JPH09176514A - Organic pigment having modified surface and production thereof - Google Patents
Organic pigment having modified surface and production thereofInfo
- Publication number
- JPH09176514A JPH09176514A JP28232596A JP28232596A JPH09176514A JP H09176514 A JPH09176514 A JP H09176514A JP 28232596 A JP28232596 A JP 28232596A JP 28232596 A JP28232596 A JP 28232596A JP H09176514 A JPH09176514 A JP H09176514A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- gas
- fluorine
- polar
- treatment
- 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
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は表面改質有機顔料お
よびその製造方法、特に分散性に優れた表面改質有機顔
料およびその製造方法に関する。本発明の表面改質有機
顔料は、印刷インキ、筆記用インキ、塗料、記録材料、
化粧品、顔料樹脂捺染剤等として特に有用である。TECHNICAL FIELD The present invention relates to a surface-modified organic pigment and a method for producing the same, and more particularly to a surface-modified organic pigment having excellent dispersibility and a method for producing the same. The surface-modified organic pigment of the present invention is a printing ink, a writing ink, a paint, a recording material,
It is particularly useful as a cosmetic, a pigment resin printing agent, and the like.
【0002】[0002]
【従来の技術】有機顔料は、印刷用インキ、筆記用イン
キ、塗料全般、記録材料、化粧品、捺染剤の着色材等と
して使用される。水および有機溶剤に不溶ないし難溶で
ある点で染料と区別され、例えば、油性塗料ではボイル
油その他の乾燥性油類、水性インキでは粘着剤等を含有
する水溶液中に分散させて用いられる。顔料を保持する
これらの乾燥性油類や水溶液はビヒクルあるいは展色剤
と呼ばれる。2. Description of the Related Art Organic pigments are used as printing inks, writing inks, paints in general, recording materials, cosmetics, and colorants for textile printing agents. It is distinguished from dyes in that it is insoluble or sparingly soluble in water and organic solvents. For example, it is used by being dispersed in an aqueous solution containing boil oil or other drying oils in oil-based paints and adhesives in water-based inks. These drying oils and aqueous solutions that retain the pigment are called vehicles or color spreaders.
【0003】顔料を含有する製品の特性は、ビヒクル中
における顔料粒子の分散性に大きく依存する。しかし、
有機顔料の表面は一般に親水性に劣るため、水性イン
キ、水性塗料などでは長期的な分散安定性を保つことが
難しい。この結果、筆記用具が目づまりを起こしたり、
塗料中の顔料が凝集沈降し色むらが生じる等の問題があ
った。かかる問題を解決するためには顔料粒子表面の親
水性の改善が重要と考えられる。The properties of pigment-containing products are highly dependent on the dispersibility of the pigment particles in the vehicle. But,
Since the surface of an organic pigment is generally inferior in hydrophilicity, it is difficult to maintain long-term dispersion stability with water-based inks and water-based paints. As a result, the writing instrument may cause clogging,
There is a problem that the pigment in the paint is aggregated and settled to cause color unevenness. In order to solve this problem, it is considered important to improve the hydrophilicity of the pigment particle surface.
【0004】顔料表面に親水性を付与する方法として以
下の方法が従来提案されている。例えば、特開平6−8
0901号公報では、フッ素ガスで顔料を処理し分散性
の改良を行なっている。しかし、有機顔料は発色団等と
して種々の官能基や不飽和結合を有する。このため、本
来反応性に富んだフッ素ガスが顔料粒子の表面と接触す
ると、顔料化合物の種類によってはC−F共有結合が形
成されて親水性がむしろ低下したり、或いは強い電子吸
引基であるフッ素原子が直接結合するために顔料の色相
が変化するなどの問題がある。また、フッ素ガスによる
処理は反応の進行が速いため、フッ素ガスの導入部近く
では過度にフッ素化反応が進み、著しい場合には分解反
応が起こり変色の原因になるカーボンやタールが生じ、
他方、害導入部から離れた部分では顔料表面が十分に改
質されない実質的に未反応の粒子が残留する場合があ
る。The following methods have been conventionally proposed as methods for imparting hydrophilicity to the surface of a pigment. For example, JP-A-6-8
In 0901, the pigment is treated with fluorine gas to improve the dispersibility. However, organic pigments have various functional groups and unsaturated bonds as chromophores. Therefore, when the fluorine gas, which is originally highly reactive, comes into contact with the surface of the pigment particles, a C—F covalent bond is formed depending on the type of the pigment compound to lower the hydrophilicity, or it is a strong electron withdrawing group. There is a problem that the hue of the pigment is changed because the fluorine atom is directly bonded. Further, since the treatment with fluorine gas progresses rapidly, the fluorination reaction proceeds excessively in the vicinity of the introduction portion of the fluorine gas, and when it is remarkable, a decomposition reaction occurs and carbon or tar that causes discoloration occurs,
On the other hand, there are cases where substantially unreacted particles that do not sufficiently modify the surface of the pigment remain in the portion away from the harm-introducing portion.
【0005】[0005]
【発明が解決しようとする課題】本発明は、色相や耐光
性、耐候性等、顔料本来の特性を害することなく、簡便
にかつ処理対象の顔料粉体の全体に亘って均一に親水性
を付与する表面処理方法を提供する。また、かかる処理
方法により製造される、分散性等に優れた特性を有する
表面改質有機顔料を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention provides a simple and uniform hydrophilic property over the entire pigment powder to be treated, without impairing the original properties of the pigment such as hue, light resistance and weather resistance. Provided is a surface treatment method to be applied. Another object of the present invention is to provide a surface-modified organic pigment produced by such a treatment method and having excellent properties such as dispersibility.
