JPS58129073A - Ink erasing material - Google Patents

Abstract

PURPOSE:A desensitizing ink erasing material, consisting of a solution prepared by dissolving a low-volatile desensitizing organic compound which is a solid at ordinary temperature in an organic solvent having a specific boiling point or below, capable of effectively erasing scripts written in an ink containing a colorless dye and a developer, and written further even just after the erasing. CONSTITUTION:An ink erasing material prepared by dissolving a desensitizing organic compound, e.g. benzoguanamine (228 deg.C melting point) or p-aminoacetanilide, (164 deg.C melting point), having >=60 deg.C melting point and <=1mm.Hg vapor pressure at 150 deg.C in a solvent, e.g. methanol, acetone or toluene, having <=160 deg.C boiling point to give preferably 2-40wt% concentration. The resultant ink erasing material solution is preferably microencapsulated, and the formed microcapsules are hardened by a binder to form a solid rubber eraser for use.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides handwriting with an ink consisting of a color developer having a phenolic hydroxyl group, a colorless electron-donating organic compound that develops color with the color developer, and a solvent that does not inhibit the color reaction. This relates to an erasing material for erasing.

p-nonylphenol, novolac type phenolic resin,
A color developer with a phenolic hydroxyl group such as styrenated alkylphenol, a lactone that develops color with this color developer, and a colorless electron-donating organic compound (hereinafter referred to as a colorless dye base) such as spirobenzobilane, which inhibits this color development reaction. A patent application has already been filed by the same applicant as the present application (Japanese Patent Application No. 56-15
5342). This ink contains a colorless dye developed by a color developer, and as it is darkly colored like normal oil-based ink, it can produce dark and clear handwriting, and it also contains alcohol, ether, and ester. ,
It can be easily erased using polar compounds such as amides and amines. That is, it is believed that the color complex generated by the reaction between the color developer and the colorless dye base is decomposed by the desensitizing action of the polar compound, resulting in complete colorlessness.

However, if the polar compound used as the ink eraser is easily volatilized, once the eraser completely evaporates from the erased surface, the colorless dye base will react with the developer again, causing the handwriting to disappear. There is a tendency for the color to recover. On the other hand, if the polar compound of the erasing material is stable over time and does not easily volatize, it will show stable erasability over a long period of time after erasing and will not recover the color, but if the same ink is used immediately after erasing, When writing on the erased surface, the rewritten handwriting tends to become colorless again due to the eraser remaining on the erased surface.

Therefore, the present inventors have an object to provide a desensitizing erasing material that can effectively erase handwriting made with colorless dye-developer ink as described above, and also allows writing on the erased surface with the same ink immediately after erasing. As a result of intensive research with the aim of If a solid desensitizing organic compound is used, the brightness is completed within about 3 minutes after erasing.

That is, the ink erasing material of the present invention is made of a solution in which a desensitizing organic compound having a melting point of 60°C or higher and a vapor pressure of 1 g+sHg or lower at 150°C is dissolved in a solvent having a boiling point of 160°C or lower.

As a desensitizing organic compound that is solid at room temperature as described above,
In the present invention, a low volatility material having a melting point of 60° C. or higher and a vapor pressure of 11 Hg or lower at 150° C. can be used. If the melting point is below 60℃, there is a risk that it will melt in direct sunlight, and the vapor pressure at 150℃ is 1
If it is more than 11 HIJ, the desensitizing organic compound will volatilize over time due to its easy volatility, making it impossible to maintain the erasing action permanently. Examples of such desensitizing organic compounds include benzoguanamine (-.

9.228°C), 4.4'-sulfonylbis(acetanilide) (-,0,290°C), allouric acid (m, p
.

100°C), p-aminoacetanilide (m, p.

164°C), 1-methyl-N-7enyl-N(phenylmethyl)-4-piperidiamine (1,1).

115°C), benzacetin (m, p, 189°C),
4-Butoxy-N-hydroxybenzeneacetamide (
ugliness, p, 153°C), 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl carbamate (m
, p, 150℃), futon (m, p, 131℃),
Diaminodiphenylmethane (m, p, 92°C), dianisidine (s, p, 137°C), 4-(phenylmethylphenol carbamate (a, p, 147°C), galactitol (*, p, 188°C), phthalic acid diphenyl 1 stel (m, p, 73°C), rudoflazine (s.

p, 159°C), 4-(methylsulfamoyl)-sulfanilanilide (m, p, 141°C), 4.4-
Tetramethyldiaminodiphenylmethane (gm, p.

90°C), polyvinylpyrrolidone, polyvinyl acetate, ketone resin, oligo-N-methylmorpholinium propylene oxide, polyacrylate, polymethacrylate, and the like.

