JPH09249821A - Coated pigment, pigment composition containing the same and used for coloration and coating material - Google Patents
Coated pigment, pigment composition containing the same and used for coloration and coating materialInfo
- Publication number
- JPH09249821A JPH09249821A JP6049096A JP6049096A JPH09249821A JP H09249821 A JPH09249821 A JP H09249821A JP 6049096 A JP6049096 A JP 6049096A JP 6049096 A JP6049096 A JP 6049096A JP H09249821 A JPH09249821 A JP H09249821A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- parts
- coated
- resin
- coated pigment
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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、分散性の改良され
た被覆顔料、該被覆顔料を含み、熱可塑性樹脂等の着色
に用いられる着色用顔料組成物、ならびにインキ，塗料
等の被覆剤に関する。本発明の被覆顔料は、プラスチッ
ク系あるいはゴム系の複合材料に関する分野でも有用で
ある。TECHNICAL FIELD The present invention relates to a coating pigment having an improved dispersibility, a coloring pigment composition containing the coating pigment and used for coloring a thermoplastic resin, etc., and a coating material for inks, paints and the like. . The coated pigment of the present invention is also useful in the field of plastic-based or rubber-based composite materials.
【０００２】[0002]
【従来の技術】顔料は一般に、塗料、インキ等の媒体中
で凝集を起こす傾向がある。塗料やインキの貯蔵中又は
乾燥時に顔料粒子の凝集が起きると、色調の変化、着色
力の低下、他顔料との混色時における色別れおよび流動
性の低下等の原因となる。従来、当問題の解決方法とし
て、凝集防止剤や分散助剤の添加、例えば顔料置換誘導
体の添加等が提案されたが、これまでのところこれらの
方法では十分ではなく、また添加物に由来する諸物性の
低下や添加物がブリードするなど問題があった。BACKGROUND OF THE INVENTION Pigments generally have a tendency to agglomerate in media such as paints and inks. Agglomeration of pigment particles during storage or drying of a paint or ink causes a change in color tone, a decrease in tinting strength, color separation when mixing with other pigments, and a decrease in fluidity. Conventionally, as a method for solving this problem, addition of an anti-aggregation agent or a dispersion aid, for example, addition of a pigment-substituted derivative has been proposed, but so far, these methods are not sufficient and are derived from additives. There were problems such as deterioration of various physical properties and bleeding of additives.
【０００３】また、これらの分散剤が使用された熱可塑
性樹脂着色用組成物は、着色された熱可塑性樹脂を１０
数ミクロン径で高速紡糸したり、フィルム化するなど高
度な顔料分散が求められる場合には、満足な顔料分散性
が得られないことがある。すなわち、顔料分散不良によ
る紡糸時の糸切れ、溶融紡糸機のフィルターの目詰ま
り、フィルムでの成形不良などである。さらに顔料の凝
集は引張強度や曲げ強度および衝撃強度等の機械物性を
低下させる要因ともなりやすい。これらの問題を解決す
るために、熱可塑性樹脂着色用組成物の加工方法の改良
や強力混練機により顔料分散性を向上させる努力が行わ
れてきたが、いずれも十分な顔料分散能を発揮するもの
ではなかった。Further, a composition for coloring a thermoplastic resin in which these dispersants are used is used in a composition for coloring a thermoplastic resin.
When a high degree of pigment dispersion is required, such as spinning at a diameter of several microns or forming a film, satisfactory pigment dispersibility may not be obtained. That is, yarn breakage during spinning due to poor pigment dispersion, clogging of a filter of a melt spinning machine, poor molding in a film, and the like. Further, the aggregation of the pigment is likely to be a factor that deteriorates mechanical properties such as tensile strength, bending strength and impact strength. In order to solve these problems, efforts have been made to improve the pigment dispersibility by improving the processing method of the thermoplastic resin coloring composition and by using a strong kneader, but all exhibit sufficient pigment dispersing ability. It was not something.
【０００４】そこで、顔料粒子表面を高分子物質で被覆
することにより凝集を防止する方法も提案されている。
例えば、顔料、溶媒、高分子物質からなる系で相分離を
発生させ高分子物質を顔料粒子表面に吸着させる方法
（コアセルベーション法）、顔料と高分子エマルジョン
とを強撹拌することにより高分子物質を顔料粒子表面に
吸着させる方法、顔料存在下で分散重合を行い高分子物
質を顔料粒子表面に吸着させる方法、モノマーを顔料表
面に吸着させた後、その界面で重合を開始させる方法
（界面重合法）などである。しかしながら、吸着という
現象は平衡反応であって、系の環境が変化すれば当然、
脱離も起こり得る。Therefore, a method of preventing the agglomeration by coating the surface of the pigment particles with a polymeric substance has also been proposed.
For example, a method of causing phase separation in a system consisting of a pigment, a solvent, and a polymer substance to adsorb the polymer substance on the surface of the pigment particles (coacervation method), or a method of vigorously stirring the pigment and the polymer emulsion A method of adsorbing a substance on the surface of a pigment particle, a method of adsorbing a polymer substance on the surface of a pigment particle by dispersion polymerization in the presence of a pigment, a method of adsorbing a monomer on the surface of a pigment and then initiating polymerization at the interface Polymerization method) and the like. However, the phenomenon of adsorption is an equilibrium reaction, and naturally if the environment of the system changes,
Desorption can also occur.
【０００５】従って、単に、高分子物質を顔料粒子表面
に吸着させただけでは、その後の取り扱いによっては吸
着した高分子物質が脱離してしまう場合もあり、その場
合、凝集防止効果がなくなるだけでなく、脱離した高分
子物質が物性の低下を招くこともある。このような脱離
を防ぐために被覆剤と顔料とを共有結合により連結させ
る方法も提案されているが、反応性官能基を有する顔料
は極一部に限られているのが現状である。また、コアセ
ルベーション法と界面重合法との併用等により顔料粒子
表面上で高分子網目を形成させる方法が提案されている
が、未だ十分な効果は得られてはいない。特に熱可塑性
樹脂の着色分野において、その着色は、樹脂の融点近傍
の高温度下で高剪断をかけて行われており、このような
条件下においても十分な効果を奏する被覆顔料は未だ見
いだされてはいない。Therefore, if the polymer substance is simply adsorbed on the surface of the pigment particles, the adsorbed polymer substance may be desorbed depending on the subsequent handling. In that case, the effect of preventing the aggregation is lost. In some cases, the desorbed polymer substance may cause deterioration of physical properties. In order to prevent such elimination, a method of connecting a coating agent and a pigment by a covalent bond has been proposed, but the present situation is that the number of pigments having a reactive functional group is very limited. Further, a method of forming a polymer network on the surface of pigment particles by using a coacervation method and an interfacial polymerization method in combination has been proposed, but a sufficient effect has not been obtained yet. Particularly in the coloring field of thermoplastic resins, the coloring is carried out by applying high shear at a high temperature in the vicinity of the melting point of the resin, and a coated pigment that exerts a sufficient effect even under such conditions has not yet been found. Not.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記種々の
欠点を改良し、インキ、塗料、熱可塑性樹脂等の着色に
際して色相、着色力、分散性に優れた被覆顔料、該被覆
顔料を含み、色相、着色力、分散性に優れた着色用顔料
組成物ならびに被覆剤の提供を目的とする。The present invention improves the above-mentioned various drawbacks and includes a coating pigment excellent in hue, tinting strength and dispersibility in coloring inks, paints, thermoplastic resins, etc. The present invention aims to provide a pigment composition for coloring and a coating agent which are excellent in hue, tinting strength and dispersibility.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明は、顔
料を、第３級アミノ基を有するビニル共重合体の中和物
にエポキシ基とα，β−不飽和二重結合とを有する化合
物を付加させた反応性水可溶樹脂で被覆してなる被覆顔
料を提供する。また、本発明は、反応性水可溶樹脂が、
第３級アミノ基を有するビニル共重合体の中和物に、第
３級アミノ基１モルに対してエポキシ基０．０１〜１モ
ルの割合で、エポキシ基とα，β−不飽和二重結合とを
有する化合物を付加させた樹脂であることを特徴とする
上記被覆顔料を提供する。さらに、本発明は、顔料１０
０重量部に対して、０．５〜５０重量部の反応性水可溶
樹脂で被覆することを特徴とする上記被覆顔料を提供す
る。さらに、本発明は、上記被覆顔料を含む着色用顔料
組成物を提供する。さらに、本発明は、上記被覆顔料を
含む被覆剤を提供する。That is, the present invention provides a pigment, which is a compound having an epoxy group and an α, β-unsaturated double bond in a neutralized product of a vinyl copolymer having a tertiary amino group. Provided is a coated pigment which is coated with a reactive water-soluble resin to which is added. In addition, the present invention is a reactive water-soluble resin,
In the neutralized product of the vinyl copolymer having a tertiary amino group, the epoxy group and the α, β-unsaturated double bond are added in an amount of 0.01 to 1 mole of the epoxy group to 1 mole of the tertiary amino group. There is provided the above coated pigment, which is a resin to which a compound having a bond is added. Furthermore, the present invention provides a pigment 10
The coated pigment is coated with 0.5 to 50 parts by weight of a reactive water-soluble resin with respect to 0 parts by weight. Furthermore, the present invention provides a pigment composition for coloring containing the above coated pigment. Furthermore, the present invention provides a coating agent containing the above coated pigment.
【０００８】[0008]
【発明の実施の形態】第３級アミノ基を有するビニル共
重合体は、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アク
リレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アク
リレート等の第３級アミノ基を有するモノマーと、他の
ビニルモノマーとを共重合させることにより得られる。
第３級アミノ基を有するモノマーは、ビニル共重合体中
１０重量％以上を占めることが好ましい。１０重量％未
満では、得られる反応性水可溶樹脂の親水性が低く、水
系での顔料の被覆処理が困難となる。BEST MODE FOR CARRYING OUT THE INVENTION A vinyl copolymer having a tertiary amino group has a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate. It is obtained by copolymerizing the monomer which it has with another vinyl monomer.
The monomer having a tertiary amino group preferably accounts for 10% by weight or more in the vinyl copolymer. If it is less than 10% by weight, the hydrophilicity of the resulting reactive water-soluble resin is low and it becomes difficult to coat the pigment with an aqueous system.
