JPH02191685A - Non-baked pencil lead - Google Patents
Non-baked pencil leadInfo
- Publication number
- JPH02191685A JPH02191685A JP999189A JP999189A JPH02191685A JP H02191685 A JPH02191685 A JP H02191685A JP 999189 A JP999189 A JP 999189A JP 999189 A JP999189 A JP 999189A JP H02191685 A JPH02191685 A JP H02191685A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- pencil lead
- thermosetting resin
- initial condensate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 4
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 4
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000004898 kneading Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000001054 red pigment Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- -1 Diaryl phthalate Chemical compound 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 210000001747 pupil Anatomy 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は主として、色鉛筆用の芯、水輪鉛筆芯、マント
処理されている合成樹脂フィルム用の芯、シャープペン
シル用の芯等に関するもので、格段に優れた曲げ強度と
古き味を有し、大幅に製造コストを削減した非焼成鉛筆
芯を提供するものであ（従来の技術）
従来の非焼成鉛筆芯は、結合剤として一種または二種以
上の存機高分子物質が用いられているが、結合剤の種類
によって製造方法が制約され、次の四つに大別すること
ができる。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention mainly relates to colored pencil leads, water ring pencil leads, cape-treated synthetic resin film leads, mechanical pencil leads, etc. , provides a non-fired pencil lead that has exceptional bending strength and an old-fashioned appearance, and significantly reduces manufacturing costs (prior technology). Although more than one species of existing polymeric substances are used, the manufacturing method is restricted depending on the type of binder and can be roughly classified into the following four types.
（ｉ）水溶性樹脂を水に溶解、膨潤させて混練後、押出
成形、乾燥する湿式法。(i) A wet method in which a water-soluble resin is dissolved in water, swollen, kneaded, extruded, and dried.
（ｉｉ）熱可塑性樹脂を溶剤、もしくは可塑剤で軟化さ
せ、混練、押出成形後、その溶剤、もしくは可塑剤を乾
燥除去する湿式法。(ii) A wet method in which a thermoplastic resin is softened with a solvent or a plasticizer, and after kneading and extrusion molding, the solvent or plasticizer is removed by drying.
（ｉｉ）熱可塑性樹脂を加熱溶融させて混練後、押出成
形する乾式法。(ii) A dry method in which a thermoplastic resin is heated and melted, kneaded, and then extruded.
（ｉｖ）熱硬化性樹脂初期縮合物と、または必要に応じ
て熱可塑性樹脂とを加熱溶融させて混練、押出成形後、
加熱して硬化、架橋させる乾式法。(iv) After heating and melting the thermosetting resin initial condensate or, if necessary, the thermoplastic resin, kneading and extrusion molding,
A dry method that heats, cures, and crosslinks.
しかし、いずれの方法も一長一短で以下の性質を持つ。However, each method has the following characteristics, with advantages and disadvantages.
（ｉ）は水を用いるため、配合組成物の粘度が低く、分
散、混練性が良く、比較的低い温度で作業でき、着色材
の変色も少ない。しかし、ワックスの融点以下の温度で
乾燥しなければならｒ、４時間がかかる。Since (i) uses water, the viscosity of the blended composition is low, the dispersion and kneading properties are good, it can be worked at relatively low temperatures, and there is little discoloration of the coloring material. However, it must be dried at a temperature below the melting point of the wax, which takes 4 hours.
（１１）は配合組成物の年度が低く、分散、混練性が良
く、比較的低い温度で乾燥しなければならず、時間がか
かり、また、衛生上の問題から、乾燥させた溶剤、もし
くは可塑剤を廃棄する設備のコストもかかる。(11) has a low age of the compounded composition, has good dispersion and kneading properties, requires drying at a relatively low temperature, takes time, and is hygienic, so dry solvents or plastic The cost of equipment to dispose of the agent is also high.
