JP6100646B2 - Water-based ink composition for ballpoint pen and ballpoint pen incorporating the same - Google Patents
Water-based ink composition for ballpoint pen and ballpoint pen incorporating the same Download PDFInfo
- Publication number
- JP6100646B2 JP6100646B2 JP2013172795A JP2013172795A JP6100646B2 JP 6100646 B2 JP6100646 B2 JP 6100646B2 JP 2013172795 A JP2013172795 A JP 2013172795A JP 2013172795 A JP2013172795 A JP 2013172795A JP 6100646 B2 JP6100646 B2 JP 6100646B2
- Authority
- JP
- Japan
- Prior art keywords
- ink
- ballpoint pen
- water
- tip
- ink composition
- 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.)
- Expired - Fee Related
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- 239000003513 alkali Substances 0.000 description 1
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- 239000002304 perfume Substances 0.000 description 1
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- 235000019271 petrolatum Nutrition 0.000 description 1
- RCMHUQGSSVZPDG-UHFFFAOYSA-N phenoxybenzene;phosphoric acid Chemical class OP(O)(O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 RCMHUQGSSVZPDG-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- 235000013824 polyphenols Nutrition 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
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- 239000004302 potassium sorbate Substances 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical class CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000004962 sulfoxyl group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- 235000012756 tartrazine Nutrition 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
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- 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
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- 239000012749 thinning agent Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- 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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- 239000000080 wetting agent Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Pens And Brushes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明はボールペン用水性インキ組成物に関する。更には、インキの垂れ下がりを抑制できるボールペン用水性インキ組成物と、それを用いたボールペンに関する。 The present invention relates to a water-based ink composition for ballpoint pens. Furthermore, the present invention relates to a water-based ink composition for ballpoint pens that can suppress ink sag and a ballpoint pen using the same.
従来、ボールペン用水性インキをインキ収容管に直接内蔵し、該インキの後端にインキ逆流防止体を備えたボールペンレフィルを軸筒に収容したボールペンが多数市場に出回っている。
特に、キャップを有しない出没式ボールペンにおいては、ペン先下向き状態で保管した際にインキ滴がペン先先端に溜まる、所謂、垂れ下がりを生じ易いため、収容するインキの粘度を調整することで抑制している。収容されるインキが比較的高粘度である場合、ペン先からのインキの垂れ下がりをある程度抑制できるものの、ドライアップ性能の悪化や、筆跡に線割れを生じる等、筆記性能を悪化する虞がある(例えば、特許文献1乃至2参照)。
これに対して、前記筆記性能を満足するために低粘度のインキを用いた場合、筆記時に紙繊維等がボールと小口の間に挟みこんだり、落下等によりチップ先端が傷付いたり変形することで、インキ流通路が広がってしまった際にインキの垂れ下がりやボタ落ちを生じることがある。
2. Description of the Related Art Conventionally, many ballpoint pens have been put on the market in which water-based ink for ballpoint pens is directly built in an ink storage tube, and a ballpoint pen refill provided with an ink backflow preventer at the rear end of the ink is stored in a shaft cylinder.
In particular, in a retractable ballpoint pen that does not have a cap, ink droplets accumulate at the tip of the pen tip when stored in a state where the tip of the pen point downwards, so-called sag is likely to occur, so it is suppressed by adjusting the viscosity of the ink to be stored. ing. When the ink stored has a relatively high viscosity, the ink dripping from the pen tip can be suppressed to some extent, but there is a risk that the writing performance will be deteriorated, such as the deterioration of dry-up performance and the occurrence of line cracks in the handwriting ( For example, see Patent Documents 1 and 2.)
On the other hand, if low-viscosity ink is used to satisfy the writing performance, paper fibers or the like may be pinched between the ball and the small mouth during writing, or the tip of the chip may be damaged or deformed due to dropping or the like. Then, when the ink flow path is widened, ink drooping or dripping may occur.
本発明はボールペンのペン先が露出した状態で生じる問題点を解消するものであって、即ち、使用時や保管時にペン先のインキ流通路が広がってしまった場合であっても、インキ粘度に左右されることなくインキの垂れ下がりを効果的に抑制することができ、優れた筆記性能を長期に亘って発現できるボールペン用水性インキ組成物とそれを内蔵したボールペンを提供するものである。 The present invention solves the problem that occurs when the pen tip of the ballpoint pen is exposed, that is, even when the ink flow path of the pen tip is widened during use or storage, the ink viscosity is reduced. The present invention provides a water-based ink composition for a ballpoint pen that can effectively suppress ink sag without being influenced and can exhibit excellent writing performance over a long period of time, and a ballpoint pen incorporating the same.