【０００９】他のビニルモノマーのうち低分子量のもの
としては、メチル（メタ）アクリレート、エチル（メ
タ）アクリレート、ブチル（メタ）アクリレート、ヘキ
シル（メタ）アクリレート、２−エチルヘキシル（メ
タ）アクリレート、ラウリル（メタ）アクリレート、ス
テアリル（メタ）アクリレート等の（メタ）アクリル酸
のＣ1 〜Ｃ22のアルキルエステル、アリルアクリレート
等の（メタ）アクリル酸のＣ2 〜Ｃ8 アルケニルエステ
ル、アリルオキシエチルアクリレート等の（メタ）アク
リル酸のＣ3 〜Ｃ19アルケニルオキシアルキルエステ
ル、スチレン、α- メチルスチレン、ｏ- クロロスチレ
ン、ビニルトルエン、ジビニルベンゼン等のスチレン系
モノマ−、アクリル酸ヒドロキシエステル、アクリロニ
トリル、ブチロニトリル等のニトリル含有モノマー、酢
酸ビニル、ビニルカルバゾール、トリメチロールプロパ
ントリ（メタ）アクリレート、グリコールジ（メタ）ア
クリレート、アルキルジ（メタ）アクリレート、アクリ
ルアミド等が挙げられる。Among the other vinyl monomers having a low molecular weight, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl ( meth) acrylates, alkyl esters of C 1 -C 22 stearyl (meth) acrylate of (meth) acrylic acid, such as allyl acrylate (meth) C 2 -C 8 alkenyl esters of acrylic acid, such as allyloxyethyl acrylate (meth) C 3 -C 19 alkenyloxy alkyl esters of acrylic acid, styrene, alpha-methyl styrene, o- chlorostyrene, vinyl toluene, styrene monomer, such as divinylbenzene -, hydroxy acrylic acid ester, acrylonitrile, butyronitrile Nitrile-containing monomers, vinyl acetate, vinyl carbazole, trimethylolpropane tri (meth) acrylate, glycol di (meth) acrylate, alkyl di (meth) acrylate, acrylamide, and the like.
【００１０】また、オリゴマーおよびポリマーとして
は、ポリブタジエンポリオール、ポリオレフィンポリオ
ール、ポリエーテルポリオール、アクリルポリオール、
ポリエステルポリオール等の水酸基含有反応性オリゴマ
ーをトルエンジイソシアナート、イソホロンジイソシア
ナート等のジイソシアナート化合物で鎖延長し、末端イ
ソシアナート基に２−ヒドロキシエチル（メタ）アクリ
レート等の水酸基含有α, β−重合性化合物を反応させ
ることによって得られる化合物、ジオールとジカルボン
酸との重縮合、あるいはカプロラクトンの開環重縮合に
より得られるポリエステルのカルボン酸末端を２−ヒド
ロキシ（メタ）アクリレート、ペンタエリスリトールト
リ（メタ）アクリレート等の水酸基および（メタ）アク
リロイル基を含有する化合物と反応させた化合物、末端
アクリロイル変性ポリブタジエン等が挙げられる。他の
ビニルモノマーは、１種もしくは２種以上併用してもよ
い。As the oligomer and polymer, polybutadiene polyol, polyolefin polyol, polyether polyol, acrylic polyol,
A hydroxyl group-containing reactive oligomer such as polyester polyol is chain-extended with a diisocyanate compound such as toluene diisocyanate or isophorone diisocyanate, and a hydroxyl group-containing α, β such as 2-hydroxyethyl (meth) acrylate is added to the terminal isocyanate group. A compound obtained by reacting a polymerizable compound, a polycondensation of a diol and a dicarboxylic acid, or a polyester obtained by ring-opening polycondensation of caprolactone has a carboxylic acid terminal of 2-hydroxy (meth) acrylate, pentaerythritol tri ( Examples thereof include a compound reacted with a compound having a hydroxyl group and a (meth) acryloyl group such as (meth) acrylate, and acryloyl-modified polybutadiene having a terminal. Other vinyl monomers may be used alone or in combination of two or more.
【００１１】第３級アミノ基を有するビニル共重合体は
塩酸、硝酸、硫酸、蟻酸、酢酸、プロパン酸、ブタン
酸、（メタ）アクリル酸、コハク酸等の酸で中和された
後、エポキシ基とα，β−不飽和二重結合とを有する化
合物を付加させることにより反応性水可溶樹脂となる。
エポキシ基とα，β−不飽和二重結合とを有する化合物
の付加量は、使用形態に応じて任意に選択できるが、お
おむね第３級アミノ基１モルに対してエポキシ基０．０
１〜１モルの範囲が適当である。０．０１モル未満で
は、得られる反応性水可溶樹脂の架橋性能が乏しくな
る。エポキシ基とα，β−不飽和二重結合とを有する化
合物としては、グリシジル（メタ）アクリレート、グリ
シジルアリルエーテル等が挙げられる。The vinyl copolymer having a tertiary amino group is neutralized with an acid such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, propanoic acid, butanoic acid, (meth) acrylic acid, succinic acid, and then epoxy. A reactive water-soluble resin is obtained by adding a compound having a group and an α, β-unsaturated double bond.
The addition amount of the compound having an epoxy group and an α, β-unsaturated double bond can be arbitrarily selected according to the use form, but is generally about 0.0 mol of the epoxy group to 1 mol of the tertiary amino group.
A range of 1 to 1 mol is suitable. If it is less than 0.01 mol, the crosslinking performance of the resulting reactive water-soluble resin will be poor. Examples of the compound having an epoxy group and an α, β-unsaturated double bond include glycidyl (meth) acrylate and glycidyl allyl ether.
【００１２】反応性水可溶樹脂で被覆される顔料は、有
機顔料及び無機顔料のいずれでもよく、体質顔料や金属
顔料も含む。有機顔料としては、例えば、マダーレー
キ、ロッグウッドレーキ、コチニールレーキ等の天然染
料系顔料、ナフトールグリーンＢ、ナフトールグリーン
Ｙ等のニトロソ系顔料、ナフトールＳ、リソールファス
トイエロー２Ｇ等のニトロ系顔料、パーマネントレッド
４Ｒ、ブリリアントファストスカーレット、ハンザイエ
ロー、ベンジジンイエロー等の不溶性アゾ系顔料、リソ
ールレッド、レーキレッドＣ、レーキレッドＤ等の難溶
性アゾ系顔料、ブリリアントカーミン６Ｂ、パーマネン
トレッドＦ５Ｒ、ピグメントスカーレット３Ｂ、ボルド
ー１０Ｂ等の可溶性アゾ系顔料、フタロシニンブルー、
フタロシアニングリーン、スカイブルー等のフタロシア
ニン系顔料、ローダミンレーキ、マラカイトグリーンレ
ーキ、メチルバイオレットレーキ等の塩基性染料系顔
料、ピーコックブルーレーキ、エオシンレーキ、キノリ
ンイエローレーキ等の酸性染料系顔料、インダンスレン
ブルー、チオインジゴマルーン等の建染料系顔料、アリ
ザリンレーキ等の媒染料系顔料、キナクリドンレッド、
キナクリドンバイオレット、ペリレンレッド、ペリレン
スカーレット、イソインドリノンイエロー、ジオキサジ
ンバイオレット、アニリンブラック、有機蛍光顔料など
が挙げられる。The pigment coated with the reactive water-soluble resin may be either an organic pigment or an inorganic pigment, and also includes an extender pigment and a metal pigment. Examples of organic pigments include natural dye-based pigments such as mudder lake, logwood lake, and cochineal lake, nitroso-based pigments such as naphthol green B and naphthol green Y, nitro-based pigments such as naphthol S and resole fast yellow 2G, and permanent red 4R. , Brilliant Fast Scarlet, Hansa Yellow, Benzidine Yellow and other insoluble azo pigments, Resole Red, Lake Red C, Lake Red D and other insoluble azo pigments, Brilliant Carmine 6B, Permanent Red F5R, Pigment Scarlet 3B, Bordeaux 10B, etc. Soluble azo pigment, phthalosinin blue,
Phthalocyanine pigments such as phthalocyanine green and sky blue, basic dye pigments such as rhodamine lake, malachite green lake, methyl violet lake, acid dye pigments such as peacock blue lake, eosin lake, quinoline yellow lake, indanthrene blue , Thioindigo maroon and other building dye pigments, alizarin lake and other mordant pigments, quinacridone red,
Examples include quinacridone violet, perylene red, perylene scarlet, isoindolinone yellow, dioxazine violet, aniline black and organic fluorescent pigments.
【００１３】無機顔料としては、例えば、クレー、バラ
イト、雲母、黄土等の天然物、黄鉛、亜鉛黄、バリウム
黄等のクロム酸塩、紺青等のフェロシアン化物、銀朱、
カドミウム黄、硫化亜鉛、アンチモン白、カドミウムレ
ッド等の硫化物、硫酸バリウム、硫酸鉛、硫酸ストロン
チウム等の硫酸塩、亜鉛華、チタン白、ベンカラ、鉄
黒、酸化クロム等の酸化物、水酸化アルミニウム等の水
酸化物、ケイ酸カルシウム、グンジョウ等のケイ酸塩、
炭酸カルシウム、炭酸マグネシウム等の炭酸塩、カーボ
ンブラック、松煙、ボーンブラック、グラファイト等の
炭素、アルミニウム粉、ブロンズ粉、亜鉛末等の金属
粉、ヒ酸塩、燐酸塩などが挙げられる。Examples of the inorganic pigments include natural products such as clay, barite, mica and ocher, chromate salts such as yellow lead, zinc yellow and barium yellow, ferrocyanide compounds such as dark blue, silver vermilion, etc.
Cadmium yellow, zinc sulfide, antimony white, sulfides such as cadmium red, sulfates such as barium sulfate, lead sulfate, strontium sulfate, zinc oxide, titanium white, Benkara, iron black, oxides such as chromium oxide, aluminum hydroxide Such as hydroxide, calcium silicate, silicate such as Gunjou,
Examples thereof include carbonates such as calcium carbonate and magnesium carbonate, carbon black, pine smoke, bone black, carbon such as graphite, aluminum powder, bronze powder, metal powder such as zinc dust, arsenate and phosphate.
【００１４】本発明の被覆顔料は、反応性水可溶樹脂の
水ないしアルコール含有水の酸性溶液と顔料とを均一に
混合分散させて反応性水可溶樹脂を顔料表面に吸着させ
顔料を被覆することにより得られる。ここで用いる顔料
は、乾燥顔料であっても、水または有機溶剤を含んだ湿
潤状態の顔料であってもよい。さらに、顔料を反応性水
可溶樹脂で被覆した後、ラジカル開始剤を加えて樹脂間
の架橋を行うことにより、樹脂を顔料に固定化させるこ
とが好ましい。また、反応性水可溶樹脂を顔料に吸着さ
せる際にアルカリを添加し、系をアルカリ性として樹脂
を不溶化させ吸着効率を上げても良い。その際のｐＨ
は、用いる反応性水可溶樹脂に依存し一概には規定でき
ない。また、添加するアルカリ種についても特に限定は
なく一般に用いられているものでよい。In the coated pigment of the present invention, an acidic solution of the reactive water-soluble resin in water or alcohol-containing water and the pigment are uniformly mixed and dispersed, and the reactive water-soluble resin is adsorbed on the surface of the pigment to coat the pigment. It is obtained by doing. The pigment used here may be a dry pigment or a wet pigment containing water or an organic solvent. Furthermore, it is preferable to fix the resin to the pigment by coating the pigment with the reactive water-soluble resin and then adding a radical initiator to crosslink the resin. In addition, an alkali may be added when the reactive water-soluble resin is adsorbed on the pigment to make the system alkaline so as to insolubilize the resin to improve the adsorption efficiency. PH at that time
Depends on the reactive water-soluble resin used and cannot be specified unconditionally. Further, the alkali species to be added is not particularly limited and may be one generally used.
