JP6580384B2 - Direct liquid writing instrument and ink cartridge used therefor - Google Patents
Direct liquid writing instrument and ink cartridge used therefor Download PDFInfo
- Publication number
- JP6580384B2 JP6580384B2 JP2015121810A JP2015121810A JP6580384B2 JP 6580384 B2 JP6580384 B2 JP 6580384B2 JP 2015121810 A JP2015121810 A JP 2015121810A JP 2015121810 A JP2015121810 A JP 2015121810A JP 6580384 B2 JP6580384 B2 JP 6580384B2
- Authority
- JP
- Japan
- Prior art keywords
- ink
- writing instrument
- direct liquid
- pen
- core
- 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.)
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- 238000003860 storage Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
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- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
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- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- DSOWAKKSGYUMTF-GZOLSCHFSA-M sodium;(1e)-1-(6-methyl-2,4-dioxopyran-3-ylidene)ethanolate Chemical compound [Na+].C\C([O-])=C1/C(=O)OC(C)=CC1=O DSOWAKKSGYUMTF-GZOLSCHFSA-M 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 235000012756 tartrazine Nutrition 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 229960000943 tartrazine Drugs 0.000 description 1
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 1
- OLSOUGWNONTDCK-UHFFFAOYSA-J tetrasodium 5-amino-3-[[4-[4-[(8-amino-1-hydroxy-3,6-disulfonatonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(N=NC3=CC=C(C=C3OC)C=3C=C(C(=CC=3)N=NC=3C(=CC4=CC(=CC(N)=C4C=3O)S([O-])(=O)=O)S([O-])(=O)=O)OC)=C(O)C2=C1N OLSOUGWNONTDCK-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
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- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Landscapes
- Pens And Brushes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、インキがインキ貯蔵部からペン芯を介してペン先へ誘導される直液式筆記具とそれに用いられるインキカートリッジに関する。
The present invention relates to a direct liquid writing instrument in which ink is guided from an ink storage unit to a pen tip via a pen core, and an ink cartridge used therefor .
従来、多数の薄い円盤体が互いに僅かな間隙(櫛溝状間隔)を開け並列配置され、前記円盤体を軸方向に縦貫するスリット状のインキ誘導溝及び該溝より太幅の通気溝が設けられ、軸心にインキ貯蔵部からペン先へインキを誘導するためのインキ誘導芯が配置されてなる、所謂ペン芯を介して、インキ貯蔵部からペン先へインキを誘導するタイプの筆記具(直液式筆記具という)が広く使用されている。
前記ペン芯は通常、合成樹脂材料から成形されており、その表面が相対的に疎水性であるため、水性インキを適用する場合には、インキの表面張力を調整したり、界面活性剤を添加することで、ペン芯との親和性(濡れ性)を向上させている(例えば、特許文献1参照)。
また、前記直液式筆記具においては、経済性が高く環境配慮の観点から、インキ貯蔵部が交換可能なカートリッジタイプの筆記具が用いられる傾向がある(例えば、特許文献2参照)。
Conventionally, a large number of thin disk bodies are arranged in parallel with a slight gap (comb groove-like interval) between them, and a slit-shaped ink guide groove that passes through the disk body in the axial direction and a ventilation groove wider than the groove are provided. A writing instrument of a type that guides ink from the ink storage section to the pen tip via a so-called pen core, in which an ink guide core for guiding the ink from the ink storage section to the pen tip is arranged at the shaft center. Liquid writing instruments) are widely used.
The pen core is usually molded from a synthetic resin material, and its surface is relatively hydrophobic. Therefore, when applying water-based ink, the surface tension of the ink is adjusted or a surfactant is added. By doing so, the affinity (wetting property) with a pen core is improved (for example, refer patent document 1).
In addition, the direct liquid writing instrument tends to use a cartridge-type writing instrument in which the ink storage unit can be replaced from the viewpoint of high economic efficiency and environmental consideration (see, for example, Patent Document 2).
前記特許文献1の技術では、非イオン系界面活性剤の添加により、インキの表面張力を下げることで生じていたペン先からのインキのボタ落ちやペン芯内のインキ回収不良を生じることなく、ペン芯の濡れ性を良化させるものであるが、適用される筆記具の構造によっては、筆記時のインキ吐出が安定性に欠くものであった。特に、前記水性インキを特許文献2のようなインキカートリッジタイプの筆記具に適用した場合、初期的な筆記時(即ち、最初に接続されたカートリッジを使い切るまでの間)にはインキ吐出安定性が得られるものの、新しいカートリッジに交換した際には、交換時に気泡を巻き込むことで、インキ貯蔵部からペン先へのインキ供給が不安定となり、筆記時のインキ吐出安定性が得られず、均一な筆跡が安定して得られないことがあった。 In the technique of the above-mentioned Patent Document 1, without adding a nonionic surfactant, without causing ink drop from the pen tip and poor ink recovery in the pen core, which has occurred by lowering the surface tension of the ink, Although it improves the wettability of the pen core, depending on the structure of the writing instrument to be applied, ink ejection during writing lacks stability. In particular, when the water-based ink is applied to an ink cartridge type writing instrument as in Patent Document 2, ink ejection stability is obtained during initial writing (that is, until the first connected cartridge is used up). However, when replacing the cartridge with a new one, the air supply from the ink reservoir to the pen tip becomes unstable due to the inclusion of air bubbles during the replacement, and the ink ejection stability during writing cannot be obtained. May not be obtained stably.
本発明は、前述のペン芯を備えた筆記具に適用する水性インキにおいて、ペン先からのインキのボタ落ちやペン芯内のインキ回収不良を生じることなくペン芯性能を発現でき、初期的なインキ吐出安定性を付与できることはもちろん、インキカートリッジタイプの直液式筆記具に適用した場合であっても、カートリッジ交換後のペン先へのインキ供給を長期に亘って安定持続できる、筆記時のインキ吐出安定性とカートリッジ交換性に優れた筆記具用水性インキ組成物を内蔵した直液式筆記具とそれに用いられるインキカートリッジを提供するものである。
The present invention is a water-based ink that is applied to a writing instrument having the above-described pen core, and can exhibit pen core performance without causing ink drop off from the pen nib and ink recovery failure in the pen core. Ink ejection at the time of writing that can stably provide ink supply to the pen tip after replacement of the cartridge for a long time even when applied to ink cartridge type direct liquid writing instruments as well as providing ejection stability It is an object of the present invention to provide a direct liquid type writing instrument incorporating a water-based ink composition for a writing instrument excellent in stability and cartridge exchangeability, and an ink cartridge used therefor .
