KR100364510B1 - The white ink composite for marker-pen and its manufacturing method - Google Patents

Abstract

The present invention relates to a white ink for a marker pen, and thus the present invention is to solve the above-mentioned problems, the process of erasing after writing on the writing board to improve the initial erasability of the white ink as well as the late erasure after drying It is an object of the present invention to provide a white ink composition for a marker pen and a method for producing the same, which can be erased cleanly from the present invention. To achieve the above object, the present invention provides a pigment and vinyl of 10% to 30% by weight based on 100% by weight of the total composition. A white ink composition for a marker pen composed of a resin, a solvent, a mold releasing agent, and other additives, wherein the releasing agent is a phthalate ester type, a monobasic acid ester of a fatty acid having 6 or more carbon atoms and an aliphatic alcohol, a polyunsaturated polyhydric acid (HLB) or less. Oxyethylenealkyl nonylphenyl ether, polyoxyethylenealkyl ethers up to HLB 8 and HLB 8 Can be achieved by providing an under polyoxyethylene least one member selected from alkyl phosphate ester of an ether and a molecular weight of 300 or more, characterized in that a mixture consisting of an aliphatic dibasic acid ester marker pens white ink composition.

Description

White ink composition for marker pens and its manufacturing method

The present invention relates to a white ink for a marker pen, and more particularly, to improve the initial erasability of the white ink during writing as well as the late erasure after drying, so that the white ink for the marker pen can be erased cleanly in the process of erasing after writing on the writing board. A composition and a method for producing the same.

Background Art Conventionally, blackboards used in classrooms, seminar rooms, conference rooms, and offices have black or green surfaces, and in recent years, green blackboards have been used to protect eyesight. It has been described.

However, in the process of writing or erasing letters using chalk on the blackboard, a large amount of chalk powder is generated and the interior is contaminated. Especially, the generated chalk powder easily penetrates into the human body during the breathing process and causes various lung diseases. There was a problem acting as.

Due to the above problems, a colored marker pen used for a white board or the like is known, and the marker pen has an ink solution embedded therein, and the ink solution is absorbed by an absorbent such as a sponge installed on the marker nib inside the marker pen. By letting out the pen through the pen tip to have the function of writing instruments.

In the above, the whiteboard has a white background color, and the marker pen for writing on the writing surface is written using various colors with good wipeability, but in general, when the background color is white, eyes are easily tired due to reflection of light. There was a problem that the learning effect was lowered due to the disability.

In order to solve the above problems, the method of manufacturing white ink for marker pens of Korean Patent Application No. 94-9740 and the black ink composition and its manufacturing method of Japanese Patent Application No. 7-110554 are used as pigments. Titanium oxide is used and isopropyl alcohol and acetone as a vinyl resin, solvent, and polyoxyethylene lauryl ether, polyoxyethylene oleincetyl ether as a releasing agent, and isoctyl stearate and dioctyl adipate as other additives. Disclosed is a technique of manufacturing a white ink which enables writing using the prepared white ink on a green-based writing board by adding a white ink.

In more detail, in the method for preparing a white ink for a marker pen of Korean Patent Application No. 94-9740, 9 to 12 wt% of titanium oxide and 1 to 1.5 wt% of calcium carbonate are mixed and pulverized, and the vinyl resin is 1.5 to 1.8. By weight, 50 to 60% by weight of IPA (isopropyl alcohol) is mixed and heated in a hot bath at 95 to 110 ℃ for about 20 to 30 minutes to produce a mucus stock solution, and then ISO (isooctyl stearate) 8 to 11% by weight, 2.8 to 3.2% by weight of LA3 (polyoxyethylene lauryl ether), 0.8 to 1.2% by weight of EA3 (polyoxyethylene oleincetyl ether) and 10 to 12% by weight of acetone were added and mixed, followed by DOA (dioctyl). Adipate) discloses a technique for producing a white ink for a marker pen by adding and mixing 7 to 8.5% by weight.

In addition, in Japanese Patent No. 2524689, "Black ink composition and manufacturing method," 9 to 12 wt% titanium oxide, 0.9 to 1.2 wt% calcium carbonate, 1.8 to 2.2 wt% vinyl resin, 30 to 40 wt% Isopropyl alcohol, 8-11 wt% isooctylstearate, 2.8- 3.2 wt% polyoxyethylene lauryl ether, 0.8-1.2 wt% polyoxyethylene olecetyl ether, 30-40 wt% ethyl alcohol And 7 to 8.5 weights of dioctyl adipate and the like.