【0006】[0006]
【課題解決の手段】本発明は、有機顔料の表面に予め親
水基を誘導する極性分子を付着させた後にフッ素ガスで
処理することにより、フッ素ガスの吸着を緩和し、顔料
の発色性を損なわずに親水性を改善し、その結果として
有機顔料の分散安定性を顕著に高めたものである。According to the present invention, a polar molecule that induces a hydrophilic group is attached to the surface of an organic pigment in advance and then treated with fluorine gas to reduce the adsorption of fluorine gas and impair the color developability of the pigment. Without improving the hydrophilicity, the dispersion stability of the organic pigment is remarkably enhanced.
【0007】すなわち、本発明によれば以下の表面改質
有機顔料およびその製造方法が提供される。 (1)顔料を極性ガスに接触させて顔料表面に極性ガス
を吸着させた後に、フッ素ガスによって表面処理したこ
とを特徴とする表面改質有機顔料。 (2)顔料を極性ガスに接触させて顔料表面に極性ガス
を吸着させた後に、フッ素ガスによって表面処理するこ
とを特徴とする表面改質有機顔料の製造方法。 (3)不活性ガスで25〜100vol%に希釈した極性
ガスに顔料を接触させて顔料粒子表面に該極性ガスを吸
着させた後、該顔料を0.01〜30vol%に希釈したフ
ッ素ガスに接触させる上記(2)に記載の表面改質有機顔
料の製造方法。 (4)極性ガスの吸着を−80〜50℃で行なう上記
(2)または(3)に記載の表面改質有機顔料の製造方法。 (5)フッ素ガスによる処理を−80〜300℃で行な
う上記(2)〜(4)のいずれかに記載の表面改質有機顔料の
製造方法。 (6)極性ガスがC、S、Nの少なくなくとも1種類の
元素とOとを含む親水基を形成する基を有する化合物で
ある上記(2)〜(5)のいずれかに記載の表面改質有機顔料
の製造方法。 (7)フッ素ガスによる処理の後、顔料表面に残留する
酸性成分を揮発ないし中和して除去する上記(6)に記載
の製造方法。That is, according to the present invention, the following surface-modified organic pigment and a method for producing the same are provided. (1) A surface-modified organic pigment characterized in that the pigment is brought into contact with a polar gas to adsorb the polar gas on the surface of the pigment, and then the surface is treated with a fluorine gas. (2) A method for producing a surface-modified organic pigment, which comprises contacting a pigment with a polar gas to adsorb the polar gas on the surface of the pigment, and then performing surface treatment with a fluorine gas. (3) A pigment is brought into contact with a polar gas diluted to 25 to 100 vol% with an inert gas to adsorb the polar gas on the surface of the pigment particles, and then the pigment is diluted to 0.01 to 30 vol% with fluorine gas. The method for producing a surface-modified organic pigment according to (2) above, which comprises contacting. (4) Adsorption of polar gas at −80 to 50 ° C.
The method for producing the surface-modified organic pigment according to (2) or (3). (5) The method for producing a surface-modified organic pigment according to any one of (2) to (4) above, wherein the treatment with fluorine gas is performed at -80 to 300 ° C. (6) The surface according to any one of (2) to (5) above, wherein the polar gas is a compound having a group that forms a hydrophilic group containing at least one element of C, S and N and O. Method for producing modified organic pigment. (7) The production method according to (6) above, wherein after the treatment with the fluorine gas, the acidic component remaining on the surface of the pigment is volatilized or neutralized to be removed.
【0008】[0008]
【発明の実施の形態】本発明の有機顔料の製造方法は、
極性ガスを顔料粒子の表面に吸着させる第1工程と、第
1工程で得られた顔料をさらにフッ素ガスで処理する第
2工程とを有し、必要であれば第2工程で生じた粒子表
面の酸性成分を中和または除去する第3工程をさらに含
むものである。BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an organic pigment of the present invention comprises:
The particle surface generated in the second step, which has a first step of adsorbing a polar gas on the surface of the pigment particles, and a second step of further treating the pigment obtained in the first step with fluorine gas. It further comprises a third step of neutralizing or removing the acidic component of.
【0009】(I)第1工程(極性ガスの吸着) 本処理工程では、顔料を極性ガスに接触させて顔料表面
に極性ガスを吸着させる。本工程で使用する極性ガスと
は、フッ素と結合して親水基を形成する常温付近で気体
の化合物(一般的には極性化合物)を云う。かかる化合物
としては、C、S、Nの少なくなくとも1種類の元素と
Oとを構成元素として含むものが適当である。極性ガス
の具体例としてはCO、CO2 、SO2 、NO2などが
挙げられる。なお、NO2の親水化機構は不明である
が、同様の効果が得られるので本発明では極性ガスに含
む。 (I) First Step (Adsorption of Polar Gas) In this treatment step, the pigment is brought into contact with the polar gas to adsorb the polar gas on the surface of the pigment. The polar gas used in this step refers to a compound (generally a polar compound) that is a gas around normal temperature and forms a hydrophilic group by bonding with fluorine. As such a compound, a compound containing at least one element of C, S, and N and O as constituent elements is suitable. Specific examples of the polar gas include CO, CO 2 , SO 2 , NO 2 and the like. Although the mechanism for making NO 2 hydrophilic is unknown, it is included in the polar gas in the present invention because the same effect can be obtained.