本発明は、ペン先と、筆記具本体に着脱可能なインキカートリッジ形態のインキ貯蔵部と、多数の円盤体が櫛溝状の間隔を開け並列配置され、前記円盤体を軸方向に縦貫するスリット状のインキ誘導溝及び該溝より太幅の通気溝が設けられ、軸心にインキ貯蔵部からペン先へインキを誘導するためのインキ誘導芯が配置されてなるペン芯と、から構成され、前記インキ貯蔵部に、水と、着色剤と、ポリオキシエチレンポリオキシプロピレングリコール及び/又はポリオキシエチレンポリオキシプロピレンアルキルエーテルと、シリカ又はシリコーン樹脂の乳化物を含む水性インキ組成物を内蔵する直液式筆記具を要件とする。
更に、前記乳化物がインキ組成物全量中0.01〜5重量%の範囲で添加されることを要件とする。
更に、前記ペン先が、金属製パイプの先端にボールを抱持するボールペンチップであり、前記金属製パイプ内に中芯が配置され、前記金属パイプの内径Bと、中芯の外径Cが、B/C≦2であることを要件とする。
更には、前記いずれかに記載の直液式筆記具に用いられるインキカートリッジを要件とする。
The present invention relates to a pen tip, an ink storage unit in the form of an ink cartridge that can be attached to and detached from the writing instrument body, and a plurality of disc bodies arranged in parallel at intervals of a comb groove shape, and a slit shape penetrating the disc body in the axial direction. the ink guiding grooves and ventilation grooves of large width are provided from the groove, is composed of a pen core which ink guiding core is disposed for guiding the ink from the ink reservoir to the axis to the pen tip, the A direct liquid containing a water-based ink composition containing water, a colorant, polyoxyethylene polyoxypropylene glycol and / or polyoxyethylene polyoxypropylene alkyl ether, and an emulsion of silica or silicone resin in the ink reservoir. Require a formula writing instrument .
Furthermore, it is required that the emulsion is added in the range of 0.01 to 5% by weight in the total amount of the ink composition.
Furthermore, the pen point is a ballpoint pen tip that holds a ball at the tip of a metal pipe, a core is disposed in the metal pipe, and an inner diameter B of the metal pipe and an outer diameter C of the core are , B / C ≦ 2 .
Furthermore, the ink cartridge used for any of the direct liquid writing instruments described above is a requirement.
本発明により、ペン芯を備えた筆記具に適用することで、良好なペン芯性能を発揮するとともに、インキ吐出安定性を長期に亘って得ることができる。特に、インキカートリッジタイプの直液式筆記具に適用した場合には、初期的にはもちろん、インキカートリッジ交換後であっても、ペン先へのインキ供給が安定して持続されるとともに、筆記時には均一な筆跡が長期に亘って形成できる、インキ吐出安定性に優れた筆記具用水性インキ組成物となり、インキカートリッジ交換時のインキ追従性(カートリッジ交換性能)に優れたインキカートリッジや直液式筆記具が得られる。
特に、特定の乳化物をインキ中に追加することで、インキカートリッジ交換に伴う長期的な連続使用に対しても安定したインキ吐出性が維持できる。
By applying to the writing instrument provided with the pen lead by this invention, while exhibiting favorable pen lead performance, ink discharge stability can be obtained over a long period of time. In particular, when applied to an ink cartridge type direct liquid writing instrument, the ink supply to the pen tip is stably maintained even after replacement of the ink cartridge at the beginning, and is uniform during writing. a handwriting can be formed over a long period, Ri Do a water based ink composition for a writing instrument which is excellent in ink ejection stability, ink cartridge replacement time of the ink follower of excellent ink cartridges and Chokuekishiki writing instrument (cartridge exchange performance) Is obtained.
In particular, by adding a specific emulsion to the ink, it is possible to maintain a stable ink ejection property even for long-term continuous use accompanying ink cartridge replacement.
一般に、ペン芯を備えた直液式筆記具に適用される水性インキは、表面張力が高すぎる場合、櫛溝部にインキを保持できず、筆記具内部の気圧変化によって誘導芯を介してペン先からインキのボタ落ちが発生したり、特に毛細管力の低いペン先においては筆跡にウスや途切れが発生する。また、表面張力が低すぎる場合、筆記具内部の気圧変化によって櫛溝部に保持されたインキが回収できない等の問題が生じるため、表面張力を規定するように様々なインキ組成が適用されている。これに対して本発明では、ポリオキシエチレンポリオキシプロピレングリコールやポリオキシエチレンポリオキシプロピレンアルキルエーテルを用いることで、表面張力によらず前記不具合を解消できるとともに、表面張力の調整だけでは得られなかったインキカートリッジ交換時のインキ供給安定性(カートリッジ交換性)が付与できることを見出した。 In general, water-based ink applied to a direct liquid writing instrument equipped with a pen core cannot retain ink in the comb groove when the surface tension is too high, and ink from the pen tip via the induction core due to a change in atmospheric pressure inside the writing instrument. In the case of a pen tip having a low capillary force, a hand or a break occurs in the handwriting. In addition, when the surface tension is too low, a problem such as that the ink held in the comb groove portion cannot be recovered due to a change in atmospheric pressure inside the writing instrument arises. Therefore, various ink compositions are applied so as to regulate the surface tension. On the other hand, in the present invention, by using polyoxyethylene polyoxypropylene glycol or polyoxyethylene polyoxypropylene alkyl ether, the above problems can be solved regardless of the surface tension, and it cannot be obtained only by adjusting the surface tension. In addition, the present inventors have found that ink supply stability (cartridge exchangeability) at the time of ink cartridge replacement can be imparted.
前記ポリオキシエチレンポリオキシプロピレンアルキルエーテルは、一般式(1)で表される化合物であり、エチレンオキサイドとプロピレンオキサイドとが任意の配列で重合した構造を持つランダムコポリマーである。また、ポリオキシエチレンポリオキシプロピレングリコールは、一般式(1)の式中のRがHの化合物である。
R−O−(C3H6O)m(C2H4O)n−H (1)
〔式中のRはアルキル基を示し、m及びnはそれぞれ独立して1〜40の数を示す〕
前記一般式のRで表されるアルキル基としては、例えば、炭素数2〜8、好ましくは2〜4のものが適用できる。また、m及びnで示されるエチレンオキサイド、プロピレンオキサイドの付加モル数としては、それぞれ独立して1〜40であり、好ましくは1〜24である。
特に、分子量が800〜3500のものは、添加によるインキ粘度の上昇が生じ難い点から好適である。
The polyoxyethylene polyoxypropylene alkyl ether is a compound represented by the general formula (1), and is a random copolymer having a structure in which ethylene oxide and propylene oxide are polymerized in an arbitrary arrangement. Polyoxyethylene polyoxypropylene glycol is a compound in which R in the formula of general formula (1) is H.
R—O— (C 3 H 6 O) m (C 2 H 4 O) n —H (1)
[Wherein R represents an alkyl group, and m and n each independently represents a number of 1 to 40]
Examples of the alkyl group represented by R in the general formula include those having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. The number of moles of ethylene oxide and propylene oxide added represented by m and n is independently 1 to 40, preferably 1 to 24.
In particular, those having a molecular weight of 800 to 3500 are preferred from the viewpoint that the ink viscosity is hardly increased by addition.
