CN113493630A - Environment-friendly water-soluble colored pencil lead and preparation method thereof - Google Patents
Environment-friendly water-soluble colored pencil lead and preparation method thereof Download PDFInfo
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- CN113493630A CN113493630A CN202010266021.3A CN202010266021A CN113493630A CN 113493630 A CN113493630 A CN 113493630A CN 202010266021 A CN202010266021 A CN 202010266021A CN 113493630 A CN113493630 A CN 113493630A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D13/00—Pencil-leads; Crayon compositions; Chalk compositions
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Abstract
The invention discloses an environment-friendly water-soluble colored pencil lead which comprises the following components in parts by weight: 40-60 parts of water-washed kaolin, 5-10 parts of emulsifier, 20-40 parts of tragacanth, 10-20 parts of natural mineral wax, 10-15 parts of acid-base indicator, 5-20 parts of pH regulator, 5-15 parts of carbon dioxide fluid and 4-12 parts of acetic acid. Has the advantages that: a large number of hydrogen bonds are arranged in the refill material, when the refill is dipped in water for drawing, the part positioned at the outermost layer of the refill is rapidly mixed with water energy, and the water-soluble effect of drawing is good.
Description
Technical Field
The invention relates to the technical field of colored pencil leads, in particular to an environment-friendly water-soluble colored pencil lead and a preparation method thereof.
Background
The water-soluble colour pencil is a colour pencil used for painting on watercolour paper, and features that it has the performance of ordinary colour pencil, can be dissolved in water to generate a watercolour picture, and is more convenient to use than watercolour. The water-soluble colored pencil is convenient to draw, the picture after drawing forming has better presentation effect, is not only suitable for the drawing requirement of children over 3 years old, but also suitable for the practical drawing and effect design drawing of general professionals, and has very good market selling prospect. When the existing colored pencil lead is used for drawing on drawing paper, the water-soluble effect is not ideal.
Disclosure of Invention
One of the purposes of the invention is to provide an environment-friendly colored pencil lead which is not easy to break and smooth to write.
In order to achieve the purpose, the invention adopts the technical scheme that: an environment-friendly water-soluble colored pencil lead comprises a composition treated by 5-15 parts by weight of carbon dioxide fluid, wherein the composition comprises the following components in parts by weight: 40-60 parts of water-washed kaolin, 5-10 parts of emulsifier, 20-40 parts of tragacanth, 10-20 parts of natural mineral wax, 10-15 parts of acid-base indicator, 5-20 parts of pH regulator and 4-12 parts of acetic acid.
Preferably, the emulsifier is hydroxyethyl methyl cellulose.
Preferably, the emulsifier is an anionic surfactant.
Preferably, the emulsifier is a fatty acid soap.
Preferably, the acid-base indicator is a flavophenolphthalein acid-base indicator.
Preferably, the pH adjuster is sodium bicarbonate.
The invention also aims to provide a preparation method of the environment-friendly colored pencil lead, which is simple in preparation method.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an environment-friendly water-soluble colored pencil lead comprises the following specific preparation steps:
1) acidifying modification: adding 40-60 parts by weight of washing kaolin into a reaction kettle, and then introducing 5-15 parts by weight of carbon dioxide fluid, wherein the carbon dioxide fluid is provided with an entrainer, the entrainer is 4-12 parts by weight of acetic acid, the reaction temperature is 40-50 ℃, the pressure is 18-22 MPa, and the reaction time is 20-40 min;
2) mixing: continuously adding 10-15 parts by weight of an acid-base indicator into a reaction kettle, wherein the reaction temperature is 40-50 ℃, the pressure is 18-22 MPa, and the reaction time is 10-20 min, then adding 5-10 parts by weight of an emulsifier, 20-40 parts by weight of tragacanth and 10-20 parts by weight of natural mineral wax, wherein the reaction temperature is 80-90 ℃, the pressure is 60-120 MPa, and the reaction time is 20-40 min;
3) color matching: adding 5-20 parts by weight of pH regulator into a reaction kettle for color matching, wherein the reaction temperature is 80-90 ℃, the pressure is 60-120 MPa, and the reaction time is 5-15 min, so as to obtain a mixture;
4) and (3) extrusion drying: and extruding the mixture into a pen core and drying.
