JPH02133477A - Water-based erasable marking pen ink composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which is free of problems of toxicity and odor and can give an easily erasable writing by mixing water with a colorant, a specified room temperature film-forming resin and a specified release agent. CONSTITUTION:Water as a solvent is mixed with a colorant dissolved or dispersed in water (e.g., carbon black dispersed with the aid of a dispersant of an ammonium salt of a styrene/butyl acrylate/methacrylic acid copolymer), at least one room temperature film-forming resin selected from an emulsion or hydrogel of polyvinyl acetate, a vinyl acetate copolymer, an alkyd resin or a urethane resin and a water-solubilized vinyl acetate copolymer, alkyd resin and a urethane resin (e.g., a hydrosol of a vinyl acetate/ethyl acrylate/ acrylic acid copolymer) and a release agent which is at least one difficulty volatile liquid compound selected from among an aliphatic carboxylic ester, a higher hydrocarbon and a higher alcohol each of which is normally liquid (e.g., butyl stearate).

Description

[Detailed Description of the Invention] The present invention relates to an aqueous erasable marking pen ink composition, and particularly to an aqueous, non-absorbent or non-permeable writing surface, typically relates to a marking pen ink composition that has excellent erasability of handwriting written on a writing surface called a so-called white board.

Conventional ■ Thorn ± Erasable markings that were previously written on a non-absorbent or non-permeable writing surface and were wiped off from the writing surface by lightly rubbing them with a dry cloth or soft paper to erase the handwriting. Various pen ink compositions are known. Such conventional erasable marking pen ink compositions generally include:
In addition to organic solvents, pigments, and resins, they contain an additive called a release agent. For example, in Japanese Patent Publication No. 62-9149, surfactants are included in addition to aliphatic dibasic acid esters and aliphatic-basic acid esters. and saturated aliphatic carboxylic acid triglycerides are dissolved in an organic solvent.

However, as described above, such conventional erasable marking pen ink compositions use ketones or alcohols as solvents. In particular, among these solvents, ketones are highly toxic. Among alcohols, methanol is highly toxic and has a bad odor. Ethanol, on the other hand, although less toxic, increases raw material costs.

On the other hand, conventionally, for example, as described in JP-A-60-179478 and JP-A-60-219273, a resin emulsion such as polyvinyl acetate resin as a release agent is used as a dye or as a colorant. BACKGROUND ART Water-based ink compositions containing water together with pigments and certain surfactants are known.

However, since such ink compositions use a resin emulsion as a release agent, similar to so-called strippable paints, when writing on a non-absorbing surface, after drying,
The above-mentioned resin emulsion forms a continuous film on the writing surface, so the handwriting is peeled off in a continuous film, and if the handwriting is lightly rubbed, the handwriting is easily peeled off from the writing surface. It cannot be said that it has excellent erasability.

As a result of intensive research to solve the above-mentioned problems in conventional oil-based and water-based erasable marking pen ink compositions, the present inventors have developed a resin emulsion or resin emulsion that has film-forming properties at room temperature. Hydrosol, or a resin that is originally water-insoluble but has been made water-soluble by salt formation with a base, is used as a carrier for colorants in handwriting, and as a so-called release agent for such handwriting, a resin that is liquid at room temperature and hardly volatile is used. Aliphatic carboxylic acid esters, higher hydrocarbons, e.g.
By using an aqueous emulsion of liquid paraffin or higher alcohol, it is possible to obtain an aqueous erasable marking pen ink composition that has excellent erasability and allows only the handwritten portion rubbed with a dry cloth to be easily peeled off from the writing surface. The present invention was created by discovering what could be done.

