JPH07150083A - Aqueous white pigment composition - Google Patents
Aqueous white pigment compositionInfo
- Publication number
- JPH07150083A JPH07150083A JP32323793A JP32323793A JPH07150083A JP H07150083 A JPH07150083 A JP H07150083A JP 32323793 A JP32323793 A JP 32323793A JP 32323793 A JP32323793 A JP 32323793A JP H07150083 A JPH07150083 A JP H07150083A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- white pigment
- water
- pigment composition
- weight
- 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.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、修正液や筆記具用イン
キなどに使用される水性白色顔料組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous white pigment composition used for correction fluids, inks for writing instruments and the like.
【０００２】[0002]
【従来の技術】従来、修正液や筆記具用インキなどに使
用される水性白色顔料組成物は、白色顔料と結合材と水
とを少なくとも含むものである。2. Description of the Related Art Conventionally, an aqueous white pigment composition used for a correction fluid, an ink for writing instruments, etc. contains at least a white pigment, a binder and water.
【０００３】白色顔料は、酸化チタン、酸化亜鉛などが
あるが、特に、隠蔽性の高い酸化チタンが多く用いられ
ている。White pigments include titanium oxide, zinc oxide and the like, but in particular, titanium oxide having a high hiding property is often used.
【０００４】結合材は、ポリビニルアルコール、水溶性
アクリル樹脂などの水溶性樹脂や、アクリル系エマルシ
ョン、酢酸ビニル系エマルションなどの水分散性樹脂が
用いられている。As the binder, a water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin, or a water-dispersible resin such as an acrylic emulsion or a vinyl acetate emulsion is used.
【０００５】[0005]
【発明が解決しようとする課題】酸化チタンは、隠蔽力
が高く白色の着色材として現在多く用いられている。し
かし酸化チタンを白色の着色材として用いた場合、その
比重が高いため経時的に沈降、分離し、その沈殿は、所
謂ハードケーキとなりやすく、沈殿の再分散が困難であ
る。本発明は、沈降分離が小さく、沈殿の再分散が容易
な白色顔料として酸化チタンを用いた水性白色顔料組成
物を提供することを課題とする。Titanium oxide is currently widely used as a white colorant because of its high hiding power. However, when titanium oxide is used as a white colorant, its specific gravity is high, and therefore it precipitates and separates over time, and its precipitate easily becomes a so-called hard cake, and it is difficult to redisperse the precipitate. An object of the present invention is to provide an aqueous white pigment composition using titanium oxide as a white pigment that has a small sedimentation separation and is easy to redisperse the sediment.
【０００６】[0006]
【課題を解決するための手段】本発明は、吸油量３０
（ｇ／１００ｇ）以上、等電点がｐＨ７以下の酸化チタ
ンと、キサンタンガムと、水とを少なくとも含む水性白
色顔料組成物を要旨とする。The present invention has an oil absorption of 30.
The gist is an aqueous white pigment composition containing at least (g / 100 g) and having an isoelectric point of pH 7 or less, xanthan gum, and water.
