CN117136221A - Colored pencil lead, method for manufacturing colored pencil lead, and refill product comprising colored pencil lead and refill case for accommodating colored pencil lead - Google Patents
Colored pencil lead, method for manufacturing colored pencil lead, and refill product comprising colored pencil lead and refill case for accommodating colored pencil lead Download PDFInfo
- Publication number
- CN117136221A CN117136221A CN202280025830.2A CN202280025830A CN117136221A CN 117136221 A CN117136221 A CN 117136221A CN 202280025830 A CN202280025830 A CN 202280025830A CN 117136221 A CN117136221 A CN 117136221A
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- Prior art keywords
- pencil lead
- colored pencil
- colorant
- organic solvent
- boiling point
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- NISZMWZPLJGKCC-UHFFFAOYSA-N lissamine flavine FF free acid Chemical compound C1=CC(C)=CC=C1N(C1=O)C(=O)C2=C3C1=CC=CC3=C(N)C(S(O)(=O)=O)=C2 NISZMWZPLJGKCC-UHFFFAOYSA-N 0.000 description 1
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- JQZWHMOVSQRYRN-UHFFFAOYSA-M n-(2-chloroethyl)-n-ethyl-3-methyl-4-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]aniline;chloride Chemical compound [Cl-].CC1=CC(N(CCCl)CC)=CC=C1C=CC1=[N+](C)C2=CC=CC=C2C1(C)C JQZWHMOVSQRYRN-UHFFFAOYSA-M 0.000 description 1
- ZTBANYZVKCGOKD-UHFFFAOYSA-M n-(2-chloroethyl)-n-methyl-4-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]aniline;chloride Chemical compound [Cl-].C1=CC(N(CCCl)C)=CC=C1C=CC1=[N+](C)C2=CC=CC=C2C1(C)C ZTBANYZVKCGOKD-UHFFFAOYSA-M 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- KXXXUIKPSVVSAW-UHFFFAOYSA-K pyranine Chemical compound [Na+].[Na+].[Na+].C1=C2C(O)=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 KXXXUIKPSVVSAW-UHFFFAOYSA-K 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- FZUOVNMHEAPVBW-UHFFFAOYSA-L quinoline yellow ws Chemical compound [Na+].[Na+].O=C1C2=CC=CC=C2C(=O)C1C1=NC2=C(S([O-])(=O)=O)C=C(S(=O)(=O)[O-])C=C2C=C1 FZUOVNMHEAPVBW-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- JADVWWSKYZXRGX-UHFFFAOYSA-M thioflavine T Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C1=[N+](C)C2=CC=C(C)C=C2S1 JADVWWSKYZXRGX-UHFFFAOYSA-M 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
- B43K19/02—Pencils with graphite; Coloured pencils
-
- 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
- C09D11/00—Inks
- C09D11/16—Writing inks
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention provides a colored pencil lead which has excellent color rendering property, erasability, smooth writing feeling and excellent storage stability of handwriting, a manufacturing method of the colored pencil lead, and a replacement core product comprising the colored pencil lead and a replacement core shell for accommodating the colored pencil lead. The colored pencil lead of the present invention comprises a porous core body comprising a constitutional material, an inorganic binder material, a colorant, and a high-boiling point organic solvent having a boiling point of 250 ℃ or higher, and a nonvolatile liquid filled in pores of the porous core body. The method for producing the colored pencil lead comprises bringing a colorant solution containing a colorant and a high-boiling point organic solvent into contact with a porous base material obtained by firing, and then into contact with a nonvolatile liquid in which the colorant is not soluble, and filling voids of the porous core with the nonvolatile liquid. The refill product of the present invention includes the colored pencil lead and a case.
Description
Technical Field
The invention relates to a color pencil lead. More specifically, the present invention relates to a color pencil lead excellent in color rendering properties and smooth in writing feeling.
Background
Conventionally, a color pencil lead used for an automatic pencil or the like is produced by extruding a kneaded product containing a binder such as a clay and a base material such as boron nitride as main components, optionally containing an organic polymer compound or the like, and then firing the extruded product at a high temperature to obtain a white porous base material, and impregnating pores of the white porous base material with an ink containing a dye. In order to express various colors, various materials are required to realize more excellent color development, and improvements in erasability, stability with time, writing feeling, and the like are also required for such color pencil cores.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2019-099633
Disclosure of Invention
Problems to be solved by the invention
The invention provides a colored pencil lead which has excellent color rendering of handwriting, high stability with time and smooth writing feeling.
Means for solving the problems
The color pencil lead according to the present invention is characterized by comprising a porous core body and a nonvolatile liquid, wherein the porous core body comprises a constitutional material, an inorganic binder, a colorant, and a high-boiling-point organic solvent having a boiling point of 250 ℃ or higher, the colorant is soluble in the porous core body, the nonvolatile liquid does not dissolve the colorant, and pores of the porous core body are filled with the colorant, the high-boiling-point organic solvent, and the nonvolatile liquid.
In addition, the method for manufacturing a color pencil lead according to the present invention is characterized by comprising:
(a) A kneading step of kneading the physical material and the inorganic binder to prepare a mixture;
(b) An extrusion step of extruding the mixture to form a linear molded article;
(c) A firing step of firing the linear molded article to produce a porous base material;
(d) An impregnation step of bringing a colorant solution containing a colorant and a high-boiling-point organic solvent having a boiling point of 250 ℃ or higher into contact with the porous substrate to impregnate the porous substrate;
(e) A drying step of heating the porous base material after the impregnation step at a temperature of 200 ℃ or lower to form a porous core;
(f) And a filling step of bringing a nonvolatile liquid in which the colorant is not dissolved into contact with the porous core, and filling voids in the porous core with the nonvolatile liquid.
Effects of the invention
By writing using the colored pencil lead of the present invention, handwriting excellent in color rendering can be formed. In addition, the color pencil lead according to the present invention can obtain a smooth writing feeling when writing. The colored pencil lead of the present invention is also excellent in storage stability, color development over time and erasability.
Drawings
Fig. 1 is a perspective view of an alternate core article according to the present invention.
Fig. 2 is a longitudinal cross-sectional view of an alternative core housing that can be used with the present invention.
Fig. 3 is a cross-sectional view of an alternative core housing that can be used with the present invention.
Fig. 4 is a longitudinal cross-sectional view of another alternative core housing that can be used with the present invention.
Fig. 5 is a cross-sectional view of another alternative core housing that can be used with the present invention.
Fig. 6 is a longitudinal cross-sectional view of yet another alternative core housing that can be used with the present invention.
Fig. 7 is a cross-sectional view of yet another alternative core housing that can be used with the present invention.
Detailed Description
< colored pencil lead >
The following describes the structure of the color pencil lead of the present invention.
