KR100375741B1 - Solidifying Microcapsulation Ink - Google Patents

Abstract

The ink composition is mixed with solvent, colorant, and resin release agent so that the writing is smooth and the powder is not blown out when erasing, the separation and sedimentation of the ink composition does not occur, and the writing is possible after long-term storage even when the cap is opened. To provide a solid microcapsule ink prepared by microencapsulation and solidifying using.

Film forming materials include polyamide, nylon, polyterephthalate, polyurethane, acrylic acid ester, polymethacrylic acid ester, polystyrene, divinylbenzene, polyisocyanate, polyol, polyamine, acid chloride, organic amine, acid amide, polyacrylic acid, Gelatin, starch, gum arabic, rosin, polyvinyl alcohol, polyvinylidene chloride, cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl chloride, acrylic resin, polyester, polyethylene, polypropylene, epoxy resin, phenol Select one or more from resin, silicone resin, etc., and use them alone and / or mixed.

Description

Solid Microcapsulation Ink

The present invention relates to a solid microcapsule ink that can be used for writing boards such as whiteboards and can be used in a rod shape.

In general, for writing boards such as white boards, a writing instrument called a white board pen or a board pen for a white board board is used.

The writing instrument includes a method of writing through a fibrous tip by storing a liquid ink composition comprising a colorant, a resin release agent, and a solvent in a fibrous tip, and a method of writing through a fibrous tip while keeping the ink itself in an ink reservoir. have.

When writing on the writing board using a conventional writing instrument as described above, erase is performed by friction using an eraser.

In the above-described conventional writing implements, liquid ink is used, so that the coloring agent and the release agent in the composition are sedimented and separated in the fiber absorbent body or the ink storage container, thereby causing the writing line to be light and partially erasing property.

In addition, when the evaporation of the solvent rapidly occurs and the cap is left open, the ink dries at the writing edge and solidifies, so that writing is not performed smoothly when it is to be used again.

An object of the present invention is to solve the above problems, it is possible to write smoothly, the powder does not fly during erasing, the separation and sedimentation of the ink composition does not occur, the ink composition to enable writing after long-term storage even in the cap open state To provide a solid microcapsule ink microencapsulated.

1 is a perspective view showing one embodiment of a solid microcapsule ink according to the present invention.

Figure 2 is a schematic cross-sectional view showing a method for forming a writing in one embodiment of a solid microcapsule ink according to the present invention.

The solid microcapsule ink proposed by the present invention is prepared by microencapsulating and solidifying an ink composition obtained by mixing a solvent, a colorant, and a resin release agent using a film forming material.

The ink composition described above may also change composition of a solvent (solid forming material) or the like for improving workability and solidifying.

Fatty acid salt is used as the solid-forming material as a solvent for solidification in the above.

Lauric acid, palmitic acid, stearic acid, etc. can be used as a fatty acid which comprises said fatty acid salt.

And as the alkali metal salt of fatty acid, lithium salt, sodium salt, potassium salt, ammonium salt and the like can be used.

Examples of the film forming material include polyamide, nylon, polyterephthalate, polyurethane, acrylic acid ester, polymethacrylic acid ester, polystyrene, divinylbenzene, polyisocyanate, polyol, polyamine, acid chloride, organic amine, acid amide, poly Acrylic acid, gelatin, starch, gum arabic, rosin, polyvinyl alcohol, polyvinylidene chloride, cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl chloride, acrylic resin, polyester, polyethylene, polypropylene, epoxy resin Select from phenol resin, silicone resin, etc., and use it individually and / or by mixing two or more kinds.

It is preferable to select and use the said film forming substance in the range of about 1 to 20 weight%, and about 5 to 10 weight% is more preferable.

It is preferable to perform the microencapsulation operation so that the average particle diameter of the microcapsules is in the range of approximately 0.1 to 5 μm.

If the average particle diameter of the microcapsules is less than 0.1㎛ in the above, it is difficult to manufacture, if larger than 5㎛ there are many difficulties in solidification due to the destruction of the capsule during the solidification operation.

