JP2021098811A - Water-based ink composition for writing instruments, and writing instrument and water-based ink product using the same - Google Patents
Water-based ink composition for writing instruments, and writing instrument and water-based ink product using the same Download PDFInfo
- Publication number
- JP2021098811A JP2021098811A JP2019231367A JP2019231367A JP2021098811A JP 2021098811 A JP2021098811 A JP 2021098811A JP 2019231367 A JP2019231367 A JP 2019231367A JP 2019231367 A JP2019231367 A JP 2019231367A JP 2021098811 A JP2021098811 A JP 2021098811A
- Authority
- JP
- Japan
- Prior art keywords
- water
- ink composition
- based ink
- writing
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000126 substance Substances 0.000 claims abstract description 55
- 239000003086 colorant Substances 0.000 claims abstract description 27
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 claims description 15
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- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- LJZULWUXNKDPCG-UHFFFAOYSA-N nonane-1,2-diol Chemical compound CCCCCCCC(O)CO LJZULWUXNKDPCG-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001965 potato dextrose agar Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-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
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Landscapes
- Pens And Brushes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、筆記具用水性インキ組成物、およびそれを用いた筆記具、ならびに水性インキ製品に関する。さらに詳しくは、抗菌性能、顔料の分散安定性、安全性に優れた筆記具用水性インキ組成物およびそれを用いた筆記具、並びに水性インキ製品に関する。 The present invention relates to a water-based ink composition for writing tools, a writing tool using the same, and a water-based ink product. More specifically, the present invention relates to a water-based ink composition for writing instruments having excellent antibacterial performance, pigment dispersion stability, and safety, a writing instrument using the same, and a water-based ink product.
筆記具用水性インキ組成物（以下、場合により「水性インキ組成物」または「インキ組成物」と表す）は、一般に水を主溶剤として含んでなるため、細菌、黴、または酵母などの微生物が繁殖しやすい。微生物が繁殖するとインキ組成物の腐敗などが起こり、粘度などインキ組成物の物性に変化が生じたり、インキ組成物中に析出物や凝集物などの異物が発生したり、インキ組成物の変色を起こすなど、インキ組成物としての機能が損なわれることがあった。そこで、抗菌性物質をインキ組成物に添加し、微生物などの繁殖を抑制することが盛んに行われている（特許文献１、２および３参照）。
しかしながら、インキ組成物に同一の抗菌性物質を使用し続けた場合、抗菌性物質に耐性を持つ微生物（以下、耐性菌という）が発生して繁殖する可能性があり、保存安定性の改良に余地があった。
Since water-based ink compositions for writing tools (hereinafter, sometimes referred to as "water-based ink compositions" or "ink compositions") generally contain water as a main solvent, microorganisms such as bacteria, molds, and yeasts propagate. It's easy to do. Propagation of microorganisms causes putrefaction of the ink composition, changes in the physical properties of the ink composition such as viscosity, foreign substances such as precipitates and agglomerates in the ink composition, and discoloration of the ink composition. The function as an ink composition may be impaired, such as by raising the ink. Therefore, an antibacterial substance is actively added to an ink composition to suppress the growth of microorganisms and the like (see Patent Documents 1, 2 and 3).
However, if the same antibacterial substance is continuously used in the ink composition, microorganisms resistant to the antibacterial substance (hereinafter referred to as resistant bacteria) may be generated and propagated, which improves storage stability. There was room.
耐性菌の繁殖という問題に対して、インクジェット用インク組成物や、ボールペン用インキ組成物に、２種類以上の抗菌性物質を含有させ、保存安定性を改良することが検討されている（特許文献４および５参照）。
しかしながら、特許文献４および５において開示されるインキ組成物は、耐性菌に対する抗菌性能や、大腸菌、緑膿菌、黄色ブドウ球菌、カンジダアルビカンス、コウジカビ（黒カビ）への抗菌性能が十分ではなく、改良の余地があった。
In response to the problem of propagation of resistant bacteria, it has been studied to include two or more kinds of antibacterial substances in an ink composition for an inkjet or an ink composition for a ballpoint pen to improve storage stability (Patent Documents). See 4 and 5).
However, the ink compositions disclosed in Patent Documents 4 and 5 do not have sufficient antibacterial performance against resistant bacteria and antibacterial performance against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Candida albicans, and Aspergillus aureus (black mold), and are improved. There was room for.
また、インキ瓶などの開閉口を備えるインキ保管容器にインキ組成物が収容されている場合や、万年筆などの櫛歯状のインキ保留部を有するインキ流量調節体を備える筆記具にこのようなインキ組成物を用いた場合、上記のような問題が発生する可能性は特に高い。
例えば、インキ保管容器に収容されていた従来のインキ組成物を万年筆で利用した場合、抗菌性能が十分ではないため、インキ供給機構に、微生物の繁殖などに起因する析出物や凝集物などの異物が生じてしまい、インキ組成物を供給する流路が狭くなることがある。この結果、インキの供給量が少なくなり、筆跡がかすれるなど、筆記性に影響が出る可能性がある。さらに、異物の量が増加したり凝集物などが大きくなると、インキを供給する流路が異物などにより塞がれ、インキを供給することができなくなり、筆記不能となる可能性がある。また、異物の発生量が少ないインキ組成物であっても、万年筆などのインキを繰返し充填して使用する筆記具に用いた場合、使用開始時は筆記性が良好であるが、充填と使用を繰り返すことにより、インキを供給する流路に異物が徐々に堆積し、筆記性への影響が大きくなっていく。さらに充填と使用を繰り返すと、該流路への異物の堆積がさらに進行し、流路が塞がれ、やはり筆記不能となる可能性がある。
Further, when the ink composition is contained in an ink storage container having an opening / closing port such as an ink bottle, or in a writing tool having an ink flow control body having a comb-shaped ink holding portion such as a fountain pen, such an ink composition is used. When using an object, the above-mentioned problems are particularly likely to occur.
For example, when a conventional ink composition stored in an ink storage container is used with a fountain pen, the antibacterial performance is not sufficient, so that the ink supply mechanism has foreign substances such as precipitates and aggregates caused by the growth of microorganisms. May occur and the flow path for supplying the ink composition may be narrowed. As a result, the amount of ink supplied is reduced, and the handwriting may be blurred, which may affect the writing performance. Further, when the amount of foreign matter increases or the agglomerates become large, the flow path for supplying ink is blocked by foreign matter or the like, and ink cannot be supplied, which may make writing impossible. Further, even if the ink composition generates a small amount of foreign matter, when it is used for a writing instrument that is repeatedly filled with ink such as a fountain pen, the writing property is good at the start of use, but the filling and use are repeated. As a result, foreign matter gradually accumulates in the flow path for supplying ink, and the influence on writeability becomes large. If the filling and use are repeated, the accumulation of foreign matter in the flow path further progresses, the flow path may be blocked, and writing may not be possible.
さらに、インキ組成物が保管容器に収容されており、該容器から水性インキ組成物を分取して筆記具に充填して使用する場合など、インキ組成物自体が、外気に触れる機会が多いと、微生物が混入する機会も多くなる。この結果、耐性菌を含む微生物が異常繁殖してしまう傾向が強く、抗菌性物質の添加量によっては、抗菌性能が十分に発揮されないという課題や、着色剤の分散安定性が低下するという課題を有していた。 Further, when the ink composition is stored in a storage container and the water-based ink composition is separated from the container and filled in a writing tool for use, the ink composition itself has many opportunities to come into contact with the outside air. Opportunities for contamination with microorganisms also increase. As a result, there is a strong tendency for microorganisms including resistant bacteria to proliferate abnormally, and depending on the amount of the antibacterial substance added, there is a problem that the antibacterial performance is not sufficiently exhibited and a problem that the dispersion stability of the colorant is lowered. Had had.
本発明は、顔料の分散安定性が良好で、抗菌性能に優れるなど、インキの保存安定性に優れた筆記具用水性インキ組成物およびそれを用いた筆記具、ならびに水性インキ製品を提供するものである。 The present invention provides a water-based ink composition for writing tools, a writing tool using the same, and a water-based ink product, which have excellent storage stability of ink, such as good dispersion stability of pigments and excellent antibacterial performance. ..
本発明は、筆記具用水性インキ組成物に、着色剤と、炭素数が４〜１０のアルカンジオールを含有する水性インキ組成物とすることなどにより上記課題が解決された。
すなわち、本発明は、
「１．水と、着色剤と、抗菌性物質とを含む筆記具用水性インキ組成物であって、前記抗菌性物質が、炭素数が４〜１０のアルカンジオールであり、筆記具用水性インキ組成物の総質量に対する前記抗菌性物質の総添加量が、１，０００〜１００，０００ｐｐｍであることを特徴とする、筆記具用水性インキ組成物。
２．前記着色剤が、自己分散型カーボンブラックであることを特徴とする、第１項に記載の筆記具用水性インキ組成物。
３．前記抗菌性物質が、イソチアゾリン系抗菌性物質をさらに含んでなることを特徴とする、第１項〜第２項のいずれか１項に記載の筆記具用水性インキ組成物。
４．第１項〜第３項のいずれか１項に記載の筆記具用水性インキ組成物を充填してなる筆記具。
５．第１項〜第３項のいずれか１項に記載の筆記具用水性インキ組成物をインキ保管容器に収容してなる水性インキ製品。」である。
The present invention has solved the above problems by using a water-based ink composition for writing tools containing a colorant and an alkanediol having 4 to 10 carbon atoms.
That is, the present invention
"1. A water-based ink composition for writing tools containing water, a colorant, and an antibacterial substance, wherein the antibacterial substance is an alkanediol having 4 to 10 carbon atoms, and the water-based ink composition for writing tools. A water-based ink composition for stationery, wherein the total amount of the antibacterial substance added to the total mass of the ink composition is 1,000 to 100,000 ppm.