【００１５】反応性水可溶樹脂の使用量は、使用する顔
料の粒径すなわち比表面積に依存すると共に、その顔料
の使用形態にも依存する。樹脂量は樹脂壁の厚みと樹脂
壁の強度に影響を与えるため、樹脂壁の損傷が予測され
る場合、例えば、高顔料濃度で高剪断下にさらされる場
合には量を多くすることが好ましい。しかし、あまり量
を増やすと樹脂単独の凝集体を生じさせたりして最終製
品の物性に悪影響を及ぼす恐れがある。また、少なすぎ
ても被覆が不完全となり十分な効果が得られない。反応
性水可溶樹脂の量はおおむね、顔料１００部に対し０．
５〜５０重量部である。The amount of the reactive water-soluble resin used depends not only on the particle size of the pigment used, that is, the specific surface area, but also on the usage form of the pigment. Since the amount of resin affects the thickness of the resin wall and the strength of the resin wall, it is preferable to increase the amount when damage to the resin wall is predicted, for example, when the resin wall is exposed to high pigment concentration and high shear. . However, if the amount is excessively increased, aggregates of the resin alone may be generated, which may adversely affect the physical properties of the final product. Also, if the amount is too small, the coating will be incomplete and a sufficient effect cannot be obtained. The amount of the reactive water-soluble resin was about 0.
5 to 50 parts by weight.
【００１６】上記混合物を均一に混合分散させるには、
一般の合成等に用いられる撹拌羽根を用いることができ
るが、乾燥顔料などの用いる顔料が著しく凝集している
場合には、サンドミル，アトライター，ビーズミル，コ
ロイドミル，ボールミル，超音波破砕機やホモミキサー
等の分散機を用いてもよい。また、この際に分散助剤と
して極少量の界面活性剤を添加してもよい。得られた被
覆顔料の水性分散体は、そのまま用いても良いし、ろ別
乾燥、スプレードライヤーあるいは凍結乾燥等により乾
燥して用いることもできる。また、アンモニア、苛性ソ
ーダなどのアルカリを加え非水分散性とすることもでき
る。To uniformly mix and disperse the above mixture,
Stirring blades used for general synthesis can be used, but if the pigments used such as dry pigments are significantly aggregated, sand mill, attritor, bead mill, colloid mill, ball mill, ultrasonic crusher or homogenizer. A disperser such as a mixer may be used. At this time, a very small amount of surfactant may be added as a dispersion aid. The obtained aqueous dispersion of the coated pigment may be used as it is, or may be dried by filtration, spray drying, freeze drying or the like. It is also possible to add an alkali such as ammonia or caustic soda to make it non-aqueous dispersible.
【００１７】本発明の被覆顔料は、酸可溶型の水性樹脂
で被覆されているため、酸性水溶液中での分散に優れて
おり、水性インキや水性塗料等への使用に極めて有用で
ある。さらに、顔料を被覆架橋後に、残存する第３級ア
ミノ基に再びエポキシキ基とα，β−不飽和二重結合と
を有する化合物を付加させることにより反応性被覆顔料
を得ることもでき、ＵＶインキやＵＶ塗料等への使用に
も極めて有用である。また、本発明の被覆顔料は、分散
性が優れるため、熱可塑性樹脂等の着色に用いられる顔
料組成物にも好適に用いられる。Since the coated pigment of the present invention is coated with an acid-soluble aqueous resin, it is excellent in dispersion in an acidic aqueous solution and is extremely useful for use in aqueous inks and coatings. Furthermore, after coating and cross-linking the pigment, a reactive coated pigment can be obtained by adding a compound having an epoxy group and an α, β-unsaturated double bond to the remaining tertiary amino group again. It is also extremely useful for use in UV paints and UV paints. Further, since the coated pigment of the present invention has excellent dispersibility, it is suitably used for a pigment composition used for coloring a thermoplastic resin or the like.
【００１８】[0018]
【実施例】以下の実施例で本発明をさらに詳しく説明す
る。なお、実施例および比較例において、部は重量部
を、％は重量％をそれぞれ意味する。 （反応性水可溶樹脂の合成例１）ラウリルメタクリレー
ト３６０部、N,N-ジメチルアミノエチルメタクリレート
１５０部、イソプロピルアルコール３２０部をセパラブ
ルフラスコに仕込み、錨型攪拌羽根で分速２００回転で
攪拌し、窒素雰囲気下８０℃に昇温後、2,2'−アゾビス
（イソブチロニトリル）（以降ＡＩＢＮと略記する）４
部を加え重合を開始した。重合を開始して４時間後、さ
らにＡＩＢＮを１部加えて２時間保持した後、空気をバ
ブリングして空気雰囲気下に戻し、酢酸６０部とグリシ
ジルメタクリレート８１．５部（第３級アミノ基１モル
に対してエポキシ基０．６モルの割合）を加え、２時間
保持して重合を完結せしめ、固形分６０．９％の樹脂溶
液を得た。The present invention will be described in more detail by the following examples. In Examples and Comparative Examples, “parts” means “parts by weight” and “%” means “% by weight”. (Synthesis Example 1 of Reactive Water-Soluble Resin) 360 parts of lauryl methacrylate, 150 parts of N, N-dimethylaminoethyl methacrylate and 320 parts of isopropyl alcohol were charged in a separable flask and stirred with an anchor type stirring blade at a speed of 200 rpm. After heating to 80 ° C. under a nitrogen atmosphere, 2,2′-azobis (isobutyronitrile) (hereinafter abbreviated as AIBN) 4
Parts were added to initiate polymerization. After 4 hours from the start of the polymerization, 1 part of AIBN was further added and held for 2 hours, and then air was bubbled to return to an air atmosphere, and 60 parts of acetic acid and 81.5 parts of glycidyl methacrylate (tertiary amino group 1 An epoxy group (0.6 mol ratio relative to the mol) was added and maintained for 2 hours to complete the polymerization, and a resin solution having a solid content of 60.9% was obtained.
【００１９】（反応性水可溶樹脂の合成例２）スチレン
３６０部、N,N-ジエチルアミノエチルメタクリレート２
７５部、イソプロピルアルコール４９７．８部をセパラ
ブルフラスコに仕込み、錨型攪拌羽根で分速２００回転
で攪拌し、窒素雰囲気下８０℃に昇温後、ＡＩＢＮ４．
７部を加え重合を開始した。重合を開始して４時間後、
さらにＡＩＢＮを1 ．２部加えて２時間保持した後、空
気をバブリングして空気雰囲気下に戻し、酢酸９０部と
グリシジルメタクリレート２１０．８部（第３級アミノ
基１モルに対してエポキシ基１モルの割合）を加え、２
時間保持して重合を完結せしめ、固形分５９．０％の樹
脂溶液を得た。Synthesis Example 2 of Reactive Water-Soluble Resin 360 parts of styrene, N, N-diethylaminoethyl methacrylate 2
75 parts and 497.8 parts of isopropyl alcohol were charged in a separable flask, stirred with an anchor type stirring blade at a speed of 200 rpm, and heated to 80 ° C. under a nitrogen atmosphere, and then AIBN4.
Polymerization was started by adding 7 parts. 4 hours after starting the polymerization,
Further, set AIBN to 1. After adding 2 parts and holding for 2 hours, bubbling air is returned to the air atmosphere, and 90 parts of acetic acid and 210.8 parts of glycidyl methacrylate (1 mol of epoxy group to 1 mol of tertiary amino group) are added. Plus 2
Polymerization was completed by holding for a period of time to obtain a resin solution having a solid content of 59.0%.
【００２０】（反応性水可溶樹脂の合成例３）イソプロ
ピルアルコール１４０６部、エタノール１４０６部エチ
レングリコールモノメチルエーテル６９４部をセパラブ
ルフラスコに仕込み、窒素雰囲気下８０℃に昇温後、メ
チルメタクリレート１００部、エチルアクリレート８０
部、アクリルアミド１４．２部、メタクリル酸ピペリジ
ノエチル１９７部、N,N-ジメチルアミノエチルメタクリ
レート１５０部、ＡＩＢＮ７．９部よりなる混合物を約
２時間かけて滴下し、さらに２時間加熱を続けＡＩＢＮ
を４部加えて２時間保持した後、空気をバブリングして
空気雰囲気下に戻し、酢酸６０部とグリシジルメタクリ
レート１．３６部（第３級アミノ基１モルに対してエポ
キシ基０．０１モルの割合）を加え、２時間保持して重
合を完結せしめ、固形分３０．１％の樹脂溶液を得た。(Synthesis Example 3 of Reactive Water-Soluble Resin) 1406 parts of isopropyl alcohol, 1406 parts of ethanol and 694 parts of ethylene glycol monomethyl ether were charged in a separable flask, heated to 80 ° C. under a nitrogen atmosphere, and then 100 parts of methyl methacrylate. , Ethyl acrylate 80
Part, acrylamide 14.2 parts, piperidinoethyl methacrylate 197 parts, N, N-dimethylaminoethyl methacrylate 150 parts, AIBN 7.9 parts was added dropwise over about 2 hours, and heating was continued for another 2 hours.
Was added for 4 hours and then air was bubbled back to return to the air atmosphere, and 60 parts of acetic acid and 1.36 parts of glycidyl methacrylate (1 mol of the tertiary amino group and 0.01 mol of the epoxy group were added). Ratio) was added and maintained for 2 hours to complete the polymerization to obtain a resin solution having a solid content of 30.1%.
【００２１】（製造例１）反応性水可溶樹脂の合成例１
で得られた樹脂溶液４１部と水５０００部を反応容器に
入れ８０℃で撹拌下、フタロシアニン顔料「リオノール
ブルーＦＧ７３５１」（東洋インキ製造社製）５００部
を投入し、４時間撹拌を続けた。その後、系内を窒素置
換した後、ＡＩＢＮ０．２５部を添加し４時間熟成した
後、濾過水洗し、８０℃で２４時間乾燥して乾燥被覆顔
料を得た。Production Example 1 Synthesis Example 1 of Reactive Water-Soluble Resin
41 parts of the resin solution obtained in 1. and 5000 parts of water were put into a reaction vessel and stirred at 80 ° C., 500 parts of a phthalocyanine pigment “Rionol Blue FG7351” (manufactured by Toyo Ink Mfg. Co., Ltd.) was added, and stirring was continued for 4 hours. . Then, the system was replaced with nitrogen, 0.25 part of AIBN was added, the mixture was aged for 4 hours, washed with filtered water, and dried at 80 ° C. for 24 hours to obtain a dry coated pigment.