（ｉｊ）は配合組成物を混練、成形後の状態で完成品と
なｔ−）、乾燥、硬化等の後処理が不要なため、工程が
短くなる。しかと、７．混練、成形時の温度を高くしな
ければならず、着色材の変色や、ワックス類の劣化が起
きやすい。また、体質材を大量に配合するため、粘度が
高く、混練性が悪く、芯の機械的強度も弱い。In (ij), the compounded composition is kneaded and molded into a finished product (t-), and post-treatments such as drying and curing are not required, so the process is shortened. Shikato, 7. The temperature during kneading and molding must be high, which tends to cause discoloration of the colorant and deterioration of the wax. Furthermore, since a large amount of extender is blended, the viscosity is high, the kneading properties are poor, and the mechanical strength of the core is weak.
（１■）は混練、成形時の温度制御が適当であれば、後
処理の硬化時間も工程も短くなる。しかし、温度制御は
容易ではないし、混練、成形時の温度が高いため、着色
材の変色や、ワックス類の劣化が起きやすい。For (1), if temperature control during kneading and molding is appropriate, the curing time and process of post-treatment will be shortened. However, temperature control is not easy, and the high temperatures during kneading and molding tend to cause discoloration of the colorant and deterioration of the waxes.
（発明が解決しようとする問題点）
本発明の目的は、従来用いられている結合剤の欠点を解
決することにより工程時間を短縮、コストを削減し、か
つ実用面においても折れ難く、滑らかな書き味を有する
非焼成鉛筆芯を捉供するものである。(Problems to be Solved by the Invention) The purpose of the present invention is to shorten the process time and reduce costs by solving the drawbacks of conventionally used binders, and also to create a material that is hard to break and smooth in practical use. It captures and provides a non-fired pencil lead that has a writing feel.
（問題点峻解決するための手段）
本発明者は上記問題点を解決するために、鋭意研究の結
果、製造工数を減らして製造コストを削減し、分散、混
練性を上げ、優れた機械的強度、滑らかな書き味を有す
る非焼成鉛筆芯を得るには、比較的低温、かつ、、低粘
度での混練、成形をｉｊ梵とする結合剤として１、軟化
点の低い熱硬化性樹脂初期縮合物、及び７、混練性を上
げるために該初期縮合物と最終的「共重合して硬化せし
める反応性可塑剤としての千ツマ−を加え、更に好まし
くは、熱硬化性樹脂初期縮合物にジアリルフタレート系
ブリポリ“７−１及び該初期縮合物と共重合可能なモノ
マーにジアリルフタレート系モノマーヲ用いることによ
り、目的とする非焼成鉛筆芯が得られることに想到し、
本発明を完成させた。(Means for solving the problem) In order to solve the above problems, the inventor of the present invention has conducted intensive research to reduce the number of manufacturing steps, reduce the manufacturing cost, improve dispersion and kneading properties, and achieve an excellent mechanical In order to obtain a non-fired pencil lead with strength and smooth writing, it is necessary to knead and mold at a relatively low temperature and low viscosity. 1. As a binder, a thermosetting resin with a low softening point is used at the initial stage. 7. In order to improve kneading properties, a reactive plasticizer which is copolymerized and cured with the initial condensate is added, and more preferably, a thermosetting resin is added to the initial condensate. By using a diallyl phthalate-based monomer as a monomer copolymerizable with diallyl phthalate-based Buri-Poly "7-1" and the initial condensate, it was conceived that the desired non-fired pencil lead could be obtained,
The present invention has been completed.
本発明に用いられる熱硬化性樹脂初期縮合物は、低温で
軟化し、モノマーは該初期縮合物と共重合可能なもので
あれば、いずれも使用可能であるが、芯に成形した場合
の強度、書き味が優れている、白色で淡色系の色芯にも
使用できる、付加重合で硬化し揮発性物質を放出しない
等の理由から、熱硬化性樹脂初期縮合物としてジアリル
フタレート系プリポリマーが、該初期縮合物と共重合ｎ
Ｊ能なモノマーとしてジアリルフタレート系モノマーが
好ましい。The thermosetting resin initial condensate used in the present invention softens at low temperatures, and any monomer can be used as long as it is copolymerizable with the initial condensate, but the strength when molded into a core is Diaryl phthalate prepolymers are used as initial condensates of thermosetting resins because of their excellent writing quality, their ability to be used for white and light-colored color cores, and their ability to cure through addition polymerization and do not emit volatile substances. , copolymerized with the initial condensate n
Diaryl phthalate monomers are preferred as the J-functional monomers.
