JPS60161470A - Ink for writing utensil - Google Patents

Abstract

PURPOSE:To provide the titled ink composed of a specific amount of a polyvinyl butyral resin, a lower monohydric alcohol, a polyester plasticizer, etc., having a specific viscosity and a specific surface tension, capable of giving a durable written mark on a non-absorbing surface, and forming a coating film releasable in the form of a film. CONSTITUTION:The objective ink can be prepared by compounding (A) preferably 5-20wt% polyvinyl butyral resin (PVB) (based on the whole ink composition) with (B) a lower monohydric alcohol, (C) 5-50pts.wt. (based on 100pts. of PVB) of a polyester plasticizer (e.g. the reaction product of a dibasic acid component such as sebacic acid with a glycol component such as ethylene glycol) and (D) a dye and/or a pigment. EFFECT:A fine and minute painting can be achieved since the utensil is provided with a fiber pen point or a molded resin pen point.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ink for writing instruments, and more particularly, the ink has the performance of a strippable paint on a non-absorbing surface and does not attack a wide range of painted surfaces and surfaces such as plastics. The present invention also relates to an ink for a writing instrument that allows ink to be ejected from a writing instrument having a fiber nib or a resin-molded nib.

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.

And a plasticizer is added to form pane 1~, an automobile.

1. For temporary surface protection of aircraft mechanical parts, metal household appliances, other ferrous and non-ferrous metal products, glass products, plastic molded products, rubber products, etc., and can be completely removed immediately before using these products. It is a coating material made of various materials, and is applied in the same way as ordinary paints by methods such as spray painting, brush painting, or dipping.

Recently, pigments and/or dyes have been added to strippable paints to create single-colored strippable baits, which are being used for decoration of glass windows and the like.

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 has been difficult to erase the ink 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 9 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 and the surrounding area.

Therefore, the inventor of the present invention improved the retention of handwriting (paint film) on the non-absorbing surface, made it possible to peel it off completely continuously in the form of a film at any time, and also made it possible to remove fine details and fine details. 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 so that it can be painted.

However, organic solvents and common plasticizers 1, such as DBP, DOP, BOP, used in the above-mentioned writing instrument inks,
, phthalate plasticizers such as BBP, DOA, D
Fatty acid ester plasticizers such as OZ and DO5, TCP,
TBP, T.

Phosphate ester plasticizers such as P and aromatic carboxylic ester plasticizers such as TOTM have high solubility and migration properties, and therefore are suitable for various painted surfaces.

Alternatively, if it is applied (written) on a plastic with low resistance, the surface will be attacked, and dyes and pigments may migrate to the painted surface and the plastic.

Continuous peelability over time tends to be poor.

The present inventor has developed a resin in order to improve the above-mentioned points.

As a result of various studies regarding organic solvents and plasticizers, the present invention was finally completed.

That is, 1 the present invention comprises a polyvinyl butyral resin and a lower-
Alcohol, polyester plasticizer, dye and/or
The gist of the present invention is an ink for a writing instrument, which is made of at least a pigment or a pigment, and is capable of continuous peeling of handwriting that meets the following conditions.

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

The viscosity is 60 cps/25°C or less. The surface tension is 20 to 35 dyne/cm.

The present invention will be explained in detail below.

Polyvinyl butyral resin is a binder for ink and exhibits releasability of ink, and is a strippable coat.

Polyvinyl butyral resin (hereinafter abbreviated as PVB) is used as the strippable paint.

Commercially available PVB includes Denka Butyral #2000-
Ll #3000-1. -#xoo.

-2, #50On-4.4+4000-1°-1t40
'0O-2 (manufactured by Denki Kagaku Kogyo ■).

S-LEC BL-1, BL-2, BL-5゜BX-L,
Examples include BM-1, BM-2, and BM-5 (manufactured by Okisui Kagaku Kogyo ■).

In order to maintain good handwriting (paint film) and enable continuous peeling, it is preferable that the resin concentration in the ink is high. Therefore, when considering ink discharge, the PVB used should have a low resin solution viscosity. preferred.

Therefore, the resin preferably has an average degree of polymerization of 1000 or less.

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.

Lower-hydric alcohols are less likely to attack painted surfaces and plastics, dry quickly and dissolve the resin,
methanol, ethanol.

Examples include n-propatool, isopropatool, n-butanol, 5ee-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, 5ee-amyl alcohol, and n-hexanol.

In addition to the above-mentioned alcohol, although it is not a good solvent for resins, it can improve the solubility of polyester plasticizers, adjust drying properties,
For purposes such as viscosity adjustment, aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents may be used in combination.

Polyester plasticizers 1. Add plasticity to the paint film, which has the disadvantage of not attacking the painted surface or not peeling off after a long period of time after application (writing), as seen with ordinary plasticizers. It is something.

Polyester plasticizer has a dibasic acid component.

Reacting the glycol component with a chain stopper (-hydric alcohol or -basic organic acid), or
It can be easily obtained by reacting a dibasic acid component with a glycol component.

Typical dibasic acid components are sebacic acid, adipic acid, phthalic acid, etc. 2 Typical glycol components are ethylene glycol, propylene glycol, butylene glycol, etc. Chain stoppers are C4 to CI8.
A certain degree of aliphatic monohydric alcohol or -basic acid.

