JPS60179477A - Ink for writing utensil - Google Patents

Abstract

PURPOSE:To provide ink for writing utensils, which can be written on non- absorptive surfaces and whose handwriting can be well retained and continuously peeled off, containing a polyvinyl butyral resin, a lower monohydric alcohol, an alcohol-soluble epoxy resin and a dye under specified conditions. CONSTITUTION:The titled ink having a viscosity of 40cps or below at 25 deg.C and a surface tension of 20-35dyne/cm contains at least a polyvinyl butyral resin, a lower monohydric alcohol, an alcohol-soluble epoxy resin (e.g. polyglycol type epoxy resin) and a dye and/or a pigment in such a quantity that the quantity of the resin accounts for 5-20wt% of the entire quantity of ink. The ink can be written on non-absorptive surfaces, and its handwriting can be well retained without causing the migration of the dye or pigment toward the coated surface and the handwriting can be easily, continuously peeled off.

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.

Additionally, plasticizers are added to make paint for automobiles.

1. For temporary surface protection of aircraft mechanical parts, metal household appliances, low-ferrous and non-ferrous metal products, glass products, plastic molded products, rubber products, etc., and completely removed immediately before using these products. It is a coating material that has been made to be able to coat with water, and is applied in the same way as regular paints, such as by spray painting, brush painting, or dipping.

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

However, large areas are spray painted.

Although brush painting is possible, it is difficult to paint details and 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 using a solvent that is soluble in the ink.

Also, although there is a so-called whiteboard marker ink that can be erased on non-absorbent surfaces, it has extremely low adhesion of handwriting to the whiteboard.
L, ; (It is designed so that it can be easily wiped away with paper, etc., so it only requires one move.

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 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 a writing instrument that has a fiber nib or a resin-molded nib so that it can be painted.

However, the organic solvents used in the above-mentioned writing instrument inks and the usual mediating agents 1, such as DBP, DOP, etc.
Phthalate ester plasticizers such as , B OP , +3 BP, fatty acid ester plasticizers such as DOA, DOZ, DO8, T 01 ), T 13 P
.

Phosphate ester plasticizers such as T Ol', aromatic carboxylic ester plasticizers such as TOTM.

It has high solubility and migration properties, so it can be used on various painted surfaces.

Alternatively, when applied (written) on a plastic with low resistance, the surface is 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 conducting various inspections on organic solvents and lubricants, the present invention was finally completed.

That is, 1 the present invention comprises a polyvinyl butyral resin and a lower-
The gist of the present invention is an ink for a writing instrument comprising at least a hydric alcohol, an alcohol-soluble epoxy resin, 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 resin used is 5 to 20% of the total amount of writing instrument ink.
Be a weight clerk.

O viscosity must be 60 cps/25°C or less.

The surface tension should be between 20 and 5 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 strippable and coatable.

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

Commercially available PV 11 includes Denka Butyral #2'
0OO-L, @3000-1. @5000-'2. :i
30.0O-4, #: 4000-1'.

##4000-2C or higher, manufactured by Denki Kagaku Kogyo ■).

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

B, XL, BM-1, 13M-2, BM-8 (above,
Examples include Building Blocks Chemical Industry (Kansei).

In order to maintain good handwriting (#i film) and enable continuous peeling, it is preferable that the resin concentration in the ink is high. Consideration A: It is preferable to do so.

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

Taking the above points into consideration, and after careful consideration, the amount of resin to be used is preferably 5 to 20 wt1% of 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.

+1-propanol, isopropanol, 11-butanol, 5ec-butanol, t'crt-buknol,
+1-amyl alcohol, isoamyl alcohol, 5e
Examples include c-amyl alcohol and 1-hexanol.

In addition to the above-mentioned alcohol, aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents may be mixed and used in order to control dryness and viscosity, although they are not good solvents. You can also do it.

Alcohol-soluble epoxy resin does not have the disadvantages of ordinary plasticizers, such as not attacking the painted surface or not peeling off after a long period of time after application (writing). It gives

The alcohol-soluble epoxy resin is an epoxy resin obtained by triglycidylating polyglycol type Evogin Iiγ (JIL) lf-role propane.

A copolymer of Taehokin resin and bisphenol type epoxy resin made by triglycidylating trimethylolpropane, a mixture thereof, and an epoxy resin made by tetraglycidylating pentaerythritol.