Preferably, the adding amount of the water-washed kaolin in the acidification modification step is 45-55 parts by weight, the introducing amount of the carbon dioxide fluid is 7-10 parts by weight, and the adding amount of the acetic acid is 7-10 parts by weight.
Preferably, in the extrusion drying step, the drying temperature is 50-70 ℃, the relative humidity of air is 30-50%, and the drying time is 2-7 d.
Preferably, the air relative humidity in the extrusion drying step is 40-45%.
Compared with the prior art, the invention has the advantages that:
1. acetic acid is used for carrying out acid modification on the washed kaolin, and part of aluminum in the washed kaolin is migrated to form a certain acid active center. Due to the existence of the acidic active center, the acidic modified water-washed kaolin is connected with carbonic acid through hydrogen bonds, so that the acidic modified water-washed kaolin is uniformly distributed in a carbon dioxide fluid in the form of small particle suspended matters. The cresol red, the hydroxyethyl methyl cellulose, the astragalus glue and the natural mineral wax can be dissolved in the carbon dioxide supercritical fluid, and have better fluidity and transfer performance. Macroscopically, all substances in the mixed solution are uniformly mixed, and no particulate matters can be obviously observed by naked eyes. Microscopically, the two end groups of the hydroxyethyl methyl cellulose are chemically coupled with the modified water-washed kaolin and the modified tragacanth, and the cresol red is physically entangled, so that the interface adhesion of the modified water-washed kaolin is improved, a shear band needs to be generated on a section and a large amount of energy needs to be dissipated when the pen core is impacted and broken, and the aim of improving the flexural strength is fulfilled;
2. in the core pressing process, the pressure is changed into normal pressure, and the carbon dioxide solid is changed into a gas state from a solid state. In the strong air pressure enhancement process, the violent flowing of the air flow drives the mixture to be mixed, so that the uniformity of the mixture is further increased. The refill material has a large number of hydrogen bonds, when the refill is dipped in water for drawing, the part positioned at the outermost layer of the refill is quickly mixed with water energy, and the water-soluble effect of drawing is good;
3. along with the change of the air humidity, the color of the picture can also be changed, the picture is not in a static state any more, and different visual effects can be generated under different environments, so that the interestingness and the ornamental value of the drawing are greatly increased. The pencil lead material has a large number of hydrogen bonds, so that the water absorption of the pencil drawn on the paper is far larger than that of the paper, and water vapor in the air enters the pencil part on the paper firstly. Because the astragaloside and the natural mineral wax exist in the pencil lead, a water-blocking tape is formed at the boundary of the part coated with the pencil and the blank part on the paper. The water-blocking tape can effectively prevent pencils absorbing water vapor from diffusing.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
an environment-friendly water-soluble colored pencil lead comprises a composition treated by 5 parts by weight of carbon dioxide fluid, wherein the composition comprises the following components in parts by weight: 40 parts of washing kaolin, 5 parts of hydroxyethyl methyl cellulose, 20 parts of tragacanth, 10 parts of natural mineral wax, 10 parts of cresol red, 5-20 parts of sodium bicarbonate and 4 parts of acetic acid, wherein the washing kaolin is special washing kaolin sold by Hangzhou Chongke new material company Limited.