【００２２】（製造例２）反応性水可溶樹脂の合成例１
で得られた樹脂溶液４１部と水５０００部を反応容器に
入れ８０℃で撹拌下、フタロシアニン顔料の水性湿潤ケ
ーキ「リオノールブルーＦＧ７３３４Ｐ」（東洋インキ
製造社製，顔料分４６％）１０８７部を投入し、４時間
撹拌を続けた。その後、系内を窒素置換した後、ＡＩＢ
Ｎ０．２５部を添加し４時間熟成した後、これを入口温
度２２０℃，出口温度１００℃に調整したスプレードラ
イヤーで乾燥し、乾燥被覆顔料を得た。Production Example 2 Synthesis Example 1 of Reactive Water-Soluble Resin
41 parts of the resin solution obtained in above and 5000 parts of water were placed in a reaction vessel and stirred at 80 ° C., and 1087 parts of an aqueous wet cake of phthalocyanine pigment “Rionol Blue FG7334P” (manufactured by Toyo Ink Mfg. Co., Ltd., pigment content 46%) was added. It was charged and the stirring was continued for 4 hours. Then, after purging the system with nitrogen, AIB
After adding 0.25 part of N and aging for 4 hours, this was dried with a spray dryer adjusted to an inlet temperature of 220 ° C. and an outlet temperature of 100 ° C. to obtain a dry coated pigment.
【００２３】（製造例３）反応性水可溶樹脂の合成例１
で得られた樹脂溶液４１部と水５０００部を反応容器に
入れ８０℃で撹拌下、フタロシアニン顔料の水性湿潤ケ
ーキ「リオノールブルーＦＧ７３３４Ｐ」（東洋インキ
製造社製，顔料分４６％）１０８７部を投入し、４時間
撹拌を続けた。その後、入口温度２２０℃，出口温度１
００℃に調整したスプレードライヤーで乾燥し、乾燥被
覆顔料を得た。Production Example 3 Synthesis Example 1 of Reactive Water-Soluble Resin
41 parts of the resin solution obtained in above and 5000 parts of water were placed in a reaction vessel and stirred at 80 ° C., and 1087 parts of an aqueous wet cake of phthalocyanine pigment “Rionol Blue FG7334P” (manufactured by Toyo Ink Mfg. Co., Ltd., pigment content 46%) was added. It was charged and the stirring was continued for 4 hours. After that, the inlet temperature 220 ℃, the outlet temperature 1
It was dried with a spray dryer adjusted to 00 ° C to obtain a dry coated pigment.
【００２４】（製造例４）反応性水可溶樹脂の合成例１
で得られた樹脂溶液４１部と水５０００部を反応容器に
入れ８０℃で撹拌下、キナクリドン顔料「ファストゲン
スーパー マゼンタ ＲＥ０３」（大日本インキ化学
工業社製）５００部を投入し、３時間ホモミキサーで分
散を行った。希水酸化ナトリウムを加えてｐＨ９とし、
さらに２時間撹拌を続けた。系内を窒素置換した後、Ａ
ＩＢＮ１．５部を添加し４時間熟成し、被覆顔料の水性
分散体を得た。濾過水洗し、８０℃で２４時間乾燥して
乾燥被覆顔料を得た。Production Example 4 Synthesis Example 1 of Reactive Water-Soluble Resin
41 parts of the resin solution obtained in the above and 5000 parts of water were put into a reaction vessel and stirred at 80 ° C., 500 parts of quinacridone pigment “Fastgen Super Magenta RE03” (manufactured by Dainippon Ink and Chemicals, Inc.) was added, and homogenized for 3 hours. Dispersion was performed with a mixer. Add dilute sodium hydroxide to bring the pH to 9,
Stirring was continued for another 2 hours. After replacing the system with nitrogen,
1.5 parts of IBN was added and the mixture was aged for 4 hours to obtain an aqueous dispersion of coated pigment. It was filtered, washed with water and dried at 80 ° C. for 24 hours to obtain a dry coated pigment.
【００２５】（製造例５）反応性水可溶樹脂の合成例２
で得られた樹脂溶液4.1 部とイソプロピルアルコール５
００部を反応容器に入れ８０℃で撹拌下、酸化チタン
「タイペークＣＲ−８０」（石原産業社製）５００部を
投入し、２時間撹拌を続けた。その後、系内を窒素置換
した後、ＡＩＢＮ０．２５部を添加し４時間熟成した
後、濾過水洗し、８０℃で２４時間乾燥して乾燥被覆顔
料を得た。Production Example 5 Synthesis Example 2 of Reactive Water-Soluble Resin
4.1 parts of the resin solution obtained in step 5 and isopropyl alcohol 5
100 parts of the reaction mixture was placed in a reaction vessel, 500 parts of titanium oxide "Taipec CR-80" (manufactured by Ishihara Sangyo Co., Ltd.) was added under stirring at 80 ° C., and stirring was continued for 2 hours. Then, the system was replaced with nitrogen, 0.25 part of AIBN was added, the mixture was aged for 4 hours, washed with filtered water, and dried at 80 ° C. for 24 hours to obtain a dry coated pigment.
【００２６】（製造例６）反応性水可溶樹脂の合成例１
で得られた樹脂溶液４１０部と水５０００部を反応容器
に入れ８０℃で撹拌下、弁柄「トダカラー１８０ＥＤ」
（戸田工業社製）５００部を投入し、4 時間撹拌を続け
た。さらにその後、系内を窒素置換した後、ＡＩＢＮ
０．２５部を添加し４時間熟成した後、濾過水洗し、８
０℃で２４時間乾燥して乾燥被覆顔料を得た。Production Example 6 Synthesis Example 1 of Reactive Water-Soluble Resin
410 parts of the resin solution obtained in the above and 5000 parts of water were put into a reaction vessel and stirred at 80 ° C. under a valve handle “Toda Color 180ED”.
500 parts (manufactured by Toda Kogyo Co., Ltd.) was added and stirring was continued for 4 hours. After that, after replacing the inside of the system with nitrogen, AIBN
After 0.25 parts was added and the mixture was aged for 4 hours, it was filtered and washed with water, and 8
It was dried at 0 ° C. for 24 hours to obtain a dry coated pigment.
【００２７】（製造例７）反応性水可溶樹脂の合成例３
で得られた樹脂溶液３３３．３部と水５０００部を反応
容器に入れ８０℃で撹拌下、縮合アゾイエロー顔料「ク
ロモフタルイエローＧＲ」（チバ・ガイギー社製）５０
０部を投入し、４時間撹拌を続けた。その後、系内を窒
素置換した後、ＡＩＢＮ０．２５部を添加し４時間熟成
した後、濾過水洗し、８０℃で２４時間乾燥して乾燥被
覆顔料を得た。Production Example 7 Synthesis Example 3 of Reactive Water-Soluble Resin
333.3 parts of the resin solution obtained in 1. and 5000 parts of water were put in a reaction vessel and stirred at 80 ° C., and condensed azo yellow pigment “Chromophtal yellow GR” (manufactured by Ciba Geigy) 50
0 part was added and stirring was continued for 4 hours. Then, the system was replaced with nitrogen, 0.25 part of AIBN was added, the mixture was aged for 4 hours, washed with filtered water, and dried at 80 ° C. for 24 hours to obtain a dry coated pigment.
【００２８】（製造例８）フタロシアニン顔料「リオノ
ールグリーン ２Ｙ−３０１」（東洋インキ製造社製）
５００部を用いた以外は、製造例４と同様にして乾燥被
覆顔料を得た。(Production Example 8) Phthalocyanine pigment "Rionol Green 2Y-301" (manufactured by Toyo Ink Mfg. Co., Ltd.)
A dry coated pigment was obtained in the same manner as in Production Example 4 except that 500 parts were used.
【００２９】（製造例９）反応性水可溶樹脂の合成例１
で得られた樹脂溶液４１部と水４１４８部を反応容器に
入れ８０℃で撹拌下、ベンジジンイエロー顔料の水性湿
潤ケーキ「リオノールイエローＧＧＴ」（東洋インキ製
造社製，顔料分３７％）１３５１部を投入し、4 時間撹
拌を続けた。その後、系内を窒素置換した後、ＡＩＢＮ
０．２５部を添加し４時間熟成した後、濾過水洗し、被
覆顔料の水性湿潤ケーキを得た。Production Example 9 Synthesis Example 1 of Reactive Water-Soluble Resin
41 parts of the resin solution obtained in 4 and 4148 parts of water were placed in a reaction vessel and stirred at 80 ° C., 1351 parts of an aqueous wet cake of benzidine yellow pigment “Rionol Yellow GGT” (Toyo Ink Mfg. Co., Ltd., pigment content 37%). Was added and stirring was continued for 4 hours. Then, after purging the system with nitrogen, AIBN
After 0.25 part was added and the mixture was aged for 4 hours, it was filtered and washed with water to obtain an aqueous wet cake of coated pigment.
【００３０】（製造例１０）キナクリドン顔料「ファス
トゲン スーパー マゼンタ ＲＥ０３」の代わりにキ
ナクリドン顔料「シンカシャレッドＹＲＴ７５９Ｄ」
（チバ・ガイギー社製）を用いた以外は、製造例４と同
様にして乾燥被覆顔料を得た。 （製造例１１）キナクリドン顔料「ファストゲン スー
パー マゼンタ ＲＥ０３」の代わりに群青「グンジョ
ウ＃２０００」（第一化成工業社製）を用いた以外は、
製造例４と同様にして乾燥被覆顔料を得た。(Production Example 10) Instead of quinacridone pigment "Fastgen Super Magenta RE03", quinacridone pigment "Shinkasha Red YRT759D"
A dry coated pigment was obtained in the same manner as in Production Example 4 except that (Ciba Geigy) was used. (Production Example 11) A quinacridone pigment "Fastgen Super Magenta RE03" was used instead of ultramarine "Gunjou # 2000" (manufactured by Daiichi Kasei Kogyo Co., Ltd.).
A dry coated pigment was obtained in the same manner as in Production Example 4.
