WO2022210535A1 - Color pencil lead, method for manufacturing color pencil lead, and refill product comprising color pencil lead and refill case in which same is accommodated - Google Patents
Color pencil lead, method for manufacturing color pencil lead, and refill product comprising color pencil lead and refill case in which same is accommodated Download PDFInfo
- Publication number
- WO2022210535A1 WO2022210535A1 PCT/JP2022/015010 JP2022015010W WO2022210535A1 WO 2022210535 A1 WO2022210535 A1 WO 2022210535A1 JP 2022015010 W JP2022015010 W JP 2022015010W WO 2022210535 A1 WO2022210535 A1 WO 2022210535A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pencil lead
- colored pencil
- organic solvent
- coloring agent
- lead
- Prior art date
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 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
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 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
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Images
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
Definitions
- the present invention relates to a colored pencil lead. More specifically, it relates to a colored pencil lead which is excellent in coloring and has a smooth writing feel.
- colored pencil leads used in mechanical pencils and the like are mainly composed of an extender such as boron nitride and a binder such as clay.
- a white porous substrate obtained by firing at a high temperature is impregnated with an ink containing a dye in the pores thereof.
- it is desirable to use various materials and equipment to achieve better color development in order to express a variety of color tones. is also desired to be improved.
- the present invention provides a colored pencil core which is excellent in handwriting color development, has high stability over time, and provides a smooth writing feel.
- the colored pencil lead according to the present invention is body material and an inorganic binder; a coloring agent; a porous core containing a high-boiling organic solvent capable of dissolving the coloring agent and having a boiling point of 250° C. or higher;
- the coloring agent, the high-boiling organic solvent, and the low-volatility liquid are filled in the pores of the porous core.
- the method for producing a colored pencil lead comprises: (a) a kneading step of kneading an extender and an inorganic binder to prepare a mixture; (b) an extrusion step of extruding the mixture to form a linear form; (c) a sintering step of sintering the linear molded product to create a porous substrate; (d) an impregnation step of contacting and impregnating the porous substrate with a coloring agent solution containing a coloring agent and a high-boiling organic solvent having a boiling point of 250° C.
- the colored pencil lead according to the present invention By writing with the colored pencil lead according to the present invention, it is possible to form handwriting with excellent coloring. In addition, a smooth writing feeling can be obtained when writing with the core of the colored pencil according to the present invention. In addition, the colored pencil lead according to the present invention has high storage stability, and is excellent in color developability and erasability over time.
- FIG. 1 is a perspective view of a refill product according to the present invention
- FIG. FIG. 2 is a vertical cross-sectional view of a refill case that can be used in the present invention.
- Fig. 2 is a cross-sectional view of a refill lead case that can be used in the present invention
- FIG. 4 is a longitudinal sectional view of another refill case that can be used in the present invention.
- FIG. 10 is a cross-sectional view of another refill lead case that can be used in the present invention;
- FIG. 10 is a vertical cross-sectional view of still another refill case that can be used in the present invention.
- FIG. 10 is a cross-sectional view of still another extra lead case that can be used in the present invention.
- the porous core used for the colored pencil core of the present invention contains a filler and an inorganic binder as main components.
- the filler include white ones such as titanium oxide, mica, talc, boron nitride, alumina and calcium carbonate, and colored ones such as molybdenum disulfide, tungsten disulfide and graphite.
- white ones such as titanium oxide, mica, talc, boron nitride, alumina and calcium carbonate
- colored ones such as molybdenum disulfide, tungsten disulfide and graphite.
- inorganic binder examples include clays such as kaolinites, hallosites, montmorillonites, sericites and bentonites, ceramics, zeolites, diatomaceous earth, activated clay, silica, aluminum phosphate, silicone resins, and silicone rubbers. etc., and these can be used singly or in combination.
- the compounding ratio of the filler and the inorganic binder, which are the main components of the porous core is not particularly limited, it is preferably 9:1 to 7:3 in mass ratio.
- the porous core is typically a combination of a porous base material, a coloring agent and a high boiling point organic solvent.
- the coloring agent may be localized in a part of the porous substrate containing an extender or an inorganic binder as a main component, or may be dispersed uniformly throughout the porous substrate. It is preferably localized in a part of the sex core. Specifically, it is preferable that the coloring agent is adhered or adsorbed in the pores of the porous substrate. At this time, the coloring agent may be in the state of fine particles or in the state of being dissolved or dispersed in a high boiling point organic solvent, which will be described later.
- the coloring agent When the coloring agent is present in the final colored pencil lead in such a state, the coloring agent is prevented from penetrating into the paper during writing, and the coloring property and erasability are improved.
- the colorant typically forms a layer or phase within the pores. That is, it generally forms a uniform or non-uniform layer or adheres to the inner surface of the pores in a mass.
- the term "pores" means pores in a base material such as a porous base material obtained by removing an organic solvent from a pencil lead.
- a porous base material obtained by removing an organic solvent from a pencil lead.
- an organic solvent or the like may penetrate into the pores, and the pores of the porous core mean the pores after removing the organic solvent or the like from the porous core. .
- the porous core contains a filler, an inorganic binder, a coloring agent, and a high-boiling organic solvent.
- a pencil lead is generally manufactured by molding a mixture of an extender and a binder and then firing the molded mixture, but the same method can be applied to the present invention. That is, it can be produced by baking a mixture of an extender and an inorganic binder, and adsorbing or adhering a coloring agent and a high boiling point organic solvent to the formed porous substrate (details will be described later).
- the filler, the inorganic binder, the coloring agent, and the high boiling point organic solvent may be mixed and baked. It is preferred to use a boiling point organic solvent.
- the former method even a coloring agent with low heat resistance and a high boiling point organic solvent having a boiling point lower than the firing temperature can be used.
- a mixture containing an extender, an inorganic binder, an inorganic substance, a water-soluble resin, and, if necessary, a coloring agent is compressed under high pressure, and then immersed in water or a solvent to remove the inorganic substance or the water-soluble resin.
- a porous core can also be produced by removing the water-soluble resin or 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%, and more preferably in the range of 10 to 40%. is more preferable, and a range of 20 to 40% is particularly preferable. If the porosity is less than 1%, the amount of the coloring agent and the refractory liquid present in the pores is reduced, resulting in poor color development and a slight resistance to writing. There is a tendency that the strength of the porous core thus formed is reduced and that it is likely to break. When the porosity is in the range of 1 to 50%, the coloring property is good, the writing feeling is smooth, and the strength of the fired colored pencil core can be maintained, which is preferable.
- the porosity of the porous base material used in the present invention can be measured by the following method with reference to JIS R1634 (1998). First, the dry mass (W1) of the porous substrate is measured. Next, the substrate is immersed in a highly permeable liquid (for example, benzyl alcohol) to allow the pores of the porous substrate to absorb the liquid until it is saturated, and then the weight in the liquid (W2) is measured. Further, the porous substrate is taken out of the liquid, and after removing the liquid adhering to the surface thereof, the liquid-saturated mass (W3) is measured. Using these measured values, the porosity is determined by the following formula (1).
- a highly permeable liquid for example, benzyl alcohol
- the porosity of the colored pencil lead or porous core can also be measured by the same method. However, before applying the measuring method for the porosity of the porous substrate, it is necessary to remove the organic solvent or the like by heating or reducing the pressure. When measuring the porosity of a colored pencil lead or a porous core body, even if the solvent or the like is removed, a small amount of the organic solvent or the like may remain in the pores. Therefore, there may be a slight difference between the porosity of the porous substrate and the porosity of the colored pencil lead or the porous core. Taking such differences into account, the porosity of the porous substrate is preferably in the range of 5-50%, more preferably in the range of 10-40%, and more preferably in the range of 20-40%. It is particularly preferred to have
- a dye or pigment can be used as the coloring agent.
- a colored pigment obtained by dyeing a resin with a dye or the like can be used.
- dyes may have low heat resistance, but they easily penetrate into porous substrates when taken as a solution, which facilitates the production of the pencil lead according to the present invention. Therefore, the coloring agent is a dye. is preferred.
- the dyes that can be used in the present invention are not particularly limited, and include general dyes and fluorescent dyes.
- Examples of general dyes include oil-soluble dyes, acid dyes, basic dyes, and metal dyes.
