CN115710443A - Degradable liquid chalk and preparation method thereof - Google Patents
Degradable liquid chalk and preparation method thereof Download PDFInfo
- Publication number
- CN115710443A CN115710443A CN202211426864.0A CN202211426864A CN115710443A CN 115710443 A CN115710443 A CN 115710443A CN 202211426864 A CN202211426864 A CN 202211426864A CN 115710443 A CN115710443 A CN 115710443A
- Authority
- CN
- China
- Prior art keywords
- parts
- titanium dioxide
- liquid chalk
- chalk
- byk
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a degradable liquid chalk and a preparation method thereof, wherein the preparation raw materials comprise the following components in parts by weight: 8-20 parts of film-forming resin, 8-30 parts of titanium dioxide, 0-3 parts of water-based pigment, 0.5-4 parts of emulsifier, 1-3 parts of dispersant, 1-2 parts of stabilizer, 0.5-2 parts of flatting agent, 1-3 parts of humectant, 33-76 parts of deionized water and 30-50 parts of solvent. The chalk disclosed by the invention has good writing feeling and good cleaning effect, is easier to erase after writing, has a good erasing effect on an uneven writing surface, can degrade film-forming substances dropped after erasing in biological or other forms, and can avoid plastic pollution.
Description
Technical Field
The invention relates to the technical field of teaching stationery, relates to the field of C09D13/00, and more particularly relates to degradable liquid chalk and a preparation method thereof.
Background
The chalk is used as an important teaching tool and can be frequently and massively used in the teaching process. The traditional chalk is mainly made of calcium sulfate, calcium carbonate and the like, a large amount of dust is generated when the chalk is erased, and further the harm is caused to the body health of a user and surrounding people, and the problem that the dust is generated in the using process is reduced or avoided by inventing the liquid chalk aiming at the problem.
The film forming agent is an important component of liquid chalk and has important influence on the performance of the liquid chalk, most of the film forming agents used in the reported documents are polymer resins, and due to the nondegradable property of the resins, the film forming agents can cause certain plastic pollution problem which is difficult to avoid after the resins are erased. For example, CN 101457055A discloses an aqueous liquid chalk, in which polyvinyl butyral is used as a film forming agent, which has certain elasticity but is not degradable, and is not easy to erase due to its good adhesion.
CN102020892A discloses a preparation method of water-erasing teaching ink, in which substances such as methyl cellulose and carboxymethyl cellulose are used as film-forming agents, and although the film-forming agents can be degraded in natural environment, the film-forming materials have no elasticity, and the cleaning effect after writing is not ideal, so that the teaching ink obtained by using the invention can be written after the blackboard is dried after water-erasing, and the efficiency is low.
Disclosure of Invention
Aiming at the problems, the invention discloses a degradable liquid chalk which is prepared from the following raw materials in parts by weight: 8-20 parts of film-forming resin, 8-30 parts of titanium dioxide, 0-3 parts of water-based pigment, 0.5-4 parts of emulsifier, 1-3 parts of dispersing agent, 1-2 parts of stabilizer, 0.5-2 parts of flatting agent, 1-3 parts of humectant, 33-76 parts of deionized water and 30-50 parts of solvent.
For example, the preparation raw materials comprise the following components in parts by weight: 10 parts of film-forming resin, 20 parts of titanium dioxide, 1.5 parts of emulsifier, 1.5 parts of dispersant, 1.5 parts of stabilizer, 1 part of flatting agent, 1 part of humectant, 63.5 parts of deionized water and 40 parts of solvent.
Such as: the preparation raw materials comprise the following components in parts by weight: 15 parts of film-forming resin, 10 parts of titanium dioxide, 2 parts of water-based pigment, 2 parts of emulsifier, 1 part of dispersant, 1 part of stabilizer, 1 part of flatting agent, 1 part of humectant, 67 parts of deionized water and 45 parts of solvent.
In one embodiment, the film-forming resin is selected from one or more of polycaprolactone, caprolactone-lactic acid copolymer, and polycitraconic acid octanediol ester.
Preferably, the film-forming resin is polycaprolactone.
Further preferably, the average molecular weight of the polycaprolactone is 60000-80000.
In one embodiment, the titanium dioxide is selected from one of rutile type titanium dioxide and anatase type titanium dioxide.
Preferably, the titanium dioxide is anatase titanium dioxide. Such as available from Touchuan, blue chemical, model number BA01-01.