本発明の配合組成物は、結合剤が」１記の熱硬化性樹脂
初期縮合物、及び該初！ＵＩＭ合物と共重合可能なモノ
マーが少なくとも含有されていなければならない、その
結合剤としての配合量は、全配合組成物量の６０重量％
まで、添加、配合することができるが、書き味の面から
見ると、５〜４０重量％が好ましい、その他の配合組成
物は公知の結合剤、着色材、ワックス、体質材は全て用
いることができ、特に限定しない。The blended composition of the present invention is characterized in that the binder is a thermosetting resin initial condensate as described in 1. It must contain at least a monomer copolymerizable with the UIM compound, and its amount as a binder is 60% by weight of the total amount of the blended composition.
However, from the viewpoint of writing quality, it is preferable to add and blend up to 5 to 40% by weight.For other compounding compositions, all known binders, colorants, waxes, and extenders can be used. Yes, there are no particular restrictions.
（作 用）
本発明によって得られる結合剤として少なくとも熱硬化
性樹脂初期縮合物、及び該初期縮合物と共重合可能なモ
ノマーが添加、配合された非焼成鉛筆芯は下記の優れた
長所を有する。(Function) The non-fired pencil lead obtained according to the present invention, in which at least a thermosetting resin initial condensate and a monomer copolymerizable with the initial condensate are added and blended as a binder, has the following excellent advantages. .
（１）熱硬化性樹脂初期縮合物と共重合可能なモノマー
が、該初期縮合物の可塑剤の役目をするため、低温での
流動特性、分散、混練性が良い。(1) Since the monomer copolymerizable with the thermosetting resin initial condensate serves as a plasticizer for the initial condensate, the fluidity, dispersion, and kneading properties at low temperatures are good.
（２）流動特性が良く、また体質材、着色材等とのぬれ
性も良いため、機械的強度に優れた鉛箪芯が得られる。(2) Since it has good flow characteristics and good wettability with extenders, colorants, etc., a lead commode core with excellent mechanical strength can be obtained.
（３）比較的低温で混練、成形が可能であるので、熱に
よる着色材の変色、ワックスの劣化が少ない。(3) Since it is possible to knead and mold at relatively low temperatures, there is little discoloration of the coloring material or deterioration of the wax due to heat.
（４）成形後の加熱硬化時間は従来の湿式法の乾燥時間
よりも極めて短時間である。(4) The heat curing time after molding is much shorter than the drying time of the conventional wet method.
（実 施 例） 次に本発明を実施例により具体的に説明する。(Example) Next, the present invention will be specifically explained using examples.
実施例Ｉ。Example I.
ジアリルオルソフタレートプリポリマー１８重瞳部、ジ
アリルオルソフタレートモノマー２重量部、硬化剤０．
５重量部、カスターワックス２０重ν部、タルク４５重
量部、レーキ系赤色顔料１５重量部から成る配合組成物
をニーダ−で混合、分散させた後、２本ロールで混練し
、混練物をベレ７）化し、単軸スクリュー型押出機にて
８０°Ｃで押出成形し、更に通常の方法にて１００℃で
１時間硬化後、直径３ｍの非焼成赤色鉛筆芯を得た。Diallyl orthophthalate prepolymer 18-fold pupil, diallyl orthophthalate monomer 2 parts by weight, curing agent 0.
A blended composition consisting of 5 parts by weight of castor wax, 20 parts by weight of castor wax, 45 parts by weight of talc, and 15 parts by weight of lake-based red pigment was mixed and dispersed in a kneader, then kneaded with two rolls, and the kneaded product was leveled. 7), extrusion molded at 80°C using a single-screw extruder, and further cured at 100°C for 1 hour using a conventional method to obtain an unfired red pencil lead with a diameter of 3 m.
