ink for hollow pen should have physical properties such as viscosity of 2.0-9.0cP (25 deg.C) and surface tension of 35dyne/cm (15-25 deg.C) or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a hollow pen ink that is most suitable for film drawing.

Hollow pens are widely used for purposes such as peeping, drafting, designing, and making block copies, but the nib is made of a metal pipe with an outer diameter of 01 to 20 (the tip of the pipe is hard chrome plated). Perform 1.

There are also books with two-piece paper and hard wood attached. ) The ink for these hollow pens is generally carbon black dispersed in water (pigment ink is also used. 17 However, pigment ink dries quickly, so leave the nib with the cap removed. When this happens, the tip of the pen nib rips in a short period of time, resulting in unstable ink ejection.

Therefore, the user always pays attention to the condition of the pen tip.

Furthermore, there is the hassle of having to devise a method of use, such as taking care to prevent the ink from drying inside the pen. In addition, with the spread of computers in recent years, hollow pens have come to be used for automatic drafting using computers, and when using pigment ink, the ink ejection is stable during continuous drawing. It is possible to draw lines with uniform density, but once the nib is left in the air, the ink dries at the tip of the nib within a short time.
Ink ejection is obstructed, resulting in blurred lines during the first drawing, or gaps in appearance such as no ink coming out at all.

In order to solve these foreclosures,
Dye inks containing a certain amount of solvent, such as those shown in 174, have also been developed, but these inks are rarely used for general feeding, but they can also be used for drawing on certain matte films. When this was done, the bleeding became particularly noticeable, and a drawing line that was 1 to 6 times wide was spread by 1 to 2, which was a serious defect for a drafting ink.

Therefore, the inventors of the present invention have developed an invention that does not bleed handwriting (drawing lines) not only on general paper but also on special paper such as pine film.

The optimum handwriting (line) density can be obtained for purposes such as drafting and creating one-size-fits-all assignments.

■ Even if the nib of a hollow pen is left in the air, the ink will not dry and the ink discharge will be stable.
Can withstand continuous and discontinuous use.

As a result of extensive research in order to obtain ink for hollow pens, the present invention has been completed. That is, the present invention uses at least one water-soluble dye represented by the general formula (+1).

The gist of the invention is an ink for hollow pens comprising at least a water-soluble organic solvent and water.

(In the formula, X represents a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group.) At least one soluble dye must be used.

This means that when a water-soluble dye represented by the above general formula (11) is used, the handwriting (printing lines) becomes more water-resistant than when a water-based ink used in felt-tip pens is used, which uses an acid dye. 2. For example, when writing on paper that does not easily absorb ink, such as matte film or tracing paper, and applying water to the handwriting (drawing lines), the acid dye used for conventional felt-tip pens can be used. When used for other purposes, the handwriting (drawing lines) are almost completely erased (21) With the ink of the present invention, the handwriting (drawing lines) are only slightly fainter, and since dye is used, Compared to the pigment ink using carphone black, the problem of vibrating and twisting due to the drying of the pen tip has been significantly improved.1. In order to satisfy the above requirements, we conducted various studies on the amount of water-soluble dye represented by the general formula (1), the physical properties and amount of water-soluble organic solvent used, and the physical properties of the obtained ink. This is a hollow pen with the best ink.

6- The present invention will be explained in detail by showing each component used in the present invention below.

Specific examples of the water-soluble dye represented by the general formula (1) used in the present invention include Water Fluff 1o o -
T, (manufactured by Orient Chemical Industry Co., Ltd., O,T.

Tie left black 19. Dye water black L-200 <Orient Chemical Industry Co., Ltd. represented by the following structural formula
aNB Ri, Kayaras Black G Conch (Nippon Kayaku ■
These dyes are used in an amount of 5 to 20% based on the total amount of the ink.

5 weight -%" 9 below, handwriting (1illii) is used for drafting.
If the concentration is 20 wt.% or more, the dye will settle in the ink over time, causing fIAif formation.

7- Water-soluble organic solvents are used for the purpose of improving the solubility of dyes and preventing ink from drying at the pen tip.
H9), and the surface tension is 35dyne/(7n
(a, t 15-25'(j') or more can be used, and the amount used is 5-25% of the overall ink view.Water-soluble with a boiling point below 120°C Using an organic solvent improves the drying properties of handwriting (stitch lines), but the ink at the pen tip dries more quickly.

If you use a water-soluble organic solvent that is unsuitable for automatic drafting, it will improve the drying of the ink at the pen tip, but it will make the handwriting (drawings) noticeably dryer. 17〈It is slow, which is still not desirable as an automatic drafting pocket.