2. The water-based ink composition for stationery according to item 1, wherein the colorant is a self-dispersing carbon black.
3. 3. The water-based ink composition for stationery according to any one of items 1 to 2, wherein the antibacterial substance further contains an isothiazolin-based antibacterial substance.
4. A writing tool filled with the water-based ink composition for writing tools according to any one of items 1 to 3.
5. A water-based ink product obtained by housing the water-based ink composition for writing tools according to any one of items 1 to 3 in an ink storage container. ".
本発明によれば、顔料の分散安定性が良好で、高い抗菌性能を有し、保存安定性に優れた筆記具用水性インキ組成物を提供することができる。 According to the present invention, it is possible to provide a water-based ink composition for writing instruments having good dispersion stability of pigments, high antibacterial performance, and excellent storage stability.
以下、本発明の実施の形態について、詳細に説明する。なお、本明細書において、配合を示す「部」、「％」、「比」などは特に断らない限り質量基準であり、含有量とは、水性インキ組成物の質量を基準としたときの構成成分の質量％である。 Hereinafter, embodiments of the present invention will be described in detail. In the present specification, "part", "%", "ratio", etc. indicating the composition are based on mass unless otherwise specified, and the content is a configuration based on the mass of the water-based ink composition. It is the mass% of the component.
本発明による筆記具用水性インキ組成物は、水と、着色剤と、抗菌性物質と、を含んでなるものであって、前記抗菌性物質が、炭素数が４〜１０のアルカンジオールであり、筆記具用水性インキ組成物の総質量に対する前記抗菌性物質の総添加量が、１，０００〜１００，０００ｐｐｍであることを一つの特徴とする。 The water-based ink composition for writing utensils according to the present invention comprises water, a colorant, and an antibacterial substance, and the antibacterial substance is an alkanediol having 4 to 10 carbon atoms. One feature is that the total amount of the antibacterial substance added to the total mass of the water-based ink composition for writing tools is 1,000 to 100,000 ppm.
＜着色剤＞
本発明による筆記具用水性インキ組成物は、着色剤を含んでなる。
着色剤としては、通常、筆記具用水性インキ組成物に用いる顔料、染料を使用することができる。
<Colorant>
The water-based ink composition for writing tools according to the present invention comprises a colorant.
As the colorant, pigments and dyes used in water-based ink compositions for writing instruments can be usually used.
顔料としては、水性媒体に分散可能であれば特に制限されるものではない。例えば、無機顔料、有機顔料、加工顔料などが挙げられるが、具体的にはカーボンブラック、アニリンブラック、群青、黄鉛、酸化チタン、酸化鉄、フタロシアニン系、アゾ系、キナクリドン系、キノフタロン系、スレン系、トリフェニルメタン系、ペリノン系、ペリレン系、ジオキサジン系、アルミ顔料、パール顔料、蛍光顔料、蓄光顔料などが挙げられる。その他、着色樹脂粒子体として顔料を媒体中に分散させてなる着色体を公知のマイクロカプセル化法などにより樹脂壁膜形成物質からなる殻体に内包又は固溶化させたマイクロカプセル顔料を用いても良い。また、顔料は、予め界面活性剤や樹脂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などを用いてもよい。
染料としては、溶媒に溶解可能であれば特に制限されるものではない。例えば、直接染料、酸性染料、塩基性染料、含金染料、および各種造塩タイプ染料等が採用可能である。
これらの顔料および染料は、単独又は２種以上混合して使用してもかまわない。
The pigment is not particularly limited as long as it can be dispersed in an aqueous medium. For example, inorganic pigments, organic pigments, processed pigments, etc. are mentioned, and specific examples thereof include carbon black, aniline black, ultramarine, yellow lead, titanium oxide, iron oxide, phthalocyanine, azo, quinacridone, quinophthalone, and slene. Examples include system, triphenylmethane type, perinone type, perylene type, dioxazine type, aluminum pigment, pearl pigment, fluorescent pigment, phosphorescent pigment and the like. In addition, even if a microcapsule pigment obtained by encapsulating or solidifying a colored body in which a pigment is dispersed in a medium as a colored resin particle body in a shell made of a resin wall film forming substance by a known microencapsulation method or the like is used. good. Further, as the pigment, an aqueous dispersion pigment product or the like which is finely and stably dispersed in an aqueous medium by using a surfactant or a resin in advance may be used.
The dye is not particularly limited as long as it can be dissolved in a solvent. For example, direct dyes, acid dyes, basic dyes, gold-containing dyes, various salt-forming type dyes, and the like can be adopted.
These pigments and dyes may be used alone or in combination of two or more.
これらの着色剤の中でも、筆跡の耐水性、耐光性に優れることから、顔料が好ましく、特に、筆跡の濃度や耐水性に優れることから、自己分散型カーボンブラックが好ましい。
自己分散型カーボンブラックとは、分散剤を用いることなく、水性媒体中に分散することが可能となるカーボンブラックをいい、例えば、カーボンブラックに物理的処理または化学的処理を施すことで、カーボンブラックの表面に親水性の官能基などを有するものをいう。自己分散型カーボンブラックは分散剤などの成分を含まないため、強制分散型のカーボンブラック分散体と比較し良好な発色が得られる。また、再分散性に優れるため、筆記具の筆記先端やインキ流量調節体などにインキ組成物が固着してしまった際にも容易に洗浄が可能である。
Among these colorants, pigments are preferable because they are excellent in water resistance and light resistance of handwriting, and self-dispersive carbon black is particularly preferable because they are excellent in concentration and water resistance of handwriting.
Self-dispersing carbon black refers to carbon black that can be dispersed in an aqueous medium without using a dispersant. For example, carbon black is physically or chemically treated. A substance having a hydrophilic functional group or the like on the surface of the carbon black. Since the self-dispersion type carbon black does not contain a component such as a dispersant, better color development can be obtained as compared with the forced dispersion type carbon black dispersion. Further, since it is excellent in redispersibility, it can be easily washed even when the ink composition is stuck to the writing tip of a writing instrument or an ink flow rate adjusting body.
前記物理的処理としては、例えば、真空プラズマ処理などが挙げられ、前記化学的処理としては、例えば、水中で酸化剤により酸化する湿式酸化法や、ｐ−アミノ安息香酸を顔料表面に結合させることによりフェニル基を介してカルボキシル基を結合させる方法などが挙げられる。 Examples of the physical treatment include vacuum plasma treatment, and examples of the chemical treatment include a wet oxidation method of oxidizing with an oxidizing agent in water and binding of p-aminobenzoic acid to the pigment surface. A method of bonding a carboxyl group via a phenyl group and the like can be mentioned.
本発明に用いることができる自己分散型カーボンブラックとしては特に限定されず、例えば、市販品では、オリヱント化学工業株式会社製のマイクロジェットシリーズ、キャボット社製のＣＡＢ−Ｏ−ＪＥＴシリーズ、東海カーボン株式会社製のＡｑｕａ−Ｂｌａｃｋシリーズ、冨士色素株式会社製のＦｕｊｉ−ＪＥＴ Ｂｌａｃｋシリーズなどが挙げられる。 The self-dispersing carbon black that can be used in the present invention is not particularly limited. For example, commercially available products include Microjet series manufactured by Orient Chemical Industries Co., Ltd., CAB-O-JET series manufactured by Cabot Corporation, and Tokai Carbon Co., Ltd. Examples include the Aqua-Black series manufactured by the company and the Fuji-JET Black series manufactured by Fuji Dye Co., Ltd.
これらの自己分散型カーボンブラックは、アニオン性、カチオン性などの自己分散型カーボンブラックが挙げられるが、後述する抗菌性物質である炭素数が４〜１０のアルカンジオールを添加しても分散安定性に影響が出にくいことから、アニオン性の自己分散型カーボンブラックを用いることが好ましい。また、自己分散型カーボンブラックは、それぞれ、単独で、又は２種以上を混合して用いることができる。但し、２種以上を混合して用いる際には、カーボンブラックの分散安定性に影響を与えない様に、そのイオン性が同じであることが好ましく、表面の親水基が同じであることがより好ましい。 Examples of these self-dispersing carbon blacks include self-dispersing carbon blacks such as anionic and cationic, but dispersion stability even when alcandiol having 4 to 10 carbon atoms, which is an antibacterial substance described later, is added. It is preferable to use anionic self-dispersing carbon black because it does not easily affect. In addition, the self-dispersive carbon black can be used alone or in combination of two or more. However, when two or more types are mixed and used, it is preferable that the ionicity is the same so as not to affect the dispersion stability of carbon black, and the hydrophilic groups on the surface are the same. preferable.
水性インキ組成物における自己分散型カーボンブラックの含有量は、水性インキ組成物の総質量を基準として、１〜２０質量％であることが好ましく、１〜１０質量％であることがより好ましく、さらには、１〜５質量％であることが好ましい。自己分散型カーボンブラックの含有量が前記範囲内であると、筆記先端へのインキ追従性能の低下を防止できるとともに、発色が良好な筆跡を得ることができる。 The content of the self-dispersing carbon black in the water-based ink composition is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the water-based ink composition. Is preferably 1 to 5% by mass. When the content of the self-dispersing carbon black is within the above range, it is possible to prevent deterioration of the ink following performance to the writing tip and to obtain a handwriting with good color development.
＜抗菌性物質＞
本発明による筆記具用水性インキ組成物は、抗菌性物質として、炭素数が４〜１０のアルカンジオールを用いる。炭素数が４〜１０のアルカンジオールは、従来の抗菌性物質よりも安全性が高いものである。
<Antibacterial substance>
The water-based ink composition for writing tools according to the present invention uses an alkanediol having 4 to 10 carbon atoms as an antibacterial substance. Alkanediols having 4 to 10 carbon atoms are safer than conventional antibacterial substances.
