WO2022080188A1 - 鉛筆芯 - Google Patents
鉛筆芯 Download PDFInfo
- Publication number
- WO2022080188A1 WO2022080188A1 PCT/JP2021/036803 JP2021036803W WO2022080188A1 WO 2022080188 A1 WO2022080188 A1 WO 2022080188A1 JP 2021036803 W JP2021036803 W JP 2021036803W WO 2022080188 A1 WO2022080188 A1 WO 2022080188A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- pencil lead
- rosin
- pencil
- graphite
- Prior art date
Links
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- 239000011347 resin Substances 0.000 claims abstract description 52
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- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- RRBYUSWBLVXTQN-UHFFFAOYSA-N tricyclene Chemical compound C12CC3CC2C1(C)C3(C)C RRBYUSWBLVXTQN-UHFFFAOYSA-N 0.000 description 1
- RRBYUSWBLVXTQN-VZCHMASFSA-N tricyclene Natural products C([C@@H]12)C3C[C@H]1C2(C)C3(C)C RRBYUSWBLVXTQN-VZCHMASFSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- 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
-
- 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
Definitions
- This specification relates to a pencil lead that can achieve both improvement in the density of writing lines and improvement in fixing property, and does not easily stain the writing hand.
- the impregnating component comprises silicone oil or the like and an organic substance having a polar group having 14 to 50 carbon atoms (C 14 to C 50 ).
- C 14 to C 50 carbon atoms
- a pencil lead that is impregnated into the pores of a fired pencil lead to achieve both a dark handwriting and a fixing property of a drawn line is known (see, for example, Patent Document 2).
- "good fixing property" means that the place where the stain due to rubbing is estimated to be more than 20% is suppressed to about 20%, which is not enough.
- the peeling strength between the boron nitride, the sintered body made of carbon, and the adhesive material filled in the pores of the sintered body, and the adhesive material and the drafting film to be written is high. It is 50 g / 2.5 cm or more, and has an adhesive substance (adhesive wax, a mixture of wax and resin) mixed in the pores of the firing core, and has high strength, high concentration, and excellent fixability to drafting film.
- a “lead core” is disclosed (see, for example, Patent Document 3). This "lead core” is excellent in fixing property to a drafting film, and is considered to be too adhesive to a paper surface.
- a pencil lead composed of a calcined core containing graphite dispersed and an oil impregnated in the pores of the calcined core, wax and a rosin-based resin and / or petroleum resin are used as at least a part of the oil.
- a pencil lead impregnated with a compatible substance with and has both a concentration improvement on a paper surface and an improvement in fixability (see, for example, Patent Document 4).
- the "improvement of fixability" referred to here suppresses stains due to rubbing to about 10% at an estimated value, and is considered to be insufficient.
- the pores of the white or monochromatic porous fired core are impregnated with a specific pigment, jojoba oil, etc., and are excellent in color development, drawing density, drawing taste, light resistance, and mechanical strength.
- the pencil lead is disclosed (see, for example, Patent Document 5). This pencil lead does not use graphite, and does not disclose or give consideration to its fixability on paper.
- Japanese Unexamined Patent Publication No. 5-271604 (detailed description of the invention, examples, etc.) JP-A-2005-314620 (Claims, detailed description of the invention, etc.) Japanese Unexamined Patent Publication No. 60-105598 (Detailed description of the invention, Examples, etc.) JP-A-3-31377 (Claims, detailed description of the invention, etc.) JP-A-2002-179975 (Claims, detailed description of the invention, etc.)
- the present disclosure is intended to solve the problem, and it is possible to highly achieve both the improvement of the density of the writing line and the improvement of the fixing property, and the writing hand and the like are also soiled.
- the purpose is to provide a pencil lead that is difficult to stick to.
- the present inventor intends to solve this problem in view of the above-mentioned conventional problems, and by impregnating the pores of a black porous fired core containing at least graphite with a specific oil component or the like. We have found that a pencil lead of the above purpose can be obtained, and have completed this disclosure.