Also, the surface tension is 35rl yn e/nt1 (15~
If the following water-soluble organic solvents (in 25'O) are used, the surface tension of the ink decreases, so handwriting (printing lines) smear becomes noticeable, making it unsuitable for use as an ink for drafting.

8- It is difficult to prevent the ink from drying and solidifying, and if the concentration is 20% by weight or more, the handwriting (printing line) will dry too slowly even if a water-soluble organic solvent with excellent moisturizing properties is used. occurs.

A specific example of a water-soluble organic solvent that satisfies each of the above requirements and can be used in the present invention is ethylene chloride:
at760ao+Hg/).

5T==46.49a, yneA-fIL(a, t20
°c)) propylene glycol (at bp=187.6)
(at760mHf)ST=72.0dyne//c1
rl (at25°C)) trimethylene glycol (bp
=214.4'o(at760mTl9), 5
T=45.17dyne/II (at25°a))1.
3-Butanediol (bp=207.5'O(a t
760mH.

5T=37.8dyne/(m(at25°0))r-
Butyrolact 7 (bp=204'c(at760sl)
Hg).

=9-8T=47.0dyne/Cm(at18.8°C))
Formamide (1) p=210.5°O (at760s
wHf).

5T-58,35d, yne/(m(at20°O))
Tetrahydrofurfuryl alcohol (bp=178'o (at760m) 1F), 5T=
3767+18//C1'n(at25'0))N-
1 + 17 Ho 11/ MuTmit'(hp=153'
Q(et76[1!mHg).

5T=36.76dvne/Cm, (at20°a))
Monoethanolamine (hp=170.95'o(at
760ia+H9).

5T = 48.89ayne/Cm (at 20°c)) dimethyl sulfoxide (1) p = i89°c (a, t76
0+a+T(g').

5T=4 546 yne//m (at 20°C)) 7 moles (bp-12894°O (at 760mH9)
.

5T=67.63dyne/Crn(at20°0 N
- Methifure 2 pyrrolidone (hp-=202'O(at760allHg), 5
T=41 dyne/Cm (+3 t25'o)). (However, bp indicates the boiling point and ST indicates the surface tension.) Water is the main solvent, and the amount used is 55 to 90% by weight based on the total amount of ink.

10- Also, the physical property regulations of the ink of the present invention are that the viscosity of the ink is 2.0.
~9. At OcP (a, t25°n), the surface tension of tsu, tsu, i, no 1 is 35dyOe7'cn+(qt+5-2
It must be "s'c'l" -. Viscosity is 2.0
If it is less than cD, too much ink will be ejected from the pen tip, resulting in poor handwriting (printing) dryness. Also, 9. OcP
If it is above, the ink discharge will be lower than 2. Handwriting (stroke)
It's blurred.

This can lead to breakage.

Furthermore, the surface tension of the ink is 35dynθ/1n (
If it is less than at15 to 25゛Q), there is a tendency for handwriting (drawing lines) to smear noticeably. Depending on the composition of the ink used for drafting, the width of the handwriting (painting, strokes) may vary depending on the composition of the ink.
If the tracing paper is used for a long time, it may smear and spread 5 to 5 times more than when it was used, resulting in a dull, hard-to-see color tone.

Note that the hollow pen ink of the present invention is slightly hil'.
It is necessary to add each of the 9 items of i + self to l, but if necessary, in addition to the above-mentioned component ingredients, for the purpose of fine-tuning 11 of each color, use dimensional dyes and F-contact dyes for each vinegar. 1°, +4<,
Polyvinyl 7'l・co-f has a characteristic of V-(Nki's)', 1 degree of damage, and 11 points in handwriting knee abrasion fastness.
11 tons of polyvinyl vinyl, polymethyl 1'nylnythyl, poly+xyethylene, methyl
Water such as p, t, It, polymer to total amount of ink =
y + shi + 5 cars 1 sho or less rice add Z, can also be done, in-
1-In order to add the action of I・Yl and to make the +fiL ejection of the ink in the clam fertilizer more sl-l'l', the surface tension of the ink was 35ayneA (at 15-25'n).
Various anionic and/or nonionic gel surface activating agents are placed in a large frame to prevent formation of scum, ink leakage, and obstruction of ink output due to ink rot. 7s7. Hue, /-le, pentachlorophenol.