Any solvent that can dissolve the desensitizing organic compound described above which is solid at room temperature can be used as the solvent, but in the present invention it is necessary to use a volatile solvent with a boiling point of 160° C. or lower.

If a less volatile solvent with a boiling point of 160° C. or higher is used, the desensitizer in a solution state will remain on the erased surface, making it impossible to rewrite immediately. Such solvents include, for example, methanol, ethanol, tetrahydrofuran, acetone, ethyl acetate, butyl acetate, toluene, xylene, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, dimethyl. Formamide etc. can be used.

When preparing an erasing material by dissolving the above-mentioned desensitizing organic compound which is solid at room temperature in these solvents, it is preferable to dissolve the desensitizing organic compound to a concentration of 2 to 40% by weight. .

In addition, in order to improve the fixing properties and migration properties of the erasing material, resins that do not hinder rewriting properties, such as petroleum resins, polyester,
Polystyrene, styrene-butadiene copolymer, etc. may be added to the erasing material solution as necessary.

To erase handwriting made with colorless dye-developer ink using such an erasing phase solution, apply the erasing phase solution onto the handwriting with a brush, or apply it to a container for a writing instrument such as a sign marker or felt-tip pen. Can be filled and used.

An even simpler method of use may be to microcapsule the above erasing phase solution, solidify the capsules with a curing agent, and use them like a solid eraser. To microcapsule the elimination phase solution, conventionally used coacervation method, tn 5 itu 11 method, submerged drying method, etc. can be employed. In addition, by setting the particle size of the capsule to 100 to 1000 μm and the film thickness to 3 to 40 μm, the capsule can be easily crushed by light friction, allowing the core material, the erasing phase solution, to be applied effectively, and it also has excellent stability over time. It can have sex.

As the solidifying agent for solidifying the capsules, a slight am-forming agent such as baked stone kola, a resin liquid, a wax such as crayon or Frepas, or Otsu can be appropriately selected and used. In addition, when solidifying, to adjust the applicability and solid strength, etc., fillers such as calcium carbonate, talc, and clay, disinfectants, wax,
Auxiliary materials such as oil may be added.

As explained above, the erasing material of the present invention is composed of a solution in which a desensitizing organic compound that is solid at room temperature with a boiling point of 60°C or higher is dissolved in a volatile solvent with a boiling point of 160°C or lower. Since the eraser is no longer effective, even if the same colorless dye-developer ink is immediately written on the surface coated with the eraser, it will not become colorless again. Furthermore, the desensitizing organic compound itself has a vapor pressure of iss+ at 150°C.

Due to the use of extremely low volatility compounds such as:
The erased marks are maintained stably over time and do not regain color.

Furthermore, by microcapsulating the erasing phase solution and solidifying it using a solidifying agent, it is possible to attach it to a part of a writing instrument like an eraser and use it easily.

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

Example 1 [Synopsis of colorless dye-developer ink] p-nonylphenol [developer] 3 parts Crystal violet lactone [11.5 parts colorless dye cyclohexylbenzene (solvent) 2.5 parts phenol resin [hytanol] #1501J 2 parts (manufactured by Hitachi Chemical)
[Color developer and viscosity modifier] Mix the above components and mix 10
The mixture was stirred at 0°C for 30 minutes to obtain blue ink. This ink is used in ballpoint pens (JIS S 6039-1980
A writing instrument that can be erased with the erasable material of the present invention was prepared by filling a junior high school grade E type) with the erasable material of the present invention.

[Preparation of erasing material]

4.4'-methylenebis(acetanilide) (*, p,
236℃) 2+1 methanol
4g ethanol
4 g of each of the above components were mixed and stirred at 50° C. for 1 hour to obtain an elimination phase solution of the present invention. This was filled into an oil-based marker part (MM50 manufactured by Pentel) to prepare an eraser. When the handwriting of the ballpoint pen was lightly rubbed two to three times with this eraser, the handwriting was completely erased. After 20 seconds of erasing, I wrote again on the erased surface with the same ballpoint pen, and the handwriting was clearly written, and this handwriting did not erase as time passed.

For comparison, an eraser phase solution prepared in exactly the same manner as above was used, except that triethanolamine, a desensitizing organic compound that is liquid at room temperature, was used in place of 4,4'-methylenebis(acetanilide). When I lightly rubbed the handwriting with the ballpoint pen mentioned above two or three times, I was able to completely erase the handwriting, but after 1 minute, 5 minutes, 1 hour, and 1 day, I rubbed the same ballpoint pen on the erased surface. When I wrote it down again, the handwriting was instantly erased.