前記ポリオキシエチレンポリオキシプロピレングリコールやポリオキシエチレンポリオキシプロピレンアルキルエーテルとして、具体的には、ユニルーブ50MB−2、同50MB−5、同50MB−11、同50MB−26、同50MB−72、同50MB−168、同75DE−25、同75DE−60、同75DE−170(以上、日油製)、
カーポールGH−5、同GH−10、同GH−200、同MH−20、同MH−70、同MH−150、同MH−500(以上、アデカ製)等を挙げることができる。
Specific examples of the polyoxyethylene polyoxypropylene glycol and the polyoxyethylene polyoxypropylene alkyl ether include unilube 50MB-2, 50MB-5, 50MB-11, 50MB-26, 50MB-72, 50MB-168, 75DE-25, 75DE-60, 75DE-170 (above, NOF Corporation),
Carpol GH-5, GH-10, GH-200, MH-20, MH-70, MH-150, MH-500 (above, manufactured by ADEKA) and the like.
前記ポリオキシエチレンポリオキシプロピレングリコールやポリオキシエチレンポリオキシプロピレンアルキルエーテルはインキ組成物全量中、0.1〜10重量%、好ましくは1〜5重量%の範囲で添加することができる。
0.1重量%未満では十分なインキ吐出性能を付与することは困難であり、また、10重量%を越えて添加しても一定以上のインキ吐出性能の向上は認められないので、これ以上の添加を要しない。
The polyoxyethylene polyoxypropylene glycol or polyoxyethylene polyoxypropylene alkyl ether can be added in the range of 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the total amount of the ink composition.
If it is less than 0.1% by weight, it is difficult to give sufficient ink ejection performance, and even if added in excess of 10% by weight, no improvement in ink ejection performance beyond a certain level is observed. No addition is required.
更に、シリカ又はシリコーン樹脂を乳化剤で乳化した乳化物を併用することで、前記効果を維持したまま、インキカートリッジ交換後のペン先へのインキ供給がより安定化され、長期に亘って均一な筆跡を形成できる。特に、前記安定性効果は長期経時後においても維持されるため、長期間ストックされた複数のインキカートリッジが用いられるとともに、単一の筆記具本体が長期に亘って使用され続けるカートリッジ式筆記具においてより有用なものとなる。 Furthermore, by using an emulsion obtained by emulsifying silica or silicone resin with an emulsifier, the ink supply to the nib after the ink cartridge replacement is further stabilized while maintaining the above effect, and the handwriting is uniform over a long period of time. Can be formed. In particular, since the stability effect is maintained even after a long period of time, a plurality of ink cartridges stocked for a long period of time are used, and it is more useful for a cartridge-type writing instrument in which a single writing instrument body continues to be used for a long period of time. It will be something.
前記シリカやシリコーン樹脂を乳化する乳化剤としては、親水性の強いものと親油性の強いもののいずれを用いることも可能である。具体的に、親水性の強い乳化剤としては、アルカリセッケン、有機アミンセッケン、および高級アルコールの硫酸エステル、トウイーン類の非イオン活性剤、植物ゴム(アラビアゴム、アブラミン、カゼイン等)、アルギン酸、カルボキシメチルセルローズ、サポニン等が例示でき、親油性の強いものとしては、重金属セッケン、ラノリン、ロジン、コレステリンシ、レシチン、非イオン界面活性剤の中の多価アルコールの脂肪酸エステル等が例示できる。
特に、シリカやシリコーン樹脂に対する乳化性が高く、少量で高い効果を発現することから、シリコーン系界面活性剤やソルビタン系界面活性剤が有効である。
As an emulsifier for emulsifying the silica or the silicone resin, either one having strong hydrophilicity or one having strong lipophilicity can be used. Specifically, strong emulsifiers include alkaline soaps, organic amine soaps, sulfates of higher alcohols, tweens nonionic active agents, vegetable gums (gum arabic, abramin, casein, etc.), alginic acid, carboxymethyl Cellulose, saponin and the like can be exemplified, and those having strong lipophilicity include heavy metal soap, lanolin, rosin, cholesterol, lecithin, fatty acid ester of polyhydric alcohol in nonionic surfactant and the like.
In particular, silicone-based surfactants and sorbitan-based surfactants are effective because they have high emulsifying properties for silica and silicone resins and exhibit high effects in a small amount.
前記乳化物はインキ組成物全量中0.01〜5重量%、好ましくは0.1〜3重量%の範囲で添加される。
0.01重量%未満では所期の効果を得ることは困難であり、又、5重量%を越えて添加しても前記効果の向上は認められないので、これ以上の添加を要しない。
The emulsion is added in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total amount of the ink composition.
If it is less than 0.01% by weight, it is difficult to obtain the desired effect, and even if it is added in excess of 5% by weight, no improvement of the effect is observed, so no further addition is required.
前記着色剤としては、水性媒体に溶解もしくは分散可能な染料及び顔料が使用可能であり、その具体例を以下に例示する。
前記染料としては、酸性染料、塩基性染料、直接染料等を使用することができる。
酸性染料としては、ニューコクシン(C.I.16255)、タートラジン(C.I.19140)、アシッドブルーブラック10B(C.I.20470)、ギニアグリーン(C.I.42085)、ブリリアントブルーFCF(C.I.42090)、アシッドバイオレット6B(C.I.42640)、ソルブルブルー(C.I.42755)、ナフタレングリーン(C.I.44025)、エオシン(C.I.45380)、フロキシン(C.I.45410)、エリスロシン(C.I.45430)、ニグロシン(C.I.50420)、アシッドフラビン(C.I.56205)等が用いられる。
塩基性染料としては、クリソイジン(C.I.11270)、メチルバイオレットFN(C.I.42535)、クリスタルバイオレット(C.I.42555)、マラカイトグリーン(C.I.42000)、ビクトリアブルーFB(C.I.44045)、ローダミンB(C.I.45170)、アクリジンオレンジNS(C.I.46005)、メチレンブルーB(C.I.52015)等が用いられる。
直接染料としては、コンゴーレッド(C.I.22120)、ダイレクトスカイブルー5B(C.I.24400)、バイオレットBB(C.I.27905)、ダイレクトディープブラックEX(C.I.30235)、カヤラスブラックGコンク(C.I.35225)、ダイレクトファストブラックG(C.I.35255)、フタロシアニンブルー(C.I.74180)等が用いられる。
As the colorant, dyes and pigments that can be dissolved or dispersed in an aqueous medium can be used, and specific examples thereof are illustrated below.
As the dye, an acid dye, a basic dye, a direct dye, or the like can be used.
Examples of the acid dye include New Coxin (CI. 16255), Tartrazine (CI. 19140), Acid Blue Black 10B (CI. 20470), Guinea Green (CI. 42085), Brilliant Blue FCF. (CI.42090), Acid Violet 6B (C.I.42640), Soluble Blue (C.I.42755), Naphthalene Green (C.I.44025), Eosin (C.I.45380), Phloxin (C.I. 45410), erythrosine (C.I. 45430), nigrosine (C.I. 50420), acid flavin (C.I. 56205) and the like are used.
