JP4297526B2 - Ink composition for pigment marker - Google Patents

Description

（５） 前記ポリエーテル・エステルアミン塩の含有量が、インキ組成物全量に対して０．１〜１０重量％である請求項１に記載の顔料マーカー用インキ組成物。
（６） 前記ポリエーテル・エステルアミン塩の含有量が、インキ組成物全量に対して０．１〜１０重量％である請求項２に記載の顔料マーカー用インキ組成物。
（７） 前記ポリエーテル・エステルアミン塩の含有量が、インキ組成物全量に対して０．１〜１０重量％である請求項３に記載の顔料マーカー用インキ組成物。
（８） 前記ポリエーテル・エステルアミン塩の含有量が、インキ組成物全量に対して０．１〜１０重量％である請求項４に記載の顔料マーカー用インキ組成物。
（９） 酸化チタンの含有量が、インキ組成物全量に対して５〜６０重量％である請求項１〜８の何れか一つに記載の顔料マーカー用インキ組成物。
【０００８】
【発明の実施の形態】
以下に、本発明の実施の形態を詳しく説明する。
本発明の顔料マーカー用インキ組成物は、酸化チタン、樹脂及び該樹脂を溶解する有機溶剤からなる顔料マーカー用インキ組成物において、ポリエーテル・エステルアミン塩を含有することを特徴とするものである。
【０００９】
本発明に用いるポリエーテル・エステルアミン塩は、酸化チタン、樹脂及び該樹脂を溶解する有機溶剤からなる顔料マーカー用インキ組成物中に含有させることにより、長期間未使用状態で放置された場合に酸化チタンのケーキングが起ってもボール撹拌が容易となり、再分散等に優れた作用を有するものとなる（この点等に関しては更に実施例等で説明する）。
【００１０】
本発明に用いるポリエーテル・エステルアミン塩として、例えば、下記一般式（Ｉ）〜（ＩＶ）から選択される化合物の１種又は２種以上の混合物が挙げられる。
Ｒ_１−（ＣＨ_２ＣＨ_２Ｏ）ｎ−ＯＳＯ_３ＮＨ_４………（Ｉ）
Ｒ_２−（ＣＨ_２ＣＨ_２Ｏ）ｎ−ＯＣＯＮＨ_４ ………（II）
Ｒ_３−（ＣＨ_２ＣＨ_２Ｏ）ｎ−ＯＰＯ_３ＮＨ_４………（III）
〔上記式（Ｉ）〜（III）中のＲ_１〜Ｒ_３は、夫々炭素数１〜４のアルキル基又は水素を示し、ｎは、夫々４５〜５００の整数である。〕
【００１１】
【化３】

【００１２】
具体的なポリエーテル・エステルアミン塩としては、
例えば、ＣＨ_３（ＣＨ_２ＣＨ_２Ｏ）ｎ−ＯＳＯ_３ＮＨ_４、
ＣＨ_３（ＣＨ_２ＣＨ_２Ｏ）ｎ−ＯＣＯＮＨ_４、
ＣＨ_３（ＣＨ_２ＣＨ_２Ｏ）ｎ−ＯＰＯ_３ＮＨ_４
等を挙げることができ、ｎはいづれも１８０〜３５０の整数（分布を有するもの）であり、特に好ましくは、ｎはいづれも２５０の整数であることが望ましい。これらのポリエーテル・エステルアミン塩の分子量は、１０００〜２００００、好ましくは、５０００〜１５０００である。この分子量を１０００〜２００００の範囲内とすることにより、更にボール撹拌が容易となり、再分散等に優れる顔料マーカー用インキ組成物となる。
【００１３】
また、上記のポリエーテル・エステルアミン塩の含有量としては、インキ組成物全量に対して０．１〜１０重量％、好ましくは、０．２〜５重量％である。
含有量が０．１重量％未満であると、本発明の効果が得られず、１０重量％を越えると、粘度が高くなり、筆記描線にかすれが生じてしまい、好ましくない。
【００１４】
本発明に用いる酸化チタンは、ルチル型、アナターゼ型のいずれでもよいが、隠蔽力の点からルチル型が望ましい。
酸化チタンの含有量については、特に限定はないが、インキ組成物全量に対して、５〜６０重量％の範囲で選ばれる。
酸化チタンの含有量が５重量％未満であると、マーキングペン等による塗布量程度では隠蔽力が得られる程度のインキが塗布できず、６０重量％を越えると、インキの粘度が高くなりすぎ、アクリル繊維体やポリエチレンテレフタレート（ＰＥＴ）繊維体又はこれらの混合繊維体などからなる気孔率６０〜７０％等のペン芯を透過できず、好ましくない。
【００１５】
本発明に用いる有機溶剤としては、例えば、アルコール系溶剤、炭化水素系溶剤、グリコールエーテル系溶剤、芳香族系溶剤、ケトン系溶剤、エステル系溶剤等が挙げられ、これらの溶剤は単独あるいは２種以上混合して使用することができ、その使用量はインキ組成物全量に対して、５〜９０重量％が望ましい。