In general, the white ink for marker pen is used on the dark board surface, so a large amount of white pigment is required because the dark color of the board surface must be sufficiently concealed, but the white ink prepared by the above method is a white pigment of TiO2. Since the content is too low as 9 to 12% by weight, a problem arises that the whiteness of the black board is too low to obtain a proper whiteness.

Accordingly, attempts have been made to increase the content of titanium oxide, a white pigment, from 20% to 30% by weight, but as the content of solids increases, the viscosity increases along with a decrease in dispersion stability in which precipitates are formed during long-term storage. There have been many problems, such as poorly leaking.

In addition, due to the deterioration of dispersion stability, due to the viscosity of the release agent itself is not uniformly mixed with a solvent or a resin does not erase cleanly in the process of writing after writing on the writing plate, thereby causing a problem that the writing plate is contaminated.

Accordingly, the present invention is to solve the above-described problems, the white ink composition for the marker pen to be erased in the process of erasing after writing on the writing board to improve the initial erasability of the white ink as well as the late erasure after drying And to provide a method of manufacturing the same.

In order to achieve the above object, the present invention is a white ink composition for a marker pen composed of 10% to 30% by weight of a pigment and a vinyl resin, a solvent, a mold release agent and other additives based on 100% by weight of the total composition, wherein Phthalate esters, monobasic acid esters of fatty acids having 6 or more carbon atoms and aliphatic alcohols, polyoxyethylene alkyl nonylphenyl ethers of up to 8 HLB (Hydrophile Lipophile Balance), polyoxyethylene alkyl ethers of up to HLB 8 and poly of up to HLB 8 It can achieve by providing the white ink composition for marker pens characterized by mixing at least 1 sort (s) chosen from the phosphate ester of oxyethylene alkyl ether, and the aliphatic dibasic acid ester of molecular weight 300 or more.

In addition, in order to more effectively prepare the white ink composition, the present invention first stirs and dissolves the vinyl resin in a stirrer containing a solvent, and dissolves the phthalate ester-based, monobasic acid ester of a fatty acid having 6 or more carbon atoms and an aliphatic alcohol. At least one selected from phosphate esters of polyoxyethylene alkyl nonylphenyl ethers of HLB (Hydrophile Lipophile Balance) 8 or less, polyoxyethylene alkyl ethers of HLB 8 or less and polyoxyethylene alkyl ethers of HLB 8 or less and molecular weight 300 Marker, characterized in that to adjust the viscosity to 30mPas to 80mPas by adding and mixing a release agent and other additives consisting of a mixture of the aliphatic dibasic acid esters above and adding 20% by weight to 30% by weight of the pigment again for about 3 hours Provided is a method for producing a white ink for a pen.

Hereinafter, the white ink composition for a marker pen of the present invention and a manufacturing method thereof will be described in more detail. In the present invention, first, a vinyl resin is gradually dissolved in a stirrer containing a solvent to dissolve and stir.

In the above solvent, isopropyl alcohol, ethanol and various organic solvents that are commonly used may be used, and in particular, it is preferable to select and use a solvent capable of dissolving vinyl resin more effectively, and the amount of the solvent is usually added. Added within.

In the present invention, an isopropyl alcohol solvent and ethanol, which have little odor as an organic solvent and have little toxicity, are used in a mixed manner.

As described above, a vinyl resin is added to improve the coating property of the ink prepared in the stirrer containing the solvent, adhesion with the writing plate surface, dispersion stability of the pigment, viscosity control and erasability of the ink.

At this time, as the vinyl resin, polyvinyl butyral resin, polyvinylpyrrolidone, polyvinylacetate, polyacetate, vinyl acetate acryl copolymer or vinyl chloride acetate Although vinyl copolymer resin can be used, in particular, when polyvinyl butyral resin is used, proper adhesiveness is imparted to the writing surface, and as the solvent is volatilized after writing, a film is formed on the writing surface to erase the handwriting. In the present invention, polyvinyl butyral resin was used in the present invention, and the amount of the polyvinyl butyral resin was added in the range of 2% by weight to 7% by weight in consideration of the dispersibility and storage stability of the pigment.

As described above, a vinyl resin is added to the solvent, and then, to the solution, a phthalate ester, monobasic acid ester of 6 or more carbon atoms and an aliphatic alcohol, a polyoxyethylene alkyl nonylphenyl ether having an HLB (Hydrophile Lipophile Balance) 8 or less, Additive mixing and release agent and other additives constituted by mixing at least one selected from phosphate esters of polyoxyethylene alkyl ethers of HLB 8 or less and polyoxyethylene alkyl ethers of HLB 8 or less and aliphatic dibasic acid esters having a molecular weight of 300 or more 20 wt% to 30 wt% of the pigment is added again.