炭素数が４〜１０のアルカンジオールとしては、アルキル基が直鎖や分岐のいずれのものも用いることができ、２つの水酸基が置換する炭素原子もいずれの位置のものであってもよい。
具体的には、１，２−ブタンジオール、１，３ブタンジオール、１，４−ブタンジオール、２，３ブタンジオール、イソペンタンジオール、１，２−ペンタンジオール、１、３−ペンタンジオール、１，４−ペンタンジオール、１，５−ペンタンジオール、３−メチル−１，３−ブタンジオール、２，４−ペンタンジオール、２，２−ジメチル−１，３−プロパンジオール、１，２−ヘキサンジオール、１，３−ヘキサンジオール、１，４−ヘキサンジオール、１，５−ヘキサンジオール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、２−メチル−２，４−ペンタンジオール、２，５−ヘキサンジオール、１，２−ヘプタンジオール、１，３−ヘプタンジオール、１，４−ヘプタンジオール、１，５−ヘプタンジオール、１，６−ヘプタンジオール、１，７−ヘプタンジオール、１，２−オクタンジオール、１，８−オクタンジオール、２−エチル−１，３−ヘキサンジオール、２，５−ジメチル−２，５−ヘキサンジオール、１，２−ノナンジオール、１，９−ノナンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、１，２−デカンジオール、１，１０−デカンジオールなどを挙げることができる。
これらの中でも、抗菌性能の高さ、臭い、配合のし易さなどの観点から、炭素数が５〜８のアルカンジオールが好ましく、炭素数が５のアルカンジオールがより好ましい。特に、３−メチル−１，３−ブタンジオールは、抗菌性能が高く、着色剤の分散安定性や、水性インキ組成物の抗菌性能や、筆跡のにじみや裏抜け等の筆記性能性に対して、良好であるため好ましい。
これらは、１種単独で使用してもよく、２種以上を併用してもよい。
As the alkanediol having 4 to 10 carbon atoms, any one having a linear alkyl group or a branched alkyl group can be used, and the carbon atom substituted by the two hydroxyl groups may be at any position.
Specifically, 1,2-butanediol, 1,3 butanediol, 1,4-butanediol, 2,3 butanediol, isopentandiol, 1,2-pentanediol, 1,3-pentanediol, 1, 4-pentanediol, 1,5-pentanediol, 3-methyl-1,3-butanediol, 2,4-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,2-hexanediol, 1,3-Hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,5-Hexanediol, 1,2-Heptanediol, 1,3-Heptanediol, 1,4-Heptanediol, 1,5-Heptanediol, 1,6-Heptanediol, 1,7-Heptanediol, 1, , 2-octanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-nonanediol, 1,9-nonanediol , 2-Butyl-2-ethyl-1,3-propanediol, 1,2-decanediol, 1,10-decanediol and the like.
Among these, alkanediols having 5 to 8 carbon atoms are preferable, and alkanediols having 5 carbon atoms are more preferable, from the viewpoints of high antibacterial performance, odor, ease of blending, and the like. In particular, 3-methyl-1,3-butanediol has high antibacterial performance, and is resistant to dispersion stability of colorants, antibacterial performance of water-based ink compositions, and writing performance such as handwriting bleeding and strike-through. , Which is preferable because it is good.
These may be used alone or in combination of two or more.
従来の抗菌性物質である、１，２−ベンズイソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オンなどの抗菌性物質は、着色剤として特に自己分散型カーボンブラックを用いた際に抗菌効果が低下する傾向にある。これは、１，２−ベンズイソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オンなどの抗菌性物質が自己分散型カーボンブラックに吸着されることにより、ビヒクルの抗菌性能が低下し、インキ組成物本来の抗菌性能が得られにくくなるためと考えられる。 Conventional antibacterial substances such as 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one are In particular, when self-dispersing carbon black is used as the colorant, the antibacterial effect tends to decrease. This is a carbon black in which antibacterial substances such as 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and 2-n-octyl-4-isothiazolin-3-one are self-dispersed. It is considered that the antibacterial performance of the vehicle is lowered by being adsorbed on the ink composition, and it becomes difficult to obtain the original antibacterial performance of the ink composition.
しかしながら、炭素数が４〜１０のアルカンジオールは、従来の抗菌性物質と比較して安全性が高いため、インキ中により多く添加することが可能となることから、自己分散型カーボンブラックに吸着されてもなお、ビヒクルの抗菌性能を低下させることなく、インキ本来の抗菌性能を維持できるためと考えられる。
また、炭素数が４〜１０のアルカンジオールは、イソチアゾリン系抗菌性物質などの抗菌性物質を併用した場合においても、自己分散型カーボンブラックの分散安定性を損なうことがなく、抗菌性能に相乗効果を与えることができるので好ましい。より抗菌性能を考慮すれば、１，２−ベンズイソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オンなどのイソチアゾリン系抗菌性物質の中から１種以上選択して、炭素数が４〜１０のアルカンジオールと併用して用いることが好ましく、より抗菌性能や後述する耐性菌性能を考慮すれば、イソチアゾリン系抗菌性物質を２種以上選択することが好ましく、より考慮すれば、イソチアゾリン系抗菌性物質を３種以上選択することが好ましい。
However, alkanediols having 4 to 10 carbon atoms are safer than conventional antibacterial substances and can be added more in ink, so that they are adsorbed on self-dispersing carbon black. Nevertheless, it is considered that the original antibacterial performance of the ink can be maintained without deteriorating the antibacterial performance of the vehicle.
In addition, alkanediol having 4 to 10 carbon atoms does not impair the dispersion stability of self-dispersing carbon black even when an antibacterial substance such as an isothiazolin-based antibacterial substance is used in combination, and has a synergistic effect on antibacterial performance. Is preferable because it can be given. Considering more antibacterial performance, isothiazolin-based antibacterial properties such as 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 2-methyl-4-isothiazolin-3-one. It is preferable to select one or more of the substances and use them in combination with alcandiol having 4 to 10 carbon atoms. Considering the antibacterial performance and the resistance bacteria performance described later, 2 isothiazolin-based antibacterial substances are used. It is preferable to select three or more species, and more preferably, three or more isothiazolin-based antibacterial substances are selected.
本発明に用いる炭素数が４〜１０のアルカンジオールは、筆記具のインキタンク内の移動性、すなわち、インキ反転性を低下させることがない。従来の抗菌性物質は、十分な抗菌性能が得られるだけの量をインキ組成物に添加すると、インキ反転性が低下するおそれがあったが、本発明に用いる炭素数が４〜１０のアルカンジオールは、抗菌性能とインキ反転性能とを両立させることができるため、好ましい。 The alkanediol having 4 to 10 carbon atoms used in the present invention does not reduce the mobility of the writing instrument in the ink tank, that is, the ink reversibility. In the conventional antibacterial substance, if an amount sufficient to obtain sufficient antibacterial performance is added to the ink composition, the ink reversibility may be lowered, but the alkanediol having 4 to 10 carbon atoms used in the present invention may be deteriorated. Is preferable because it can achieve both antibacterial performance and ink reversal performance.
本発明による筆記具用水性インキ組成物を好適に用いることができる筆記具として、インキ流量を調節する適宜のインキ流量調節体を介してペン先が軸筒端部に取り付けられ、前記軸筒内に水性インキ組成物を収容するインキタンクが備えられた構造の筆記具などが挙げられる。
この種の筆記具は、横置きの状態やペン先が上向きの状態から、筆記するためにペン先を下向きの状態にした際に、インキタンクに収容された水性インキ組成物が、インキタンクの内壁を伝ってペン先方向へ流下することで、筆記が可能となる。（この水性インキ組成物の移動性をインキ反転性と称する。）
インキタンクを含む筆記具の多くの部品は樹脂で構成されることが多く、それらは疎水性であるため、水性インキ組成物の濡れ性が不足すると、筆記具のペン先を下向きの状態にしても、表面張力による抗力のため水性インキ組成物は流下せずに、元の位置に留まってしまう。この状態では、ペン先まで水性インキ組成物が供給されず、筆跡がかすれたり、筆記できなくなることがあった。
しかしながら、本発明に用いる炭素数が４〜１０のアルカンジオールは、十分な抗菌性能が得られる量を水性インキ組成物に添加しても、水性インキ組成物のインキタンクに対する濡れ性に影響を及ぼさないので、水性インキ組成物のインキタンク内におけるインキ反転性が低下せず、筆記具を横置きの状態やペン先が上向きの状態から、筆記するためにペン先を下向きの状態にした際にも、水性インキ組成物がインキタンク内で元の位置に留まらず、ペン先方向へインキを円滑に流下させることができる。
As a writing instrument that can preferably use the water-based ink composition for writing instruments according to the present invention, a pen tip is attached to the end of the shaft cylinder via an appropriate ink flow rate adjusting body that adjusts the ink flow rate, and the water-based ink composition is contained in the shaft cylinder. Examples thereof include a writing instrument having a structure provided with an ink tank for accommodating an ink composition.
In this type of writing instrument, when the pen tip is turned downward for writing from the horizontal position or the pen tip facing up, the water-based ink composition contained in the ink tank is applied to the inner wall of the ink tank. Writing is possible by flowing down in the direction of the pen tip. (The mobility of this water-based ink composition is referred to as ink reversibility.)
Many parts of a writing instrument, including an ink tank, are often made of resin, which are hydrophobic, so if the water-based ink composition lacks wettability, the writing instrument's nib can be turned downwards. Due to the resistance due to surface tension, the water-based ink composition does not flow down and stays in its original position. In this state, the water-based ink composition was not supplied to the pen tip, and the handwriting may be faint or writing may not be possible.