具体的な溶剤としては、イソブチルアルコール、エタノール、イソプロピルアルコール、メチルシクロヘキサン、トルエン、キシレン、ジプロピレングリコール、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ポリプロピレングリコール、アセトン、メチルイソブチルケトン、メチルエチルケトン、酢酸エチル、酢酸プロピルなどが挙げられる。
【００１６】
本発明に用いる樹脂は、前記溶剤に可溶であればいかなるものでも良く、例えば、ガムロジン、マレイン酸樹脂、アルキッド樹脂、フェノール樹脂、ケトン樹脂、テルペン樹脂、アクリル樹脂、芳香族炭化水素系樹脂、石油樹脂などが挙げられ、これらは単独あるいは２種以上混合して使用でき、その使用量はインキ組成物全量に対して、１〜５０重量％が望ましい。
具体的な樹脂として、ヒタノール１１４０（日立化成（株））、アクリディックＡ−１７２（大日本インキ化学工業（株））、ベッコゾールＥＲ−３３０３（大日本インキ化学工業（株））、エステルガムＡＡＧ（荒川化学工業（株））、マルキードNo６（荒川化学工業（株））、ＹＳポリスターＳ１４５（安原樹脂工業（株））などが挙げられる。
【００１７】
更に、本発明の顔料マーカー用インキ組成物には、前記成分以外に、必要に応じて、無機顔料、有機顔料、アゾ系、アントラキノン系、フタロシアニン系等の染料や、アニオン系、ノニオン系、カチオン系などの界面活性剤、酸化ポリエチレン系、重合植物油などの粘度調整剤などの各種添加剤を配合してもかまわない。
【００１８】
本発明の顔料マーカー用インキ組成物は、上記各配合成分を、ボールミル、ビーズミル、サンドミル、ロールミル、ホモミキサー、ディゾルバー、超音波などの顔料分散機の中から最適な手段を選択して、分散することにより製造することができる。なお、上述のポリエーテル・エステルアミン塩は、分散前、分散後に配合しても構わないものである。
【００１９】
【実施例】
次に、実施例及び比較例に基づき本発明を更に詳細に説明するが、本発明は、これらの実施例によって限定されるものではない。
【００２０】
〔実施例１〕
酸化チタン“ＪＲ−７０１”（テイカ（株）製） ３５重量％
ＣＨ_３（ＣＨ_２ＣＨ_２Ｏ）ｎ−ＯＳＯ_３ＮＨ_４〔ｎ＝２５０〕 ２重量％
アルキッド樹脂“ベッコゾールＰ−４７０−７０”
（大日本インキ（株））製 ８重量％
テルペンフェノール樹脂“ＹＳポリスターＴ−１１５”
（ヤスハラケミカル（株））製 １５重量％
キシレン ４０重量％
上記成分中、酸化チタン、ベッコゾール、ポリエーテル・エステルアミン塩、キシレンの一部を順次加え、撹拌機で２時間のプレミキシングを行い、ビーズミルにて分散処理を行い、ミルベースを作り、その後、テルペンフェノール、残りのキシレンを加え、撹拌機にて撹拌し、顔料マーカー用インキ組成物となる白インキを調製した。
【００２１】
〔比較例１〕
実施例１において、ポリエーテル・エステルアミン塩を配合せずにキシレンを４２重量％とした以外は、実施例１と同様に調製した。
【００２２】
〔実施例２〕
酸化チタン“ＪＲ−７０１”（テイカ（株）製） ３５重量％
ＣＨ_３（ＣＨ_２ＣＨ_２Ｏ）ｎ−ＯＣＯＮＨ_４〔ｎ＝２５０〕 ２重量％
アルキッド樹脂“ベッコゾールＰ−４７０−７０”
（大日本インキ（株））製 ８重量％
テルペンフェノール樹脂“ＹＳポリスターＴ−１１５”
（ヤスハラケミカル（株））製 １５重量％
キシレン ４０重量％
上記成分中、酸化チタン、ベッコゾール、ポリエーテル・エステルアミン塩、キシレンの一部を順次加え、撹拌機で２時間のプレミキシングを行い、ビーズミルにて分散処理を行い、ミルベースを作り、その後、テルペンフェノール、残りのキシレンを加え、撹拌機にて撹拌し、顔料マーカー用インキ組成物となる白インキを調製した。
【００２３】
〔比較例２〕
実施例２において、ポリエーテル・エステルアミン塩を配合せずにキシレンを４２重量％とした以外は、実施例１と同様に調製した。
【００２４】
〔実施例３〕
酸化チタン“Ｒ−９３１”（デュポンジャパン（株）製） ３５重量％
ＣＨ_３（ＣＨ_２ＣＨ_２Ｏ）ｎ−ＯＰＯ_３ＮＨ_４〔ｎ＝２５０〕 ２重量％
アルキッド樹脂“ベッコゾールＯＤＥ−２３０−７０”
（大日本インキ（株））製 ８重量％
ロジン変性マレイン酸樹脂“マルキード３３号”
（荒川化学工業（株））製 ５重量％