【０００７】以下、詳細に説明する。白色顔料として用
いる酸化チタンは、通常、その分散性及び耐候性を向上
させるために、シリカ及び／又はアルミナ等で表面処理
を行なっている。この表面処理層の状態は吸油量に大き
く影響し、特に多孔質となった場合、吸油量が多くな
る。また、粒子の溶液中での電気的特性を示す等電点
は、表面状態によって変わるが、処理剤であるシリカ、
アルミナの等電点が大きく異なっている（シリカはｐＨ
２、アルミナはｐＨ９である）ため、表面処理剤の処理
比率に大きく影響される。本発明の白色顔料として使用
する酸化チタンは、吸油量３０（ｇ／１００ｇ）以上、
等電点がｐＨ７以下のものを用いる。これは、酸化チタ
ンに吸着したキサンタンガムで弱い凝集体を生成し、酸
化チタンの沈降を極力抑え、且つ、ハードケーキを防止
するためである。このような酸化チタンの具体例として
は、チタニックスＪＲ−８００（吸油量３０、等電点ｐ
Ｈ４．６）、同ＪＲ−８０１（吸油量４０、ｐＨ５．
６）（以上、テイカ（株）製）などが挙げられる。酸化
チタンの使用量は、水性白色顔料組成物全量に対して２
０〜６０重量％が好ましい。The details will be described below. Titanium oxide used as a white pigment is usually surface-treated with silica and / or alumina in order to improve its dispersibility and weather resistance. The state of the surface treatment layer has a great influence on the oil absorption amount, and particularly when it becomes porous, the oil absorption amount increases. In addition, the isoelectric point showing the electrical characteristics of the particles in the solution varies depending on the surface state, but is silica as a treatment agent,
The isoelectric points of alumina are very different (silica has a pH
2. Alumina has a pH of 9), so it is greatly affected by the treatment ratio of the surface treatment agent. Titanium oxide used as the white pigment of the present invention has an oil absorption of 30 (g / 100 g) or more,
An isoelectric point having a pH of 7 or less is used. This is because xanthan gum adsorbed on titanium oxide forms weak aggregates, suppresses sedimentation of titanium oxide as much as possible, and prevents hard cake. Specific examples of such titanium oxide include Titanics JR-800 (oil absorption 30, isoelectric point p.
H4.6), the same JR-801 (oil absorption 40, pH 5.
6) (above, manufactured by Teika Co., Ltd.) and the like. The amount of titanium oxide used is 2 based on the total amount of the aqueous white pigment composition.
0 to 60% by weight is preferable.
【０００８】尚、本発明において、等電点とは、粒子
（本発明においては、アルミナ、シリカなどにより表面
処理された酸化チタン）の電気二重層の電位がゼロにな
る溶液の水素イオン濃度（ｐＨ）を意味する。In the present invention, the isoelectric point means the concentration of hydrogen ions in a solution in which the electric double layer of particles (in the present invention, titanium oxide surface-treated with alumina, silica, etc.) has a zero potential. pH) is meant.
【０００９】また、吸油量は、２ｇの酸化チタンをガラ
ス板上に取り、煮あまに油を少量ずつ滴下し、金属へら
でよく混ぜ、煮あまに油と酸化チタンとの混合物がパテ
状となり成形性を持つまでの添加量の、酸化チタン１０
０ｇとして換算した煮あまに油の量（ｇ）である。For the oil absorption, 2 g of titanium oxide was placed on a glass plate, the oil was dropped little by little on the boiled linseed and mixed well with a metal spatula, and the mixture of boiled linseed oil and titanium oxide became putty-like. Addition amount of titanium oxide 10 until it has moldability
The amount (g) of boiled linseed oil converted as 0 g.
【００１０】キサンタンガムは酸化チタンと結合しハー
ドケーキの生成を防ぐ為に使用するものである。キサン
タンガムはグルコース２個、マンノース２個およびグル
クロン酸１個を構成単位とする結合ブロックの反復より
なる高分子量の多糖である。グルクロン酸は通常カリウ
ム、ナトリウムあるいはカルシウム塩となっている。具
体例としては、ケルザン、ケルザンＳ、ケルザンＦ、ケ
ルザンＡＲ、ケルザンＭ、ケルザンＤ（以上、三晶
（株）製）、コージン、コージンＦ、コージンＴ、コー
ジンＫ（以上、（株）興人製）等が挙げられる。キサン
タンガムの使用量は水性白色顔料組成物全量に対し０．
１〜０．６重量％が好ましい。Xanthan gum is used to bind with titanium oxide and prevent the formation of hard cake. Xanthan gum is a high molecular weight polysaccharide consisting of repeating binding blocks consisting of two glucose, two mannose and one glucuronic acid as structural units. Glucuronic acid is usually a potassium, sodium or calcium salt. Specific examples thereof include Kelzan, Kelzan S, Kelzan F, Kelzan AR, Kelzan M, Kelzan D (above, Sansan Co., Ltd.), Kojin, Kojin F, Kojin T, Kojin K (above, Kojin Co., Ltd.). Manufactured) and the like. The amount of xanthan gum used was 0. 0 based on the total amount of the aqueous white pigment composition.
1 to 0.6% by weight is preferable.
