JPH0142305B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel peelable white and ink composition that can be used in the same way as conventional white and ink ink and can be easily peeled off after use (after drying). Sumi ink is primarily used to write letters and pictures on blank paper with a writing instrument such as a brush, but it is also used to write letters and pictures on major signboards (display boards). For example, it is used to write letters on funeral signboards. However, ordinary ink is not designed with the assumption that it will be erased after writing, so
There are problems such as inconvenience depending on the application. For example, when ink is applied to a funeral signboard,
Funeral signboards are usually made from a single board of expensive Japanese cypress, so in order to use it repeatedly, the letters written in ink must be erased. In addition to requiring labor to cut the surface of a single board of Japanese cypress with a plane, etc., cutting reduces the thickness of a single board of Japanese cypress, making it impossible to use it repeatedly. In addition, when ink is applied to a synthetic resin board that has virtually no water absorption, the ink ink can be erased after use, but ink has the property of being difficult to write on boards that have no water absorption. Moreover, the erasing process was troublesome because it caused secondary contamination with India ink. Furthermore, since ordinary India ink has very poor water resistance, characters written with ink are easily stained when exposed to rainwater or the like. In addition, as a method of repeatedly using the display board by writing characters, etc. on the display board, etc. and erasing the characters, etc. after use, it is possible to use the display board, etc. for welcome display boards at hotels, etc., and display boards displaying meeting names, etc. There is a method of writing letters etc. on a black display board with white juice and washing off the white juice letters after use. However, using this method requires troublesome work such as washing off the white text and drying the display board, and furthermore, since the white text is not substantially water resistant, it is difficult to display the text using the white text. Boards shall not be hung in areas exposed to rain. In view of the above points, the inventors of the present invention have conducted various studies with the aim of providing white ink and India ink that can be easily erased after use. - It has been discovered that a India India ink composition can achieve the above objectives. The present invention was made based on the above findings, and
A black or white coloring agent is added to a liquid film-forming substance, and an amide compound, an anionic surfactant, and a polyhydric alcohol are added, and the film-forming substance is a (meth)acrylic acid ester-based A water-dispersed resin obtained from one or more monomers selected from the group consisting of monomers, aromatic vinyl monomers, vinyl ester monomers, and acrylonitrile monomers. The present invention provides a peelable white/India ink composition. In addition, the peelable white/black ink composition of the present invention specifically refers to a peelable white juice composition or a peelable black ink composition, and a white colorant (white pigment) is used as the colorant. The former composition is formed when a black pigment is used, and the latter composition is formed when a black pigment is used. The peelable white/India ink composition of the present invention will be described in detail below. Specific examples of monomers for obtaining the water-dispersed resin, which is the liquid film-forming substance in the peelable white/black ink composition of the present invention, include the following. Examples of (meth)acrylic acid ester monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate. , butyl methacrylate, methacrylic acid 2
Examples include ethylhexyl, and among these, preferred are ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and the like. Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl vasatinate, and the like. Among these, vinyl acetate, vinyl vasatinate, and the like are preferred. Examples of aromatic vinyl monomers include styrene, methylstyrene, dimethylstyrene, ethylstyrene, butylstyrene, benzylstyrene,
Examples include chlorstyrene, and among these, styrene, methylstyrene, etc. are preferred. Examples of acrylonitrile monomers include:
Examples include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. When obtaining the water-dispersed resin in the present invention, each of the above-mentioned monomers may be used alone or in combination of two or more. Moreover, other monomers can also be used in combination with the above-mentioned monomers. Other monomers that can be used include, for example, ethylenically unsaturated monomers having a carboxyl group, crosslinkable monomers, (meth)acrylic acid amide monomers, halogenated vinyl monomers, and olefins. Examples include monomers. Examples of the ethylenically unsaturated monomer having a carboxyl group include maleic acid, fumaric acid, maleic anhydride, crotonic acid, acrylic acid, methacrylic acid, itaconic acid, etc., but preferably acrylic acid, Methacrylic acid, itaconic acid, etc. are used. Examples of the crosslinkable monomer include divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, hexylene glycol dimethacrylate, ethylene glycol diacrylate, hexylene glycol diacrylate, Examples include glycidyl acrylate and glycidyl methacrylate. Other monomers include acrylamide,
Methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N,N' dimethyl acrylamide, hydroxyethylacrylamide, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, aminoethyl acrylate, aminoethyl methacrylate , vinylpyridine, vinyl chloride, vinylidene chloride, vinyl fluoride, ethylene, propylene, butadiene, and the like. In obtaining the water-dispersed resin of the present invention, one or more of the above monomers may be selectively used in any combination, but as the water-dispersed resin forming the peelable white/ink composition of the present invention, is 100 parts by weight of butyl acrylate monomer and 15 to 200 parts by weight, preferably 20 to 150 parts by weight, more preferably 20 parts by weight of acrylonitrile monomer, methyl methacrylate monomer, or styrene monomer. A water-dispersed resin obtained by using a combination of a butyl acrylate monomer and an acrylonitrile monomer in the above weight ratio is particularly preferred. Further, as the water-dispersed resin in the present invention, any water-dispersed resin can be used as long as it is a water-dispersed resin obtained from the above-mentioned monomers, but generally the above-mentioned monomers are homopolymerized or copolymerized under emulsion polymerization conditions. A water-dispersed resin obtained by a method of forming the resin by the above-mentioned method or a method of solution polymerizing the above-mentioned combination monomers and then emulsifying them is used, and preferably a water-dispersed resin obtained by the former method is used. In addition, the water-dispersed resin used in the present invention is generally not limited by its viscosity, solid content, PH, glass transition temperature (Tg), molecular weight, average particle diameter, etc., but generally has a solid content ( JIS-
K6823) Concentration is 10-70% by weight, preferably 20-70
Weight%, particularly preferably 30 to 65% by weight, viscosity (BH type rotational viscometer 20rpm25℃) 10 to
10,000 cps, preferably 500 to 8,000 cps, particularly preferably 500 to 5,000 cps, PH of 2 to 10, preferably 3
~9, particularly preferably 4~9, average particle size 0.01
~0.6μ, preferably 0.02-0.5μ, particularly preferably
0.05 to 0.5μ is used, and in particular, by using one whose solid content concentration and viscosity are within the above-mentioned preferred ranges, a high quality peelable white/India ink composition of the present invention can be formed. . The resin concentration in the solid content of the water-dispersed resin is usually 99 to 90%, preferably 97 to 92%. In addition, forming the water-dispersed resin in the present invention,
Homopolymers or copolymers obtained from the above monomers are those whose glass transition temperature (hereinafter abbreviated as Tg) is generally 229 to 303K, more preferably 233 to 283K, and those with Tg in the above range are used. By using a water-dispersed resin made of a homopolymer or a polymer, it is possible to obtain the releasable white and ink composition of the present invention, which exhibits excellent releasability and tack throughout winter and summer. Note that the Tg is calculated using the following formula. Calculation formula for Tg 1/Tg=W ₁ /Tg ₁ +W ₂ /Tg ₂ +...+Wn/Tgn Tg and Tgn are expressed in absolute temperature. Wn indicates the weight fraction of each monomer component of the polymer. The Tg of each monomer polymer is shown in Table 1 below.

