WO2001098417A1 - Mine de crayon de couleur non cuite - Google Patents
Mine de crayon de couleur non cuite Download PDFInfo
- Publication number
- WO2001098417A1 WO2001098417A1 PCT/JP2001/005237 JP0105237W WO0198417A1 WO 2001098417 A1 WO2001098417 A1 WO 2001098417A1 JP 0105237 W JP0105237 W JP 0105237W WO 0198417 A1 WO0198417 A1 WO 0198417A1
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- WIPO (PCT)
- Prior art keywords
- pencil lead
- fired
- plate
- alumina
- water
- Prior art date
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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
Definitions
- the present invention relates to a non-fired color pencil lead, and more particularly, to a non-fired color pencil lead having improved core moldability and coloring property at the time of drawing, and in particular, improved bending strength of the core. It relates to a non-fired colored pencil lead that can be erased with an eraser. Furthermore, non-fired colored pencil cores that have improved water resistance, are easy to perform quality control work, do not contain asbestos like conventional talc, and maintain excellent safety It is also about. Background art
- a conventional non-baked colored pencil lead simultaneously contains, in its composition, a water-soluble resin as a binder, and a box and / or an oil or fat. For this reason, since the water-soluble resin as the binder and the wax, Z, or fats and oils are difficult to uniformly mix at the compounding stage, there is a problem that the moldability is poor. In addition, since wax and / or fats and oils impede the binding force of the water-soluble resin during the core molding process, there is a problem that the bending strength when used as a colored pencil core is low. In particular, in order to obtain colored pencils whose handwriting can be erased with an eraser, it is necessary to use oily substances that are liquid at room temperature as waxes and oils or fats and oils. The problem described above becomes prominent.
- a non-fired colored pencil lead blended with a sorbitan fatty acid ester-based surfactant has been conventionally proposed in order to increase the coloring amount without lowering the bending strength of the lead (Japanese Patent Laid-Open No. 51- 1 5 3 0 2 3).
- Japanese Patent Laid-Open No. 51- 1 5 3 0 2 3 Japanese Patent Laid-Open No. 51- 1 5 3 0 2 3.
- a non-fired colored pencil core in which a surfactant such as a sorbitan fatty acid ester and a polyoxyethylene sorbitan fatty acid ester is blended (Japanese Patent Application Laid-Open No. 200-200). 0—7 9 7 6).
- the non-fired colored pencil lead containing a surfactant has a hydrophilic surfactant, and the strength of the lead under high humidity can be improved when the surfactant is a hydrophilic surfactant.
- the water resistance of the non-fired pencil lead is not always sufficient because the water resistance of the handwriting decreases. Therefore, non-baked colored pencil cores containing a hydrophilic surfactant are often not suitable for applications requiring water resistance.
- the non-fired colored pencil lead containing talc as a constitutional material can improve the bending strength because the scaly talc is texture-oriented in one direction, and can also improve the bending strength. Due to the physical properties of talc, such as abrasion and slipperiness, it is possible to obtain the characteristics of a non-fired colored pencil lead such as good drawing quality.
- talc is a natural mineral and may contain asbestos, which has been pointed out in recent years as a potential source of adverse effects on the human body, depending on where it is collected from. .
- a non-fired colored pencil lead made of a building material that does not require such work has the same amount of coloring (coloring property) as before, and has physical properties such as bending strength and good drawing taste. It is necessary to prepare.
- the present invention includes a coloring material, a binder, a body material, wax and Z or fats and oils, and a hydrophilic surfactant, in order to secure good moldability and bending strength of the core, which are the above-mentioned problems.
- a non-fired colored pencil lead containing a polyoxyethylene adduct of fats and oils as a hydrophilic surfactant is employed.
- the hydrophilic surfactant a polyoxyethylene adduct of at least one of fats and oils among polyoxyethylene castor oil and polyoxyethylene hardened castor oil is preferable.
- the non-calcined pencil lead containing a polyoxyethylene adduct of fats and oils as a hydrophilic surfactant when containing wax and / or fats and oils, in particular, converts the oily substance which is liquid at ordinary temperature into wax and fat. Even if it is contained as Z or fats and oils, the core has good moldability and bending strength.