- Salt-forming dyes 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, salt-forming dyes of an acid dye and an organic amine, and the like. More specifically, Bali Fast Black 1802, Bas Fast Black 1805, Bali Fast Black 1807, Bali Fast Violet 1701, Bali Fast Violet 1704, Bali Fast Violet 1705, Bali Fast Blue 1601, Bali Fast Blue 1605, and Bali Fast Blue 1613.
- fluorescent dyes include Basic Yellow 1, 40, Basic Red 1, 1:1, 13, Basic Violet 1, 7, 10, 11:1, Basic Orange 22, Basic Blue 7, Basic Green 1, Acid Yellow 3, Acid 7, Acid Red 52, 77, 87, 92, Acid Blue 9, Disperse Yellow 121, 82, 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.
- These dyes may be used alone or in combination of two or more in order to adjust the color of the handwriting within the range that does not affect the performance of the colored pencil lead. Furthermore, these dyes may be used in combination with other dyes.
- Any pigment can also be used as the coloring agent. Ultra-fine pigments, processed pigments, and the like can also be used.
- Any resin such as acrylic resin, styrene-acrylonitrile resin, styrene resin, nitrogen-containing resin, polyethylene resin, or polypropylene resin can be used as the resin constituting the coloring pigment. Dyes to be combined with these resins can be selected from those described above.
- nitrogen-containing resins or styrene-acrylonitrile resins are preferably used in consideration of solubility in high-boiling organic solvents, dispersibility and dispersion stability, and dyeability with dyes.
- nitrogen-containing resins are more preferred.
- melamine resins, polyamide resins, urethane resins, urea resins, benzoquanamine resins, and the like are preferable.
- melamine resins or polyamide resins are preferred, and melamine resins are more preferred, from the viewpoint of dissolution stability in high boiling point organic solvents.
- coloring pigments examples include the NKS-1000 series, MPI-500 series (manufactured by Nihon Shokuryo Kagaku Co., Ltd.), FNP series, and FM series (manufactured by Shinroihi Co., Ltd.).
- color pigments may be used in combination of two or more, for example, for the purpose of adjusting the color of the handwriting within the range that does not impair the effects of the present invention.
- dyes may be used in combination with these color pigments.
- a fluorescent colorant it is also preferable to use a fluorescent colorant.
- a coloring agent By using such a coloring agent, it is possible to obtain a handwriting having fluorescence and to obtain a handwriting that is richer in color development. This makes it easy to use not only for simply leaving characters, but also for situations such as drawing and marking.
- the content of the coloring agent in the total weight of the colored pencil core varies depending on the type, but is preferably 0.1 to 30% by mass, more preferably 0.2 to 25% by mass. It is preferably 1 to 20% by mass.
- the porous substrate containing the filler and the inorganic binder is impregnated with a coloring agent solution in which the coloring agent is dissolved in a solvent, and then the necessary It can be easily produced by removing part of the solvent according to (details will be described later). For this reason, it is preferable that the solvent used in the production is capable of dissolving the colorant used.
- the colored pencil lead according to the present invention contains a high-boiling organic solvent capable of dissolving the colorant contained in the colored pencil lead and having a boiling point of 250°C or higher.
- a solvent can impart excellent color developability and writing feel to the lead of the colored pencil according to the present invention.
- it since it has a high boiling point, it is difficult to volatilize during the manufacturing process and storage, and it is possible to maintain stable performance.
- the expression that the high boiling point organic solvent is capable of dissolving the colorant means that the solubility of the colorant in the high boiling point organic solvent is 10 g/100 g or more at 20°C. It means that 10 g or more of the colorant dissolves in 100 g.
- glycol ethers contain both an ether group and a hydroxyl group in their structure, and are generally characterized by high solubility in dyes and resins, and high affinity with other organic solvents.
- high-boiling organic solvents include diethylene glycol monophenyl ether (phenyldiglycol, 283° C.), diethylene glycol monobenzyl ether, (302° C.), triethylene glycol monobutyl ether (butyl triglycol, 271° C.), Ethylene glycol monobenzyl ether (256°C) etc.
- the numerical value in a parenthesis shows a boiling point (the same applies below).
- a carboxylic acid ester of polyalkylene glycol or a carboxylic acid ester of alcohol can be used as the high-boiling organic solvent.
- higher fatty acids and higher alcohols with a boiling point of 250°C or higher can also be used.
- carboxylic acids with 10 or more carbon atoms such as decanoic acid (259°C) and oleic acid (360°C)
- alcohols with 12 or more carbon atoms such as dodecyl alcohol (259°C) and myristyl alcohol (292°C), ).
- higher fatty acids may corrode the lead of colored pencils used in mechanical pencils and come into contact with metal parts, so care should be taken.
- the content of the high boiling point organic solvent contained in the colored pencil lead according to the present invention is appropriately adjusted according to the purpose. It is preferably 20% by mass, more preferably 1 to 15% by mass.
- the content of high boiling organic solvent can be measured by any method. For example, by a method such as thermogravimetry, it can be confirmed that the colored pencil lead contains a high-boiling organic solvent.
- the colored pencil lead according to the present invention can contain an organic solvent (hereinafter sometimes referred to as a low boiling point organic solvent) other than the high boiling point organic solvent.
- the low boiling point organic solvent referred to here is also different from the low-volatility liquid described later. Specifically, it is an organic solvent having a boiling point of less than 250° C. and capable of dissolving the coloring agent.
- the low boiling point organic solvent capable of dissolving the colorant means that the solubility of the colorant in the low boiling point organic solvent is 10 g/100 g or more at 20°C, that is, the low boiling point organic solvent at 20°C It means that 10 g or more of the colorant dissolves in 100 g. The higher the solubility of the coloring agent, the higher the storage stability of the colored pencil lead.
- the low boiling point organic solvents those with relatively high boiling points, for example, those with a boiling point of 150° C. or more and less than 250° C. can generally be expected to compensate for the effects such as improved writing quality obtained with high boiling point organic solvents. .
- those having a relatively low boiling point for example, those having a boiling point of less than 150° C. are generally effective in reducing the viscosity of the colorant solution when the porous substrate is impregnated with the colorant during the manufacturing process. be.
- the boiling point of the low boiling point solvent is preferably 100° C. or lower, more preferably 90° C. or lower, even more preferably 85° C. or lower, and even more preferably 80° C. or lower.
- the difference between BPH and BPL is preferably 100 degrees or more, more preferably. is greater than or equal to 150 degrees. Due to the difference in boiling points between the high boiling point organic solvent and the low boiling point organic solvent, it is possible to remove only the low boiling point organic solvent in the manufacturing process described below. As a result, a colored pencil lead having excellent color developability and writing feel brought about by the high boiling point organic solvent is obtained. In addition, the high boiling point organic solvent is difficult to volatilize during the manufacturing process and storage, and can maintain stable performance.
- low boiling point organic solvents examples include: triethylene glycol monomethyl ether (249° C.), 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.), ethyl alcohol (78° C.), ethyl acetate (77° C.), Acetone (56°C) etc.
- isopropyl alcohol methyl ethyl ketone, ethyl alcohol, ethyl acetate, or acetone are preferably used.
- the pores of the above-mentioned porous core are filled with a hardly volatile liquid.
- This low-volatility liquid further improves the feel of writing.
- a low-volatility liquid is a liquid that is incapable of dissolving a coloring agent and is difficult to volatilize at room temperature.
- insoluble does not mean that the colorant has zero solubility, but means that it is substantially insoluble.
- the solubility of the coloring agent in the refractory liquid is preferably lower than the solubility in the above-described high-boiling organic solvent. More specifically, the solubility of the coloring agent in the refractory liquid at 20° C. is 10 g/100 g. preferably less than, more preferably 5 g/100 g or less
- the boiling point of the hardly volatile liquid is not particularly limited, it is preferably a liquid that does not volatilize at 250°C or lower.
- the stability of the colored pencil core over time is maintained at a high level, and the writing feel is improved.
- the replacement lead product contains an organic solvent
- the replacement lead and the case may fuse together in the case of the replacement lead product, but the colored pencil lead contains a refractory liquid. This makes it possible to improve such fusion.
- the SP value of the resin material to be used is 6-8.