[Table] Furthermore, the emulsion polymerization method, which is a preferred polymerization method for obtaining the water-dispersed resin used in the present invention from the monomers, can be carried out according to known methods. That is, this emulsion polymerization can be carried out in an aqueous medium in the presence of a catalyst and in the coexistence of a surfactant and/or a protective colloid. The surfactants used in the above emulsion polymerization include anionic surfactants such as sodium oleate, semi-hardened beef tallow soda, fatty acid salts such as potassium oleate, sodium lauryl sulfate,
Higher alcohol sulfate ester soda, lauryl alcohol sulfate ester triethanolamine salt,
Higher alcohol sulfate ester salts such as lauryl alcohol sulfate ammonium salt, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, alkylnaphthalene sulfonates such as sodium alkylnaphthalene sulfonate, and formalin condensates of naphthalene sulfonate. ,
Examples include dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate, alkyl phosphates, and those obtained by adding ethylene oxide to the above anionic surfactants. The above may be used in combination. In addition, the anionic surfactant may include nonionic surfactants, such as polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether,
polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonyl phenyl ether and polyoxyethylene octylphenyl ether;
Polyoxyethylene alkyl esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; sorbitan esters such as sorbitan monolaurate and sorbitan monostearate; polyoxyethylene sorbitan alkyl esters such as polyoxyethylene sorbitan monolaurate , polyoxyethylene polypropylene block polymer, polyethylene glycol, etc. can also be used in combination. Furthermore, amphoteric surfactants such as betaine-type amphoteric surfactants such as dimethylalkyl betaine, lauryl betaine, and stearyl betaine, small amounts of cationic surfactants, etc. can also be used in combination. Examples of protective colloids used in the emulsion polymerization include partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salts, and its salts, and natural polysaccharides such as guar gum. These can be used alone or in combination. Furthermore, examples of catalysts used in the emulsion polymerization include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, hydrogen peroxide, hydroperoxides such as tert-butyl hydroperoxide, and cumene hydroperoxide. Examples include oxides, and preferred examples include persulfates and hydrogen peroxide. Further, as the polyvinyl alcohol used as a protective colloid, anionized polyvinyl alcohol is preferably used, for example, from 1 to 10% by weight, more preferably from 0.5 to 5% by weight, based on the total amount of monomers.
The weight percentage is used in order to obtain physical properties such as improving the leveling property when applying the peelable white/India ink composition of the present invention, increasing the strength of the film during peeling, and making it easy to peel even a thin film. In a preferred embodiment, the anionized polyvinyl alcohol is produced by copolymerizing an alkali olefin sulfonic acid salt and vinyl acetate in the presence of an alcohol solvent such that the content of the alkali olefin sulfonic acid salt is 0.5 to 7 mol%. Modified polyvinyl alcohol obtained by saponifying a copolymer is mentioned, and a commercially available product is Goselan L-3266 (saponification degree 86-89%, polymerization degree 250-300, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.).
Co., Ltd.). Further, during emulsion polymerization, a reducing agent may be used in combination, if desired. Examples include ascorbic acid, tartaric acid, citric acid, reducing organic compounds such as glucose, sodium thiosulfate, sodium sulfite,
Examples include sodium bisulfite and sodium metabisulfite. The reaction temperature in emulsion polymerization can be selected as appropriate, and examples thereof include temperatures of about 40 to about 90°C. During the reaction, the entire amount of a given surfactant can be added to the reaction system, but it is also possible to add a part to the reaction system in advance to start the reaction and then add the rest continuously or at intervals during the reaction. It can also be added in portions, and the latter is preferred. Further, each monomer can be added all at once, added in portions, or added continuously, but it is preferable to add them continuously from the viewpoint of reaction control. In addition to the surfactants and catalysts mentioned above, during emulsion polymerization
A PH regulator, polymerization degree regulator, antifoaming agent, etc. can be added as appropriate. The peelable white/black ink composition of the present invention uses the water-dispersed resin obtained as described above as a film-forming material, adds a black pigment or a white pigment as a coloring agent, and contains an amide compound, an anion, etc. The amount of water-dispersed resin in the peelable white/ink composition is preferably 80 to 99% by weight, more preferably 85 to 97% by weight. The above-mentioned black pigments include carbon black,