- non-fired colored pencil lead containing coloring material, binder, extender, wax and Z or fats and oils, and a hydrophilic surfactant, and a water-repellent substance are used to make the lead strong and handy under high humidity. Can be improved in water resistance.
- the most preferred embodiment of the non-fired colored pencil lead further containing a water-repellent substance according to the present invention includes, but is not limited to, coloring materials, binders, extenders, wax and Z or fats and oils, hydrophilic surfactants
- non-calcined color lead brush core containing plate-like alumina and / or plate-like alumina hydrate is molded. Since the plate-like alumina and Z or plate-like alumina hydrate are oriented in one direction, it exhibits the same bending strength as a conventional non-fired colored pencil lead using talc, and the assembling material does not contain asbestos No firing because no confirmation work is required
- the quality control work, which is part of the manufacture of colored pencil leads, is simple, and it does not contain asbestos, unlike conventional talc, and is excellent in safety.
- the non-fired colored pencil lead of the present invention contains a coloring material, a binder, a body material, wax and / or fats and oils, and a hydrophilic surfactant, and contains a polyoxyethylene adduct of oils and fats as a hydrophilic surfactant. It is.
- hydrophilic surfactant used in the present invention known hydrophilic surfactants can be used, but those which do not inhibit the coloring of colored pencils are preferable.
- hydrophilic surfactant a polyoxyethylene adduct of fats and oils is preferable when good moldability and bending strength of the core are required.
- Known hydrophilic surfactants may be used in combination of two or more. Further, in order to further improve the compatibility between the binder contained in the present invention and the box, Z or fats and oils, the hydrophilic surfactant can be used together with the lipophilic surfactant.
- the fats and oils in the above-mentioned polyoxetylene adduct of fats and oils are esters of fatty acids and glycerin, but the fats and oils referred to here can be used irrespective of nature or synthesis.
- vegetable fats and oils include cottonseed oil, coconut oil, castor oil, olive oil, soybean oil, safflower oil, jojoba oil, sunflower oil and the like.
- the above-mentioned hard oil can be used as the vegetable natural fats and oils.
- Animal natural oils and fats include, for example, beef tallow, whale oil and fish oil.
- the above-mentioned hardened oil can also be used for animal natural fats and oils.
- polyoxyethylene castor oil or polyoxyethylene hardened castor oil is particularly preferred. Therefore, as a preferred embodiment of the present invention, it is important to use a non-sintered colored pencil lead containing at least one of polyoxyethylene castor oil and polyoxyethylene hardened castor oil.
- polyoxyethylene castor oil or the polyoxyethylene hardened castor oil polyoxyethylene castor oil (HLB: 10.0) in which the number of added moles n of ethylene oxide chains is 36 mol is used. It is most suitable to make the water-soluble resin, which is the binder contained in the non-baked colored pencil lead, and the wax and / or the fats and oils more evenly mixed.
- the content of the polyoxyethylene adduct of the above fats and oils is 0.1 to 10.0% by weight based on the total amount of the raw material composition (solid content). %, Preferably 2.5-3.5% by weight.
- the content of the above hydrophilic surfactant is less than 0.1% by weight, the content is too small.
- the molding of the lead is required.
- the bending strength of the core is low even if it is molded, and the practicality is reduced.
- the content of the hydrophilic surfactant exceeds 10.0% by weight, the water resistance decreases.
- any known binder can be used, but a binder having strength and rigidity is desirable.
- CMC sodium carboxymethylcellulose sodium
- CMC ammonium carboxymethylcellulose ammonium
- methylcellulose hydroxyethylcellulose
- nitrocellulose polyvinyl alcohol
- bentonite and other known water-soluble compounds
- a water-insoluble polymer compound can be used regardless of whether it is synthesized or natural. These can be used alone or in combination.
- a known water-soluble resin or a known clay mineral is used.
- a solvent such as water may be added to use as a binder solution.
- the content of the binder is 2 to 15% by weight, preferably 3 to 10% by weight, based on the total amount of the raw material composition (solid content).