The applicant finds that the added titanium dioxide, especially anatase titanium dioxide, has good shielding performance and color rendering property, is more clean to write, has more vivid color, has a band gap width larger than that of rutile titanium dioxide, and ensures that photoproduction electrons and holes are not easily compounded on the surface. However, the anatase titanium dioxide is not easy to disperse and the writing is not smooth enough, and in the experimental process of the applicant, the applicant creatively discovers that the average molecular weight of the film-forming resin, particularly polycaprolactone, is controlled to be 60000-80000, the writing feeling is good, and the cleaning effect is good. Polycaprolactone has elasticity, can be erased in a relatively large elastic film integral mode when being erased, the part in the pit can be pulled up together by an external resin film without breaking, so that the part in the pit can be erased completely, polycaprolactone has biodegradability, and the resin film can be degraded if flowing into the environment after being erased, so that plastic pollution to the environment can not be caused. When polycaprolactone average molecular weight is 60000-80000, the chain segment number that the molecular chain contains is more, in order to realize centrobaric migration, chain segment synergistic action many times that need accomplish, under the effect of emulsifier and solvent, can reduce solid, interfacial tension between the liquid, the dispersion of titanium white powder has been guaranteed to effective moist granule, when polycaprolactone average molecular weight is less, chain segment migration resistance is little, the smoothness is good, but write the film slowly, touch not dry handwriting yet when writing easily, the face is unclean, and when polycaprolactone average molecular weight is great, chain segment migration resistance is big, titanium white powder dispersion is inhomogeneous, write unsmoothly, easy disconnected china ink.
<xnotran> , C.I. 7,C.I. 11,C.I. 1,C.I. 1,C.I. 3,C.I. 12,C.I. 13,C.I. 14,C.I. 17,C.I. 35,C.I. 37,C.I. 42,C.I. 55,C.I. 95,C.I. 97,C.I. 98,C.I. 100,C.I. 110,C.I. 117,C.I. 120,C.I. 155,C.I. 1,C.I. 2,C.I. 3,C.I. 5,C.I. 7,C.I. 22,C.I. 23,C.I. 31,C.I. 38,C.I. 48,C.I. 1,C.I. 2 C.I. 15 , . </xnotran>
In one embodiment, the emulsifier is selected from one or more of polyvinyl alcohol, gelatin, span80, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, tween 80.
Preferably, the emulsifier is Tween80, CAS accession No.: 9005-65-6.
In one embodiment, the dispersant is selected from one or more of AEO-8, AEO-9, AEO-10, AEO-15, DISPERBYK-110, DISPERBYK-142, DISPERBYK-160, DISPERBYK-161, polyethylene glycol 200, polyethylene wax.
Preferably, the dispersant is DISPERBYK-110, such as available from Jinan san and chemical company, inc., model number DISPERBYK-110.
In one embodiment, the stabilizing agent is selected from one or more of sodium iminodisuccinate, sodium carboxymethylcellulose, and sodium alginate.
Preferably, the stabilizer is a compound of sodium carboxymethylcellulose and sodium alginate, and the mass ratio is (5-10): 1.
in one embodiment, the leveling agent is selected from one or more of hydrophobic polyurethane, polyacrylic acid and carboxymethyl cellulose, BYK-333, BYK-307, BYK-377, BYK-378, BYK-352, BYK-354, and BYK-358.
Preferably, the leveling agent is carboxymethyl cellulose.
In one embodiment, the humectant is selected from any one of propylene glycol, glycerin, ethylene glycol.
In one embodiment, the solvent is selected from one or more of dichloromethane, acetone, ethyl acetate.
Preferably, the solvent is dichloromethane.
In one embodiment, the mass ratio of the film-forming resin to the solvent is (1-3): (7-9).
The invention also discloses a preparation method of the degradable liquid chalk, which comprises the following steps:
(1) Dissolving the film-forming resin in a solvent to obtain a solution a; then adding the solution a into water containing an emulsifier and stirring at a high speed to obtain emulsion b; then evaporating the solvent in the solution b in a decompression or heating mode to obtain a remainder which is emulsion c;
(2) Adding titanium dioxide, a dispersing agent and pigment into water, and stirring at a high speed or grinding and dispersing to obtain a dispersion liquid;
(3) And (3) adding the dispersion liquid obtained in the step (2), a stabilizer and a humectant into the emulsion c obtained in the step (1), and uniformly dispersing in a high-shear disperser at a high speed to obtain the liquid chalk.