【００３１】（製造例１２）キナクリドン顔料「ファス
トゲン スーパー マゼンタ ＲＥ０３」の代わりにカ
ーボンブラック「三菱カーボン＃１０」（三菱化学社
製）を用いた以外は、製造例４と同様にして乾燥被覆顔
料を得た。 （製造例１３）キナクリドン顔料「ファストゲン スー
パー マゼンタ ＲＥ０３」の代わりにカーボンブラッ
ク「三菱カーボンＭＡ−１００」（三菱化学社製）を用
いた以外は、製造例５と同様にして乾燥被覆顔料を得
た。(Production Example 12) A dry-coated pigment was produced in the same manner as in Production Example 4, except that carbon black "Mitsubishi Carbon # 10" (manufactured by Mitsubishi Chemical Corporation) was used in place of the quinacridone pigment "Fastgen Super Magenta RE03". Got (Production Example 13) A dry-coated pigment was obtained in the same manner as in Production Example 5, except that carbon black "Mitsubishi Carbon MA-100" (manufactured by Mitsubishi Chemical Co., Ltd.) was used instead of the quinacridone pigment "Fastgen Super Magenta RE03". It was
【００３２】（製造例１４）反応性水可溶樹脂樹脂の合
成例１で得られた樹脂溶液４１部と水５０００部を反応
容器に入れ８０℃撹拌下、カーボンブラック「三菱カー
ボンＭＡ−１００」（三菱化学社製）５００部を投入
し、４時間撹拌を続けた。その後、系内を窒素置換した
後、ＡＩＢＮ０．２５部を添加し４時間熟成した後、空
気をバブリングして系内を空気置換し、グリシジルメタ
クリレート３.4部を添加し２時間後、濾過水洗し、８０
℃で２４時間乾燥して乾燥被覆顔料を得た。Production Example 14 Reactive Water-Soluble Resin 41 parts of the resin solution obtained in Synthesis Example 1 of resin and 5000 parts of water were placed in a reaction vessel and stirred at 80 ° C. under a carbon black “Mitsubishi Carbon MA-100”. 500 parts (manufactured by Mitsubishi Chemical Co., Ltd.) were added and stirring was continued for 4 hours. Then, after purging the system with nitrogen, 0.25 part of AIBN was added and aged for 4 hours, then air was bubbled to replace the system with air, 3.4 parts of glycidyl methacrylate was added, and 2 hours later, filtered and washed with water. Then 80
Drying was performed at 24 ° C. for 24 hours to obtain a dry coated pigment.
【００３３】（実施例１）製造例１で得られた被覆顔料
の熱可塑性樹脂中での分散を確認するために、以下の手
順でマスターバッチを作製し評価した。 製造例１で得られた被覆顔料 ４０部 ポリエチレン「三菱ポリエチＵＪ７９０Ｇ」（三菱化学社製）６０部 上記２成分をニーダーで混練し、スクリュー直径６５ｍ
ｍの押出成形機でペレット化し、マスターバッチを得
た。この際ストランド切れや脈流を生じることなしに順
調にマスターバッチを得ることができた。ポリプロピレ
ン「三井ノーブレンＪＨ−Ｇ」（三井石油化学工業社
製）１００部に、得られたマスターバッチ２部を混合し
て、縦型テスト紡糸機（富士フィルター社製スピニング
テスター）にて、ホッパー下２３０℃、混練部、ダイス
部２３０℃にて紡糸後３倍延伸を行い、５デニールのポ
リプロピレン繊維を得た。紡糸性、目詰まり性、延伸性
共問題なく良好な分散性を示した。Example 1 In order to confirm the dispersion of the coated pigment obtained in Production Example 1 in a thermoplastic resin, a masterbatch was prepared and evaluated in the following procedure. Coated pigment obtained in Production Example 1 40 parts Polyethylene "Mitsubishi Poly UJ790G" (manufactured by Mitsubishi Chemical Corporation) 60 parts The above two components were kneaded with a kneader, and the screw diameter was 65 m.
m was extruded into pellets to obtain a masterbatch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of polypropylene "Mitsui Noblen JH-G" (manufactured by Mitsui Petrochemical Industry Co., Ltd.) was mixed with 2 parts of the obtained masterbatch, and a vertical test spinning machine (spinning tester manufactured by Fuji Filter Co., Ltd.) was used under a hopper. After spinning at 230 ° C., kneading section, and die section at 230 ° C., stretching was performed 3 times to obtain a polypropylene fiber having 5 denier. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.
【００３４】未分散顔料の目詰まり性を比較するため
に、得られたマスターバッチ２３．３部をポリプロピレ
ン「三井ノーブレンＪＨ−Ｇ」１００部に混合し、先端
に５００メッシュの金網を装着したスクリュー径が３０
ｍｍの単軸押出機で混合物を３Ｋｇ押し出し、先端部で
の圧力上昇値を測定し、未分散顔料の目詰まり性をそれ
ぞれ評価した。また、顔料の分散発色性を比較するため
に、得られたマスターバッチ２部を酸化チタンマスター
バッチ「ＴＥＴ１２５３４Ｗ−Ｔ」（東洋インキ製造社
製）５部とポリプロピレン「三井ハイポールＪ８００」
（三井石油化学工業社製，メルトフローレート：２２）
１００部に配合したものを２本ロールミルで混練し冷却
プレスで２ｍｍ厚のプレートに成形した。次に、色差計
ＫＵＲＡＢＯ Ｃｏｌｏｒ−７Ｅ（ＫＵＲＡＢＯ社製）
を用いて波長６４０ｎｍの反射率を測定し、その反射率
におけるＫｕｂｅｌｋａ−Ｍｕｎｋ関数値（ｋ／ｓ値）
を求め発色強度とした。以上の結果を表１に示す。In order to compare the clogging properties of undispersed pigments, 23.3 parts of the obtained masterbatch was mixed with 100 parts of polypropylene "Mitsui Noblen JH-G", and a screw equipped with a 500-mesh wire mesh at the tip. Diameter is 30
3 kg of the mixture was extruded with a mm single-screw extruder, the pressure rise value at the tip was measured, and the clogging property of the undispersed pigment was evaluated. Further, in order to compare the dispersion coloring properties of the pigments, 2 parts of the obtained masterbatch was used as 5 parts of titanium oxide masterbatch "TET12534W-T" (manufactured by Toyo Ink Mfg. Co., Ltd.) and polypropylene "Mitsui Hypol J800".
(Mitsui Petrochemical Co., Ltd., melt flow rate: 22)
A mixture of 100 parts was kneaded with a two-roll mill and formed into a plate having a thickness of 2 mm by a cooling press. Next, color difference meter KURABO Color-7E (manufactured by KURABO)
Was used to measure the reflectance at a wavelength of 640 nm, and the Kubelka-Munk function value (k / s value) at the reflectance was measured.
Was calculated as the coloring intensity. Table 1 shows the above results.
【００３５】さらに、メルトフローレート：６．５のポ
リエチレン「ハイゼックス２１００Ｊ」（三井石油化学
工業社製）１００部に、得られたマスターバッチ３部を
混合して、射出成形機にて背圧０Ｋｇ／ｃｍ2 でプレー
トに成形した。得られた成形品の機械的物性，表面の色
ムラおよび顔料分散性度を評価した結果およびマスター
バッチの生産性を表２にまとめる。Furthermore, 100 parts of polyethylene "Hi-Zex 2100J" (manufactured by Mitsui Petrochemical Industry Co., Ltd.) having a melt flow rate of 6.5 was mixed with 3 parts of the obtained masterbatch, and a back pressure of 0 kg was obtained with an injection molding machine. Molded into plates at / cm 2 . Table 2 summarizes the results of evaluating the mechanical properties, surface color unevenness, and pigment dispersibility of the obtained molded product, and the productivity of the master batch.
【００３６】（実施例２〜３）製造例１で得られた被覆
顔料の代わりに製造例２〜３で得られた被覆顔料を用い
た以外は、実施例１と同様にしてマスターバッチを得
た。この際ストランド切れや脈流を生じることなしに順
調にマスターバッチを得ることができた。さらに、得ら
れたマスターバッチを用いて実施例１と同様に紡糸を行
ったところ目詰まり性、延伸性共問題なく良好な分散性
を示した。実施例１と同様に各種評価をし、結果を表
１、２に示す。(Examples 2 to 3) A masterbatch was obtained in the same manner as in Example 1 except that the coated pigment obtained in Production Examples 2 to 3 was used in place of the coated pigment obtained in Production Example 1. It was At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Furthermore, when the obtained masterbatch was used to carry out spinning in the same manner as in Example 1, good dispersibility was exhibited without any problems in clogging and stretchability. Various evaluations were performed in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
【００３７】（比較例１）製造例１で得られた被覆顔料
の代わりに未処理のフタロシアニン顔料「リオノールブ
ルーＦＧ７３３０」を用いた以外は、実施例１と同様に
してマスターバッチを得た。この際ストランド切れや脈
流を生じることなしに順調にマスターバッチを得ること
ができた。しかし、得られたマスターバッチを用いて実
施例１と同様に紡糸を行ったところ目詰まりによる糸切
れが発生した。実施例１と同様に各種評価をし、結果を
表１、２に示す。Comparative Example 1 A masterbatch was obtained in the same manner as in Example 1 except that the untreated phthalocyanine pigment "Rionol Blue FG7330" was used in place of the coated pigment obtained in Production Example 1. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. However, when the obtained masterbatch was used for spinning in the same manner as in Example 1, yarn breakage due to clogging occurred. Various evaluations were performed in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
【００３８】（比較例２）製造例１で得られた被覆顔料
の代わりに、未処理のフタロシアニン顔料の水性湿潤ケ
ーキ「リオノールブルーＦＧ７３３４Ｐ」を８０℃で２
４時間乾燥させたものを用いた以外は実施例１と同様に
してマスターバッチを得た。この際ストランド切れや脈
流を生じることなしに順調にマスターバッチを得ること
ができた。しかし、得られたマスターバッチを用いて実
施例１と同様に紡糸を行ったところ目詰まりによる糸切
れが発生した。実施例１と同様に各種評価をし、結果を
表１、２に示す。Comparative Example 2 Instead of the coated pigment obtained in Production Example 1, an untreated phthalocyanine pigment aqueous wet cake "Rionol Blue FG7334P" was used at 80.degree.
A masterbatch was obtained in the same manner as in Example 1 except that the one dried for 4 hours was used. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. However, when the obtained masterbatch was used for spinning in the same manner as in Example 1, yarn breakage due to clogging occurred. Various evaluations were performed in the same manner as in Example 1, and the results are shown in Tables 1 and 2.
【００３９】（実施例４） 製造例４で得られた被覆顔料 ２０部 ポリエチレン「ＵＪ７９０Ｇ」 （三菱化学社製，メルトフローレート：５０） ６５部 ポリエチレンワックス「ＮＬ５００」 （三井石油化学工業社製） １５部 上記３成分を３本ロールミルで混練し、スクリュー直径
６５ｍｍの押出成形機でペレット化し、マスターバッチ
を得た。この際ストランド切れや脈流を生じることなし
に順調にマスターバッチを得ることができた。タルク２
０％を含有するポリエチレン組成物１００部に、得られ
たマスターバッチ３部を混合して、射出成形機にて背圧
０Ｋｇ／ｃｍ2 でプレートを成形し、実施例１と同様に
各種の評価をした。結果を表２にまとめる。(Example 4) Coated pigment obtained in Production Example 4 20 parts Polyethylene "UJ790G" (Mitsubishi Chemical Co., melt flow rate: 50) 65 parts Polyethylene wax "NL500" (Mitsui Petrochemical Co., Ltd.) 15 parts The above three components were kneaded with a three-roll mill and pelletized with an extruder having a screw diameter of 65 mm to obtain a masterbatch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Talc 2
100 parts of a polyethylene composition containing 0% was mixed with 3 parts of the obtained masterbatch, and a plate was molded with an injection molding machine at a back pressure of 0 kg / cm 2 , and various evaluations were performed in the same manner as in Example 1. Did. The results are summarized in Table 2.