And it is preferable to carry out the microencapsulation operation so that the film average thickness of the microcapsules is in the range of approximately 0.01 to 1 μm.

When the film average thickness of the microcapsules is less than 0.01㎛, the operation is difficult, and when larger than 1㎛, the breakage of the capsule due to friction at the time of writing does not occur smoothly, the writeability is reduced.

In the encapsulation (microcapsulation) method that performs the microcapsulation (microcapsulation) is a chemical method, a physicochemical method, a physical mechanical method and the like.

The interfacial polymerization method for preparing microcapsules using an interfacial polymerization reaction in which a monomer is dissolved in two solvents which are not mixed by the chemical method and the polymer is synthesized at the interface of the nutrient solution, and one of the two phases which do not mix with each other When the monomer and the catalyst are dissolved in the monomer, the monomer generates a polymerization reaction at the interface and a uniform film is formed on the surface of the core material. In situ polymerization method for preparing microcapsules and the material to be encapsulated are previously dispersed in the polymer solution. For example, there is an orifice coating method in which the solution is adjusted to a desired mold and the polymer is cured to form a film.

In the above-mentioned physicochemical method, when another substance (precipitant, etc.) is added to hydrophilic colloid (especially polymer solution) or the environment such as temperature is changed, colloid-rich liquid (disperse phase) and colloid-deficient liquid (continuous phase) Phase separation method using coacervation to separate the dog phase and forming microcapsules with coacervate, a colloid-rich phase (droplet), and a core in a solvent in which a film-forming material as a wall material is dissolved. In-liquid drying method to disperse a solution or solid consisting of an ink composition as a substance, gradually disperse it in a solvent which is not mixed with the solvent, and to remove the first solvent to precipitate at the interface of the core ink composition to form microcapsules. Solid wax, fat cells, polyethylene, etc. Melting dispersion cooling method and the like to be formed using the microcapsules.

The phase separation method can be divided into a phase separation method (simple coacervation and complex coacervation) from an aqueous solution system and a phase separation method (combination method of a good solvent and a poor solvent and a method using a temperature difference) from an organic solution system.

The physicomechanical method includes an air suspension coating method (Wurster method) that physically adsorbs a film forming material, which is a wall material, to form a microcapsule on the surface of an ink composition, which is a core material, and sprays it in hot air by dispersing fine droplets Spray drying method for forming microcapsules by drying method and spraying film forming material, which is a wall material, from the top while the particles are mixed by the rotation of the plate and the particles inside come to the surface. Plate coating method for uniformly applying a wall material to form microcapsules.

Among the various encapsulation methods described above, encapsulation can be easily performed by chemical method, solidification using solid-forming material, and encapsulation and solidification by spray drying method. It is preferable because it is simple.

As the ink composition described above, it is possible to use an ink composition which is generally used.

As the solvent, ethylalcohol, methylalcohol, n-propylalcohol, isopropylalcohol, ethylene glycol monophenyl ether, benzyl Benzyl alcohol, propylene glycol, dipropylene glycol, 1.3-dibuthylene glycol, hexnlene glycol, propylene glycol Propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl Dipropylene glycol monobuthyl ether, dipropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (N-methyl-2-pyrolidone) and the like can be used alone or / or in combination of two or more, in addition to the various commonly used solvents can be used.

As the release agent, fatty acid esters are mainly used, and for example, mixed fatty acid triesters of trimethopropane lauric acid and stearic acid, trimethyropropane capric acid triester, trimethyropropane lauric acid triester, It is possible to use isodecyl alcohol and esters of isononanoic acid and the like.

As said coloring agent, both the pigment and dye used for an erasable writing board can be used.

In the above colorant, pigments include carbon black (PIGMENT BLACK 6, PIGMENT BLACK7), phthalocyanine blue (PIGMENT BLUE 15, PIGMENT BLUE 16), and C.I. Pigment BLUE 60, phthalocyanine green (PIGMENT GREEN 7, PIGMENT GREEN 36), monoazo pigment (HANSA YELLOW, HANSA ORANGE PIGMENT), disazo pigment, lake red (CI PIGMENT 53: 1), carmine (CI PIGMENT RED 57: 1), oxide (IRON OXIDE PIGMENT, CHROMINUM OXIDE) can be selected.