Examples of white pigments include titanium oxide, zinc white, lithopone, zinc sulfide, and basic lead sulfate. 1~ inside
Added at 20% by weight. The above-mentioned amide compound has the function of imparting releasability to the removable white/ink composition of the present invention without leaving any haze on the substrate after peeling, and examples of the amide compound include stearic acid amide. , organic carboxylic acid amides such as ricinoleic acid amide, oleic acid amide, lauric acid amide,
Examples include ethylene bisamide such as ethylene bisstearamide, alkyl sulfanamide carboxylic acids such as stearin sulfanamide carboxylic acid, and salts thereof, and preferred examples include stearic acid amide and sodium alkyl sulfanamide carboxylate. , the amount used is preferably 0.1 to 8% by weight in the peelable white/India ink composition of the present invention,
Particularly preferably 0.5 to 6% by weight, even more preferably
It is 0.5 to 4% by weight. In addition, the anionic surfactant mainly functions to impart releasability to the peelable white/India ink composition of the present invention after a long period of time, and Examples of the surfactant include anionic surfactants that can be used during emulsion polymerization to obtain the water-dispersed resin, preferably sodium uralyl sulfate, sodium dodecylbenzenesulfonate, etc. The amount used is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 7% by weight, and even more preferably 0.1 to 3% by weight in the peelable white/India ink composition of the present invention. In addition, the polyhydric alcohol has the function of imparting good releasability to the releasable white/India ink composition of the present invention, mainly when heated (solar heat or heating during drying). Examples of the alcohol include ethylene glycol, propylene glycol, glycerin, catechol, butanediol, pentanediol, erythritol, glycerin monoalkyl ester, polyethylene glycol, polypropylene glycol, and preferably ethylene glycol, propylene glycol, glycerin, etc. The amount used is as follows in the peelable white/India ink composition of the present invention:
Preferably 0.01 to 5% by weight, particularly preferably 0.05
~3% by weight, more preferably 0.1~2% by weight. In addition, the amide compound, anionic surfactant, and polyhydric alcohol have a ratio of 100:5:1 to 100:
It is preferable to use a weight ratio of 50:30 in terms of peelability and cloudiness of the peeled surface. In addition to the above-mentioned additives, the peelable white/black ink composition of the present invention also contains wax, a film forming aid, an antifoaming agent, a plasticizer, a thickener, a PH regulator, a preservative, an antifungal agent, An antifreeze agent or the like can be added as appropriate. Wax is a natural or synthetic wax, paraffin,
Refers to waxes such as natural animal and plant-based whale oil, carnauba wax, beeswax, mutton tallow, candelilla wax, montan wax, Chinese wax, wood wax, petroleum-based paraffin wax, petrolatum, liquid paraffin, synthetic polyethylene, polypropylene, etc. wax, glycerin fatty acid ester, etc. Preferred examples include liquid paraffin and synthetic wax emulsion. Wax has the effect of further increasing the peelability of the peelable white/India ink composition of the present invention after drying, and the amount used is about 0 to 6 parts by weight, preferably 0.5 parts by weight, based on 100 parts by weight of the water-dispersed resin. ~4
Parts by weight. Examples of film forming aids include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dibutyl carbitol, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, and ethyl carbitol. Examples include acetate, butyl carbitol acetate, benzyl alcohol, benzyl acetate, toluene, xylene, petroleum hydrocarbons, texanol, etc., and preferred are butyl carbitol, butyl cellosolve acetate, butyl carbitol acetate, texanol, etc. Peelable white/
When the ink composition forms a film, it has the effect of lowering the film formation temperature, and the amount used is generally about 0.5 to 15 parts by weight, preferably about 1 to 8 parts by weight, based on 100 parts by weight of the water-dispersed resin. . Antifoaming agents are, for example,
Silica silicone type, silicone type, metal soap type, fatty acid amide type, fatty acid ester type, polyether type, polyglycol type, organic phosphoric acid type, higher alcohol type, sulfonated fatty acid type, oil bath polymer type, etc. , preferably silicone-based, silica-silicone-based, metal soap-based, fatty acid amide-based, or a combination thereof, etc., when transporting, subdividing, and applying the peelable white/India ink composition of the present invention. The amount used is generally 100 parts by weight of the water-dispersed resin.