Above phthalate esters, monobasic acid esters of fatty acids having 6 or more carbon atoms and aliphatic alcohols, polyoxyethylene alkyl nonylphenyl ethers of HLB 8 or less, polyoxyethylene alkyl ethers of HLB 8 or less, and HLB 8 or less The release agent or one or more mixed release agents selected from phosphate esters of polyoxyethylene alkyl ethers has good compatibility with pigments and resins in the ink composition, which improves dispersion stability performance and improves initial erasability. .

In addition, the aliphatic dibasic acid ester having a molecular weight of 300 or more improves the dispersibility of the pigment and is uniformly dispersed in the pigment and the resin, so that after writing using an ink prepared on a writing board, it is present in the dried handwriting film for a long time to be erased later. Will be improved.

Therefore, aliphatic dibasic acid ester releasing agent and phthalate ester type having a molecular weight of 300 or more as described above, monobasic acid ester of 6 or more carbon atoms and aliphatic alcohol, polyoxyethylene alkyl nonylphenyl ether having a HLB (Hydrophile Lipophile Balance) 8 or less, By mixing one or more release agents selected from phosphate esters of polyoxyethylene alkyl ethers of HLB 8 or less and polyoxyethylene alkyl ethers of HLB 8 or less, it is possible to improve early erasure and late erasure.

In particular, in order to maximize the above effects, phthalate ester based on 100% by weight of the total composition, monobasic acid esters of fatty acids having 6 or more carbon atoms and aliphatic alcohols, and polyoxyethylene alkyl nonylphenyl ether having an HLB (Hydrophile Lipophile Balance) 8 or less 5 wt% to 15 wt% of at least one release agent selected from phosphate esters of polyoxyethylene alkyl ethers of HLB 8 or less and polyoxyethylene alkyl ethers of HLB 8 or less and aliphatic dibasic acid ester release agents of at least 300 molecular weights It is preferable to comprise and mix% -10weight%.

At this time, phthalate ester type, monobasic acid ester of fatty acid with 6 or more carbon atoms and aliphatic alcohol, polyoxyethylene alkyl nonylphenyl ether of HLB 8 or less, polyoxyethylene alkyl ether of HLB 8 or less, and polyoxyethylene alkyl ether of HLB 8 or less If the addition amount of one or more mold release agents selected from phosphate esters is less than 5% by weight, there is a problem that the initial eraseability of the prepared ink decreases, and when the amount exceeds 15% by weight, the viscosity of the ink composition is increased. Since the problem of the outflow of the prepared ink is not easy to occur, the addition amount is preferably added to 5% by weight to 15% by weight.

The phthalate ester-based may be used as dimethylphthalate, diethylphthalate, dibutylphthalate or dioctylphthalate.

In addition, hexyllaurate, ethylolate, methyllaurate, butyllaurate, isomethylstearate as monobasic acid esters of fatty acids having 6 or more carbon atoms and aliphatic alcohols. Methylstearate, isooctadecylstearate, methylpalmitate, methylolate, methylolate, ethylolate, isooctadecylpalmitate, methylmyri Methylmyristate, cetylisooctylate, isostearyllaurate, isopropylmyristate, oleyl-2-ethylhexylate, and the like. .

Moreover, products, such as HLB 5.7 and HLB 7.5, can be used for the polyoxyethylene alkyl nonylphenyl ether of HLB8 or less according to the added mole number of ethylene oxide.

Usable as polyoxyethylene alkyl ethers below HLB 8 include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, and polyoxyethylene steeyl. Aryl ether, polyoxyethyleneocyl ether, polyoxyethylene oleylcetyl ether, polyoxyethylene cetyl stearyl ether, etc. There are several grades, including HLB 4.9, HLB 5, HLB 5.1, HLB 5.4, HLB 6.6, HLB 7.1, and HLB 8.

In addition, various grades such as HLB 5.6, HLB 6.6, HLB 7, and HLB 7.1 may be used for the phosphate ester of polyoxyethylene alkyl ether of HLB 8 or less, depending on the number of moles of ethylene oxide added.

In addition, when the amount of the aliphatic dibasic acid ester-based release agent having a molecular weight of 300 or more is less than 5% by weight, the late erasure property decreases, leaving a mark on the writing board.If the content exceeds 10% by weight, the ink viscosity is increased. It is preferable that the amount of the aliphatic dibasic acid ester-based release agent having a molecular weight of 300 or more is added in an amount of 5% by weight to 10% by weight.