- the Fedors solubility parameter, the Hildebrand solubility parameter, the Hansen solubility parameter, etc. are known as the SP value, but the Fedors solubility parameter is used as the solubility parameter in the present invention.
- the low-volatility liquid preferably has a low viscosity in order to facilitate impregnation into the pores of the porous core.
- the surface tension of the refractory liquid is excellent in impregnating the pores of the porous core, and the refractory liquid is impregnated evenly throughout the porous core, resulting in excellent writing and erasability. It is preferably 35 mN/m or less, more preferably 30 mN/m or less, and even more preferably 25 mN/m or less, so that a colored pencil lead with good resistance can be obtained.
- surface tension can be measured by the method specified in JIS K2241 under conditions of a temperature of 25°C.
- preferred low-volatility liquids include those selected from the group consisting of silicone oil, fluorine-based oil, mineral oil, vegetable oil, and liquid paraffin, with silicone oil being more preferred.
- Silicone oil has a small change in viscosity due to temperature and is excellent in stability. When used in a pencil, it hardly corrodes parts such as the opening at the tip of the mechanical pencil, the chuck, and the lead housing cylinder, which are made of metal materials.
- silicone oil dimethylsilicone and methylphenylsilicone are particularly preferred, and modified silicone is also preferred.
- the coloring agent is difficult to dissolve.
- liquid paraffin preferably has 14 or more carbon atoms.
- the content of the hardly volatile liquid relative to the total weight of the colored pencil lead is preferably 5-40% by mass, more preferably 8-45% by mass, and more preferably 10-35% by mass.
- the colored pencil lead according to the present invention may contain various additives within a range that does not affect its performance.
- Specific additives include surfactants, preservatives, antifungal agents, resins, and the like.
- the shape of the colored pencil lead according to the present invention is not particularly limited, it is generally a linear body with a circular cross section.
- the cross-sectional diameter of a colored pencil lead for a mechanical pencil is preferably 0.2 to 2.0 mm, more preferably 0.3 to 0.7 mm.
- the length is preferably 30 to 100 mm, more preferably 40 to 70 mm.
- the cross-sectional diameter is preferably 0.5 to 3.0 mm, preferably 0.8 to 2.0 mm. .
- the length is not limited, but is generally 1,000 mm or less, since long colored pencil cores are often sandwiched between pieces of wood or the like during the manufacturing process and then cut.
- the colored pencil lead according to the present invention can achieve high physical strength by using a porous base material produced by firing. This is presumably because the coloring agent forms a uniform or non-uniform layer or adheres to the inner surface of the pores in a lump.
- the bending strength of the colored pencil lead according to the present invention is preferably 120 MPa or more. It is more preferably 180 MPa or more. The bending strength can be measured by the method specified in JIS S 6005:2007.
- the colored pencil lead according to the present invention can be configured so as not to contain an acidic component.
- Colored pencil leads are often used in mechanical pencils and the like, so they often come into contact with metal materials. Therefore, by adopting a structure that does not contain an acidic component, it is possible to suppress corrosion of the metal portion of the mechanical pencil. Therefore, it is preferred that the colored pencil lead according to the invention does not contain acidic materials.
- the manufacturing method of the colored pencil lead according to the present invention is not particularly limited. however, (a) a kneading step of kneading an extender and an inorganic binder to prepare a mixture; (b) an extrusion step of extruding the mixture to form a linear form; (c) a sintering step of sintering the linear molded product to create a porous substrate; (d) an impregnation step of contacting and impregnating the porous substrate with a coloring agent solution containing a coloring agent and a high-boiling organic solvent having a boiling point of 250° C.
- a method comprising a filling step of contacting the porous core with a refractory liquid in which the coloring agent cannot be dissolved, and filling the pores of the porous core with the refractory liquid. It is preferably manufactured by This method will be described below.
- the colored pencil lead according to the present invention is generally preferably formed into a linear body having a circular cross-sectional shape, it is extruded into a linear molded article.
- (c) Firing Step The obtained linear shaped product is dried as necessary and then fired to form a porous base material.
- the organic solvent contained in the mixture is removed, and the filler and the inorganic binder are sintered to form a porous substrate.
- the sintering conditions are not particularly limited as long as the material is sintered to form a porous base material.
- the temperature during firing can be increased continuously or stepwise.
- the rate of temperature increase in such a case can be, for example, 10 to 100° C./hr. It is also preferable to bake at a constant temperature for a certain period of time, for example, about 0.5 to 2 hours after raising the temperature to the set temperature.
- each of these conditions can be arbitrarily combined according to the purpose.
- the temperature is raised from room temperature to 650 ° C. at a rate of 10 ° C./hr, and then the temperature is maintained at 650 ° C. for 1 hour and fired.
- Conditions such as firing at 1000° C. for one hour can be employed.
- Impregnation step After cooling the formed porous substrate as necessary, the porous substrate is brought into contact with a solution containing a coloring agent and a high boiling point organic solvent. In this process, the pores present in the porous substrate are penetrated by the colorant solution.
- a method for impregnation normal pressure impregnation or reduced pressure/pressure impregnation 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, based on the total mass of the solution. , 10 to 40% by weight is particularly preferred. If the content is less than this range, the content of the coloring agent tends to be low, resulting in poor color development.
- the stability of the solution over time may decrease, such as the colorant precipitating over time.
- a surfactant may be added to the solution in order to improve the solubility and stability of the colorant.
- a mixed solvent in which a high boiling point organic solvent is combined with a low boiling point organic solvent is used as a solvent for the colorant solution
- the viscosity of the colorant solution is lowered to facilitate impregnation. It becomes easier to form voids in the pores.
- the pores of the core are easily impregnated with the refractory liquid, and the effect obtained by impregnating the wick with the refractory liquid can be sufficiently obtained.
- a low boiling point organic solvent is preferably a solvent that evaporates at 100° C. or lower, more preferably 90° C. or lower, and still more preferably 80° C. or lower. More preferably, aliphatic alcohols having 1 to 4 carbon atoms are preferred.
- the blending ratio of the high boiling point organic solvent and the low boiling point organic solvent can be adjusted according to the difference in boiling points and the solubility of the colorant. is preferably 1:1 to 1:15, more preferably 1:1 to 1:12, even more preferably 1:1.5 to 1:10, 1:1.5 ⁇ 1:7 is particularly preferred.
- the conditions at this time are not particularly limited, but, for example, a temperature of 60° C. for 6 to 12 hours can be employed. Normal pressure impregnation, reduced pressure, and pressure impregnation can be used to fill the refractory liquid.
- a refill lead product according to the present invention is obtained by housing the above-described colored pencil lead in a refill lead case. It is preferable that a resin material having a solubility parameter different from that of the refractory liquid by 1.5 or more is disposed on a portion of the inner surface of the refill lead case that can be contacted by the pencil lead.
- the refill lead case is made of a material with relatively high hardness, but is generally made of resin from the viewpoint of ease of manufacture and cost. However, if a suitable resin is not selected, the colored pencil lead and the resin material may adhere to each other.
- the difference between the SP value of the non-volatile liquid contained in the colored pencil lead and the SP value of the resin constituting the lead case is sufficiently large. found to be Such adhesion naturally occurs at the part of the refill case that comes into contact with the colored pencil lead, so the SP value of the resin placed in that part of the refill case is sufficiently different from the SP value of the refractory liquid. It is good if there is Specifically, the difference between the SP value of the refractory liquid and the SP value of the resin material disposed in the portion where the colored pencil lead contacts is preferably 1.5 or more, and the difference is 2.0 or more. is more preferable, a difference of 3.0 or more is more preferable, and a difference of 5.0 or more is even more preferable.
- the difference between the SP value of the refractory liquid and the SP value of the resin material is preferably 1.5 or more, but either one may be larger.
- the SP value of the refractory liquid and the SP value of the resin material are not particularly limited as long as these relative differences are satisfied.
- silicone oil with an SP value of 7.2 is used as the non-volatile liquid
- the SP value of the resin material must be 5.7 or less, or 8.7 or more.
- resin materials that meet these conditions include polystyrene (8.6 to 9.7), vinyl acetate resin (9.4), vinyl chloride (9.5 to 9.7), and polycarbonate (9.7).