The porous core used in the colored pencil lead of the present invention comprises a physical material and an inorganic binder as main components. Examples of the constitutional material include white materials such as titanium oxide, mica, talc, boron nitride, aluminum oxide, and calcium carbonate, and colored materials such as molybdenum disulfide, tungsten disulfide, and graphite. The colored pencil lead of the present invention preferably forms vivid handwriting. In addition, in the case of forming a fluorescent color writing by using a fluorescent colorant as a colorant, a material that does not hinder the development thereof is preferable. Therefore, in order to form handwriting with high brightness, white constitutional material is preferably used. In particular, if boron nitride is used, the physical material color development is not hindered, and the strength of the color pencil lead is increased, which is preferable.
Examples of the inorganic binder include clays such as kaolinite, halloysite, montmorillonite, sericite, and bentonite, ceramics, zeolite, diatomaceous earth, activated clay, silica, aluminum phosphate, silicone resin, and silicone rubber, and these may be used alone or in combination.
The mixing ratio of the constitutional material as the main component of the porous core and the inorganic binder is not particularly limited, and is preferably 9:1 to 7:3 in terms of mass ratio.
In the present invention, the porous core is typically formed by combining a colorant and a high boiling point organic solvent in a porous base material. The colorant may be locally present in a part of the porous base material mainly composed of a physical material or an inorganic binder, or may be uniformly dispersed throughout the porous base material, and preferably locally present in a part of the porous core. Specifically, the colorant is preferably attached to or adsorbed in the pores of the porous substrate. In this case, the colorant may be in the form of fine particles or may be dissolved or dispersed in a high-boiling point organic solvent described later. By allowing the colorant to exist in the final colored pencil lead in such a state, penetration of the colorant into the paper during writing can be suppressed, and the color development and erasability can be improved. Here, the colorant typically forms a layer or phase within the pores. That is, a uniform or non-uniform layer is generally formed on the inner side of the air hole, or attached in a block shape. In the present invention, the pores refer to the pores in the porous base material, for example, from which the matrix such as the organic solvent is removed from the pencil lead. For example, in a porous core, an organic solvent or the like may permeate into pores, and the pores of the porous core are the pores after the organic solvent or the like is removed from the porous core.
In the present invention, the porous core is composed of a constitutional material, an inorganic binder, a colorant, and a high-boiling point organic solvent. In general, the pencil lead is manufactured by molding a mixture of a physical material and a binder and then firing the molded mixture, but the same method can be applied to the present invention. That is, the porous base material can be produced by calcining a mixture of a constitutional material and an inorganic binder to adsorb or adhere a colorant and a high-boiling point organic solvent to the porous base material (see below for details). In addition, the constitutional material, the inorganic binder, the colorant, and the high-boiling point organic solvent may be mixed and fired, and in such a case, a colorant having high heat resistance or a high-boiling point organic solvent having a boiling point higher than the firing temperature is preferably used. On the other hand, in the former method, even a colorant having low heat resistance and a high boiling point organic solvent having a boiling point lower than the firing temperature can be used.
The porous core may be produced by compressing a mixture containing a physical material, an inorganic binder, an inorganic substance, a water-soluble resin, and the like, and optionally a coloring material under high pressure, and immersing the mixture in water, a solvent, or the like to remove the inorganic substance, the water-soluble resin, and the like.
The porosity of the porous core used in the present invention is not particularly limited, but is preferably in the range of 1 to 50%, more preferably in the range of 5 to 50%, still more preferably in the range of 10 to 40%, and particularly preferably in the range of 20 to 40%. If the porosity is less than 1%, the amount of the colorant and the nonvolatile liquid present in the pores becomes small, and there is a tendency that color difference is developed or a slight resistance is generated to the pen, and if it is more than 50%, the strength of the obtained porous core tends to be lowered and broken easily. If the porosity is in the range of 1 to 50%, the color developing property is also good, the writing feeling is smooth, and the strength of the calcined color pencil lead can be maintained, which is preferable.
The porosity of the porous substrate used in the present invention can be measured by the following method with reference to JIS R1634 (1998). First, the dry quality of the porous substrate was measured (W1). Then, the porous substrate is immersed in a liquid (e.g., benzyl alcohol) having good permeability, and the pores of the porous substrate are allowed to absorb the liquid until the porous substrate is saturated, and then the mass (W2) in the liquid is measured. Then, the porous matrix was removed from the liquid, and the liquid adhering to the surface thereof was scraped off, and then the saturation mass (W3) was measured. Using these measured values, the porosity was determined by the following formula (1).
Porosity = (W3-W1)/(W3-W2) ×100 (1)
The porosity of the colored pencil core or the porous core can also be measured by the same method. However, before the above method for measuring the porosity of a porous substrate is applied, it is necessary to remove the organic solvent or the like by heating or reducing the pressure. In the case of measuring the porosity of the colored pencil core or the porous core, even if the solvent or the like is removed, there is a possibility that a small amount of the organic solvent or the like remains in the pores. Therefore, there is a case where the porosity of the porous base material is slightly different from the porosity of the colored pencil lead or the porous core body. Considering such a difference, the porosity of the porous base material is preferably in the range of 5 to 50%, more preferably in the range of 10 to 40%, and particularly preferably in the range of 20 to 40%.
As the colorant, a dye or pigment may be used. In addition, a colored pigment formed by dyeing a resin with a dye or the like may also be used. In general, the heat resistance of the dye is sometimes low, but the dye is preferably a dye because the dye easily penetrates into the porous base material when the pencil lead of the present invention is produced.
The dye usable in the present invention is not particularly limited, and conventional dyes or fluorescent dyes can be exemplified.
As examples of conventional dyes, oil-soluble dyes, acid dyes, basic dyes, gold-containing dyes, and the like can be cited. Examples of the salt-forming dye of these dyes include salt-forming dyes of an acid dye and a basic dye, salt-forming dyes of a basic dye and an organic acid, and salt-forming dyes of an acid dye and an organic amine. More specifically, valifast Black 1802, valifast Black1805, valifast Black 1807,Valifast Violet 1701, valifast Violet 1704, valifast Violet 1705, valifast Blue 1601, valifast Blue 1605, valifast Blue1613, valifast Blue 1621, valifast Blue 1631, valifast Red 1320, valifast Red 1355, valifast Red 1360, valifast Yellow 1101, valifast Yellow 1151, nigrosine Base EXBP, nigrosine Base EX, BASE OF BASIC DYES ROB-B, BASE OF BASIC DYES RO G-B, BASE OF BASIC DYES VPB-B, BASE OF BASIC DYES VB-B, BASE OF BASIC DYES MVB-3 (Charpy Chemie, kogyo Co., ltd.), aizen Spilon Black GMH-specialty, aizen Spilon Violet CRH, aizen Spilon Blue GNH, aizen Spilon Blue 2BNH, aizen Spilon Blue C-RH, aizen Spilon Red C-GH, aizen Spilon Red C-BH, aizen Spilon Red C-PH, aizen Spilon Yellow C-GNH, aizen Spilon Yellow C-2, S.P.T.111, S.P.T.T.S. SLE.111, N.T.T.T.T.T.S. SLOGL.B.T.T.T.Song.Song.T.Song.Chemical.S. Chemicals.K.K.Chemicals.K.K.Chemicals.K.K.Chemicals.K.K.Chemicals.