- the amount of the binder is more than 15% by weight of the total amount of the raw material composition (solid content)
- the drawing quality is deteriorated
- the abrasion hardly occurs, and the practicality is deteriorated.
- it is blended in less than 2% by weight of the total amount of the raw material composition (solid content)
- it is difficult to form a core and it is difficult to obtain the strength as a pencil lead.
- waxes and fats and oils used in the present invention known waxes and fats and oils can be used regardless of whether they are solid or liquid at normal temperature, as long as they do not inhibit the color development by the colorant.
- Wax and Z or fats and oils can be used alone or in combination irrespective of synthetic or natural.
- the non-fired color pencil lead of the present invention when used as a non-fired color pencil lead that can be erased with an eraser, it is preferable to use, as the oil and fats, the oils and fats that are liquids at room temperature.
- the above-mentioned hydrophilic surfactant causes the oily substance that is liquid at normal temperature to exist without loosing the binding force of the binder.
- the handwriting attached to the paper surface is a non-fired colored pencil lead that can be erased with an eraser because the colorant particles and extender particles covered with the binder are formed as a group with a liquid oily substance at room temperature. be able to.
- PEX, Z or fats and oils are blended to give coloring and coloring, etc., but their content is 1 to 20% by weight based on the total amount of the raw material composition (solid content). It is preferably 3 to 10% by weight. When the amount is less than 1% by weight, the drawing taste and the coloring property are deteriorated. When the amount exceeds 20% by weight, it is difficult to obtain the strength as a pencil lead.
- the above wax, Z or fats and oils when they are blended, they may be blended as a ⁇ / W emulsion.
- the surfactant used in the O / W emulsion is not particularly limited.
- the hydrophilic surfactant and the wax and Z or fats and oils are preliminarily mixed and this mixture is blended.
- the colorant used in the present invention is not particularly limited, and any of commonly used inorganic pigments and organic pigments having a coloring effect and beautiful coloring can be used alone or in combination. it can.
- flake pigments such as pearl pigments, metal powder pigments, and glass flake pigments can also be used.
- the content is 0.1 to 20% by weight, preferably 1 to 15% by weight, based on the total amount of the raw material composition (solid content). If the above content is more than 20% by weight of the total amount of the raw material composition (solid content), If it is, the drawing taste will be reduced, and it will be difficult to obtain the strength as a pencil lead. On the other hand, if the content is less than 1% by weight of the total amount of the raw material composition (solid content), color development is not always sufficient if the content is less than 0.1% by weight.
- the non-baked color pencil lead of the present invention when used for applications requiring water resistance in handwriting, it is preferable to further contain a water-repellent substance.
- a water-repellent substance By including a water-repellent substance in the non-fired color pencil lead, even if the non-fired color pencil lead contains a hydrophilic surfactant, the moisture resistance (moisture resistance) of the lead and the water resistance of the handwriting can be ensured. it can.
- the water repellent substance a known water repellent may be used.
- water-repellent substance those in which the water-repellent substance is dispersed in an aqueous medium are preferable because the water-repellent substance can be finely present in the molded body of the non-sintered color pencil lead, so that the strength becomes stronger.
- a surfactant-free ow emulsion is more preferable, and in particular, it is most preferable to use a paraffin emulsion.
- the o / w emulsion containing no surfactant is mixed as a raw material, only the water-repellent substance, which is an oily component, remains as an active component after drying in the manufacturing process. And water resistance of the handwriting.
- the above water-repellent substance particularly ⁇ zw emulsion containing no surfactant, especially paraffin wax emulsion, is used as an active ingredient (water-repellent component or wax component) in an amount of 0.1 to the total amount of the raw material composition (solid content). ⁇ 5.0 wt% is preferred, with the optimal range being 1.5-4.5 wt%. If the water-repellent substance is less than 0.1% by weight with respect to the total amount of the raw material composition (solid content), the water resistance and the moisture resistance decrease, and if it exceeds 5.0% by weight, moldability, bending strength and eraser are used. Erasability decreases.
- any known extender can be used, but an extender that does not impair coloring and coloring is preferable.