Examples of basic dyes include chrysoidine (C.I. 11270), methyl violet FN (C.I. 42535), crystal violet (C.I. 42555), malachite green (C.I. 42000), Victoria blue FB ( CI 44045), rhodamine B (C.I. 45170), acridine orange NS (C.I. 46005), methylene blue B (C.I. 52015) and the like are used.
As direct dyes, Congo Red (C.I. 22120), Direct Sky Blue 5B (C.I. 24400), Violet BB (C.I. 27905), Direct Deep Black EX (C.I. 30235), Kaya Las Black G Conch (C.I. 35225), Direct Fast Black G (C.I. 35255), Phthalocyanine Blue (C.I. 74180) and the like are used.
前記顔料としては、カーボンブラック、群青などの無機顔料や銅フタロシアニンブルー、ベンジジンイエロー等の有機顔料の他、予め界面活性剤等を用いて微細に安定的に水媒体中に分散された水分散顔料製品等が用いられ、例えば、C.I.Pigment Blue 15:3B〔品名:S.S.Blue GLL、顔料分22%、山陽色素株式会社製〕、C.I.Pigment Red 146〔品名:S.S.Pink FBL、顔料分21.5%、山陽色素株式会社製〕、C.I.Pigment Yellow 81〔品名:TC Yellow FG、顔料分約30%、大日精化工業株式会社製〕、C.I.Pigment Red220/166〔品名:TC Red FG、顔料分約35%、大日精化工業株式会社製〕等を挙げることができる。
蛍光顔料としては、各種蛍光性染料を樹脂マトリックス中に固溶体化した合成樹脂微細粒子状の蛍光顔料が使用できる。
その他、パール顔料、金色、銀色のメタリック顔料、蓄光性顔料、修正ペン等に用いられる二酸化チタン等の白色顔料、アルミニウム等の金属粉、更には熱変色性組成物、光変色性組成物、香料等を直接又はマイクロカプセル化したカプセル顔料等を例示できる。
Examples of the pigment include inorganic pigments such as carbon black and ultramarine blue, and organic pigments such as copper phthalocyanine blue and benzidine yellow, as well as water-dispersed pigments that are finely and stably dispersed in an aqueous medium in advance using a surfactant or the like. For example, C.I. I. Pigment Blue 15: 3B [Product Name: S.P. S. Blue GLL, pigment content 22%, manufactured by Sanyo Color Co., Ltd.], C.I. I. Pigment Red 146 [Product Name: S.P. S. Pink FBL, pigment content 21.5%, manufactured by Sanyo Dye Co., Ltd.], C.I. I. Pigment Yellow 81 [Product name: TC Yellow FG, pigment content about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.], C.I. I. Pigment Red220 / 166 [Product name: TC Red FG, pigment content: about 35%, manufactured by Dainichi Seika Kogyo Co., Ltd.].
As the fluorescent pigment, a fluorescent pigment in the form of fine particles of a synthetic resin in which various fluorescent dyes are formed into a solid solution in a resin matrix can be used.
In addition, pearl pigments, gold and silver metallic pigments, luminous pigments, white pigments such as titanium dioxide used in correction pens, metal powders such as aluminum, thermochromic compositions, photochromic compositions, and fragrances Examples thereof include capsule pigments directly or microencapsulated.
前記熱変色性組成物としては、(イ)電子供与性呈色性有機化合物、(ロ)電子受容性化合物、(ハ)前記両者の呈色反応の生起温度を決める反応媒体からなる可逆熱変色性組成物が好適であり、マイクロカプセルに内包させて可逆熱変色性マイクロカプセル顔料として適用される。
前記可逆熱変色性組成物としては、特公昭51−44706号公報、特公昭51−44707号公報、特公平1−29398号公報等に記載された、所定の温度(変色点)を境としてその前後で変色し、高温側変色点以上の温度域で消色状態、低温側変色点以下の温度域で発色状態を呈し、前記両状態のうち常温域では特定の一方の状態しか存在せず、もう一方の状態は、その状態が発現するのに要した熱又は冷熱が適用されている間は維持されるが、前記熱又は冷熱の適用がなくなれば常温域で呈する状態に戻る、ヒステリシス幅が比較的小さい特性(ΔH=1〜7℃)を有する可逆熱変色性組成物をマイクロカプセル中に内包させた加熱消色型のマイクロカプセル顔料が適用できる。
The thermochromic composition includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible thermochromic composition comprising a reaction medium that determines the temperature at which the color reaction occurs. The composition is suitable and is encapsulated in microcapsules and applied as a reversible thermochromic microcapsule pigment.
Examples of the reversible thermochromic composition include those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., at a predetermined temperature (discoloration point). Discolored before and after, decolored state in the temperature range above the high temperature side discoloration point, color development state in the temperature range below the low temperature side discoloration point, only one specific state exists in the normal temperature range among the two states, The other state is maintained as long as the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. A heat decolorable microcapsule pigment in which a reversible thermochromic composition having relatively small characteristics (ΔH = 1 to 7 ° C.) is encapsulated in a microcapsule can be applied.
更に、特公平4−17154号公報、特開平7−179777号公報、特開平7−33997号公報、特開平8−39936号公報等に記載されている比較的大きなヒステリシス特性(ΔH=8〜50℃)を示すものも適用できる。
また、特開2005−1369号公報、特開2006−137886号公報、特開2006−188660号公報、特開2008−45062号公報、特開2008−280523号公報等に記載されている大きなヒステリシス特性を示す、即ち、温度変化による着色濃度の変化をプロットした曲線の形状が、温度を変色温度域より低温側から上昇させていく場合と逆に変色温度域より高温側から下降させていく場合とで大きく異なる経路を辿って変色し、完全発色温度以下の低温域での発色状態、又は完全消色温度以上の高温域での消色状態が、特定温度域(実質的二相保持温度域)で色彩記憶性を有する可逆熱変色性組成物を内包させたマイクロカプセル顔料を用いることもできる。
尚、前記色彩記憶性を有する可逆熱変色性組成物として具体的には、完全発色温度を冷凍室、寒冷地等でしか得られない温度、即ち−50〜0℃、好ましくは−40〜−5℃、より好ましくは−30〜−10℃、且つ、完全消色温度を摩擦体による摩擦熱、ヘアドライヤー等身近な加熱体から得られる温度、即ち50〜95℃、好ましくは50〜90℃、より好ましくは60〜80℃の範囲に特定し、ΔH値を40〜100℃に特定することにより、常態(日常の生活温度域)で呈する色彩の保持に有効に機能させることができる。
Furthermore, comparatively large hysteresis characteristics (ΔH = 8 to 50) described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. C.) can also be applied.
In addition, the large hysteresis characteristics described in JP-A-2005-1369, JP-A-2006-137886, JP-A-2006-188660, JP-A-2008-45062, JP-A-2008-280523, etc. In other words, the shape of the curve plotting the change in color density due to the temperature change is the case where the temperature is raised from the lower temperature side than the color change temperature range and the case where the temperature is lowered from the higher temperature side than the color change temperature range. The color changes in a very different route, and the color development state in the low temperature range below the complete color development temperature, or the color erase state in the high temperature range above the complete color erase temperature is a specific temperature range (substantially two-phase holding temperature range). It is also possible to use a microcapsule pigment encapsulating a reversible thermochromic composition having color memory.