- the pencil lead of the present disclosure contains at least graphite in the pores of the black porous fired core, and at least octyldodecyl erucate, oleyl oleate, octyldodecyl oleate, isopropyl palmitate, 2-ethylhexyl palmitate.
- the compound or jojoba oil it is preferable to impregnate at least one selected from a terpene phenol resin, a rosin ester resin, a ketone resin and a rosin-modified phenol resin.
- the compound or jojoba oil is preferably contained in the impregnated oil in an amount of 60% by mass or more.
- a pencil lead that can achieve both improvement in the density of writing lines and improvement in fixing property, and is less likely to stain the writing hand or the like.
- the pencil lead of the present disclosure contains at least graphite in the pores of a black porous fired core, at least octyldodecyl erucate, isopropyl palmitate, octyldodecyl oleate, oleyl oleate, 2-ethylhexyl palmitate, propylene. It is characterized by impregnating a compound selected from glycol monooleate.
- the porous calcined core containing at least graphite and black can be obtained by a conventionally used compounding material and a manufacturing method, and any porous calcined core containing at least graphite and black can be obtained.
- the compounding material type and manufacturing method are not particularly limited.
- the pencil lead is for a mechanical pencil, it contains at least graphite as a compounding material, and for a black porous fired lead other than a mechanical pencil, at least graphite, an extender and a ceramic binder, etc. Is preferably contained.
- other components include polyvinyl chloride, polyvinyl alcohol, phenol resin, pitch, cellulose, polyacrylonitrile as binders, and metal nanoparticles with an average particle size of 100 nm or less as nanoparticles.
- a base material composed of these nanoparticles, carbon particles such as fullerene, Ca-Zn stearate as a stabilizer, Sodium stearate, magnesium stearate, dioctylphthalate as a plasticizer, dioctyl adipate, diisobutyl phthalate, and for fired pencil leads, other components include coloring materials, lubricants, binder components, various silicone oils, lard, acrylic resin, epoxy. Resins, celluloids and other thermoplastic resins, organic solvents and the like can be used.
- Examples of graphite that can be used include natural graphite such as scaly natural graphite, artificial graphite, kish graphite, expanded graphite, expanded graphite, and the like, and examples of the ceramic binder include crystalline or amorphous SiO 2 . Examples thereof include Si 3 N 4 , Al 2 O 3 , ZrO, MgO, boron nitride, B 2 O 3 , Al N and the like, and these may be used alone or in combination of two or more.
- the average particle size in the present disclosure refers to a volume average diameter (mv value) weighted by volume from the measurement results in the laser diffraction / scattering method. For example, in nanoparticles, the average particle size is used. It can be measured using a nanotrack [UPA-EX150 (internal probe type) manufactured by Nikkiso Co., Ltd.].
- the constitutional material is not particularly limited as long as it is used for a conventional pencil lead, and any of them can be used.
- white constitutional materials such as boron nitride, kaolin, talc, mica, and calcium carbonate, and colored constitutional materials can be used depending on the hue of the pencil lead, and of course, a mixture of these several types can also be used.
- boron nitride, kaolin, and talc are preferable because of their physical characteristics and shape.
- the binder component is not particularly limited as long as it is used for a conventional pencil lead, and any of them can be used.
- celluloses such as carboxylmethylcellulose, polyvinyls such as polyvinylpyronidone, polyethers such as polyoxyethylene, acrylic acids such as polyacrylic acid, inorganic polymers such as tetraethyl orthosilicate (TEOS) condensate, and montmorillonite.
- TEOS tetraethyl orthosilicate
- montmorillonite Such as clay, ceramic glass and the like.
- thermoplastic resin examples include polyvinyl alcohol, polyvinyl chloride, polyvinyl chloride, polyamide, polyethylene, polypropylene, and polyetheretherketone.
- the organic solvent used is preferably a plasticizer capable of dissolving the above thermoplastic resin, and specifically, dioctyl phthalate, dibutyl phthalate, tricresyl phosphate, dioctyl adipate, diallyl isophthalate, propylene carbonate, alcohols, etc. Ketones, esters and the like can be used.