キシレン ３８重量％
染料“オイルイエロー＃１０５”（オリエント化学（株））製 ２重量％
上記成分中、酸化チタン、ベッコゾール、ポリエーテル・エステルアミン塩、キシレンの一部を順次加え、撹拌機で２時間のプレミキシングを行い、ビーズミルにて分散処理を行い、ミルベースを作り、その後、ロジン変性マレイン酸樹脂、残りのキシレンを加え、撹拌機にて撹拌し、白インキを調製した。次いで、染料を加え、撹拌機を用いて顔料マーカー用インキ組成物となる黄色インキを調製した。
【００２５】
〔比較例３〕
実施例２において、ポリエーテル・エステルアミン塩を配合せずにキシレンを４０重量％とした以外は、同様に製造し黄色インキを調製した。
【００２６】
〔実施例４〕
酸化チタン“Ｒ−９３１”（デュポンジャパン（株）製） ３５重量％
【化４】

アルキッド樹脂“ベッコゾールＯＤＥ−２３０−７０”
（大日本インキ（株））製 ８重量％
ロジン変性マレイン酸樹脂“マルキード３３号”
（荒川化学工業（株））製 ５重量％
キシレン ３８重量％
染料“オイルイエロー＃１０５”（オリエント化学（株））製 ２重量％
上記成分中、酸化チタン、ベッコゾール、ポリエーテル・エステルアミン塩、キシレンの一部を順次加え、撹拌機で２時間のプレミキシングを行い、ビーズミルにて分散処理を行い、ミルベースを作り、その後、ロジン変性マレイン酸樹脂、残りのキシレンを加え、撹拌機にて撹拌し、白インクを調製した。次いで、染料を加え、撹拌機を用いて顔料マーカー用インキ組成物となる黄色インキを調製した。
【００２７】
〔比較例４〕
実施例４において、ポリエーテル・エステルアミン塩を配合せずにキシレンを４０重量％とした以外は、同様に製造し黄色インキを調製した。
【００２８】
上記で得られた実施例１〜４及び比較例１〜４のインキをバルブ機構を備えたマーキングペン〔軸体：内径φ１４ｍｍ（外径φ１５ｍｍ）、長さ１０ｃｍのアルミニウム管製、ペン芯：アクリル繊維体、φ４．５ｍｍ、長さ２１．５ｍｍ、気孔率６０％、撹拌ボール：直径φ８ｍｍ、２個）に約６．２ｃｃに充填し、１ケ月室温下で静置した後、手による振とうを行い、撹拌ボールが動き出すまでの回数で評価を行った。
これらの結果を下記表１に示す。
【００２９】
【表１】

【００３０】
上記表１の結果から明らかなように、本発明範囲となるポリエーテル・エステルアミン塩を含有した実施例１〜４は、本発明の範囲外となる比較例１〜４に較べて、撹拌ボールが動き出すまでの回数がきわめて少なく、ボール撹拌が容易になり、再分散性に優れていることが判明した。
【００３１】
【発明の効果】
本発明によれば、ポリエーテル・エステルアミン塩の効果により、ボール撹拌が容易になり、再分散性に優れ、長時間保存後も沈降物が生じにくいインキが得られ、これを用いて安定した描線を得ることができる顔料マーカー用インキ組成物が提供される。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to an ink composition for pigment marker which has titanium oxide or titanium oxide and other colorant dispersed in a vehicle and is opaque at the time of writing and has a concealing property, and more specifically, titanium oxide in liquid. The present invention relates to an ink composition for a pigment marker which has been improved so as to prevent sedimentation, separation, and redispersion with a stirring ball after sedimentation.
[0002]
[Prior art]
Conventionally, an ink formed by dispersing titanium oxide or titanium oxide and another colorant in a vehicle has been used for a marking pen.