- talc, kaolin, calcium carbonate, alumina silicate, muscovite, magnesium carbonate, silica and the like can be exemplified. These can be appropriately selected from these and used alone or in combination.
- kaolin and muscovite are most suitable as constitution materials.
- the content of the extender is Raw material composition (solid content): 60 to 80% by weight, preferably 65 to 75% by weight of the total amount. If the blending amount of the extender is more than 80% by weight of the total amount of the raw material composition (solid content), the moldability into a core shape is reduced. (Plate alumina and / or plate alumina hydrate)
- the non-fired color pencil lead of the present invention may contain plate-like alumina and Z or plate-like alumina hydrate as part or all of the constitutional material contained in the non-fired color pencil lead.
- plate-like alumina and Z or plate-like alumina hydrate instead of talc as part or all of the body material, plate-like alumina and Z or plate-like alumina hydrate include asbestos Since there is no need to worry and there is no need for complicated quality control work in the production performed when talc is used, the non-fired colored pencil lead of the present invention is excellent in safety and workability.
- the above-mentioned plate-like alumina and / or plate-like alumina hydrate is not particularly limited, but is a non-fired color pencil lead containing plate-like alumina and / or plate-like alumina hydrate which is a constitutional material.
- any material may be used as long as it exhibits a bending strength and drawing quality that are at least as high as those obtained when talc is contained in the core of a non-baked color pencil.
- a non-fired colored pencil lead containing plate-like alumina and / or 7 or plate-like alumina hydrate as a constitutional material is formed by forming plate-like alumina and Z or plate-like alumina hydrate in one direction during molding, similar to conventional talc.
- the non-fired color pencil lead of the present invention can be obtained by using both a plate-like alumina and / or a plate-shaped alumina hydrate and a safe material other than talc as the filler contained in the non-fired color pencil lead. It can be used as a non-fired colored pencil lead having safety.
- the plate-like alumina and Z or plate-like alumina hydrate may be in the form of a hexagonal plate or a disk as long as the particles in the powder are substantially plate-like.
- the particles in the powder of the alumina or hydrated alumina hydrate may not have a uniform shape due to the pulverization.
- the above plate-like alumina and Z or plate-like alumina hydrate are particularly limited as polymorphs. Rather than shall, the plate-like alumina alpha-Alpha 1 2 0 3, even ⁇ _ 1 2 ⁇ 3 and 0 _ eight 1 2 ⁇ 3 alone or a mixture of selected from the group consisting of well, the plate-like alumina hydrate a- A 1 2 O 3 hydrate, r- A 1 2 ⁇ trihydrate and 0- A 1 2 ⁇ 3 alone selected from the group consisting of hydrate or it may be filed with a mixture of two or more, but only an a 1 2 0 3 ratio tabular alumina, be a plate-like alumina hydrate Gahi one a 1 2 ⁇ 3 Taukappa hydrate, surface Since there are no holes, a relatively large amount of plate-like alumina can be used during the compounding of the non-fired colored pencil lead without deteriorating the strength, and it is preferable because the dispersion is easy.
- plate-like alumina hydrate When plate-like alumina hydrate is used, it may be plate-like alumina monohydrate, plate-like alumina dihydrate or plate-like alumina trihydrate.
- the plate-like alumina and / or plate alumina hydrate is not intended to be particularly limited constant as manufacturing method, for example, Q - A 1 2 0 3 and 7 or 0 - eight 1 2 ⁇ 3 hydrate If it is a product, aluminum hydroxide obtained by the Bayer method is subjected to hydrothermal synthesis treatment using a crystal inhibitor such as Na 2 SiO 3 after adjusting the particle size (350 ° C. or more, 200 atm or less) It can be obtained by any method.
- a crystal inhibitor such as Na 2 SiO 3
- the particle size of the plate-like alumina and / or plate-like alumina hydrate is not particularly limited, but those having a particle size of 0.1 to 20 m can be suitably used.
- the aspect ratio of the particles of the plate-like alumina and / or plate-like alumina hydrate is not particularly limited, but the plate-like alumina and Z or plate-like alumina water having an average value of 2 to 50 is used.