- the calcined pencil core is a component (graphite, carbon black, nanoparticles, constitutional material, surfactant) used for each pencil core type, for example, a calcined pencil lead for mechanical pencils and a calcined pencil lead other than a mechanical pencil.
- Perfume, thermoplastic resin, organic solvent, etc. can be kneaded, molded, dried and fired in a non-oxidizing atmosphere.
- the above-mentioned graphite or carbon black 30 to 70% by mass, based on the total amount of the pencil lead compounding composition (a).
- thermoplastic synthetic resin 30 to 60% Using 0.01 to 1% by mass of nanoparticles, other components (c) thermoplastic synthetic resin 30 to 60%, (d) organic solvent 0 to 30% capable of dissolving the thermoplastic synthetic resin. Is dispersed and mixed with a Henshell mixer, kneaded with a pressurized kneader and two rolls, molded by an extrusion molding machine, dried at 110 to 250 ° C. in an electric furnace, and a lead for forming a pencil lead before firing. Can be manufactured by molding the pencil lead body and firing it in an atmosphere of an inert gas such as nitrogen at 800 to 1400 ° C. for 20 to 40 hours.
- an inert gas such as nitrogen at 800 to 1400 ° C. for 20 to 40 hours.
- At least octyldodecyl erucate and isopropyl palmitate are contained in the pores of a black porous calcined core containing at least graphite obtained by a conventionally used compounding material and manufacturing method.
- the desired pencil lead can be obtained by impregnating with a compound selected from octyldodecyl oleate, oleyl oleate, 2-ethylhexyl palmitate, and propylene glycol monooleate.
- it can be impregnated with jojoba oil, which is a mixture containing octyldodecyl erucate.
- the jojoba oil used in the present disclosure is a vegetable oil extracted from the seeds of jojoba (Simmondsia chinensis) by pressing, etc. , Strong resistance to oxidation, high stability, refined oil of pressed oil, deodorized oil, hydrogenated oil, etc. can be used, and if there is a commercially available product, they can be used.
- the (total) content of at least one selected from the above compounds may be contained in the impregnated oil in an amount of 60% by mass or more from the viewpoint of exerting the effect of the present invention. It is preferably more preferably 80 to 100% by mass.
- the above-mentioned octyldodecyl erucate, jojoba oil which is a mixture containing the octyldodecyl erucate, isopropyl palmitate, octyldodecyl oleate, oleyl oleate, 2-ethylhexyl palmitate, and propylene glycol monooleate are conventional dimethyl silicone oils.
- a terpene phenol resin in addition to at least one selected from the above compounds (including jojoba oil), a terpene phenol resin, a rosin ester resin, and a ketone resin can be obtained from the viewpoint of further improving the effect of the present disclosure, particularly improving the fixability. It is desirable to use at least one selected from the rosin-modified phenolic resin and the rosin-modified phenol resin in combination.
- the terpene phenol resin that can be used is a copolymer of a terpene compound and phenols by cationic polymerization under a Friedel-Crafts catalyst.
- the above-mentioned terpene compound is generally a polymer of isoprene (C 5 H 8 ) and is classified into monoterpenes (C 10 H 16 ), sesquiterpenes (C 15 H 24 ), diterpenes (C 20 H 32 ) and the like. Is a compound whose basic skeleton is.
- monoterpenes, sesquiterpenes and diterpenes are preferable, and sesquiterpenes and monoterpenes are more preferably used.
- terpine compounds examples include myrcene, aloosimene, ossimen, ⁇ -pinene, ⁇ -pinene, dipentene, limonene, ⁇ -ferrandrene, ⁇ -terpinene, ⁇ -terpinene, terpineol, 1,8-cineole, 1,4.
- ⁇ -pinene, ⁇ -pinene, limonene, myrcene, aloosimene, and ⁇ -terpinene are preferable.
- phenols examples include phenol, cresol, xylenol, propylphenol, norylphenol, hydroquinone, resorcin, methoxyphenol, bromophenol, bisphenol A, and bisphenol F. Of these, phenol and cresol are preferable.
- the terpene phenol resin is a kind of so-called tack fire (adhesive-imparting resin), and is usually considered to be an amorphous oligomer having a molecular weight of several hundreds to several thousand.