In general, the mechanism of these marking pens supplies ink to a pen body such as a fiber bundling body or a hollow plastic rod through an ink storage unit containing a hard sphere serving as a stirring ball and a valve mechanism. .
In order for ink to flow out from these pen bodies and ink with sufficient concealment properties to come out, the viscosity must be as low as 30 mPa · sec or less.
[0003]
It is very difficult to disperse and stabilize titanium oxide having a large specific gravity in such a low-viscosity vehicle. That is, after ink adjustment, titanium oxide having a large specific gravity settles and separates in a short time.
Therefore, in the marking pen provided with the above mechanism, a hard ball having a diameter of about 8 mm is previously placed in the ink storage unit, and when the marking pen is used, the marking pen is shaken to stir the ink by the action of the hard ball, This is intended to redisperse titanium oxide.
[0004]
However, when the marking pen is left unused for a long period of time, caking of the precipitated titanium oxide occurs, and the hard ball is buried in the cake and, when redispersed, it is necessary to shake the marking pen considerably. There is a problem.
Furthermore, if the titanium oxide cake collected at the bottom is hard, it is necessary to shake the marking pen further, and it is difficult to move the ball.
[0005]
In order to solve such problems, for example, JP-A-60-190480 discloses a pigment marker using a pigment obtained by surface-treating a pigment such as titanium oxide having a polar surface with a phosphate ester. Ink compositions are known, and JP-A-6-107964 discloses titanium oxide obtained by subjecting the surface of titanium oxide to alumina treatment, a (meth) acrylic resin having a carboxyl group, and an alcohol solvent such as ethanol. There is known a white pigment composition containing the above.
