JPS60137975A - Ink for writing utensils - Google Patents

Abstract

PURPOSE:To provide titled ink of specific properties, with the resultant holograph capable of continuous exfoliation while high in its retainability, comprising specific amount of exfoliative resin as binder, organic solvent for said resin, dye, ethylene oxide-added fluorine-based surfactant. CONSTITUTION:The objective ink with a viscosity <=60cps/25 deg.C and surface tension 20-35 dyne/cm comprising (A) 5-20wt% based on the whole weight of the final ink, of an exfoliative resin (e.g. polyvinyl butyral resin), (B) organic solvent (e.g. ethanol), (C) pref. 3-30wt% of dye and/or pigment and (D) e.g. 0.1- 5wt% of ethylene oxide-added fluorine-based surfactant and/or silicone block copolymer (e.g. a copolymer from dimethylsiloxane and ethylene oxide and/or propylene oxide).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ink for writing instruments, and more specifically, the present invention relates to an ink for writing instruments, and more specifically, it has the performance of IJ brim paint, and has the properties of a fiber pen nib and a resin-molded pen nib. This invention relates to an ink for a writing instrument that allows the ink to be ejected from a writing instrument.

Traditionally, strippable paints are polyvinyl chloride and vinyl chloride-vinyl acetate copolymers.

Polyvinyl butyral, cellulose derivatives, etc. are used as resin components, and these resin components are combined with ketones, chlorinated hydrocarbons, alcohols, and aromatics.

Dissolves in good solvents such as hydrocarbons and esters.

Then, plasticizers are added to make paint for automobiles.

9 For the purpose of temporary surface protection of aircraft mechanical parts, metal household appliances, their base metal and non-ferrous metal products, glass products, plastic molded products, rubber products, etc., these products must be completely peeled off immediately before use. It is a paint that can be applied to the surface of the paint, and is applied using methods such as spray painting, brush painting, or dipping, just like regular paints.

Recently, pigments and/or dyes have been added to strippable paints to produce two-colored strippable paints, which are also being used for decorative purposes such as glass windows.

However, large areas are spray painted.

Although it is possible to paint with a brush, it is difficult to paint details or fine patterns using conventional painting methods.

On the other hand, when painting details or fine patterns, there are regular oil-based paint markers, but these are difficult to remove, and when erasing, it is necessary to use organic solvents that can be used in the ink,
Alternatively, it is difficult to erase the ink by using a solvent that is soluble in the ink.

Also, although there is so-called whiteboard marker ink as an erasable permanent marker ink on non-absorbent surfaces, it has extremely low adhesion of handwriting to the whiteboard and can be easily wiped off with a piece of cloth. Therefore, there are 2 moves.

It was erased by just touching it with a finger, and it was extremely weak in retaining handwriting. Furthermore, since the adhesion is low and the cohesive force of the handwriting itself is low, when erasing the handwriting, the eraser dust (powder) scatters and contaminates the hand, clothes, and surrounding area.

Therefore, the present invention improves the retention of handwriting (paint film) on the non-absorbing surface, makes it possible to completely and continuously peel it off in a film form at any time, and makes it possible to apply fine details and fine coatings. We have previously proposed an ink for writing instruments that can be ejected from writing instruments that have a fiber nib or a resin-molded nib to enable this.

However, the peelable resin used in the above-mentioned writing instrument ink generally has high polarity, so when writing on a highly polar non-absorbing surface such as acrylic resin or vinyl chloride resin, it has a high affinity and has poor handwriting fixation. is good, and continuous peelability tends to be poor.

The present invention was finally completed as a result of various studies on additives in order to improve the above-mentioned points.

That is, the present invention provides an ink for writing instruments, which uses a peelable resin as a binder, and comprises at least an organic solvent of the resin, a dye and/or a pigment, an ethylene oxide-added fluorine surfactant, and/or a silicone block copolymer. Il+-)te.

The gist of the present invention is to provide a common ink for dispensing that can continuously peel off foil traces that meet the following conditions.

<Conditions> 0 The amount of peelable resin used is 5% of the total amount of writing instrument ink.
~20% by weight.

O Viscosity must be 60 c p g / 25 ° C or less.

The present invention will be described in detail below.The surface tension is 20 to 35 dyne/α.

Peelable resin is a binder for ink and exhibits the peelability of ink.Polyvinyl-butyral resin (hereinafter abbreviated as PVB) is used as Strinoha Full Coat and Stritz<Full Paint.
, vinyl chloride-vinyl acetate copolymer resin (hereinafter referred to as PVC
-PVAC), cellulose derivatives, etc. can be used.

Commercially available PVB includes Denka Butyral<#2ooo
-L, +5ooo-1. tt3000-2, $300
0-4, $4000-1.

04000-2 (manufactured by Denki Kagaku Kogyo ■).

S-LEC BL-, 1, BL-2, BL-8.

BX-L, BM-1, BM-2, BM-8 (and above,
(Manufactured by Tanemizu Chemical Industry ■).