Examples of the fluorescent dye include basic yellow 1, basic yellow 40, basic red 1, basic red 1:1, basic red 13, basic violet 1, basic violet 7, basic violet 10, basic violet 11:1, basic orange 22, basic blue 7, basic green 1, acid yellow 3, acid yellow 7, acid red 52, acid red 77, acid red 87, acid red 92, acid blue 9, disperse yellow 121, disperse yellow 82, disperse yellow 83, disperse orange 11, disperse red 58, disperse blue 7, direct yellow 85, direct orange 8, direct red 9, direct blue 22, direct green 6, solvent yellow 44, solvent red 49, solvent blue 5, solvent green 7, and the like.
In the range of not affecting the performance of the color pencil lead, these dyes may be used alone or in combination of 2 or more for the purpose of adjusting the color of handwriting, etc. Moreover, other dyes may be used in combination with these dyes.
As the colorant, any pigment may be used. Further, ultrafine pigments, processed pigments, and the like may also be used.
In addition, a colored pigment formed by dyeing a resin with a dye or the like may also be used. Such a coloring pigment is preferable because the color rendering property can be improved.
As the resin constituting the coloring pigment, any resin such as an acrylic resin, a styrene-acrylonitrile resin, a styrene resin, a nitrogen-containing resin, a polyethylene resin, or a polypropylene resin can be used. The dyes combined with these resins may be selected from the above-mentioned dyes.
Among these resins, a nitrogen-containing resin or a styrene-acrylonitrile resin is preferably used, and a nitrogen-containing resin is more preferably used, in view of solubility in a high-boiling point organic solvent, dispersibility and dispersion stability, dyeability based on a dye or the like, and the like. Among the nitrogen-containing resins, melamine resins, polyamide resins, polyurethane resins, urea resins, benzomelamine resins, or the like are preferable. Further, among these resins, melamine resins or polyamide resins are preferable, and melamine resins are more preferable, in terms of solubility stability in a high boiling point organic solvent.
Examples of the coloring pigment include NKS-1000 series, MPI-500 series (manufactured by Nippon fluorescent chemical Co., ltd.), FNP series, and FM series (manufactured by Siro Co., ltd.).
These coloring pigments may be used in combination of 2 or more kinds within a range not impairing the effect of the present invention, for example, for the purpose of adjusting handwriting color. Further, a dye may be used in combination with these colored pigments.
In the present invention, a fluorescent colorant is preferably used. By using such a coloring agent, handwriting having fluorescence can be obtained, and handwriting having more abundant color rendering can be obtained. This makes it easy to use the device in a scene such as drawing and marking, as well as simply leaving text.
The content of the colorant relative to the total mass of the colored pencil lead varies depending on the kind thereof, and is preferably 0.1 to 30% by mass, more preferably 0.2 to 25% by mass, and still more preferably 1 to 20% by mass.
In the case of forming the porous core by combining the colorant with the porous base material, the porous base material including the constitutional material and the inorganic adhesive material can be easily produced by impregnating the porous base material with a colorant solution in which the colorant is dissolved in a solvent, and then removing a part of the solvent as necessary (see details below). Therefore, the solvent used in the production is preferably capable of dissolving the colorant used.
The colored pencil lead of the present invention comprises a high boiling point organic solvent having a boiling point of 250 ℃ or higher, which is capable of dissolving a colorant contained in the colored pencil lead. Such a solvent can impart excellent color rendering properties and writing feeling to the color pencil lead of the present invention. Further, since the boiling point is high, the resin is less likely to volatilize during the production process and storage, and stable performance can be maintained.
The high-boiling organic solvent is capable of dissolving the colorant, and means that the solubility of the colorant in the high-boiling organic solvent is 10g/100g or more at 20 ℃, that is, 10g or more of the colorant is dissolved with respect to 100g of the high-boiling organic solvent at 20 ℃. The higher the solubility of the colorant, the higher the storage stability of the color pencil lead tends to be, and the solubility is more preferably 30g/100g or more, and further preferably 40g/100g or more.
Such a solvent may be arbitrarily selected from the viewpoints of solubility of the colorant used, other performances, and the like, and is preferably an aromatic glycol ether or an aliphatic glycol ether. The glycol ether has a structure containing both an ether group and a hydroxyl group, and is generally characterized by high solubility in dyes, resins, and the like, and high affinity to other organic solvents and the like.
Specific examples of such a high boiling point organic solvent include diethylene glycol monophenyl ether (phenyldiglycol, 283 ℃), diethylene glycol monobenzyl ether (302 ℃), triethylene glycol monobutyl ether (butyltriethylene glycol, 271 ℃), ethylene glycol monobenzyl ether (256 ℃), and the like. The values in parentheses indicate boiling points (hereinafter, referred to as "boiling points").
In addition, as the high boiling point organic solvent, a carboxylic acid ester of polyalkylene glycol or a carboxylic acid ester of alcohol can be used.
Further, higher fatty acids and higher alcohols having a boiling point of 250℃or higher may be used. Specifically, carboxylic acids having 10 or more carbon atoms, such as decanoic acid (259 ℃), oleic acid (360 ℃) and the like, and alcohols having 12 or more carbon atoms, such as dodecanol (259 ℃) and myristyl alcohol (292 ℃), can be cited. Note that, higher fatty acids may cause corrosion even when the colored pencil lead is used in a mechanical pencil and is in contact with a metal member, and therefore attention is paid.
Among the organic solvents, some are liquid at normal temperature and pressure, and when heated under normal pressure conditions, sublimate or denature by chemical reaction, and the like, and therefore, the exact boiling point cannot be measured. Even such an organic solvent may be used as a high boiling point organic solvent. In this case, for example, when the temperature is kept at 250 ℃ under normal pressure, if the weight reduction rate after 30 minutes is 10 mass% or less, the boiling point of the high-boiling organic solvent can be regarded as 250 ℃ or more.
The content of the high-boiling organic solvent contained in the colored pencil lead of the present invention may be appropriately adjusted according to the purpose, and the content of the high-boiling organic solvent is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, based on the total mass of the colored pencil lead. The content of the high-boiling organic solvent can be measured by any method. For example, it can be confirmed by a thermogravimetry method or the like that the colored pencil lead contains a high boiling point organic solvent.