However, such conventional ink compositions for pigment markers still cause titanium oxide caking when the marking pen is left unused for a long period of time. At present, there is a problem that is necessary, and it is desired that an ink composition for a pigment marker, which can easily be stirred with a ball even when titanium oxide caking occurs and is excellent in redispersion, is desired.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to solve this problem in view of the above-described conventional problems and the present situation. In an ink composition for a pigment marker comprising titanium oxide, a resin, and an organic solvent for dissolving the resin, An object of the present invention is to provide an ink composition for a pigment marker which is easy to stir the ball even if titanium oxide caking occurs when left in use, and is excellent in redispersion.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-described conventional problems and the present situation, the present inventors can achieve the above object by using a specific polyether ester salt in an ink composition for a pigment marker. Based on this finding, the present invention has been completed. That is, the ink composition for a pigment marker of the present invention exists in the following (1) to (9).
(1) A pigment marker characterized in that it contains at least a polyether ester amine salt of the following general formula (I) in a pigment marker ink composition comprising titanium oxide, a resin, and an organic solvent that dissolves the resin. Ink composition.
_{R 1 - (CH 2 CH 2} O) n-OSO 3 NH 4 ......... (I)
[R ₁ in Formula (I) represents an alkyl group having 1 to 4 carbon atoms or hydrogen, and n is an integer of 45 to 500. ]
(2) A pigment marker comprising at least a polyether ester amine salt having the following general formula (II) in a pigment marker ink composition comprising titanium oxide, a resin and an organic solvent for dissolving the resin Ink composition.
_{R 2 - (CH 2 CH 2} O) n-OCONH 4 ......... (II)
[R ₂ in Formula (II) represents an alkyl group having 1 to 4 carbon atoms or hydrogen, and n is an integer of 45 to 500. ]
(3) A pigment marker ink composition comprising titanium oxide, a resin, and an organic solvent that dissolves the resin, containing at least a polyether ester amine salt having a molecular weight of 5000 to 20000 comprising the following general formula (III) An ink composition for a pigment marker characterized by the above.
_{R 3 - (CH 2 CH 2} O) n-OPO 3 NH 4 ......... (III)
[R ₃ in Formula (III) represents an alkyl group having 1 to 4 carbon atoms or hydrogen, and n is an integer of 45 to 500. ]
(4) A pigment marker ink composition comprising titanium oxide, a resin, and an organic solvent that dissolves the resin, and at least a polyether ester amine salt having a molecular weight of 5000 to 20000 comprising the following general formula (IV): An ink composition for a pigment marker characterized by the above.
[Chemical formula 2]

(5) The ink composition for a pigment marker according to claim 1, wherein the content of the polyether ester amine salt is 0.1 to 10% by weight based on the total amount of the ink composition.
(6) The pigment marker ink composition according to claim 2, wherein the content of the polyether ester amine salt is 0.1 to 10% by weight based on the total amount of the ink composition.
(7) The pigment marker ink composition according to claim 3, wherein the content of the polyether ester amine salt is 0.1 to 10% by weight based on the total amount of the ink composition.
(8) The pigment marker ink composition according to claim 4, wherein the content of the polyether ester amine salt is 0.1 to 10% by weight based on the total amount of the ink composition.
(9) The pigment marker ink composition according to any one of claims 1 to 8, wherein the titanium oxide content is 5 to 60% by weight based on the total amount of the ink composition.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
The ink composition for a pigment marker of the present invention is a pigment marker ink composition comprising titanium oxide, a resin, and an organic solvent that dissolves the resin, and contains a polyether esteramine salt. .
[0009]
The polyether ester amine salt used in the present invention is contained in an ink composition for a pigment marker composed of titanium oxide, a resin and an organic solvent for dissolving the resin, and when left unused for a long period of time. Even if titanium oxide caking occurs, the ball can be easily stirred and has an excellent effect on redispersion and the like (this will be further described in Examples and the like).
[0010]
Examples of the polyether ester amine salt used in the present invention include one or a mixture of two or more compounds selected from the following general formulas (I) to (IV).