- a powder of a Japanese product can be suitably used. Note that the aspect ratio is the average diameter (am) of the particles divided by the thickness ( ⁇ ).
- the above-mentioned plate-like alumina and / or plate-like alumina hydrate are used alone, but may be mixed.
- the content of platy alumina and / or platy alumina hydrate is such that the combined content of platy alumina and platy alumina hydrate is based on the total solid content of the raw material composition of the unfired pencil lead.
- the content is preferably 2 to 85% by weight, and more preferably 5 to 80% by weight.
- the coloring property is reduced.
- the plate-like alumina and Z or plate-like alumina hydrate may be made of one of plate-like alumina and plate-like alumina hydrate alone, and may have a shape and particle size. It may be composed of a plurality of types having different compositions and the like, or may be a mixture of a plurality of types of plate-like alumina and plate-like alumina hydrate.
- additives such as an antiseptic agent, a fungicide, a lubricant, etc., as necessary, in addition to a solvent such as water or alcohol for dissolving the water-soluble resin, may be used. Can be contained.
- the method for producing a non-fired colored pencil lead of the present invention can be basically prepared by mixing the above components and molding into a specific shape.
- the raw materials are kneaded using a kneader (such as a kneader), and water is appropriately evaporated at 60 ° C for 4 hours while kneading.
- a kneader such as a kneader
- water is appropriately evaporated at 60 ° C for 4 hours while kneading.
- a plunger-type extruder for example, into a 3 mm diameter pencil lead, and dried (for example, at 70 ° C for 12 hours). can do.
- a non-fired colored pencil lead can be obtained by further impregnating the molded product with fats and oils and resins.
- Example 10 13 and Comparative Example 36 a non-fired colored pencil lead was obtained by the following production method using the raw materials and formulations shown in Table 2.
- a previously prepared mixture of the hydrophilic surfactant and the fats and oils or Z or wax was added and kneaded, and further, a water-repellent substance was added and kneaded.
- the blending amount of each raw material in the raw material composition in Table 2 is expressed as a solid content in% by weight, and water was used as a solvent.
- the components in Tables 1 and 2 are as follows.
- Waxes and / or fats and oils liquid paraffin (B-Showa Shell Sekiyu K.K., trade name: Orange Oil)
- Lipophilic surfactant Sorbitan sesquioleate (Nikko Chemicals, trade name "SO-15")
- the bending strength was measured according to JIS-S-6005. That is, a load is applied to the center of the unfired color pencil lead supported between both fulcrums, the load when the unfired color pencil lead breaks is measured, and the value is substituted into the calculation formula defined in the JIS test method and the numerical value is substituted. I asked. The following criteria were used to evaluate the values.
- the bending strength after storage at 80% humidity was measured and evaluated in the same manner as in the above bending strength test after storage for 6 hours in an environment at 80% humidity.
- the coloring amount was calculated by calculating the difference between the weight of the core after writing 25 m and the weight of the core before writing, and evaluated according to the following criteria.
- ⁇ Coloring amount superior to that of a conventional and practically used colored pencil.
- ⁇ Coloring amount similar to that of a conventional color pencil that is practically used.
- X The amount of coloring is inferior to that of a conventionally used colored pencil.
- Proposal X indicates that 40% or more of the molded cores were broken apart during molding or drying, and ⁇ , 35 indicates that the broken cores were less than 40% to 35% or more. Those with less than 30% or more were rated as ⁇ , and those with less than 30% were rated as ⁇ .
- the colored pencils of Examples and Comparative Examples were used to write on drawing paper, and the erasability of the eraser was evaluated according to the following criteria.
- the eraser used was a product name “RC_60” manufactured by Rabbit Corporation.
- the non-fired colored pencil cores of Examples 1, 2, and 5 to 9, which are non-fired color pencil cores containing polyoxyethylene adducts of fats and oils as surfactants, are hydrophilic surfactants.
- the bending strength and moldability were higher than practical levels and were good.
- the unfired colored pencil cores of Examples 1, 2, and 6 had bending strength and moldability of the core.