その結果を表に示す。The results are shown in the table.
比較例１
ポリビニルアルコール２０重量部、カスターワンラス２
０重喰部、タルク４５重量部、レーキ系赤色ｆＭ料１５
ｆｆｉ量部、水１００重量部から成る配合組成物をニー
ダ−で混合、分散させた後、２本ロールで混練しながら
水分調整し、混練物をペレット化し、単軸スクリュー型
押出機にて押出成形し、６０°Ｃで６０時間水分乾燥後
、直径３ＩＩＩｍの非焼成赤色鉛筆芯を得た。その結果
を表に示す。Comparative Example 1 20 parts by weight of polyvinyl alcohol, Castor Wanlas 2
0 parts by weight, 45 parts by weight of talc, 15 parts by weight of lake red fM material
After mixing and dispersing a blended composition consisting of parts by weight of ffi and 100 parts by weight of water using a kneader, the moisture content was adjusted while kneading with two rolls, the kneaded product was pelletized, and extruded using a single screw extruder. After molding and moisture drying at 60°C for 60 hours, an unfired red pencil lead with a diameter of 3IIIm was obtained. The results are shown in the table.
比較例２
ＡＳ樹脂２０重量部、ステアリン酸カルシウム１５重量
部、カスターワックス５重量部、タルク４５重量部、レ
ーキ系赤色顔料１５重量部から成る配合組成物をニーダ
−で混合、分散させた後、２木ロールで混練し、混練物
をペレット化し、単軸スクリュー型押出機にて１８０”
Ｃで押出成形し、直径３ｒｍの非焼成赤色鉛筆芯を得た
。その結果を表に示す。Comparative Example 2 After mixing and dispersing a composition consisting of 20 parts by weight of AS resin, 15 parts by weight of calcium stearate, 5 parts by weight of castor wax, 45 parts by weight of talc, and 15 parts by weight of lake-based red pigment, Knead with wooden rolls, turn the kneaded material into pellets, and use a single screw extruder to make 180”
C. to obtain an unfired red pencil lead with a diameter of 3 rm. The results are shown in the table.
実施例２
ジアリルオルソフタレートプリポリマー３６重量部、ジ
アリルオルソフタレートモノマー４重量部、硬化剤１重
に部、ステアリン酸マグネシウム１５重量部、タルク３
０重量部、レーキ系赤色顔料１５重量部から成る配合組
成物をニーダーで混合、分散させた後、２本ロールで混
練し、混練物をプランジャー型押出機にて１００°Ｃで
押出成形し、更に通常の方法にて１００℃で１時間硬化
後、直径０．５−の非焼成赤色鉛筆芯を得た。その結果
を表に示す。Example 2 36 parts by weight of diallyl orthophthalate prepolymer, 4 parts by weight of diallyl orthophthalate monomer, 1 part by weight of curing agent, 15 parts by weight of magnesium stearate, 3 parts by weight of talc
A blended composition consisting of 0 parts by weight and 15 parts by weight of a lake-based red pigment was mixed and dispersed in a kneader, then kneaded with two rolls, and the kneaded product was extruded at 100°C with a plunger type extruder. After curing at 100° C. for 1 hour in a conventional manner, an unfired red pencil lead with a diameter of 0.5 mm was obtained. The results are shown in the table.
比較例３
セルロイ１４０重景部、ステアリン酸マグネシウム１５
重量部、タルク３０重量部、レーキ系赤色顔料１５重量
部、酢酸エチル１００重量部から成る配合組成物をニー
ダ−で混合、分散させた後、２本ロールで混練しながら
溶剤量を調整し、混練物をプランジャー型押出機にて８
０℃で押出成形し、更に溶剤量を６０℃で９０時間乾燥
後、直径０．５−の非焼成赤色鉛筆芯を得た。その結果
を表に示す。Comparative Example 3 Celluloy 140 heavy area, magnesium stearate 15
After mixing and dispersing a composition consisting of 30 parts by weight of talc, 15 parts by weight of lake-based red pigment, and 100 parts by weight of ethyl acetate in a kneader, the amount of solvent was adjusted while kneading with two rolls, The kneaded material is passed through a plunger type extruder at 8
After extrusion molding at 0°C and further drying the solvent at 60°C for 90 hours, an unfired red pencil lead with a diameter of 0.5 mm was obtained. The results are shown in the table.