Commercially available PVI-PVAC is Denka Vinyl T41.
000A, #1000AS, $1000C, #1000
C3, +1000G, 61000L (manufactured by Denki Kagaku Kogyo ■), Eslec A.

C, M (manufactured by Tanemizu Chemical Industry ■) + Geon44
Examples include 0-L2,427-T and 427-8,427-C (manufactured by Nippon Zeon).

In addition, as a cellulose derivative, ethyl heptanyl 0-/(
(manufactured by Vercules) and ethyl hydroxyethyl cellulose (manufactured by Vercules).

In order to maintain good handwriting (coating film) and enable continuous peeling, it is preferable that the resin concentration in 2-7 is high. A lower viscosity is preferable in consideration of ink discharge.

Therefore, the average degree of polymerization of the resin is 2. For example, in PVB, it is 1000 or less, but in PVC-PVAC, it is 500.
The following are preferably used:

As a result of various studies in consideration of the above points, the amount of resin to be used is preferably 5 to 20% by weight based on the ink, although it varies depending on the average degree of polymerization of the resin.

The organic solvent dissolves the resin.

Solvents for PVB are generally alcohols such as ethanol, isopropanol, 5ec-butanol, n-butanol, and methyl cellosolve.

These include glycol ether esters such as ethyl cellosolve and selonlube acetate.

As a solvent for PVC-PVAC, generally.

These include ketones such as methyl ethyl ketone and methyl ibutyl ketone, and esters such as ethyl acetate and butyl acetate.

Solvents for cellulose derivatives include esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, toluene,
There are aromatic hydrocarbons such as quinlennat, ethyl hydroxyethylina, aromatic hydrocarbons such as badruene and cinnabar cellulose, and ethyl acetate.

Esters such as butyl acetate, alcohols such as ethanol, propatool, butanol.

These include aliphatic hydrocarbons such as mineral spirits.

In addition to the above-mentioned solvents, although they are not good solvents for resins, they can be used in combination with other solvents for purposes such as controlling dryness and viscosity.

Dyes and/or pigments are used for coloring, and dyes that are soluble in the organic solvent are used, and pigments can be either inorganic or organic.

The amount of dye and/or pigment used is preferably 5 to 30%.

Next, two physical properties that the ink of the present invention should have are: 1) surface tension: 20-35 dyne/m; viscosity: 60cp
s/25°C or less.

That is, when the surface tension of 2 is less than 20 dyne/cm, it is 2 paper.

When used as a general-purpose oil-based marker on cloth, etc., the handwriting tends to smear, and if the applied surface is made of a low polarity resin such as polyethylene resin or polypropylene resin, the leveling property of the handwriting is poor and repellency occurs. This is because it becomes easier.

In addition, when the viscosity is 6Qcps/25℃ or higher, fiber pen nibs,
This is because the ink ejection from the resin-molded pen tip becomes poor and tends to fade.

Ethylene oxide-added fluorosurfactant and/or precone block copolymer.

After adjusting the surface tension of the ink and writing on the non-absorbing surface,
By transferring to the interface between the handwriting (coating film) and the non-absorbing surface, continuous releasability is improved.

The ethylene oxide-added fluorine-based surfactant is a surfactant in which ethylene oxide is added to a perfluoro compound, and commercially available products include 200% ethylene oxide-added surfactant. 251 (manufactured by Neos), Surflon S-341 (manufactured by Asahi Glass), Florado FC-45
0゜FC-431 (manufactured by 3M), F-Top E
F122A, EF122B (manufactured by Shin Akita Kasei)
These can be used alone or in combination.

Silicone block copolymers are copolymers of dimethylsiloxane and ethylene oxide and/or propylene oxide, and commercially available silicone block copolymers include:
L-720, L-7001, L-7002, L-750
0, L-7600, L-7604 (manufactured by Nippon Unicar), etc., and can be used alone or in combination.

If the amount of the ethylene oxide-added fluorine surfactant and/or silicone block copolymer used is less than 0.1% by weight based on the total amount of ink, there will be little effect, and 5% by weight or less.
With the above, no better effect can be expected, so 01~
5% by weight is preferred.

Incidentally, a small amount of a wetting agent, a dispersing agent, etc. which assist in dispersing the pigment may also be added as appropriate.

The ink for writing instruments of the present invention is used by dissolving or dispersing the above-mentioned components to form an ink, and then filling it into a writing instrument having a fiber nib or a resin-molded nib.

Hereinafter, the present invention will be described in detail according to Examples. In the Examples, "Part-1" indicates "Part-I by weight.

Example 18 Denka Butyral 4#2'000-L (PVB manufactured by Denki Kagaku Kogyo 10 parts) Ethanol 72〃 n-furinol 8゜F-TOP EF-122A (ethylene oxide 0.
5〃Fluorinated surfactant, manufactured by Shin Akita Kasei ■) Val
ifast Blue 1603S (manufactured by Orient ■,
Dye) 5 Dissolved to obtain blue ink.