本発明は、DE値が2〜5の範囲にあり、水媒体中での平均粒子径が1〜10μmの範囲にあるデキストリンと、着色剤と、水とを少なくとも含有するボールペン用水性インキ組成物を要件とする。
更に、前記デキストリンが馬鈴薯由来であること、前記デキストリンがインキ組成物全量中0.5〜10重量%の範囲で添加されることを要件とする。
更には、前記いずれかのボールペン用水性インキ組成物を内蔵したボールペンを要件とし、前記ボールペンが出没式形態であることを要件とする。
The present invention relates to a water-based ink composition for ballpoint pens that contains at least a dextrin having a DE value in the range of 2 to 5 and an average particle diameter in the range of 1 to 10 μm in the aqueous medium, a colorant, and water. Is a requirement.
Furthermore, it is required that the dextrin is derived from potato and that the dextrin is added in a range of 0.5 to 10% by weight in the total amount of the ink composition.
Furthermore, it is a requirement that the ballpoint pen contains any of the above-mentioned water-based ink compositions for ballpoint pens, and that the ballpoint pen is in a retractable form.
本発明により、インキ粘度を調整することなくインキの垂れ下がりを抑制でき、更に、ペン先のインキ流通路が不用意に広がってしまった場合であっても、インキの垂れ下がりやボタ落ちを効果的に抑制することができると共に、良好な筆跡が安定して得られる筆記性能に優れたボールペン用水性インキ組成物とそれを内蔵したボールペンを提供できる。 According to the present invention, ink drooping can be suppressed without adjusting the ink viscosity, and even if the ink flow path of the nib is inadvertently spread, ink dripping or dripping can be effectively prevented. It is possible to provide a water-based ink composition for ballpoint pens that can be suppressed and has excellent writing performance that can stably obtain good handwriting, and a ballpoint pen incorporating the same.
本発明は、ボールペン用水性インキ組成物中に、DE値(Dextrose Equivalent値)が2〜5の範囲にあり、水媒体中での平均粒子径が1〜10μmの範囲にあるデキストリン(粒状デキストリン)を添加することにより、インキ粘度を調整することなくインキの垂れ下がりが抑制できるものである。特に、異物がボールと小口の間に挟み込まれたり、落下等によりチップ先端が傷付いて変形することで予期せずインキ流通路が広がった場合であっても、前記デキストリンがインキ流通路を塞いでインキの垂れ下がりやボタ落ちを抑制することが可能となる。尚、汎用のデキストリンが水媒体に溶解するのに対し、前記デキストリン(粒状デキストリン)は柔軟性に富む粒状体として存在するため、前述の効果が発現できるとともに、通常の筆記時にはボールの回転により伸長・変形を繰り返すことにより、筆記性能に対して悪い影響を及ぼすことなく使用できる。
特に、馬鈴薯由来であるDE値が2〜5のデキストリンは、比重が水に近いため、水性インキ中での安定性が高く有用である。
The present invention relates to a dextrin (granular dextrin) having a DE value (Dextrose Equivalent value) in the range of 2 to 5 and an average particle diameter in the range of 1 to 10 μm in the aqueous ink composition for ballpoint pens. By adding, ink drooping can be suppressed without adjusting the ink viscosity. In particular, the dextrin blocks the ink flow path even if the ink flow path expands unexpectedly due to foreign matter being pinched between the ball and the small mouth, or the tip of the tip being damaged and deformed due to dropping or the like. Therefore, it is possible to suppress dripping or dripping of ink. While general-purpose dextrin dissolves in an aqueous medium, the dextrin (granular dextrin) exists as a flexible granular material, so that the above-mentioned effects can be exhibited, and during normal writing, it is elongated by rotation of the ball. -By repeating the deformation, it can be used without adversely affecting the writing performance.
In particular, dextrin having a DE value of 2 to 5 derived from potato is useful because it has high specific gravity in water-based ink because its specific gravity is close to that of water.
また、従来汎用のデキストリンにおいて、DE値が2〜5のものは、平均粒子径が200〜350μmと大きいため、ボールペン用インキへの適用は困難であったが、平均粒子径を1〜10μmの範囲に調整することで前述の効果が発現できるものとなった。
前記デキストリンの粒子径が1μm未満である場合、変形したインキ流通路を塞ぎ難くなるため、インキの垂れ下がりが生じ易くなり、粒子径が10μmを超える場合、インキ流通路から流出し難くなるため、筆記時に筆跡カスレ等を生じ易くなる。尚、粒子径が2〜5μmの範囲にあるものは粒子が均一に揃っており、特に効果が高いため、好適である。 尚、平均粒子径はレーザー回折法、体積基準による値である。
Moreover, in the conventional general-purpose dextrin, those having a DE value of 2 to 5 have a large average particle diameter of 200 to 350 μm, and thus it was difficult to apply to the ink for ballpoint pens, but the average particle diameter was 1 to 10 μm. By adjusting to the range, the above-described effects can be exhibited.