（発明の効果）
本発明による、結合剤として、少なくとも熱硬化性樹脂
初期縮合物、及び該初期縮合物と共重合可能なモノマー
が添加、配合された非焼成鉛筆芯は、上記の試験結果で
も明らかなように、着色材の変色も無く、優れた機械的
強度と、滑らかな書き味を有し、かつ、硬化等の加熱時
間を短縮し、大幅に製造コストを削減するものである。(Effects of the Invention) The non-fired pencil lead according to the present invention, in which at least a thermosetting resin initial condensate and a monomer copolymerizable with the initial condensate are added and blended as a binder, does not meet the above test results. As is clear, there is no discoloration of the coloring material, it has excellent mechanical strength and a smooth writing feel, and the heating time for curing etc. is shortened, resulting in a significant reduction in manufacturing costs.
＊） ＪＩＳ Ｓ ６００５−１９８４に準じた
。*) According to JIS S 6005-1984.
Claims (1)
、及び該初期縮合物と共重合可能なモノマーが添加、配
合されていることを特徴とする非焼成鉛筆芯。 ２、熱硬化性樹脂初期縮合物が、ジアリルフタレート系
プリポリマーであり、該初期縮合物と共重合可能なモノ
マーが、ジアリルフタレート系モノマーであることを特
徴とする特許請求の範囲第１項の非焼成鉛筆芯。[Scope of Claims] 1. A non-fired pencil lead characterized in that at least a thermosetting resin initial condensate and a monomer copolymerizable with the initial condensate are added and blended as a binder. 2. The thermosetting resin initial condensate is a diallyl phthalate prepolymer, and the monomer copolymerizable with the initial condensate is a diallyl phthalate monomer. Unfired pencil lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1009991A JP2698409B2 (en) | 1989-01-20 | 1989-01-20 | Non-fired pencil lead |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1009991A JP2698409B2 (en) | 1989-01-20 | 1989-01-20 | Non-fired pencil lead |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02191685A true JPH02191685A (en) | 1990-07-27 |
| JP2698409B2 JP2698409B2 (en) | 1998-01-19 |
Family
ID=11735331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1009991A Expired - Lifetime JP2698409B2 (en) | 1989-01-20 | 1989-01-20 | Non-fired pencil lead |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2698409B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937330A (en) * | 2014-05-16 | 2014-07-23 | 安硕文教用品（上海）股份有限公司 | High-temperature-resistant colored pencil core and preparation method thereof |
| CN110181973A (en) * | 2019-06-12 | 2019-08-30 | 界首市菁华科技信息咨询服务有限公司 | A kind of clay pencil of yellow glue and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4912300A (en) * | 1972-05-16 | 1974-02-02 | ||
| JPS5149826A (en) * | 1974-10-26 | 1976-04-30 | Pentel Kk | ENPITSUSHINNOSEIZOHOHO |
-
1989
- 1989-01-20 JP JP1009991A patent/JP2698409B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4912300A (en) * | 1972-05-16 | 1974-02-02 | ||
| JPS5149826A (en) * | 1974-10-26 | 1976-04-30 | Pentel Kk | ENPITSUSHINNOSEIZOHOHO |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937330A (en) * | 2014-05-16 | 2014-07-23 | 安硕文教用品（上海）股份有限公司 | High-temperature-resistant colored pencil core and preparation method thereof |
| CN110181973A (en) * | 2019-06-12 | 2019-08-30 | 界首市菁华科技信息咨询服务有限公司 | A kind of clay pencil of yellow glue and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2698409B2 (en) | 1998-01-19 |
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