However, the alcandiol having 4 to 10 carbon atoms used in the present invention does not affect the wettability of the water-based ink composition with respect to the ink tank even if an amount capable of obtaining sufficient antibacterial performance is added to the water-based ink composition. Therefore, the ink reversibility of the water-based ink composition in the ink tank does not deteriorate, and even when the writing tool is placed horizontally or the pen tip is turned upward, the pen tip is turned downward for writing. , The water-based ink composition does not stay in the original position in the ink tank, and the ink can flow smoothly toward the pen tip.
本発明の筆記具用水性インキ組成物に用いる炭素数が４〜１０のアルカンジオールの添加量としては、水性インキ組成物の総質量を基準として、１，０００〜１００，０００ｐｐｍであることが好ましい。より好ましくは、１，０００〜５０，０００ｐｐｍである。この範囲より少ないと、抗菌性能が若干劣る傾向や、着色剤として顔料を用いた場合に、顔料の分散安定性が低下する傾向が見られ、この範囲より多いと、インキ反転性や、筆跡のにじみや裏抜け等の筆記性能に対して影響を及ぼす恐れがある。前記範囲にあると、抗菌性能が十分に得られ、顔料の分散安定性に対しても効果的に働き、インキ反転性や、筆跡のにじみや裏抜け等の筆記性能に対しても影響が少なく、かつ十分な安全性を確保することができるので、好ましい。 The amount of the alkanediol having 4 to 10 carbon atoms used in the water-based ink composition for writing tools of the present invention is preferably 1,000 to 100,000 ppm based on the total mass of the water-based ink composition. More preferably, it is 1,000 to 50,000 ppm. If it is less than this range, the antibacterial performance tends to be slightly inferior, and when a pigment is used as a colorant, the dispersion stability of the pigment tends to decrease. It may affect the writing performance such as bleeding and strike-through. Within the above range, sufficient antibacterial performance is obtained, it works effectively on the dispersion stability of pigments, and there is little influence on ink reversibility and writing performance such as handwriting bleeding and strike-through. Moreover, it is preferable because sufficient safety can be ensured.
本発明の筆記具用水性インキ組成物に用いる炭素数が４〜１０のアルカンジオールの添加量としては、着色剤を基準として、質量比で、１：３〜１：０．０３であることが好ましく、１：１〜１：０．１であることがより好ましい。この範囲にあると、着色剤の分散安定性や、水性インキ組成物の抗菌性能や、筆跡のにじみや裏抜け等の筆記性能に対して、良好であるため好ましい。 The amount of the alkanediol having 4 to 10 carbon atoms used in the water-based ink composition for writing tools of the present invention is preferably 1: 3 to 1: 0.03 in terms of mass ratio based on the colorant. , 1: 1 to 1: 0.1, more preferably. Within this range, the dispersion stability of the colorant, the antibacterial performance of the water-based ink composition, and the writing performance such as bleeding and strike-through of handwriting are good, which is preferable.
本発明の筆記具用水性インキ組成物は、インキ組成物の性能を損なわない範囲で、さらにイソチアゾリン系抗菌性物質を用いることが好ましい。
具体的には、１，２−ベンズイソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オン、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、４，５−ジクロロ−２−オクチル−４−イソチアゾリン−３−オンなどが挙げられる。
炭素数が４〜１０のアルカンジオールとイソチアゾリン系抗菌性物質を併用すると、着色剤として顔料を用いた場合に、顔料の分散安定性を損なうことなく、抗菌性能に相乗効果を与え、分散安定性と抗菌性能を維持しつつ、抗菌性物質の総量を少なくすることが可能となり、より皮膚刺激性等の安全性に優れた水性インキ組成物となるため、好ましい。
特に、１，２−ベンズイソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オンは、アルカリ性でも抗菌性物質が分解してしまうことがなく、耐熱性が良く、エイムズ試験が陰性であり、皮膚刺激性が弱く、無臭のインキ組成物を得ることができるので好ましい。
また、複数のイソチアゾリン系抗菌性物質を併用すると、各々の耐性菌に対する抗菌性能に加えて、他方の耐性菌に対する抗菌性能が強化されるので、より好ましい。
In the water-based ink composition for writing tools of the present invention, it is preferable to use an isothiazolin-based antibacterial substance as long as the performance of the ink composition is not impaired.
Specifically, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl- Examples thereof include 4-isothiazolin-3-one and 4,5-dichloro-2-octyl-4-isothiazolin-3-one.
When an alkanediol having 4 to 10 carbon atoms and an isothiazolin-based antibacterial substance are used in combination, when a pigment is used as a colorant, a synergistic effect is given to the antibacterial performance without impairing the dispersion stability of the pigment, and the dispersion stability. It is preferable because the total amount of antibacterial substances can be reduced while maintaining the antibacterial performance, and the water-based ink composition has more excellent safety such as skin irritation.
In particular, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 2-methyl-4-isothiazolin-3-one decompose antibacterial substances even if they are alkaline. It is preferable because it has good heat resistance, is negative in the Ames test, has weak skin irritation, and can obtain an odorless ink composition.
Further, it is more preferable to use a plurality of isothiazolin-based antibacterial substances in combination because the antibacterial performance against each resistant bacterium is enhanced in addition to the antibacterial performance against the other resistant bacterium.
本発明の筆記具用水性インキ組成物は、炭素数が４〜１０のアルカンジオールとイソチアゾリン系抗菌性物質を併用しても良いが、その添加量比としては、炭素数が４〜１０のアルカンジオールを基準として、質量比で、１：０．１〜１：０．０００１であることが好ましく、１：０．１〜１：０．００１であることがより好ましく、１：０．０５〜１：０．００１であることがさらに好ましい。この範囲にあると、着色剤の分散安定性や、水性インキ組成物の抗菌性能に対して、良好であるため好ましい。 In the water-based ink composition for writing utensils of the present invention, an alkanediol having 4 to 10 carbon atoms and an isothiazoline-based antibacterial substance may be used in combination, but the addition amount ratio thereof is an alkanediol having 4 to 10 carbon atoms. The mass ratio is preferably 1: 0.1: 1: 0.0001, more preferably 1: 0.1: 1: 0.001, and 1: 0.05 to 1 : 0.001 is more preferable. Within this range is preferable because it is good for the dispersion stability of the colorant and the antibacterial performance of the water-based ink composition.
本発明の筆記具用水性インキ組成物は、炭素数が４〜１０のアルカンジオールと２−フェノキシエタノールを併用することができる。
炭素数が４〜１０のアルカンジオールと２−フェノキシエタノールを併用すると、着色剤として顔料を用いた場合に、顔料の分散安定性を損なうことなく、抗菌性能に相乗効果を与え、分散安定性、抗菌性能を維持しつつ、抗菌性物質の総量を少なくすることが可能となり、より皮膚刺激性等の安全性に優れた水性インキ組成物となるため、好ましい。
In the water-based ink composition for writing tools of the present invention, alkanediol having 4 to 10 carbon atoms and 2-phenoxyethanol can be used in combination.
When alkanediol having 4 to 10 carbon atoms and 2-phenoxyethanol are used in combination, when a pigment is used as a colorant, it gives a synergistic effect on antibacterial performance without impairing the dispersion stability of the pigment, resulting in dispersion stability and antibacterial activity. It is preferable because it is possible to reduce the total amount of antibacterial substances while maintaining the performance, and the water-based ink composition is more excellent in safety such as skin irritation.
本発明の筆記具用水性インキ組成物は、炭素数が４〜１０のアルカンジオールと２−フェノキシエタノールを併用しても良いが、その添加量比としては、炭素数が４〜１０のアルカンジオールを基準として、質量比で、１：１０〜１：０．１であることが好ましく、１：２〜１：０．５であることがより好ましい。この範囲にあると、着色剤の分散安定性や、水性インキ組成物の抗菌性能に対して、良好であるため好ましい。 In the water-based ink composition for writing utensils of the present invention, alkanediol having 4 to 10 carbon atoms and 2-phenoxyethanol may be used in combination, but the addition amount ratio is based on alkanediol having 4 to 10 carbon atoms. The mass ratio is preferably 1: 10 to 1: 0.1, more preferably 1: 2 to 1: 0.5. Within this range is preferable because it is good for the dispersion stability of the colorant and the antibacterial performance of the water-based ink composition.
本発明の筆記具用水性インキ組成物は、インキ組成物の性能を損なわない範囲で、炭素数が４〜１０のアルカンジオールと、イソチアゾリン系抗菌性物質と、２−フェノキシエタノールとを併用してもよい。
炭素数が４〜１０のアルカンジオールと、イソチアゾリン系抗菌性物質と、２−フェノキシエタノールを併用すると、抗菌性能に相乗効果を与え、着色剤の分散安定性や、抗菌性能を維持しつつ、より皮膚刺激性等の安全性に優れた水性インキ組成物となるため、好ましい。
In the water-based ink composition for writing tools of the present invention, an alkanediol having 4 to 10 carbon atoms, an isothiazolin-based antibacterial substance, and 2-phenoxyethanol may be used in combination as long as the performance of the ink composition is not impaired. ..
When alkanediol having 4 to 10 carbon atoms, isothiazolin-based antibacterial substance, and 2-phenoxyethanol are used in combination, a synergistic effect is given to the antibacterial performance, and the skin is more stable while maintaining the dispersion stability of the colorant and the antibacterial performance. It is preferable because it is a water-based ink composition having excellent safety such as irritation.
＜水＞
水としては、特に制限はなく、例えば、水道水、イオン交換水、限外ろ過水または蒸留水などを用いることができる。
<Water>
The water is not particularly limited, and for example, tap water, ion-exchanged water, ultrafiltered water, distilled water, or the like can be used.
＜その他の成分＞
本発明による筆記具用水性インキ組成物は、本発明の効果を損なわない範囲で、濡れ剤、水溶性有機溶剤、ｐＨ調整剤、保湿剤、防錆剤などの各種添加剤を含むことができる。
<Other ingredients>
The water-based ink composition for writing tools according to the present invention may contain various additives such as a wetting agent, a water-soluble organic solvent, a pH adjuster, a moisturizer, and a rust preventive, as long as the effects of the present invention are not impaired.