- the non-fired colored pencil cores of Examples 5 and 7 have only improved moldability due to the difference in the type and amount of the water-repellent substance. It was confirmed that only the moldability of the baked colored pencil lead was improved due to the large amount of the hydrophilic surfactant.
- the non-baked colored pencil cores of Examples 1 to 5 which contain a water-repellent substance together with a hydrophilic surfactant, can maintain the normal bending strength well and prevent the bending strength from decreasing after storage at 80% humidity. It has good eraser erasability, colorability and moldability, and has a well-balanced performance as a non-fired colored pencil lead erasable with an eraser.
- the non-fired colored pencil lead of Example 6 contained a hydrophilic surfactant and did not contain a water-repellent substance, so although the bending strength was improved, the bending strength after storage at a humidity of 80% was obtained. Therefore, it was judged that the moisture resistance of the core and the handwriting was reduced.
- the non-fired color pencil lead of Example 8 was a non-fired color pencil lead containing a polyoxyethylene adduct of fats and oils as a hydrophilic surfactant, but the hydrophilic surfactant was added to the total solid content of the raw material composition.
- the content is more than 10.0% by weight, so that the water resistance is lowered because the hydrophilicity is too strong.
- the water resistance is improved as compared with Example 9, and the humidity is kept at 80%.
- the bending strength was improved to the extent that a test could be performed.
- the content of a non-fired colored pencil lead containing less than 0.1% by weight of the polyoxyethylene adduct of fats and oils with respect to the total solid content of the raw material composition is as follows.
- a non-fired colored pencil lead containing an oily substance that is liquid at room temperature it is difficult to mold the lead, and the bending strength of the lead is weak even when it is molded. Sex had declined.
- a surfactant-free w / w emulsion especially a non-baked colored pencil lead containing a paraffin-based emulsion, has an effective component (water-repellent component or wax component).
- water-repellent component or wax component water-repellent component or wax component.
- Comparative Example 4 in which more than 5.0% by weight of the total solid content of the raw material composition was blended, molding became difficult, and even if the molding was performed, the bending strength and the eraser erasability were reduced. .
- the content of the water-repellent substance was less than 0.1% by weight as the solid content relative to the total solid content of the raw material composition, the water resistance and the moisture resistance decreased.
- Comparative Example 2 in which only a water-repellent substance was added without containing a hydrophilic surfactant, molding was not possible, and it was difficult to form a colored pencil lead itself. Note that “1” in the physical property column of Table 1 indicates that the numerical value could not be measured or evaluated.
- the non-fired colored pencil cores of Examples 10 to 13 had the same or higher bending strength and drawability than those using talc (Comparative Examples 4 to 6), and had good moldability and eraser erasability. there were.
- the non-fired colored pencil cores of Examples 10 to 13 had good coloring properties in addition to bending strength, drawability, moldability, and erasability.
- the present invention includes a coloring agent, a binder, an extender, a wax and Z or fats and oils, and a hydrophilic surfactant, and contains a polyoxyethylene adduct of fats and oils as the hydrophilic surfactant. Since it is a non-baked color pencil lead, the core has good moldability and bending strength even when it contains a liquid oil at room temperature as wax and Z or fats and oils. In the case of a non-fired colored pencil lead that contains a water-repellent substance together with a coloring material, a binder, a building material, wax and Z or fats and oils, and a hydrophilic surfactant, the moisture resistance of the lead and the water resistance of the handwriting are further improved. Can be improved.
- the present invention is a non-calcined pencil lead containing plate-like alumina and Z or plate-like alumina hydrate, it does not contain asbestos and is excellent in safety.
- it has the same coloring amount (coloring property) as the conventional one, has a bending strength, and has good physical properties such as good drawing taste, as compared with the conventional one containing talc as a constitutional material. Therefore, it is possible to provide a practical non-fired colored pencil lead excellent in safety.