- the SP value of resin materials tends to be higher than the SP value of refractory liquids.
- the SP value of the resin material is preferably 8.5-15.
- the refill lead product according to the present invention allows the remaining amount of stored pencil lead to be visually recognized from the outside. Therefore, it is preferable to use a transparent resin material for the case. Therefore, it is preferable to use a resin having high toughness, excellent moldability, and transparency, and it is particularly preferable to use polycarbonate (9.7) or acrylonitrile styrene resin (12.8).
- the shape of the extra lead case is not particularly limited, and any conventionally known shape can be adopted.
- a replacement lead case is adopted that includes a storage portion that stores a colored pencil lead, and a lid portion that temporarily seals and deforms an opening provided in the storage portion so that the colored pencil lead can be taken out.
- the lid any object generally called a lid can be adopted.
- the opening provided in the storage unit is temporarily closed to hold the colored pencil lead in the replacement lead case, and when necessary, it can be removed, moved, or rotated. By deforming, it is possible to take out the colored pencil lead from the opening of the storage part.
- FIG. 1 As the simplest shape, as shown in FIG. 1, it is composed of a cylindrical housing portion 101 with one end closed and a lid portion 102 fitted into an opening formed at one end of the housing portion.
- a refill lead case can be exemplified.
- the colored pencil lead 103 housed in the replacement lead case can be taken out from the housing portion by removing the lid portion 102 from the housing portion 101 .
- a specific resin material is arranged in part of the part of the refill lead case that can come into contact with the colored pencil lead.
- all the inner surfaces of the space defined by the inner surface of the accommodating portion and the bottom surface 102a of the lid after fitting come into contact with the colored pencil lead of the refill lead case. part that can be done.
- a specific resin material is arranged in a part of the part of the refill lead case that can come into contact with the colored pencil lead.
- the expression that a resin material is placed in a specific portion means, for example, forming that portion with a resin material, arranging a component formed of a resin material, or coating that portion with a resin material. do.
- this can be realized by forming the entire accommodating portion from a specific resin material.
- the lid portion may be made of a resin material, or the inner surface of the housing portion may be covered with a resin material.
- the ratio of the area where the specific resin material is arranged to the total area of the portion where the colored pencil lead and the replacement lead case can come into contact is high.
- the area of the portion where the specific resin material is disposed is preferably 50% or more, preferably 80% or more, of the total area of the portion of the refill lead case that can come into contact with the colored pencil lead. is more preferred, and 90% or more is particularly preferred.
- a specific resin material be placed on all of the parts of the refill lead case that can come into contact with the colored pencil lead. Therefore, in the refill lead case of FIG. 1, although it depends on the size, by molding the accommodating portion with a resin material having a specific SP value, adhesion of the colored pencil lead can be suppressed.
- a refill lead case as shown in FIGS. 2 and 3 can be adopted.
- This is a replacement lead case in which a lid part 202 is detachably attached to a storage part 201 capable of storing a replacement lead.
- the lid portion 202 is formed with an engaging piece 202a protruding from the lower end, and the accommodating portion is formed with a recessed portion 201a that matches the engaging piece 202a.
- the protruding part and the recessed part can be exchanged and formed.
- a refill lead case as well, by forming the entire accommodating portion 201 using a specific resin material, adhesion of colored pencil leads can be suppressed.
- the inner surface of the housing portion 201 may be coated with a specific resin material.
- a refill lead case as shown in FIGS. 4 and 5 can be adopted.
- This case is also a refill lead case in which a lid part 402 is detachably attached to a storage part 401 for storing colored pencil leads.
- the lid portion 402 is formed with an engagement piece 402a projecting from the lower end, and the housing portion 401 is formed with a concave portion 401a that matches the engagement piece 402a.
- the protrusion and recessed portions can be engaged with each other to stably attach the lid to the receptacle.
- the protruding part and the recessed part can be exchanged and formed.
- by forming the entire accommodating portion 401 using a specific resin material adhesion of colored pencil leads can be suppressed.
- a refill lead case as shown in FIGS. 6 and 7 can also be adopted.
- This case accommodates a colored pencil lead inside an accommodating portion 601 .
- the colored pencil lead By rotating the lid portion 602 around the rotating shaft 602D, the colored pencil lead can be held in the storage portion and the colored pencil lead can be taken out from the lead outlet 603.
- the exit 603 for the colored pencil lead can be opened by turning the lid 602 upright, and the exit 603 can be closed by laying down the lid 602 .
- a non-circular mounting hole 604E is formed in the lid portion fixing member 604, and a cut groove 604F is formed in the lid portion fixing member 604 crossing the mounting hole so that the mounting hole can be expanded. It is configured.
- an arcuate groove is formed in the lid portion fixing member on the side opposite to the outlet, and a rotating shaft 602D having a non-circular cross section is formed in the lid portion.
- the end on the rotating shaft side is formed in a semicircular shape, and the rim of the semicircular end is formed with a protruding portion having an appropriate width in the back direction from the front wall, and the rotating shaft of the lid portion It is rotatably attached to the attachment hole of the fixing member.
- the rotating shaft of the lid is engaged with the mounting hole of the lid fixing member, and the protuberance forms a notch crossing the mounting hole of the lid fixing member. It is designed to cover.
- Coloring agent blue dye
- phenyldiglycol 10 parts by mass
- Low boiling point organic solvent ethyl alcohol
- Resin ketone resin
- the porous base material obtained in the firing process was immersed in the coloring agent solution while being heated to 30°C, and held for 6 hours.
- the porous substrate was held at 80° C. for 6 hours to evaporate and remove the low boiling point organic solvent in the pores of the porous substrate to obtain a porous core.
- Example 102 to 110 Comparative Examples 101 to 103
- a colored pencil lead was obtained in the same manner as in Example 101, except that each component was changed to those listed in Table 1. It was confirmed from thermogravimetry and production conditions that the colored pencil leads of Examples 102 to 110 and Comparative Example 102 contained a high-boiling organic solvent. Comparative Examples 102 and 103 were not filled with the hardly volatile liquid. [evaluation] The performance of the obtained colored pencil lead was evaluated by the following methods.
- High-quality paper (equivalent to writing paper A specified in the old JIS P3201) is prepared using colored pencil cores. Paper is made from 100% chemical pulp, and has a weighing range of 40 to 157 g/m 2 and a whiteness of 75.0% or more. ), and the writing feeling at that time was evaluated by a sensory test (writing feeling 1). Also, the coloring property of the obtained handwriting (handwriting coloring property 1). Furthermore, after production, using the baked colored pencil core left in an environment of 25 ° C. for 4 weeks, writing is performed on the high-quality paper, and the writing taste at that time (writing taste 2) and the color development of the handwriting obtained (handwriting color development 2). was evaluated by a sensory test.
- Blue dye B Oil Blue 613 (manufactured by Orient Chemical Industry Co., Ltd.) Red dye R: Spiron Red C-PH (manufactured by Hodogaya Chemical Industry Co., Ltd.)
- Pink fluorescent pigment P NKS1007 (manufactured by Nihon Shokuryo Kagaku Co., Ltd., a mixture of polyamide resin and C.I. Basic Violet 11:1)
- Yellow fluorescent pigment Y: NKS1005 manufactured by Nippon Shokuryo Kagaku Co., Ltd., a mixture of polyamide resin and C.I.
- Examples 201 to 202, Comparative Example 201 The resulting colored pencil leads were accommodated in the replacement lead cases shown in FIG. 2 to obtain replacement lead products.
- the resin material used for the housing portion of this replacement lead case is as shown in Table 2, and 90% or more of the area of the portion of this replacement lead case that can come into contact with the colored pencil lead is composed of the resin material. .
- Blue dye B Oil Blue 613 (manufactured by Orient Chemical Industry Co., Ltd.)