It is 0.001 to 1 part by weight. The peelable white/India ink composition of the present invention has the composition as described above, and the composition of each component in the peelable white/India ink composition of the present invention is summarized as follows. Part by weight Water-dispersed resin 85 ~ 97 Amide compound 0.5 ~ 6 Anionic surfactant 0.1 ~ 3 Polyhydric alcohol 0.1 ~ 2 Film forming aid 0.8 ~ 8 Wax 0.4 ~ 4 Antifoaming agent 0.001 ~ 1 Preservative 0.01 ~ 2 Adhesive: 0.01 to 5 Plasticizer: 0 to 2 Colorant (for black pigment) 1 to 10 (for white pigment) 1 to 20 The peelable white/black ink composition of the present invention has the above-mentioned composition. The peelable white ink composition of the present invention can be used to write letters on designated signboards, display boards, etc. in the same manner as ordinary ink ink, and forms a releasable film after drying. For example, if it becomes necessary to rewrite the letters, etc. on a signboard, display board, etc. after use, the letters, etc. can be erased simply by peeling off the film, and the peelable white/ink ink composition of the present invention can be used again to rewrite the letters. Other characters, etc. can be written on the signboard, display board, etc., and therefore, the signboard, display board, etc. can be used repeatedly without requiring any special work to rewrite the characters, etc. Furthermore, by selectively using various additives, the removable white/ink composition of the present invention can be used to print letters, etc. with appropriate adhesion, appropriate gloss, and appropriate water resistance on wooden boards, synthetic resin boards, etc. It can be used as a composition that can be easily written on various plates such as metal plates and forms a film that can be easily peeled off without staining them, especially for funeral signboards and weddings in hotels, etc. Suitable for writing letters on ceremony display boards, welcome display boards, etc. Examples of the peelable white/India ink composition of the present invention will be given below to specifically clarify the effects of the present invention. Example 1 Water was added to a 2-capacity glass flask equipped with a stirrer.
400g, anion-modified poval (Goselan L-
3266) Add 5g and dissolve. On the other hand, 370 butyl acrylate was added to a surfactant aqueous solution obtained by dissolving 20 g of polyoxyethylene nonyl phenyl ether (approximately 30 moles of ethylene oxide added) and 3 g of sodium dodecylbenzenesulfonate in 130 g of water.
g and 230 g of acrylonitrile were added and mixed with stirring to obtain a monomer mixture. Next, after purging the inside of the flask with nitrogen, 50 g of the monomer mixture, 50 g of 4% ammonium persulfate aqueous solution, and 50 g of 4% sodium metabisulfite were added to the aqueous solution in the flask while maintaining the reaction temperature at 70°C. The mixture was added over a period of time to effect emulsification and polymerization to obtain an emulsion with a solid content of approximately 50%. To 100 parts of the obtained emulsion, 3 parts of sodium lauryl sulfanamide carboxylate and sodium lauryl sulfate were added.
1.8 parts of 30% salt aqueous solution, 0.5 parts of ethylene glycol,
Add 3 parts of black pigment (International Color Black, manufactured by International Paint Co., Ltd.), a thickener, and adjusting water, viscosity approximately 2700 cps, solid content approximately 47%, PH 6.2
A black ink composition was obtained. The above India ink composition was applied to a plywood formed by adhering a vinyl chloride resin film with a wood grain pattern to the surface to a coating thickness of approximately 200 μm, and
After heating and drying at .degree. C. for 2 hours, peel resistance was measured and found to be 195 g/cm. Further, the character "large" was written with a brush using the above India ink composition, and the writing feel, appearance after being left at room temperature for one day, and releasability were measured. The writing quality was extremely smooth and better than that of ordinary India ink, and the appearance of the letters had a suitable gloss.The letters "Dai" could be easily peeled off without any resistance to peeling, and there was no residue left after peeling. Furthermore, even when the surface of the plywood was wiped with a wet cloth after the letters "large" were peeled off, the black color did not come off, the letters did not disappear, or they did not smudge. Example 2 Water was added to a 2-capacity glass flask equipped with a stirrer.