【００１１】水は溶剤である。Water is a solvent.
【００１２】尚、上記必須成分の他に、従来知られてい
る有色顔料を併用したり、酸化チタンや前記有色顔料の
分散安定性のために分散剤や沈降防止剤を、定着性向上
のため結合材を、塗布性能を良好にならしめる為にフロ
ー向上剤やレベリング剤を適宜添加することもできる。
また、塗布したときの塗膜の乾燥性調整のためエタノー
ル、２−プロパノール、エチレングリコール、グリセリ
ンなどの水溶性有機溶剤を使用してもよい。In addition to the above essential components, conventionally known color pigments may be used in combination, or a dispersant or an anti-settling agent may be used for the dispersion stability of titanium oxide or the color pigments, and a fixing agent may be used for improving the fixability. A flow improver or a leveling agent may be appropriately added to the binder to improve the coating performance.
Further, a water-soluble organic solvent such as ethanol, 2-propanol, ethylene glycol or glycerin may be used to adjust the drying property of the coating film when applied.
【００１３】本発明の白色顔料組成物は、従来知られて
いる方法で製造できる。例えば、キサンタンガムを除く
上記各成分をボールミル、アトライター、サンドグライ
ンダー等の撹拌分散機を使用して分散混合後、あらかじ
め水に溶かしたキサンタンガム水溶液をターボミキサー
で再度混合するなどの方法が採用できる。The white pigment composition of the present invention can be produced by a conventionally known method. For example, it is possible to employ a method in which each of the above components except xanthan gum is dispersed and mixed using a stirring and dispersing machine such as a ball mill, an attritor, or a sand grinder, and then an aqueous xanthan gum solution previously dissolved in water is mixed again with a turbo mixer.
【００１４】[0014]
【作用】酸化チタンとキサンタンガムと水とを少なくと
も含む水性白色顔料組成物は、ｐＨが７以上となる。こ
の時、使用する酸化チタンの等電点はｐＨ７以下なの
で、酸化チタンは組成物中で負に帯電する。このため、
酸化チタンと、キサンタンガムが水溶化し溶出したカリ
ウム、ナトリウムあるいはカルシウムイオンとが結合し
てしまい、酸化チタンとキサンタンガムのカルボキシル
基との吸着点が少なくなる。その結果、酸化チタンの初
期分散性は低下するが、樹脂分子が酸化チタンから外側
に伸びて、酸化チタンとキサンタンガムとの合計の径が
大きくなり、粒子同志が接近しにくくなり、強固な凝集
体を形成しにくくなる。また、吸油量３０（ｇ／１００
ｇ）以上の酸化チタンは、シリカ、アルミナよりなる厚
い多孔質表面処理層を有するため、粒子のカサが高くな
るので酸化チタンの沈降が小さくなる。このため、本発
明の水性白色顔料組成物における酸化チタンは沈降分離
が小さく、その沈殿は、再分散容易である。The aqueous white pigment composition containing at least titanium oxide, xanthan gum and water has a pH of 7 or more. At this time, since the isoelectric point of titanium oxide used is pH 7 or less, titanium oxide is negatively charged in the composition. For this reason,
Titanium oxide binds to the potassium, sodium, or calcium ions eluted from the xanthan gum to dissolve it, and the number of adsorption points between titanium oxide and the carboxyl group of xanthan gum is reduced. As a result, the initial dispersibility of titanium oxide decreases, but the resin molecules extend outward from titanium oxide, the total diameter of titanium oxide and xanthan gum increases, and it becomes difficult for particles to approach each other, resulting in a strong aggregate. Formation becomes difficult. In addition, oil absorption 30 (g / 100
g) Since the above titanium oxide has a thick porous surface-treated layer made of silica and alumina, the dryness of the particles becomes high, and the sedimentation of the titanium oxide becomes small. Therefore, the titanium oxide in the aqueous white pigment composition of the present invention has a small sedimentation separation, and the sedimentation is easy to redisperse.