When the particle diameter of the dextrin is less than 1 μm, it becomes difficult to block the deformed ink flow path, so that the ink is liable to sag. When the particle diameter exceeds 10 μm, it is difficult to flow out of the ink flow path. Occasionally handwriting scraps are likely to occur. A particle having a particle diameter in the range of 2 to 5 μm is preferable because the particles are evenly arranged and particularly effective. The average particle diameter is a value based on a laser diffraction method and a volume basis.
前記デキストリンはインキ組成物全量に対して0.5〜10重量%、好ましくは1〜5重量%の範囲で配合される。0.5重量%未満では垂れ下がり防止効果が得られ難く、また、5重量%を越えて配合しても効果の向上は見られないため、これ以上の添加は要さない。 The dextrin is blended in the range of 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total amount of the ink composition. If it is less than 0.5% by weight, it is difficult to obtain a drooping prevention effect, and even if it exceeds 5% by weight, no improvement 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すべて使用可能であり、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, all dyes and pigments that can be dissolved or dispersed in an aqueous medium can be used, and specific examples thereof will be exemplified 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、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, phosphorescent pigments, white pigments such as titanium dioxide, metal powders such as aluminum, thermochromic compositions, photochromic compositions, perfumes, etc. directly or microcapsules Examples of the capsule pigments are as follows.
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。
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℃)を示すものや、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、特定温度域で色彩記憶性を有する可逆熱変色性組成物を内包させ加熱消色型のマイクロカプセル顔料も適用できる。
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。
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.
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), and exhibit large hysteresis characteristics described in JP-A-2006-137886, JP-A-2006-188660, JP-A-2008-45062, JP-A-2008-280523, In other words, the shape of the curve plotting the change in color density due to temperature change differs greatly between when the temperature is raised from the lower temperature side than the color change temperature range and when the temperature is lowered from the higher temperature side than the color change temperature range. The color changes following the path, 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 in the specific temperature range. Microcapsule pigment was contained a reversible thermochromic composition heated decolorizable having chroma memory property can be applied.
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、インキ組成物中1〜35重量%、好ましくは2〜30重量%の範囲で用いられる。 The colorant can be used singly or in combination of two or more, and is used in the range of 1 to 35% by weight, preferably 2 to 30% by weight in the ink composition.
更に必要に応じて、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。
Further, if necessary, 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.
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、ベンゾトリアゾール、トリルトリアゾール、2,5−ジメルカプト−1,3,4−チアジアゾール、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、ノニオン系界面活性剤、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、インキの浸透性を向上させるフッ素系界面活性剤やノニオン系の界面活性剤を使用してもよい。
更に、アスコルビン酸類、エリソルビン酸類、α−トコフェロール、カテキン類、合成ポリフェノール、コウジ酸、アルキルヒドロキシルアミン、オキシム誘導体、α−グルコシルルチン、α−リポ酸、ホスホン酸塩、ホスフィン酸塩、亜硫酸塩、スルホキシル酸塩、亜ジチオン酸塩、チオ硫酸塩、二酸化チオ尿素等を添加して化学的に気泡を除去することもできる。
また、N−ビニル−2−ピロリドンのオリゴマー、N−ビニル−2−ピペリドンのオリゴマー、N−ビニル−2−ピロリドン、N−シクロヘキシル−2−ピロリドン、ε−カプロラクタム、N−ビニル−ε−カプロラクタムのオリゴマー等の増粘抑制剤を添加することで、出没式形態での機能を高めることもできる。
更に、潤滑剤を添加することができ、例えば、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、リン酸エステル系活性剤、β−アラニン型界面活性剤、N−アシルアミノ酸、N−アシルメチルタウリン、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、α−リポ酸、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, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, 2,5-dimercapto- Rust preventives such as 1,3,4-thiadiazole, saponin, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3 , 5,6-tetrachloro-4- (methylsulfonyl) pyridine, etc., antiseptic or antifungal agent, urea, nonionic surfactant, sorbit, mannitol, sucrose, glucose, reduced starch hydrolyzate, pyrophosphate Wetting agents such as sodium, antifoaming agents, fluorosurfactants and noni that improve ink permeability The emissions-based surfactant may be used.
Furthermore, ascorbic acids, erythorbic acids, α-tocopherol, catechins, synthetic polyphenols, kojic acid, alkylhydroxylamine, oxime derivatives, α-glucosylrutin, α-lipoic acid, phosphonate, phosphinate, sulfite, sulfoxyl Bubbles can also be removed chemically by adding acid salts, dithionites, thiosulfates, thiourea dioxide or the like.