_{R 1 - (CH 2 CH 2} O) n-OSO 3 NH 4 ......... (I)
_{R 2 - (CH 2 CH 2} O) n-OCONH 4 ......... (II)
_{R 3 - (CH 2 CH 2} O) n-OPO 3 NH 4 ......... (III)
[R _{1 to} R ₃ in the above formulas (I) to (III) each represent an alkyl group having 1 to 4 carbon atoms or hydrogen, and n is an integer of 45 to 500, respectively. ]
[0011]
[Chemical 3]

[0012]
As concrete polyether esteramine salt,
For _{example, CH 3 (CH 2 CH 2} O) n-OSO 3 NH 4,
_{CH 3 (CH 2 CH 2 O} ) n-OCONH 4,
_{CH 3 (CH 2 CH 2 O} ) n-OPO 3 NH 4
N is an integer of 180 to 350 (having a distribution), and particularly preferably, n is an integer of 250. The molecular weight of these polyether ester amine salts is 1000-20000, preferably 5000-15000. By setting the molecular weight within the range of 1000 to 20000, the ball stirring is further facilitated, and the pigment marker ink composition is excellent in redispersion and the like.
[0013]
The content of the polyether ester amine salt is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total amount of the ink composition.
If the content is less than 0.1% by weight, the effects of the present invention cannot be obtained, and if it exceeds 10% by weight, the viscosity increases and the writing lines are blurred, which is not preferable.
[0014]
The titanium oxide used in the present invention may be either a rutile type or an anatase type, but a rutile type is desirable in terms of hiding power.
Although there is no limitation in particular about content of a titanium oxide, it selects in the range of 5 to 60 weight% with respect to the ink composition whole quantity.
If the content of titanium oxide is less than 5% by weight, an ink that can provide a hiding power cannot be applied at a coating amount with a marking pen or the like, and if it exceeds 60% by weight, the viscosity of the ink becomes too high. This is not preferable because it cannot transmit a pen core having a porosity of 60 to 70% made of an acrylic fiber body, a polyethylene terephthalate (PET) fiber body, or a mixed fiber body thereof.
[0015]
Examples of the organic solvent used in the present invention include alcohol solvents, hydrocarbon solvents, glycol ether solvents, aromatic solvents, ketone solvents, ester solvents, and the like. They can be mixed and used, and the amount used is preferably 5 to 90% by weight based on the total amount of the ink composition.
Specific solvents include isobutyl alcohol, ethanol, isopropyl alcohol, methylcyclohexane, toluene, xylene, dipropylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, polypropylene glycol, acetone, methyl isobutyl ketone, methyl ethyl ketone. , Ethyl acetate, propyl acetate and the like.
[0016]
The resin used in the present invention may be any resin as long as it is soluble in the solvent. For example, gum rosin, maleic resin, alkyd resin, phenol resin, ketone resin, terpene resin, acrylic resin, aromatic hydrocarbon resin, Petroleum resins and the like can be mentioned, and these can be used alone or in combination of two or more. The amount used is preferably 1 to 50% by weight based on the total amount of the ink composition.
Specific resins include hitanol 1140 (Hitachi Chemical Co., Ltd.), Acridic A-172 (Dainippon Ink Chemical Co., Ltd.), Beckosol ER-3303 (Dainippon Ink Chemical Co., Ltd.), and ester gum AAG. (Arakawa Chemical Industry Co., Ltd.), Marquide No. 6 (Arakawa Chemical Industry Co., Ltd.), YS Polystar S145 (Yasuhara Resin Industry Co., Ltd.) and the like.
[0017]
In addition to the above components, the pigment marker ink composition of the present invention includes, as necessary, dyes such as inorganic pigments, organic pigments, azo series, anthraquinone series, and phthalocyanine series, anionic series, nonionic series, and cationic groups. Various additives such as a surfactant, a viscosity modifier such as a polyethylene oxide and a polymerized vegetable oil may be blended.
[0018]
In the ink composition for a pigment marker of the present invention, each of the above-mentioned blending components is dispersed by selecting an optimum means from among pigment dispersing machines such as a ball mill, a bead mill, a sand mill, a roll mill, a homomixer, a dissolver, and an ultrasonic wave. Can be manufactured. The above-mentioned polyether / ester amine salt may be blended before or after dispersion.