本発明による筆記具用水性インキ組成物は、筆記具に用いる際にインキ流量調節体の濡れ性を向上させるために、各種濡れ剤を用いることができる。濡れ剤としては、特に限定されないがポリエーテルアミンを用いることが好ましい。ポリエーテルアミンは、着色剤として自己分散型カーボンブラックを用いた場合に、自己分散型カーボンブラックの分散安定性の向上と、インキ流量調節体に対する濡れ性を適度に保つことができる。 In the water-based ink composition for writing tools according to the present invention, various wetting agents can be used in order to improve the wettability of the ink flow rate adjusting body when used in writing tools. The wetting agent is not particularly limited, but it is preferable to use a polyether amine. When a self-dispersing carbon black is used as the colorant, the polyether amine can improve the dispersion stability of the self-dispersing carbon black and can appropriately maintain the wettability with respect to the ink flow rate adjusting body.
また、前記ポリエーテルアミンは、インキ流量調節体に対する濡れ性を適度に保つことができるため、インキ流量調節体の機能を十分に得ることができ、筆記具を横置きの状態やペン先が上向きの状態から、筆記するためにペン先を下向きの状態にした際にも、筆記先端方向へインキ組成物を円滑に流下させることができ、筆記先端からのインキ吐出性を良好に維持することが可能となり、また、インキ流量調節体に余剰なインキがスムーズに流入するため、インキのボタ落ち現象を抑制することができる。さらに、ポリエーテルアミンを用いた筆記具用水性インキ組成物は、筆記具に内蔵して筆記した際に、紙面への浸透性が高くなって筆跡がにじんでしまったり、裏抜けしてしまったりすることがなく、良好な筆跡を得ることができる。 Further, since the polyether amine can maintain an appropriate wettability with respect to the ink flow rate adjusting body, the function of the ink flow rate adjusting body can be sufficiently obtained, and the writing instrument is placed horizontally or the pen tip is directed upward. Even when the pen tip is turned downward for writing from the state, the ink composition can be smoothly flowed down toward the writing tip, and the ink ejection property from the writing tip can be maintained well. In addition, since excess ink smoothly flows into the ink flow control body, it is possible to suppress the ink dripping phenomenon. Furthermore, the water-based ink composition for writing instruments using polyetheramine becomes highly permeable to the paper surface when writing by incorporating it in the writing instrument, and the handwriting may bleed or strike through. Good handwriting can be obtained.
本発明に用いることができるポリエーテルアミンのＨＬＢ値は、１０〜２０であることが好ましい。これは、ポリエーテルアミンのＨＬＢ値が１０以上であると、水に完全に溶解し、着色剤として自己分散型カーボンブラックを用いた場合に、自己分散型カーボンブラックと凝集物を作ることがないので、インキ組成物中での分散安定性に影響を及ぼすことがない為である。 The HLB value of the polyether amine that can be used in the present invention is preferably 10 to 20. This is because when the HLB value of the polyether amine is 10 or more, it is completely dissolved in water, and when self-dispersing carbon black is used as the colorant, it does not form aggregates with the self-dispersing carbon black. Therefore, it does not affect the dispersion stability in the ink composition.
また、前記ポリエーテルアミンの平均酸化エチレン付加モル数（ＥＯ数）は、１０〜３５であることが好ましく、１３〜３０であることがより好ましい。前記ポリエーテルアミンの平均酸化エチレン付加モル数（ＥＯ数）が上記数値の範囲内であれば、水への溶解性が高いため、ポリエーテルアミンの効果を安定して得ることができる。 The average number of moles of ethylene oxide added (the number of EOs) of the polyether amine is preferably 10 to 35, more preferably 13 to 30. When the average number of moles of ethylene oxide added (number of EOs) of the polyether amine is within the above value range, the solubility in water is high, so that the effect of the polyether amine can be stably obtained.
前記ポリエーテルアミンとしては、ポリオキシエチレンステアリルアミン、ポリオキシエチレン（２０）アルキル（Ｃ１４−Ｃ１８）アミン、ポリオキシエチレン牛脂アルキルアミン、ポリオキシエチレンアルキルアミンエーテル、ポリオキシエチレンラウリルアミン、ポリオキシエチレンアルキル（ヤシ）アミンなどが挙げられる。 Examples of the polyether amine include polyoxyethylene stearylamine, polyoxyethylene (20) alkyl (C14-C18) amine, polyoxyethylene beef alkylamine, polyoxyethylene alkylamine ether, polyoxyethylene laurylamine, and polyoxyethylene. Alkyl (palm) amine and the like can be mentioned.
筆記具用水性インキ組成物における前記ポリエーテルアミンの含有量は、水性インキ組成物の総質量を基準として、０．１〜２．０質量％であることが好ましく、０．５〜１．０質量％であることがより好ましい。 The content of the polyether amine in the water-based ink composition for writing tools is preferably 0.1 to 2.0% by mass, preferably 0.5 to 1.0% by mass, based on the total mass of the water-based ink composition. More preferably.
水溶性有機溶剤としては、（ｉ）エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、またはグリセリンなどのグリコール類、（ｉｉ）メタノール、エタノール、１−プロパノール、２−プロパノール、イソプロパノール、イソブタノール、ｔ−ブタノール、プロパギルアルコール、アリルアルコール、３−メチル−１−ブチン−３−オール、エチレングリコールモノメチルエーテルアセタートやその他の高級アルコールなどのアルコール類、および（ｉｉｉ）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、３−メトキシブタノール、または３−メトキシ−３−メチルブタノールなどのグリコールエーテル類などが挙げられる。これらの水溶性有機溶剤は単独又は２種以上混合して使用してもかまわない。 Examples of the water-soluble organic solvent include (i) glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, or glycerin, and (ii) methanol, ethanol, 1-propanol, 2-propanol, isopropanol, isobutanol, t. -Alcohols such as butanol, propanol alcohol, allyl alcohol, 3-methyl-1-butin-3-ol, ethylene glycol monomethyl ether acetate and other higher alcohols, and (iii) ethylene glycol monomethyl ether, ethylene glycol mono. Examples thereof include glycol ethers such as ethyl ether, 3-methoxybutanol, or 3-methoxy-3-methylbutanol. These water-soluble organic solvents may be used alone or in combination of two or more.
水溶性有機溶剤の中でも、水と水に溶解可能な水溶性有機溶剤からなる混合溶媒を用いることが好ましく、これは、着色剤として自己分散型カーボンブラックを用いた場合に、自己分散型カーボンブラックと、炭素数が４〜１０のアルカンジオールをインキ中において安定化させ、耐ドライアップ性能の効果を得られやすいためである。
さらに、耐ドライアップ性能の向上を考慮すると、前記水溶性有機溶剤の中でも、グリコール類を選択して用いることが好ましい。これは、前記グリコール類を用いることで、グリコール類の吸湿効果をインキ組成物に付与することができるためであり、より耐ドライアップ性能の向上を考慮すれば、多価アルコールを用いることが好ましく、多価アルコール溶剤の中でも、エチレングリコール、ジエチレングリコール、グリセリンの中から１種以上を選択して用いることが好ましい。
着色剤として、自己分散型カーボンブラックのような顔料を用いた場合、ペン先を大気中に放置した際に生じるドライアップ時の書き出し性能が劣りやすいため、効果的であり、さらに、ノック式、スライド式、回転繰り出し式などの出没式筆記具では、ペン先が定常的に大気中に放置されるため、チップ先端部が乾燥して、書き出し時にカスレなどが生じやすいため効果的であり、好ましい。
Among the water-soluble organic solvents, it is preferable to use a mixed solvent composed of water and a water-soluble organic solvent that is soluble in water, and this is a self-dispersing carbon black when a self-dispersing carbon black is used as a colorant. This is because alcandiol having 4 to 10 carbon atoms is stabilized in the ink, and the effect of dry-up resistance can be easily obtained.
Further, in consideration of improvement in dry-up resistance, it is preferable to select and use glycols among the water-soluble organic solvents. This is because the hygroscopic effect of glycols can be imparted to the ink composition by using the glycols, and it is preferable to use a polyhydric alcohol in consideration of further improvement in dry-up resistance. Among the polyhydric alcohol solvents, it is preferable to select and use one or more of ethylene glycol, diethylene glycol and glycerin.
When a pigment such as self-dispersing carbon black is used as the colorant, it is effective because the writing performance at the time of dry-up, which occurs when the pen tip is left in the air, tends to be inferior. A sliding type, rotary feeding type, or other infestation type writing tool is effective because the pen tip is constantly left in the air, so that the tip of the tip dries and blurring or the like is likely to occur during writing.
水溶性有機溶剤の添加量は、インキの安定性や、筆跡のトギレやカスレが改善された良好な筆跡が得られることや、耐ドライアップ性能の向上を考慮すると、水性インキ組成物に対して０．１〜１０質量％であることが好ましく、０．１〜７質量％であることがより好ましい。 The amount of the water-soluble organic solvent added is higher than that of the water-based ink composition in consideration of the stability of the ink, good handwriting with improved handwriting and blurring, and improvement of dry-up resistance. It is preferably 0.1 to 10% by mass, more preferably 0.1 to 7% by mass.