【００１５】[0015]
実施例１ チタニックスＪＲ−８０１ ５０．０重量部 ケルザンＡＲの３重量％水溶液 １５．０重量部 水 ３０．０重量部 ケルザンＡＲの３重量％水溶液を除く上記成分をボール
ミルにて２４時間分散処理後、ターボミキサーでケルザ
ンＡＲの３重量％水溶液を混合し、ｐＨが７．２の水性
白色顔料組成物を得た。Example 1 Titanics JR-801 50.0 parts by weight 3% by weight aqueous solution of Kelzan AR 15.0 parts by weight water 30.0 parts by weight The above components except 3% by weight aqueous solution of Kelzan AR were dispersed in a ball mill for 24 hours. Then, a Kerzan AR 3 wt% aqueous solution was mixed with a turbo mixer to obtain an aqueous white pigment composition having a pH of 7.2.
【００１６】実施例２ チタニックスＪＲ−８００ ５０．０重量部 ケルザンＭの３重量％水溶液 １０．０重量部 水 ２５．０重量部 ジュリマーＳＥＫ１０１ ２６．７重量部 （アクリル系エマルジョン、固形分３９〜４１％、日本純薬（株）製） エチレングリコール ５．０重量部 ヘキサメタリン酸ソーダ２５％水溶液 １．３重量部 ケルザンＭの３重量％水溶液を除く上記成分をボールミ
ルにて２４時間分散処理後、ターボミキサーでケルザン
ＡＲの３重量％水溶液を混合し、ｐＨが７．３の水性白
色顔料組成物を得た。Example 2 Titanics JR-800 50.0 parts by weight Kerzan M 3% by weight aqueous solution 10.0 parts by weight water 25.0 parts by weight Jurimer SEK101 26.7 parts by weight (acrylic emulsion, solid content 39 to 39 parts by weight) 41%, manufactured by Nippon Pure Chemical Co., Ltd.) Ethylene glycol 5.0 parts by weight Sodium hexametaphosphate 25% aqueous solution 1.3 parts by weight After the above components except the 3% by weight aqueous solution of Kelzan M are dispersed in a ball mill for 24 hours, A Kerzan AR 3 wt% aqueous solution was mixed with a turbo mixer to obtain an aqueous white pigment composition having a pH of 7.3.
【００１７】実施例３ チタニックスＪＲ−８０１ ５０．０重量部 コージンの３重量％水溶液 １０．０重量部 水 ３０．０重量部 ジョンクリルＪ−７１１ ２６．７重量部 （アクリル系エマルジョン、固形分４２％、ジョンソンポリマー（株）製） ヘキサメタリン酸ソーダ２５％水溶液 １．３重量部 コージンの３重量％水溶液を除く上記成分をボールミル
にて２４時間分散処理後、ターボミキサーでケルザンＡ
Ｒの３重量％水溶液を混合し、ｐＨが７．３の水性白色
顔料組成物を得た。Example 3 Titanics JR-801 50.0 parts by weight Kojin's 3% by weight aqueous solution 10.0 parts by weight water 30.0 parts by weight Johncryl J-711 26.7 parts by weight (acrylic emulsion, solid content 42%, manufactured by Johnson Polymer Co., Ltd. 25% sodium hexametaphosphate aqueous solution 1.3 parts by weight The above components excluding the 3% by weight aqueous solution of kogin are dispersed in a ball mill for 24 hours, and then Kerzan A by a turbo mixer.
A 3% by weight aqueous solution of R was mixed to obtain an aqueous white pigment composition having a pH of 7.3.
【００１８】比較例１ 実施例１においてチタニックスＪＲ−８０１の代わり
に、チタニックスＪＲ−６００Ｅ（酸化チタン、等電
点：ｐＨ８．０、吸油量：２１、テイカ（株）製）を用
いた他は、実施例１と同様になして、ｐＨが７．２の水
性白色顔料組成物を得た。Comparative Example 1 Instead of Titanics JR-801 in Example 1, Titanics JR-600E (titanium oxide, isoelectric point: pH 8.0, oil absorption: 21, manufactured by Teika Co., Ltd.) was used. Otherwise in the same manner as in Example 1, an aqueous white pigment composition having a pH of 7.2 was obtained.