400g, anion-modified poval (Goselan L-
3266) Add 5g and dissolve. On the other hand, 370 butyl acrylate was added to a surfactant aqueous solution obtained by dissolving 20 g of polyoxyethylene nonyl phenyl ether (approximately 30 moles of ethylene oxide added) and 3 g of sodium dodecylbenzenesulfonate in 130 g of water.
g and 230 g of acrylonitrile were added and mixed with stirring to obtain a monomer mixture. Next, after purging the inside of the flask with nitrogen, 50 g of the monomer mixture, 50 g of 4% ammonium persulfate aqueous solution, and 50 g of 4% sodium metabisulfite were added to the aqueous solution in the flask while maintaining the reaction temperature at 70°C. The mixture was added over a period of time to effect emulsification and polymerization to obtain an emulsion with a solid content of approximately 50%. To 100 parts of the obtained emulsion were added 3 parts of an equivalent mixture of sodium lauryl sulfanamide carboxylate, liquid paraffin, and 1.8 parts of a 30% aqueous solution of sodium lauryl sulfate salt.
parts, 0.5 parts of ethylene glycol, 3 parts of butyl carbitol, 1.0 parts of tributoxyphosphate,
Add 0.1 part of antifoaming agent, 0.1 part of preservative, 3 parts of black pigment (International Color Black, manufactured by International Paint Co., Ltd.), thickener, and adjusting water to obtain a viscosity of approx.
A India ink composition of 2700 cps, solid content of approximately 47%, and pH 6.2 was obtained. The above India ink composition was applied to a plywood formed by adhering a vinyl chloride resin film with a wood grain pattern to the surface to a coating thickness of approximately 200 μm, and
After heating and drying at .degree. C. for 2 hours, peel resistance was measured and found to be 100 g/cm. Further, the character "large" was written with a brush using the above India ink composition, and the writing feel, appearance after being left at room temperature for one day, and releasability were measured. The writing quality was extremely smooth and better than that of ordinary India ink, and the appearance of the letters had a suitable gloss.The letters "Dai" could be easily peeled off without any resistance to peeling, and there was no residue left after peeling. Furthermore, even when the surface of the plywood was wiped with a wet cloth after the letters "large" were peeled off, the black color did not come off, the letters did not disappear, or they did not smudge. Example 3 Water was added to a 2-capacity glass flask equipped with a stirrer.
400g, anion-modified poval (Goselan L-
3266) and 2 g of a 30% aqueous solution of sodium lauryl sulfate salt and dissolve. On the other hand, 390 butyl acrylate was added to a surfactant aqueous solution obtained by dissolving 5 g of polyoxyethylene nonyl phenyl ether (approximately 30 moles of ethylene oxide added) and 20 g of a 30% aqueous solution of sodium lauryl sulfate in 130 g of water.
g, acrylonitrile 180 g, and methyl methacrylate 30 g were added and mixed with stirring to obtain a monomer mixture. Next, after purging the inside of the flask with nitrogen, 50 g of the monomer mixture, 50 g of 4% ammonium persulfate aqueous solution, and 50 g of 4% sodium metabisulfite were added to the aqueous solution in the flask while maintaining the reaction temperature at 70°C. The mixture was added over a period of time to effect emulsification and polymerization to obtain an emulsion with a solid content of approximately 50%. To 100 parts of the obtained emulsion were added sodium lauryl sulfanamide carboxylate, 2.5 parts of an equivalent mixture of liquid paraffin, and dodecylbenzenesulfonic acid.
0.5 parts Na, 0.3 parts ethylene glycol, 2 parts butyl carbitol, 0.3 parts tributoxyphosphate
1 part, antifoaming agent 0.1 part, preservative 0.1 part, black pigment (International Color Black, manufactured by International Paint Co., Ltd.) 3 parts, thickener, adjusting water, viscosity approx. 3100 cps, solid content approx. A black ink composition of 45% and pH 6.0 was obtained. The peel resistance of the obtained India ink composition was measured in the same manner as in Example 1, and it was found to be 150 g/cm. Furthermore, when the character "dai" was written with a brush, the written character did not sag, had a smooth writing feel, and exhibited excellent releasability. Example 4 Instead of 3 parts of the black pigment used in Example 2, 10 parts of 50% TiO ₂ previously dispersed in water was used,
Same as Example 2 except that the amount of thickener was increased,
A white juice composition with a viscosity of about 4800 cps and a solid content of about 58% was obtained. The obtained white juice composition was subjected to the same test as in Example 1. As a result, the peel resistance is 95g/cm
It was good. Furthermore, the results of writing the word "large" with a brush were also excellent in terms of writing feel, gloss, and releasability, as in Examples 1 and 2, except for the difference in whether the color was black or white. Example 5 Instead of 3 parts of the black pigment used in Example 3, 10 parts of a 50% TiO ₂ aqueous dispersion previously dispersed in water was used.