【００４０】（実施例５） ポリエチレン「スミカセンＧ−８０８」 （住友化学工業社製，軟化温度：７８℃） ４０部 製造例５で得られた被覆顔料 ２０部 製造例６で得られた被覆顔料 ４０部 上記３成分を３本ロールミルで混練し、スクリュー直径
６５ｍｍの押出成形機でペレット化し、マスターバッチ
を得た。この際ストランド切れや脈流を生じることなし
に順調にマスターバッチを得ることができた。実施例５
と同様にしてプレートを成形し各種評価をした。結果を
表２に示す。Example 5 Polyethylene "Sumikasen G-808" (Sumitomo Chemical Co., Ltd., softening temperature: 78 ° C.) 40 parts Coated pigment obtained in Production Example 20 20 parts Coated pigment obtained in Production Example 6 40 parts The above three components were kneaded with a three-roll mill and pelletized with an extruder having a screw diameter of 65 mm to obtain a masterbatch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Example 5
A plate was molded in the same manner as in, and various evaluations were performed. Table 2 shows the results.
【００４１】（実施例６） 製造例７で得られた被覆顔料 １０部 ポリエチレン「スミカセンＧ−８０１」 （住友化学工業社製，軟化温度８３℃） ９０部 上記２成分を３本ロールミルで混練し、スクリュー直径
６５ｍｍの押出成形機でペレット化し、マスターバッチ
を得た。この際ストランド切れや脈流を生じることなし
に順調にマスターバッチを得ることができた。エチレン
・酢酸ビニル共重合体樹脂「サンテックＥＶＡ」（旭化
成工業社製）１００部に、得られたマスターバッチ１０
部を混合して、射出成形機にて背圧０Ｋｇ／ｃｍ2 でプ
レートに成形し、実施例１と同様にして、各種の評価を
した。結果を表２にまとめる。Example 6 Coated pigment obtained in Production Example 10 10 parts Polyethylene "Sumikasen G-801" (Sumitomo Chemical Co., Ltd., softening temperature 83 ° C.) 90 parts The above two components were kneaded with a three-roll mill. , And pelletized with an extruder having a screw diameter of 65 mm to obtain a masterbatch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of ethylene-vinyl acetate copolymer resin "Suntech EVA" (manufactured by Asahi Kasei Kogyo Co., Ltd.), and the obtained masterbatch 10
The parts were mixed and molded into a plate with a back pressure of 0 Kg / cm 2 using an injection molding machine, and various evaluations were performed in the same manner as in Example 1. The results are summarized in Table 2.
【００４２】（実施例７） 製造例８で得られた被覆顔料 ５部 ポリエチレン「ペトロセン ３５６」 （東ソー社製，メルトフローレート：１００） ９５部 上記３成分を３本ロールミルで混練し、スクリュー直径
６５ｍｍの押出成形機でペレット化し、マスターバッチ
を得た。この際ストランド切れや脈流を生じることなし
に順調にマスターバッチを得ることができた。ポリプロ
ピレン系樹脂「三井ハイポールＪ７４０」（三井石油化
学工業社製）１００部に、得られたマスターバッチ１０
部を混合して、射出成形機にて背圧０Ｋｇ／ｃｍ2 でプ
レートに成形し、実施例１と同様にして、各種の評価を
した。結果を表２にまとめる。(Example 7) Coated pigment obtained in Production Example 8 5 parts Polyethylene "Petrosene 356" (manufactured by Tosoh Corporation, melt flow rate: 100) 95 parts The above three components were kneaded with a three-roll mill, and screw diameter was obtained. A masterbatch was obtained by pelletizing with a 65 mm extruder. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained masterbatch 10 was added to 100 parts of polypropylene resin "Mitsui High Pole J740" (manufactured by Mitsui Petrochemical Industry Co., Ltd.).
The parts were mixed and molded into a plate with a back pressure of 0 Kg / cm 2 using an injection molding machine, and various evaluations were performed in the same manner as in Example 1. The results are summarized in Table 2.
【００４３】（比較例３〜６）実施例４〜７において被
覆顔料の代わりに処理前の顔料を用いた以外は同様であ
る。Comparative Examples 3 to 6 The same as in Examples 4 to 7 except that the untreated pigment was used in place of the coated pigment.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【表２】 *1 無着色樹脂の機械物性(100％）に対するマスターバ
ッチで着色された樹脂の機械的物性の保持率。 ○：96％以上 △：90〜96％ ×：90％未満 *2 成型品表面の色ムラを目視で評価した。 ○：色ムラなし △：色ムラ少々あり ×：色ムラ顕著[Table 2] * 1 Retention rate of mechanical properties of resin colored by masterbatch against mechanical properties (100%) of uncolored resin. ：: 96% or more △: 90 to 96% ×: less than 90% * 2 Color unevenness on the surface of the molded product was visually evaluated. ○: no color unevenness Δ: slight color unevenness ×: noticeable color unevenness
【００４６】*3 被着色樹脂 100部とマスターバッチ 3
部を配合した混練物をプレス温度 170℃の条件下でプレ
ス加工し、 0.1ｍｍ厚さのフィルムを得た。得られたフ
ィルム中の顔料の粗大粒子の大きさとその数をLuzex450
画像処理機（東洋インキ製造社製）で測定した。 5：50μｍ以下の粒子数 700個／ｃｍ2 未満 4：50μｍ以下の粒子数 700〜1000個／ｃｍ2 3：50μｍ以下の粒子数 1000〜7000個／ｃｍ2 2：50μｍ以下の粒子数 7000〜 27000個／ｃｍ2 1：50μｍ以下の粒子数 27000個／ｃｍ2 以上 *4 スクリュー直径65ｍｍの押出成型機によるマスター
バッチの生産性。 ○：良好 ×：不良* 3 100 parts of resin to be colored and masterbatch 3
The kneaded product containing 1 part was pressed at a pressing temperature of 170 ° C. to obtain a film having a thickness of 0.1 mm. The size and number of coarse particles of pigment in the obtained film were measured by Luzex 450.
It measured with the image processing machine (made by Toyo Ink Mfg. Co., Ltd.). 5: 50 μm or less particles less than 700 particles / cm 2 4: 50 μm or less particles 700 to 1000 particles / cm 2 3: 50 μm or less particles 1000 to 7000 particles / cm 2 2: 50 μm or less particles 7000 to 27,000 particles / cm 2 1: 50 μm or less particles 27,000 particles / cm 2 or more * 4 Masterbatch productivity with an extruder with a screw diameter of 65 mm. ：: good ×: bad
【００４７】（実施例８）ロジン変成フェノール樹脂
「タマノール３６１」（荒川化学社製）５０部に対しア
マニ油２０部、インキ溶剤「５号ソルベント」（日本石
油社製）３０部を加え、２００℃に加熱して溶解させ
た。このビヒクル９８部にオクチル酸アルミニウム２部
を加えオフセットインキ用ビヒクルとした。オフセット
インキ用ビヒクル７０部を紙コップに入れ、これに製造
例１で得られた被覆顔料２０部を加え均一になるよう混
合撹拌してプレミックスインキを作成した。このプレミ
ックス用インキを３本ロールで練肉すると２パスで粗粒
子が消失したのに対し、未処理の顔料では４パスで粗粒
子が消失した。このことは被覆処理により分散性が向上
したことを示唆している。また、タック９．０〜９．５
に調整したインキをアート紙へ展色刷りし６０度光沢値
を測定したところ、未処理顔料使用時に比べ処理顔料を
用いた場合は５．０％高光沢であった。Example 8 To 50 parts of rosin-modified phenolic resin "Tamanol 361" (manufactured by Arakawa Chemical Co., Ltd.), 20 parts of linseed oil and 30 parts of ink solvent "No. 5 solvent" (manufactured by Nippon Oil Co., Ltd.) were added to prepare 200 parts. It was heated to 0 ° C. and dissolved. To 98 parts of this vehicle, 2 parts of aluminum octylate were added to prepare a vehicle for offset ink. 70 parts of a vehicle for offset ink was put in a paper cup, 20 parts of the coated pigment obtained in Production Example 1 was added thereto, and the mixture was stirred uniformly to prepare a premix ink. When this premix ink was kneaded with 3 rolls, coarse particles disappeared in 2 passes, whereas coarse particles disappeared in 4 passes with untreated pigment. This suggests that the dispersibility was improved by the coating treatment. In addition, the tack is 9.0 to 9.5.
When the 60% gloss value was measured by color-printing the ink adjusted to (1) on art paper, it was 5.0% higher gloss when using the treated pigment than when using the untreated pigment.
【００４８】（実施例９）実施例８で用いたオフセット
インキ用ビヒクル７０部を紙コップに入れ、これに製造
例７で得られた被覆顔料２０部を加え均一になるよう混
合撹拌してプレミックスインキを作成した。このプレミ
ックス用インキを３本ロールで練肉すると２パスで粗粒
子が消失したのに対し、未処理の顔料では４パスで粗粒
子が消失した。このことは被覆処理により分散性が向上
したことを示唆している。また、タック９．０〜９．５
に調整したインキをアート紙へ展色刷りしたときの光沢
は、未処理顔料使用時に比べに比べ処理顔料を用いた場
合は４．３％高光沢であった。(Example 9) 70 parts of the vehicle for offset ink used in Example 8 was put in a paper cup, 20 parts of the coated pigment obtained in Production Example 7 was added thereto, and the mixture was stirred uniformly to prepare a mixture. Created a mixed ink. When this premix ink was kneaded with 3 rolls, coarse particles disappeared in 2 passes, whereas coarse particles disappeared in 4 passes with untreated pigment. This suggests that the dispersibility was improved by the coating treatment. In addition, the tack is 9.0 to 9.5.
The gloss of the ink adjusted in accordance with Example 1 when printed on art paper was 4.3% higher than that of the untreated pigment when the treated pigment was used.
【００４９】（実施例１０）製造例８で得られた被覆顔
料１０部、ライムロジン系ワニス（固形分２０％、トル
エン７５％、可塑剤５％）９０部及び直径３ｍｍのガラ
スビーズを２２０ｃｃのマヨネーズビンにいれ、ペイン
トコンディショナーで30分間分散して濃色インキを得
た。濃色インキの６０度光沢値を測定したところ、未処
理の顔料使用時に比べ４％高光沢であった。また、ザー
ンカップ＃３で粘度を測定したところ未処理の顔料使用
時には４６秒であったのに対し被覆顔料使用時には３３
秒であった。(Example 10) 10 parts of the coated pigment obtained in Production Example 8, 90 parts of lime rosin varnish (solid content 20%, toluene 75%, plasticizer 5%) and glass beads having a diameter of 3 mm of 220 cc mayonnaise. Put in a bottle and disperse with a paint conditioner for 30 minutes to obtain a dark ink. When the 60 ° gloss value of the dark ink was measured, it was 4% higher than that when the untreated pigment was used. Further, when the viscosity was measured by Zahn cup # 3, it was 46 seconds when the untreated pigment was used, while it was 33 seconds when the coated pigment was used.