- Pink fluorescent pigment P NKS1007 (manufactured by Nihon Shokuryo Kagaku Co., Ltd., a mixture of polyamide resin and C.I. Basic Violet 11:1)
- AS acrylonitrile styrene resin (SP value 12.8)
- PC polycarbonate (SP value: 9.7)
- SO1 Dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96-50cs, SP value: 7.3, surface tension: 20.8 N / m)
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Abstract
Description
体質材と、
無機結合材と、
着色剤と、
前記着色剤を溶解可能であり、沸点が250℃以上の高沸点有機溶媒と
を含んでなる多孔性芯体、および
前記着色剤を溶解不能である難揮発性液体
を含んでなり、
前記着色剤、前記高沸点有機溶媒、および前記難揮発性液体が前記多孔性芯体の気孔中に充填されていることを特徴とするものである。 The colored pencil lead according to the present invention is
body material and
an inorganic binder;
a coloring agent;
a porous core containing a high-boiling organic solvent capable of dissolving the coloring agent and having a boiling point of 250° C. or higher;
The coloring agent, the high-boiling organic solvent, and the low-volatility liquid are filled in the pores of the porous core.
(a)体質材と無機結合材を混練して混合物を調製する混練工程、
(b)前記混合物を押出成形して線状成形物を作成する押出工程、
(c)前記線状成形物を焼成して、多孔性基材を作成する焼成工程、
(d)着色剤と沸点が250℃以上の高沸点有機溶媒を含む着色剤溶液を前記多孔性基材に接触させて含浸させる含浸工程、
(e)含浸工程後の前記多孔性基材を200℃以下の温度で加熱して、多孔性芯体を形成させる乾燥工程、
(f)前記多孔性芯体に、前記着色剤を溶解不能である難揮発性液体を接触させて、前記多孔性芯体の空隙に前記難揮発性液体を充填する充填工程
を含んでなることを特徴とするものである。 Further, the method for producing a colored pencil lead according to the present invention comprises:
(a) a kneading step of kneading an extender and an inorganic binder to prepare a mixture;
(b) an extrusion step of extruding the mixture to form a linear form;
(c) a sintering step of sintering the linear molded product to create a porous substrate;
(d) an impregnation step of contacting and impregnating the porous substrate with a coloring agent solution containing a coloring agent and a high-boiling organic solvent having a boiling point of 250° C. or higher;
(e) a drying step of heating the porous substrate after the impregnation step at a temperature of 200° C. or less to form a porous core;
(f) A filling step of contacting the porous core with a refractory liquid in which the colorant cannot be dissolved, and filling the voids of the porous core with the refractory liquid. It is characterized by
本発明による色鉛筆芯の構成について説明すると以下の通りである。 <Colored pencil lead>
The configuration of the colored pencil lead according to the present invention is described below.
ジエチレングリコールモノフェニルエーテル(フェニルジグリコール、283℃)、
ジエチレングリコールモノベンジルエーテル、(302℃)、
トリエチレングリコールモノブチルエーテル(ブチルトリグリコール、271℃)、
エチレングリコールモノベンジルエーテル(256℃)
などが挙げられる。なお、括弧内の数値は沸点を示す(以下同様)。 Specific examples of such high-boiling organic solvents include diethylene glycol monophenyl ether (phenyldiglycol, 283° C.),
diethylene glycol monobenzyl ether, (302° C.),
triethylene glycol monobutyl ether (butyl triglycol, 271° C.),
Ethylene glycol monobenzyl ether (256°C)
etc. In addition, the numerical value in a parenthesis shows a boiling point (the same applies below).
トリエチレングリコールモノメチルエーテル(249℃)、
フェニルセルロルブ(247℃)、
プロピレングリコールモノメチルエーテル(243℃)、
ベンジルアルコール(205℃)、
3-メトキシー3―メチル-1-ブタノール(174℃)、
キシレン(139℃)、
トルエン(111℃)、
イソプロピルアルコール(82℃)、
メチルエチルケトン(79℃)、
エチルアルコール(78℃)、
エチルアセテート(77℃)、
アセトン(56℃)
などが挙げられる。 Examples of such low boiling point organic solvents include:
triethylene glycol monomethyl ether (249° C.),
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.),
ethyl alcohol (78° C.),
ethyl acetate (77° C.),
Acetone (56°C)
etc.
本発明による色鉛筆芯の製造方法は特に限定されない。しかしながら、
(a)体質材と無機結合材を混練して混合物を調製する混練工程、
(b)前記混合物を押出成形して線状成形物を作成する押出工程、
(c)前記線状成形物を焼成して、多孔性基材を作成する焼成工程、
(d)着色剤と沸点が250℃以上の高沸点有機溶媒を含む着色剤溶液を前記多孔性基材に接触させて含浸させる含浸工程、
(e)含浸工程後の前記多孔性基材を200℃以下の温度で加熱して、多孔性芯体を形成させる乾燥工程、
(f)前記多孔性芯体に、前記着色剤を溶解不能である難揮発性液体を接触させて、前記多孔性芯体の空隙に前記難揮発性液体を充填する充填工程
を含んでなる方法により製造することが好ましい。以下にこの方法について説明する。 <Manufacturing method of colored pencil core>
The manufacturing method of the colored pencil lead according to the present invention is not particularly limited. however,
(a) a kneading step of kneading an extender and an inorganic binder to prepare a mixture;
(b) an extrusion step of extruding the mixture to form a linear form;
(c) a sintering step of sintering the linear molded product to create a porous substrate;
(d) an impregnation step of contacting and impregnating the porous substrate with a coloring agent solution containing a coloring agent and a high-boiling organic solvent having a boiling point of 250° C. or higher;
(e) a drying step of heating the porous substrate after the impregnation step at a temperature of 200° C. or less to form a porous core;
(f) A method comprising a filling step of contacting the porous core with a refractory liquid in which the coloring agent cannot be dissolved, and filling the pores of the porous core with the refractory liquid. It is preferably manufactured by This method will be described below.
まず、体質材と無機結合材を混練して混合物を調製する。この混合物は多孔性基材の主成分となるものである。混合に際しては、必要に応じて有機溶媒、可塑剤などを添加を添加することができる。ここで用いられる有機溶媒は、原料混合物に流動性を持たせ、混合物を均一にするためのものであり、焼成工程においてほぼ完全に除去されるものであり、上記した高沸点有機溶媒、低沸点有機溶媒、および難揮発性液体とは独立したものである。 (a) Kneading step First, the filler and the inorganic binder are kneaded to prepare a mixture. This mixture is the main component of the porous substrate. At the time of mixing, an organic solvent, a plasticizer, etc. can be added as required. The organic solvent used here is intended to give fluidity to the raw material mixture and to make the mixture uniform, and is almost completely removed in the firing process. Independent of organic solvents and refractory liquids.
引き続き、形成された混合物を押出成形して線状成形物を作成する。本発明による色鉛筆芯は、一般に断面形状が円形である線状体に成形することが好ましいので、押し出し成形によって線状成形物とされる。 (b) an extrusion step;
Subsequently, the formed mixture is extruded to form linear moldings. Since the colored pencil lead according to the present invention is generally preferably formed into a linear body having a circular cross-sectional shape, it is extruded into a linear molded article.
得られた線状成形物を必要に応じて乾燥した後、焼成して、多孔性基材を作成する。焼成によって、上記の混合物に含まれる有機溶媒が除去され、体質材と無機結合材とが焼結して多孔性基材が形成される。焼成条件は、材料が焼結して多孔性基材が形成される条件であれば特に限定されないが、例えば最高温度は650~1000℃とすることができる。また、急激な温度変化を避けるために、焼成時の温度を連続的または段階的に上昇させることもできる。このような場合の昇温速度は例えば10~100℃/hrとすることができる。また、設定された温度まで上昇させた後に、一定温度で一定時間、例えば0.5~2時間程度、焼成することも好ましい。さらに、目的に応じてこれらの各条件を任意に組み合わせることができる。例えば酸素雰囲気中で、常温から650℃までを10℃/hrで昇温し、その後650℃を1時間保って焼成する条件や、常温から1000℃までを100℃/hrで昇温し、その後1000℃を1時間保って焼成する条件などが採用できる。 (c) Firing Step The obtained linear shaped product is dried as necessary and then fired to form a porous base material. By firing, the organic solvent contained in the mixture is removed, and the filler and the inorganic binder are sintered to form a porous substrate. The sintering conditions are not particularly limited as long as the material is sintered to form a porous base material. Also, in order to avoid sudden temperature changes, the temperature during firing can be increased continuously or stepwise. The rate of temperature increase in such a case can be, for example, 10 to 100° C./hr. It is also preferable to bake at a constant temperature for a certain period of time, for example, about 0.5 to 2 hours after raising the temperature to the set temperature. Furthermore, each of these conditions can be arbitrarily combined according to the purpose. For example, in an oxygen atmosphere, the temperature is raised from room temperature to 650 ° C. at a rate of 10 ° C./hr, and then the temperature is maintained at 650 ° C. for 1 hour and fired. Conditions such as firing at 1000° C. for one hour can be employed.