The colored pencil lead of the present invention may contain an organic solvent (hereinafter, sometimes referred to as a low boiling point organic solvent) different from the high boiling point organic solvent. The low boiling point organic solvent herein is also different from the nonvolatile liquid described later. Specifically, the organic solvent has a boiling point lower than 250 ℃ and is capable of dissolving the colorant. Here, the low-boiling organic solvent being capable of dissolving the colorant means that the solubility of the colorant with respect to the low-boiling organic solvent is 10g/100g or more at 20 ℃, that is, the colorant is dissolved by 10g or more with respect to 100g of the low-boiling organic solvent at 20 ℃. The higher the solubility of the colorant, the higher the storage stability of the color pencil lead tends to be, and the solubility is more preferably 30g/100g or more, and further preferably 40g/100g or more.
Among the low-boiling organic solvents, organic solvents having a relatively high boiling point, for example, organic solvents having a boiling point of 150 ℃ or higher and less than 250 ℃ are generally expected to compensate for the effect of improving the pencil feel obtained from the high-boiling organic solvents. In addition, substances having a low boiling point, for example, substances having a boiling point lower than 150 ℃ are generally effective for reducing the viscosity of the colorant solution when the colorant is impregnated into the porous substrate during the production process. However, these relatively low boiling substances are often rarely contained in colour pencil leads, since they are mostly or completely removed during the manufacturing process. The boiling point of the low boiling point solvent is preferably 100 ℃ or less, more preferably 90 ℃ or less, further preferably 85 ℃ or less, further preferably 80 ℃ or less.
In addition, if attention is paid to the boiling point BP of the high-boiling point organic solvent in the present invention H BP with low boiling point organic solvents L If the difference in BP H And BP L The difference is preferably 100 degrees or more, more preferably 150 degrees or more. By providing a difference in boiling point between the high-boiling point organic solvent and the low-boiling point organic solvent, only the low-boiling point organic solvent can be removed in the production process described later. As a result, a colored pencil lead having excellent color rendering properties and writing feeling by a high-boiling point organic solvent is obtained. In addition, the high boiling point organic solvent is not easily volatilized during the manufacturing process and storage, and stable performance can be maintained.
Examples of such low boiling point organic solvents include
Triethylene glycol monomethyl ether (249 ℃),
phenylcellulose (247 ℃ C.),
propylene glycol monomethyl ether (243 ℃ C.),
Benzyl alcohol (205 ℃ C.),
3-methoxy-3-methyl-1-butanol (174 ℃ C.),
xylene (139 ℃ C.),
toluene (111 ℃ C.),
isopropyl alcohol (82 ℃ C.),
methyl ethyl ketone (79 ℃ C.),
ethanol (78 ℃ C.),
ethyl acetate (77 ℃ C.),
Acetone (56 ℃ C.) and the like.
Among them, isopropyl alcohol, methyl ethyl ketone, ethanol, ethyl acetate or acetone is preferably used.
As the colored pencil lead of the present invention, the pores of the porous core are filled with a nonvolatile liquid. By using the nonvolatile liquid, the writing feeling at writing is further improved.
In the present invention, the nonvolatile liquid means a liquid which does not dissolve a colorant and is not easily volatilized at ordinary temperature. Here, insoluble does not mean that the solubility of the colorant is zero, but means substantially insoluble. The solubility of the colorant in the hardly volatile liquid is preferably lower than the above-mentioned solubility in the high-boiling organic solvent, more specifically, the solubility of the colorant in the hardly volatile liquid at 20℃is preferably less than 10g/100g, and more preferably 5g/100g or less.
The boiling point of the nonvolatile liquid is not particularly limited, but is preferably a liquid which does not volatilize at 250 ℃.
By using such a nonvolatile liquid, the stability of the color pencil core with time can be maintained at a high level, and the writing feeling at the time of writing can be improved. In addition, in the replacement core product for replacement, if the core contains an organic solvent, there is a possibility that the replacement core and the casing are welded in the casing of the replacement core product, but such welding can be improved by containing a nonvolatile liquid in the color pencil core.
Such improvement of the fusion bonding is also affected by the material of the case, but the solubility parameter (hereinafter, may be referred to as SP value) of the nonvolatile liquid used in the present invention and the SP value of the resin material used in the replacement core case described later satisfy a specific relationship, and a remarkable improvement effect is exhibited. As will be described later, the SP value of the hardly volatile liquid is preferably 6 to 8. Here, as the SP value, there are known a Fedors solubility parameter, a Hildebrand solubility parameter, a Hansen solubility parameter, and the like, and in the present invention, the Fedors solubility parameter is taken as the solubility parameter.
In addition, the nonvolatile liquid is preferably low in viscosity so as to facilitate impregnation into pores of the porous core.
The surface tension of the nonvolatile liquid is preferably 35mN/m or less, more preferably 30mN/m or less, and even more preferably 25mN/m or less, from the viewpoint of obtaining a color pencil lead excellent in writing feeling and erasability by excellent impregnation of the nonvolatile liquid into the pores of the porous core, uniform impregnation of the nonvolatile liquid into the entire porous core, and non-uniformity. The surface tension may be measured by a method specified in JIS K2241 at a temperature of 25 ℃.
Specific examples of the preferable nonvolatile liquid include nonvolatile liquids selected from silicone oils, fluorine-based oils, mineral oils, vegetable oils and liquid paraffin, and among them, silicone oils are more preferable. Since silicone oil has small viscosity change due to temperature and excellent stability, it is possible to form a color pencil lead that is less susceptible to environmental changes and time by using silicone oil as a nonvolatile liquid, and when the color pencil lead is used in a mechanical pencil, there are few cases in which the front end opening portion of the mechanical pencil made of a metal material, a chuck, a core receiving tube, and the like are corroded. The silicone oil is particularly preferably dimethyl silicone or methyl phenyl silicone, and modified silicone is also preferable. In addition, the colorant is preferably not easily dissolved. By making the colorant difficult to dissolve, penetration of the colorant into the paper together with the nonvolatile liquid can be suppressed in the formed handwriting, and erasability can be improved. Further, as the liquid paraffin, liquid paraffin having 14 or more carbon atoms is preferable.
The content of the nonvolatile liquid with respect to the total mass of the colored pencil lead is preferably 5 to 40% by mass, more preferably 8 to 45% by mass, and still more preferably 10 to 35% by mass.
The colored pencil lead of the present invention may contain various additives within a range that does not affect its performance. Specific examples of the additives include surfactants, preservatives, mold inhibitors, resins, and the like.