- Other terpene-based resins of terpene phenolic resins include terpene resins, aromatic-modified terpene resins and hydrogenated terpene resins.
- the hydrogenated terpene phenol resin obtained by hydrogenating the terpene phenol resin may be used.
- terpene phenol resin if there is a commercially available terpene phenol resin, they can be used.
- they are commercially available under the trade names of Polystar series and Mighty Ace series manufactured by Yasuhara Chemical Co., Ltd. and are easily available. Specific examples thereof include YS Polystar T30, YS Polystar T80, and YS Polystar T160 (all manufactured by Yasuhara Chemical Co., Ltd.).
- the rosin ester resin used in the present disclosure is a rosin resin containing abietic acid as a main component, a disproportionate rosin resin and a hydrogenated rosin resin, a dimer of a resin acid such as abietic acid (polymerized rosin resin), and the like, using alcohol. It is a resin obtained by esterification.
- the hydroxyl value is adjusted to the above range by containing a part of the hydroxyl groups of the alcohol used for esterification in the resin without being used for esterification.
- the alcohol include polyhydric alcohols such as ethylene glycol, glycerin and pentaerythritol.
- the resin obtained by esterifying the rosin resin is the rosin ester resin
- the resin obtained by esterifying the disproportionate rosin resin is the disproportionate rosin ester resin
- the resin obtained by esterifying the hydrogenated rosin resin is the hydrogenated rosin ester resin and the polymerized rosin.
- the resin obtained by esterifying the resin is a polymerized rosin ester resin, and any of these can be used in the present disclosure.
- the rosin ester resin include ester gum HP manufactured by Arakawa Chemical Industry Co., Ltd. and Haritac F85 manufactured by Harima Chemicals Co., Ltd.
- ketone resin a commercially available product can be used, and examples thereof include ketone resin K-90 (manufactured by Arakawa Chemical Industry Co., Ltd.).
- rosin-modified phenolic resin examples include the following. P-alkylphenols such as p-octylphenol and p-nonylphenol, paraformaldehyde, and rosin are dissolved in toluene, reacted under an acid or alkali catalyst, and then glycerin, pentaerythritol, or rosin is melted at 200 ° C.
- examples thereof include formaldehyde-modified phenolic resins, and examples of commercially available products include Tamanol 135, Tamanol 350, and Tamanol 354 manufactured by Arakawa Chemical Industry Co., Ltd.
- the desired pencil lead can be obtained by impregnating the pores of the above-mentioned black porous fired core containing at least graphite with at least one selected from the above compounds (including jojoba oil) as an impregnating component.
- at least one selected from the above compounds (including jojoba oil) it is preferably selected from a pencil phenol resin, a rosin ester resin, a ketone resin and a rosin-modified phenol resin (these are referred to as "Group A").
- each of the above is used.
- the (total) content of at least one selected from the compounds (including jojoba oil) shall be 60% by mass or more (40% by mass or less in Group A) in the impregnated oil in terms of writing taste and wear amount. Is preferable, and more preferably 60 to 80% by mass (20 to 40% by mass in the group A).
- the method for impregnating the pores of the porous calcined core having the above constitution is not particularly limited, but for example, at least one selected from the above compounds (including jojoba oil) (60 to 100 mass of each compound). %) Or, in addition to the above compound (including jojoba oil) (60% by mass or more), at least one selected from terpylene phenol resin, rosin ester resin, ketone resin and rosin-modified phenol resin (group A), as it is.
- a black porous calcined core containing at least graphite in a solution obtained by diluting these with a solvent such as ethylene glycol, ethanol, 2-ethylhexanol, butyl cellsolve, dipropylene glycol monomethyl ether, isopropanol, or propylene glycol. It can be carried out by dipping, if necessary, heating and dipping, and after sufficiently impregnating with reduced pressure and pressurization, the solvent is removed (dried).
- the (total) impregnation amount of the above compound (including jojoba oil) or the terpene phenol resin in addition to the above compound (including jojoba oil) is added to the pores of the black porous calcined core containing at least graphite.