(b) For divination, the erasable marking pen ink composition according to the present invention comprises: (water as an ali agent, (b) a coloring agent dissolved or dispersed in water, (c) (
At least one selected from the group consisting of: 1) an emulsion or hydrosol of polyvinyl acetate, vinyl acetate copolymer, alkyd resin, or urethane resin; and (2) water-solubilized vinyl acetate copolymer, alkyd resin, or urethane resin. One type of resin that has film-forming properties at room temperature, and (d) (1) an aliphatic carboxylic acid ester that is liquid at room temperature, (2) a higher hydrocarbon that is liquid at room temperature, and (3) a higher alcohol that is liquid at room temperature. At least one kind of 'f, flN selected from the group consisting of
It is characterized by containing an aqueous emulsion of a liquid compound.

In the marking pen ink composition according to the present invention,
Water is used as a solvent. The amount of water in the ink composition is usually 50-90%, preferably 60-8%.
It is in the range of 0% by weight.

In the marking pen ink composition according to the invention, pigments are preferably used as colorants. Examples of pigments include phthalocyanine-based pigments such as carbon black and copper phthalocyanine blue, ab-based pigments, quinacridone-based pigments, anthraquinone-based pigments, dioxane-based pigments, indigo-based pigments, thioindigo-based pigments, perinone-based pigments, perylene-based pigments, indolenone-based pigments, and azo-azomethine-based pigments. Any one can be used. Dispersions made by dispersing various pigments in water are already commercially available, and such commercially available products can be preferably used in the present invention as well. Since the pigment dispersion described above may contain various resin dispersants, surfactants, etc. as pigment dispersants, the ink composition according to the present invention also contains such resins, surfactants, etc. It may be contained. Pigment dispersants are known per se, and are usually used in an amount of 1 to 300 parts by weight, preferably 5 to 100 parts by weight, per 1 part by weight of the pigment.

In the present invention, dyes can also be used as colorants. In this case, water-soluble dyes are preferably used as the dyes.

The colorant is usually contained in an ink composition in an amount of 1 to 30% by weight, preferably 5 to 20% by weight. When containing too much colorant,
Since the viscosity of the ink composition is too high, the writing properties are poor and the erasability is also reduced. On the other hand, if the content of the colorant is too low, the density of the handwriting will be too low, which is not practical.

In the ink composition according to the present invention, when written on a non-absorbing surface and after water evaporates, the handwriting has a coating or layer made of a resin containing the colorant, and this resin coating or layer does not peel off as described below. Emulsions or hydrosols of water-insoluble resins that have film-forming properties at room temperature so that they can be separated from the agent layer, or resins that are originally water-insoluble but have been made water-solubilized by salt formation with a base (hereinafter, these These resins are sometimes referred to as room-temperature film-forming resins.).

In the present invention, such room-temperature film-forming resins include (1) emulsions or hydrosols of polyvinyl acetate, vinyl acetate copolymers, alkyd resins, or urethane resins, and (2) water-solubilized vinyl acetate copolymers. At least one selected from the group consisting of polymers, alkyd resins, and urethane resins is preferably used.

Comonomers in the emulsion or hydrosol or water-solubilized vinyl acetate copolymer include vinyl ester compounds other than vinyl acetate, such as vinyl propionate, vinyl versatate, and unsaturated carboxylic acids, such as acrylic acid. , methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, citraconic acid, etc., or vinyl hydrocarbons such as ethylene, propylene, styrene, α-methylstyrene, etc. These may be mixed and used as a comonomer. Furthermore, in addition to the above, esters of the aforementioned unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, methyl methacrylate, and dimethyl maleate can also be used as comonomers. Moreover, the vinyl acetate copolymer may be a graft copolymer to polyvinyl acetate.

In particular, specific examples of preferable vinyl acetate copolymers include vinyl acetate-acrylic acid copolymers, vinyl acetate-acrylic acid copolymers,
Methacrylic acid copolymer, vinyl acetate styrene-acrylic acid copolymer, vinyl acetate-styrene-maleic anhydride copolymer, vinyl acetate-acrylic acid-methyl acrylate copolymer, vinyl acetate-methacrylic acid-methyl acrylate Examples include copolymers, vinyl acetate-acrylic acid-ethyl acrylate copolymers, vinyl acetate-methacrylic acid-methyl methacrylate copolymers, vinyl acetate-maleic anhydride copolymers, and the like.