【0010】本処理工程においては極性ガスを顔料粉体
の表面全体に亘って均一に吸着させることが重要であ
る。このため、本工程の処理温度は−80℃〜50℃が
適当であり、好ましくは−30℃〜40℃、より好まし
くは−20℃〜30℃の範囲で行なう。処理温度が50
℃より高いと極性ガスの吸着量が減少し、フッ素ガスの
吸着を緩和する効果が不十分になる場合がある。−80
℃以下に冷却することは経済上好ましくない。In this treatment step, it is important that the polar gas is uniformly adsorbed on the entire surface of the pigment powder. Therefore, the treatment temperature in this step is suitably -80 ° C to 50 ° C, preferably -30 ° C to 40 ° C, and more preferably -20 ° C to 30 ° C. Processing temperature is 50
If the temperature is higher than ° C, the amount of polar gas adsorbed may decrease, and the effect of alleviating the adsorption of fluorine gas may become insufficient. -80
It is economically unfavorable to cool to below ℃.
【0011】不活性ガスを用いて希釈した極性ガスを用
いることにより、顔料表面への吸着量を効果的に制御で
き、顔料表面に均一に極性ガスを吸着させることができ
る。この場合、極性ガスの濃度は25〜100vol%、
好ましくは30vol%以上、より好ましくは35vol%以
上が適当である。該極性ガスの濃度が25vol%を下回
ると顔料表面への吸着量が少なくなり、十分な処理効果
が得られない。不活性ガスの種類は特に限定されず、窒
素、アルゴン、ヘリウム、四フッ化炭素など何れでも良
い。By using a polar gas diluted with an inert gas, the adsorption amount on the pigment surface can be effectively controlled, and the polar gas can be uniformly adsorbed on the pigment surface. In this case, the concentration of polar gas is 25-100 vol%,
It is preferably 30 vol% or more, more preferably 35 vol% or more. If the concentration of the polar gas is less than 25 vol%, the amount adsorbed on the surface of the pigment will be small and a sufficient treatment effect cannot be obtained. The type of inert gas is not particularly limited, and may be nitrogen, argon, helium, carbon tetrafluoride, or the like.
【0012】極性ガスによる処理時間は、顔料の量と不
活性ガス濃度等によって異なるが、顔料に接触処理した
後の極性ガス濃度が平衡に達すれば良い。あるいは予め
吸着量を設定し、これに達した時点で極性ガスの導入を
終了しても良い。また、極性ガスの吸着は一定量のガス
を仕込んで行なうバッチ法でも、連続的に極性ガスを流
す連続法のいずれの方法でもよい。さらに、ガス中に顔
料を流下する等の方法で行うこともできる。これらの方
法で極性ガスの吸着を行う場合、前処理は必要としない
が、予め予備加熱ないし減圧等により有機顔料表面の吸
着物および容器内のガスを除いた後に極性ガスを導入す
るのが好ましい。The treatment time with the polar gas differs depending on the amount of the pigment and the concentration of the inert gas, but it suffices that the concentration of the polar gas after the contact treatment with the pigment reaches an equilibrium. Alternatively, the adsorption amount may be set in advance, and the introduction of the polar gas may be terminated when the adsorption amount is reached. Further, the adsorption of the polar gas may be performed by either a batch method in which a fixed amount of gas is charged or a continuous method in which the polar gas is continuously flowed. Further, it may be carried out by a method of flowing a pigment down in a gas. When the polar gas is adsorbed by these methods, pretreatment is not necessary, but it is preferable to introduce the polar gas after removing the adsorbate on the surface of the organic pigment and the gas in the container by preheating or depressurizing. .
【0013】(II)第2工程(フッ素ガスの吸着) 本処理工程では、表面に極性ガスを付着させた顔料をフ
ッ素ガスに接触させて表面処理する。本工程の処理温度
は、親水性表面効果を得るため−80℃〜300℃が適
当であり、好ましくは−30℃〜150℃、より好まし
くは−20℃〜150℃の範囲が適当である。フッ素ガ
スは反応性が激しいため処理温度が300℃よりも高い
と接触時間、フッ素ガス流量を抑制しても、有機顔料が
劣化、変色し、またフッ素ガスの吸着が不均一になり易
い。なお−80℃以下に冷却することは経済上好ましく
ない。この工程で温度、フッ素ガス濃度、接触時間をコ
ントロールすることにより必要量のフッ素を強固に基体
と結合させることができる。 (II) Second Step (Adsorption of Fluorine Gas) In this treatment step, the pigment having a polar gas attached to the surface is brought into contact with the fluorine gas for surface treatment. In order to obtain the hydrophilic surface effect, the treatment temperature in this step is suitably -80 ° C to 300 ° C, preferably -30 ° C to 150 ° C, more preferably -20 ° C to 150 ° C. Fluorine gas is highly reactive, so if the treatment temperature is higher than 300 ° C., even if the contact time and the flow rate of fluorine gas are suppressed, the organic pigment deteriorates and discolors, and the adsorption of fluorine gas tends to be non-uniform. It is economically unfavorable to cool it to -80 ° C or lower. By controlling the temperature, fluorine gas concentration, and contact time in this step, the required amount of fluorine can be firmly bonded to the substrate.