Further, oligomers of N-vinyl-2-pyrrolidone, oligomers of N-vinyl-2-piperidone, N-vinyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, ε-caprolactam, N-vinyl-ε-caprolactam By adding a thickening inhibitor such as an oligomer, it is possible to enhance the function in the intruding form.
Further, a lubricant can be added, for example, metal soap, polyalkylene glycol fatty acid ester, ethylene oxide addition type cationic surfactant, phosphate ester type surfactant, β-alanine type surfactant, N-acyl amino acid, N-acylmethyltaurine, 2,5-dimercapto-1,3,4-thiadiazole and its salts and oligomers, 3-amino-5-mercapto-1,2,4-triazole, thiocarbamate, dimethyldithiocarbamate , Α-lipoic acid, condensates of N-acyl-L-glutamic acid and L-lysine, salts thereof, and the like are used.
また、インキ組成物中に剪断減粘性付与剤を添加することもでき、例えば、水に可溶乃至分散性の、キサンタンガム、ウェランガム、構成単糖がグルコースとガラクトースの有機酸修飾ヘテロ多糖体であるサクシノグリカン(平均分子量約100乃至800万)、グアーガム、ローカストビーンガム及びその誘導体、ヒドロキシエチルセルロース、アルギン酸アルキルエステル類、メタクリル酸のアルキルエステルを主成分とする分子量10万〜15万の重合体、グルコマンナン、寒天やカラゲニン等の海藻より抽出されるゲル化能を有する増粘多糖類、ベンジリデンソルビトール及びベンジリデンキシリトール又はこれらの誘導体、架橋性アクリル酸重合体、無機質微粒子、ポリグリセリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンアルキルエーテル・ポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、脂肪酸アミド等のHLB値が8〜12のノニオン系界面活性剤、ジアルキル又はジアルケニルスルホコハク酸の塩類等を例示でき、単独或いは混合して使用することもできる。
更に、N−アルキル−2−ピロリドンとアニオン系界面活性剤の混合物、ポリビニルアルコールとアクリル系樹脂の混合物を用いることもできる。
インキの剪断減粘性とは静止状態あるいは応力の低い時は高粘度で流動し難い性質を有し、応力が増大すると低粘度化して良流動性を示すレオロジー特性を言うものであり、チクソトロピー性あるいは擬似可塑性とも呼ばれる液性を意味している。
In addition, a shear thinning agent can be added to the ink composition. For example, xanthan gum, welan gum, or a constituent monosaccharide that is soluble or dispersible in water is an organic acid-modified heteropolysaccharide of glucose and galactose. Succinoglycan (average molecular weight of about 1 to 8 million), guar gum, locust bean gum and derivatives thereof, hydroxyethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 based on alkyl esters of methacrylic acid, Glycomannan, thickening polysaccharide with gelling ability extracted from seaweed such as agar and carrageenin, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxy Ethylene sorbitan Nonionic surfactants having a HLB value of 8 to 12, such as fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ether / polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid amide, dialkyl or dialkenyl sulfosucci Acid salts and the like can be exemplified, and they can be used alone or in combination.
Furthermore, a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, a mixture of polyvinyl alcohol and an acrylic resin can also be used.
Ink shear thinning is a rheological property that has a high viscosity and is difficult to flow in a static state or when stress is low, and it exhibits low fluidity and good fluidity when stress increases. It means liquidity called pseudo plasticity.
本発明のインキ組成物は粘度に関係なく前述の効果を発現するものであるが、特に垂れ下がりに不利な低粘度インキ(例えば、20℃での測定値が、1〜20mPa・sの範囲にあるもの)で高い効果が発揮される。前記した粘度を満たすインキでは、垂れ下がりと耐乾燥性を満足させる他、筆記性能、即ち、筆記感、初期書き出し、筆跡の乾燥性や良好な筆跡の形成を満足させることができる。
また、インキの粘性特性として、剪断減粘指数〔粘度計による剪断応力値(T)及び剪断速度(j)値の流動学的測定により導かれる、実験式(T=Kjn:但し、Kは計算された定数である)を適用して計算されるn値〕が、0.4〜0.9の範囲、好ましくは0.5〜0.8の範囲のインキにおいて、より有効に作用する。
The ink composition of the present invention exhibits the above-mentioned effects regardless of the viscosity, but it is a low-viscosity ink that is particularly disadvantageous for drooping (for example, the measured value at 20 ° C. is in the range of 1 to 20 mPa · s. High effect is demonstrated. The ink satisfying the above-described viscosity can satisfy the sagging and drying resistance, and also can satisfy the writing performance, that is, writing feeling, initial writing, handwriting drying property and good handwriting formation.
In addition, as a viscosity characteristic of the ink, an empirical formula (T = Kj n : where K is derived from a rheological measurement of a shear thinning index [shear stress value (T) and shear rate (j) value by a viscometer] N value calculated by applying a calculated constant) works more effectively in inks in the range of 0.4 to 0.9, preferably in the range of 0.5 to 0.8.