Specifically, as the reversible thermochromic composition having color memory, a complete color development temperature can be obtained only in a freezing room, a cold district, etc., that is, −50 to 0 ° C., preferably −40 to − 5 ° C., more preferably −30 to −10 ° C., and complete decoloring temperature obtained from a frictional heat generated by a friction body, a heating body such as a hair dryer, that is, 50 to 95 ° C., preferably 50 to 90 ° C. More preferably, by specifying the range of 60 to 80 ° C. and specifying the ΔH value of 40 to 100 ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily life temperature range).
前記着色剤は一種又は二種以上を適宜混合して使用することができ、インキ組成中1〜30重量%、好ましくは2〜20重量%の範囲で用いられる。
また、着色剤として顔料を用いた場合、必要に応じて顔料分散剤を添加できる。前記顔料分散剤としてはアニオン、ノニオン等の界面活性剤、ポリアクリル酸、スチレンアクリル酸等のアニオン性高分子、PVP、PVA等の非イオン性高分子等が用いられる。
The colorant may be used singly or in combination of two or more, and is used in the range of 1 to 30% by weight, preferably 2 to 20% by weight in the ink composition.
Further, when a pigment is used as the colorant, a pigment dispersant can be added as necessary. Examples of the pigment dispersant include surfactants such as anions and nonions, anionic polymers such as polyacrylic acid and styreneacrylic acid, and nonionic polymers such as PVP and PVA.
また、水に相溶性のある従来汎用の水溶性有機溶剤を用いることができる。具体的には、エタノール、プロパノール、ブタノール、グリセリン、ソルビトール、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、エチレングリコール、ジエチレングリコール、チオジエチレングリコール、ポリエチレングリコール、プロピレングリコール、ブチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテルアセテート、スルフォラン、2−ピロリドン、N−メチル−2−ピロリドン等が挙げられる。
尚、前記水溶性有機溶剤は一種又は二種以上を併用して用いることができ、2〜60重量%、好ましくは5〜35重量%の範囲で用いられる。
In addition, a conventional general-purpose water-soluble organic solvent compatible with water can be used. Specifically, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono Examples include ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, and N-methyl-2-pyrrolidone.
In addition, the said water-soluble organic solvent can be used 1 type or in combination of 2 or more types, and is used in 2 to 60 weight%, Preferably it is 5 to 35 weight%.
更に、紙面への固着性や粘性を付与するために水溶性樹脂を添加することもできる。前記水溶性樹脂としては、アルキッド樹脂、アクリル樹脂、スチレンマレイン酸共重合物、セルロース誘導体、ポリビニルピロリドン、ポリビニルアルコール、デキストリン等が挙げられる。前記水溶性樹脂は一種又は二種以上を併用することができ、インキ組成中1〜30重量%の範囲で用いられる。 Furthermore, a water-soluble resin can be added in order to impart adhesion and viscosity to the paper surface. Examples of the water-soluble resin include alkyd resins, acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin. The water-soluble resin can be used alone or in combination of two or more, and is used in the range of 1 to 30% by weight in the ink composition.
また、インキ中には界面活性剤や水溶性切削油を添加することもできる。これらの界面活性剤や水溶性切削油は、インキ物性を調整するのに有用であり、所望の表面張力値への調整においても効果的に作用する。 Further, a surfactant or a water-soluble cutting oil can be added to the ink. These surfactants and water-soluble cutting oils are useful for adjusting the ink physical properties, and also act effectively in adjusting to a desired surface tension value.
前記界面活性剤としては、例えば、リン酸エステル系界面活性剤、シリコーン系界面活性剤、フッ素系界面活性剤、アセチレングリコール系界面活性剤、アニオン系界面活性剤、ノニオン系界面活性剤等が挙げられる。
尚、リン酸エステル系界面活性剤は、金属類に対して吸着力があるため、ボールやチップ本体に対して吸着することで高い潤滑性を示す。よって、ボールペン形態の筆記具においてはより有用である。
Examples of the surfactant include phosphate ester surfactants, silicone surfactants, fluorine surfactants, acetylene glycol surfactants, anionic surfactants, nonionic surfactants, and the like. It is done.
In addition, since phosphate ester type | system | group surfactant has adsorption power with respect to metals, it shows high lubricity by adsorb | sucking with respect to a ball | bowl or a chip | tip main body. Therefore, it is more useful in a ballpoint pen-type writing instrument.
前記リン酸エステル系界面活性剤としては、ポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルキルアリールエーテルのリン酸モノエステル、ポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルキルアリールエーテルのリン酸ジエステル、リン酸トリエステル、或いはその誘導体等が例示でき、これらのリン酸エステル系界面活性剤は、単独又は二種以上混合して使用される。その中でもインキ経時安定性を考慮すれば、ポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルキルアリールエーテルのリン酸モノエステル、リン酸ジエステルが最も好適である。 Examples of the phosphoric ester surfactant include phosphoric acid monoester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, phosphoric diester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, phosphoric acid triester Or the derivative | guide_body etc. can be illustrated and these phosphate ester type surfactants are used individually or in mixture of 2 or more types. Among these, in view of ink aging stability, phosphoric acid monoesters and phosphoric acid diesters of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether are most preferable.
その他、必要に応じて、炭酸ナトリウム、リン酸ナトリウム、酢酸ソーダ等の無機塩類、水溶性のアミン化合物等の有機塩基性化合物等のpH調整剤、トリルトリアゾール、サポニン等の防錆剤、石炭酸、1、2−ベンズチアゾリン3−オンのナトリウム塩、安息香酸ナトリウム、デヒドロ酢酸ナトリウム、ソルビン酸カリウム、パラオキシ安息香酸プロピル、2,3,5,6−テトラクロロ−4−(メチルスルフォニル)ピリジン等の防腐剤或いは防黴剤、尿素、ソルビット、マンニット、ショ糖、ぶどう糖、還元デンプン加水分解物、ピロリン酸ナトリウム等の湿潤剤、消泡剤を使用してもよい。
更に、ボールペン形態の筆記具に適用する際には潤滑剤を添加することができ、金属石鹸、ポリアルキレングリコール脂肪酸エステル、エチレンオキサイド付加型カチオン活性剤、ジカルボン酸型界面活性剤、β−アラニン型界面活性剤、2,5−ジメルカプト−1,3,4−チアジアゾールやその塩やオリゴマー、3−アミノ−5−メルカプト−1,2,4−トリアゾール、チオカルバミン酸塩、ジメチルジチオカルバミン酸塩、N−アシル−L−グルタミン酸とL−リジンとの縮合物やその塩等が用いられる。
In addition, as necessary, inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, pH adjusters such as organic basic compounds such as water-soluble amine compounds, rust preventives such as tolyltriazole and saponin, coalic acid, 1,2-benzthiazolin-3-one sodium salt, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, etc. Preservatives or antifungal agents, urea, sorbit, mannitol, sucrose, glucose, reduced starch hydrolyzate, wetting agents such as sodium pyrophosphate, and antifoaming agents may be used.