A white juice composition having a viscosity of about 4500 cps and a solid content of about 57% was obtained in the same manner as in Example 3, except that the amount of the thickener was increased. The obtained white juice composition was subjected to the same test as in Example 1. As a result, the peel resistance was 125g/
cm and was excellent. Furthermore, the result of writing the word "large" with a brush was similar to Examples 1 and 2, except for the difference in whether the color was black or white, and the writing quality, gloss, and releasability were good. Examples 6 to 9 Surfactant and resin composition during emulsion production,
Various compositions were obtained in the same manner as in Example 1, except that the additives were changed as shown in Table 1 below.
The obtained compositions were each subjected to the same tests as in Example 1. The results are shown in Table 2 below together with the results of Examples 1-5 and Reference Examples 1-2. The peelability in Table 2 was evaluated using a 10-point scale, with 10 indicating that the sample could be easily and completely peeled off, and 1 indicating that the sample could not be peeled off. In addition, water resistance was evaluated using a 10-point system, and the surface of the plywood with letters on it was exposed to 12 points in the rain.
A score of 10 indicates that no particular change was observed as a result of exposure over time, and a score of 1 indicates that the letters lost their shape. Table 2 also shows the Tg of the resin that is a component of the composition. Reference Example 1 Commercially available Indian ink was applied to a coating thickness of approximately 200μ on the plywood formed by adhering the vinyl chloride resin film with a wood grain pattern to the surface used in Example 1, and heated at 30°C. After drying with heat for 2 hours, I tried to peel it off, but the film could not be peeled off. Also, write the word "dai" with a brush using the above ink,
After leaving it at room temperature for one day, I observed its appearance, and found that it had no shine, and when I wiped it with a damp cloth, some of the letters disappeared, and the area around the letters became dark and unreadable. The letter ``large'' cannot be removed, so I wiped it off vigorously with a rag, but a faint black mark of the letter ``large'' remained, and ink remained in the small dents that I could not remove.
Therefore, the plywood used in the experiment could not be reused. Reference Example 2 On the plywood used in Example 1, 100 parts of a 50% TiO aqueous dispersion was used instead of 100 parts of the emulsion used in Example 2, and the same formulation as Example 2 was used except that the black pigment was omitted. Solid content obtained by adding the same amount of additives: approx.
After applying a 60% white juice composition and drying it thoroughly, I tried to peel it off, but the film could not be peeled off. In addition, the character ``large'' was written with a brush using the white juice composition, and after being left at room temperature for one day, the appearance was observed, but the gloss was poor, and when wiped with a wet cloth, part of the character disappeared easily. It became illegible. Since the letter "large" could not be removed, I wiped it off vigorously with a rag, but it took a lot of effort to completely clean the plywood surface.

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Claims (1)

[Scope of Claims] 1. A liquid film-forming substance containing a black or white coloring agent and containing an amide compound, an anionic surfactant, and a polyhydric alcohol, the film-forming substance comprising: Obtained from one or more monomers selected from the group consisting of (meth)acrylic acid ester monomers, aromatic vinyl monomers, vinyl ester monomers, and acrylonitrile monomers. Peelable white ink composition, which is a water-dispersed resin. 2 The above water-dispersed resin has a glass transition temperature of
229-303K, the peelable white/India ink composition according to claim 1. 3. The peelable white/India ink composition according to claim 1, wherein the water-dispersed resin contains a protective colloid. 4. The peelable white/India ink composition according to claim 3, wherein the protective colloid is anionized polyvinyl alcohol.