The shape of the color pencil core of the present invention is not particularly limited, and is usually a linear body having a circular cross section. The size of the ink is preferably 0.2 to 2.0mm, and more preferably 0.3 to 0.7mm in cross-sectional diameter as a color pencil lead for a mechanical pencil, for example. The length is preferably 30 to 100mm, more preferably 40 to 70mm. Further, when applied to a conventional colored pencil held in a support such as wood, the cross-sectional diameter is preferably 0.5 to 3.0mm, more preferably 0.8 to 2.0mm. In general, a color pencil is usually cut after a long color pencil core is sandwiched in wood or the like during the manufacturing process, and thus the length is not limited, and is usually 1,000mm or less.
The colored pencil lead of the present invention can realize high physical strength if a porous base material produced by firing is used. This is considered to be due to the fact that the colorant forms a uniform or non-uniform layer on the inner side of the air hole, or adheres in a lump. The bending strength of the colored pencil lead of the present invention is preferably 120MPa or more. More preferably 180MPa or more. Here, the bending strength can be used in JIS S6005: 2007, by a method defined in the following.
The colored pencil lead of the present invention may be configured to be free of an acidic component. Since color pencil leads are often used for mechanical pencils, they are often in contact with metallic materials. Therefore, by setting the composition to a composition that does not contain an acidic component, corrosion of the metal portion of the mechanical pencil can be suppressed. The colour pencil lead according to the invention is therefore preferably free of acidic materials.
Method for manufacturing colour pencil lead
The method for manufacturing the colored pencil lead of the present invention is not particularly limited. But is preferably manufactured by a process comprising:
(a) A kneading step of kneading the physical material and the inorganic binder to prepare a mixture;
(b) An extrusion step of extruding the mixture to prepare a linear molded article;
(c) A firing step of firing the linear molded article to produce a porous base material;
(d) An impregnation step of bringing a colorant solution containing a colorant and a high-boiling-point organic solvent having a boiling point of 250 ℃ or higher into contact with the porous substrate to impregnate the porous substrate;
(e) A drying step of heating the porous base material after the impregnation step at a temperature of 200 ℃ or lower to form a porous core;
(f) And a filling step of bringing a nonvolatile liquid in which the colorant is not dissolved into contact with the porous core, and filling voids in the porous core with the nonvolatile liquid. This method is described below.
(a) Mixing process
First, a mixture is prepared by kneading a physical material and an inorganic binder. The mixture becomes the main component of the porous substrate. In the mixing, an organic solvent, a plasticizer, and the like may be added as necessary. The organic solvent used herein is used to render the raw material mixture fluid and uniform, and is almost completely removed in the firing step, independently of the above-mentioned high boiling point organic solvent, low boiling point organic solvent and nonvolatile liquid.
(b) Extrusion process
Then, the resulting mixture was extruded to prepare a linear molded article. The color pencil lead of the present invention is preferably molded into a linear body having a circular cross-sectional shape, and thus is preferably molded into a linear body by extrusion molding.
(c) Firing step
The obtained linear molded article is dried as needed, and then fired to produce a porous substrate. By firing, the organic solvent contained in the mixture is removed, and the constitutional material and the inorganic binder are sintered to form a porous base material. The firing conditions are not particularly limited as long as the material is sintered to form a porous substrate, and the maximum temperature may be 650 to 1000 ℃. In order to avoid abrupt temperature changes, the temperature during firing may be continuously or stepwise increased. The temperature rise rate in this case may be set to, for example, 10 to 100 ℃/hr. It is also preferable that the material is heated to a predetermined temperature and then burned at a predetermined temperature for a predetermined time, for example, about 0.5 to 2 hours. Further, these conditions may be arbitrarily combined according to purposes. For example, a condition in which the temperature is raised from room temperature to 650 ℃ at 10 ℃/hr and then kept at 650 ℃ for 1 hour in an oxygen atmosphere, a condition in which the temperature is raised from room temperature to 1000 ℃ at 100 ℃/hr and then kept at 1000 ℃ for 1 hour, and the like can be employed.
(d) Impregnation process
After cooling the porous substrate thus formed as needed, the porous substrate is brought into contact with a solution containing a colorant and a high-boiling point organic solvent. In this step, the colorant solution permeates into pores existing in the porous base material. As the impregnation method, an atmospheric impregnation method or a reduced pressure and pressurized impregnation method can be used.
The colorant content of the colorant solution is not particularly limited, but the concentration of the colorant is preferably 5 to 50% by mass, more preferably 5 to 45% by mass, and particularly preferably 10 to 40% by mass, based on the total mass of the solution. If the content of the colorant is less than this range, the color developing property tends to be deteriorated, and if the content is more than this range, the color developing property tends to be not improved according to the amount of the colorant added, and there is a concern that the stability of the solution such as the precipitation of the colorant with time tends to be low. In order to improve the solubility and stability of the colorant, a surfactant may be added to the solution.
In addition, if a mixed solvent in which a low boiling point organic solvent is combined with a high boiling point organic solvent is used as the solvent for the colorant solution, the viscosity of the colorant solution becomes low, impregnation becomes easy, and voids in pores are easily formed in the subsequent drying step. In this case, the nonvolatile liquid is easily impregnated into the pores of the core, and the effect obtained by impregnating the nonvolatile liquid can be sufficiently obtained. As such a low boiling point organic solvent, a solvent which evaporates at 100 ℃ or lower is preferable, and a solvent which evaporates at 90 ℃ or lower is more preferable, and 80 ℃ or lower is still more preferable. More preferably an aliphatic alcohol having 1 to 4 carbon atoms. The mixing ratio of the high boiling point organic solvent to the low boiling point organic solvent can be prepared according to the difference in boiling points and the solubility of the colorant, and for example, the ratio of the mass of the high boiling point organic solvent to the mass of the low boiling point organic solvent is preferably 1:1 to 1:15, more preferably 1:1 to 1:12, still more preferably 1:1.5 to 1:10, and particularly preferably 1:1.5 to 1:7.
(e) Drying process
Next, the porous substrate after the impregnation step is heated, and a part of the solvent contained in the solution impregnated in the pores is removed. As a result, the colorant and the high boiling point organic solvent remain, adsorb, or adhere to the inside of the pores. Then, a part of the solvent is removed by heating or impregnation of the porous substrate with the solvent is performed to form voids in the pores, thereby forming a porous core. The drying is performed at a temperature of 200 ℃ or lower, but in the case where a solvent having a relatively low boiling point is contained in the colorant solution, it may be performed at a lower temperature, for example, 100 ℃ or lower. If the drying treatment can be performed at a low temperature, energy costs can be reduced, so that it is preferable.
(f) Filling process
After cooling the porous core formed as required, the nonvolatile liquid is brought into contact. Through this step, the voids formed in the porous core are filled with the nonvolatile liquid. The conditions in this case are not particularly limited, and for example, conditions of 60℃and 6 to 12 hours may be employed. The nonvolatile liquid may be filled by an atmospheric impregnation method, a vacuum impregnation method, or a pressurized impregnation method.