【0014】フッ素ガスについても、不活性ガスを用い
て希釈することにより顔料表面への吸着量が制御され、
粒子表面に均一に吸着させることができる。フッ素ガス
濃度は0.01〜30vol%が好ましく0.1〜10vol%
がより好ましい。フッ素ガス濃度が0.01vol%を下回
るとフッ素ガスの吸着量が少なく十分な効果が得られな
い。一方、フッ素ガス濃度が30 vol%を上回るとフッ
素ガスの反応が激しいために顔料の劣化や変色あるいは
フッ素ガスの吸着が不均一になる。フッ素ガスの種類は
第1工程と同様に窒素、アルゴン、ヘリウム等の何れで
も良い。Also with respect to fluorine gas, the amount adsorbed on the pigment surface is controlled by diluting with an inert gas,
It can be adsorbed uniformly on the particle surface. The fluorine gas concentration is preferably 0.01 to 30 vol% and 0.1 to 10 vol%
Is more preferred. If the concentration of fluorine gas is less than 0.01 vol%, the amount of fluorine gas adsorbed is small and a sufficient effect cannot be obtained. On the other hand, when the fluorine gas concentration exceeds 30 vol%, the reaction of the fluorine gas is so vigorous that the pigment is deteriorated or discolored or the fluorine gas is not adsorbed uniformly. The type of fluorine gas may be nitrogen, argon, helium or the like as in the first step.
【0015】フッ素ガスによる表面改質は一定量のガス
を仕込んで行なうバッチ法でも、連続的に一定時間ガス
を流す連続法のいずれの方法でもよい。また、ガス中に
顔料を流下する等の方法によって行ってもよい。顔料の
表面改質が均一に進むようにフッ素ガスの濃度、導入量
および処理温度に対して処理時間を適宜調整する。一般
的には、有機顔料の種類や量、ガスの導入量、装置の形
状等にもよるが、フッ素の導入量がフッ素量/有機顔料
の比で0.01〜6mmol/gになるように反応時間を調整
する。この値が0.01mmol/g未満では効果がなく、6m
mol/gを上回るとフッ素の吸着量が過剰になり、顔料の
劣化、変色を来す原因となる。The surface modification with fluorine gas may be carried out by either a batch method in which a fixed amount of gas is charged or a continuous method in which a gas is continuously supplied for a fixed time. Alternatively, it may be carried out by a method of flowing a pigment down into a gas. The treatment time is appropriately adjusted with respect to the concentration of fluorine gas, the introduction amount, and the treatment temperature so that the surface modification of the pigment proceeds uniformly. Generally, depending on the type and amount of organic pigment, the amount of gas introduced, the shape of the device, etc., the amount of fluorine introduced should be 0.01 to 6 mmol / g in terms of the amount of fluorine / organic pigment. Adjust the reaction time. If this value is less than 0.01 mmol / g, there is no effect and 6 m
If it exceeds mol / g, the amount of fluorine adsorbed becomes excessive, which causes deterioration and discoloration of the pigment.
【0016】なお、第1工程と第2工程は同一容器で行
なってもよく、また、第1工程終了後、極性ガスで処理
した顔料をフッ素ガスに対して耐蝕性のある他の反応容
器に移して第2工程を行なってもよい。同一容器で第2
工程を行なう場合は、容器内に残留する極性ガスがフッ
素ガスと反応してフッ素ガスを消費し、また、その際に
発生する発熱によって顔料の劣化を来すことがないよう
に、極性ガスによる処理の後に、通気して残留ガスを排
除するか不活性ガスを導入して容器内部の残留ガスを置
換あるいは希釈することが好ましい。The first step and the second step may be carried out in the same container, and after the completion of the first step, the pigment treated with the polar gas is placed in another reaction vessel having a corrosion resistance to fluorine gas. You may transfer and may perform a 2nd process. Second in the same container
When carrying out the process, the polar gas remaining in the container reacts with the fluorine gas to consume the fluorine gas, and the heat generated at that time does not cause deterioration of the pigment. After the treatment, it is preferable to ventilate the residual gas or introduce an inert gas to replace or dilute the residual gas inside the container after the treatment.
【0017】顔料粒子表面での反応は必ずしも明確では
ないが、基本的には、第1工程において粒子表面に極性
ガスが吸着して表面を覆い、第2工程において導入され
たフッ素ガスが粒子表面の極性ガスと反応し、顔料粒子
の表面で極性ガスの種類に応じて−SO2F、−SO
3H、−COF、−COOH等の親水基が形成され、こ
れらの親水基が有機顔料表面に化学的に結合した構造を
生じるものと考えられる。その結果として、色調を損な
わず、しかも分散性に優れた表面改質有機顔料が得られ
る。特に、フッ素ガスが有機顔料表面と直接に反応する
割合が極めて低いので、表面改質処理が均一に行われ、
フッ素単独で表面処理した場合よりも優れた特性を有す
る有機顔料が得られる。Although the reaction on the pigment particle surface is not always clear, basically, in the first step, polar gas is adsorbed on the particle surface to cover the surface, and the fluorine gas introduced in the second step is introduced into the particle surface. reacts with the polar gas, -SO 2 F in the surface of the pigment particles according to the type of polar gases, -SO
It is considered that hydrophilic groups such as 3 H, —COF, and —COOH are formed, and these hydrophilic groups chemically bond to the surface of the organic pigment. As a result, a surface-modified organic pigment that does not impair the color tone and is excellent in dispersibility can be obtained. In particular, since the proportion of fluorine gas that directly reacts with the surface of the organic pigment is extremely low, the surface modification treatment is performed uniformly,
It is possible to obtain an organic pigment having excellent properties as compared with the case where the surface treatment is performed with fluorine alone.