Seconds.
【００５０】（実施例１１）製造例１１で得られた被覆
顔料８部、アルキッド樹脂ワニス「フタルキッド２３５
−５０」（日立化成工業社製）２０部、メラミン樹脂ワ
ニス「メラン２８」（日立化成工業社製）１０部、キシ
レン５０部およびシンナー１２部を直径２ｍｍのスチー
ルビーズと共に２２０ｃｃのマヨネーズビンに入れペイ
ントコンディショナーで３０分間分散して油性塗料を作
成した。これをブリキ板にスプレーコーターで塗布し、
２００℃で１０分間焼き付けを行った。塗面の６０度光
沢値を測定したところ、未処理の顔料使用時に比べ５％
高光沢であった。(Example 11) 8 parts of the coated pigment obtained in Production Example 11, alkyd resin varnish "Phtalkid 235"
-50 "(manufactured by Hitachi Chemical Co., Ltd.), melamine resin varnish" Melan 28 "(manufactured by Hitachi Chemical Co., Ltd.) 10 parts, xylene 50 parts and thinner 12 parts are put together with steel beads having a diameter of 2 mm into a 220 cc mayonnaise bottle. An oil paint was prepared by dispersing for 30 minutes with a paint conditioner. Apply this to a tin plate with a spray coater,
Baking was performed at 200 ° C. for 10 minutes. When the 60 degree gloss value of the coated surface was measured, it was 5% compared to when untreated pigment was used.
It had a high gloss.
【００５１】（実施例１２） ｍ−キシレンビスステアリン酸アミド「スリパックスＺＸＳ」 （日本化成社製） １００部 製造例１２で得られた被覆顔料 １０部 負帯電制御剤「ポントロンＥ８１」（オリエント化学社製 ) ３部 ポリプロピレンワックス「ビスコール５５０Ｐ」 （三洋化成工業社製） ２部 ポリスチレン「エスプライト２Ｖ」（昭和電工社製） ５部 上記５成分を混合し、２本ロールミルで１３０℃で加熱
混練をしてミルベースを得、これをハンマーミルで粗粉
砕し、続いてジェットミルで微粉砕した後分級して、平
均粒子径１３μｍのトナー（着色樹脂組成物）を得た。
得られたトナーを酸化鉄粉「ＥＦＶ２００」（日本鉄粉
社製）をキャリアとして混合し、トナー濃度５％の現像
剤を作成した。(Example 12) m-xylene bisstearic acid amide "Sripax ZXS" (manufactured by Nippon Kasei Co., Ltd.) 100 parts Coated pigment obtained in Production Example 12 10 parts Negative charge control agent "Pontron E81" (Orient Chemical Co., Ltd.) 3 parts Polypropylene wax "Viscor 550P" (manufactured by Sanyo Kasei Co., Ltd.) 2 parts Polystyrene "Esprite 2V" (manufactured by Showa Denko KK) 5 parts The above 5 components are mixed and heated and kneaded with a two-roll mill at 130 ° C. Thus, a mill base was obtained, which was roughly pulverized by a hammer mill, finely pulverized by a jet mill and then classified to obtain a toner (colored resin composition) having an average particle diameter of 13 μm.
The obtained toner was mixed with iron oxide powder "EFV200" (manufactured by Nippon Iron Powder Co., Ltd.) as a carrier to prepare a developer having a toner concentration of 5%.
【００５２】（実施例１３）製造例１２で得られた被覆
顔料の代わりに製造例１３で得られた被覆顔料を用いた
以外は、実施例１２と同様である。 （比較例７）製造例１２で得られた被覆顔料の代わりに
未処理のカーボンブラック「三菱カーボン＃１０」を用
いた以外は、実施例１２と同様である。Example 13 The procedure of Example 12 was repeated, except that the coated pigment obtained in Production Example 13 was used instead of the coated pigment obtained in Production Example 12. (Comparative Example 7) The same as Example 12 except that untreated carbon black "Mitsubishi Carbon # 10" was used in place of the coated pigment obtained in Production Example 12.
【００５３】実施例１２〜１３及び比較例７で得られた
現像剤を複写機「ＮＣ３０００」（コピア社製）を改造
した現像機に入れて、Ａ４用紙で１／３が黒べたの未定
着画像を作成した。続いてこれを上部がテフロン、下部
がシリコンゴムの加熱ロール式定着試験機を用い、ロー
ル温度が１００〜２４０℃まで段階的に変化させ、線速
８００ｃｍ／分で通して定着評価を行った。定着性は、
定着画像にセロテープを貼って引き剥がし、そのＩＤ
（画像濃度）を測定することにより判定した。ホットセ
ット温度は、黒べた部と接したロール部分が、白抜け部
と再度接した部分のＩＤを測定し、他の白抜け部のＩＤ
より５％以上増加した最低温度とした。更に複写機「Ｎ
Ｃ３０００」（コピア社製）を用いて温度３０℃−湿度
８０％の条件下で連続複写試験を行った。また得られた
現像剤の貯蔵安定性を温度５０℃−湿度８０％で２４時
間の条件下で評価した。詳細な結果は表３に示した。The developers obtained in Examples 12 to 13 and Comparative Example 7 were put in a developing machine modified from a copying machine "NC3000" (manufactured by Copia), and 1/3 of A4 paper was black and unfixed. I created an image. Subsequently, using a heating roll type fixing tester in which the upper part is Teflon and the lower part is silicon rubber, the roll temperature was changed stepwise from 100 to 240 ° C. and passed through at a linear velocity of 800 cm / min for fixing evaluation. The fixability is
Attach the cellophane tape to the fixed image and peel it off, then ID
It was judged by measuring (image density). For the hot setting temperature, measure the ID of the part where the roll part in contact with the black solid part again contacts the blank part, and the ID of the other blank part
The minimum temperature increased by 5% or more. Furthermore, the copier "N
A continuous copying test was carried out under the conditions of a temperature of 30 ° C. and a humidity of 80% using “C3000” (manufactured by Copia). The storage stability of the obtained developer was evaluated at a temperature of 50 ° C. and a humidity of 80% for 24 hours. Detailed results are shown in Table 3.
【００５４】[0054]
【表３】 [Table 3]
【００５５】 [0055]
【００５６】（実施例１４） 製造例９で得られた被覆顔料の水性湿潤ケーキ（顔料分：３７％）１０３０部 エチレン・ビニルアルコール共重合体樹脂「ソアライトＫ」 （日本合成化学工業） ４０部 ドデシルベンゼンスルフォン酸ソーダ ５部 キシレン ９０部 水 ６００部 上記５成分をディスパーに入れ、混合分散して顔料水性
ペーストを作成した。次にこの顔料水性ペーストをフラ
ッシャーに入れ、１５０℃に昇温しながら撹拌した。水
分は蒸発し、内容物が高粘度となってきたところで取り
出し、スプレードライヤーで乾燥させて着色樹脂組成物
を得た。得られた着色樹脂組成物１７部にカルナバワッ
クス（ｍｐ：８３℃）７９部、パラフィンワックス（ｍ
ｐ：５５℃）１７部及びポリスチレン樹脂「エスブライ
ト５００ＳＢ」（住友化学工業社製）のキシレン１５％
溶液１１３部を加え、ガラスビーズの入ったアトライタ
ーで２時間分散して感熱インキを作成した。この感熱イ
ンキを厚さ６ｍｍのポリエチレンテレフタレートフィル
ム上に、ソルベントコーティング法によって、乾燥後の
塗布厚が４μｍとなるように１００℃２分間の条件で塗
工して、熱転写記録媒体を得た。塗工性は良好であっ
た。(Example 14) 1030 parts of aqueous wet cake (pigment content: 37%) of the coated pigment obtained in Production Example 9 40 parts of ethylene / vinyl alcohol copolymer resin "Solarite K" (Nippon Gosei Kagaku Kogyo) Sodium dodecylbenzene sulfonate 5 parts Xylene 90 parts Water 600 parts The above 5 components were put in a disper and mixed and dispersed to prepare a pigment aqueous paste. Next, this pigment aqueous paste was put into a flasher and stirred while heating to 150 ° C. The water was evaporated, and when the content became highly viscous, it was taken out and dried with a spray dryer to obtain a colored resin composition. To 17 parts of the obtained colored resin composition, 79 parts of carnauba wax (mp: 83 ° C.) and paraffin wax (m
p: 55 ° C) 17 parts and polystyrene resin "Esbright 500SB" (Sumitomo Chemical Co., Ltd.) xylene 15%
113 parts of the solution was added and dispersed for 2 hours with an attritor containing glass beads to prepare a thermal ink. This heat-sensitive ink was applied onto a polyethylene terephthalate film having a thickness of 6 mm by a solvent coating method so that the coating thickness after drying was 4 μm at 100 ° C. for 2 minutes to obtain a thermal transfer recording medium. The coatability was good.
【００５７】（比較例８）製造例９で得られた被覆顔料
の水性湿潤ケーキの代わりに未処理のベンジジンイエロ
ー顔料の水性湿潤ケーキ「リオノールイエローＧＧＴ」
を用いた以外は、実施例１４と同様にして感熱インキを
作成し、感熱転写記録媒体を得た。Comparative Example 8 Instead of the aqueous wet cake of the coated pigment obtained in Production Example 9, an untreated aqueous wet cake of benzidine yellow pigment "Rionol Yellow GGT".
A thermal ink was prepared in the same manner as in Example 14 except that was used to obtain a thermal transfer recording medium.
【００５８】（実施例１５） マイクロクリスタリンワックス（ｍｐ：７５℃） ７０部 製造例１１で得られた被覆顔料 ２０部 エチレン・酢酸ビニル共重合体樹脂「ＤＱＤＪ−７１９７」 （日本ユニカー社製，メルトフローレート：３５０） １０部 上記２成分を混合し、３本ロールミルで１６０℃で加熱
混練をしてミルベース（着色樹脂組成物）を得た。得ら
れたミルベースを実施例１４と同様にして感熱インキを
作成し、感熱転写記録媒体を得た。塗工性は良好であっ
た。(Example 15) Microcrystalline wax (mp: 75 ° C) 70 parts Coated pigment obtained in Production Example 11 20 parts Ethylene / vinyl acetate copolymer resin "DQDJ-7197" (manufactured by Nippon Unicar Co., Ltd., melt Flow rate: 350) 10 parts The above two components were mixed and heated and kneaded at 160 ° C. with a three-roll mill to obtain a mill base (colored resin composition). A heat-sensitive ink was prepared from the obtained mill base in the same manner as in Example 14 to obtain a heat-sensitive transfer recording medium. The coatability was good.