Emulsions and hydrosols of polyvinyl acetate and vinyl acetate copolymers as described above are easily available as commercial products.

In addition, water-solubilized vinyl acetate copolymer is water-solubilized vinyl acetate copolymer as described above by salt formation with an inorganic or organic base, Mention may be made of metal salts, organic salts such as ammonium salts and organic amine salts. Such water-solubilized vinyl acetate copolymers are also available as commercial products.

Similarly, water-solubilized alkyd resins can be salt-formed by neutralizing alkyd resins with free carboxyl groups obtained from excess polybasic acids and polyhydric alcohols with alkali metal bases, ammonium bases, organic amines, etc. These are also available as commercially available products.

Water-solubilized urethane resins can also be made water-solubilized by, for example, having a carboxyl group in the main chain of the polymer, and neutralizing this carboxyl group with an alkali metal base, ammonium base, organic amine, etc. to form a salt. These are also available as commercial products.

Furthermore, emulsions and hydrosols of alkyd resins and urethane resins are also available as commercial products.

In the ink composition according to the present invention, the above-mentioned resin is
The resin content is 0.1 to 15% by weight, preferably 0.1 to 15% by weight.
It is contained in a range of 3 to 10%.

When too much resin is contained, the viscosity of the ink composition is too high, resulting in poor writability and poor erasability. On the other hand, if the resin content is too low, the erasability of handwriting will be poor.

The ink composition according to the present invention thus contains an emulsion or hydrosol of a resin that is originally water-insoluble, or a water-solubilized resin, and as described below, when written, such resin absorbs a colorant. Since it contains and forms a film as a carrier for the colorant, handwriting has excellent water resistance and also has stable erasability regardless of temperature and humidity conditions.

Next, in the ink composition according to the present invention, as a handwriting release agent, a non-volatile aliphatic carboxylic acid ester that is liquid at room temperature, a non-volatile higher hydrocarbon that is liquid at normal temperature, or a non-volatile high hydrocarbon that is liquid at normal temperature The higher alcohol is contained in an aqueous emulsion state.

As the aliphatic carboxylic acid ester, Este/L/
Car base fl esters, dibasic acid diesters, mono- or diesters of dihydric alcohols, mono-, di- or triesters of trihydric alcohols, etc. are preferably used.

Particularly preferred examples include - basic acid esters, especially higher fatty acid esters such as propyl myristate, butyl valmitate, butyl stearate, octyl stearate, butyl isostearate, and aliphatic dibasic acid dialkyl esters such as dodecanoic acid. Dioctyl, dipropyl adipate, dioctyl sebacate, dioctyl azelate, etc., propylene glycol monostearate which is a dihydric alcohol ester, decanoic acid diester of propylene glycol, natural or synthetic fatty acid triglyceride or trimethylol which is a trihydric alcohol triester. Examples include propane triisostearate. These may be used alone or as a mixture of two or more.

As the refractory higher hydrocarbon used as a stripping agent, what is usually called liquid paraffin or squalane is preferably used, but even if it is partially oxidized, such as oxidized polyethylene wax, for example, good. In addition, the higher alcohol which is liquid at room temperature is not particularly limited, but examples of alcohol, hexyl alcohol, octyl alcohol, lauryl alcohol, etc. are preferably used.

Such aqueous emulsions of aliphatic carboxylic acid esters, higher hydrocarbons, or higher alcohols can be prepared by conventional emulsification methods.

Moreover, commercially available products can also be used. Furthermore, two or more of the above aqueous emulsions can be blended into the ink composition, if necessary.