[0019]
【Example】
Next, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to these examples.
[0020]
[Example 1]
Titanium oxide “JR-701” (manufactured by Teika) 35% by weight
_{CH 3 (CH 2 CH 2 O} ) n-OSO 3 NH 4 [n = 250] 2 wt%
Alkyd resin "Beccosol P-470-70"
8% by weight (Dainippon Ink Co., Ltd.)
Terpene phenol resin "YS Polystar T-115"
15% by weight (Yasuhara Chemical Co., Ltd.)
40% by weight of xylene
Add titanium oxide, beccosol, polyether esteramine salt, and xylene in order from the above ingredients, premix for 2 hours with a stirrer, disperse with a bead mill, make a mill base, and then terpene. Phenol and the remaining xylene were added and stirred with a stirrer to prepare a white ink to be an ink composition for a pigment marker.
[0021]
[Comparative Example 1]
Example 1 was prepared in the same manner as in Example 1 except that xylene was changed to 42% by weight without blending the polyether esteramine salt.
[0022]
[Example 2]
Titanium oxide “JR-701” (manufactured by Teika) 35% by weight
_{CH 3 (CH 2 CH 2 O} ) n-OCONH 4 [n = 250] 2 wt%
Alkyd resin "Beccosol P-470-70"
8% by weight (Dainippon Ink Co., Ltd.)
Terpene phenol resin "YS Polystar T-115"
15% by weight (Yasuhara Chemical Co., Ltd.)
40% by weight of xylene
Add titanium oxide, beccosol, polyether esteramine salt, and xylene in order from the above ingredients, premix for 2 hours with a stirrer, disperse with a bead mill, make a mill base, and then terpene. Phenol and the remaining xylene were added and stirred with a stirrer to prepare a white ink to be an ink composition for a pigment marker.
[0023]
[Comparative Example 2]
In Example 2, it was prepared in the same manner as in Example 1 except that xylene was changed to 42% by weight without blending the polyether esteramine salt.
[0024]
Example 3
Titanium oxide “R-931” (manufactured by DuPont Japan) 35% by weight
_{CH 3 (CH 2 CH 2 O} ) n-OPO 3 NH 4 [n = 250] 2 wt%
Alkyd resin "Beccosol ODE-230-70"
8% by weight (Dainippon Ink Co., Ltd.)
Rosin-modified maleic resin “Marquide 33”
5% by weight (Arakawa Chemical Industries)
Xylene 38% by weight
Dye "Oil Yellow # 105" (Orient Chemical Co., Ltd.) 2% by weight
Titanium oxide, beccosol, polyether esteramine salt, and xylene are added in order from the above ingredients, premixed with a stirrer for 2 hours, dispersed in a bead mill, mill base, and then rosin The modified maleic acid resin and the remaining xylene were added and stirred with a stirrer to prepare a white ink. Subsequently, dye was added and the yellow ink used as the pigment marker ink composition was prepared using the stirrer.
[0025]
[Comparative Example 3]
In Example 2, a yellow ink was prepared in the same manner except that xylene was changed to 40% by weight without blending a polyether esteramine salt.
[0026]
Example 4
Titanium oxide “R-931” (manufactured by DuPont Japan) 35% by weight
[Formula 4]

Alkyd resin "Beccosol ODE-230-70"
8% by weight (Dainippon Ink Co., Ltd.)
Rosin-modified maleic resin “Marquide 33”
5% by weight (Arakawa Chemical Industries)
Xylene 38% by weight
Dye "Oil Yellow # 105" (Orient Chemical Co., Ltd.) 2% by weight
Titanium oxide, beccosol, polyether esteramine salt, and xylene are added in order from the above ingredients, premixed with a stirrer for 2 hours, dispersed in a bead mill, mill base, and then rosin The modified maleic resin and the remaining xylene were added and stirred with a stirrer to prepare a white ink. Subsequently, dye was added and the yellow ink used as the pigment marker ink composition was prepared using the stirrer.