Further cleaning or the like may be performed as needed to obtain the colored pencil lead of the present invention.
< replacement core Shell and replacement core product >)
The replaceable core product of the present invention is a product in which the colored pencil lead is accommodated in a replaceable core case. Further, it is preferable that a resin material having a solubility parameter different from the solubility parameter of the nonvolatile liquid by 1.5 or more is disposed on a part of a portion of the inner surface of the refill case, which is accessible to the pencil core. The refill case is made of a material having relatively high hardness in order to protect the color pencil core, but is generally made of a resin in view of ease of manufacture and cost. However, if an appropriate resin is not selected as the resin, the colored pencil lead may adhere to the resin material.
According to the studies of the present inventors, it is found that such adhesion can be suppressed when the difference between the SP value of the nonvolatile liquid contained in the color pencil core and the SP value of the resin constituting the refill case is sufficiently large. Such adhesion naturally occurs at the portion of the refill case that is in contact with the colored pencil lead, and therefore the SP value of the resin disposed at this portion of the refill case may be sufficiently different from the SP value of the nonvolatile liquid. Specifically, the difference between the SP value of the nonvolatile liquid and the SP value of the resin material disposed at the portion where the color pencil core contacts is preferably 1.5 or more, more preferably 2.0 or more, still more preferably 3.0 or more, and still more preferably 5.0 or more.
The difference between the SP value of the nonvolatile liquid and the SP value of the resin material is preferably 1.5 or more, but any of them may be used. In addition, the SP value of the nonvolatile liquid and the SP value of the resin material are not particularly limited as long as they satisfy the relative difference. For example, in the case of using silicone oil having an SP value of 7.2 as the nonvolatile liquid, the SP value of the resin material needs to be 5.7 or less, or 8.7 or more. Examples of the resin materials satisfying such conditions include polystyrene (8.6 to 9.7), vinyl acetate resin (9.4), vinyl chloride (9.5 to 9.7), polycarbonate (9.7), polyacetal (11.1), acrylonitrile-styrene resin (12.8), and acrylonitrile-butadiene-styrene copolymer synthetic resin (12.1 to 15.0). In general, the SP value of the resin material tends to be higher than that of a difficult-to-volatilize liquid. The SP value of the resin material is preferably 8.5 to 15.
In the refill product of the present invention, the remaining amount of the stored pencil lead is preferably visible from the outside. Therefore, the case is preferably made of a resin material having transparency. Therefore, a resin having high firmness, excellent moldability and transparency is preferably used, and polycarbonate (9.7) and acrylonitrile styrene resin (12.8) are particularly preferably used.
In the present invention, the shape of the replaceable core case is not particularly limited, and any shape known in the prior art may be used. For example, a replaceable core case may be used that includes a storage portion for storing a color pencil core and a cover portion that temporarily closes an opening portion provided in the storage portion and allows the color pencil core to be removed by deforming the opening portion. Here, the cover may be any member commonly referred to as a cover. Specifically, the member is configured to temporarily close an opening provided in the storage portion during transportation or storage, hold the color pencil core in the refill case, and, if necessary, deform such as detachment, movement, or rotation, so that the color pencil core can be taken out from the opening of the storage portion.
As the simplest shape, a replaceable core case is exemplified, which is composed of a cylindrical housing portion 101 having one end closed and a lid portion 102 fitted into an opening portion formed at one end of the housing portion, as shown in fig. 1. By removing the cover 102 from the storage part 101, the color pencil core 103 stored in the refill case can be taken out from the storage part.
In the refill product of the present invention, a specific resin material is disposed on a part of the refill case where the refill case can be brought into contact with the colored pencil core. In the refill case shown in fig. 1, the inner side surface of the space defined by the inner side surface of the receiving portion and the bottom surface 102a of the fitted cap portion is entirely a portion of the refill case that can be brought into contact with the color pencil core. In the present invention, a specific resin material is disposed on a part of the replaceable core case where the replaceable core case can be brought into contact with the colored pencil core.
Here, disposing the resin material in the specific portion means, for example, forming the portion from the resin material, disposing a member formed from the resin material, or covering the portion from the resin material. In the case of a replacement core case having a shape as shown in fig. 1, for example, it is possible to form all the storage sections from a specific resin material. Of course, the cover portion may be formed of a resin material, or the inner surface of the housing portion may be covered with a resin material.
In the present invention, if a specific resin material is disposed on a part of the replaceable core case where the color pencil leads can be brought into contact, adhesion of the color pencil leads to the replaceable core case can be suppressed. However, it is preferable that the ratio of the area where the specific resin material is disposed to the total area of the portion where the color pencil core and the refill case can contact is high. Specifically, the area of the portion where the specific resin material is disposed is preferably 50% or more, more preferably 80% or more, and particularly preferably 90% or more, relative to the total area of the portion of the refill case that can be brought into contact with the color pencil core. Preferably, the specific resin material is disposed in the entire portion of the refill case that can be brought into contact with the colored pencil lead. Therefore, in the replacement core case of fig. 1, although also depending on the size, by forming the receiving portion with a resin material having a specific SP value, the adhesion of the color pencil core can be suppressed.
Alternatively, a replacement core housing as shown in fig. 2 and 3 may be used. This is a refill case in which a cover 202 is detachably attached to a storage section 201 capable of storing refill. In the replacement core case, an engagement piece 202a protruding from the lower end is formed in the cover 202, and a recess 201a that matches the engagement piece 202a is formed in the receiving portion. By forming in this way, when the engaging piece 202a of the cover is combined in such a manner as to match the recessed portion 201a of the housing, the protruding portion and the recessed portion can be engaged with each other, and the cover can be stably mounted to the housing. The protruding portion and the recessed portion may also be formed interchangeably. In such a refill case, adhesion of the color pencil lead can be suppressed by forming the entire housing portion 201 with a specific resin material. The inner surface of the housing portion 201 may be covered with a specific resin material.
Alternatively, a replacement core housing as shown in fig. 4 and 5 may be used. The case is also a replaceable core case in which the cover 402 is detachably attached to the storage section 401 for storing the color pencil core. By forming the engaging piece 402a protruding from the lower end of the cover 402 and forming the recess 401a corresponding to the engaging piece 402a in the housing 401 in this manner, the protruding portion and the recess can be engaged with each other when the engaging piece 402a of the cover is combined so as to correspond to the recess 401a of the housing, and the cover can be stably attached to the housing. The protrusions and depressions may also be formed interchangeably. In such a refill case, the adhesion of the color pencil lead can be suppressed by forming the entire housing portion 401 with a specific resin material.
