JPS60170676A - Ink for writing utensil - Google Patents

Abstract

PURPOSE:To provide the titled ink for felt pen, etc., containing a fluorine-containing surfactant, capable of maintaining a proper flow rate of the ink to give a continuous written mark even after leaving the pen in opened strate or after the continuous use for a long period, and assuring the constant writing smoothness. CONSTITUTION:For example, preferably 0.01-5wt% fluorine-containing surfactant (preferably a nonionic surfactant) is added to an ink composition containing a solvent (preferably an organic solvent), a binder, a dye and/or pigment, and if necessary, a dispersion assistant, a peel assistant, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to inks for writing instruments, and particularly to inks for use in writing instruments generally referred to as felt-tip pens, marking pens, felt-tip pens, markers, brush pens, and the like.

[Prior art]

The components of this type of ink for writing instruments that have been conventionally used include dyes, pigments, dispersion aids, binders, release aids, and solvents, and a large number of products are currently on the market.

However, the current situation is that none of these writing instruments are fully satisfactory in use.

One of its drawbacks is that if you leave the cap open, the solvent in the ink may evaporate, resulting in blurred handwriting or, in extreme cases, no writing at all.

In addition, if you continue to write a large amount of characters because the ink supply speed to the pen tip is not fast enough, the amount of ink at the pen tip will decrease, causing blurring as described above. have.

In order to solve these drawbacks, it is conceivable to increase the amount of solvent to lower the evaporation ratio and improve the flow of ink. However, this method has the decisive drawback of lowering the image density, so it cannot be used in practice. Rather, in currently available writing instruments, the amount of solvent added is limited to the minimum amount necessary for proper ink flow, in order to increase the image density. Therefore, even if good results are obtained with a new writing utensil that you have just started using, as mentioned above, if you leave the cap open or if you continue to write a large amount of letters, the letters etc. This results in blurred writing or inability to write at all.

By the way, in recent years, instead of penetrating or absorbent writing surfaces such as paper, painted boards like whiteboards, plastics,
There are commercially available writing instruments that allow you to draw lines on a non-permeable or non-absorbent writing surface such as metal or glass, and then wipe them off later with a dry cloth or a cloth dampened with water, if necessary.

However, these types of writing utensils have the disadvantage of poor flow into the inlet as described above, as well as the fact that after writing,
If you leave it for a long time or depending on the material of the writing surface, especially if there is not enough liquid and the lines become blurred, they may not be erased later.
, it may be necessary to wipe it off with a solvent (e.g. methanol), and even in that case, depending on the material of the writing surface,
It has the disadvantage that irremovable embedding remains, that is, the erasability is poor. The reason for the deterioration in erasability is thought to be that the adhesive strength of the binder becomes stronger after the solvent evaporates, exceeding the anti-adhesion effect of the release agent in the ink components. The balance between the binder and release agent is lost, the ratio of release agent decreases, and handwriting is erased.
<It is possible that it will become.

Furthermore, if there is less solvent in the ink, the lubricity of the pen tip on the substrate surface will be insufficient, and in extreme cases, the pen tip may scratch the substrate surface. JP-A No. 53-54747 discloses that by coexisting a release agent that dissolves well in an organic solvent and an α-olefin with a melting temperature of 30 to gO°C in the ink composition, JP-A No. 53-54747 The publication discloses a method of improving the flowability and erasability of ink by coexisting a stripping agent and wax that dissolve in an organic solvent in the ink composition.However, these methods - Compared to ink containing no olefin or wax, the effect of improving ink flowability and erasability is recognized, but the degree of improvement cannot be said to be sufficient for practical use.Also, the erasability after being left for a long time It is also insufficient.

On the other hand, in order to prevent or reduce the deterioration of the erasability of handwriting marks, pigment particles are surrounded and adsorbed and coagulated to make them easier to wipe off, or the handwritten marks are moistened with an additive that is completely incompatible with the resin. A method has also been proposed in which it is possible to erase particles by turning them into coarse particles (for example,
-39g9/Th JP-A-119-. 29 Publication etc.). However, even with these methods, erasability deteriorates after a long period of time has passed after writing. Furthermore, Tokukai Showa S Otsu-q/
No. 27, (A) aliphatic dibasic acid ester, (B
A method of improving the erasability by using in combination an inorganic acid ester activator (C) an aliphatic alcohol ester of an aliphatic-basic acid having a total carbon number of 20 or more has been disclosed, but the erasability is still poor. Not improved enough.