- the (total) impregnation amount of at least one selected from the rosin ester resin, the ketone resin and the rosin-modified phenol resin (group A) is not particularly limited, but varies depending on the pencil type, porosity, etc.
- the effect of the present disclosure can be sufficiently exerted in an amount of about 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, based on the weight.
- the above-mentioned when the pores of the black porous calcined core containing at least graphite are impregnated with at least the above compound (including jojoba oil), the above-mentioned is also preferable.
- the above-mentioned is also preferable.
- it is contained by impregnating at least one selected from a terpene phenol resin, a rosin ester resin, a ketone resin and a rosin-modified phenol resin in addition to a compound (including jojoba oil), it permeates and easily collapses when the core wears.
- Example 1 A black porous calcined core (firing pencil lead) containing at least graphite was produced by the following method.
- Scale-like natural graphite 40 parts by mass Nanoparticles: Diamond nanoparticles (particle size: mv value 50 nm) 0.4 parts by mass Polyvinyl chloride 40 parts by mass Sodium stearate 1 part by mass Dioctylphthalate 15 parts by mass Dioctylphthalate with the above nanoparticles Disperse with a bead mill for 180 minutes, mix and disperse the other above materials with a Henshell mixer (mixing and dispersion time 20 minutes, the same applies hereinafter), knead with a pressure kneader and a roll, and after molding, dry the dioctylphthalate and then nitrogen (N).
- N nitrogen
- a fired pencil core having a diameter of 0.565 mm and a length of 60 mm was produced by firing in an atmosphere at 1000 ° C. for 10 hours.
- this fired pencil core was immersed in a mixed oil of 70% by mass of jojoba oil (NIKKOL jojoba oil S, manufactured by Nikko Chemicals) and 30% by mass of terpene phenol resin A (YS Polystar T160, manufactured by Yasuhara Chemicals).
- NIKKOL jojoba oil S manufactured by Nikko Chemicals