形成された多孔性基材を必要に応じて冷却した後、着色剤と高沸点有機溶媒とを含む溶液に多孔性基材を接触させる。この工程において、多孔性基材中に存在する気孔に着色剤溶液が浸透する。含浸する方法としては、常圧含浸または減圧、加圧含浸法を用いることができる。 (d) Impregnation step After cooling the formed porous substrate as necessary, the porous substrate is brought into contact with a solution containing a coloring agent and a high boiling point organic solvent. In this process, the pores present in the porous substrate are penetrated by the colorant solution. As a method for impregnation, normal pressure impregnation or reduced pressure/pressure impregnation can be used.
引き続き、含浸工程後の多孔性基材を加熱して、気孔内に含浸している溶液に含まれる溶媒の一部を除去する。この結果、気孔内に着色剤と高沸点有機溶媒が残留し、吸着または付着する。そして、加熱によって溶媒の一部が除去されたり、多孔性基材への溶媒の含浸が進行して気孔内に空隙が形成され、多孔性芯体が形成される。乾燥は、200℃以下の温度で行われるが、着色剤溶液に比較的沸点が低い溶媒が含まれる場合には、より低い温度、例えば100℃以下で行うことができる。低い温度で乾燥処理ができればエネルギーコストを低減することができるので好ましい。 (e) Drying Step Subsequently, the porous substrate after the impregnation step is heated to remove part of the solvent contained in the solution impregnating the pores. As a result, the colorant and the high-boiling organic solvent remain in the pores and are adsorbed or adhered. Then, by heating, part of the solvent is removed, or the impregnation of the solvent into the porous base material progresses to form voids in the pores, thereby forming the porous core. Drying is carried out at a temperature of 200° C. or less, but can be carried out at a lower temperature, for example 100° C. or less, if the colorant solution contains a solvent with a relatively low boiling point. If the drying treatment can be performed at a low temperature, energy costs can be reduced, which is preferable.
必要に応じて形成された多孔性芯体を冷却した後、難揮発性液体を接触させる。この工程によって、多孔性芯体に形成された空隙に難揮発性液体が充填される。このときの条件は特に限定されないが、例えば60℃の温度で6時間~12時間の条件が採用できる。難揮発性液体の充填には常圧含浸または減圧、加圧含浸法を用いることができる。 (f) Filling Step After cooling the formed porous core as necessary, it is brought into contact with a refractory liquid. Through this process, the voids formed in the porous core are filled with the low-volatility liquid. The conditions at this time are not particularly limited, but, for example, a temperature of 60° C. for 6 to 12 hours can be employed. Normal pressure impregnation, reduced pressure, and pressure impregnation can be used to fill the refractory liquid.
本発明による替芯製品は、前記した色鉛筆芯を、替芯ケースに収容したものである。そして、その替芯ケースの内面の、鉛筆芯が接触し得る部分の一部に前記難揮発性液体の溶解度パラメーターと1.5以上異なる溶解度パラメーターを有する樹脂材料を配置されていることが好ましい。替芯ケースは、色鉛筆芯を保護するために、比較的硬度の高い材料で構成されるが、製造容易性やコストの観点から樹脂で形成されることが一般的である。しかし、この樹脂として適切なものを選択しないと、色鉛筆芯と樹脂材料とが付着してしまうことがある。 <Replacement lead cases and replacement lead products>
A refill lead product according to the present invention is obtained by housing the above-described colored pencil lead in a refill lead case. It is preferable that a resin material having a solubility parameter different from that of the refractory liquid by 1.5 or more is disposed on a portion of the inner surface of the refill lead case that can be contacted by the pencil lead. In order to protect the colored pencil lead, the refill lead case is made of a material with relatively high hardness, but is generally made of resin from the viewpoint of ease of manufacture and cost. However, if a suitable resin is not selected, the colored pencil lead and the resin material may adhere to each other.
[混練工程、押出工程、および焼成工程]
窒化ホウ素 45質量部
シリカ 45質量部
ポリビニルアルコール 10質量部
水 100質量部
上記配合物をニーダー、三本ロールにて水分を蒸発しながら加熱混練し、得られた混練物を所定の径にて押出成形を行い、線状成形物を得た。この線状成形物をアルゴンガス中において 、昇温速度10℃/時間で600℃まで昇温し5時間保持し、その後、酸素雰囲気として 、100℃/hrで昇温し、900℃で1時間焼成して、気孔率が25%、断面直径が0.55mmの多孔性基材を得た。 [Production Example 101]
[Kneading process, extrusion process, and baking process]
Boron nitride 45 parts by mass Silica 45 parts by mass Polyvinyl alcohol 10 parts by mass Water 100 parts by mass The above mixture is heated and kneaded with a kneader and a triple roll while water is evaporated, and the resulting kneaded product is extruded to a predetermined diameter. Molding was performed to obtain a linear molding. This linear molding was heated to 600°C at a rate of 10°C/hr in argon gas and held for 5 hours, then heated at 100°C/hr in an oxygen atmosphere and held at 900°C for 1 hour. After firing, a porous substrate with a porosity of 25% and a cross-sectional diameter of 0.55 mm was obtained.
着色剤(青色染料) 30質量部
高沸点有機溶媒(フェニルジグリコール) 10質量部
低沸点有機溶媒(エチルアルコール) 50質量部
樹脂(ケトン樹脂) 10質量部
上記配合物を30℃で、均一に混合するまで攪拌をし、着色剤溶液を得た。 [Impregnation process]
Coloring agent (blue dye) 30 parts by mass High boiling point organic solvent (phenyldiglycol) 10 parts by mass Low boiling point organic solvent (ethyl alcohol) 50 parts by mass
Resin (ketone resin) 10 parts by mass The above formulation was stirred at 30°C until uniformly mixed to obtain a colorant solution.
含浸工程を経た多孔性基材を、80℃で6時間保持をして、多孔性基材の気孔中の低沸点有機溶媒を蒸発させて除去して、多孔性芯体を得た。 [Drying process]
After the impregnation step, the porous substrate was held at 80° C. for 6 hours to evaporate and remove the low boiling point organic solvent in the pores of the porous substrate to obtain a porous core.
乾燥工程で得られた多孔性芯体を、シリコーンオイル中に80℃に加温した状態で浸漬し、6時間保持をし、色鉛筆芯を得た。次に色鉛筆芯の表面に付着した過剰のシリオーンオイルを、遠心分離機にて振り切って除去し、12.5質量%のシリコーンオイルが含浸された実施例101の色鉛筆芯を得た。また、この色鉛筆芯について、熱重量測定を行ったところ、フェニルジグリコールが含有されていることが確認できた。その含有率は、1質量%以上であった。 [Filling process]
The porous core obtained in the drying step was immersed in silicone oil heated to 80° C. and held for 6 hours to obtain a colored pencil core. Next, excess silicone oil adhering to the surface of the colored pencil lead was removed by shaking off with a centrifuge to obtain a colored pencil lead of Example 101 impregnated with 12.5% by mass of silicone oil. Moreover, when this colored pencil lead was subjected to thermogravimetric measurement, it was confirmed that phenyldiglycol was contained. The content was 1% by mass or more.
実施例101に対して、各成分を表1に記載されたものに変更したほかは同様にして色鉛筆芯を得た。実施例102~110および比較例102の色鉛筆芯には熱重量測定および製造条件から、高沸点有機溶媒が含まれることが確認された。なお、比較例102および103は、難揮発性液体の充填を行わなかった。
[評価]
得られた色鉛筆芯の性能について、以下の方法で評価した。 [Examples 102 to 110, Comparative Examples 101 to 103]
A colored pencil lead was obtained in the same manner as in Example 101, except that each component was changed to those listed in Table 1. It was confirmed from thermogravimetry and production conditions that the colored pencil leads of Examples 102 to 110 and Comparative Example 102 contained a high-boiling organic solvent. Comparative Examples 102 and 103 were not filled with the hardly volatile liquid.