Has the beneficial effects that:
1. by adding the anatase titanium dioxide, the obtained liquid powder has good shielding performance and color rendering property, and is more clear for writing and more vivid in color.
2. By adding polycaprolactone and controlling the average molecular weight to be 60000-80000, the writing sense is good, the cleaning effect is good, erasing is easier after writing, the writing surface with unevenness is also well erasable, and the film-forming substances falling after erasing can be degraded in biological or other forms, so that plastic pollution can be avoided.
3. Under the action of the dispersing agent and the humectant, the pen point is kept wet, and the pen cannot be dried even if the pen cap is not covered for a long time, so that smooth writing cannot be realized.
Detailed Description
Example 1
The embodiment 1 discloses degradable liquid chalk, which is prepared from the following raw materials in parts by weight: 8 parts of polycaprolactone, 8 parts of titanium dioxide, 0.5 part of water-based pigment, 0.5 part of Tween80, 1 part of dispersing agent, 1 part of stabilizing agent, 0.5 part of flatting agent, 1 part of humectant, 33 parts of deionized water and 30 parts of dichloromethane.
The polycaprolactone is purchased from Shenzhen Guanghua Weber GmbH, model number is Esun600C, and average molecular weight is 60000.
The titanium dioxide is anatase titanium dioxide which is purchased from gallery and blue chemical engineering and has the model of BA01-01.
The water-based pigment is C.I. pigment red 7, and the CAS number is 6471-51-8.
The Tween80, CAS accession number: 9005-65-6.
The dispersant is DISPERBYK-110 which is purchased from Jinan san and chemical Co., ltd, and the model is DISPERBYK-110.
The stabilizer is a compound of sodium carboxymethylcellulose and sodium alginate, and the mass ratio of the stabilizer to the sodium alginate is 5:1.
the leveling agent is carboxymethyl cellulose which is purchased from Shandong national chemical Co., ltd, CAS number 9000-11-7.
The humectant is propylene glycol.
In another aspect, this embodiment 1 discloses a method for preparing the liquid chalk, which comprises the following steps:
step 1: firstly, 8 parts of polycaprolactone is taken and dissolved to obtain a polycaprolactone solution, and the polycaprolactone solution is dissolved in 30 parts of dichloromethane to obtain a solution a. Then the solution a was added to a beaker containing 0.5 parts of Tween80 and 23 parts of deionized water under high-speed stirring to obtain an emulsion b, and then methylene chloride was removed by reduced pressure to obtain an emulsion c.
Step 2: 8 parts of titanium dioxide, 0.5 part of water-based pigment and 1 part of dispersing agent are added into 10 parts of deionized water under the condition of high-speed stirring to obtain a dispersion liquid.
And step 3: and (3) adding the dispersion liquid obtained in the step (2), 1 part of stabilizing agent, 1 part of flatting agent and 1 part of humectant into the emulsion a, and stirring at a high speed for dispersing to obtain the liquid chalk.
Example 2
The embodiment 2 discloses a degradable liquid chalk, which comprises the following raw materials in parts by weight: 20 parts of polycaprolactone, 30 parts of titanium dioxide, 3 parts of water-based pigment, 4 parts of Tween80, 3 parts of dispersing agent, 2 parts of stabilizing agent, 2 parts of flatting agent, 3 parts of humectant, 76 parts of deionized water and 50 parts of dichloromethane.
The polycaprolactone is purchased from Shenzhen Guanghua Weber GmbH, model number is Esun600C, and average molecular weight is 60000.
The titanium dioxide is anatase titanium dioxide which is purchased from gallery and blue chemical engineering and has the model of BA01-01.
The water-based pigment is C.I. pigment red 7, and the CAS number is 6471-51-8.
The Tween80, CAS accession number: 9005-65-6.
The dispersant is DISPERBYK-110 which is purchased from Jinan san and chemical Co., ltd, and the model is DISPERBYK-110.
The stabilizer is a compound of sodium carboxymethylcellulose and sodium alginate, and the mass ratio of the stabilizer to the sodium alginate is 10:1.
the leveling agent is carboxymethyl cellulose which is purchased from Shandong national chemical Co., ltd, CAS number 9000-11-7.
The humectant is glycerol.