[Purpose of the invention]

Therefore, it is an object of the present invention to provide an ink for a writing instrument which allows a suitable amount of ink to flow out and produces good lines even when the ink is left with the cap open or used continuously for a long period of time.

Another object of the present invention is to provide an ink for a clam marking tool that allows good ink liquid flow even when the amount of solvent is used without reducing the image density.

Another object of the present invention is to provide an erasable ink for writing instruments that has good erasability and allows handwriting to be easily erased even after a long period of time has passed after being written on.

[Structure of the invention]

As a result of intensive research, the present inventors have found that the above object can be achieved by incorporating a fluorine-based surfactant into the ink component, and have completed the present invention.

That is, the present invention is an ink for a writing instrument characterized by containing a fluorosurfactant. The inks for writing instruments of the present invention include those based on organic solvents and those based on aqueous solvents.

As the fluorine-based surfactant, anionic, cationic, or nonionic surfactants can be used.

Particularly preferred are liquid or wax-like substances for improving erasability, and nonionic surfactants for improving anti-drying properties. As a specific example, F
C-'130゜"c-1I3/ (manufactured by 3M), Megafac F-/G/, same-/Guko, same/1lt2-o
, F-74', 7. Same F-74'4t, Same F-/4t
D, F-32g, F-/7θ, F-/7/l
Same F-/7U, Same F-/731 Same F-/'/9. Same F-
7g3. Same F-/za! I (Dainippon Ink Chemical Industry)
(manufactured by). The amount of the fluorosurfactant added varies depending on the solvent and additives used, but is preferably 0.007 to 70% by weight of the total weight of the ink composition (hereinafter, all percentages indicate weight%). ~
3% is particularly preferred. When the amount added is small, the effect is weak, and on the contrary, when the amount added is large, the drying properties of the image tend to deteriorate. These fluorosurfactants can be used alone or in combination with one or more of them.

In addition to the fluorosurfactant, the ink composition of the present invention contains
It contains a solvent, a binder, a dye and/or a pigment, and a dispersion aid, a peeling aid, etc. as necessary. As these inks, those conventionally used for ink such as a sign bene, a marking bene, a felt bene, a marker or a brush pen can be used. Examples of solvents include water, lower aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, lower alcohol esters of lower fatty acids such as ethyl acetate, ethyl acetate, and butyl noropionate, and lower alcohol esters of acids such as benzene, toluene, and xylene. Aromatic hydrocarbons, ethanol, n-propanol,
lower aliphatic and alicyclic alcohols such as improno, nol, n-butanol, imbutanol, cyclohexanol, and glycol monoalkyl ethers such as ethylene glycol methyl ether, ethylene glycol monoethyl ether, methoxybutanol;
It is also possible to use mixtures thereof.

Organic solvents are particularly preferred. When selecting a solvent, it is preferable to give sufficient consideration to the dispersibility of the pigment and the solubility of the resin, rank the evaporation rate of the solvent, and mix them appropriately. These solvents are typically 1IO-90 based on the ink composition.
% preferably θ~lr, t% is used. As a binder, rosin, alkyd resin, phenol resin, polyvinyl/I/f5-le, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-acrylonitrile copolymer,
Vinyl resins such as vinylidene chloride-vinyl chloride copolymer, cellulose resins such as ethyl cellulose and acetyl cellulose, and other commercially available resins for ink.
For example, Acridic A-11O! re^-ti, ob
.

A-gθq, A-g//, Super Beckamin J-g2
θ, 4'7-30g, Petscosol J-5-g (above,
Dainippon Ink & Chemicals■), Marquido-ni/, 71Lλ
, As -A6-yaza, boiled 3/, boiled 3, arakido g
It can be effectively used by using resins such as θ'l-240 (hereinafter referred to as Jyuyo Kagaku Kogyo ■) alone or in combination. These resins are useful for stably dispersing the pigment in the ink composition, and give the ink composition appropriate viscosity and adhesion to the writing surface. 20
%, preferably 3 to 73%. As a pigment,
There are various dyes such as water-soluble dyes, oil-soluble dyes, disperse dyes, vat dyes, and various pigments such as inorganic pigments, organic pigments, resin-processed pigments, etc., which can be used alone or in combination in the ink. To provide transparency, it is preferable to use solvent-soluble dyes, and to provide opacity, use pigments with high intensity and fine particles, composite pigments, and oil-soluble dyes in combination with these pigments. The pigment is preferably one that can be stably dispersed in the ink composition as fine particles. In this sense, a wood-processed pigment in which a pigment is kneaded into a resin is preferably used in the present invention. When a processed pigment is used, the pigment is dispersed very stably and well in an organic solvent, which is advantageous in that there is no need to particularly incorporate a resin into the ink composition.