- terpene phenol resin A terpene phenol resin A
- Example 2 to 18 and Comparative Examples 1 to 5 The fired pencil lead obtained in Example 1 was immersed in a mixed oil having the composition shown in Table 1 below or each compound (including jojoba oil), impregnated in the same manner as in Example 1, and the pencil lead was formed. Manufactured. In addition, as in the above Example 1, the impregnation amount in each core body is shown in Table 1 below by weight measurement.
- the pencil lead of the present disclosure can be suitably used for a wooden axis pencil lead, a mechanical pencil, and the like.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
筆跡の濃度向上を図った場合、色材としての黒鉛を多量に筆記面に移すことになるため、相対する性能として、定着性(描線を擦ったときの汚れにくさ)が挙げられる。即ち、筆跡の濃度向上を目指せば定着性が劣り、逆に定着性を良好にすれば筆跡の濃度に難が出てくると言える。
例えば、焼成芯体の気孔中に油状物を含浸してなる鉛筆芯において、前記油状物が、常温で固体状のシリコーンオイル等の油状物と、この固体状の油状物と非相溶性の常温で液状の油状物とを、焼成鉛筆芯の細孔内に含浸させ、描線の反射濃度と、描線の定着性について検討を行っている焼成鉛筆芯が知られている(例えば、特許文献1参照)。ここでの「定着性良好」とは、擦過による汚れが推定20%超であるところを10%台に抑制させるものであり充分とはいえなかった。
更に本出願人より、白色若しくは単色の多孔質焼成芯の気孔内に、特定の顔料と、ホホバ油等を含浸して、発色性、描線濃度、描き味、耐光性、及び、機械強度に優れた鉛筆芯が開示されている(例えば、特許文献5参照)。この鉛筆芯では、黒鉛を使用するものではなく、紙面への定着性についての開示や配慮はなされていないものである。
前記黒色の多孔質焼成芯体の気孔中に、前記エルカ酸オクチルドデシルを含む混合物であるホホバ油を含浸することが好ましい。
前記化合物又はホホバ油に加え、テルペンフェノール樹脂、ロジンエステル樹脂、ケトン樹脂及びロジン変性フェノール樹脂から選ばれる少なくとも1種を含浸することが好ましい。
前記化合物又はホホバ油は、含浸油中に60質量%以上含まれることが好ましい。
本開示の目的及び効果は、特に請求項において指摘される構成要素及び組み合わせを用いることによって認識され且つ得られるものである。上述の一般的な説明及び後述の詳細な説明の両方は、例示的及び説明的なものであり、特許請求の範囲に記載されている本開示を制限するものではない。
例えば、鉛筆芯がシャープペンシル用では、配合材料として、黒鉛を少なくとも含有するものであり、また、シャープペンシル以外の黒色の多孔質焼成芯体では、少なくとも黒鉛と、体質材とセラミック結合材などとを含有することが好ましい。
また、シャープペンシル用多孔質焼成芯体では、その他の成分として、結合材としてポリ塩化ビニル、ポリビニルアルコール、フェノール樹脂、ピッチ、セルロース、ポリアクリロニトリル、ナノ粒子として、平均粒径100nm以下の金属ナノ粒子、ダイヤモンドナノ粒子、これらのナノ粒子等からなる母材に対してアモルファスカーボン、黒鉛、ダイヤモンド及びセラミック材料などを被覆した被覆ナノ粒子、フラーレンなどのカーボン粒子、安定剤として、ステアリン酸Ca-Zn、ステアリン酸ナトリウム、ステアリン酸マグネシウム、可塑剤としてジオクチルフタレート、ジオクチルアジペート、フタル酸ジイソブチル、焼成鉛筆芯では、その他の成分として、色材、潤滑剤、バインダー成分、各種シリコーンオイル、ラード、アクリル樹脂、エポキシ樹脂、セルロイド及びその他の熱可塑性樹脂、有機溶剤等を用いることができる。
なお、本開示(後述する実施例等を含む)における平均粒径は、レーザー回折・散乱法における測定結果から体積で重みづけされた体積平均径(mv値)をいい、例えば、ナノ粒子では、ナノトラック〔日機装社製、UPA-EX150(内部プローブ型)〕を用いて測定することができる。