In the ink composition according to the present invention, the aliphatic carboxylic acid ester, higher hydrocarbon or higher alcohol as a release agent contains 1 to 20% by weight of the ink composition.
It is preferably contained in a range of 5 to 15% by weight. In the ink composition, if the amount of the aliphatic carboxylic acid ester, higher hydrocarbon, or higher alcohol is less than 1% by weight, sufficient handwriting erasability cannot be obtained; Even if too much is added, the handwriting will become elongated, staining the writing surface, and will even reduce the erasability of the handwriting.

In the ink composition according to the present invention, a water-soluble polyhydric alcohol is preferably blended as a release aid in order to enhance the effect of the release agent.

Examples of such polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol,
Tripropylene glycol, polyethylene glycol with molecule position 200-600, molecule ttlo 00-3000
Polypropylene glycol, glycerin, trimethylolpropane and the like can be mentioned. Such polyhydric alcohol is blended in the ink composition in an amount of 20% by weight or less, preferably 10% by weight or less. When it is incorporated in an excessive amount exceeding 20% by weight in the ink composition, it is not preferable because the viscosity of the ink composition becomes excessively high and the writability deteriorates.

Furthermore, various surfactants may be contained as other peeling aids. Any of anionic, nonionic, cationic, and amphoteric surfactants can be used as such surfactants. However, in particular, nonionic surfactants and anionic surfactants such as carboxylic acid type, sulfonic acid type, sulfuric acid ester type, phosphoric acid ester type, etc. having polyoxyethylene chains, amphoteric surfactants of alkyl betaine type, fluorine type surfactants, etc. Activators and the like are preferably used. The surfactant is usually contained in an amount of 10 weight percent or less, preferably in a range of 0.2 to 5 weight percent. When blended in excess, the erasability of handwriting is reduced.

The handwriting produced by the ink composition according to the present invention on a non-absorbent or non-permeable writing surface is affected by a single shot of water, that is, when the handwriting dries, the resin contains the coloring agent and the writing is completed. On the other hand, the emulsion of the aliphatic carboxylic acid ester, higher hydrocarbon or higher alcohol as the release agent is destroyed, and a continuous oily layer is interposed between the non-absorbent writing surface and the resin film. Since the handwriting is formed, the handwriting has erasability.

The surfactant as a peeling aid has the effect of assisting in the separation of the oily layer and the pigment-containing resin film in handwriting during writing. However, surfactants also improve the leveling property during writing, and also cause the release agent emulsion to be unevenly distributed in the handwriting before it dries on the writing surface (thus imparting erasability to the handwriting after it dries). It also has effects.In particular,
These effects are remarkable when fluorosurfactants are used.

Furthermore, the ink composition according to the present invention can be used as a drying accelerator for improving the drying properties of handwriting, to the extent that it does not destroy the emulsion contained in the ink composition, and preferably 15% or less based on the ink composition. may contain lower aliphatic alcohol in the range of 1 to 10% by weight. In particular, ethanol, propatool or butanol are preferably used.

In addition to the above, the ink composition may also contain any pH adjuster, preservative, preservative, etc. that are usually added to aqueous ink compositions, if necessary.

The erasable marking ink composition according to the present invention uses water as a solvent, a resin that has film-forming properties at room temperature, and an aliphatic carbon which is liquid at room temperature and is hardly volatile as a release agent. Since it is an aqueous ink composition in which an acid ester, higher hydrocarbon, or higher alcohol is dispersed in an aqueous emulsion state, there are almost no problems of toxicity, odor, or irritating odor of conventional oil-based ink compositions, and moreover, it does not have the above-mentioned problems. After the handwriting dries, the release agent forms a continuous oily layer on the writing surface and separates the resin film containing the colorant from the writing surface, so it is similar to conventional oil-based erasable marking pens. By lightly rubbing the handwriting with cloth, paper, etc., only the scratched portion can be easily peeled off and erased.

Furthermore, according to the ink composition of the present invention, since the release agent is a hardly volatile liquid substance, even after a long period of time has passed after writing,
Since it still exists between the writing surface and the resin layer containing the colorant, the erasability of the handwriting is effectively maintained.