Specific examples of such processed pigments include Bubi Print Black X Otsu 01 Bubi Print Blue 0g, Bubi Print Orange 3. ? ,/A,
Examples include Microlith Black C-T and Microlith Red BR- manufactured by CIBA. Note that dyes that are not soluble in solvents can also be used in the same way as pigments.

The content of pigment in the ink composition varies depending on its type and the required concentration on the writing surface, but is usually 7 to 70%.
is sufficient. Examples of dispersion aids include polyoxyethylene glycol monostearate, polyoxyethylene sorbitan monostearate, and various Daysno Rron series (Kusumoto Kasei ■).If these pigment dispersion aids are used, it will be easier to disperse pigments. It is possible to expand the range of resin selection. In other words, when dispersing a pigment in a resin solvent solution, it is necessary to achieve a uniform and stable dispersion without sedimentation or agglomeration, but this stability depends on the type and concentration of the pigment, solvent, and resin. change. The type is greatly influenced by polarity, and it is also thought that electrostatic repulsion of fine pigment particles is also related. Also, the higher the concentration, that is, the viscosity, the more the precipitation of the pigment can be delayed. In this way, the selection of resin and the concentration used are determined by the pigment-solvent from the viewpoint of dispersibility, and the higher the concentration, the better the stable coating, but the flow of the liquid and the drying From a sexual point of view, the lower the better.

On the other hand, when a dispersion aid is added, stable dispersion can be obtained over a wide range even when it is difficult to obtain a stable dispersion without addition, or even when sedimentation is rapid at low *i.

This is thought to be because the dispersion aid is oriented on the surface of the pigment particles and repels (or prevents collisions with) the particles. As peeling aids, higher fatty acid esters, phthalic acid diesters, sulfuric esters of polyoxyethylene alkyl ethers, sulfuric esters of polyoxyethylene alkyl phenyl ethers, phosphoric esters of polyoxyethylene alkyl ethers, phosphoric esters of polyoxyethylene alkyl ethers, etc. Phosphoric acid ester, polyester of polyglycol and dibasic acid, triglyceride consisting of saturated fatty acids, glyco-IL@, higher alkyl ether of ethylene glycol, higher alkyl ether of diethylene glycol,
Higher alcohol, liquid rough fin, α-olefin,
and waxes such as paraffin wax, microcrystalline wax, low molecular wax, polyethylene wax, and ceresin, as well as JP-A-3! ;-/3'799 As stated in Publication No. O, each scale Noni Ball series (manufactured by Sanyo Chemical Co., Ltd.,
ethylene oxide adduct of nonylfer), Zanmorin oT-70 (manufactured by Sanyo Chemical, sodium dioctyl sulfosuccinate), Furofane 20/2E <Sanyo Chemical
(manufactured by Kao Atlas ■, polyoxyethylene alkyl ether), various noniolite series (manufactured by Kyoeisha Yushi Kagaku Kogyo ■, nonionic surfactants), Zolronik (manufactured by Kyoeisha Yushi Kagaku Kogyo ■, nonionic surfactants), A surfactant having an HLB of 70 or more, such as a nonionic surfactant derived from an ethylene oxide adduct of Polyzorobire/manufactured by Asahi Denka Kogyo ■, can be used alone or in combination.

The container used to contain the ink composition of the present invention may be any felt pentaiso container widely used in the writing instrument industry. For example, containers that use cotton or felt for filling in the tank inside the container, knock-type containers that fill ink directly into a hollow tank and adjust the flow rate by opening and closing the pulp, and pen nibs that are similar to brush tips. Examples include brush-in type containers, but since these containers are already commercially available and well-known, detailed explanations will be omitted.