【0018】第1工程を省略すると、フッ素ガスの吸着
が過度に進行するため黒色に変質した有機顔料が増加
し、また表面処理が不均一になるので色相の均一性や親
水性、分散性が不良になる。なお、顔料の黒変は、有機
顔料とフッ素ガスが過度に反応した結果生成するカーボ
ンやタールが原因と考えられる。なお従来の表面処理法
において、フッ素ガスによる処理を空気中で行うことが
知られているが、空気中のO2やCO2の濃度程度では上
記第1工程の極性ガスによる処理効果は到底得られな
い。If the first step is omitted, the adsorption of fluorine gas proceeds excessively, the amount of organic pigments that have changed to black increases, and the surface treatment becomes non-uniform, so that the hue uniformity, hydrophilicity and dispersibility are improved. breaking bad. The blackening of the pigment is considered to be caused by carbon or tar generated as a result of excessive reaction between the organic pigment and the fluorine gas. In the conventional surface treatment method, it is known that the treatment with fluorine gas is performed in the air, but the treatment effect by the polar gas in the first step can be quite achieved at a concentration of O 2 or CO 2 in the air. I can't.
【0019】第1工程、第2工程のいずれにおいても有
機顔料を均一に処理し、凝集を防止し、あるいは粒径を
制御するために処理工程中撹拌や振盪することが好まし
い。撹拌方法は、流動床式や撹拌羽根あるいはボールミ
ルなどを広く用いることができる。In both the first step and the second step, it is preferable to uniformly treat the organic pigment, prevent agglomeration, or agitate or shake during the treatment step in order to control the particle size. As the stirring method, a fluidized bed type, stirring blade, ball mill, or the like can be widely used.
【0020】(III)第3工程(中和工程) 第2工程の終了後、酸性ガス成分が顔料粒子表面に残留
している場合には、これを揮発し、あるいは中和して除
去する。酸性ガス成分は未反応の極性ガスまたはフッ素
ガス、又は、これらが反応して生じたHFや各種の反応
生成物であり、これらが顔料表面に残留していると、顔
料を製品に使用した場合に分散安定性を損なったり、腐
食の原因となる虞があるので好ましくない。 (III) Third Step (Neutralization Step) After the completion of the second step, if the acidic gas component remains on the surface of the pigment particles, it is volatilized or neutralized to be removed. The acidic gas component is unreacted polar gas or fluorine gas, or HF and various reaction products generated by the reaction of these, and if these remain on the pigment surface, when the pigment is used in a product. This is not preferable because it may impair the dispersion stability and cause corrosion.
【0021】酸性ガス成分を揮発させて除去する場合に
は、処理した顔料粒子を不活性ガス中、好ましくは不活
性ガス気流中、150℃以下、好ましくは100℃以下
に加熱する。酸性ガス成分を中和する場合には、アンモ
ニアガス等の塩基性ガスを不活性ガスに同伴させ顔料中
に導入するか、水およびアルカリ水溶液を用いた処理を
適宜行なう。酸性ガスの残存量にもよるが通常、塩基濃
度は低くてよい。When the acidic gas component is removed by volatilization, the treated pigment particles are heated in an inert gas, preferably in an inert gas stream, to 150 ° C. or lower, preferably 100 ° C. or lower. When the acidic gas component is neutralized, a basic gas such as ammonia gas is introduced into the pigment by entraining it in an inert gas, or treatment with water and an alkaline aqueous solution is appropriately performed. Usually, the base concentration may be low, although it depends on the remaining amount of acidic gas.
【0022】(IV)その他 本発明が有効に適用される有機顔料の種類は広範囲に及
ぶが、例えば、染付けレーキ、アゾ系、フタロシアニン
系、ベンズイミダゾール系、ニトロ系、ニトロソ系、縮
合多環系顔料として、アントラキノン系、インジゴ−チ
オインジゴ系、ペリノン系、ペリレン系、フタロン系、
ジオキサジン系、キナクリドン系、イソインドリノン
系、金属錯体顔料、メチン−アゾメチン系、ジケトピロ
ロピロール系等が挙げられる。なお実施例および比較例
で使用した顔料を表4に示した。 (IV) Others The types of organic pigments to which the present invention can be effectively applied are wide-ranging. As a pigment, anthraquinone type, indigo-thioindigo type, perinone type, perylene type, phthalone type,
Examples thereof include dioxazine type, quinacridone type, isoindolinone type, metal complex pigments, methine-azomethine type, diketopyrrolopyrrole type and the like. The pigments used in Examples and Comparative Examples are shown in Table 4.
【0023】本発明の表面改質方法では、フッ素の過激
な吸着が抑制されて顔料の表面改質が均一に進む。この
結果、顔料の黒変が殆ど発生せず、得られる表面改質顔
料は水性媒体中での分散性が長期に亘って優れている。
従って、本発明の表面改質顔料は、油性のみならず水性
系の製品に幅広く用いることができる。具体的には、凸
版インキ、彫刻凹版インキ、グラビアインキ、フレキソ
インキ、オフセットインキ、スクリーンインキ等の印刷
インキ、絵の具、クレヨン、パステル、マーカー、サイ
ンペン、ボールペン等の筆記用インキ、電着塗料、缶用
塗料、自動車用塗料等の塗料全般、感熱転写用あるいは
インキジェットプリンター等での記録材料、プラスチッ
ク用着色剤、ゴム用着色剤、紙着色剤等、顔料樹脂捺染
剤などの広範囲の応用が期待される。In the surface modification method of the present invention, the radical adsorption of fluorine is suppressed and the surface modification of the pigment proceeds uniformly. As a result, almost no blackening of the pigment occurs, and the obtained surface-modified pigment has excellent dispersibility in an aqueous medium for a long period of time.
Therefore, the surface-modified pigment of the present invention can be widely used for not only oily products but also aqueous products. Specifically, letterpress ink, engraving intaglio ink, gravure ink, flexo ink, offset ink, screen ink, and other printing inks, paints, crayons, pastel, markers, felt-tip pens, ballpoint pens, and other writing inks, electrodeposition paints, cans. Applications such as paints for automobiles, paints for automobiles, recording materials for thermal transfer or ink jet printers, colorants for plastics, colorants for rubber, paper colorants, pigment resin printing agents, etc. are expected. To be done.