Sodium, paraoxyammonium, monoaroic acid alkyl ester,
A fungicide such as kehydroacetate I''Th sodium is added to the preservative, and when the ink comes into contact with metal parts, benzotriazole is used as necessary to prevent metal corrosion.
- Anti-corrosion and anti-corrosion of chile diamide 4 acetate salt ~11 is also added as appropriate 1. It is also possible to lp by 1'. Also, in case),
,-,-r 17t9! f, +) In order to improve the resolution of the ink and suppress the drying of the ink at the pen tip, we added urea, ethylene door element, etc., and reduced the drying time of the ink at the handwriting (staging line) and the pen tip. For the purpose of $&Qljj 74, there is no problem in adding hygroscopic sugars such as SoJ Rechtol and Mannitol. Adjust the pH of the ink as necessary.

In order to improve the stability of the ink over time, sodium hydroxide 1. 4. Add alkaline substances such as sodium carbonate, potassium hydroxide, potassium carbonate, and decathorium phosphate.

I/KID of the present invention: The above-mentioned ink components can be appropriately selected according to the required characteristics of the ink, and can be manufactured by a simple operation of mixing and dissolving, but it can be manufactured more easily by appropriate heating and stirring. .

16- The present invention will be explained in more detail with reference to Examples below.
In the examples, "parts" simply indicate "parts by weight."

Example 1 Water Black 100-L 55.0 parts (dye content 20% aqueous solution) Enalen glycol 150 parts Enalen urea 100 parts 25% aqueous solution) 01 parts Polyvinylpyrrolidone (K=+5) 2.0 parts Water
178 parts A mixture of the above ingredients was mixed at 3 [1 to 40'O
A black ink having a viscosity of 4.1 cP (at 25'C) and a surface tension of 39.5+]yne10r+ (at 21°C) was obtained.

This in-j is L'1.3. t], a hollow pen with a diameter of 5- (a ceramic pipe is attached to the nib/' A end) After tasting Cζ, I performed a quality test.

Encounter (turn) around.

Water Black L -20055, 0 parts (dye content 2
0% water soluble) Walklet+2 (for color Al11 adjustment) 03 parts (Orient Chemical Industry (prepared, acid dye) 1' Noo-Orange 418 (Ika6jll adjustment Ltl) 0.2 parts (same) Ethylene glycol 100 stains 1 Ethylene urea 50 parts Turbitol 05 PVA117 (1 part % aqueous solution) 3. [T (Kuraray's pure vinyl alcohol) Polyvinyl pyrrolid (K = 30.10% Mizunuma liquid) 20
Part Pentachlorophenol Luna lium (10% aqueous solution) 01 part Hydroxide l-II 1 part (25% aqueous solution #) 0.2
Department water 2
37 parts The acetic acid mixture of each of the above ingredients was stirred at 30-40°C for 2 hours, and then filtered to a viscosity of 3.8 cP (at 25
°O), surface tension 43.0dyne/l'm1(a t
A black ink of 23'Q'l was obtained.

Using this ink, the same procedure as in Example 1 was carried out, and the results were evaluated by the quality department.

Comparative Example 1 (addition of low-boiling self-solvent) Walkfrack 1no-L (20% aqueous solution excluding dye) 5
5 parts Ethylene glycol 1 10 parts Ethanol 50 parts (boiling point 7862
°O(at760mT(g), 8-plane tension 22.1d
yne/cln(a, t25°O)) ethylene urea
50 parts Sorhitol
04 parts Sodium pentachlorophenol (10% aqueous solution) 01 part Sodium hydroxide (25% aqueous solution*) 0.2 parts P
VA117 (5% aqueous solution) 40 parts (it'll'/Rare special holihinyl alcohol) water
2
03 parts The above-mentioned formulation of each component was stirred at 30-40'C for 2 hours and then filtered to give a viscosity of 4.2 cP (at 25'oC).
), surface tension 39.2 ayne/Cm (at20'r
) black ink was obtained.

Using this ink, a quality test was conducted in the same manner as in Example 1.

Comparative Example 2 (Addition of high boiling point solvent) Water Black 100-L (20% aqueous solution excluding dye) 400 parts Water Red 4=2 (for color tone adjustment) 02 parts (Orient Chemical (acid dye) Water Yellow 1 (color tone) For adjustment) 01 part ethylene glycol 70■1 Naoji Klicoh J
80 parts (boiling point 2B2'O(at
760 mHg), surface tension 53.8 dyne%tn (a
t20'0)) Ethylene urea 8
0 parts pentac fj lophenol sodium (10% aqueous solution) 01 parts 17-hydroxide) IIum (25% aqueous solution) 0.1 parts polyhinylvirolitone (K=15'1 2.0 parts water
545 parts A mixture of the above ingredients was stirred at 30-40°0 for 2 hours L*
Vi filtration was performed to obtain a black ink with a viscosity of 3.1 cP (at 25°C), a surface tension of 3B, and 7 dvne/f″m (at 21°C’). Using this ink, a quality material was prepared in the same manner as in Example 1. I took a risk.