[evaluation]
The performance of the obtained colored pencil lead was evaluated by the following methods.
色鉛筆芯を用いて、上質紙(旧JIS P3201に規定される筆記用紙Aに相当するもの。化学パルプ100%を原料に抄造され、秤量範囲40~157g/m2、白色度75.0%以上)に筆記し、その時の書き味を官能試験により評価した(書き味1)。また、得られる筆跡の発色性(筆跡発色性1)。
さらに、製造後、25℃環境下で4週間放置した焼成色鉛筆芯を用いて、前記上質紙に筆記し、その時の書き味(書き味2)および得られる筆跡の発色性(筆跡発色性2)を官能試験により評価した。
(書き味1および2の評価基準)
A :非常に滑らかに筆記可能。
B :滑らかに筆記可能。
C :筆感がややざらつき重い。
D :筆感がざらつき重い。
(筆跡発色性1および2の評価基準)
S:非常に発色が良い。
A:発色が良い。
B:発色がやや劣るが、良好。
C:発色に劣る。
D:筆記はできるが、発色が非常に劣る。
E:筆記できず、筆跡を視認できない。 [Evaluation method for writing feel and handwriting color development]
High-quality paper (equivalent to writing paper A specified in the old JIS P3201) is prepared using colored pencil cores. Paper is made from 100% chemical pulp, and has a weighing range of 40 to 157 g/m 2 and a whiteness of 75.0% or more. ), and the writing feeling at that time was evaluated by a sensory test (writing feeling 1). Also, the coloring property of the obtained handwriting (handwriting coloring property 1).
Furthermore, after production, using the baked colored pencil core left in an environment of 25 ° C. for 4 weeks, writing is performed on the high-quality paper, and the writing taste at that time (writing taste 2) and the color development of the handwriting obtained (handwriting color development 2). was evaluated by a sensory test.
(Evaluation criteria for writing taste 1 and 2)
A: Writing is possible very smoothly.
B: Smoothly writable.
C: Writing feeling is slightly rough and heavy.
D: Writing feeling is rough and heavy.
(Evaluation Criteria for Handwriting Color Development 1 and 2)
S: Very good color development.
A: Good color development.
B: Slightly inferior in color development, but good.
C: Inferior in color development.
D: Writing is possible, but color development is very poor.
E: Unable to write, no visible handwriting.
JIS S 6050-2008に開示されているプラスチック字消しの消し能力試験に準拠して筆跡を消去し、その時の消去性を官能試験により評価した(消去性1)。また、筆記後、25℃環境下で4週間放置した筆記線を用いて、JIS S 6050-2008に開示されているプラスチック字消しの消し能力試験に準拠して筆跡を消去し、その時の消去性を官能試験により評価した(消去性2)。なお、既存品とは、株式会社パイロットコーポレーション製のシャープペンシル芯「商品名:ネオックス・カラーイーノ(イエロー)」をいう。
(消去性1および2の評価基準)
A: 既存品より良い。
B: 既存品と同等。
C: 消去不能。 [Evaluation method for handwriting erasability]
The handwriting was erased according to the erasability test for plastic erasers disclosed in JIS S 6050-2008, and the erasability at that time was evaluated by a sensory test (erasability 1). In addition, after writing, using the writing line left for 4 weeks in a 25 ° C. environment, the handwriting was erased in accordance with the erasability test of the plastic eraser disclosed in JIS S 6050-2008. was evaluated by a sensory test (erasability 2). In addition, the existing product refers to a mechanical pencil lead "trade name: Neox Colorino (yellow)" manufactured by Pilot Corporation.
(Evaluation criteria for erasability 1 and 2)
A: Better than existing products.
B: Equivalent to existing products.
C: Not erasable.
青色染料B: オイルブルー613(オリエント化学工業株式会社製)
赤色染料R: スピロンレッドC-PH(保土谷化学工業株式会社製)
ピンク色蛍光顔料P: NKS1007(日本蛍光化学株式会社製、ポリアミド樹脂とC.I. Basic Violet 11:1の混合物)
黄色蛍光顔料Y: NKS1005(日本蛍光化学株式会社製、ポリアミド樹脂とC.I. Basic Yellow 40の混合物)
界面活性剤: ノイゲンEA-137(第一工業製薬株式会社製)
SO1:ジメチルシリコーンオイル(信越化学工業(株)製、商品名:KF-96-50cs。表面張力:20.8N/m)
SO2:メチルフェニルシリコーンオイル(信越化学工業(株)製、商品名:KF-96-100cs)
[実施例201~202、比較例201]
製造例101に対して、各成分を表2に記載されたものに変更したほかは同様にして各例の色鉛筆芯を得た。各例の色鉛筆芯には熱重量測定および製造条件から、高沸点有機溶媒が含まれることが確認された。なお、比較例201は、難揮発性液体の充填を行わなかった。
Blue dye B: Oil Blue 613 (manufactured by Orient Chemical Industry Co., Ltd.)
Red dye R: Spiron Red C-PH (manufactured by Hodogaya Chemical Industry Co., Ltd.)
Pink fluorescent pigment P: NKS1007 (manufactured by Nihon Shokuryo Kagaku Co., Ltd., a mixture of polyamide resin and C.I. Basic Violet 11:1)
Yellow fluorescent pigment Y: NKS1005 (manufactured by Nippon Shokuryo Kagaku Co., Ltd., a mixture of polyamide resin and C.I. Basic Yellow 40)
Surfactant: Neugen EA-137 (Daiichi Kogyo Seiyaku Co., Ltd.)
SO1: Dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96-50cs. Surface tension: 20.8 N/m)
SO2: Methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96-100cs)
[Examples 201 to 202, Comparative Example 201]
A colored pencil lead of each example was obtained in the same manner as in Production Example 101, except that each component was changed to that described in Table 2. It was confirmed from thermogravimetry and production conditions that the colored pencil lead of each example contained a high-boiling organic solvent. In addition, Comparative Example 201 was not filled with the hardly volatile liquid.
得られた色鉛筆芯を、それぞれ図2に示された替芯ケースに収容して替芯製品とした。この替芯ケースの収容部に用いた樹脂材料は表2に示すとおりであり、この替芯ケースの色鉛筆芯に接触し得る部分の面積のうち、90%以上がその樹脂材料で構成されている。 [Examples 201 to 202, Comparative Example 201]
The resulting colored pencil leads were accommodated in the replacement lead cases shown in FIG. 2 to obtain replacement lead products. The resin material used for the housing portion of this replacement lead case is as shown in Table 2, and 90% or more of the area of the portion of this replacement lead case that can come into contact with the colored pencil lead is composed of the resin material. .
各替芯製品について、50℃で14日間、替芯ケースの収容部の内面に、色鉛筆芯が接触した状態で保持して、芯の付着性を以下の基準により評価した。 [Evaluation method for colored pencil lead adhesion]
Each refill lead product was held at 50° C. for 14 days with the colored pencil lead in contact with the inner surface of the housing portion of the refill lead case, and the adhesion of the lead was evaluated according to the following criteria.
A: 色鉛筆芯が収容部に全く付着しない
B: 色鉛筆芯が収容部にわずかに付着するが、容易に剥離する
C: 色鉛筆芯が収容部に付着した (Evaluation criteria for adhesion)
A: The colored pencil core does not adhere to the container at all. B: The colored pencil core adheres slightly to the container, but is easily peeled off. C: The colored pencil core adheres to the container.
実施例101と同様の評価方法によって評価した。 [Evaluation method for writing feel and handwriting color development]
It was evaluated by the same evaluation method as in Example 101.