【0024】[0024]
【実施例】以下に本発明の実施例を比較例と共に示す。
なお、以下の実施例は本発明の範囲を限定するものでは
ない。はじめに、実施例ないし比較例における有機顔料
の評価方法を以下に示す。EXAMPLES Examples of the present invention will be described below together with comparative examples.
In addition, the following examples do not limit the scope of the present invention. First, the evaluation methods of organic pigments in Examples and Comparative Examples are shown below.
【0025】(イ)分散試験1 0.2gの試料顔料(表面改質顔料、未処理品)を比色
管(直径24mm、長さ100mm)に入れ、50gの水を加え
て振盪撹拌し、試料を水中に均一に分散させ、24時間
後、水相の着色状態を目視で観察し、未処理顔料を試料
として用いた場合を基準として有機顔料の水性媒体への
親和性を判定した。判定は分散液の着色状態を基準と
し、着色が非常に濃いもの(表中◎印)、濃いもの(表
中○印)、薄いもの(表中×印)の3段階で行った。着
色の濃いものが分散性に優れる。 (A) Dispersion test 1 0.2 g of the sample pigment (surface-modified pigment, untreated product) was placed in a colorimetric tube (diameter 24 mm, length 100 mm), 50 g of water was added, and the mixture was shaken and stirred, The sample was uniformly dispersed in water, and after 24 hours, the coloring state of the aqueous phase was visually observed, and the affinity of the organic pigment to the aqueous medium was determined based on the case where the untreated pigment was used as the sample. Judgment was made on the basis of the coloring state of the dispersion liquid, and was carried out in three stages: very dark (o in the table), dark (o in the table), and light (x in the table). Thickly colored ones have excellent dispersibility.
【0026】(ロ)分散試験2 試料顔料(表面改質顔料、未処理品)、水溶性アクリル
樹脂(シ゛ョンクリルJ-61:シ゛ョンソン ホ゜リマー社製)、ガラスビーズ
(1φ)、ジメチルアミノエタノール(試薬特級:和光
純薬社製)および水を以下の配合に従ってマヨネーズ瓶
に入れ、ペイントコンディショナーで4時間、振盪撹拌
し、試料を水中に均一に分散させて水性インキを製造す
る。得られたインキを分散試験1と同様の比色管に入
れ、50℃で2か月間静置し、顔料の沈降度合を目視観
察して試料の分散安定性を判定した。水性インキ組成物
の配合例(重量部)は試料顔料(5部)、アクリル樹脂
(15部)、ジメチルアミノエタノール(4.5部)、
ガラスビーズ(30部)および水(45.5部)であ
る。判定は試料とした顔料の沈殿物を基準とし、沈殿物
が観察されるもの(表中×印)、顔料の沈殿物が観察さ
れず従って分散液が着色されるもの(表中◎印)の2段
階で判定した。 (B) Dispersion test 2 Sample pigment (surface-modified pigment, untreated product), water-soluble acrylic resin (John Cryl J-61: manufactured by Johnson Polymer), glass beads (1φ), dimethylaminoethanol (reagent) (Special grade: manufactured by Wako Pure Chemical Industries, Ltd.) and water are put in a mayonnaise bottle according to the following formulation, and shaken and stirred with a paint conditioner for 4 hours to uniformly disperse the sample in water to produce an aqueous ink. The obtained ink was placed in the same colorimetric tube as in Dispersion Test 1 and allowed to stand at 50 ° C. for 2 months, and the degree of sedimentation of the pigment was visually observed to determine the dispersion stability of the sample. The formulation example (parts by weight) of the water-based ink composition is sample pigment (5 parts), acrylic resin (15 parts), dimethylaminoethanol (4.5 parts),
Glass beads (30 parts) and water (45.5 parts). Judgment was based on the pigment precipitate used as a sample, and the precipitate was observed (marked with X in the table), and the pigment precipitate was not observed and the dispersion was colored (marked with ◎ in the table). It was judged in two stages.
【0027】(ハ) 分散試験3 0.2gの試料顔料(表面改質顔料、未処理品)を分散
試験1と同様の比色管に入れ、50gの水を加えて振盪
撹拌し試料を水中に均一に分散させる。24時間後、水
の界面(メニスカス)に浮上する黒色に変質した有機顔
料の量を目視で観察し、フッ素化反応の均一性を判定し
た。判定は界面に浮上する黒色変質有機顔料の量を基準
とし、殆どないもの(表中◎印)、少量(1mm厚以下、
表中○印)、多量(1〜10mm厚、表中×印)の3段階
で判定した。 (C) Dispersion test 3 0.2 g of the sample pigment (surface-modified pigment, untreated product) was placed in the same colorimetric tube as in the dispersion test 1, 50 g of water was added, and the mixture was shaken and stirred to make the sample in water. Evenly disperse After 24 hours, the amount of the organic pigment that changed to black and floated on the water interface (meniscus) was visually observed to determine the uniformity of the fluorination reaction. Judgment is based on the amount of the black alteration organic pigment that floats on the interface, and there is almost no (the ◎ mark in the table), a small amount (1 mm thickness or less,
Judgment was made in three stages: ○ in the table) and a large amount (1 to 10 mm thickness, x in the table).