Comparative Example 3 (ink containing a large amount of water-soluble sulfuric solvent) Water Black 100-I.

(20% water soluble (excluding dye)/Pl) 45.0 parts ethylene glycol 600 parts tenlumamide
50 parts sodium pentachlorophenol (10% aqueous solution) 01 part water
199 parts of a mixture of each of the above ingredients at 30-40゛O
After stirring for an hour, it was filtered and the viscosity was 2.8 cP (at 25').
o), surface tension 39.5 dyne/cmr at21
A black ink was obtained.

18- A quality test was conducted in the same manner as in Example 1 using this ink.

Water Black 100-L (dye content 20% water soluble) 55.0 parts ethylene glycol 30 parts ethylene urea 1 part sodium pentachlorophenol (10% Aqueous solution) 01 parts 7 Sodium oxide (25% aqueous solution) 01 parts Polyhinylvirolitone (K230) 2.0 parts Water
298 parts The above-mentioned blend of each component was stirred at 30-40'C for 2 hours and then filtered to form a black ink with a viscosity of 3.0 cP (at 25'o), a surface tension of 39.7 dyne/cm, (at 20'o). I got it. 12 using this ink in the same manner as in Example 1.
We conducted quality tests: tests.

Comparative example 5 (high viscosity ink) Water black 100-T.

(Dye content 20% water soluble* > 55.0 parts Ethylene glycol 100 parts Ethylene urea 100 parts Sodium pentachlorophenol (10% water soluble) 01 parts Metrose 90EIH-15000 (1% water solution) 20
0 parts (Shin-Etsu Chemical (stock system, Hydroxyp 1) Bylmethylcellulose D-suth thickener) Water
49 parts A blend of the above ingredients was stirred at 60-40°C for 2 hours and filtered to give a viscosity of 13.1 cP (a, t25°C).
), surface tension\41.1 (lyn e/Cm(a
A black ink with a temperature of t21°C was obtained. Using this ink, a quality test was conducted in the same manner as in Example 1.JLLM (low viscosity ink) Water Black 100-T.

(Dye content 20% water soluble'Q) so, o part ethylene glycol 80 parts ethylene urea 30 parts penkuku 1 colophenol sodium (10% aqueous solution) 01 parts After stirring in O for 2 hours, filter to obtain a viscosity of 1.8 cP (at 25°a) + surface tension of 41.2 d.
A black ink of yne//c'm (a, t21°C) was obtained. Comparative Example 7 A quality test was conducted in the same manner as in Example 1 using Kono ink. (Ink with low 9-plane tension) Water Black L-2CIO (20% dye content aqueous solution) 550 parts Water orency + 18 (For color tone adjustment) 0.5 parts Ethylene glycol 10.0 parts Ethylene urea 50 parts Sorbitol
05 parts PVA117 (10% aqueous solution) 4.0 parts Sodium pentachlorophenol (10% aqueous solution) 01 parts 21- Florado FC-4500, 4 parts (Fluorinated surfactant manufactured by Sumitomo 3M (Bung 4) Water
245 parts A mixture of the above ingredients was stirred at 30-40°C for 2 hours (viscosity 3.9 cP (a)
t25°a) + surface tension 33.1dynezfm(at
A black ink was obtained at a temperature of 21°C.

Using this ink, quality tests were conducted in the same manner as in Example 1.

Comparative Example 8 (Ink whose dye is different from that represented by general formula (1) above) Water Black R-4558, 0 parts (Nicrosine acid dye manufactured by Orient Chemical T Co., Ltd.) Water Orange $18 (for color tone adjustment) ) 07 parts Ethylene glycol 100 parts Ethyl, /7 urea 50 parts PVA117 (10% aqueous solution) 600 parts Bare)') D Rofeno I Renodium (10% aqueous solution, #) 0.1 part 22- Water
762 parts of a blend of each of the above ingredients at 30-40'O
After stirring for 2 hours, filter 1. Viscosity filter 4 c P (
a, t 25 'O) r Surface tension 41.3dyne
A black ink of at22'0 was obtained.

A quality test was conducted in the same manner as in Example 1 using this ink.