In another aspect, this embodiment 2 discloses a method for preparing the liquid chalk, which comprises the following steps:
step 1: firstly, 20 parts of polycaprolactone is taken and dissolved to obtain a polycaprolactone solution, and the polycaprolactone solution is dissolved in 50 parts of dichloromethane to obtain a solution a. Then the solution a is added into a beaker containing 4 parts of Tween80 and 55 parts of deionized water under high-speed stirring to obtain emulsion b, and then the dichloromethane is removed through decompression to obtain emulsion c.
And 2, step: adding 30 parts of titanium dioxide, 3 parts of water-based pigment and 3 parts of dispersing agent into 21 parts of deionized water under the condition of high-speed stirring to obtain a dispersion liquid.
And step 3: and (3) adding the dispersion liquid obtained in the step (2), 2 parts of stabilizing agent, 2 parts of flatting agent and 3 parts of humectant into the emulsion a, and stirring at a high speed for dispersing to obtain the liquid chalk.
Example 3
The embodiment 3 discloses a degradable liquid chalk, which comprises the following preparation raw materials in parts by weight: 15 parts of polycaprolactone, 10 parts of titanium dioxide, 2 parts of water-based pigment, 2 parts of Tween80, 1 part of dispersing agent, 1 part of stabilizing agent, 1 part of flatting agent, 1 part of humectant, 67 parts of deionized water and 45 parts of dichloromethane.
The polycaprolactone is purchased from Shenzhen Guanghua Weber GmbH, model number is Esun600C, and average molecular weight is 60000.
The titanium dioxide is anatase titanium dioxide which is purchased from gallery and blue chemical engineering and has the model of BA01-01.
The water-based pigment is C.I. pigment red 7, and the CAS number is 6471-51-8.
The Tween80, CAS accession number: 9005-65-6.
The dispersant is DISPERBYK-110 which is purchased from Jinan san and chemical Co., ltd, and the model is DISPERBYK-110.
The stabilizer is a compound of sodium carboxymethylcellulose and sodium alginate, and the mass ratio of the stabilizer to the sodium alginate is 8:1.
the leveling agent is carboxymethyl cellulose which is purchased from Shandong national chemical Co., ltd, CAS number 9000-11-7.
The humectant is propylene glycol.
In another aspect, this embodiment 3 discloses a method for preparing the liquid chalk, which comprises the following steps:
step 1: firstly, 15 parts of polycaprolactone is taken and dissolved to obtain a polycaprolactone solution, and the polycaprolactone solution is dissolved in 45 parts of dichloromethane to obtain a solution a. Then the solution a is added into a beaker containing 2 parts of Tween80 and 45 parts of deionized water under high-speed stirring to obtain emulsion b, and then dichloromethane is removed by reduced pressure to obtain emulsion c.
And 2, step: 10 parts of titanium dioxide, 2 parts of water-based pigment and 1 part of dispersing agent are added into 22 parts of deionized water under the condition of high-speed stirring to obtain a dispersion liquid.
And step 3: and (3) adding the dispersion liquid obtained in the step (2), 1 part of stabilizing agent, 1 part of flatting agent and 1 part of humectant into the emulsion a, and stirring at a high speed for dispersing to obtain the liquid chalk.
Example 4
This embodiment 4 discloses a degradable liquid chalk, which comprises, by weight, 10 parts of polycaprolactone, 20 parts of titanium dioxide, 1.5 parts of Tween80, 1.5 parts of a dispersant, 1.5 parts of a stabilizer, 1 part of a leveling agent, 1 part of a humectant, 63.5 parts of deionized water, and 40 parts of dichloromethane.
The polycaprolactone is purchased from Shenzhen Guanghua great industry GmbH, has the model number of Esun600C and has the average molecular weight of 60000.
The titanium dioxide is anatase titanium dioxide which is purchased from gallery and blue chemical engineering and has the model of BA01-01.
The Tween80, CAS accession number: 9005-65-6.
The dispersant is DISPERBYK-110 which is purchased from Jinan san and chemical Co., ltd, and the model is DISPERBYK-110.
The stabilizer is a compound of sodium carboxymethylcellulose and sodium alginate, and the mass ratio of the stabilizer to the sodium alginate is 8:1.
the leveling agent is carboxymethyl cellulose which is purchased from Shandong national chemical Co., ltd, CAS number 9000-11-7.
The humectant is propylene glycol.