Particularly, it is preferable to use an aliphatic dibasic acid ester system having a molecular weight of 300 or more, which improves the dispersibility of the pigment by using a fatty acid ester having a molecular weight of 300 or more, and writes using a prepared ink. The release agent does not penetrate into the fine pores can be improved even after a long time.

Examples of the aliphatic dibasic acid esters include dinormal acid dihexyl, adidiethyl diethyl hexyl, dioctylazelite, dioctylsebacate or dibutyl sebacate. have.

As a pigment, 20 to 30% by weight may be used. In this case, as a usable pigment, all conventionally used white pigments such as titanium oxide or calcium carbonate may be used, but in the present invention, titanium oxide is considered in consideration of whiteness, gloss, and dispersibility. Was used.

In particular, in the above, the vinyl resin, the releasing agent and other additives were added to the solvent, and then the pigment was added, but the vinyl resin was added to the solvent, followed by the addition of the pigment to premix and disperse by passing through dynomil or tribonola. You may add a mold release agent and another additive here.

As described above, the vinyl resin, the releasing agent, the other additives and the pigment are added to the solvent, followed by dispersion stirring for about 3 hours to adjust the viscosity to 30 mPas to 80 mPas.

In this case, when the viscosity is less than 30 mPas, the viscosity of the prepared ink is low, so that dispersibility is lowered, and pigment precipitation occurs. When the viscosity is more than 80 mPas, the viscosity of the prepared ink is high, and the outflow of ink is poor. Since the problem of not being able to obtain the white concentration occurs, it is preferable to adjust the viscosity of the white ink to 30 mPas to 80 mPas.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following description.

<Examples 1 to 9>

Slowly add 70 g of polybutyral resin to a stirrer containing 400 g of isopropyl alcohol (31212 ml) and 200 g of ethanol (교반 160 ml) as a solvent, and dissolve and dissolve the phthalate ester and aliphatic dibasic acid having a molecular weight of 300 or more as a release agent. The ester was mixed and added in the ratio shown in Table 1 below, and then 30 g of dioctyl adipate was mixed with other additives, and again, 250 g of titanium oxide having a particle size of 0.3 μm was added to the pigment, followed by dispersion and stirring for 3 hours. After preparing, using the prepared white ink, the viscosity, outflow condition, storage stability, initial erasing property and late erasing property were measured by the following method and are shown in Table 1.

- Viscosity -

Approximately 400 g of ink prepared in a 50 ml beaker was added, and the temperature was adjusted to 25 ° C., and when the viscometer rotating plate was rotated two times at 20 rpm using a Rotor NO.1 with a TOKIMEC.BH type viscometer, the scale was read and the viscosity was read. It was.

-Spill Status-

Marker with NIB with a diameter of 5.0 mm and a porosity of 65% or more. Measure 10m line on a green board and measure the amount of ink consumed by 0.1mg. Then, if the ink consumption is more than 300mg per 10m, It was good and less than that. The specification for the ink consumption of macafen is 300 mg to 400 mg per 10 m.

-Storage stability-

Take a 10g of ink prepared in a built-in macapen container with an 8mm diameter steel ball, assemble it, store it at room temperature for 2 months with the NIB upwards, and then drop the ball when the NIB of the macapen downwards. Storage stability was checked as follows.

(Double-circle): The NIB is directed downward and the ball falls.

(Circle): The ball falls when it shakes once or twice after making NIB face down.

(Triangle | delta): The ball falls when it shakes 3-4 times after making NIB face down.

×: The ball falls when the NIB is turned downward and shaken five times or more.

Initial Erase

The green board was placed horizontally, and the stroke was spirally drawn with a marker pen containing ink prepared and left to dry at room temperature for 1 day, and then completely erased with a marker pen eraser.

◎: Cleared.

(Circle): A thin line mark looks weak.

(Triangle | delta): A peeling mark was seen and the peeling line was not partially erased.

X: The peeling line was not erased.

Long-term erasure

The green board was placed horizontally, and a spiral line was drawn with a maca pen containing ink prepared and left to dry at room temperature for 1 month, and then completely erased with a marker pen eraser.

◎: Cleared.

(Circle): A thin line mark looks weak.

(Triangle | delta): A peeling mark was seen and the peeling line was not partially erased.