ピンク色蛍光顔料P: NKS1007(日本蛍光化学株式会社製、ポリアミド樹脂とC.I. Basic Violet 11:1の混合物)
AS:アクリロニトリルスチレン樹脂 (SP値12.8)
PC:ポリカーボネート (SP値:9.7)
SO1:ジメチルシリコーンオイル(信越化学工業(株)製、商品名:KF-96-50cs、SP値:7.3、表面張力:20.8N/m)
Pink fluorescent pigment P: NKS1007 (manufactured by Nihon Shokuryo Kagaku Co., Ltd., a mixture of polyamide resin and C.I. Basic Violet 11:1)
AS: acrylonitrile styrene resin (SP value 12.8)
PC: polycarbonate (SP value: 9.7)
SO1: Dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96-50cs, SP value: 7.3, surface tension: 20.8 N / m)
102 蓋部
102a 蓋部の底面
103 色鉛筆芯
201 収容部
201a 係合片
202 蓋部
202a 凹陥部
401 収容部
401a 凹陥部
402 蓋部
402a 係合片
601 収容部
602 蓋部
602D 回転軸
603 出口
604 蓋部固定部材
604E 取付穴 101
Claims (14)
- 体質材と、
無機結合材と、
着色剤と、
前記着色剤を溶解可能であり、沸点が250℃以上の高沸点有機溶媒と
を含んでなる多孔性芯体、および
前記着色剤を溶解不能である難揮発性液体
を含んでなり、
前記着色剤、前記高沸点有機溶媒、および前記難揮発性液体が前記多孔性芯体の気孔中に充填されていることを特徴とする色鉛筆芯。 body material and
an inorganic binder;
a coloring agent;
a porous core containing a high-boiling organic solvent capable of dissolving the coloring agent and having a boiling point of 250° C. or higher;
A colored pencil lead, wherein the coloring agent, the high-boiling organic solvent, and the low-volatility liquid are filled in the pores of the porous core. - 前記難揮発性液体が、シリコーンオイル、フッ素系オイル、鉱油、植物油、および流動パラフィンからなる群から選択されるものである、請求項1に記載の色鉛筆芯。 The colored pencil lead according to claim 1, wherein the low-volatility liquid is selected from the group consisting of silicone oil, fluorinated oil, mineral oil, vegetable oil, and liquid paraffin.
- 前記高沸点有機溶媒が、芳香族グリコールエーテル、または脂肪族グリコールエーテルである、請求項1または2に記載の色鉛筆芯。 The colored pencil lead according to claim 1 or 2, wherein the high-boiling organic solvent is an aromatic glycol ether or an aliphatic glycol ether.
- 前記色鉛筆芯の総質量を基準とした、前記高沸点有機溶媒の含有率が0.5~20質量%である、請求項1~3のいずれか1項に記載の色鉛筆芯。 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% by mass based on the total mass of the colored pencil lead.
- 20℃における前記着色剤の前記高沸点有機溶媒に対する溶解度が、10g/100g以上である、請求項1~4のいずれか1項に記載の色鉛筆芯。 The colored pencil lead according to any one of claims 1 to 4, wherein the solubility of the coloring agent in the high-boiling organic solvent at 20°C is 10 g/100 g or more.
- 20℃における前記着色剤の前記難揮発性液体に対する溶解度が、20℃における前記着色剤の前記高沸点有機溶媒に対する溶解度よりも低い、請求項1~5のいずれか1項に記載の色鉛筆芯。 The colored pencil lead according to any one of claims 1 to 5, wherein the solubility of the coloring agent in the refractory liquid at 20°C is lower than the solubility of the coloring agent in the high-boiling organic solvent at 20°C.
- 前記体質材が、酸化チタン、雲母、タルク、窒化ホウ素、アルミナ、および炭酸カルシウムからなる群から選択される、請求項1~6のいずれか1項に記載の色鉛筆芯。 The colored pencil lead according to any one of claims 1 to 6, wherein said extender is selected from the group consisting of titanium oxide, mica, talc, boron nitride, alumina, and calcium carbonate.
- 前記無機結合材が、粘土類、セラミックス類、ゼオライト、珪藻土、活性白土、シリカ、リン酸アルミニウム、シリコーン樹脂、およびシリコーンゴムからなる群から選択される、請求項1~7のいずれか1項に記載の色鉛筆芯。 The inorganic binder is selected from the group consisting of clays, ceramics, zeolite, diatomaceous earth, activated clay, silica, aluminum phosphate, silicone resin, and silicone rubber, according to any one of claims 1 to 7 Colored pencil lead as described.
- 前記多孔性芯体の気孔率が、1~50%である、請求項1~8のいずれか1項に記載の色鉛筆芯。 The colored pencil lead according to any one of claims 1 to 8, wherein the porous core has a porosity of 1 to 50%.
- 前記多孔性芯体が焼成芯体である、請求項1~9のいずれか1項に記載の色鉛筆芯。 The colored pencil lead according to any one of claims 1 to 9, wherein the porous core is a fired core.
- (a)体質材と無機結合材を混練して混合物を調製する混練工程、
(b)前記混合物を押出成形して線状成形物を作成する押出工程、
(c)前記線状成形物を焼成して、多孔性基材を作成する焼成工程、
(d)着色剤と沸点が250℃以上の高沸点有機溶媒を含む着色剤溶液を前記多孔性基材に接触させて含浸させる含浸工程、
(e)含浸工程後の前記多孔性基材を200℃以下の温度で加熱して、多孔性芯体を形成させる乾燥工程、
(f)前記多孔性芯体に、前記着色剤を溶解不能である難揮発性液体を接触させて、前記多孔性芯体の空隙に前記難揮発性液体を充填する充填工程
を含んでなることを特徴とする、色鉛筆芯の製造方法。 (a) a kneading step of kneading an extender and an inorganic binder to prepare a mixture;
(b) an extrusion step of extruding the mixture to form a linear form;
(c) a sintering step of sintering the linear molded product to create a porous substrate;
(d) an impregnation step of contacting and impregnating the porous substrate with a coloring agent solution containing a coloring agent and a high-boiling organic solvent having a boiling point of 250° C. or higher;
(e) a drying step of heating the porous substrate after the impregnation step at a temperature of 200° C. or less to form a porous core;
(f) A filling step of contacting the porous core with a refractory liquid in which the colorant cannot be dissolved, and filling the voids of the porous core with the refractory liquid. A method for manufacturing a colored pencil lead, characterized by: - 前記着色剤溶液が、さらに沸点が250℃未満の低沸点有機溶媒を含んでなる、請求項11に記載の方法。 The method according to claim 11, wherein the colorant solution further comprises a low-boiling organic solvent having a boiling point of less than 250°C.
- 請求項1~10のいずれか1項に記載の色鉛筆芯と、それを収容した替芯ケースとを具備する、替芯製品。 A replacement lead product comprising the colored pencil lead according to any one of claims 1 to 10 and a replacement lead case containing it.
- 前記替芯ケースの内面の、前記色鉛筆芯が接触し得る部分の一部に、前記難揮発性液体の溶解度パラメーターと1.5以上異なる溶解度パラメーターを有する樹脂材料を配置したことを特徴とする、請求項13に記載の替芯製品。 A resin material having a solubility parameter different from the solubility parameter of the refractory liquid by 1.5 or more is arranged on a part of the inner surface of the replacement lead case that can be contacted by the colored pencil lead. The refill product according to claim 13.
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KR1020237036693A KR20230163478A (en) | 2021-03-29 | 2022-03-28 | Colored pencil lead, a manufacturing method of colored pencil lead, and a replacement lead product comprising a colored pencil lead and a replacement lead case accommodating the same. |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2009029906A (en) * | 2007-07-26 | 2009-02-12 | Mitsubishi Pencil Co Ltd | Solid drawing material |
WO2015129583A1 (en) * | 2014-02-27 | 2015-09-03 | 三菱鉛筆株式会社 | Colored pencil lead |
JP2019099633A (en) * | 2017-11-30 | 2019-06-24 | 株式会社パイロットコーポレーション | Burned color pencil lead |
JP2020193305A (en) * | 2019-05-30 | 2020-12-03 | 株式会社パイロットコーポレーション | Calcined color pencil lead |
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JP2009029906A (en) * | 2007-07-26 | 2009-02-12 | Mitsubishi Pencil Co Ltd | Solid drawing material |
WO2015129583A1 (en) * | 2014-02-27 | 2015-09-03 | 三菱鉛筆株式会社 | Colored pencil lead |
JP2019099633A (en) * | 2017-11-30 | 2019-06-24 | 株式会社パイロットコーポレーション | Burned color pencil lead |
JP2020193305A (en) * | 2019-05-30 | 2020-12-03 | 株式会社パイロットコーポレーション | Calcined color pencil lead |
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