Further, a replacement core housing as shown in fig. 6 and 7 may be employed. The housing accommodates a color pencil core in the accommodation portion 601. By rotating the cover 602 around the rotation shaft 602D, the color pencil core can be held in the storage section or taken out from the core outlet 603. Specifically, the cap 602 is rotated to be raised, whereby the outlet 603 of the color pencil core can be opened, and the cap 602 is laterally lowered to close the outlet 603. In this replaceable core case, a non-circular mounting hole 604E is formed in the cover fixing member 604, and a slit 604F is formed in the cover fixing member 604 so as to extend across the mounting hole, and the mounting hole is formed so as to be expandable. A notch formed by an arc is formed in the cover fixing member on the opposite side to the outlet, and a rotation shaft 602D having a non-circular cross section is formed in the cover. The end of the rotation shaft side is formed in a semicircle shape, a bulge part with proper width is formed on the edge of the end of the semicircle shape from the back surface direction of the front wall, and the rotation shaft of the cover part is rotatably installed on the installation hole of the cover part fixing part. Here, when the cover is laterally laid down to close the outlet, the rotation shaft of the cover is engaged with the mounting hole of the cover fixing member, and the cutout groove crossing the mounting hole of the cover fixing member is covered with the ridge portion. When the lid is raised to open the outlet, the raised portion of the lid contacts the stopper portion of the circular arc-shaped slot of the lid fixing member to stop the rotation of the lid. In such a refill case, the adhesion of the color pencil lead can be suppressed by forming the entire housing portion 601 with a specific resin material.
Examples
Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto.
Production example 101
[ mixing step, extrusion step and firing step ]
The above-mentioned complex was heated and kneaded while evaporating water by a kneader or a three-roll mill, and the obtained kneaded product was extrusion molded to a predetermined diameter to obtain a linear molded product. The linear molded article was heated to 600℃in argon at a heating rate of 10℃per hour and held for 5 hours, then an oxygen atmosphere was formed, the temperature was raised at 100℃per hour, and the resultant was fired at 900℃for 1 hour to obtain a porous substrate having a porosity of 25% and a cross-sectional diameter of 0.55 mm.
[ impregnation Process ]
The above complex was stirred at 30 ℃ until uniformly mixed to obtain a colorant solution.
The porous substrate obtained in the firing step was immersed in the colorant solution while being heated to 30 ℃ and kept for 6 hours.
[ drying Process ]
The porous substrate subjected to the impregnation step was kept at 80 ℃ for 6 hours, and the low-boiling organic solvent in the pores of the porous substrate was evaporated and removed to obtain a porous core.
[ filling procedure ]
The porous core obtained in the drying step was immersed in silicone oil in a state heated to 80 ℃ and kept for 6 hours, to obtain a colored pencil lead. Then, excess silicone oil adhering to the surface of the color pencil core was removed by centrifugal separation to obtain a color pencil core of example 101 impregnated with 12.5 mass% silicone oil. Further, the color pencil lead was subjected to thermogravimetry, and as a result, it was confirmed that the pencil lead contained phenyldiglycol. The content thereof is 1 mass% or more.
Examples 102 to 110 and comparative examples 101 to 103
The same procedure was conducted except that the components of example 101 were changed as shown in table 1, and a color pencil lead was obtained. From the thermogravimetry and the production conditions, it was confirmed that the color pencil cores of examples 102 to 110 and comparative example 102 contained high boiling point organic solvents. Comparative examples 102 and 103 were not filled with a nonvolatile liquid.
[ evaluation ]
The performance of the obtained colored pencil lead was evaluated by the following method.
[ evaluation method of writing feeling and handwriting color rendering ]
Using a colored pencil lead, a high-quality paper (paper corresponding to writing paper A specified in JIS P3201, manufactured from 100% chemical pulp, and having a gram weight of 40 to 157 g/m) 2 Whiteness of 75.0% or more), and the writing feeling at this time (writing feeling 1) was evaluated by sensory test. And the color rendering of the resulting handwriting (handwriting color rendering 1).
Further, after the production, the above-mentioned high-quality paper was used for writing using a baked colored pencil lead placed in an environment at 25 ℃ for 4 weeks, and the writing feeling (writing feeling 2) at this time and the color development of the obtained handwriting (handwriting color development 2) were evaluated by sensory test.
(evaluation criteria for writing feeling 1 and 2)
A: writing can be performed very smoothly.
B: can write smoothly.
C: the pen feel is slightly thick and heavy.
D: the pen feel is thick and heavy.
(evaluation criteria for handwriting color developability 1 and 2)
S: the color development is very good.
A: the color development is good.
B: the color development was slightly worse but good.
C: and (5) color difference is displayed.
D: can write, but shows very poor color development.
E: the handwriting cannot be written and cannot be visually recognized.
[ evaluation method of handwriting erasability ]
The scratch was erased according to the erasure ability test of plastic erasure disclosed in JIS 6050-2008, and the erasability at this time (erasability 1) was evaluated by sensory test. In addition, after writing, writing was erased according to the erasure ability test for plastic erasure disclosed in JIS S6050-2008 using a writing line left in an environment of 25 ℃ for 4 weeks, and the erasability at this time (erasability 2) was evaluated by sensory testing. The conventional product is a brand name of an automatic pencil manufactured by jejun, jejun コ: to tap and tap one (yellow) ".
(evaluation criteria for erasability 1 and 2)
A: better than the existing products.
B: equivalent to the existing products.
C: cannot be erased.
/>
In the table:
blue dye B: oil blue 613 (made by the company of the chemical industry, d.)
Red dye R: spilon Red C-PH (manufactured by BaoGu chemical Co., ltd.)
Pink fluorescent pigment P: NKS1007 (a mixture of a polyamide resin and C.I. basic violet 11:1, manufactured by Japanese fluorescent chemical Co., ltd.)
Yellow fluorescent pigment Y: NKS1005 (a mixture of a polyamide resin and C.I. basic yellow 40, manufactured by Japanese fluorescent chemical Co., ltd.)
And (2) a surfactant: is manufactured by Kagaku Kogyo Co., ltd., EA-137)
SO1: dimethicone (trade name: KF-96-50cs, manufactured by Xinyue chemical industries, ltd.; surface tension: 20.8N/m).
SO2: methyl phenyl silicone oil (trade name: KF-96-100cs, manufactured by Xinyue chemical industry Co., ltd.)
Examples 201 to 202 and comparative example 201
The same operations were performed for production example 101 except that the components were changed as shown in table 2, and color pencil cores of the respective examples were obtained. The inclusion of a high boiling point organic solvent in each of the colored pencil leads was confirmed by thermogravimetry and production conditions. Comparative example 201 was not filled with a nonvolatile liquid.