用いる有機溶剤は、上記熱可塑性樹脂を溶解し得る可塑剤となるものが好ましく、具体的には、ジオクチルフタレート、ジブチルフタレート、トリクレジルホスフェート、ジオクチルアジペート、ジアリルイソフタレート、プロピレンカーボネート、アルコール類、ケトン類、エステル類などを用いることができる。
例えば、鉛筆芯がシャープペンシル用の製造では、好ましくは、強度、濃度、書き味の点から、鉛筆芯配合組成物全量に対して、(a)上記黒鉛やカーボンブラック30~70質量%、(b)ナノ粒子0.01~1質量%を用いて、その他の成分である(c)熱可塑性合成樹脂30~60%、(d)該熱可塑性合成樹脂を溶解し得る有機溶剤0~30%を、ヘンシェルミキサーで分散混合し、加圧ニーダー、二本ロールで混練し、押出成型機により成型した後、電気炉で110~250℃で乾燥して、焼成前の鉛筆芯形成用の芯体を成形し、窒素などの不活性ガス雰囲気下で800~1400℃、20~40時間で焼成することにより鉛筆芯体を製造することができる。
好ましくは、エルカ酸オクチルドデシルを含む混合物であるホホバ油を含浸することができる。
本開示に用いるホホバ油は、ホホバ(Simmondsia chinensis)の種子から圧搾等により抽出される植物油で、主にエルカ酸オクチルドデシルを含む直鎖長鎖エステル(液状ワックス)であり一般的な植物油と異なり、酸化への耐性が強く、安定性も高く、圧搾油の精製油、脱臭油および水素添加油などを用いることができ、市販品があれば、それらを使用することができる。
上記エルカ酸オクチルドデシル、該エルカ酸オクチルドデシルを含む混合物であるホホバ油、パルミチン酸イソプロピル、オレイン酸オクチルドデシル、オレイン酸オレイル、パルミチン酸2-エチルヘキシル、プロピレングリコールモノオレエートは、従来のジメチルシリコーン油などの含浸油に較べ、上述の黒色の多孔質焼成芯体の気孔中に含浸処理等を施すと、今までにない筆記描線の濃度向上と、定着性の向上とを高度に両立でき、筆記している手などに汚れも付きにくい鉛筆芯が得られるものとなる。
上記テルペン化合物は、一般に、イソプレン(C5H8)の重合体で、モノテルペン(C10H16)、セスキテルペン(C15H24)、ジテルペン(C20H32)等に分類され、これらを基本骨格とする化合物である。これらの中で、本開示では、モノテルペン、セスキテルペン、ジテルペンが好ましく、セスキテルペン、モノテルペンがより好ましく用いられる。これらテルペン化合物としては、例えば、ミルセン、アロオシメン、オシメン、α-ピネン、β-ピネン、ジペンテン、リモネン、α-フェランドレン、α-テルピネン、γ-テルピネン、テルピノレン、1,8-シネオール、1,4-シネオール、α-テルピネオール、β-テルピネオール、γ-テルピネオール、カンフェン、トリシクレン、サビネン、パラメンタジエン類、カレン類が挙げられる。これらの中では、α-ピネン、β-ピネン、リモネン、ミルセン、アロオシメン、α-テルピネンが好ましい。
テルペンフェノール樹脂は、いわゆるタッキファイヤー(粘着性付与樹脂)の一種であり、通常分子量が数百~数千までの無定形オリゴマーであるとされている。テルペンフェノール樹脂の他のテルペン系樹脂には、テルペン樹脂、芳香族変性テルペン樹脂ならびに水素化テルペン樹脂が存在する。本開示では、テルペンフェノール樹脂を水素添加処理して得られた水添テルペンフェノール樹脂であってもよい。
本開示では、テルペンフェノール樹脂の市販品があれば、それらを使用することができ、例えば、ヤスハラケミカル社製のポリスターシリーズやマイティーエースシリーズの商品名で市販されており容易に入手できる。具体的には、YSポリスターT30、YSポリスターT80、YSポリスターT160(以上、ヤスハラケミカル社製)などが挙げられる。
なお、ロジン樹脂をエステル化した樹脂がロジンエステル樹脂、不均化ロジン樹脂をエステル化した樹脂が不均化ロジンエステル樹脂、水添ロジン樹脂をエステル化した樹脂が水添ロジンエステル樹脂、重合ロジン樹脂をエステル化した樹脂が重合ロジンエステル樹脂であり、本開示では、これらのいずれも用いることができる。
上記ロジンエステル樹脂としては、例えば、荒川化学工業社製のエステルガムHP、ハリマ化成社製のハリタックF85などが挙げられる。