【0028】実施例1 第1表に示す処理条件(SF-1〜SF-14)で以下の工程に
従い銅フタロシアニンブルー顔料の表面改質処理を行な
った。 第1工程 銅フタロシアニンブルー顔料(リオノールフ゛ルーFG-7351:東洋
インキ社製)50gを撹拌装置付きのテフロンコーティ
ング SUS製反応管に投入し、反応管の内部を減圧(1Tor
r)して処理系から空気および他の付着物を除いた後に、
反応管内を表中の温度に保ち、窒素ガスで表中の濃度に
希釈した極性ガス(SO2、CO2、CO、O2、NO2)を導入し
た。吸着平衡に達した後、反応管容量の3倍量の窒素ガ
スを20秒間流して反応管内に残留する未吸着の極性ガ
スを除いた。 Example 1 A surface modification treatment of a copper phthalocyanine blue pigment was carried out according to the following steps under the treatment conditions (SF-1 to SF-14) shown in Table 1. First step 50 g of copper phthalocyanine blue pigment (Lionol blue FG-7351: manufactured by Toyo Ink Co., Ltd.) is charged into a Teflon coating SUS reaction tube equipped with a stirrer, and the inside of the reaction tube is depressurized (1 Torr).
r) to remove air and other deposits from the treatment system,
The inside of the reaction tube was maintained at the temperature shown in the table, and a polar gas (SO 2 , CO 2 , CO, O 2 , NO 2 ) diluted with nitrogen gas to the concentration shown in the table was introduced. After reaching the adsorption equilibrium, nitrogen gas in an amount three times the reaction tube volume was flowed for 20 seconds to remove unadsorbed polar gas remaining in the reaction tube.
【0029】第2工程 反応管内の顔料を撹拌しつつ、窒素ガスで希釈したフッ
素ガスを反応管内に導入した。この間、反応管内の温度
を表中の温度に保った。表中の処理時間が経過後、窒素
ガスを導入して管内ガスを置換し表面改質を停止させ
た。 第3工程 反応管内を50℃に加熱し、窒素ガスを反応管内部に充
填して排出されるガス中にフッ素ガスが認められなくな
った後に表面改質有機顔料を取り出し、前述の分散試験
1〜3を行なった。結果を第3表に示した。Second Step While stirring the pigment in the reaction tube, fluorine gas diluted with nitrogen gas was introduced into the reaction tube. During this period, the temperature inside the reaction tube was maintained at the temperature shown in the table. After the lapse of the treatment time in the table, nitrogen gas was introduced to replace the gas in the tube to stop the surface modification. Step 3 The inside of the reaction tube is heated to 50 ° C., nitrogen gas is filled into the reaction tube, and after the fluorine gas is no longer observed in the gas discharged, the surface-modified organic pigment is taken out and the dispersion test 1 to 3 was performed. The results are shown in Table 3.
【0030】実施例2〜14 銅フタロシアニンブルー顔料に代えて、第3表に示す各
種顔料を用いた他は実施例1と同様にして顔料の表面処
理を行なった。これらの結果を第3表にまとめて示し
た。 Examples 2 to 14 The pigments were surface-treated in the same manner as in Example 1 except that the various pigments shown in Table 3 were used instead of the copper phthalocyanine blue pigment. These results are summarized in Table 3.
【0031】比較例1〜14 第1工程の極性ガスによる処理を省略し、第2工程のフ
ッ素ガスによる処理のみを第2表の条件に従って行なっ
た他は、実施例1〜14と同様の条件で顔料の表面処理
を行った。分散試験の結果を第3表にまとめて示した。 Comparative Examples 1 to 14 Conditions similar to those of Examples 1 to 14 except that the treatment with the polar gas in the first step was omitted and only the treatment with the fluorine gas in the second step was performed according to the conditions in Table 2. The surface treatment of the pigment was carried out. The results of the dispersion test are summarized in Table 3.
【0032】比較例1B〜14B 上記実施例1〜14および比較例1〜14の分散効果を
比較するための対照として、実施例および比較例におい
て用いた顔料を表面処理せず、それぞれの分散性を試験
した。結果を第3表にまとめて示した。 Comparative Examples 1B-14B As a control for comparing the dispersion effects of the above Examples 1-14 and Comparative Examples 1-14, the pigments used in the Examples and Comparative Examples were not surface-treated and their respective dispersibility was determined. Was tested. The results are summarized in Table 3.
【0033】 [0033]
【0034】 [0034]
【0035】 [0035]
【0036】 [0036]
【0037】これらの結果から明らかなように、従来の
フッ素ガス処理のみを行った場合には(比較例1〜1
4)、水性媒体中の分散性は中程度であるが、水性イン
ク中での分散性はいずれも劣り、またこれら比較例の全
てにおいて顔料の黒変が少量〜多量認められた。一方、
本発明の方法に従って極性ガスの吸着とフッ素ガスによ
る処理を順次施した有機顔料は優れた親水性を有し(分
散試験1)、しかも水性インキ等に用いた場合にも高い
分散安定性を発揮する(分散試験2)。また、顔料の黒
変がほとんど生成せず、過度なフッ素化が抑えられてい
る(分散試験3)。フッ素処理に際しての化学反応が予
め顔料表面に吸着されている極性ガスによって緩和さ
れ、顔料表面全体に均一に進行するためであると考えら
れる。As is clear from these results, when only the conventional fluorine gas treatment was performed (Comparative Examples 1 to 1)
4), the dispersibility in the aqueous medium is moderate, but the dispersibility in the aqueous ink is poor, and a small amount to a large amount of pigment blackening is observed in all of these comparative examples. on the other hand,
The organic pigment, which has been subjected to the adsorption of polar gas and the treatment with fluorine gas in order according to the method of the present invention, has excellent hydrophilicity (dispersion test 1), and exhibits high dispersion stability even when used in aqueous ink and the like. Do (dispersion test 2). Moreover, almost no black discoloration of the pigment was generated, and excessive fluorination was suppressed (dispersion test 3). It is considered that the chemical reaction at the time of the fluorine treatment is relaxed by the polar gas previously adsorbed on the surface of the pigment and uniformly proceeds on the entire surface of the pigment.