Example 2 Denka Vinyl #100OA (PVC-PVAC manufactured by Denki Kagaku Kogyo ■ 10 parts) Methyl in butyl ketone 50 # Ki/Lene 20 # Kronos KR-380 (manufactured by Titanium Industries ■, 30 Titanium oxide pigment) L-7500 (Solicone block copolymer, manufactured by Nini Enika HI) 1 # Homogenol L-18 (1 dispersant manufactured by Kao Sekiken ■) 1 part Denka vinyl + 100OA
After dissolving in a solvent, block KR-3 was formed using a ball mill.
80 was dispersed to obtain white ink.

Example 6 Eslenoku BL-1 (manufactured by Tsukisui Kagaku Kogyo ■, PVB'1
1 0 parts ethanol 50 # n-butanol 10 xy/lene 25 phthalonanine green (M'R) 1 on ftop EF-122B (ethylene oxide Q, 5
rr-added fluorinated surfactant, manufactured by Shin Akita Kasei ■) Homogenol L + 8 Q, 5 nDOP (Oiri Kagaku ■
2. After dissolving Eslenok BL-1 in a solvent.

Phthalocyanine green was dispersed using a ball mill to obtain green ink.

Example 4 Eslenoku C (manufactured by Tsukisui Kagaku Kogyo ■, PVC-PVAC)
1 0 parts Methyl isobutyl ketone 40 parts Butyl acetate 25〃 Ky7lene 20〃 EF-122B σ, 2〃L
-7500. 0.5# DOP 2〃 Phthalo/Anine Blue (pigment) 10〃Pomogenol
After dissolving L18 0.5# Eslenok C in a solvent, phthalocyanine blue was dispersed in a ball mill to obtain a blue ink.

Example 5 Ethylcellulose N-7 (manufactured by Vercules) 8 parts Toluene 50 Ethanol 40 Lio/S KR-38030y L-7602 (Silicone block copolymer, 1 part
(manufactured by Nippon Unicar ■) Polyethylene glycol $400 (plasticizer) 2 Homogenol L-180, 5 parts After dissolving ethyl cellulose N-7 in a solvent, Kronos KR-380 was dispersed in a ball mill to obtain a white ink. Ta.

Example 6 Ethylhydrokine Ethylcellulose EHEC-5 Part E
XraLow (manufactured by Hubcules) Toluene 80Il Ethanol 2o Phthalo7anine blue 8F EF-122A O, 5# homogenol L + 8 Q, 3 rtEHEC-Ext
After dissolving ra Low in the solvent.

Phthalo/anine blue was dispersed using a ball mill to obtain a blue ink.

The physical property values of the inks obtained in Examples 1 to 6 are as follows.

It was as shown in Table-1.

Table-1 *1. The surface tension was measured at 25° C. using the surface tension side of Junui.

*2 Viscosity was measured at 25°C using a B-type viscosity chart.

Fill a writing instrument with a fiber nib with these inks,
When I wrote on the non-absorbent surface of highly polar acrylic resin or vinyl chloride resin, the handwriting was clear, and even though I rubbed it with two fingers after drying, the two handwritings did not disappear. Furthermore, when cellophane tape was attached to one end of the handwriting and removed after two months, the handwriting easily and continuously turned into a film and peeled off. Again 1
When I wrote it down on paper, it did not bleed.

Incidentally, when a writing instrument having a fiber nib was filled with commercially available strippable paint, the paint did not come out. Also, when I wrote on a non-absorbent surface with a commercially available oil-based pigment type whiteboard marker and rubbed it with one finger after drying, the handwriting disappeared.

As described above, the ink for writing instruments of the present invention has good retention performance for handwriting written on a non-absorbing surface and can be easily and continuously peeled off.

Patent Applicant: Pentel Co., Ltd. Procedural Jutsu 11 Seisho Ei) January 76, 1985 1988 Patent Application No. 251488 2 Name of Invention Ink for Writing Instruments 3 Relationship with the Person Who Makes the Amendment Case Patent Applicant Tsuyuuou 2 2, 1 butterfly, 1 butterfly, 103 Address: 7##2, Kokinumachi, Nihonbashi, Chuo-ku, Tokyo
Contents of Column 6, Supplement I+2 of Detailed Explanation of the Invention in No. IJJ Detail l) Amended "The present invention" in the sixth line from the top and the second line from the bottom of page 4 of the specification to read "The inventor is the inventor" do.

2) Ijl$+11''l Correct "5 copies" in the 6th line on page 15 to "6 copies".

Claims (1)

[Scope of Claims] An ink for writing instruments that uses a peelable resin as a binder, and comprises at least an organic solvent for the resin, a dye and/or a pigment, and an ethylene oxide-added fluorine surfactant and/or a silicone block copolymer. An ink for a writing instrument that can continuously peel off handwriting, and has the following conditions. Conditions> 0 The amount of peelable resin used is 5% based on the total amount of writing instrument ink.
~20% by weight. 0 viscosity is 60 cps/25°C or less. 0 surface tension is 20-55 dyne/cm.