ｐＨ調整剤としては、アンモニア、炭酸ナトリウム、リン酸ナトリウム、水酸化ナトリウムなどの塩基性無機化合物、酢酸ナトリウム、トリエタノールアミン、ジエタノールアミンなどの塩基性有機化合物、乳酸およびクエン酸などが挙げられ、水性インキ組成物の経時安定性を考慮すれば、塩基性有機化合物を用いることが好ましく、より考慮すれば、弱塩基性であるトリエタノールアミンを用いることが好ましい。これらのｐＨ調整剤は単独又は２種以上混合して使用してもかまわない。
ｐＨ調整剤の含有量は、水性インキ組成物の総質量を基準として、０．１〜１０質量％であることが好ましく、０．１〜５質量％であることがより好ましい。
Examples of the pH adjuster include basic inorganic compounds such as ammonia, sodium carbonate, sodium phosphate and sodium hydroxide, basic organic compounds such as sodium acetate, triethanolamine and diethanolamine, lactic acid and citric acid, which are aqueous. Considering the stability of the ink composition over time, it is preferable to use a basic organic compound, and more considering it, it is preferable to use triethanolamine, which is weakly basic. These pH adjusters may be used alone or in combination of two or more.
The content of the pH adjuster is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the aqueous ink composition.
保湿剤としては、前記水溶性有機溶剤の他に尿素、ソルビット、Ｎ，Ｎ，Ｎ−トリアルキルアミノ酸などが挙げられる。特に、Ｎ，Ｎ，Ｎ−トリアルキルアミノ酸は、他の保湿剤に比べ、乾燥時の水分保持力が極めて高いため、好ましい。保湿剤の添加量は、水性インキ組成物に対して、０．１〜１０質量％であることが好ましく、０．１〜５質量％であることがより好ましい。 Examples of the moisturizer include urea, sorbitol, N, N, N-trialkyl amino acids and the like in addition to the water-soluble organic solvent. In particular, N, N, N-trialkyl amino acids are preferable because they have extremely high water retention during drying as compared with other moisturizers. The amount of the moisturizer added is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the water-based ink composition.
前記Ｎ，Ｎ，Ｎ−トリアルキルアミノ酸は、下記式（１）で表せるものである。
Ｒ１〜Ｒ３としては、直鎖又は分岐鎖のアルキル基を広く用いることができる。すなわち、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基などが例示される。なおＲ１〜Ｒ３は同一であっても異なっていてもよい。具体的には、ｎ＝１のトリメチルグリシン、トリエチルグリシン、トリプロピルグリシン、トリイソプロピルグリシン、ｎ＝２のトリメチル−β−アラニン、ｎ＝３のトリメチル−γ−アミノ酪酸などが挙げられる。耐ドライアップ性能の向上や水性インキ組成物の保存安定性の向上などを考慮すると、トリメチルグリシンを選択して用いることが好ましい。 As R 1 to R 3 , linear or branched alkyl groups can be widely used. That is, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like are exemplified. Note that R 1 to R 3 may be the same or different. Specific examples thereof include n = 1 trimethylglycine, triethylglycine, tripropylglycine, triisopropylglycine, n = 2 trimethyl-β-alanine, and n = 3 trimethyl-γ-aminobutyric acid. It is preferable to select and use trimethylglycine in consideration of improvement in dry-up resistance and storage stability of the water-based ink composition.
防錆剤としては、ベンゾトリアゾールおよびその誘導体、トリルトリアゾール、ジシクロヘキシルアンモニウムナイトライト、ジイソプロピルアンモニウムナイトライト、チオ硫酸ナトリウム、サポニン、またはジアルキルチオ尿素などが挙げられる。 Examples of the rust preventive include benzotriazole and its derivatives, tolyltriazole, dicyclohexylammonium nitrate, diisopropylammonium nitrate, sodium thiosulfate, saponin, dialkylthiourea and the like.
キレート剤としては、エチレンジアミン四酢酸（ＥＤＴＡ）、ヒドロキシエチレンジアミン三酢酸（ＨＥＤＴＡ）、グリコールエーテルジアミン四酢酸（ＧＥＤＴＡ）、ニトリロ三酢酸（ＮＴＡ）、ヒドロキシエチルイミノ二酢酸（ＨＩＤＡ）、ジヒドロキシエチルグリシン（ＤＨＥＧ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、トリエチレンテトラミン六酢酸（ＴＴＨＡ）及びそれらのアルカリ金属塩、アンモニウム塩又はアミン塩などの塩が挙げられる。 Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), glycol etherdiaminetetraacetic acid (GEDTA), nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIDA), and dihydroxyethylglycine (DHEG). ), Diethylenetriaminetetraacetic acid (DTPA), triethylenetetraminehexacetic acid (TTHA) and salts such as alkali metal salts, ammonium salts or amine salts thereof.
本発明の筆記具用水性インキ組成物を充填してなる筆記具のうち、たとえば、万年筆のように、櫛歯状のインキ保留部を有するインキ流量調節体を備える筆記具は、使用者が繰返しインキを補充して使用することができ、補充インキはガラス瓶などのインキ収容器に収容されることがある。ガラス瓶は安価で成形が容易で、さらに所望の強度が得られやすいという反面、特に廉価で汎用性の高いソーダ石灰ガラスなどを用いた場合には、水性インキ組成物を長期間収容していると、水性インキ組成物中にガラス中のアルカリ成分が溶出する可能性が高く、この溶出したアルカリ成分と水性インキ組成物の成分が反応して、析出物が形成される可能性がある。従って、本発明に用いられる水性インキ組成物においては、ガラス製のインキ収容器から溶出するアルカリ成分を補足し、該アルカリ成分が水性インキ組成物中の成分と反応して水に不溶な析出物などが発生することを防ぎ、発生した析出物などによりインキ流路が塞がれて、筆跡がかすれたり、筆記不能になることを抑制することができる前記キレート剤を含んでなることが好ましい。
アルカリ成分を十分に補足できること、また、水性インキ組成物のキレート剤の配合前後の物性や性能に変化を与えにくいことなどを考慮すると、前記キレート剤の中でも、アミノカルボン酸およびその塩を用いることが好ましく、より考慮すれば、エチレンジアミン四酢酸（ＥＤＴＡ）およびその塩を用いることが好ましい。
Among the writing tools filled with the water-based ink composition for writing tools of the present invention, for example, a writing tool provided with an ink flow control body having a comb-shaped ink holding portion, such as a fountain pen, is repeatedly replenished with ink by the user. The refill ink may be stored in an ink container such as a glass bottle. Glass bottles are inexpensive, easy to mold, and easily obtain the desired strength. On the other hand, when soda-lime glass, which is inexpensive and highly versatile, is used, the water-based ink composition is stored for a long period of time. There is a high possibility that the alkaline component in the glass is eluted in the water-based ink composition, and the eluted alkaline component and the component of the water-based ink composition may react with each other to form a precipitate. Therefore, in the water-based ink composition used in the present invention, an alkaline component eluted from a glass ink container is supplemented, and the alkaline component reacts with a component in the water-based ink composition to form a water-insoluble precipitate. It is preferable to contain the chelating agent which can prevent the occurrence of such substances and prevent the ink flow path from being blocked by the generated precipitates and the like, resulting in faint handwriting or inability to write.
Considering that the alkaline component can be sufficiently supplemented and that it is difficult to change the physical properties and performance of the aqueous ink composition before and after blending the chelating agent, aminocarboxylic acid and a salt thereof should be used among the chelating agents. Is preferable, and more consideration is given, it is preferable to use ethylenediaminetetraacetic acid (EDTA) and a salt thereof.
着色剤として、自己分散型カーボンブラックのような顔料を用いた場合、分散剤を用いることなく顔料分散を安定化する効果が得られるため、インキ粘度を低粘度に調整した場合においても、顔料の沈降を抑制できることから、低粘度インキにおいて特に効果的である。
そのため、筆記具用水性インキ組成物の粘度は、Ｂ型回転粘度計を用いて、回転数６０ｒｐｍ、２０℃で測定したインキ粘度が、５０ｍＰａ・ｓ以下であることが好ましく、１．０〜１０ｍＰａ・ｓであることがより好ましい。この範囲より大きいと、特に櫛歯状のインキ保留部を有するインキ流量調節体を備える筆記具に用いた際に、筆記先端へインキが安定して供給されず、筆跡がかすれたり、筆記不能になる恐れがある。より好ましくは、１．０〜３．０ｍＰａ・ｓであり、さらに好ましくは、１．０〜２．０ｍＰａ・ｓである。インキ粘度が前記範囲内であれば、ペン芯をインキ流量調節体として配置されてなる筆記具に用いた際に、安定して筆記先端へインキが供給され、良好な筆跡が得られるなど、インキ追従性能を向上させることができるためである。
When a pigment such as self-dispersing carbon black is used as the colorant, the effect of stabilizing the pigment dispersion can be obtained without using a dispersant. Therefore, even when the ink viscosity is adjusted to a low viscosity, the pigment It is particularly effective in low-viscosity inks because it can suppress settling.
Therefore, the viscosity of the water-based ink composition for writing tools is preferably 1.0 to 10 mPa · s or less, and the viscosity of the ink measured at a rotation speed of 60 rpm and 20 ° C. using a B-type rotational viscometer is preferably 1.0 to 10 mPa · s. More preferably, it is s. If it is larger than this range, the ink will not be stably supplied to the writing tip, and the handwriting will be faint or impossible to write, especially when used in a writing instrument provided with an ink flow control body having a comb-shaped ink holding portion. There is a fear. It is more preferably 1.0 to 3.0 mPa · s, and even more preferably 1.0 to 2.0 mPa · s. If the ink viscosity is within the above range, when the pen core is used for a writing instrument arranged as an ink flow control body, the ink is stably supplied to the writing tip and good handwriting is obtained. This is because the performance can be improved.
本発明におけるインキ粘度は、Ｂ型回転粘度計（機種：ＢＬＩＩ、ローター：ＢＬアダプタ、東機産業株式会社製）により、ＪＩＳ Ｚ ８８０３：２０１１に従って、測定することができる。 The ink viscosity in the present invention can be measured by a B-type rotational viscometer (model: BLII, rotor: BL adapter, manufactured by Toki Sangyo Co., Ltd.) according to JIS Z 8803: 2011.