【００１９】比較例２ 実施例１においてチタニックスＪＲ−８０１の代わり
に、チタニックスＪＲ−８０５（酸化チタン、等電点：
６．０、吸油量：２２、テイカ（株）製）を用いた他
は、実施例１と同様になして、ｐＨが７．２の水性白色
顔料組成物を得た。Comparative Example 2 Instead of Titanics JR-801 in Example 1, Titanics JR-805 (titanium oxide, isoelectric point:
An aqueous white pigment composition having a pH of 7.2 was obtained in the same manner as in Example 1 except that 6.0, oil absorption: 22, Teika Co., Ltd. was used.
【００２０】比較例３ 実施例１においてケルザンＡＲ３重量％水溶液の代わり
に、ＰＥＯ１５（ポリエチレンオキサイド、製鉄化学
（株）製）３重量％水溶液を用いた他は、実施例１と同
様になして、ｐＨが７．２の水性白色顔料組成物を得
た。Comparative Example 3 The same procedure as in Example 1 was repeated except that a 3 wt% aqueous solution of PEO15 (polyethylene oxide, manufactured by Iron and Steel Chemical Co., Ltd.) was used in place of the Kerzan AR 3 wt% aqueous solution in Example 1. An aqueous white pigment composition having a pH of 7.2 was obtained.
【００２１】比較例４ 実施例１においてケルザンＡＲ３重量％の代わりに、Ｈ
ＰＣ−Ｈ（ヒドロキシプロピルセルロース、日本曹達
（株）製）３％水溶液を用いた他は、実施例１と同様に
なして、ｐＨが７．４の水性白色顔料組成物を得た。Comparative Example 4 Instead of 3% by weight of Kelzan AR in Example 1, H
An aqueous white pigment composition having a pH of 7.4 was obtained in the same manner as in Example 1 except that a 3% aqueous solution of PC-H (hydroxypropyl cellulose, manufactured by Nippon Soda Co., Ltd.) was used.
【００２２】以上、実施例１〜３及び比較例１〜４で得
た水性白色顔料組成物を用いて、再分散性試験及び沈降
分離試験を実施した。結果を表１に示す。Using the aqueous white pigment compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 4, the redispersibility test and the sedimentation test were carried out. The results are shown in Table 1.
【００２３】[0023]
【表１】 [Table 1]
【００２４】再分散性試験：水性白色顔料組成物を、ネ
ジ口瓶（Ｓ−５、日電理化硝子（株）製）に５０ｍｍ採
取し、８ｍｍφの鉄製ボールを１個入れ、密栓をしたま
ま５０℃にて３ヶ月放置した後、ネジ口瓶を振り、ボー
ルが動くまでの回数を測定した。Redispersibility test: 50 mm of the aqueous white pigment composition was put in a screw cap bottle (S-5, manufactured by Niden Rika Glass Co., Ltd.), one 8 mmφ iron ball was put therein, and it was sealed with a cap 50. After left at 3 ° C. for 3 months, the screw cap bottle was shaken and the number of times until the ball moved was measured.
【００２５】沈降分離試験：水性白色顔料組成物を、ネ
ジ口瓶（Ｓ−５、日電理化硝子（株）製）に５０ｍｍ採
取し、８ｍｍφの鉄製ボールを１個入れ、密栓をしたま
ま５０℃にて放置し、分離層の高さを１ヶ月毎に測定す
るSedimentation separation test: The aqueous white pigment composition was sampled in a screw cap bottle (S-5, manufactured by Niden Rika Glass Co., Ltd.) for 50 mm, one iron ball of 8 mmφ was placed therein, and the temperature was kept at 50 ° C. with a tight stopper. Let stand and measure the height of the separation layer once a month
【００２６】[0026]
【発明の効果】以上、詳細に説明したように、本発明に
係る水性白色顔料組成物は、酸化チタンの沈降分離が小
さく、しかもその沈殿がハードケーキ化せず、再分散性
が良好であるという効果を有している。尚、溶剤として
水を用いているので、人体に対する毒性、中毒性がな
く、例えば、室内などのような密閉した場所で使用して
も安全である。As described above in detail, the aqueous white pigment composition according to the present invention has a small precipitation separation of titanium oxide, does not form a hard cake, and has a good redispersibility. Has the effect. Since water is used as the solvent, it has no toxicity or toxicity to the human body and is safe to use in a sealed place such as a room.