Examples 201 to 202 and comparative example 201
The obtained colored pencil cores were respectively housed in a refill case shown in fig. 2, and a refill product was produced. As shown in table 2, the resin material used for the storage portion of the refill case is composed of 90% or more of the area of the portion of the refill case that can be in contact with the color pencil core.
[ evaluation method of adhesion of colored pencil leads ]
For each of the refill products, the adhesion of the refill was evaluated according to the following criteria, with the colored pencil lead being held in contact with the inner surface of the receiving portion of the refill case at 50 ℃ for 14 days.
(evaluation criteria for adhesion)
A: the color pencil lead is not adhered to the containing part
B: the colored pencil lead is slightly adhered to the accommodating part, but is easily peeled off
C: the colored pencil lead is attached to the containing part
[ evaluation method of writing feeling and handwriting color rendering ]
The evaluation was performed by the same evaluation method as in example 101.
Table z
Blue dye B: oil blue 613 (made by the company of the chemical industry, d.)
Pink fluorescent pigment P: NKS1007 (a mixture of a polyamide resin and C.I. basic violet 11:1, manufactured by Japanese fluorescent chemical Co., ltd.)
AS: acrylonitrile styrene resin (SP value 12.8)
PC: polycarbonate (SP value 9.7)
SO1: dimethicone (trade name: KF-96-50cs, SP value: 7.3, surface tension: 20.8N/m, manufactured by Xinyue chemical industries, ltd.)
Symbol description
101. Storage part
102. Cover part
102a bottom surface of the cover
103. Colour pencil lead
201. Storage part
201a engagement piece
202. Cover part
202a recess
401. Storage part
401a recess
402. Cover part
402a engagement piece
601. Storage part
602. Cover part
602D rotating shaft
603. An outlet
604. Cover fixing member
604E mounting hole
Claims (14)
1. A colored pencil lead characterized by comprising a porous core body and a nonvolatile liquid, wherein the porous core body comprises a constitution material, an inorganic binder material, a colorant and a high-boiling-point organic solvent which can dissolve the colorant and has a boiling point of 250 ℃ or higher, the nonvolatile liquid does not dissolve the colorant, and pores of the porous core body are filled with the colorant, the high-boiling-point organic solvent and the nonvolatile liquid.
2. The colored pencil lead of claim 1, wherein the nonvolatile liquid is selected from the group consisting of silicone oil, fluorine-based oil, mineral oil, vegetable oil, and liquid paraffin.
3. The colored pencil lead of claim 1 or 2, wherein the high boiling point organic solvent is an aromatic glycol ether or an aliphatic glycol ether.
4. The colored pencil lead according to any one of claims 1 to 3, wherein the content of the high boiling point organic solvent is 0.5 to 20 mass% based on the total mass of the colored pencil lead.
5. The colored pencil lead of any one of claims 1 to 4, wherein the colorant has a solubility in the high boiling point organic solvent of 10g/100g or more at 20 ℃.
6. The colored pencil lead of any one of claims 1 to 5, wherein the solubility of the colorant in the less volatile liquid at 20 ℃ is lower than the solubility of the colorant in the high boiling point organic solvent at 20 ℃.
7. The colored pencil lead of any one of claims 1 to 6, wherein the physical material is selected from the group consisting of titanium oxide, mica, talc, boron nitride, aluminum oxide and calcium carbonate.
8. The colored pencil lead of any one of claims 1 to 7, wherein the inorganic binder material is selected from the group consisting of clay, ceramics, zeolite, diatomaceous earth, activated clay, silica, aluminum phosphate, silicone resin, and silicone rubber.
9. The colored pencil lead of any one of claims 1 to 8, wherein the porosity of the porous core is 1 to 50%.
10. The color pencil lead according to any one of claims 1 to 9, wherein the porous core is a fired core.
11. A method for manufacturing a colored pencil lead, comprising:
(a) A kneading step of kneading the physical material and the inorganic binder to prepare a mixture;
(b) An extrusion step of extruding the mixture to form a linear molded article;
(c) A firing step of firing the linear molded article to produce a porous base material;
(d) An impregnation step of bringing a colorant solution containing a colorant and a high-boiling-point organic solvent having a boiling point of 250 ℃ or higher into contact with the porous substrate to impregnate the porous substrate;
(e) A drying step of heating the porous base material after the impregnation step at a temperature of 200 ℃ or lower to form a porous core;
(f) And a filling step of bringing a nonvolatile liquid in which the colorant is not dissolved into contact with the porous core, and filling voids in the porous core with the nonvolatile liquid.
12. The method of claim 11, the colorant solution further comprising a low boiling point organic solvent having a boiling point below 250 ℃.
13. A refill product comprising the colored pencil lead of any one of claims 1 to 10 and a refill case accommodating the colored pencil lead.
14. The refill product according to claim 13, wherein a resin material having a solubility parameter different from the solubility parameter of the nonvolatile liquid by 1.5 or more is disposed on a part of a portion of an inner surface of the refill case that is accessible to the colored pencil core.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2021055731 | 2021-03-29 | ||
| JP2021-055731 | 2021-03-29 | ||
| PCT/JP2022/015010 WO2022210535A1 (en) | 2021-03-29 | 2022-03-28 | Color pencil lead, method for manufacturing color pencil lead, and refill product comprising color pencil lead and refill case in which same is accommodated |
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| Publication Number | Publication Date |
|---|---|
| CN117136221A true CN117136221A (en) | 2023-11-28 |
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| JP (1) | JPWO2022210535A1 (en) |
| KR (1) | KR20230163478A (en) |
| CN (1) | CN117136221A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5025368B2 (en) * | 2007-07-26 | 2012-09-12 | 三菱鉛筆株式会社 | Solid drawing material |
| JP6423158B2 (en) * | 2014-02-27 | 2018-11-14 | 三菱鉛筆株式会社 | Colored pencil lead |
| JP7034684B2 (en) * | 2017-11-30 | 2022-03-14 | 株式会社パイロットコーポレーション | Fired colored pencil lead |
| JP7281967B2 (en) * | 2019-05-30 | 2023-05-26 | 株式会社パイロットコーポレーション | fired colored pencil lead |
-
2022
- 2022-03-28 WO PCT/JP2022/015010 patent/WO2022210535A1/en active Application Filing
- 2022-03-28 CN CN202280025830.2A patent/CN117136221A/en active Pending
- 2022-03-28 KR KR1020237036693A patent/KR20230163478A/en unknown
- 2022-03-28 JP JP2023511260A patent/JPWO2022210535A1/ja active Pending
- 2022-03-29 TW TW111111975A patent/TW202244206A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TW202244206A (en) | 2022-11-16 |
| JPWO2022210535A1 (en) | 2022-10-06 |
| WO2022210535A1 (en) | 2022-10-06 |
| KR20230163478A (en) | 2023-11-30 |
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