前記ボールペン用水性インキ組成物を充填するボールペンについて説明する。
筆記先端部となるボールペンチップは、例えば、金属を切削加工して内部にボール受け座とインキ導出部を形成したもの、金属製パイプの先端近傍の内面に複数の内方突出部を外面からの押圧変形により設け、前記内方突出部の相互間に、中心部から径方向外方に放射状に延びるインキ流出間隙を形成したもの等を適用でき、特に押圧変形によるチップは、ボール後端との接触面積が比較的小であり、低筆記圧でのスムーズな筆記感を与えることができる。
前記ボールペンチップに抱持されるボールは、超硬合金、ステンレス鋼、ルビー、セラミック等の外径0.1〜2.0mm、好ましくは0.2〜1.5mm、より好ましくは0.3〜1.0mmのボールが有効であり、前記チップのボール抱持部の内径とボールとの径方向の可動距離は10〜50μm、ボールの軸方向の可動距離は10〜30μmの範囲であることが好ましい。
尚、前記ボールペンチップには、チップ内にボールの後端を前方に弾発する弾発部材を配して、非筆記時にはチップ先端の内縁にボールを押圧させて密接状態とし、筆記時には筆圧によりボールを後退させてインキを流出可能に構成することもでき、不使用時のインキ漏れを抑制できる。
前記弾発部材は、金属細線のスプリング、前記スプリングの一端にストレート部(ロッド部)を備えたもの、線状プラスチック加工体等を例示でき、5〜40gの弾発力により、押圧可能に構成して適用される。
The ball-point pen filled with the water-based ink composition for ball-point pens will be described.
The ballpoint pen tip that becomes the writing tip is, for example, a metal cut and formed with a ball receiving seat and an ink lead-out portion inside, a plurality of inward protruding portions on the inner surface near the tip of the metal pipe from the outer surface It can be applied by pressing deformation, and an ink outflow gap extending radially outward from the center portion can be applied between the inward protruding portions. The contact area is relatively small, and a smooth writing feeling can be provided at a low writing pressure.
The ball held by the ballpoint pen tip is 0.1 to 2.0 mm in outer diameter, preferably 0.2 to 1.5 mm, more preferably 0.3 to 0.3 mm, such as cemented carbide, stainless steel, ruby, and ceramic. A 1.0 mm ball is effective, and the moving distance in the radial direction between the inner diameter of the ball holding portion of the chip and the ball is in the range of 10 to 50 μm, and the moving distance in the axial direction of the ball is in the range of 10 to 30 μm. preferable.
The ballpoint pen tip is provided with a resilient member for projecting the rear end of the ball forward in the tip, and when not writing, the ball is pressed against the inner edge of the tip of the tip to bring it into close contact, and when writing, it is The ball can be retracted to allow ink to flow out, and ink leakage when not in use can be suppressed.
Examples of the elastic member include a metal thin wire spring, a member provided with a straight portion (rod portion) at one end of the spring, a linear plastic processed body, and the like, and can be pressed by an elastic force of 5 to 40 g. Applied.
前記水性インキ組成物を収容する軸筒は、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート等の熱可塑性樹脂からなる成形体が、インキの低蒸発性、生産性の面で好適に用いられる。
前記軸筒にはチップを直接連結する他、接続部材を介して前記軸筒とチップを連結してもよい。
前記軸筒内に収容されるインキ組成物は、インキ組成物が低粘度である場合は軸筒前部にインキ保留部材を装着し、軸筒内に直接インキ組成物を収容する方法と、多孔質体或いは繊維加工体に前記インキ組成物を含浸させて収容する方法が挙げられる。
For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, or polyethylene terephthalate is preferably used as the shaft cylinder that accommodates the water-based ink composition in terms of low ink evaporation and productivity.
In addition to directly connecting the tip to the shaft tube, the shaft tube and the chip may be connected via a connecting member.
When the ink composition is low in viscosity, the ink composition accommodated in the shaft cylinder includes a method of mounting an ink retaining member at the front of the shaft cylinder and storing the ink composition directly in the shaft cylinder, Examples of the method include impregnating the ink composition into a material body or a fiber processed body.
更に、前記軸筒として透明、着色透明、或いは半透明の成形体を用いることにより、インキ色やインキ残量等を確認できる。
尚、前記軸筒は、ボールペン用レフィルの形態として、前記レフィルを外軸内に収容するものでもよいし、先端部にチップを装着した軸筒自体をインキ収容体として、前記軸筒内に直接インキを充填してもよい。
Furthermore, by using a transparent, colored transparent, or translucent molded body as the shaft tube, it is possible to confirm the ink color, the remaining amount of ink, and the like.