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU74555/01A AU7455501A (en) | 2000-06-23 | 2001-06-15 | Unburned color pencil lead |
DE60118184T DE60118184T2 (de) | 2000-06-23 | 2001-06-15 | Nicht-kalzinierte Farbstiftmine |
US10/312,226 US6875261B2 (en) | 2000-06-23 | 2001-06-15 | Unburned color pencil lead |
EP01941101A EP1302516B1 (en) | 2000-06-23 | 2001-06-15 | Non-calcined lead of a colored pencil |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000188893 | 2000-06-23 | ||
JP2000-188893 | 2000-06-23 | ||
JP2001-66572 | 2001-03-09 | ||
JP2001066572 | 2001-03-09 |
Publications (1)
Publication Number | Publication Date |
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WO2001098417A1 true WO2001098417A1 (fr) | 2001-12-27 |
Family
ID=26594518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/005237 WO2001098417A1 (fr) | 2000-06-23 | 2001-06-15 | Mine de crayon de couleur non cuite |
Country Status (6)
Country | Link |
---|---|
US (1) | US6875261B2 (ja) |
EP (1) | EP1302516B1 (ja) |
AT (1) | ATE321103T1 (ja) |
AU (1) | AU7455501A (ja) |
DE (1) | DE60118184T2 (ja) |
WO (1) | WO2001098417A1 (ja) |
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WO2015166859A1 (ja) * | 2014-04-28 | 2015-11-05 | 三菱鉛筆株式会社 | 固形描画材 |
JP2015209506A (ja) * | 2014-04-28 | 2015-11-24 | 三菱鉛筆株式会社 | 非焼成色鉛筆芯 |
JP2015209505A (ja) * | 2014-04-28 | 2015-11-24 | 三菱鉛筆株式会社 | 固形描画材 |
CN115505297A (zh) * | 2021-06-23 | 2022-12-23 | 滁州雄鹰笔墨科技有限公司 | 一种用于珐琅黑板的粉笔及制作方法 |
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US7217378B2 (en) * | 2003-09-10 | 2007-05-15 | Council Of Scientific & Industrial Research | Simple and efficient process for the preparation of pencil lead from spent pot-liners |
DE102006010119B3 (de) * | 2006-02-27 | 2007-08-02 | J. S. Staedtler Gmbh & Co. Kg | Farbmine für Schreib-, Zeichen- oder Malgeräte |
DE102008028445C5 (de) * | 2008-06-14 | 2012-11-08 | J. S. Staedtler Gmbh & Co. Kg | Mine für Schreib-, Zeichen- und/oder Malgeräte und Verfahren zu deren Herstellung |
DE102008034014B4 (de) * | 2008-07-15 | 2011-06-16 | J. S. Staedtler Gmbh & Co. Kg | Mine für Schreib-, Zeichen- und/oder Malgeräte |
DE102013016355B4 (de) * | 2013-10-01 | 2017-06-22 | Staedtler Mars Gmbh & Co. Kg | Mine für Schreib-, Zeichen- und/oder Malgeräte sowie Verfahren zu deren Herstellung |
DE102013020666B4 (de) * | 2013-11-29 | 2017-09-14 | Staedtler Mars Gmbh & Co. Kg | Bleimine für Schreib-, Zeichen- und/oder Malgeräte sowie Verfahren zu deren Herstellung |
US10711150B2 (en) | 2017-07-12 | 2020-07-14 | Crayola Llc | Color development writing compositions and writing instruments |
US11279654B2 (en) * | 2019-08-07 | 2022-03-22 | Alliance Designer Products Inc. | Photoluminescent premixed compositions, related methods and uses |
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JPS59120668A (ja) * | 1982-12-27 | 1984-07-12 | Nippon Emarujiyon Kk | 色鉛筆芯 |
JPH06157974A (ja) * | 1992-09-25 | 1994-06-07 | Mitsubishi Pencil Co Ltd | 非焼成色鉛筆芯及びその製造方法 |
US5595700A (en) * | 1991-05-02 | 1997-01-21 | Mitsubishi Pencil Kabushiki Kaisha | Non-baked color pencil leads and method for preparing same |