In the above-mentioned colorant, the dye may be a nigrosine dye or a solvent dye.

For example, Valifast black 1802, Valifast black 1820, Valifast black 3806, Valifast black 3807, Valifast red 1308, Valifast violet # 1701, Valifast violet # 1702, Valifast yellow-AUM, Valifast yellow # 3104 Can be used

In addition, nigrosin dyes, azen spilon dye, are manufactured by Hodogawa Chemical Co., Ltd. Spilon violet C-RH, Spilon black GMH special, Spilon yellow C-2GH, Spilon orange GRH, Spilon red C-GH, Red C-BH, Spilon pink BH, Spilon yellow-C2GH, etc. are available.

It is preferable to select the usage-amount of said coloring agent in about 0.1 to 15 weight% range, and about 4 to 10 weight% range is more preferable.

If the amount of the colorant used is less than 0.1% by weight, it is difficult to identify the writing line because the concentration is light. If the amount of the colorant is more than 15% by weight, the dispersibility and solubility of the colorant are lowered and the erasure of the writing line is lowered.

Next, a preferred embodiment of a solid microcapsule ink according to the present invention will be described.

(Example 1)

First, 82% by weight of ethanol as a solvent, 8% by weight of AS BLACK 810 (manufactured by Fuji Corporation) and 10% by weight of fatty acid ester as a peeling agent are mixed, and the mixture is stirred for 4 hours in a stirrer to completely disperse the liquid ink composition. Got.

After mixing the ink composition and the polyamide resin as a film-forming material obtained as described above, emulsify the mixture of the ink composition and the film-forming material in a protective colloidal solution, adjust the size of the particles, and proceed with the polymerization reaction to polymer wall A film is formed and microencapsulated to prepare microcapsules containing the ink composition.

A solid microcapsule ink according to the present invention was obtained by adding sodium salt, which is an alkali metal salt of stearic acid, as a solid-forming substance to 70 ° C., in the prepared microcapsules.

As shown in Fig. 2, Example 1 of the solid microcapsule ink obtained as described above was poured into a mold 4 having a diameter of 8 mm and a length of 50 mm, cooled to room temperature, and solidified into a predetermined shape (for example, a rod shape). By doing so, the solid writing body 2 as shown in Fig. 1 was manufactured.

(Example 2)

First, 82% by weight of ethanol as a solvent, 8% by weight of AS RED575 (manufactured by Fuji Corporation) and 10% by weight of fatty acid ester as a peeling agent are mixed, and the mixture is stirred for 4 hours in a stirrer to completely disperse the liquid scavenging ink composition. Got it.

After mixing the ink composition and the carboxymethyl cellulose as a film-forming material obtained as described above, emulsify the mixture of the ink composition and the film-forming material in a protective colloidal solution, adjust the size of the particles, and then proceed with the polymerization reaction to polymer wall. A film is formed and microencapsulated to prepare microcapsules containing the ink composition.

A solid microcapsule ink according to the present invention was obtained by adding sodium salt, which is an alkali metal salt of stearic acid, as a solid-forming substance to 70 ° C., in the prepared microcapsules.

As shown in Fig. 2, Example 2 of the solid microcapsule ink obtained as described above was poured into a mold 4 having a diameter of 8 mm and a length of 50 mm, cooled to room temperature, and solidified into a predetermined shape (for example, a rod shape). By doing so, the solid writing body 2 as shown in Fig. 1 was manufactured.

Using the solid cursive 2 prepared in Examples 1 and 2 described above, a test for handwriting, concentration, erasing, and strength was performed, and the results are shown in Table 1.

division Handwriting density Scavenging burglar Example 1 O O O O Example 2 O O O O

In the above, the writing test is performed by writing on a writing board called a white board. If the writing is smooth without slipping, the writing is indicated by O. If the writing is not performed well, the writing test is indicated by ×. The concentration test is performed by writing on a writing board (white board). If the density of the line is constant and there are few shades of color, it is indicated by O. If the shade of the writing line is severe, x is indicated.