In another aspect, this embodiment 4 discloses a method for preparing the liquid chalk, which includes the following steps:
step 1: firstly, 10 parts of polycaprolactone is taken and dissolved to obtain a polycaprolactone solution, and the polycaprolactone solution is dissolved in 40 parts of dichloromethane to obtain a solution a. Then the solution a was added to a beaker containing 1.5 parts of Tween80 and 40 parts of deionized water under high-speed stirring to obtain emulsion b, and then methylene chloride was removed by reduced pressure to obtain emulsion c.
Step 2: 20 parts of titanium dioxide and 1.5 parts of dispersing agent are added into 23.5 parts of deionized water under the condition of high-speed stirring to obtain dispersion liquid.
And 3, step 3: and (3) adding the dispersion liquid obtained in the step (2), 1.5 parts of stabilizing agent, 1 part of flatting agent and 1 part of humectant into the emulsion a, and stirring at a high speed for dispersing to obtain the liquid chalk.
Example 5
The difference between the embodiment 5 and the embodiment 3 is that the polycaprolactone is purchased from Shenzhen Guanhua Wei corporation, model number Esun1000C, and average molecular weight is 100000.
Example 6
The difference between the embodiment 6 and the embodiment 3 is that the polycaprolactone is purchased from Shenzhen Guanhua Wei corporation, model number Esun500C, and average molecular weight 50000.
Practice ofExample 7
The difference between this example 7 and example 3 is that the titanium dioxide is rutile titanium dioxide, which is purchased from the herboria python of the Sichuan dragon, and has the model number of R996.
And (4) performance testing:
1. writing test: the white board was written with the liquid chalk obtained in examples 1 to 7. The evaluation criteria were, a: clear handwriting, smooth writing, quick film forming and no scratch in the writing process; b: the handwriting is clearer, the writing is smoother, the film forming is quicker, and the handwriting is slightly scratched in the writing process; c: the writing is clearer, the writing is not smooth, the film forming is slow, and the scratch is serious in the writing process.
2. And (3) scrubbing test: and erasing the written note. Evaluation criteria, a: the writing brush is very clean, can write immediately and is clear and not scratched; b: the writing brush is cleaner, has slight writing traces, can write immediately and clearly, but has slight scratch; c: unclean, not write immediately, otherwise unclear.
| Writing test | Scrub test | |
| Example 1 | A | A |
| Example 2 | A | A |
| Example 3 | A | A |
| Example 4 | A | B |
| Example 5 | B | B |
| Example 6 | C | C |
| Example 7 | B | B |
Claims (10)
1. The degradable liquid chalk is characterized by comprising the following preparation raw materials in parts by weight: 8-20 parts of film-forming resin, 8-30 parts of titanium dioxide, 0-3 parts of water-based pigment, 0.5-4 parts of emulsifier, 1-3 parts of dispersant, 1-2 parts of stabilizer, 0.5-2 parts of flatting agent, 1-3 parts of humectant, 33-76 parts of deionized water and 30-50 parts of solvent.
2. The liquid chalk of claim 1, wherein the film-forming resin is selected from one or more of polycaprolactone, caprolactone-lactic acid copolymer, and poly (octylene glycol citrate).
3. The liquid chalk of claim 1, wherein the titanium dioxide is selected from one of rutile titanium dioxide and anatase titanium dioxide.
4. The liquid chalk of claim 1, wherein the emulsifier is selected from one or more of polyvinyl alcohol, gelatin, span80, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, tween 80.
5. The liquid chalk of claim 1, wherein the dispersant is selected from one or more of AEO-8, AEO-9, AEO-10, AEO-15, DISPERBYK-110, DISPERBYK-142, DISPERBYK-160, DISPERBYK-161, polyethylene glycol 200, polyethylene wax.
6. The liquid chalk of claim 1, wherein the stabilizer is selected from one or more of sodium iminodisuccinate, sodium carboxymethylcellulose, and sodium alginate.
7. The liquid chalk of claim 1, wherein the leveling agent is selected from one or more of butyl cellulose, hydrophobic polyurethane, polyacrylic acid and carboxymethyl cellulose, BYK-333, BYK-307, BYK-377, BYK-378, BYK-352, BYK-354 and BYK-358.
8. The liquid chalk of claim 1, wherein the humectant is selected from one of propylene glycol, glycerin, and ethylene glycol.
9. The liquid chalk of claim 1, wherein the solvent is selected from one or more of dichloromethane, acetone and ethyl acetate.