Further, when applied to a ballpoint pen-type writing instrument, a lubricant can be added, such as metal soap, polyalkylene glycol fatty acid ester, ethylene oxide addition type cationic surfactant, dicarboxylic acid type surfactant, β-alanine type interface. Activator, 2,5-dimercapto-1,3,4-thiadiazole and its salts and oligomers, 3-amino-5-mercapto-1,2,4-triazole, thiocarbamate, dimethyldithiocarbamate, N- A condensate of acyl-L-glutamic acid and L-lysine or a salt thereof is used.
更に、必要に応じて剪断減粘性付与剤を添加し、インキに適当な粘性を与えて実用に供することができる。用いられる剪断減粘性付与剤は従来公知のものから適宜選択することができ、その具体例としては、キサンタンガム、サクシノグリカン、カラギーナン等の多糖類、ポリアクリル酸、架橋型アクリル酸、ポリビニルアセトアミド、非イオン性界面活性剤、アニオン性界面活性剤、会合性ウレタンエマルジョン等が挙げられ、単独或いは混合して用いられる。 Furthermore, if necessary, a shear thinning agent can be added to give the ink an appropriate viscosity for practical use. The shear thinning agent to be used can be appropriately selected from conventionally known agents. Specific examples thereof include xanthan gum, succinoglycan, carrageenan and other polysaccharides, polyacrylic acid, cross-linked acrylic acid, polyvinylacetamide, Nonionic surfactants, anionic surfactants, associative urethane emulsions and the like can be mentioned, and these can be used alone or in combination.
前記水性インキ組成物は、各種チップを筆記先端部に装着し、軸筒内部(インキ貯蔵部)に直接インキを収容し、合成樹脂製の櫛溝状インキ流量調節部材(ペン芯)を介在させる構造を有するマーキングペン、ボールペン、筆ペン、万年筆等の汎用の直液式(ペン芯式)筆記具に直接充填される他、筆記具本体に着脱可能なインキカートリッジのインキ貯蔵部に充填される。 In the water-based ink composition, various tips are attached to the writing tip, the ink is directly stored in the shaft cylinder (ink storage unit), and a comb-shaped ink flow rate adjusting member (pen core) made of synthetic resin is interposed. In addition to being filled directly into general-purpose direct liquid type (pen-core type) writing instruments such as marking pens, ballpoint pens, brush pens, and fountain pens having a structure, the ink storage part of an ink cartridge detachable from the writing instrument body is filled.
前記筆記具を構成するチップのうち、マーキングペンチップとしては、例えば、繊維チップ、フェルトチップ、プラスチックチップ、毛筆等が適用でき、ボールペンチップとしては、金属製のパイプの先端近傍を外面より内方に押圧変形させたボール抱持部にボールを抱持してなるチップ、金属材料をドリル等による切削加工により形成したボール抱持部にボールを抱持してなるチップ、金属又はプラスチック製チップ内部に樹脂製のボール受け座を設けたチップ、或いは、前記チップに抱持するボールをバネ体により前方に付勢させたもの等が適用できる。尚、前記ボールは、超硬合金、ステンレス鋼、ルビー、セラミック、樹脂、ゴム等が適用でき、直径0.15mm〜2.0mmの範囲のものが好適に用いられる。更に、前記ボールには、DLCコート等の表面処理を施すこともできる。
また、万年筆形態のチップ(ペン体)としては、ステンレス板、金合金板等の金属板を先細テーパー状に裁断し、屈曲又は湾曲したものや、ペン先形状に樹脂成形したもの等が適用できる。尚、前記ペン体には中心にスリットを設けたり、先端に玉部を設けることもできる。
前述のように、本発明のインキはペン先へのインキ供給性能に優れるため、ペン先の種類によらず高い吐出安定性を発現できる点で有用である。
Among the chips constituting the writing instrument, as a marking pen tip, for example, a fiber tip, a felt tip, a plastic tip, a brush, etc. can be applied, and as a ballpoint pen tip, the vicinity of the tip of a metal pipe is inward from the outer surface. A chip formed by holding the ball in the pressed ball holding part, a chip formed by holding a ball in the ball holding part formed by cutting a metal material with a drill or the like, and a metal or plastic chip inside A chip provided with a resin ball receiving seat, or a ball held by the chip biased forward by a spring body can be applied. The ball may be made of cemented carbide, stainless steel, ruby, ceramic, resin, rubber, or the like, and those having a diameter in the range of 0.15 mm to 2.0 mm are preferably used. Further, the ball may be subjected to a surface treatment such as DLC coating.
Further, as a fountain pen-shaped tip (pen body), a metal plate such as a stainless steel plate or a gold alloy plate is cut into a taper taper shape, bent or curved, or resin-molded into a pen tip shape can be applied. . The pen body can be provided with a slit at the center or a ball at the tip.
As described above, since the ink of the present invention has excellent ink supply performance to the nib, it is useful in that high discharge stability can be expressed regardless of the type of nib.
特に、ボールペンチップは、チップ自体の毛細管力が乏しく、筆記先端へのインキ誘導力が低いため、水性インキのように表面張力が高いと吐出安定性が低下する傾向にある。そのため、特にインキ吐出性が悪い金属製パイプを用いたチップでは、チップ内に中芯を配設することで、チップ内部の毛細管力を高めた構成とすることが好ましい。
この場合、前記金属パイプの内径Bと、中芯の外径Cが、B/C≦2の範囲になるように設定することで、水性インキの詰まりや過剰吐出を発生することなく、高い吐出安定性を維持できるボールペンとなる。
In particular, a ball-point pen tip has a poor capillary force of the tip itself and a low ink induction force to the writing tip, and therefore, when the surface tension is high like water-based ink, the discharge stability tends to be lowered. For this reason, in a chip using a metal pipe with particularly poor ink ejection properties, it is preferable to provide a configuration in which the capillary force inside the chip is increased by disposing a core in the chip.
In this case, by setting the inner diameter B of the metal pipe and the outer diameter C of the core to be in the range of B / C ≦ 2, high discharge without causing clogging of water-based ink or excessive discharge. A ballpoint pen that can maintain stability.
前記ペン芯の材質としては、多数の円盤体を櫛溝状とした構造に射出成形できる合成樹脂であれば汎用のポリカーボネート、ポリプロピレン、ポリエチレン、アクリロニトリル−ブタジエン−スチレン共重合体等いずれを用いることもできるが、特に成形性が高く、ペン芯性能が得られやすい点からアクリロニトリル−ブタジエン−スチレン共重合体が好適である。 As the material of the pen core, any of general-purpose polycarbonate, polypropylene, polyethylene, acrylonitrile-butadiene-styrene copolymer, etc. may be used as long as it is a synthetic resin that can be injection-molded into a structure in which a large number of discs are comb-shaped. However, an acrylonitrile-butadiene-styrene copolymer is preferable because it has a high moldability and can easily achieve pen core performance.