In addition, the ink composition of the present invention originally contains an emulsion or hydrosol of a water-insoluble resin, or a water-solubilized resin, and when writing, such resin forms a film while containing a colorant, and the handwriting is As a result, such handwriting not only has excellent water resistance but also has stable erasability regardless of temperature and humidity conditions.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way. In the Reference Examples and Examples, parts and % indicate parts by weight and % by weight, respectively.

First, as a reference example, an example of preparing an aqueous emulsion of an aliphatic carboxylic acid ester and liquid paraffin will be shown.

Reference Example 1 60 parts of water, 35 parts of butyl stearate, and the nonionic surfactant Neugen EA-120 (manufactured by Daiichi Kogyo Seiyaku ■, H
5 parts of LB12) were stirred and emulsified using a homogenizer to obtain 100 parts of an aqueous emulsion of butyl stearate.

Reference Example 2 60 parts of water, 36 parts of dioctyl dodecanoate, 0.8 parts of nonionic surfactant Span 80 (manufactured by Kao ■), and 3.2 parts of nonionic surfactant Tween 80 (manufactured by Kao @)
(total HLB of surfactant: 12.8) was stirred and emulsified using a homomixer to obtain 100 parts of an aqueous emulsion of dioctyl dodecanoate.

Reference Example 3 65 parts of water, 150-330 parts of liquid paraffin, and nonionic surfactant Nonion H3-206 (manufactured by NOF ■)
5 parts were stirred and emulsified in a colloid mill to obtain 100 parts of an aqueous emulsion of liquid paraffin.

Example 1 An aqueous marking pen ink composition consisting of the components shown below was prepared. The amount of the component indicates the % amount as an effective amount in the ink composition, and the remainder is water.

Otsu! 1U on water Colorant Carbon black 5% Molecular weight Agent Ammonium salt of styrene-butyl acrylate methacrylic acid copolymer 2% Resin Hydrosil release agent of vinyl acetate-ethyl acrylate-acrylic acid copolymer Butyl stearate emulsion activity Agent: Anionic surfactant Preservative: 1 Colorant: Carbon black dispersant: Acrylic resin: Vinyl acetate-methacrylic acid copolymer emulsion remover: Butyl stearate emulsion: Dioctyl dodecanoate emulsion activator: Anionic type Surfactant preservative ink composition 3 Colorant Phthalocyanine blue dispersant Ammonium salt of styrene-maleic acid copolymer 6% 10% 1% Effective amount 5% 3% 6% 5% 5% 0.5% Effective amount 6 % 4 % Vinyl acetate-maleic acid copolymer emulsion 2ゝII M Agent Squalane emulsion auxiliary agent Polypropylene glycol (average molecular weight 300) Active agent Ampholytic surfactant Preservative ±Z earth paper bottom old↓ Colorant Monoazured dispersant Nonionic type Surfactant resin Polyvinyl acetate emulsion 3) Release agent
Lauryl Alcohol Emulsion Triglyceride Emulsion Nonionic Surfactant Preservative Preservative Colorant Specia Roost 0 Resin Water Solubilized Alkyd Resin 5) Resin/Black TU Vero % 8.5% 3 % 1.5 % Effective amount 5.5% 2.5% 7 % 5 % 6 % 1 % Effective amount % 5 % Release agent Octyl stearate emulsion 5 % Liquid paraffin emulsion 808 6 % Auxiliary agent Polypropylene glycol (average molecular weight 1000) 2 % Active agent
Anionic surfactant 1% preservative
Effective amount Sake/Tanori Diharai Coloring agent NLA-657 Black 16% Resin polyurethane emulsion 61 6.5% Release agent Butyl isostearate emulsion 12% Active agent Anionic surfactant 0.5% Preservative
Effective amount (Note) 1) Hiros AW
-36 (manufactured by Seiko Kagaku 0(1)) 2) Movinyl DMIH
(manufactured by Hoechst Synthetic Kyoku) 3) Polysol HR-G (manufactured by Showa Kobunshi) 4) Aqueous dispersion of pigment 5) Alloron 585 (manufactured by Nippon Shokubai Kogyo ■) 6) Ricabond GL-L839 (manufactured by Chuo Rika Kogyo ■) Using each of these ink compositions, the handwriting was written on a non-absorbent writing surface made of wax, and after 5 minutes the dried handwriting was lightly rubbed with a dry cloth. 15 at a temperature of 25°C and a humidity of 60% RH.
The same erasability (erasability over time) after being left for a day was visually inspected, and the results were graded into 4 grades: ◎: very good, ◯: good, △: slightly poor, and ×: poor. The results are shown in Table 1.