Copolymer of epoxy resin obtained by tetragly/dylation of pentaerythritol and bisphenol type epoxy resin,
and mixtures thereof.

How much alcohol-soluble epoxy resin should be used?

It is desirable that the amount is in the range of 5 to 40 parts by weight per 100 parts by weight of P V B. If it is less than 5 parts by weight, the plasticity will be almost completely lost and the film will break during peeling, resulting in poor continuous peelability. This is because if the amount is more than 40 parts by weight and 1 part by weight, it becomes sticky and tends to cause blocking, and also reduces the tensile strength, causing wrinkles and peeling.

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.

A dye and/or pigment usage ratio of 3 to 30 times is good.

Next, the ink of the present invention has a surface tension of 20 to 35 d yne /'cm as a physical property value (i: ii).
+Viscosity is less than or equal to 60 cps/25°C.

That is, when the surface tension is less than 20 dyne/'cm.

When used as a general-purpose oil-based marker on paper, 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 of the handwriting may be difficult. is bad,
This is because it becomes easier to repel and break.

Further, 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 blurring.

Therefore, in addition to the above-mentioned components, small amounts of various surfactants for adjusting surface tension, wetting agents and dispersants for aiding the dispersion of pigments, and release agents for improving releasability are also added.

The ink for lead 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 10 parts (II manufactured by Denki Kagaku Kogyo ■) VB) Ethanol 70 parts 11-butanol 10 parts Polyglycol type epoxy resin 3 parts Oleic acid amide (release agent) 15 parts Valifas
L 131ue 16038 5 parts (Orient (preparation, dye) Denka Butyral 4f-20 (J D-L, Val
ifastBlue 1603 S+Polylicol type epoxy/resin.

Blue ink was obtained by dissolving oleic acid amide in a solvent.

Comparative Example 1 A blue ink was obtained in the same manner as in Example 1, except that i) OP was used instead of the polyglycol type epoxy resin.

Example 2 S-Resoku B L -110 parts (manufactured by Tsukimizu Kagaku Kogyo Co., Ltd., PVB) Ethanol 65 parts n-butanol 10 parts Methylcyclohexane 10 parts Trimethylolpropane was trigly/dylated 2.
5 parts epoxy resin phthalocyanine green (pigment) 10 parts Disparon: #301 1 part (9-minute drink made by Hosui Kasei ■) After dissolving S-LEC BL-1 in a solvent.

Add other ingredients and ball mill Got the ink.

Comparative example 2.

Otherwise, green ink was obtained in the same manner as in Example 2.

Example 6 Denka Butyral #2600-L 10 parts ethanol
72 parts n-butanol 8 notes b penquerythritol tetra-glycidylated epoxy resin E-TOP EF-1 22A (0.2 parts fluorine surfactant, Shin Akita Kasei ■, release agent) Kronos KR, -38
0 30 parts (Titan Kogyo (ready-made, titanium oxide pigment) Disbaron @
After dissolving Denka Butyral #2000-L in a solvent, other components were added and ball milled to obtain a white ink.

Comparative Example 5 A white ink was obtained in the same manner as in Example 6, except that 'r c p was used in place of the epoxy resin obtained by tetraglycidylating pentaerythritol in Example 6.

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

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

*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 painted surface, the paint film (handwriting) was peeled off, and the case where the dye and pigment had migrated to the resin board painted surface was marked as x, and the case where no migration was observed was marked as ○.

*4. After 2 months of application (writing) on the painted surface of AIJS resin, vinyl chloride resin, acrylic resin board, and alkyd resin, apply sellotape to one end of the paint film (handwriting) and peel it off to easily and continuously peel it off into a film. The case where it peeled off was rated 0, the case where it partially peeled off was rated Δ, 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 visible, and even though I rubbed it with my hands and fingers after it dried, the handwriting 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. When I wrote it down on a piece of paper, it did not bleed.

Incidentally, when a writing instrument having a fiber nib was filled with a commercially available stripable 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,
with alcohol-soluble epoxy resin. An ink for a writing instrument which is made of at least a dye and/or a pigment and is capable of continuously peeling handwriting, and which has the following conditions. Conditions〉 ○The amount of resin used is 5 to 20% of the total amount of ink for writing instruments.
Be a weight clerk. 0 viscosity is 60 cps/25°C or less. 0 surface tension is 20 to 35 dyne/cm.