Comparative Example 9 (with a small amount of dye used) Water Fluff 100-L (dye content 20% aqueous solution) 150 parts Ethylene glycol 150 parts Ethylene urea 50 parts Sodium chlorophenol (10% aqueous solution) 01 parts Sodium hydroxide 11 parts 0.1 part of rum (25% aqueous solution) 1.
1 cause 90ST (-15000 (1% aqueous solution) 140
Department water
508 parts of a blend of each of the above ingredients at 20-60"C
1 yen? .

After stirring for a while, it was filtered and the viscosity was 5.8 cP (at 25°C).
), ff surface tension 42.4ayne/'3TL (at21
0) black ink was obtained.

We conducted a test.

Examples 1 and 2 are shown below. The quality test results of the inks obtained in Comparative Examples 1 to 9 are shown in Table 1.

<Table-1> Test methods and evaluation methods for test items (1) to (8) are shown below.

(1) Draw a straight line on various paper sheets and soil sheets from Bleeding NEET Notes ■ to ■ with a pen filled with ink.

After 1 hour, visually check the blurring of the handwriting. Rated [7].

■Tracing paper ((manufactured by Ostrituna Seisakusho) Q) Coated paper ■) Chemika T-Remat Film (Vexel F-300
) (Manufactured by Nmar T Industry 4) [Phase]) Sand matte film (Trestar Z-200
s) (Somar Kogyo Co., Ltd.) ■) Sand matte film (Trescu A-3008) (Tsumal Kogyo Co., Ltd.)
Stock system) (21 density 11:) lz- Straight lines were drawn closely with a pen on think paper, and the density was visually evaluated.

(3) Water resistance: Draw a straight line on tracing paper for 25 minutes.
- After leaving it in the room for 1 hour, I dropped water on the handwriting. After 1 minute, I wiped off the water and made a straight line to 1.71 liters (Hexcel F-500), and the 75. The degree of wear and tear was evaluated by my brother.

(5) Point: After taking pictures below -Y on the Ben filled with In-V 10 times, draw a straight line on the 1-laning paper 'C+FJ? , 1111 ~ Nobode no Hodenezume IW If Kotenhi Ii.

(6) Dryness of the stem of the brush kick;■ Tray sink paper and (2
) Chemical matte film (Vexel F-300) fc
One minute after drawing a straight line, rub the rectangular mark with your finger to evaluate how easily the ink dries.

Pen'y'V, half 26 with the IC cap closed for 1 or 2 hours
- After leaving it in a day room, draw a straight line on tracing paper and evaluate the dryness of the pen tip based on the presence or absence of blurring. After that, the ink was allowed to stand for one day at -30'a, thawed, and the static stability of the ink was evaluated based on the presence or absence of sediment and viscous matter at the bottom of the bottle.

(Evaluation of each test item is ○, L・, ×, where ○ indicates good, △ has some problems, and × indicates poor.) As shown in the test results, the hollow pen of the present invention The ink is excellent and satisfies the requirements for use in drafting, drafting, etc.

Patent applicant: Pentel Co., Ltd. 27- Procedural amendment (voluntary) March 11, 1932 Director-General of the Japan Patent Office Kazuo Wakasugi 1 Display of case 1982 Patent application No. 28652 2 Name of invention Hollow Pen use In Relationship to the person making the kilogram amendment Patent applicant address 7-2-6 Nihonbashi Koami-cho, Chuo-ku, Tokyo Contents of the amendment 1) "Polyvinylpyrrolid" on page 15, line 14 of the specification box
is corrected to "polyvinylpyrrolidone".

2) Correction of "Hydroxypropylcellulose" to "Hydroxypropylcellulose" on page 20, lines 9-10 of the specification.

Claims (1)

[Scope of Claims] (1) An ink for hollow pens comprising at least one water-soluble dye represented by the following general formula (1), a water-soluble organic solvent, and water. (In the formula, X represents a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group.) (2) The viscosity of the ink is 2.0-9.0 CP (at
25'o). and the surface tension is 35 dyne A′rIL (at15~
25'O) or more, the ink for hollow pens according to claim (1). 1- (b) The surface tension of the water-soluble organic solvent is 35 dynθ (at 15-25') and the square point is 120
Hollow pen ink according to claims (1) and (2), which has an ink of 220° 0 (at 760 Hg). (4) The amount of the water-soluble dye (1) used is 1-7% to 5-20$t% of the total amount of ink, and the amount of the water-soluble organic solvent used is 5-25% of the total amount of ink. The ink for hollow pens according to claims (1)m to (3), which is t% by weight.