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【手続補正書】[Procedure amendment]
【提出日】平成６年１１月１日[Submission date] November 1, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Name of item to be corrected] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】[0015]
【実施例】 実施例１ チタニックスＪＲ−８０１ ５０．０重量部 ケルザンＡＲの３重量％水溶液 １５．０重量部 水 ３０．０重量部 ヘキサメタリン酸ソーダの２５％水溶液 １．３重量部 ケルザンＡＲの３重量％水溶液を除く上記成分をボール
ミルにて２４時間分散処理後、ターボミキサーでケルザ
ンＡＲの３重量％水溶液を混合し、ｐＨが７．２の水性
白色顔料組成物を得た。Example 1 Titanics JR-801 50.0 parts by weight 3% by weight aqueous solution of Kelzan AR 15.0 parts by weight water 30.0 parts by weight 25% aqueous solution of sodium hexametaphosphate 1.3 parts by weight Kelzan AR The above components except the 3 wt% aqueous solution were dispersed in a ball mill for 24 hours, and then mixed with a 3 wt% aqueous solution of Kerzan AR using a turbo mixer to obtain an aqueous white pigment composition having a pH of 7.2.
Claims (1)
点がｐＨ７以下の酸化チタンと、キサンタンガムと、水
とを少なくとも含む水性白色顔料組成物。1. An aqueous white pigment composition containing at least 30 (g / 100 g) of oil absorption and titanium oxide having an isoelectric point of pH 7 or less, xanthan gum, and water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32323793A JPH07150083A (en) | 1993-11-29 | 1993-11-29 | Aqueous white pigment composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32323793A JPH07150083A (en) | 1993-11-29 | 1993-11-29 | Aqueous white pigment composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07150083A true JPH07150083A (en) | 1995-06-13 |
Family
ID=18152540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32323793A Pending JPH07150083A (en) | 1993-11-29 | 1993-11-29 | Aqueous white pigment composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07150083A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08231916A (en) * | 1995-02-22 | 1996-09-10 | Pentel Kk | Water-based white pigment ink for ball-point pen |
| JP2002212055A (en) * | 2001-01-16 | 2002-07-31 | Tsumura & Co | Liquid bathing agent composition |
| JP2011051927A (en) * | 2009-09-01 | 2011-03-17 | Sunstar Inc | Composition for oral cavity |
| JP2012233148A (en) * | 2011-04-20 | 2012-11-29 | Mitsui Chemicals Inc | Pigment for aqueous ink |
| WO2018083824A1 (en) * | 2016-11-04 | 2018-05-11 | ぺんてる株式会社 | Ink composition, writing instrument, and method for producing ink composition |
-
1993
- 1993-11-29 JP JP32323793A patent/JPH07150083A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08231916A (en) * | 1995-02-22 | 1996-09-10 | Pentel Kk | Water-based white pigment ink for ball-point pen |
| JP2002212055A (en) * | 2001-01-16 | 2002-07-31 | Tsumura & Co | Liquid bathing agent composition |
| JP4499929B2 (en) * | 2001-01-16 | 2010-07-14 | ツムラライフサイエンス株式会社 | Liquid bath composition |
| JP2011051927A (en) * | 2009-09-01 | 2011-03-17 | Sunstar Inc | Composition for oral cavity |
| JP2012233148A (en) * | 2011-04-20 | 2012-11-29 | Mitsui Chemicals Inc | Pigment for aqueous ink |
| WO2018083824A1 (en) * | 2016-11-04 | 2018-05-11 | ぺんてる株式会社 | Ink composition, writing instrument, and method for producing ink composition |
| WO2018083782A1 (en) * | 2016-11-04 | 2018-05-11 | ぺんてる株式会社 | Ink composition, writing instrument, and method for producing ink composition |
| JPWO2018083824A1 (en) * | 2016-11-04 | 2019-09-19 | ぺんてる株式会社 | Ink composition, writing instrument, and method for producing ink composition |
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