The shaft tube may be a ballpoint pen refill that accommodates the refill in the outer shaft, or the shaft tube with the tip mounted on the tip itself is used as an ink container and directly in the shaft tube. You may fill with ink.
前記軸筒を用いたボールペンは、キャップ式、出没式のいずれの形態であっても適用できる。出没式ボールペンとしては、ボールペンレフィルに設けられた筆記先端部が外気に晒された状態で外軸内に収納されており、出没機構の作動によって外軸開口部から筆記先端部が突出する構造であれば全て用いることができる。前記出没式ボールペンはペン先が常に外気に晒された状態であるため、本発明のインキ組成物が特に有効となる。
出没機構の操作方法としては、例えば、ノック式、回転式、スライド式等が挙げられる。
前記ノック式は、外軸後端部や外軸側面にノック部を有し、該ノック部の押圧により、ボールペンレフィルの筆記先端部を外軸前端開口部から出没させる構成、或いは、外軸に設けたクリップ部を押圧することにより、ボールペンレフィルの筆記先端部を外軸前端開口部から出没させる構成を例示できる。
前記回転式は、外軸に回転部(後軸等)を有し、該回転部を回すことによりボールペンレフィルの筆記先端部を外軸前端開口部から出没させる構成を例示できる。
前記スライド式は、軸筒側面にスライド部を有し、該スライドを操作することによりボールペンレフィルの筆記先端部を外軸前端開口部から出没させる構成、或いは、外軸に設けたクリップ部をスライドさせることにより、ボールペンレフィルの筆記先端部を外軸前端開口部から出没させる構成を例示できる。
尚、前記出没式ボールペンは、外軸内に一本のボールペンレフィルを収容したもの以外に、複数のボールペンレフィルを収容してなる複合タイプの出没式ボールペンであってもよい。また、前記ボールペンレフィルを構成するインキ収容管は樹脂製であってもよいし、金属製であってもよい。
The ballpoint pen using the shaft tube can be applied to either a cap type or a retractable type. The retractable ballpoint pen is stored in the outer shaft with the writing tip provided on the ballpoint pen refill exposed to the outside air, and the writing tip protrudes from the opening of the outer shaft by the operation of the retracting mechanism. Anything can be used. Since the pendulum ballpoint pen is in a state where the pen tip is always exposed to the outside air, the ink composition of the present invention is particularly effective.
Examples of the operation method of the retracting mechanism include a knock type, a rotary type, and a slide type.
The knock type has a knock portion on the outer shaft rear end portion or the outer shaft side surface, and by pressing the knock portion, the writing pen tip portion of the ballpoint pen refill is caused to protrude or retract from the outer shaft front end opening portion, or on the outer shaft. By pressing the provided clip portion, a configuration in which the writing tip portion of the ballpoint pen refill is projected and retracted from the outer shaft front end opening portion can be exemplified.
The rotary type can be exemplified by a configuration in which a rotating portion (rear shaft or the like) is provided on the outer shaft, and the writing tip portion of the ballpoint pen refill is projected and retracted from the outer shaft front end opening by turning the rotating portion.
The slide type has a slide part on the side surface of the shaft tube, and the writing tip part of the ball-point pen refill is projected and retracted from the front end opening part of the outer shaft by operating the slide, or the clip part provided on the outer shaft is slid. By doing so, it is possible to exemplify a configuration in which the writing tip portion of the ballpoint pen refill is projected and retracted from the outer shaft front end opening.
The retractable ballpoint pen may be a composite retractable ballpoint pen that accommodates a plurality of ballpoint pen refills in addition to a ballpoint refill accommodated in the outer shaft. Further, the ink storage tube constituting the ballpoint pen refill may be made of resin or metal.
前記ボールペンレフィルに収容したインキの後端にはインキ逆流防止体を充填することもできる。
前記インキ逆流防止体組成物は不揮発性液体又は難揮発性液体からなる。
具体的には、ワセリン、スピンドル油、ヒマシ油、オリーブ油、精製鉱油、流動パラフィン、ポリブテン、α−オレフィン、α−オレフィンのオリゴマーまたはコオリゴマー、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、アミノ変性シリコーンオイル、ポリエーテル変性シリコーンオイル、脂肪酸変性シリコーンオイル等があげられ、一種又は二種以上を併用することもできる。
The back end of the ink stored in the ballpoint pen refill can be filled with an ink backflow prevention body.
The ink backflow prevention body composition is composed of a non-volatile liquid or a hardly volatile liquid.
Specifically, petroleum jelly, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil, and one or more can be used in combination.