Commercially available polyester plasticizers include Adekasizer P-200. Same P-300, Same PN-150. Same PN
-250 (manufactured by Adeka Argus Chemical), Polysizer P-202. P-204, p-103 (manufactured by Dainippon Ink & Chemicals), Paraplex G-55.
Examples include the G-50 (manufactured by Rohm and Half).

The amount of polyester plasticizer used is preferably in the range of 5 to 50 parts by weight based on 100 parts by weight of PVB. Less than 5 parts by weight.

Plasticity is almost lost, and if it exceeds 50 parts by weight, it becomes sticky and tends to cause blocking. Furthermore, the strength of the coating decreases, making it more likely to tear during peeling, resulting in a decrease in continuous releasability.

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 3 to 30% by weight.

Next, as physical properties that the ink of the present invention should have, the surface tension is 20 to 35 dyneoloM, and the viscosity is 60 cp.
s/25°C or less.

That is, 1 paper if the surface tension is less than 20 dyne/cFR.

When used as a general-purpose oil-based marker on cloth, etc., the handwriting tends to smudge, 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 there is a risk of repelling. This is because it becomes easier.

Furthermore, if the viscosity is 60 cps/25° C. or more, the ink discharge from the fiber nib or the resin molded nib will be poor, and there will be a tendency for the ink to fade.

Therefore, in addition to the above-mentioned ingredients, various surfactants are used to adjust the surface tension, and wetting agents and dispersants that help disperse pigments.

A small amount of a release agent is also added to improve the removability.

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, and in the examples, "parts" indicate "parts by weight."

Example 1 Denka Butyral #2000-L 1 part (manufactured by Denki Kagaku Kogyo ■, PVB) Ethanol 72 parts n-butanol 8 parts Adekasizer P-2005 parts (manufactured by Adeka Argus Chemical ■).

Polyester plasticizer) Valifast Blue 1603 S 5 parts (manufactured by Orient ■, dye) Denka Butyral #2000-L, Valif
astBlue1603S, Adekasizer P-200
was dissolved in a solvent to obtain blue ink.

Comparative Example 1 A blue ink was obtained in the same manner as in Example 1, except that DOP was used instead of Adekacizer P-200.

Example 2 S-Lec BL-110 part (Manufactured by Tsukumi Kagaku Kogyo ■, PVB) Ethanol 60 parts n-butanol 10 parts Methylcyclohexane 15 parts Polysizer P-2022 part (Manufactured by Dainippon Ink & Chemicals.

Polyester plasticizer) Phthalocyanine green (pigment) 10 parts Disparon #301 1 part (1 dispersant manufactured by Kusumoto Kasei ■) After dissolving S-LEC BL-1 in a solvent.

Other ingredients were added and dispersed using a ball mill to obtain green ink.

Comparative example 2 Polysizer P-202 glue in Example 2.

A green ink was obtained in the same manner as in Example 2 except that A was used instead.

Example 3 Denka Butyral #: 2000-L 10 parts Ethanol 72 parts n-butanol 8 parts Balaplex G-332 parts (manufactured by Rohm & Haas).

polyester plasticizer) Kuromeno KR-38030 parts (Made by Titanium Kogyo ■.

Titanium oxide pigment) Disparon: 11:301 1 part After dissolving Denka Butyral #2000-L in a solvent, other components were added and dispersed using a ball mill to obtain a white ink.

Comparative Example 3 A white ink was obtained in the same manner as in Example 6, except that TCP was used instead of Paraplex G-35 in Example 3.

Examples 1-3. The physical properties and coating performance of the inks obtained in Comparative Examples 1 to 3 were as shown in Table 1-1.

Table-1 *1. The surface tension was measured at 25° C. using a Junoui surface tension meter.

*2 Use a B-type viscometer to measure viscosity.

Measured at 25°C.

*3. ABS resin, vinyl chloride resin, acrylic resin board,
After application (writing) on the alkyd resin coated surface, the paint film (handwriting) was removed and the case where the dye and pigment had migrated to the resin board coated surface was marked as x, and the case where no migration was observed was marked as ○.

*4. ABS resin, vinyl chloride resin, acrylic resin board,
After 2 months of application (writing) on the alkyd resin painted surface, the paint film (
Cellotape was attached to one end of the handwriting) and peeled off, and the case where it peeled off easily and continuously in the form of a film was rated 01, the case where it was partially peeled off was rated △, and the case where it did not peel off was rated x.

A writing instrument having a fiber nib was filled with the inks of these examples and used on a glass plate, aluminum plate, or iron plate.

When I wrote it on a non-absorbent surface such as a polyethylene board, the handwriting was clear and I could rub it with two fingers after drying.

The handwriting never disappeared. 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. When I wrote it down on nine pieces of 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 is a dye-based ink.

There is no transfer of pigment to the painted surface or resin plate, and it can be easily and continuously peeled off.

Patent applicant: Pentel Co., Ltd.

Claims (1)

[Claims] A polyvinyl butyral resin, a lower-hydric alcohol,
An ink for a writing instrument comprising at least a polyester plasticizer and a dye and/or a pigment, the ink for a writing instrument having the following conditions and capable of continuously peeling handwriting. <Conditions> The amount of 0##4 resin used is 5% of the total amount of writing instrument ink.
~20% by weight. O viscosity is 60 cps/25°C or less. 0 surface tension is 20 to 35 dyne/α.