〔Effect of the invention〕

According to the present invention, even if the cap is left open or used continuously for a long time, the handwriting will not be cut off.
In addition, the density of the handwriting does not decrease, the writing quality is always smooth, and the handwriting written on the surface of non-permeable or non-absorbent materials can be easily erased even after a long period of time if necessary. , an ink for subsequent writing instruments with excellent erasability can be obtained.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Examples/Comparative Example a An ink composition was prepared by mixing the toner mother liquor and resin liquid shown in Table 1 and stirring at room temperature for about 7 hours.The ink composition was assembled into a marking pen by a known method and an opaque white ink was prepared. I got a writing utensil.

Next, these marking pens were placed in a room with a temperature of 2 S° C. and a humidity of θ% RH 1, with the cap removed from the pen tip and left to stand. When the time until writing misalignment occurred was measured, Comparative Example A It was 1 l-4 minutes for the pen in Example 1, whereas it was 73 to 20 minutes for the pen in Example/. In addition, when writing in large quantities, the pen of Comparative Example A had poor fluid flow and blurred after a while, whereas the pen of Example A was unable to draw smooth lines. The required amount of liquid came out even after drawing a large amount of lines, so I was able to write well without blurring.

Examples C to 7 and Comparative Examples b to d A finely powdered pigment was added to an organic solvent according to the formulation shown in Table λ (the unit in the table is rrJ) at 100° to /200
After stirring for about 30 minutes using an RPM stirrer to fully disperse the pigment in the organic solvent, powdered resin was added to this mixture, and the mixture was stirred at a temperature of θ to 60°C for about 7 hours to dissolve the resin into an organic solvent. After dissolving in a solvent, a release agent, a fluorine-based surfactant, and in the case of a comparative example, an α-olefin and a wax were added, and the mixture was further stirred at the above temperature for 30 minutes to obtain a uniform ink composition. These ink compositions were filled into a marking pen equipped with a felt nib, and the temperature was 25°C and the humidity was θ%RH.
1.The cap was removed from the pen tip in a room with no wind and the time until memorization occurred was measured.
The results shown in Table 2 were obtained. That is, compared to the Comparative Example pen which does not contain a fluorosurfactant, the time required for the Example pen to cause blurring is about 70 times longer. Also, JP-A-33-90! ;1.9 Publication Example/and JP-A-Sho! ;! ;-3671,7 Publication Example/30~1ILθ℃, respectively
Compared to the pens of Comparative Examples c and d in which molten α-olefin and //left'P/grafine were added, the improvement is about twice as high. Good results were also obtained in Examples 3 to 7. A pen was made using the same ink composition as in Examples 3 to 7, except that it did not contain a fluorine-based surfactant. When I measured the time, it was the same as the comparative example.
-, l- minutes.

Also, using these pens, a certain number of characters of a certain size were written on an enamel board with a reflectance of θ%, and then the letters were erased. This writing/erasing test was repeated 70 times at an erasing pressure of 3θ/θ24, and all results were good. However, after writing these down/months later, the erasing pressure was 30±7.
0? When erasing with a shoulder (A), when writing on an unsaturated polyester painted surface and immediately erasing in the same manner with an erasing pressure of 30 ± 70 degrees (B), and after writing on an unsaturated polyester painted surface / When erased after a week (c), the same pen showed the same tendency in cases (a), (b), and (c), but since there were differences in erasability depending on the pen, these were A comprehensive evaluation was made.

■: Good erasability ○: I Good △: l Slightly bad ×: I Bad As is clear from the table, Example 1 is very good compared to Comparative Examples 3, and compared to Comparative Examples c and d. It was also good. Further, in Examples 3 to 7, the erasability was also very good. In addition, in Examples 3 to 3, which were prepared in the same manner except that the fluorine-based surfactant was not included, the erasability was poor as in Comparative Example.

/) C, f, (Color Index)/233
! ;2) C, 1,77 no 6g 3) C, 1,7 Hiro/60 ≠) C, 1,7 Hiro 21. O j) Asahi Dawa Co., Ltd. vinylidene chloride/acrylonitrile copolymer Saranrenone F-220 1,”) Union-Carbide Co., USA Vinyrite
VYHH Supplementary Procedures Amendment Commissioner Manabu Shiga 3, Person making the amendment Relationship to the case Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 5, Date of amendment order Voluntary 6, ? Item to be stopped Column 7 of the detailed description of the invention in the specification contains the content of the amendment.

Claims (2)

[Claims] (1) An ink for memorization tools characterized by containing a fluorine-based surfactant. (2) The ink for writing instruments according to claim 1, which is an organic solvent-based ink.