WO1999061537A1 (fr) * | 1998-05-27 | 1999-12-02 | Sakura Color Products Corporation | Mine non calcinee pour crayon couleur |
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GB1061943A (en) * | 1964-09-10 | 1967-03-15 | Carter S Ink Co | Marking composition |
JPS5996179A (ja) * | 1982-11-26 | 1984-06-02 | Lion Corp | 筆記具 |
DE3929391C1 (en) * | 1989-09-05 | 1990-05-03 | Schwan-Stabilo Schwan, 8500 Nuernberg, De | Drawing and painting material - comprises pastel type material with white pigment, colouring agents, filler, etc. |
JPH0818950B2 (ja) * | 1992-05-01 | 1996-02-28 | 花王株式会社 | 化粧料 |
DE4229555C2 (de) * | 1992-09-04 | 1994-12-22 | Johann Froescheis Lyra Bleisti | Minenförmiger Farbkörper für Malzwecke und Verfahren zu dessen Herstellung |
JPH07126568A (ja) * | 1993-11-01 | 1995-05-16 | Mitsubishi Pencil Co Ltd | 非焼成色鉛筆芯とその製造方法 |
US5813216A (en) * | 1994-11-29 | 1998-09-29 | Mitsubishi Pencil Kabushiki Kaisha | Solid writing tool and method of erasing lines drawn therewith |
JPH08302269A (ja) * | 1995-05-09 | 1996-11-19 | Bunchiyou:Kk | 固形状描画材 |
JP3909144B2 (ja) * | 1998-04-20 | 2007-04-25 | パイロットプレシジョン株式会社 | 鉛筆芯 |
US6458390B1 (en) * | 2001-07-27 | 2002-10-01 | Revlon Consumer Products Corporation | Long wearing makeup compositions |
-
2001
- 2001-06-15 AU AU74555/01A patent/AU7455501A/en not_active Abandoned
- 2001-06-15 DE DE60118184T patent/DE60118184T2/de not_active Expired - Lifetime
- 2001-06-15 WO PCT/JP2001/005237 patent/WO2001098417A1/ja active IP Right Grant
- 2001-06-15 EP EP01941101A patent/EP1302516B1/en not_active Expired - Lifetime
- 2001-06-15 AT AT01941101T patent/ATE321103T1/de not_active IP Right Cessation
- 2001-06-15 US US10/312,226 patent/US6875261B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59120668A (ja) * | 1982-12-27 | 1984-07-12 | Nippon Emarujiyon Kk | 色鉛筆芯 |
US5595700A (en) * | 1991-05-02 | 1997-01-21 | Mitsubishi Pencil Kabushiki Kaisha | Non-baked color pencil leads and method for preparing same |
JPH06157974A (ja) * | 1992-09-25 | 1994-06-07 | Mitsubishi Pencil Co Ltd | 非焼成色鉛筆芯及びその製造方法 |
WO1999061537A1 (fr) * | 1998-05-27 | 1999-12-02 | Sakura Color Products Corporation | Mine non calcinee pour crayon couleur |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015166859A1 (ja) * | 2014-04-28 | 2015-11-05 | 三菱鉛筆株式会社 | 固形描画材 |
JP2015209506A (ja) * | 2014-04-28 | 2015-11-24 | 三菱鉛筆株式会社 | 非焼成色鉛筆芯 |
JP2015209505A (ja) * | 2014-04-28 | 2015-11-24 | 三菱鉛筆株式会社 | 固形描画材 |
US10023756B2 (en) | 2014-04-28 | 2018-07-17 | Mitsubishi Pencil Company, Limited | Solid drawing material |
CN115505297A (zh) * | 2021-06-23 | 2022-12-23 | 滁州雄鹰笔墨科技有限公司 | 一种用于珐琅黑板的粉笔及制作方法 |
Also Published As
Publication number | Publication date |
---|---|
DE60118184D1 (de) | 2006-05-11 |
DE60118184T2 (de) | 2006-12-14 |
EP1302516B1 (en) | 2006-03-22 |
AU7455501A (en) | 2002-01-02 |
EP1302516A4 (en) | 2004-09-01 |
ATE321103T1 (de) | 2006-04-15 |
US6875261B2 (en) | 2005-04-05 |
EP1302516A1 (en) | 2003-04-16 |
US20040016366A1 (en) | 2004-01-29 |
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