In addition, the eraser test is performed when writing on a writing board (whiteboard) and erased with an eraser after the initial and 7 days. The initial eraser is good after writing. 7 days after the fall, it is represented by × if it is not erased by rubbing three times lightly, and the strength test indicates that the breakage load is 200gf or more and the breakage load is 200gf or less It is represented by x.

As can be seen from Table 1, when writing using the solid handwriting 2 produced using the solid microcapsule ink according to the present invention, not only the writing and erasing property is good, It appears that there are few shades of color (variation in color), so it can be used as a writing instrument for writing board.

In the above-mentioned solid writing body 2, since the liquid ink composition is wrapped in the microcapsule, it is not dried, and therefore the writing property does not deteriorate even if it is stored for a long time in the open state.

In the above, a preferred embodiment of the solid microcapsule ink according to the present invention has been described. However, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and the detailed description of the invention. It belongs to the scope of the present invention.

According to the solid microcapsule ink according to the present invention made as described above, even if stored in a long exposure state prevents the drying of the ink composition by the capsule, handwriting and erasability is always maintained uniformly, handwriting It is not necessary to use a cap in a writing instrument for edition.

In addition, since the capsule is destroyed by friction with the writing plate, writing is performed, and since the ink composition to be written is liquid, no dust is generated.

In addition, the solid microcapsule ink according to the present invention can be used to fill the writing instrument using the principle used in lipstick or glue, etc., which can adjust the amount of exposure according to the amount consumed, a board pen of a new design It is possible to provide a marker pen.

Claims (6)

The ink composition of a solvent, a coloring agent and a release agent is prepared by microencapsulating with a film forming material and solidifying with a fatty acid salt as a solid forming material. The solvent mentioned above is ethyl alcohol, methyl alcohol, normal propyl alcohol, isopropyl alcohol, ethylene glycol monophenyl ether, benzyl alcohol, propylene glycol, dipropylene glycol, 1.3-butylene glycol, hexylene glycol Lycol, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, tri Selected from propylene glycol monomethyl ether and N-methyl-2-pyrrolidone and used alone or in combination of two or more thereof, The above release agent is selected from a mixed fatty acid triester of trimethopropanelauric acid and stearic acid, a trimethiropropane capric acid triester, a trimethiropropane laurate triester, an ester of isodecyl alcohol and isononanoic acid Single or in combination of two or more, The colorants mentioned above are carbon black, phthalocyanine blue, C.I. Pigment selected from PIGMENT BLUE 60, phthalocyanine green, monoazo pigment, disazo pigment, lake red, carmine, oxide, or dye selected from nigrosine dye or oil-soluble dye is used alone or in combination of two or more. , The above film forming materials are polyamide, nylon, polyterephthalate, polyurethane, acrylic acid ester, polymethacrylic acid ester, polystyrene, divinylbenzene, polyisocyanate, polyol, polyamine, acid chloride, organic amine, acid amide, polyacrylic acid , Gelatin, starch, gum arabic, rosin, polyvinyl alcohol, polyvinylidene chloride, cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl chloride, acrylic resin, polyester, polyethylene, polypropylene, epoxy resin, It is selected from phenol resin and silicone resin and used alone or by mixing two or more kinds. 0.1-15 weight% of said coloring agents are added, The film forming material is a solid microcapsule ink to be selected and used in the range of 1 to 20% by weight. delete delete 2. The solid microcapsule ink according to claim 1, wherein the average particle diameter of the microencapsulated particles is maintained in the range of 0.1 to 5 mu m. The solid microcapsule ink according to claim 1, wherein the average thickness of the film formed by the film forming material is maintained in the range of 0.01 to 1 μm. The fatty acid constituting the fatty acid salt of claim 1 is selected from lauric acid, palmitic acid, stearic acid, The alkali metal salt of the fatty acid is a solid microcapsule ink selected from lithium salts, sodium salts, potassium salts and ammonium salts.