更に、前記ペン芯後方に配設され、水性インキを収容するインキ貯蔵部は、筆記具本体に着脱可能な構造としてインキカートリッジ形態とすることもできる。この場合、先に収容するインキを使い切った後に新たなインキカートリッジと取り替えて使用されるため、新たにインキ貯蔵部内のインキをペン先に流動させる必要が生じる。そのため、本願構成のインキの適用がより有用なものとなる。
前記インキカートリッジとしては、筆記具本体に接続することで筆記具を構成する軸筒を兼ねたものや、筆記具本体に接続した後に軸筒(後軸)を被覆して保護するものが適用できる。尚、後者においては、インキカートリッジ単体での適用の他、使用前の筆記具において、筆記具本体とインキカートリッジが接続されているものや、ユーザーが筆記具使用時に軸筒内のインキカートリッジを接続して使用を開始するように非接続状態で軸筒内に収容したもののいずれであってよい。
Furthermore, the ink storage part that is disposed behind the pen core and stores the water-based ink can be in the form of an ink cartridge as a structure that can be attached to and detached from the writing instrument body. In this case, since the ink stored in advance is used up and replaced with a new ink cartridge, it is necessary to newly cause the ink in the ink storage section to flow to the pen tip. Therefore, application of the ink of the present application configuration becomes more useful.
As the ink cartridge, one that also serves as a shaft cylinder constituting the writing instrument by being connected to the writing instrument body, or one that covers and protects the shaft cylinder (rear shaft) after being connected to the writing instrument body can be applied. In the latter case, in addition to the application of the ink cartridge alone, the writing instrument before use, in which the writing instrument body and the ink cartridge are connected, or the user uses the ink cartridge in the shaft cylinder when the writing instrument is used It may be any of those accommodated in the shaft cylinder in a non-connected state so as to start.
以下に実施例を説明するが、本発明はこれらの実施例に限定されるものではない。
以下の表に実施例及び比較例の直液式筆記具用水性インキの組成と使用した中芯の外径を示す。尚、表中の組成の数値は重量部を示す。尚、表面張力は、協和界面科学(株)製の表面張力計DY−300を用いて20℃で測定した。
Examples will be described below, but the present invention is not limited to these examples.
The table below shows the compositions of the water-based inks for direct liquid writing instruments of Examples and Comparative Examples and the outer diameter of the core used. In addition, the numerical value of a composition in a table | surface shows a weight part. The surface tension was measured at 20 ° C. using a surface tension meter DY-300 manufactured by Kyowa Interface Science Co., Ltd.
表中の原料の内容について注番号に沿って説明する。
(1)オリエント化学工業(株)製、商品名:ウォーターブラック191L
(2)山陽色素(株)製、商品名:サンダイスーパーブラックC−E:顔料分30%
(3)ダイワ化成工業(株)製、商品名:ブリリアントブルーFCF−L
(4)日油(株)製、商品名:ユニルーブ75DE−60
(5)日油(株)製、商品名:ユニルーブ50MB−11
(6)日光ケミカルズ(株)製、商品名:ニッコールNP−20
(7)AGCセイミケミカル(株)製、商品名:サーフロンS−111N
(8)第一工業製薬(株)製、商品名:プライサーフAL
(9)アーチケミカルズジャパン社製、商品名:プロキセルXL−2
(10)シリカをシリコーン系界面活性剤で乳化した乳化物、東レダウコーニング社製、商品名:FSアンチフォーム013A
(11)シリコーン樹脂をソルビタン系界面活性剤で乳化した乳化物、信越化学工業(株)製、商品名:KM−72
The contents of the raw materials in the table will be described along the note numbers.
(1) Product name: Water Black 191L, manufactured by Orient Chemical Co., Ltd.
(2) Sanyo Dye Co., Ltd., trade name: Sundai Super Black CE: 30% pigment content
(3) Product name: Brilliant Blue FCF-L, manufactured by Daiwa Kasei Kogyo Co., Ltd.
(4) NOF Corporation product name: UNILOVE 75DE-60
(5) NOF Corporation product name: UNILOVE 50MB-11
(6) Nikko Chemicals Co., Ltd., trade name: Nikkor NP-20
(7) Product name: Surflon S-111N, manufactured by AGC Seimi Chemical Co., Ltd.
(8) Product name: Prisurf AL, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
(9) Arch Chemicals Japan, trade name: Proxel XL-2
(10) Emulsion obtained by emulsifying silica with silicone surfactant, manufactured by Toray Dow Corning Co., Ltd., trade name: FS Antifoam 013A
(11) An emulsion obtained by emulsifying a silicone resin with a sorbitan surfactant, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KM-72
インキの調製
水に各成分を添加し、室温又は必要に応じて50℃〜60℃の範囲に加温して混合攪拌した後、加温したものは放冷することで各インキを調製した。
Preparation of Ink Each component was added to water, heated to room temperature or in the range of 50 ° C. to 60 ° C. as necessary, mixed and stirred, and then heated to stand to cool to prepare each ink.
筆記具Aの作製
前記各インキ組成物をボールペン形態のペン先を有するペン芯式筆記具(パイロットコーポレーション社製、Hi−TecpointV5)外装のインキ貯蔵部に0.5g充填し、キャップを嵌合することで試料用筆記具Aを作製した。尚、前記筆記具のペン芯はABS樹脂材料を射出成形することで形成した。
Preparation of writing instrument A By filling each ink composition 0.5 g into the ink storage part of the pen core type writing instrument (Pilot Corporation, Hi-Tecpoint V5) having a ballpoint pen-shaped pen tip, and fitting a cap. A sample writing instrument A was prepared. The pen core of the writing instrument was formed by injection molding an ABS resin material.
インキカートリッジの作製
ポリエチレン樹脂からなる有底筒状の成形体内部をインキ貯蔵部とし、前記各インキ組成物0.9gを充填した後、開口部内側に栓体を圧入嵌合させることでインキカートリッジを得た。
Preparation of ink cartridge The inside of a bottomed cylindrical molded body made of polyethylene resin is used as an ink storage part, and after filling 0.9 g of each ink composition, an ink cartridge is press-fitted inside the opening. Got.
筆記具Bの作製
前記筆記具Aで用いたボールペン形態のペン先を有するペン芯を使用し、インキ貯蔵部が着脱可能となる接続部(槍体)を設けた前軸に対し、インキカートリッジを収容可能な後軸を螺合することで筆記具本体とした(キャップが嵌合されている)。
前記筆記具本体に対して、先に作製したインキカートリッジを接続することで試料用筆記具Bを作製した。尚、ペン先には、内径0.5mmのステンレスパイプを用い、中芯として、0.10mm、0.30mm、0.46mmのものを使用した。
Production of writing instrument B Using a pen nib with a ball-point pen tip used in the writing instrument A, an ink cartridge can be accommodated on the front shaft provided with a connecting part (housing) that allows the ink storage part to be attached and detached. A writing instrument body was formed by screwing the rear shaft (cap is fitted).