本発明による筆記具用水性インキ組成物の２０℃における表面張力は、３０〜７０ｍＮ／ｍであることが好ましく、３５〜６５ｍＮ／ｍであることがより好ましい。水性インキ組成物の表面張力が、上記数値の範囲内であれば、櫛歯状のインキ保留部を有するインキ流量調節体を備える筆記具に用いた際、前記インキ流量調節体に対する濡れ性を適度に保つことができる。従って、インキ貯蔵部の内圧が上昇した際にも、溢出したインキがペン芯内のインキ保留部に円滑に入るため、筆記先端からのインキのボタ落ちを効果的に抑制することが可能となる。さらに、筆記面に対する濡れ性も、適切に保たれることから、得られる筆跡がにじんだり、筆跡の乾燥が進まず、こすれて筆跡が汚れてしまうことを防ぐことができる。なお、表面張力は、表面張力計測器（機種：ＤＹ−２００、協和界面科学株式会社製、２０℃環境下、白金プレート、垂直平板法）により測定して求められる。 The surface tension of the water-based ink composition for writing tools according to the present invention at 20 ° C. is preferably 30 to 70 mN / m, and more preferably 35 to 65 mN / m. When the surface tension of the water-based ink composition is within the above numerical range, the wettability to the ink flow rate adjusting body is appropriately adjusted when used in a writing tool provided with an ink flow rate adjusting body having a comb-shaped ink holding portion. Can be kept. Therefore, even when the internal pressure of the ink storage unit rises, the overflowing ink smoothly enters the ink holding portion in the pen core, so that it is possible to effectively suppress the ink dripping from the writing tip. .. Further, since the wettability to the writing surface is appropriately maintained, it is possible to prevent the obtained handwriting from bleeding or the handwriting from drying out and being rubbed and becoming dirty. The surface tension is measured by a surface tension measuring instrument (model: DY-200, manufactured by Kyowa Interface Science Co., Ltd., in a 20 ° C environment, platinum plate, vertical plate method).
＜インキ組成物の製造方法＞
本発明による筆記具用水性インキ組成物は、従来知られている任意の方法により製造することができる。具体的には、前記各成分を必要量配合し、プロペラ攪拌、ホモディスパー、ホモミキサー、遊星式攪拌機などの各種攪拌機やビーズミルなどの各種分散機などにて混合し、製造することができる。
<Manufacturing method of ink composition>
The water-based ink composition for writing tools according to the present invention can be produced by any conventionally known method. Specifically, each of the above components can be blended in a required amount and mixed with various stirrers such as a propeller stirrer, a homodisper, a homomixer, a planetary stirrer, and various dispersers such as a bead mill to produce the product.
＜筆記具＞
本発明の筆記具用水性インキ組成物は、繊維チップ、フェルトチップ、プラスチックチップまたはボールペンチップなどをペン先としたマーキングペンやボールペン、金属製のペン先を用いた万年筆などの筆記具に用いることができる。
<Stationery>
The water-based ink composition for writing instruments of the present invention can be used for writing instruments such as marking pens and ballpoint pens using fiber chips, felt-tips, plastic chips or ballpoint pens, and fountain pens using metal nibs. ..
本発明の筆記具は、水性インキ組成物を直に充填する構成のものであってもよく、水性インキ組成物を充填することのできるインキ収容体またはインキ吸蔵体を備えるものであってもよい。 The writing tool of the present invention may be configured to be directly filled with the water-based ink composition, or may be provided with an ink container or an ink occlusion body capable of filling the water-based ink composition.
本発明の筆記具におけるペン先の出没機構は、特に限定されず、ペン先を覆うキャップを備えたキャップ式、ノック式、回転式およびスライド式などが挙げられる。また、軸筒内にペン先を収容可能な出没式であってもよい。 The pen tip infestation mechanism in the writing tool of the present invention is not particularly limited, and examples thereof include a cap type having a cap covering the pen tip, a knock type, a rotary type, and a slide type. Further, it may be a retractable type that can accommodate the pen tip in the barrel.
また、筆記具におけるインキ供給機構についても特に限定されるものではなく、例えば、（１）繊維束などからなるインキ誘導芯をインキ流量調節部材として備え、水性インキ組成物をペン先に供給する機構、（２）溝歯状のインキ保留部を有する流量調節部材を備え、これを介在させ、水性インキ組成物をペン先に供給する機構、（３）弁機構によるインキ流量調節部材を備え、水性インキ組成物をペン先に供給する機構、および、（４）ペン先を具備したインキ収容体または軸筒より、水性インキ組成物を直接、ペン先に供給する機構などを挙げることができる。 Further, the ink supply mechanism in the writing tool is not particularly limited. For example, (1) a mechanism provided with an ink guide core made of a fiber bundle or the like as an ink flow rate adjusting member and supplying an aqueous ink composition to a pen tip. (2) A flow control member having a groove-toothed ink holding portion is provided, and a mechanism for supplying the water-based ink composition to the pen tip is provided. Examples thereof include a mechanism for supplying the composition to the pen tip, and (4) a mechanism for directly supplying the water-based ink composition to the pen tip from an ink container or a shaft tube provided with the pen tip.
本発明に用いる筆記具は、筆記先端とインキ貯蔵部を有し、前記筆記先端と前記インキ貯蔵部の間に、インキ貯蔵部から筆記先端にインキを供給でき、インキ貯蔵部の内圧上昇に伴い溢出したインキを一時的に保持する櫛歯状のインキ保留部を有するインキ流量調節体を配置した筆記具を用いることが好ましい。前記櫛歯状のインキ保留部を有するインキ流量調節体は、インキ貯蔵部から水性インキ組成物を筆記先端に供給し、かつ、インキ貯蔵部の内圧上昇に伴って溢出した水性インキ組成物を一時的に保持することが可能である。前記筆記具の具体的例としては、万年筆、ボールペン、カリグラフィー用ペンなどが挙げられる。 The writing instrument used in the present invention has a writing tip and an ink storage section, and ink can be supplied from the ink storage section to the writing tip between the writing tip and the ink storage section, and overflows as the internal pressure of the ink storage section rises. It is preferable to use a writing instrument in which an ink flow control body having a comb-shaped ink holding portion for temporarily holding the ink is arranged. The ink flow rate controller having the comb-shaped ink holding portion supplies the water-based ink composition from the ink storage portion to the writing tip, and temporarily discharges the water-based ink composition that overflows as the internal pressure of the ink storage portion rises. It is possible to hold the ink. Specific examples of the writing instrument include a fountain pen, a ballpoint pen, a calligraphy pen, and the like.
その他の実施形態において、筆記具は、マーキングペンであり、ペン先は、特に限定されず、例えば、繊維チップ、フェルトチップまたはプラスチックチップなどであってよく、さらに、その形状は、砲弾型、チゼル型または筆ペン型などであってよい。 In other embodiments, the writing instrument is a marking pen, and the pen tip is not particularly limited, and may be, for example, a fiber tip, a felt tip, a plastic tip, or the like, and the shape thereof is a bullet type or a chisel type. Alternatively, it may be a brush pen type or the like.
その他の実施形態において、筆記具は、ボールペンであり、インキ逆流防止体を備えたボールペンであることが好ましい。 In other embodiments, the writing instrument is a ballpoint pen, preferably a ballpoint pen provided with an ink backflow prevention body.
＜水性インキ製品＞
本発明の筆記具用水性インキ製品は、インキ組成物をインキ保管容器に収容した水性インキ製品に用いることができる。特に、インキ保管容器がインキを分取するための開閉口を有し、インキ保管容器から分取されたインキ組成物が、櫛歯状のインキ保留部を有するインキ流量調節体を有する筆記具に充填され使用される、水性インキ製品に用いることが好ましい。
<Aqueous ink products>
The water-based ink product for writing tools of the present invention can be used for a water-based ink product in which an ink composition is housed in an ink storage container. In particular, the ink storage container has an opening / closing port for separating ink, and the ink composition separated from the ink storage container is filled in a writing tool having an ink flow control body having a comb-shaped ink holding portion. It is preferable to use it for water-based ink products.
本発明に用いるインキ保管容器には、通常のインキ保管用や詰め替え用インキに使用されているインキ保管容器を用いることができる。具体的には、ガラス製のインキ瓶や、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など樹脂製の容器などが挙げられる。 As the ink storage container used in the present invention, the ink storage container used for ordinary ink storage and refill ink can be used. Specific examples thereof include glass ink bottles and resin containers such as polyethylene, polypropylene, and polyethylene terephthalate.
下記の配合組成および方法により、筆記具用水性インキ組成物を得た。
（実施例１）
自己分散型カーボンブラック１ １５．０質量％
（商品名：Ｆｕｊｉ Ｊｅｔ Ｂｌａｃｋ−２０、冨士色素株式会社製、イオン性：アニオン カーボンブラック２０％水分散体）
３−メチル−１，３ブタンジオール ３．０質量％（３０，０００ｐｐｍ相当量）
トリエタノールアミン（ｐＨ調整剤） １．０質量％
１，２−ベンズイソチアゾリン−３−オン ０．００４５質量％（４５ｐｐｍ相当量）
２−ｎ−オクチル−４−イソチアゾリン−３−オン ０．００４５質量％（４５ｐｐｍ相当量）
イオン交換水 残部
イオン交換水に抗菌性物質、ｐＨ調整剤を添加し、プロペラ攪拌により混合してベース液を得た。その後、ベース液に自己分散型カーボンブラックを添加し、プロペラ攪拌により混合して、筆記具用水性インキ組成物を得た。得られた筆記具用水性インキ組成物の粘度を、ＪＩＳ Ｚ ８８０３：２０１１に従って、Ｂ型回転粘度計（機種：ＢＬＩＩ、ローター：ＢＬアダプタ、東機産業株式会社製、サンプル量２０ｍｌ）により測定した。具体的には、２０℃、回転速度６０ｒｐｍにおけるインキ粘度は１．６０ｍＰａ・ｓであった。また、得られた水性インキ組成物の表面張力を、表面張力計測器（機種：ＤＹ−２００、協和界面科学株式会社製、２０℃環境下、白金プレート、垂直平板法）により測定したところ、５７．８ｍＮ／ｍであった。
A water-based ink composition for writing tools was obtained by the following compounding composition and method.