A preparation method of an environment-friendly water-soluble colored pencil lead comprises the following specific preparation steps:
1) acidifying modification: adding 40 parts by weight of water-washed kaolin into a reaction kettle, and then introducing 5 parts by weight of carbon dioxide fluid, wherein the carbon dioxide fluid is provided with an entrainer, the entrainer is 4 parts by weight of acetic acid, the reaction temperature is 40 ℃, the pressure is 18MPa, and the reaction time is 20 min. Acetic acid is used for carrying out acid modification on the washed kaolin, and part of aluminum in the washed kaolin is migrated to form a certain acid active center, so that the washed kaolin has equivalent activity of gas oil cracking reaction. The cracking reaction activity and the surface area of the catalyst are in positive correlation;
2) mixing: continuously adding 10 parts by weight of cresol red into a reaction kettle, wherein the reaction temperature is 40 ℃, the pressure is 18MPa, and the reaction time is 10min, then adding 5 parts by weight of hydroxyethyl methyl cellulose, 20 parts by weight of astragalus membranaceus gum and 10 parts by weight of natural mineral wax, wherein the reaction temperature is 80 ℃, the pressure is 60MPa, and the reaction time is 20 min. In the carbon dioxide supercritical fluid with the entrainer being acetic acid, the carbon dioxide and the acetic acid generate carbonic acid, and the acidic modified water-washed kaolin is connected with the carbonic acid through hydrogen bonds due to the existence of the acidic active center, so that the acidic modified water-washed kaolin is uniformly distributed in the carbon dioxide fluid in the form of small particle suspended matters. The cresol red, the hydroxyethyl methyl cellulose, the astragalus glue and the natural mineral wax can be dissolved in the carbon dioxide supercritical fluid, and have better fluidity and transfer performance. Macroscopically, all substances in the mixed solution are uniformly mixed, and no particulate matters can be obviously observed by naked eyes. Microscopically, the two end groups of the hydroxyethyl methyl cellulose are chemically coupled with the modified water-washed kaolin and the modified tragacanth, and the cresol red is physically entangled, so that the interface adhesion of the modified water-washed kaolin is improved, a shear band needs to be generated on a section and a large amount of energy needs to be dissipated when the pen core is impacted and broken, and the aim of improving the flexural strength is fulfilled;
3) color matching: adding 5-20 parts by weight of sodium bicarbonate into a reaction kettle for color matching, wherein the reaction temperature is 80 ℃, the pressure is 60MPa, and the reaction time is 5min to obtain a mixture; during toning, the pressure and temperature change, and the carbon dioxide fluid changes from a supercritical state to a solid. Changing the pH value of the mixture by using sodium bicarbonate to change the color of the mixture;
4) and (3) extrusion drying: and (3) pressing the mixed material on a core pressing machine (the tonnage of the core pressing machine is 150 tons) to obtain a pen core, controlling the diameter of the pressed pen core to be 1.0-8.0 mm, loading the pen core into a core drying tank, and heating and drying the pen core in a core drying furnace at the drying temperature of 50 ℃, the relative air humidity of 30% and the drying time of 2 d. In the core pressing process, the pressure is changed into normal pressure, and the carbon dioxide solid is changed into a gas state from a solid state. In the strong air pressure enhancement process, the violent flowing of the air flow drives the mixture to be mixed, so that the uniformity of the mixture is further increased. And simultaneously, the temperature is increased, and acetic acid in the mixture is taken away by the flowing of carbon dioxide airflow, so that no acetic acid residue exists in the pen core. A large number of hydrogen bonds are arranged in the refill material, when the refill is dipped in water for drawing, the part positioned at the outermost layer of the refill is rapidly mixed with water energy, and the water-soluble effect of drawing is good.
Example 2:
an environment-friendly water-soluble colored pencil lead comprises a composition treated by 15 parts by weight of carbon dioxide fluid, wherein the composition comprises the following components in parts by weight: 60 parts of washing kaolin, 10 parts of hydroxyethyl methyl cellulose, 40 parts of tragacanth, 20 parts of natural mineral wax, 15 parts of cresol red, 5-20 parts of sodium bicarbonate and 12 parts of acetic acid.
A preparation method of an environment-friendly water-soluble colored pencil lead comprises the following specific preparation steps:
1) acidifying modification: adding 60 parts by weight of washing kaolin into a reaction kettle, and then introducing 15 parts by weight of carbon dioxide fluid, wherein the carbon dioxide fluid is provided with 12 parts by weight of entrainer, the reaction temperature is 50 ℃, the pressure is 22MPa, and the reaction time is 40 min;
2) mixing: continuously adding 15 parts by weight of cresol red into a reaction kettle, wherein the reaction temperature is 50 ℃, the pressure is 22MPa, and the reaction time is 20min, then adding 10 parts by weight of hydroxyethyl methyl cellulose, 40 parts by weight of astragalus membranaceus gum and 20 parts by weight of natural mineral wax, wherein the reaction temperature is 80 ℃, the pressure is 60MPa, and the reaction time is 20 min;
3) color matching: adding 5-20 parts by weight of sodium bicarbonate into a reaction kettle for color matching, wherein the reaction temperature is 90 ℃, the pressure is 120MPa, and the reaction time is 15min, so as to obtain a mixture;
4) and (3) extrusion drying: and (3) pressing the mixed material on a core pressing machine (the tonnage of the core pressing machine is 150 tons) to obtain a pen core, controlling the diameter of the pressed pen core to be 1.0-8.0 mm, loading the pen core into a core drying tank, and heating and drying the pen core in a core drying furnace at the drying temperature of 70 ℃, the relative air humidity of 50% and the drying time of 3 d.