A sample writing instrument B was prepared by connecting the previously prepared ink cartridge to the writing instrument body. Note that a stainless steel pipe having an inner diameter of 0.5 mm was used as the pen tip, and 0.10 mm, 0.30 mm, and 0.46 mm were used as the center core.
前記試料筆記具を用いて以下の試験を行った。
筆記試験
筆記可能であることを確認した各試料筆記具Aを、室温にて市販のレポート用紙に手書きで1行に12個の螺旋状の丸を連続筆記した。その際の筆跡の滲みの有無を目視により確認した。
The following tests were conducted using the sample writing instrument.
Writing Test Each sample writing instrument A that was confirmed to be writable was handwritten on a commercially available report paper at room temperature by continuously writing 12 spiral circles in one line. At that time, the presence or absence of bleeding of the handwriting was confirmed visually.
ペン芯性能試験
ペン先下向き状態で保持した試料用筆記具Aを、キャップ嵌合状態で0℃、1時間放置した後、ペン先下向き状態のままキャップを外して30℃まで上昇させた際のペン芯櫛溝部へのインキ流入状態及びペン先からのインキボタ落ちの有無を観察した。更に、再び0℃に冷却した際にペン芯櫛溝部からインキ貯蔵部へのインキの回収状態を観察した。
Pen Core Performance Test Pen after holding the sample writing instrument A held in the pen tip downward state at 0 ° C. for 1 hour in the cap fitting state, then removing the cap and raising the pen tip downward state to 30 ° C. The state of ink flowing into the core comb groove and the presence or absence of ink splatter from the pen tip were observed. Further, when the ink was cooled again to 0 ° C., the state of ink collected from the pen core comb groove to the ink storage was observed.
カートリッジ交換試験
前記試料筆記具Bを、室温にてJIS P3201筆記用紙Aに走行試験機(精機工業研究所製)で螺旋状の丸を連続筆記して書き切った後、同じ構成の新しいインキカートリッジに交換し、キャップを外したペン先下向き状態で1時間放置した。その後、前記走行試験機で500m連続筆記した際の筆跡の状態を確認した。
Cartridge exchange test The sample writing instrument B was written on a JIS P3201 writing paper A at room temperature by continuously writing a spiral circle with a running tester (manufactured by Seiki Kogyo Laboratories), and then onto a new ink cartridge of the same configuration. It was exchanged and left for 1 hour in a state where the pen tip was removed with the cap removed. Then, the state of the handwriting at the time of 500 m continuous writing with the said travel test machine was confirmed.
インキ吐出性試験
筆記可能であることを確認した各試料筆記具Bを、室温にてJIS P3201筆記用紙Aに前記走行試験機で連続筆記して書き切った後、同じ構成の新しいインキカートリッジに交換し、室温にて市販のレポート用紙に手書きで1行に12個の螺旋状の丸を連続筆記した際の筆跡の状態を確認した。
Ink discharge test Each sample writing instrument B that was confirmed to be writable was written on the JIS P3201 writing paper A continuously at room temperature with the above running tester, and then replaced with a new ink cartridge of the same configuration. At the room temperature, the state of the handwriting when twelve spiral circles were continuously written in one line by hand on a commercially available report paper was confirmed.
経時性能試験
筆記可能であることを確認した各試料筆記具B及びインキカートリッジを、50℃の条件下で30日間保管した後、室温にてJIS P3201筆記用紙Aに前記走行試験機で連続筆記して書き切った。更に、使用済カートリッジを50℃にて保管された前記インキカートリッジに交換し、キャップを外したペン先下向き状態で一時間放置した。その後、前記走行試験機で100m連続筆記してインキ吐出量の計測を行った。100m連続筆記毎の計測を5回(計500m)繰り返した際のインキ吐出量と、その筆跡の状態を確認した。
前記各試験の結果を以下の表に示す。
Aging performance test Each sample writing instrument B and ink cartridge confirmed to be writable was stored for 30 days at 50 ° C., and then continuously written on JIS P3201 writing paper A at room temperature with the above running tester. I wrote it down. Further, the used cartridge was replaced with the ink cartridge stored at 50 ° C., and left for one hour in a state where the cap was removed and the pen tip faced downward. Thereafter, the ink ejection amount was measured by continuously writing 100 m with the running test machine. The ink discharge amount and the state of the handwriting when the measurement for each 100 m continuous writing was repeated 5 times (total of 500 m) were confirmed.
The results of each test are shown in the following table.
尚、試験結果の評価は以下の通りである。
筆記試験
○:良好な筆跡を示した。
×:筆跡に滲みが見られた。
ペン芯性能試験
○:円滑に流入し、ボタ落ちは発生しなかった。また、ペン芯内の全てのインキを良好に回収した。
×:流入が変則的で、ボタ落ちが発生した、またはインキが回収されず、ペン芯櫛溝部内に残留した。
カートリッジ交換試験
○:ペン先へのインキ供給が安定しており、カスレや線飛びは見られず良好な筆跡が得られた。
×:ペン先へのインキ供給が変則的で筆跡にカスレや線飛びが見られた。
インキ吐出性試験
○:良好な筆跡を示した。
×:筆跡に断続的に連続したカスレや線飛びが生じた。
経時性能試験
◎:カスレや線飛びは見られず、一定したインキ吐出で良好な筆跡が得られた。
○:僅かなカスレ箇所は見られるが、一定したインキ吐出であった。
×:ペン先へのインキ供給が変則的であり、筆跡に連続したカスレや線飛び箇所が断続的に生じた。
The evaluation of the test results is as follows.
Written test ○: A good handwriting was shown.
X: Bleeding was observed in the handwriting.
Pen core performance test ○: Inflow smoothly, but no dropout occurred. Moreover, all the ink in a pen core was collect | recovered favorably.
X: The inflow was irregular and the dropping of the ink occurred or the ink was not collected and remained in the pen core comb groove.
Cartridge replacement test ○: The ink supply to the pen tip was stable, and no smudges or line jumps were seen, and good handwriting was obtained.
X: Ink supply to the pen tip was irregular, and blurring and line jumping were observed in the handwriting.
Ink ejection test ○: Good handwriting was shown.
X: The blur and the line skip which continued intermittently in the handwriting occurred.
Aging performance test A: Scratches and line skipping were not observed, and good handwriting was obtained with constant ink ejection.
○: Slight blemishes were observed, but the ink ejection was constant.
X: The ink supply to the pen tip was irregular, and continuation of the handwriting and the skipped portions were intermittently generated.
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JP3163465B2 (en) * | 1992-12-17 | 2001-05-08 | パイロットインキ株式会社 | Water-based ink for direct liquid writing instruments |
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JP2007197486A (en) * | 2006-01-23 | 2007-08-09 | Pilot Ink Co Ltd | Color changeable black ink composition, color changeable writing utensils having the same built-in and a set of writing utensils |
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