前記不揮発性液体や難揮発性液体には、ゲル化剤を添加して好適な粘度まで増粘させることが好ましく、表面を疎水処理したシリカ、表面をメチル化処理した微粒子シリカ、珪酸アルミニウム、膨潤性雲母、疎水処理を施したベントナイトやモンモリロナイトなどの粘土系増粘剤、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸亜鉛等の脂肪酸金属石鹸、トリベンジリデンソルビトール、脂肪酸アマイド、アマイド変性ポリエチレンワックス、水添ひまし油、脂肪酸デキストリン等のデキストリン系化合物、セルロース系化合物を例示できる。
更に、前記液状のインキ逆流防止体組成物と、固体のインキ逆流防止体を併用することもできる。
It is preferable to add a gelling agent to the non-volatile liquid or the hardly volatile liquid to increase the viscosity to a suitable viscosity. Hydrophobized silica on the surface, fine-particle silica whose surface is methylated, aluminum silicate, swelling Clay-based thickeners such as bentonite and montmorillonite treated with hydrophobic mica, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, fatty acid amide, amide-modified polyethylene wax And dextrin compounds such as hydrogenated castor oil and fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow prevention body composition and a solid ink backflow prevention body composition can be used in combination.
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ボールペン用水性インキの組成と粘度を示す。尚、表中の組成の数値は重量部を示す。
各実施例、比較例のインキ粘度は、20℃でEMD型回転粘度計〔東京計器(株)製〕を用いて、100rpmで測定した。
Examples will be described below, but the present invention is not limited to these examples.
The following table shows compositions and viscosities of water-based inks for ballpoint pens of Examples and Comparative Examples. In addition, the numerical value of a composition in a table | surface shows a weight part.
The ink viscosity of each Example and Comparative Example was measured at 100 rpm using an EMD type rotational viscometer [manufactured by Tokyo Keiki Co., Ltd.] at 20 ° C.
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181L
(2)アイゼン保土谷(株)製、商品名:フロキシン
(3)冨士色素(株)製、商品名:フジSPレッド5585(固形分:20%)
(4)(イ)成分として3−(4−ジエチルアミノ−2−ヘキシルオキシフェニル)−3−(1−エチル−2−メチルインドール−3−イル)−4−アザフタリド2.0部、(ロ)成分として2,2−ビス(4′−ヒドロキシフェニル)ヘキサフルオロプロパン8.0部、(ハ)成分としてカプリン酸4−ベンジルオキシフェニルエチル50.0部からなる可逆熱変色性組成物を内包したマイクロカプセル顔料(T1:−14℃、T2:−6℃、T3:48℃、T4:60℃、ΔH:64℃、平均粒子径:2.3μm、青色から無色に色変化する)
(5)DE値:4、平均粒子径:2.7μmである馬鈴薯由来のデキストリン
(6)DE値:2〜5、粒子径:2〜5μmである馬鈴薯由来のデキストリン
(7)DE値:4、平均粒子径:204μmであるデキストリン
(8)DE値:2〜5、ワキシーコーンスターチ由来の水溶性デキストリン
(9)三井化学(株)製、商品名:ケミパールA200、平均粒子径4μm
(10)第一工業製薬(株)製、商品名:プライサーフAL、ポリオキシエチレンジスチレン化フェニルエーテルリン酸モノエステル及びジエステル混合物
(11)1,2−ベンズチアゾリン−3−オン、アビシア(株)製、商品名:プロキセルXL−2
(12)アルカリ増粘型アクリルエマルション、ローム&ハースジャパン社製、商品名:プライマルASE−60
The contents of the raw materials in the table will be described along the note numbers.
(1) Made by Orient Chemical Industry Co., Ltd., trade name: Water Black 181L
(2) Eisen Hodogaya Co., Ltd., trade name: Phloxine (3) Fuji Pigment Co., Ltd., trade name: Fuji SP Red 5585 (solid content: 20%)
(4) 2.0 parts of 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide as component (a), (b) A reversible thermochromic composition comprising 8.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane as a component and 50.0 parts of 4-benzyloxyphenylethyl caprate as a component (c) was included. Microcapsule pigment (T 1 : −14 ° C., T 2 : −6 ° C., T 3 : 48 ° C., T 4 : 60 ° C., ΔH: 64 ° C., average particle size: 2.3 μm, color change from blue to colorless )
(5) DE value: 4, dextrin derived from potato having an average particle size: 2.7 μm (6) DE value: 2-5, dextrin derived from potato having a particle size: 2-5 μm (7) DE value: 4 Dextrin having an average particle size of 204 μm (8) DE value: 2 to 5, water-soluble dextrin derived from waxy corn starch (9) manufactured by Mitsui Chemicals, Inc., trade name: Chemipearl A200, average particle size of 4 μm
(10) Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf AL, polyoxyethylene distyrenated phenyl ether phosphate monoester and diester mixture (11) 1,2-benzthiazolin-3-one, avicia ( Product name: Proxel XL-2
(12) Alkali thickened acrylic emulsion, manufactured by Rohm & Haas Japan, trade name: Primal ASE-60
インキの調製
各実施例及び比較例の配合量で増粘剤を除く各原料を混合し、20℃でディスパーにて400rpm、1時間攪拌した後、増粘剤を含むものはそれを加えて更に1時間攪拌することでボールペンインキ組成物を得た。
Preparation of ink Each raw material excluding the thickener was mixed in the blending amount of each Example and Comparative Example, and after stirring at 20 ° C. with a disper at 400 rpm for 1 hour, the one containing the thickener was further added. A ballpoint ink composition was obtained by stirring for 1 hour.