Example 3:
an environment-friendly water-soluble colored pencil lead comprises a composition treated by 10 parts by weight of carbon dioxide fluid, wherein the composition comprises the following components in parts by weight: 50 parts of washing kaolin, 7 parts of hydroxyethyl methyl cellulose, 32 parts of tragacanth, 15 parts of natural mineral wax, 13 parts of cresol red, 5-20 parts of sodium bicarbonate and 6 parts of acetic acid.
A preparation method of an environment-friendly water-soluble colored pencil lead comprises the following specific preparation steps:
1) acidifying modification: adding 50 parts by weight of water-washed kaolin into a reaction kettle, and then introducing 10 parts by weight of carbon dioxide fluid, wherein the carbon dioxide fluid is provided with an entrainer, the entrainer is 6 parts by weight of acetic acid, the reaction temperature is 45 ℃, the pressure is 20MPa, and the reaction time is 30 min;
2) mixing: continuously adding 13 parts by weight of cresol red into a reaction kettle, wherein the reaction temperature is 45 ℃, the pressure is 20MPa, and the reaction time is 20min, then adding 7 parts by weight of hydroxyethyl methyl cellulose, 32 parts by weight of astragalus membranaceus gum and 15 parts by weight of natural mineral wax, wherein the reaction temperature is 82 ℃, the pressure is 80MPa, and the reaction time is 34 min;
3) color matching: adding 5-20 parts by weight of sodium bicarbonate into a reaction kettle for color matching, wherein the reaction temperature is 82 ℃, the pressure is 80MPa, and the reaction time is 10min to obtain a mixture;
4) and (3) extrusion drying: and (3) pressing the mixed material on a core pressing machine (the tonnage of the core pressing machine is 150 tons) to obtain a pen core, controlling the diameter of the pressed pen core to be 1.0-8.0 mm, loading the pen core into a core drying tank, and heating and drying the pen core in a core drying furnace at 63 ℃ and with the relative air humidity of 45% for 5 d.
Example 4:
the difference from example 3 is that hydroxyethyl methylcellulose is replaced with fatty acid soap.
Example 5:
the difference from example 3 is that the acid-base indicator is phenolphthalein.
Example 6:
the difference from example 3 is that ammonium bicarbonate is replaced by disodium hydrogen phosphate.
Example 7:
the difference from example 3 is that no tragacanth was added.
Example 8:
an environment-friendly water-soluble colored pencil lead comprises the following components in parts by weight: 50 parts of washing kaolin, 7 parts of hydroxyethyl methyl cellulose, 15 parts of natural mineral wax, 13 parts of cresol red and 5-20 parts of sodium bicarbonate.
A preparation method of an environment-friendly water-soluble colored pencil lead comprises the following specific preparation steps:
1) adding 50 parts by weight of washing kaolin into a reaction kettle, controlling the temperature in the reaction kettle to be 45 ℃ and the pressure to be 20MPa, and placing the washing kaolin for 30min under the conditions;
2) then, 13 parts by weight of cresol red is continuously added into the reaction kettle, the temperature in the reaction kettle is kept at 45 ℃, the pressure is kept at 20MPa for 20min, then 7 parts by weight of hydroxyethyl methyl cellulose and 15 parts by weight of natural mineral wax are added, the reaction temperature is 82 ℃, the pressure is 80MPa, and the reaction time is 34 min;
3) adding 5-20 parts by weight of sodium bicarbonate into a reaction kettle for color matching, wherein the reaction temperature is 82 ℃, the pressure is 80MPa, and the reaction time is 10min to obtain a mixture;
4) and (3) extrusion drying: and (3) pressing the mixed material on a core pressing machine (the tonnage of the core pressing machine is 150 tons) to obtain a pen core, controlling the diameter of the pressed pen core to be 1.0-8.0 mm, loading the pen core into a core drying tank, and heating and drying the pen core in a core drying furnace at 63 ℃ and with the relative air humidity of 45% for 5 d.