【００５９】（比較例９）製造例１１で得られた被覆顔
料の代わりに未処理の群青「グンジョウ＃２０００」を
用いた以外は、実施例１５と同様にして感熱インキを作
成し、感熱転写記録媒体を得た。Comparative Example 9 A thermal ink was prepared in the same manner as in Example 15 except that untreated ultramarine blue "Gunjou # 2000" was used in place of the coated pigment obtained in Production Example 11, and the thermal transfer was performed. A recording medium was obtained.
【００６０】実施例１４、１５及び比較例８、９で得ら
れた感熱転写記録媒体について、転写エネルギー感度及
び転写画像品質を温度：６０〜１４０℃、圧力：２ｋｇ
／ｃｍ、熱圧着時間：３秒の条件下で熱傾斜試験器「Ｈ
Ｇ−１００」（東洋精機製作所社製）と、印字速度：６
０字／秒、８ドットのサーマルヘッドを持つ高密度のサ
ーマルプリンターとで評価した。受像紙としては熱転写
紙を使用した。詳細な結果は表４に示す。Regarding the thermal transfer recording media obtained in Examples 14 and 15 and Comparative Examples 8 and 9, the transfer energy sensitivity and the transferred image quality were temperature: 60 to 140 ° C., pressure: 2 kg.
/ Cm, thermocompression bonding time: under the condition of 3 seconds
G-100 "(manufactured by Toyo Seiki Seisakusho) and printing speed: 6
It was evaluated with a high-density thermal printer having a 0-character / second thermal head with 8 dots. Thermal transfer paper was used as the image receiving paper. Detailed results are shown in Table 4.
【００６１】[0061]
【表４】 転写画像品質：画像の濃度ムラ、均一性、鮮明性及びラ
ンダムブリッジ、ボイドの発生について、拡大写真等に
より目視評価した。 転写画像濃度：べた印字部の飽和画像反射濃度値。測定
はマクベス反射濃度計でおこなった。[Table 4] Transfer image quality: Image density unevenness, uniformity, sharpness, and random bridges and voids were visually evaluated by magnified photographs and the like. Transferred image density: A saturated image reflection density value of a solid print portion. The measurement was performed with a Macbeth reflection densitometer.
【００６２】（実施例１６）製造例１４で得られた被覆
顔料２０部、ベンゾフェノン５部、ハイドロキノン０．
５部、アルキッド樹脂ワニス「フタルキッド２３５−５
０」（日立化成工業社製）２０部、トリメチロールプロ
パントリアクリレート５５. ５部を直径３ｍｍのガラス
ビーズを２２０ｃｃのマヨネーズビンにいれ、ペイント
コンディショナーで３０分間分散した。これをブリキ板
にスプレーコーターで塗布し、６０mJ／cm2 の紫外線を
照射した。光沢、色目共に良好な塗膜を得た。未処理の
顔料について同様な試験を行ったところ硬化不良で光
沢、色目共に不良であった。(Example 16) 20 parts of the coated pigment obtained in Production Example 14, 5 parts of benzophenone, and 0.1% of hydroquinone.
5 parts, alkyd resin varnish “Phtalkid 235-5
20 parts of "0" (manufactured by Hitachi Chemical Co., Ltd.) and 55.5 parts of trimethylolpropane triacrylate were put into a 220 cc mayonnaise bottle with glass beads having a diameter of 3 mm and dispersed with a paint conditioner for 30 minutes. This was applied to a tin plate with a spray coater and irradiated with ultraviolet rays of 60 mJ / cm 2 . A coating film with good gloss and color was obtained. When a similar test was performed on the untreated pigment, curing was poor, and gloss and color were poor.
【００６３】（実施例１７）製造例２で得られた被覆顔
料１２部、クレー３部、反応性水可溶樹脂の合成例１で
得られた樹脂溶液３２部、水４５．５部、８０％酢酸
０．５部を２２０ｃｃのマヨネーズビンに入れ、ペイン
トコンディショナーで３０分間分散してフレキソインキ
を得た。得られたインキを７０℃で７２時間保存し、保
存前と保存後のインキを希釈用白インキで３０倍希釈し
て淡色インキを作成し着色力を比較したところ変化は認
められなかった。(Example 17) 12 parts of the coated pigment obtained in Production Example 2, 3 parts of clay, 32 parts of the resin solution obtained in Synthesis Example 1 of reactive water-soluble resin, 45.5 parts of water, 80 % Acetic acid (0.5 parts) was put into a 220 cc mayonnaise bottle and dispersed for 30 minutes with a paint conditioner to obtain a flexo ink. The obtained ink was stored at 70 ° C. for 72 hours, and the ink before and after storage was diluted 30 times with a white ink for dilution to prepare a light-colored ink, and when the coloring power was compared, no change was observed.
【００６４】[0064]
【発明の効果】本発明の被覆顔料は、顔料含有率の高低
にとらわれず、顔料分散性に優れており、高度な顔料分
散を要求される繊維製品や感熱インキ、印刷インキ、塗
料、現像剤等の着色において、その光沢、色相の鮮明さ
及び着色性に大きな効果を発揮するものである。また、
従来、多かった分散不良によるブツや色ムラ等の塗膜欠
陥もなく、良好な塗膜が得られる等、塗加工性にも優れ
ており、良好な塗膜物性を得られるものである。また、
成形材料である熱可塑性樹脂の着色においても極めて有
効であり、高分散、高発色を示し、色ムラのない着色が
可能となる。INDUSTRIAL APPLICABILITY The coated pigment of the present invention has excellent pigment dispersibility irrespective of the high or low pigment content, and textile products, thermal inks, printing inks, paints and developers that require high pigment dispersion. In coloring such as, it exerts a great effect on its gloss, sharpness of hue and colorability. Also,
Conventionally, there are no coating defects such as bumps and color unevenness caused by poor dispersion, and a good coating film is obtained. Also,
It is extremely effective in coloring a thermoplastic resin as a molding material, and exhibits high dispersion and high color development, and enables coloring without color unevenness.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 町田 安章 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 井口 昭義 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) Inventor Aki Machida 2-3-3 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd. (72) Akiyoshi Iguchi 2-3-3 Kyobashi, Chuo-ku, Tokyo No. Toyo Inki Manufacturing Co., Ltd.
Claims (5)
重合体の中和物にエポキシ基とα，β−不飽和二重結合
とを有する化合物を付加させた反応性水可溶樹脂で被覆
してなる被覆顔料。1. A reactive water-soluble resin obtained by adding a pigment to a neutralized product of a vinyl copolymer having a tertiary amino group and a compound having an epoxy group and an α, β-unsaturated double bond. A coated pigment obtained by coating with.
するビニル共重合体の中和物に、第３級アミノ基１モル
に対してエポキシ基０．０１〜１モルの割合で、エポキ
シ基とα，β−不飽和二重結合とを有する化合物を付加
させた樹脂であることを特徴とする請求項１記載の被覆
顔料。2. A reactive water-soluble resin, in a neutralized product of a vinyl copolymer having a tertiary amino group, in a ratio of 0.01 to 1 mole of epoxy group to 1 mole of tertiary amino group. 2. The coated pigment according to claim 1, which is a resin to which a compound having an epoxy group and an α, β-unsaturated double bond is added.
重量部の反応性水可溶樹脂で被覆することを特徴とする
請求項１または２記載の被覆顔料。3. 0.5 to 50 with respect to 100 parts by weight of the pigment.
The coated pigment according to claim 1 or 2, which is coated with a part by weight of a reactive water-soluble resin.
覆顔料を含む着色用顔料組成物。4. A coloring pigment composition containing the coated pigment according to any one of claims 1 to 3.
覆顔料を含む被覆剤。5. A coating agent containing the coated pigment according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06049096A JP3622324B2 (en) | 1996-03-18 | 1996-03-18 | Coated pigment, coloring pigment composition containing the same, and coating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06049096A JP3622324B2 (en) | 1996-03-18 | 1996-03-18 | Coated pigment, coloring pigment composition containing the same, and coating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09249821A true JPH09249821A (en) | 1997-09-22 |
| JP3622324B2 JP3622324B2 (en) | 2005-02-23 |
Family
ID=13143786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06049096A Expired - Fee Related JP3622324B2 (en) | 1996-03-18 | 1996-03-18 | Coated pigment, coloring pigment composition containing the same, and coating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3622324B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003062950A (en) * | 2001-08-23 | 2003-03-05 | Achilles Corp | Synthetic resin film |
| JP2005132462A (en) * | 2003-10-31 | 2005-05-26 | Nippon Foil Mfg Co Ltd | Packaging aluminum foil with printed display having superior infrared permeability |
| EP1637568A1 (en) * | 2004-09-17 | 2006-03-22 | Fuji Photo Film Co., Ltd. | Ink composition for inkjet recording and inkjet recording method |
| JP2006200098A (en) * | 2005-01-24 | 2006-08-03 | Meisei Kagaku Kogyo Kk | Method for color deepening fiber fabric |
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| US7754785B2 (en) | 2003-10-28 | 2010-07-13 | Toshiba Tec Kabushiki Kaisha | Pigment dispersion, precursor of ink for UV-curing type ink-jet recording, method of ink-jet recording, printed matter, and method of manufacturing pigment dispersion |
| JPWO2020195360A1 (en) * | 2019-03-28 | 2021-11-18 | 富士フイルム株式会社 | Inkjet ink for non-permeable substrates, image recording method, and manufacturing method of laminate |
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1996
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| JP2003062950A (en) * | 2001-08-23 | 2003-03-05 | Achilles Corp | Synthetic resin film |
| JP4693300B2 (en) * | 2001-08-23 | 2011-06-01 | アキレス株式会社 | Synthetic resin film |
| US7754785B2 (en) | 2003-10-28 | 2010-07-13 | Toshiba Tec Kabushiki Kaisha | Pigment dispersion, precursor of ink for UV-curing type ink-jet recording, method of ink-jet recording, printed matter, and method of manufacturing pigment dispersion |
| JP2005132462A (en) * | 2003-10-31 | 2005-05-26 | Nippon Foil Mfg Co Ltd | Packaging aluminum foil with printed display having superior infrared permeability |
| EP1637568A1 (en) * | 2004-09-17 | 2006-03-22 | Fuji Photo Film Co., Ltd. | Ink composition for inkjet recording and inkjet recording method |
| JP2006200098A (en) * | 2005-01-24 | 2006-08-03 | Meisei Kagaku Kogyo Kk | Method for color deepening fiber fabric |
| JP4510650B2 (en) * | 2005-01-24 | 2010-07-28 | 明成化学工業株式会社 | Method for deep color treatment of fiber fabric |
| JP2007119682A (en) * | 2005-10-31 | 2007-05-17 | Dainippon Ink & Chem Inc | Active energy ray curing type conductive ink composition |
| JP2008007629A (en) * | 2006-06-29 | 2008-01-17 | Dainippon Ink & Chem Inc | Aqueous coloring material and powdery coloring material |
| JPWO2020195360A1 (en) * | 2019-03-28 | 2021-11-18 | 富士フイルム株式会社 | Inkjet ink for non-permeable substrates, image recording method, and manufacturing method of laminate |
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