ボールペンレフィルの作製
ボールペンレフィルは、先端部に直径0.5mmのボールを回転可能に抱持したパイプ式ボールペンチップ(ボールを前方に弾発するボール押しバネを収容する)と、該ボールペンチップが前部に固着された接続部材と、該接続部材が先端開口部に固着され、且つ、内部にインキ及びインキ逆流防止体が収容されたインキ収容管と、該インキ収容管の後端開口部に固着された尾栓からなる。尚、前記インキ逆流防止体は、基油としてポリブテン、増粘剤として脂肪酸アマイドを用いて混練したインキ逆流防止体である。
Preparation of ballpoint pen refill The ballpoint pen refill consists of a pipe-type ballpoint pen tip (which contains a ball push spring that repels the ball forward) and a ballpoint tip that is a front part. A connection member fixed to the ink container, an ink storage tube in which the connection member is fixed to the front end opening, and an ink and an ink backflow preventer are accommodated therein, and a rear end opening of the ink storage tube. It consists of a tail plug. The ink backflow preventer is an ink backflow preventer kneaded using polybutene as the base oil and fatty acid amide as the thickener.
ボールペンの作製
後方外面にクリップを備えた軸筒の内部に、前記各ボールペンレフィルをバネ(コイルスプリング)により後方付勢状態で収容することで試料ボールペンを得た。前記ボールペンは、軸筒の後端部(ノック操作部)を前方へノック操作することにより、軸筒の先端孔よりボールペンチップが外部に突出する出没式形態である。
Production of Ballpoint Pen A sample ballpoint pen was obtained by housing each of the above ballpoint pen refills in a rear biased state by a spring (coil spring) inside a shaft cylinder having a clip on the rear outer surface. The ball-point pen has a retractable form in which a ball-point pen tip projects outward from a tip hole of the shaft cylinder by knocking a rear end portion (knock operation portion) of the shaft cylinder forward.
前記各試料ボールペンにより以下の試験を行った。
垂れ下がり試験A
各ボールペンを用いて、ボールペンチップを軸筒から露出させてチップを下向きで保持し、温度20℃、相対湿度90%の雰囲気下に20時間放置した後、チップ先端の外観を目視で観察した。
垂れ下がり試験B
各ボールペンのボールペンチップ先端に小傷を付けた後、温度20℃、相対湿度60%の雰囲気下に20時間放置し、チップ先端の外観を目視で観察した。
インキ安定性試験
筆記可能であることを確認した各ボールペンを、2000rpmで10分間、遠心処理した後、JIS P3201筆記用紙Aに手書きで直線を筆記して筆跡の状態を目視により観察した。
The following tests were conducted with the sample ballpoint pens.
Sagging test A
Using each ball-point pen, the ball-point pen tip was exposed from the shaft tube, and the tip was held downward. The tip was left in an atmosphere of a temperature of 20 ° C. and a relative humidity of 90% for 20 hours, and then the appearance of the tip of the tip was visually observed.
Sagging test B
After making small scratches on the tip of each ballpoint pen tip of each ballpoint pen, the tip was left in an atmosphere of a temperature of 20 ° C. and a relative humidity of 60% for 20 hours, and the appearance of the tip of the tip was visually observed.
Ink stability test Each ball-point pen that was confirmed to be writable was centrifuged at 2000 rpm for 10 minutes, and then a straight line was handwritten on JIS P3201 writing paper A, and the state of the handwriting was visually observed.
試験結果を以下の表に示す。
尚、テスト結果の評価の記号の内容は以下のとおり。
垂れ下がり試験A、B
○:インキの垂れ下がりは認められない。
×:チップ先端にインキ滴が認められる。
インキ安定性試験
○:一定の濃度及び線幅の筆跡が得られる。
×:筆記不能、又は、筆跡にカスレが生じる。
The contents of the test result evaluation symbols are as follows.
Sag test A, B
○: No ink sag.
X: Ink droplets are observed at the tip of the chip.
Ink stability test ○: A handwriting having a constant density and line width is obtained.
X: Writing is impossible or blurring occurs in the handwriting.
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