Example 9:
the difference from example 8 is that no tragacanth was added.
Example 10: pen core Performance measurement of examples 3 to 9
1) Measurement of flexural Strength:
the pen cores of examples 3 to 9 were dipped in water and then measured for flexural strength (n: 100) according to JIS-S-6005-2007.
2) Measurement of drawn line color development:
the pen cores of examples 3 to 9 were dipped in water using the line drawing instrument specified in JIS-S-6005-2007, and drawn to obtain a chromaticity (a) in the Lab value measured using the same spectrocolorimeter as that used in the concentration measurement method2+b2)1/2Shown (n ═ 100).
3) Determination of Water-soluble Effect:
the pen cores of examples 3 to 9 were dipped in water to draw pictures, and the water-soluble effect was visually observed.
4) Writing performance
The pen core of embodiment 3-9 was dipped in water to perform the drawing, and the writing performance was experienced.
The measurement results are shown in table 1:
as can be seen from table 1, by comparing example 3 and example 7 (or example 8 and example 9), the water-soluble colored pencil lead prepared without adding tragacanth had a decrease in flexural strength but not a high decrease, the water-soluble effect changed from excellent to good (or from poor to extremely poor) and the writing effect also changed from excellent to good, indicating that tragacanth has an effect on flexural strength but not a large effect, and that tragacanth plays a relatively important role in the water-soluble effect and the writing effect. As can be seen from comparison of example 3 and example 8, the water-soluble colored pencil lead prepared without adding the carbon dioxide supercritical fluid and acetic acid had a greatly reduced flexural strength, a greatly impaired effect on color development of drawn lines, a change from excellent to poor water-soluble effect and a change from excellent to poor writing effect, indicating that the carbon dioxide supercritical fluid and acetic acid play a crucial role in flexural strength, color development of drawn lines, water-soluble effect and writing effect.
Example 11:
measurement of the change in color with air humidity:
the pen cores of examples 3 to 9 were dipped in water using the line drawing instrument specified in JIS-S-6005-2007, and after drying the pictures, the air humidity was adjusted (from 20% to 70%) so as to obtain the chromaticity (a) in the Lab value measured using the spectrocolorimeter same as that used in the concentration measurement method2+b2)1/2Shown (n ═ 100). As shown in table 2, the chromaticity values corresponding to different humidities were recorded, and the chromaticity change due to the change in air humidity was calculated.
TABLE 2 determination of the color as a function of the humidity of the air
As can be seen from Table 2, the color of the picture changes with the change of the air humidity, and the picture is not in a static state any more, but can generate different visual effects in different environments, thereby greatly increasing the interest and the ornamental value of the drawing. The pencil lead material has a large number of hydrogen bonds, so that the water absorption of the pencil drawn on the paper is far larger than that of the paper, and water vapor in the air enters the pencil part on the paper firstly. Because the astragaloside and the natural mineral wax exist in the pencil lead, a water-blocking tape is formed at the boundary of the part coated with the pencil and the blank part on the paper. The water-blocking tape can effectively prevent pencils absorbing water vapor from diffusing.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. An environment-friendly water-soluble colored pencil lead is characterized by comprising a composition treated by 5-15 parts by weight of carbon dioxide fluid, wherein the composition comprises the following components in parts by weight: 40-60 parts of water-washed kaolin, 5-10 parts of emulsifier, 10-20 parts of natural mineral wax, 10-15 parts of acid-base indicator and 5-20 parts of pH regulator.
2. The environment-friendly water-soluble colored pencil lead as claimed in claim 1, further comprising 4-12 parts by weight of acetic acid.
3. The environment-friendly water-soluble colored pencil lead according to claim 2, further comprising 20-40 parts by weight of tragacanth.