(Example 1)
Autocovariant carbon black 1 15.0% by mass
(Product name: Fuji Jet Black-20, manufactured by Fuji Dye Co., Ltd., Ionic: Anionic carbon black 20% aqueous dispersion)
3-Methyl-1,3-butanediol 3.0% by mass (equivalent to 30,000 ppm)
Triethanolamine (pH adjuster) 1.0% by mass
1,2-Benz isothiazolin-3-one 0.0045% by mass (equivalent to 45 ppm)
2-n-octyl-4-isothiazolin-3-one 0.0045% by mass (equivalent to 45 ppm)
Ion-exchanged water balance An antibacterial substance and a pH adjuster were added to the ion-exchanged water and mixed by stirring with a propeller to obtain a base solution. Then, self-dispersing carbon black was added to the base liquid and mixed by stirring with a propeller to obtain an aqueous ink composition for writing tools. The viscosity of the obtained water-based ink composition for writing tools was measured with a B-type rotational viscometer (model: BLII, rotor: BL adapter, manufactured by Toki Sangyo Co., Ltd., sample volume 20 ml) according to JIS Z 8803: 2011. Specifically, the ink viscosity at 20 ° C. and a rotation speed of 60 rpm was 1.60 mPa · s. The surface tension of the obtained water-based ink composition was measured with a surface tension measuring instrument (model: DY-200, manufactured by Kyowa Interface Science Co., Ltd., in a 20 ° C environment, platinum plate, vertical plate method). It was .8 mN / m.
（実施例２〜４、比較例１）
イオン交換水に抗菌性物質、水溶性有機溶剤（ジエチレングリコール）、ｐＨ調整剤を添加し、プロペラ攪拌により混合してベース液を得ると共に、インキ組成物の配合を（表１）に示した配合とした以外は、実施例１と同じ方法にて、実施例２〜４、比較例１の筆記具用水性インキ組成物を得た。
(Examples 2 to 4, Comparative Example 1)
An antibacterial substance, a water-soluble organic solvent (diethylene glycol), and a pH adjuster are added to ion-exchanged water and mixed by stirring with a propeller to obtain a base liquid, and the ink composition is formulated as shown in (Table 1). The water-based ink compositions for writing tools of Examples 2 to 4 and Comparative Example 1 were obtained by the same method as in Example 1.
（分散安定性試験）
実施例１〜４、比較例１の筆記具用水性インキ組成物を、３０ｍｌスクリュー管に充填し、４週間室温にて放置し、スクリュー管の上部と底部のインキ組成物を顕微鏡にて観察した。
Ａ：上部、底部とも、顔料が均一に分散しており、分散安定性が良好であった。
Ｂ：わずかに顔料の凝集がみられ、底部に比べ、上部の顔料が少なくなっていた。
Ｃ：顔料の凝集物がみられ、底部に比べ、上部の顔料が少なくなっており、均一な分散が得られていなかった。
(Dispersion stability test)
The water-based ink compositions for writing tools of Examples 1 to 4 and Comparative Example 1 were filled in a 30 ml screw tube, left at room temperature for 4 weeks, and the ink compositions at the top and bottom of the screw tube were observed with a microscope.
A: The pigment was uniformly dispersed in both the upper part and the lower part, and the dispersion stability was good.
B: A slight aggregation of pigment was observed, and the amount of pigment at the top was less than that at the bottom.
C: Aggregates of pigments were observed, and the amount of pigments on the upper part was less than that on the bottom part, and uniform dispersion was not obtained.
（抗菌性能試験）
実施例１〜４、比較例１の筆記具用水性インキ組成物中に、アスペルギルスｓｐ．（ＢＩＴ耐性菌）を１ｍｌあたり約１．０×１０６個になるように接種し、３日間放置後の各インキ組成物を試験インキとした。この各試験インキをポテトデキストロース寒天培地による混釈平板法にて２８℃で７日間培養し、検出した菌数から抗菌性能を評価した。
Ａ：検出した菌数が、１×１００ｃｆｕ／ｍｌ未満である。
Ｂ：検出した菌数が、１×１００ｃｆｕ／ｍｌ以上１×１０２ｃｆｕ／ｍｌ未満である。
Ｃ：検出した菌数が、１×１０２ｃｆｕ／ｍｌ以上１×１０６ｃｆｕ／ｍｌ未満である。
Ｄ：検出した菌数が、１×１０６ｃｆｕ／ｍｌ以上である。
(Antibacterial performance test)
In the water-based ink composition for writing tools of Examples 1 to 4 and Comparative Example 1, Aspergillus sp. The (BIT resistant bacteria) was inoculated to be about 1.0 × 10 6 cells per 1 ml, each ink composition after being left for 3 days to obtain a test ink. Each of these test inks was cultured at 28 ° C. for 7 days by a dilution plate method using a potato dextrose agar medium, and the antibacterial performance was evaluated from the detected number of bacteria.
A: Number of detected bacteria is less than 1 × 10 0 cfu / ml.
B: Number of detected bacteria is less than 1 × 10 0 cfu / ml or more 1 × 10 2 cfu / ml.
C: The number of detected bacteria is 1 × 10 2 cfu / ml or more and less than 1 × 10 6 cfu / ml.
D: The number of detected bacteria is 1 × 10 6 cfu / ml or more.
（安全性評価）
実施例１〜４、比較例１の筆記具用水性インキ組成物の安全性を、以下の評価基準に従い評価した。
Ａ：イソチアゾリン系抗菌性物質の添加量が、１００ｐｐｍ未満である。
Ｂ：イソチアゾリン系抗菌性物質の添加量が、１００ｐｐｍ以上５００ｐｐｍ未満である。
Ｃ：イソチアゾリン系抗菌性物質の添加量が、５００ｐｐｍ以上である。
(Safety evaluation)
The safety of the water-based ink composition for writing tools of Examples 1 to 4 and Comparative Example 1 was evaluated according to the following evaluation criteria.
A: The amount of the isothiazolin-based antibacterial substance added is less than 100 ppm.
B: The amount of the isothiazolin-based antibacterial substance added is 100 ppm or more and less than 500 ppm.
C: The amount of the isothiazolin-based antibacterial substance added is 500 ppm or more.
（筆記性能試験）
実施例１〜４、比較例１の筆記具用水性インキ組成物をポリエチレン製のインキカートリッジに注入し、株式会社パイロットコーポレーション製万年筆（商品名：カスタム７４、ペン種Ｍ）に装着し、筆記用紙Ａに筆記を行った。その際の筆跡を目視により観察した。
Ａ：筆跡ににじみや裏抜けもなく、良好な筆跡が得られた。
Ｂ：筆跡ににじみや裏抜けが生じた。
Ｃ：筆跡に激しいにじみや裏抜けが生じた。
(Writing performance test)
The water-based ink composition for writing instruments of Examples 1 to 4 and Comparative Example 1 was injected into a polyethylene ink cartridge, attached to a fountain pen manufactured by Pilot Corporation (trade name: Custom 74, pen type M), and written paper A. I wrote in. The handwriting at that time was visually observed.
A: Good handwriting was obtained without bleeding or strike through.
B: There was bleeding or strike-through in the handwriting.
C: Severe bleeding and strike-through occurred in the handwriting.
（インキタンク内インキ反転性試験）
前記筆記性能試験に用いた万年筆を、ペン先が上向きの状態にして、充填されたインキタンク内の水性インキ組成物をペン先側からペン先の反対側にすべて落とした。この後、ペン先を静かに下向きの状態にした際、インキタンク内で水性インキ組成物がペン先側に流下する様子を目視にて確認し、下記基準に従ってインキタンク内のインキ反転性能を評価した。
Ａ：水性インキ組成物が、１０秒以内にインキタンクのペン先側にすべて流下した。
Ｂ：水性インキ組成物が、１０秒以内にインキタンクのペン先側に大部分が流下したが、一部流下せず、インキタンク内の壁面などに残っていた。
Ｃ：水性インキ組成物が、１０秒経過してもインキタンクのペン先側にすべて流下しなかった。
(Ink reversal test in ink tank)
The fountain pen used in the writing performance test was placed with the pen tip facing upward, and all the water-based ink composition in the filled ink tank was dropped from the pen tip side to the opposite side of the pen tip. After that, when the pen tip is gently turned downward, visually check how the water-based ink composition flows down to the pen tip side in the ink tank, and evaluate the ink reversal performance in the ink tank according to the following criteria. did.
A: The water-based ink composition all flowed down to the pen tip side of the ink tank within 10 seconds.
B: Most of the water-based ink composition flowed down to the pen tip side of the ink tank within 10 seconds, but part of it did not flow down and remained on the wall surface in the ink tank.
C: The water-based ink composition did not completely flow down to the pen tip side of the ink tank even after 10 seconds had passed.
本発明の筆記具用水性インキ組成物は、万年筆、ボールペン、筆ペン、カリグラフィーペン、各種マーカー類など、各種筆記具に用いることができる。特に、保存安定性および安全性の向上が図られていることから、万年筆やつけペンなどの、インキが外気に触れることが多い筆記具用のインキ組成物として好適に用いることができる。 The water-based ink composition for writing instruments of the present invention can be used for various writing instruments such as fountain pens, ballpoint pens, brush pens, calligraphy pens, and various markers. In particular, since the storage stability and safety are improved, it can be suitably used as an ink composition for writing instruments such as fountain pens and dip pens, which are often exposed to the outside air.
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