【0038】[0038]
【発明の効果】従来のフッ素ガスによる表面処理では有
機顔料の処理が不均一であり、局部的に過度な反応が進
行するため、水性インク等に製品化した場合に分散安定
性に問題があったが、本発明の製造方法は、極性ガスに
よる処理とフッ素ガスによる処理を組み合わせた結果、
顔料粒子の全体に亘って均一な改質処理が施され、製品
化した場合にも優れた分散安定性を有し、しかも過剰な
フッ素化が抑制されるので顔料の黒変が殆どなく、また
未反応顔料の残留等の問題が解消される。EFFECT OF THE INVENTION In the conventional surface treatment with fluorine gas, the treatment of the organic pigment is non-uniform and an excessive reaction locally proceeds, so that there is a problem in dispersion stability when it is commercialized as an aqueous ink. However, the manufacturing method of the present invention, as a result of combining the treatment with the polar gas and the treatment with the fluorine gas,
The pigment particles are uniformly modified over the entire surface and have excellent dispersion stability even when they are commercialized, and since excessive fluorination is suppressed, there is almost no blackening of the pigment, and Problems such as residual unreacted pigment are eliminated.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大森 浩太 秋田県秋田市茨島三丁目1番6号 株式会 社トーケムプロダクツ内 (72)発明者 上村 敏文 東京都中央区京橋二丁目3番13号 東洋イ ンキ製造株式会社内 (72)発明者 宮崎 修次 東京都中央区京橋二丁目3番13号 東洋イ ンキ製造株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kota Omori Inventor Kota 3-6, Ibaraki, Akita City, Akita Prefecture In Tochem Products Co., Ltd. Toyo Inki Manufacturing Co., Ltd. (72) Inventor Shuji Miyazaki 2-3-13 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd.
Claims (7)
性ガスを吸着させた後に、フッ素ガスによって表面処理
したことを特徴とする表面改質有機顔料。1. A surface-modified organic pigment, characterized in that the pigment is brought into contact with a polar gas to adsorb the polar gas on the surface of the pigment and then surface-treated with a fluorine gas.
性ガスを吸着させた後に、フッ素ガスによって表面処理
することを特徴とする表面改質有機顔料の製造方法。2. A method for producing a surface-modified organic pigment, which comprises contacting a pigment with a polar gas to adsorb the polar gas on the surface of the pigment, and then surface-treating the surface with a fluorine gas.
した極性ガスに顔料を接触させて顔料粒子表面に該極性
ガスを吸着させた後、該顔料を0.01〜30vol%に希
釈したフッ素ガスに接触させる請求項2に記載の表面改
質有機顔料の製造方法。3. A polar gas diluted to 25 to 100 vol% with an inert gas is brought into contact with the pigment to adsorb the polar gas on the surface of the pigment particles, and then the pigment is diluted to 0.01 to 30 vol% with fluorine. The method for producing a surface-modified organic pigment according to claim 2, wherein the surface-modified organic pigment is brought into contact with a gas.
う請求項2または3に記載の表面改質有機顔料の製造方
法。4. The method for producing a surface-modified organic pigment according to claim 2, wherein the adsorption of the polar gas is performed at −80 to 50 ° C.
℃で行なう請求項2〜4のいずれかに記載の表面改質有
機顔料の製造方法。5. The treatment with fluorine gas is -80 to 300.
The method for producing a surface-modified organic pigment according to any one of claims 2 to 4, which is carried out at a temperature of ° C.
1種類の元素とOとを含む親水基を形成する基を有する
化合物である請求項2〜5のいずれかに記載の表面改質
有機顔料の製造方法。6. The surface modification according to claim 2, wherein the polar gas is a compound having a group forming a hydrophilic group containing at least one element of C, S and N and O. Of producing high quality organic pigment.
残留する酸性成分を揮発ないし中和して除去する請求項
6に記載の製造方法。7. The method according to claim 6, wherein after the treatment with the fluorine gas, the acidic component remaining on the surface of the pigment is removed by volatilization or neutralization.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28232596A JPH09176514A (en) | 1995-10-27 | 1996-10-24 | Organic pigment having modified surface and production thereof |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7-303556 | 1995-10-27 | ||
JP30355695 | 1995-10-27 | ||
JP28232596A JPH09176514A (en) | 1995-10-27 | 1996-10-24 | Organic pigment having modified surface and production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH09176514A true JPH09176514A (en) | 1997-07-08 |
Family
ID=26554561
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28232596A Pending JPH09176514A (en) | 1995-10-27 | 1996-10-24 | Organic pigment having modified surface and production thereof |
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Country | Link |
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JP (1) | JPH09176514A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2228410A1 (en) | 2009-03-11 | 2010-09-15 | Clariant International Ltd. | C.I. Pigment Red 112 with improved dispersion |
-
1996
- 1996-10-24 JP JP28232596A patent/JPH09176514A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2228410A1 (en) | 2009-03-11 | 2010-09-15 | Clariant International Ltd. | C.I. Pigment Red 112 with improved dispersion |
DE102009012685A1 (en) | 2009-03-11 | 2010-09-16 | Clariant International Limited | C.I. Pigment Red 112 with improved dispersibility |
US8062416B2 (en) | 2009-03-11 | 2011-11-22 | Clariant Finance (Bvi) Limited | Pigment red 112 with enhanced dispersibility |
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