[0027]
[Comparative Example 4]
A yellow ink was prepared in the same manner as in Example 4 except that xylene was changed to 40% by weight without blending the polyether esteramine salt.
[0028]
Marking pen equipped with a valve mechanism for the inks of Examples 1 to 4 and Comparative Examples 1 to 4 obtained above [shaft body: inner diameter φ14 mm (outer diameter φ15 mm), length 10 cm made of aluminum tube, pen core: acrylic Fiber body, φ4.5 mm, length 21.5 mm, porosity 60%, stirring ball: diameter φ8 mm, 2 pieces) is filled to about 6.2 cc, left to stand at room temperature for 1 month, and then shaken by hand And evaluated by the number of times until the stirring ball started to move.
These results are shown in Table 1 below.
[0029]
[Table 1]

[0030]
As is apparent from the results of Table 1 above, Examples 1 to 4 containing polyether esteramine salts that are within the scope of the present invention are more stirred balls than Comparative Examples 1 to 4 that are outside the scope of the present invention. It has been found that the number of times until it starts to move is extremely small, ball stirring becomes easy, and redispersibility is excellent.
[0031]
【The invention's effect】
According to the present invention, the effect of the polyether ester amine salt makes it easy to stir the ball, has excellent redispersibility, and gives an ink that does not easily generate precipitates even after long-term storage. An ink composition for a pigment marker capable of obtaining a drawn line is provided.

Claims (9)

A pigment marker ink composition comprising a titanium oxide, a resin, and an organic solvent for dissolving the resin, the pigment marker ink composition comprising at least a polyether esteramine salt having the following general formula (I): object.
_{R 1 - (CH 2 CH 2} O) n-OSO 3 NH 4 ......... (I)
[R ₁ in Formula (I) represents an alkyl group having 1 to 4 carbon atoms or hydrogen, and n is an integer of 45 to 500. ] Ink composition for pigment marker comprising titanium oxide, resin and organic solvent for dissolving said resin, comprising at least a polyether esteramine salt having the following general formula (II): object.
_{R 2 - (CH 2 CH 2} O) n-OCONH 4 ......... (II)
[R ₂ in Formula (II) represents an alkyl group having 1 to 4 carbon atoms or hydrogen, and n is an integer of 45 to 500. ] A pigment marker ink composition comprising titanium oxide, a resin and an organic solvent for dissolving the resin, comprising at least a polyether esteramine salt having a molecular weight of 5000 to 20000 comprising the following general formula (III): An ink composition for a pigment marker.
_{R 3 - (CH 2 CH 2} O) n-OPO 3 NH 4 ......... (III)
[R ₃ in Formula (III) represents an alkyl group having 1 to 4 carbon atoms or hydrogen, and n is an integer of 45 to 500. ] A pigment marker ink composition comprising titanium oxide, a resin and an organic solvent for dissolving the resin, comprising at least a polyether esteramine salt having a molecular weight of 5000 to 20000 comprising the following general formula (IV): An ink composition for a pigment marker.

  2. The ink composition for a pigment marker according to claim 1, wherein the content of the polyether ester amine salt is 0.1 to 10% by weight based on the total amount of the ink composition.   The ink composition for a pigment marker according to claim 2, wherein the content of the polyether ester amine salt is 0.1 to 10% by weight based on the total amount of the ink composition.   The pigment marker ink composition according to claim 3, wherein the content of the polyether ester amine salt is 0.1 to 10% by weight based on the total amount of the ink composition.   The ink composition for a pigment marker according to claim 4, wherein the content of the polyether ester amine salt is 0.1 to 10% by weight based on the total amount of the ink composition.   The pigment marker ink composition according to any one of claims 1 to 8, wherein the content of titanium oxide is 5 to 60% by weight based on the total amount of the ink composition.