Example 2゜Polyvinyl acetate [Gosenil E50Z2J (Nippon Gosei ■
) 3 (1 Ketone resin "Hilac 110HJ (Hitachi Chemical ■ @) 1 g Ethyl acetate 5 g Methanol 5 g The above components were mixed and dissolved by heating to obtain the erasure phase solution of the present invention. This was used as parts for oil-based markers. (MM 50 manufactured by Pentel) to prepare an eraser. When the handwriting made with the ballpoint pen made in Example 1 was lightly rubbed 2 to 3 times with this eraser, the handwriting was completely erased. Erasing 30 Seconds later, when I wrote again on the erased surface with the same ballpoint pen, I was able to write clearly, and this handwriting did not erase over time.

Example 3 Ketone resin "Hilac 111" (softening point: 108 DEG C., manufactured by Hitachi Chemical Co., Ltd.) 5 g Toluene 25 g Each of the above components was mixed and dissolved by heating to obtain the elimination phase solution of the present invention. After emulsifying and dispersing 9 g of this elimination phase solution in 30 g of a 10% aqueous gelatin solution, 300 g of a 10% aqueous gum arabic solution was further added and the mixture was stirred at high speed.
was added and stirred at medium speed, and 10% acetic acid was added dropwise to adjust the pH to 4.1. This fractional solution was kept at 40°C for 2 hours, then slowly cooled to 5°C, and glutaraldehyde 0.5
- was added and left overnight.

After decantation and washing with warm water, the microcapsules were air-dried to obtain microcapsules 10,517 having a particle size of 10 to 50 μm and having the elimination phase solution as the core material.

Next, this microcapsule was solidified by the following method.

Said microcapsule 10.5 parts Paraffin wax (130F) 2.0 parts Distearyl ketone 6.0 parts Micro wax
1.0 part hydrogenated oil
1.5 parts talc
3.0 parts of each of the above components were mixed, heated and melted, stirred gently, poured into a crayon-like mold, cooled and solidified, and then taken out to obtain a solid eraser-like eraser. When the ballpoint pen handwriting made in Example 1 was rubbed with this erasing material 7 to 8 times, it was able to be completely erased. Erase 30
Seconds later, when I wrote again on the erased surface with the same ballpoint pen, I was able to write clearly, and this handwriting did not erase over time. Furthermore, once erased handwriting was not restored to color.

Example 4 In the microencapsulation of the elimination phase solution in Example 3, the process was carried out in exactly the same manner as in Example 3 except that the emulsification and dispersion was carried out under very gentle agitation. Microcapsules 10.5 (I+) having a thickness of 150 to 300 μ and a film thickness of 10 to 15 μ were obtained.

Next, this microcapsule was treated in exactly the same manner as in Example 3 to obtain a solid eraser-like eraser. When the handwriting made with the ballpoint pen made in Example 1 was rubbed 3 to 4 times using this erasing material, it was possible to completely erase it. Thirty seconds after erasing, I wrote again on the erased surface with the same ballpoint pen, and the handwriting was clearly written, and the handwriting did not erase over time. Furthermore, once erased handwriting was not restored to color.

Patent Applicant: Pendel Co., Ltd. Agent: Yudo Omata
Jodo Shigemi
Tomonosuke Araki Procedural Amendment - (Voluntary Submission) December 27, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi 1. Indication of the Case 1983 Patent Application No. 119994 2. Name of the Invention Ink Eraser 3. Case of the person making the amendment Relationship with Patent Applicant Address 7-2 Nihonbashi Koami-cho, Chuo-ku, Tokyo Name <55
1) Pendel Co., Ltd. 4, Agent Address: 104 Name (6704) Patent Attorney Yukim Omata (and 2 others) Phone Tokyo 03 (543) 003611 (Representative) 5.
Supplement 1 subject 1111 [Column for detailed explanation of the invention in Book 1 (]) Specification 4
On page 18-19, “Allophosphoric acid (ta, p, 1
00℃)," is deleted.

(2) Same! 11-Methyl-N-phenyl-N(phenylmethyl)-4-piperidiamine (*, p, 115°C>, j is deleted from page 14, line 20 to page 5, line 2).

(3) Correct "futon" in line 5-6 of the same book to "kotoin".

(4) [Luphenol force rubamate] in the same 5th line 9th line
is corrected to "luphenol)carbame 1~".

(5) “Rudoflazine (lI
l, p, 159°C), delete j.

(6) In the same book, page 7, lines 19-20, [Furepas] is changed to ``Correct to pastel j.''

that's all

Claims (1)

[Claims] 1. Melting point 60°C or higher and vapor pressure at 150°C 11
An ink erasing material made of a solution of a desensitizing organic compound with a temperature of IIIHg or less dissolved in a solvent with a boiling point of 160°C or less. 2. Melting point 60°C or higher and vapor pressure ll at 150°C
An ink erasing material made by solidifying microcapsules whose core material is a solution of a desensitizing organic compound with a temperature of 1Hg or less dissolved in a solvent with a boiling point of 160°C or less with a solidifying agent.