用いることができるロジン変性フェノール樹脂としては、次のようなものがあげられる。p-オクチルフェノール、p-ノニルフェノールのようなp-アルキルフェノールとパラホルムアルデヒド、及びロジンをトルエンに溶解させ、酸、あるいは、アルカリ触媒下で反応後、グリセリン、ペンタエリスリトール、あるいは、ロジンを200℃で溶融し、レゾール樹脂を加えて反応後、グリセリンでエステル化したロジン変性フェノール樹脂、あるいは、ロジンのグリセリンエステルにレゾール樹脂を加えて反応させたロジン変性フェノール樹脂、あるいはロジン変性アルキド樹脂とフェノール樹脂を反応させたロジン変性フェノール樹脂等が挙げられ、市販品では、荒川化学工業(株)製のタマノル135、タマノル350、タマノル354などが挙げられる。
上記化合物(ホホバ油含む)から選ばれる少なくとも1種に加え、テルペンフェノール樹脂、ロジンエステル樹脂、ケトン樹脂及びロジン変性フェノール樹脂(A群)から選ばれる少なくとも1種を含浸成分として用いる場合、上記各化合物(ホホバ油含む)から選ばれる少なくとも1種の(合計)含有量は、書き味の点、摩耗量の点から含浸油中に60質量%以上(A群は40質量%以下)含まれることが好ましく、更に好ましくは、60~80質量%(A群は20~40質量%)である。
下記方法により、少なくとも黒鉛を含み黒色の多孔質焼成芯体(焼成鉛筆芯体)を作製した。
鱗片状天然黒鉛 40質量部
ナノ粒子:ダイヤモンドナノ粒子(粒径:mv値50nm) 0.4質量部
ポリ塩化ビニル 40質量部
ステアリン酸ナトリウム 1質量部
ジオクチルフタレート 15質量部
上記ナノ粒子とジオクチルフタレートをビーズミルで180分間分散させ、他の上記材料をヘンシェルミキサーで混合分散(混合分散時間20分、以下同様)し、加圧ニーダー、ロールで混練し、成形後、ジオクチルフタレートを乾燥後、窒素(N2)雰囲気中にて1000℃、10時間で焼成処理することによって、直径0.565mm、長さ60mmの焼成鉛筆芯体を製造した。
次いで、この焼成鉛筆芯体を、ホホバ油(NIKKOL ホホバ油S、日光ケミカルズ社製)70質量%とテルペンフェノール樹脂A(YSポリスターT160、ヤスハラケミカル社製)30質量%との混合油中に浸漬し、150℃-24時間含浸処理し、鉛筆芯を製造した。なお、重量測定により、芯体中の上記含浸量は、芯体重量に対して14.5質量%であることを確認した。
上記実施例1で得た焼成鉛筆芯体を、下記表1に示す配合組成の混合油または各化合物(ホホバ油含む)中に浸漬し、上記実施例1と同様に、含浸処理し、鉛筆芯を製造した。なお、上実施例1と同様に、重量測定により、各芯体中の上記含浸量を下記表1に表記する。
これらの結果を下記表1に示す。
三菱鉛筆社製のシャープペンシル(M5-450 1P)に装填し、JIS S 6005:2007に規定されている濃度試験で筆記した鉛筆芯の描線を濃度計(コニカミノルタ社製 DENSITOMETER PDA65)で測定し、下記3段階の評価基準(平均値、n=10)で評価した。
評価基準:
A:同硬度並み
B:半硬度程度薄い
C:度以上薄い
三菱鉛筆社製のシャープペンシル(M5-450 1P)に装填し、JIS S 6005:2007に規定されている濃度試験で筆記した鉛筆芯の描線を垂直荷重500gのフェルトで描線からはみ出す様に4往復擦過し、描線の汚れが広がった部分を濃度計(コニカミノルタ社製、DENSITOMETER PDA65)で測定し、下記4段階の評価基準(平均値、n=10)で評価した。
評価基準:
A:1硬度以上汚れにくい
B:1硬度程度汚れにくい
C:半硬度分汚れにくい
D:同硬度並み
*1:NIKKOL ホホバ油S (日光ケミカルズ社製)
*2:YSポリスターT160(ヤスハラケミカル社製)
*3:YSポリスターT160(ヤスハラケミカル社製)
*4:エステルガムHP(荒川化学社製)
*5:ケトンレジンK-90(荒川化学社製)
*6:タマノル135(荒川化学社製)
*7:KF96-30cs、信越化学社製
*8:パラフィンワックス、日本精蝋株式会社製
*9:PAO-4、フィリップス社製
Claims (4)
- 少なくとも黒鉛を含み黒色の多孔質焼成芯体の気孔中に、少なくとも、エルカ酸オクチルドデシル、オレイン酸オレイル、オレイン酸オクチルドデシル、パルミチン酸イソプロピル、パルミチン酸2-エチルヘキシル、プロピレングリコールモノオレエートから選ばれる化合物を含浸することを特徴とする鉛筆芯。
- 前記黒色の多孔質焼成芯体の気孔中に、前記エルカ酸オクチルドデシルを含む混合物であるホホバ油を含浸することを特徴とする請求項1に記載の鉛筆芯。
- 前記化合物又はホホバ油に加え、テルペンフェノール樹脂、ロジンエステル樹脂、ケトン樹脂及びロジン変性フェノール樹脂から選ばれる少なくとも1種を含浸することを特徴とする請求項1又は2に記載の鉛筆芯。
- 前記化合物又はホホバ油は、含浸油中に60質量%以上含まれることを特徴とする請求項1~3の何れか一つに記載の鉛筆芯。
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