4. The environmentally friendly water-soluble colored pencil lead of claim 3, wherein the emulsifier is a fatty acid soap.
5. The environment-friendly water-soluble colored pencil lead according to claim 3, wherein the acid-base indicator is a flavophenolphthalein acid-base indicator.
6. The environmentally friendly water soluble colored pencil lead of claim 3, wherein the pH regulator is sodium bicarbonate.
7. A preparation method of an environment-friendly water-soluble colored pencil lead is characterized by comprising the environment-friendly water-soluble colored pencil lead according to any one of claims 3 to 6, and the preparation method comprises the following specific steps:
1) acidifying modification: adding 40-60 parts by weight of washing kaolin into a reaction kettle, and then introducing 5-15 parts by weight of carbon dioxide fluid, wherein the carbon dioxide fluid is provided with an entrainer, the entrainer is 4-12 parts by weight of acetic acid, the reaction temperature is 40-50 ℃, the pressure is 18-22 MPa, and the reaction time is 20-40 min;
2) mixing: continuously adding 10-15 parts by weight of an acid-base indicator into a reaction kettle, wherein the reaction temperature is 40-50 ℃, the pressure is 18-22 MPa, and the reaction time is 10-20 min, then adding 5-10 parts by weight of an emulsifier, 20-40 parts by weight of tragacanth and 10-20 parts by weight of natural mineral wax, wherein the reaction temperature is 80-90 ℃, the pressure is 60-120 MPa, and the reaction time is 20-40 min;
3) color matching: adding 5-20 parts by weight of pH regulator into a reaction kettle for color matching, wherein the reaction temperature is 80-90 ℃, the pressure is 60-120 MPa, and the reaction time is 5-15 min, so as to obtain a mixture;
4) and (3) extrusion drying: and extruding the mixture into a pen core and drying.
8. The method for preparing the environment-friendly water-soluble colored pencil lead according to claim 7, wherein the amount of the water-washed kaolin added in the step of acidification modification is 45-55 parts by weight, the amount of the carbon dioxide fluid introduced is 7-10 parts by weight, and the amount of the acetic acid added is 7-10 parts by weight.
9. The method for preparing the environment-friendly water-soluble colored pencil lead according to claim 7, wherein in the extrusion drying step, the drying temperature is 50-70 ℃, the relative humidity of air is 30-50%, and the drying time is 2-7 d.
10. The method for preparing the environment-friendly water-soluble colored pencil lead according to claim 9, wherein the air relative humidity in the extrusion drying step is 40-45%.
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| CN202010266021.3A CN113493630A (en) | 2020-04-07 | 2020-04-07 | Environment-friendly water-soluble colored pencil lead and preparation method thereof |
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| CN202010266021.3A CN113493630A (en) | 2020-04-07 | 2020-04-07 | Environment-friendly water-soluble colored pencil lead and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023248969A1 (en) * | 2022-06-24 | 2023-12-28 | 三菱鉛筆株式会社 | Pencil lead and manufacturing method for same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000053871A (en) * | 1998-08-07 | 2000-02-22 | Toray Ind Inc | Resin composition and its preparation |
| US6056810A (en) * | 1997-12-18 | 2000-05-02 | A. W. Faber-Castell | Colored lead pencil |
| CN207221921U (en) * | 2017-09-08 | 2018-04-13 | 山西琚丰高岭土有限公司 | A kind of kaolinic supercritical carbon dioxide Aided Modification equipment |
-
2020
- 2020-04-07 CN CN202010266021.3A patent/CN113493630A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6056810A (en) * | 1997-12-18 | 2000-05-02 | A. W. Faber-Castell | Colored lead pencil |
| JP2000053871A (en) * | 1998-08-07 | 2000-02-22 | Toray Ind Inc | Resin composition and its preparation |
| CN207221921U (en) * | 2017-09-08 | 2018-04-13 | 山西琚丰高岭土有限公司 | A kind of kaolinic supercritical carbon dioxide Aided Modification equipment |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023248969A1 (en) * | 2022-06-24 | 2023-12-28 | 三菱鉛筆株式会社 | Pencil lead and manufacturing method for same |
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