For comparison, oil-based erasable marking ink compositions using conventional commercially available ketone solvents or alcohol solvents were also tested in the same manner. The results are shown in Table 1.

When the writing surface was made of melamine resin or fluororesin, almost the same results as shown in Table 1 were obtained.

Example 2 The following ink compositions 7 to 10 (Ink compositions 8 to 10
(Comparative Example) was prepared, and the erasability at room temperature and the elongation of handwriting under different humidity conditions were investigated.

Table 1 (Note) 1) The solvent is ketone-based.

2) The solvent is alcohol-based.

Otsu! ] U11 Colorant Carbon black dispersant Acrylic-styrene copolymer 1) 4% 2% Resin Vinyl acetate-methyl methacrylate-acrylic acid copolymer Hydrosil release agent Butyl palmitate emulsion activator Anionic surfactant Preservative ink combination 8 (eaves 1) Colorant Carbon black dispersant Acrylic-styrene copolymer 1) Resin Water-soluble polyvinyl alcohol release agent Butyl palmitate emulsion activator Anionic surfactant Preservative ink 9 (61) Colorant Carbon black dispersant Acrylic-styrene copolymer 1' resin Water-soluble poly and nylpyrrolidone release agent Butyl valmitate emulsion % 10% 1% Effective amount 10% 1% Effective amount 10% Active agent Anionic surfactant 1 %Preservative
Effective amount of ink composition 10 (Synopsis colorant Carbon black 4% Dispersant Acrylic-styrene copolymer 1) 2% Resin Water-solubilized styrene-maleic acid copolymer 2) 7% Release agent Butyl palmitate emulsion 10% Active agent Anionic surfactant 1% Preservative Effective amount (Note) 1) Joncryl J-682 (manufactured by Johnson Company) 2) Hylos X-220 (manufactured by Seiko Kagaku ■) Indelible, ×
It shows that it stretches and the white plate becomes dirty.

2 tables Patent applicant: Sakura Crevasse Co., Ltd. Agent Patent Attorney Makino Ittobu

Claims (4)

[Claims] (1) (a) Water as a solvent; (b) Colorant dissolved or dispersed in water; (c) Emulsion or hydrosol of (1) polyvinyl acetate, vinyl acetate copolymer, alkyd resin, or urethane resin. ,as well as (2) At least one resin having film-forming properties at room temperature selected from the group consisting of water-solubilized vinyl acetate copolymer, alkyd resin, or urethane resin; (d) (1) Fat that is liquid at room temperature. group carboxylic acid ester,
An aqueous erasable material characterized by containing an aqueous emulsion of at least one kind of hardly volatile liquid compound selected from the group consisting of (2) a higher hydrocarbon that is liquid at room temperature, and (3) a higher alcohol that is liquid at room temperature. Marking pen ink composition. (2) The aqueous erasable marking pen ink composition according to claim 1, which contains a polyhydric alcohol as a release aid. (3) The aqueous erasable marking pen ink composition according to claim 1, which contains an aliphatic alcohol as a drying aid. (4) The aqueous erasable marking pen ink composition according to claim 1, which contains a surfactant.