X: The peeling line was not erased.

division Addition amount of phthalate ester (g) Addition amount of aliphatic dibasic acid ester (g) Viscosity (mPas) Spill Storage stability Initial erase Long-term erasure Example 1 0 80 30 Good △ × ◎ Example 2 60 80 45 Good ◎ ◎ ◎ Example 3 120 80 60 Good ◎ ◎ ◎ Example 4 180 80 75 Good ◎ ◎ ◎ Example 5 240 80 95 Bad ◎ ◎ ◎ Example 6 120 0 35 Good ○ ◎ × Example 7 120 60 50 Good ◎ ◎ ◎ Example 8 120 110 70 Good ◎ ◎ ◎ Example 9 120 160 85 Bad ◎ ◎ ◎

As shown in Table 1 above, the addition amount of the phthalate ester in Examples 1 to 5 carried out while the addition amount of the aliphatic dibasic acid ester was fixed to 70 g and then the addition amount of the phthalate ester was added within the scope of the present invention. 4 to 4 can confirm that the spilled state storage stability initial erasure and long-term erasure property is good, but Example 1 added below the scope of the present invention can confirm that the spilled state and long-term erasure property is good, but the initial erasure property is very It can be confirmed that the poor, Example 5 carried out beyond the scope of the present invention is good storage stability, initial erasure and long-term erasure all but good viscosity can be confirmed that the outflow state is very poor.

In addition, in Examples 6 to 9, in which the amounts of the aliphatic dibasic acid esters were added within the scope of the present invention, in Examples 6 to 9, wherein the amount of the phthalate ester was fixed to 120 g and then the amount of the aliphatic dibasic acid ester was changed. 8 indicates that the spilled state storage stability initial erasing and long-term erasure are both good, but Example 6 added in less than the scope of the present invention can confirm that the spilled state and the initial erasing property is good, but long-term erasure is very poor As can be seen, Example 5 carried out beyond the scope of the present invention is good storage stability, initial erasing and long-term erasure all but good viscosity can be confirmed that the outflow condition is very poor.

As described above, the present invention provides a white ink composition for a marker pen and a method of manufacturing the same, which improves not only the initial erasing property of the white ink during writing, but also the late erasing property after drying, so that the eraser can be erased cleanly after writing on the writing board. It is a useful invention.

Claims (9)

Ordinary pigments based on titanium dioxide, polyvinyl butyral resins, polyvinylpyrrolidone, polyvinylacetate, vinyl acetate acrylic copolymer resins or vinyl resins selected from vinyl chloride vinyl acetate copolymer resins, ethyl alcohol, propyl alcohol, In a white ink composition for a marker pen composed of a solvent selected from isopropyl alcohol, a releasing agent, an isooctyl stearate, and an dioctyl adipate, the releasing agent is dimethyl phthalate, diethyl phthalate, dibutyl phthalate or dibutyl phthalate. Phthalate ester type selected from octyl phthalate, hexyl laurate, ethyl oleate, methyl laurate, butyl laurate, isomethyl stearate, methyl stearate, isooctadecyl stearate, methyl palmitate, methyl oleate, ethylol Elate, isooctadecyl palmitate, methyl my Monobasic acid esters of fatty acids with 6 or more carbon atoms and aliphatic alcohols, HLB (Hydrophile Lipophile Balance) selected from state, cetylisooctylate, isostearyllaurate, isopropyl myristate or oleyl-2-ethylhexylate 5 to 15 weight percent of molecular weight and at least one release agent selected from phosphate esters of polyoxyethylene alkyl nonylphenyl ether of 8 or less, polyoxyethylene alkyl ether of HLB 8 or less and polyoxyethylene alkyl ether of HLB 8 or less A white ink composition for a marker pen, characterized by mixing 5 to 10% by weight of an aliphatic dibasic acid ester-based release agent of 300 or more. delete delete delete The white ink composition for a marker pen according to claim 1, wherein a product of HLB 5.7 or HLB 7.5 is used according to the added mole number of ethylene oxide as polyoxyethylene alkyl nonylphenyl ether of HLB 8 or less. The polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oscyl ether, poly Use oxyethylene oleyl cetyl ether or polyoxyethylene cetyl stearyl ether, characterized in that the use of HLB 4.9, HLB 5, HLB 5.1, HLB 5.4, HLB 6.6, HLB 7.1 or HLB 8 depending on the number of moles of ethylene oxide added White ink composition for a marker pen. The white ink composition for a marker pen according to claim 1, wherein HLB 5.6, HLB 6.6, HLB 7 or HLB 7.1 is used as the phosphate ester of polyoxyethylene alkyl ether of HLB 8 or less according to the added mole number of ethylene oxide. The method according to claim 1, wherein aliphatic dibasic acid ester dihexanyl adipic acid, diethyl 2-ethylhexyl adipic acid, dioctylazelite, dioctylsebacate or dibutyl sebacate is used. A white ink composition for a marker pen, characterized in that the configuration. delete