10. A method for preparing the liquid chalk according to any one of the claims 1-9, which is characterized by comprising the following steps:
(1) Dissolving film-forming resin in a solvent to obtain a solution a; then adding the solution a into water containing an emulsifier and stirring at a high speed to obtain emulsion b; then evaporating the solvent in the solution b in a decompression or heating mode to obtain a remainder which is emulsion c;
(2) Adding titanium dioxide, a dispersing agent and pigment into water, and stirring at a high speed or grinding and dispersing to obtain a dispersion liquid;
(3) And (3) adding the dispersion liquid obtained in the step (2), a stabilizer and a humectant into the emulsion c obtained in the step (1), and uniformly dispersing in a high-shear disperser at a high speed to obtain the liquid chalk.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211426864.0A CN115710443B (en) | 2022-11-14 | 2022-11-14 | Degradable liquid chalk and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211426864.0A CN115710443B (en) | 2022-11-14 | 2022-11-14 | Degradable liquid chalk and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115710443A true CN115710443A (en) | 2023-02-24 |
| CN115710443B CN115710443B (en) | 2023-09-26 |
Family
ID=85233141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211426864.0A Active CN115710443B (en) | 2022-11-14 | 2022-11-14 | Degradable liquid chalk and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115710443B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827514A (en) * | 2011-06-17 | 2012-12-19 | 厦门市绿科达环保科技有限公司 | Erasable white ink for dustless pen and preparation method |
| CN110818938A (en) * | 2019-12-06 | 2020-02-21 | 东莞市超智新材料有限公司 | Preparation method of matte writing film containing particles and matte writing film |
| CN113004744A (en) * | 2021-03-18 | 2021-06-22 | 广州天禧科技有限公司 | Washable biomaterial ink |
-
2022
- 2022-11-14 CN CN202211426864.0A patent/CN115710443B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827514A (en) * | 2011-06-17 | 2012-12-19 | 厦门市绿科达环保科技有限公司 | Erasable white ink for dustless pen and preparation method |
| CN110818938A (en) * | 2019-12-06 | 2020-02-21 | 东莞市超智新材料有限公司 | Preparation method of matte writing film containing particles and matte writing film |
| CN113004744A (en) * | 2021-03-18 | 2021-06-22 | 广州天禧科技有限公司 | Washable biomaterial ink |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115710443B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20100031683A (en) | Method for protecting substrates and removing contaminants from such substrates | |
| KR100737275B1 (en) | White Ink Composition for Nontoxic Marker Pen | |
| JP5984587B2 (en) | Aqueous pigment ink composition for writing board | |
| CN115710443A (en) | Degradable liquid chalk and preparation method thereof | |
| KR20090073826A (en) | Neutrality ink composition for marker pen and method of preparing the same | |
| KR100945060B1 (en) | Aqueous ink composition using food material for marker pen and method of preparing the same | |
| US20200062977A1 (en) | Writing, marking, and/or drawing liquid for capillary systems, especially for applicator implements having a capillary system, and applicator implement | |
| JP4632679B2 (en) | Shading coating solution | |
| CN113773702B (en) | Writing chalk and preparation method thereof | |
| KR20070092461A (en) | White ink composition for marker pen | |
| JPS5842672A (en) | Marking ink for writing board | |
| KR100875265B1 (en) | Nontoxic ink compositions and process for producing same | |
| JP3934427B2 (en) | Water-based erasable marking pen ink composition | |
| JPH08143807A (en) | Water-base ink composition | |
| JP6120734B2 (en) | Aqueous pigment ink composition for writing board | |
| KR101227060B1 (en) | Ink composition for board marker | |
| JP2013147524A (en) | Aqueous pigment ink composition | |
| JP7359678B2 (en) | Marking ink composition for writing boards | |
| CN114015285B (en) | Oil stain resistant ink, preparation process thereof and oil stain resistant writing pen | |
| JP7313680B2 (en) | Erasable ink composition for writing board | |
| JP2018203817A (en) | Oily marking pen ink composition for writing board and marking pen containing the same | |
| KR100364510B1 (en) | The white ink composite for marker-pen and its manufacturing method | |
| KR101460320B1 (en) | Environment friendly ink for marker pen | |
| JP6701036B2 (en) | Aqueous ink composition for writing board | |
| KR20090124483A (en) | Composition for coating white board and removing aqueous ink and preparing method the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |