JPH0848890A - Resin for dispersing aqueous pigment and aqueous pigment dispersant using the same - Google Patents
Resin for dispersing aqueous pigment and aqueous pigment dispersant using the sameInfo
- Publication number
- JPH0848890A JPH0848890A JP29945794A JP29945794A JPH0848890A JP H0848890 A JPH0848890 A JP H0848890A JP 29945794 A JP29945794 A JP 29945794A JP 29945794 A JP29945794 A JP 29945794A JP H0848890 A JPH0848890 A JP H0848890A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- pigment
- aqueous
- water
- general formula
- 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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/22—Obtaining compounds having nitrogen atoms directly bound to the phthalocyanine skeleton
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/005—Di-anthraquinonyl and derivative compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
- C09B3/14—Perylene derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/12—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton
- C09B47/16—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton having alkyl radicals substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/08—Naphthalimide dyes; Phthalimide dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
- C09B68/40—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
- C09B68/46—Aromatic cyclic groups
- C09B68/467—Heteroaromatic groups
- C09B68/4677—6-Membered rings
- C09B68/46775—Triazine
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は水性塗料または水性イン
キに使用した場合，皮膜の光沢と着色力に優れ、流動
性、貯蔵安定性が良好な水性顔料分散体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous pigment dispersion which, when used in an aqueous paint or an aqueous ink, has excellent gloss and tinting strength of a film and has good fluidity and storage stability.
【０００２】[0002]
【従来の技術】近年、資源保護、環境保全、作業の安定
性の向上等のニーズの高まりによって塗料ならびにイン
キの水性化が進行しつつある。水性塗料ならびに水性イ
ンキには、油性の場合と同様に流動性・貯蔵安定性・皮
膜の光沢・鮮明性・着色力等の特性が要求される。しか
しながら、大部分の顔料は水性ビヒクルに対して顔料分
散性等の適性が著しく劣るため通常の分散方法では満足
な特性は得られない。そこで従来より各種の添加剤、例
えば水性用顔料分散樹脂や界面活性剤の使用が検討され
てきたが上記すべての特性を満足し、既存の高品質を有
する油性塗料または油性インキに匹敵するような水性塗
料・水性インキは得られていない。即ち、ある種の水性
用分散樹脂の使用によって分散直後の皮膜の光沢・鮮明
性・着色力等はある程度改善されるが、流動性が損なわ
れる・経時によって増粘あるいはゲル化する・皮膜の物
性に悪影響を及ぼす等の実用上致命的な欠点があった。2. Description of the Related Art In recent years, water-based paints and inks have been developed due to the increasing needs such as resource protection, environmental protection, and improvement of work stability. Water-based paints and water-based inks are required to have properties such as fluidity, storage stability, film gloss, sharpness, and tinting strength as in the case of oil-based paints. However, most of the pigments have extremely poor suitability in terms of pigment dispersibility and the like with respect to the aqueous vehicle, so that satisfactory characteristics cannot be obtained by a usual dispersion method. Therefore, various additives such as a water-based pigment-dispersed resin and a surfactant have been studied in the past, but they satisfy all of the above characteristics and are comparable to existing oil-based paints or oil-based inks having high quality. Aqueous paints and inks have not been obtained. That is, the use of a certain type of aqueous dispersion resin improves the gloss, sharpness, and coloring power of the film immediately after dispersion to some extent, but the fluidity is impaired, the viscosity increases or gels over time, and the physical properties of the film. There was a practically fatal defect such as adversely affecting
【０００３】[0003]
【発明が解決しようとする課題】本発明者は上記のごと
き欠点を解決する方法として水性顔料分散体において、
樹脂中の酸性官能基をアミンで中和する際、一般式
（１）で表される有機色素化合物を中和剤として使用し
た樹脂を顔料分散用樹脂とすることが有効であることを
見出し本発明を完成するに至った。As a method for solving the above-mentioned drawbacks, the present inventor has found that in an aqueous pigment dispersion,
When neutralizing an acidic functional group in a resin with an amine, it has been found that it is effective to use a resin using an organic dye compound represented by the general formula (1) as a neutralizing agent as a pigment dispersion resin. The invention was completed.
【０００４】[0004]
【課題を解決するための手段】本願発明は、一般式
（１）で表される末端に塩基性基を有する有機色素化合
物を主成分とする中和剤で中和されていることを特徴と
する水性顔料分散用樹脂およびこれを用いて顔料を分散
したことを特徴とする水性顔料分散体である。The present invention is characterized by being neutralized with a neutralizing agent containing an organic dye compound having a basic group at the terminal represented by the general formula (1) as a main component. And a resin for dispersing an aqueous pigment, wherein the pigment is dispersed using the resin.
【０００５】一般式（１）General formula (1)
【化３】 式中、Ｑ；有機色素残基または複素環残基 Ｘ；直接結合，−ＮＨ−、−ＣＯＮＨ−Ｙ2 −、−ＳＯ
2 ＮＨ−Ｙ2 −または−ＣＨ2 ＮＨＣＯＣＨ2 ＮＨ−Ｙ
2 − （Ｙ2 ；置換基を有してもよいアルキレン基またはアリ
ーレン基） Ｙ1 ；−ＮＨ−または−Ｏ− Ｚ；水酸基、アルコキシ基または一般式（２）[Chemical 3] Wherein, Q; organic pigment residue or heterocyclic residue X; direct bond, -NH -, - CONH-Y 2 -, - SO
2 NH-Y 2 - or -CH 2 NHCOCH 2 NH-Y
2 - (Y 2; an optionally substituted alkylene group or an arylene group) Y 1; -NH- or -O- Z; a hydroxyl group, an alkoxy group or general formula (2)
【０００６】一般式（２）General formula (2)
【化４】 （Ｙ3 ；−ＮＨ−，または，−Ｏ−）、あるいはｎ＝１
の場合 −ＮＨ−Ｘ−Ｑであってもよい Ｒ1 、Ｒ2 ；それぞれ独立に置換もしくは無置換のアル
キル基またはＲ1 とＲ2 とで少なくともヘテロ環を形成
してもよい。 ｍ；１〜６の整数 ｎ；１〜４の整数 を表す。[Chemical 4] (Y 3 ; -NH-, or -O-), or n = 1
In the case of -NH-X-Q may be R < 1 >, R < 2 >; each independently a substituted or unsubstituted alkyl group or R < 1 > and R < 2 > may form at least a heterocycle. m; an integer of 1 to 6 n; an integer of 1 to 4
【０００７】一般式（１）で表される本願発明の有機色
素化合物の製造方法は特開昭６１−２４６２６１号公報
に記載されている。すなわち、一般に市販されている染
料または顔料をまず常法に従ってクロルスルホン化、ク
ロル酢酸アミドメチル化する。次に記一般式（３）で表
されるアミン類と反応させることによって本願発明の有
機色素化合物を得ることができる。The method for producing the organic dye compound of the present invention represented by the general formula (1) is described in JP-A-61-246261. That is, generally commercially available dyes or pigments are first chlorosulfonated and chloroacetic acid amidomethylated according to a conventional method. Next, the organic dye compound of the present invention can be obtained by reacting with an amine represented by the general formula (3).
【０００８】一般式（３）General formula (3)
【化５】 一般式（３）式中、 Ｙ1 ；−ＮＨ−または−Ｏ− Ｙ2 ；置換基を有してもよいアルキレン基またはアリー
レン基 Ｚ；水酸基、アルコキシ基または一般式（２） Ｒ1 、Ｒ2 ；それぞれ独立に置換もしくは無置換のアル
キル基またはＲ1 とＲ2 とで少なくともヘテロ環を形成
してもよい。 ｍ；１〜６の整数Embedded image Formula (3) wherein, Y 1; -NH- or -O- Y 2; an optionally substituted alkylene group or an arylene group Z; a hydroxyl group, an alkoxy group or general formula (2) R 1, R 2 ; each independently, a substituted or unsubstituted alkyl group or R 1 and R 2 may form at least a heterocycle. m; integer from 1 to 6
【０００９】一般式（１）におけるＱで表される有機色
素残基としては、フタロシアニン系、不溶性アゾ系、ア
ゾレーキ系、アントラキノン系、キナクリドン系、ジオ
キサジン系、ジケトピロロピロール系、アントラピリミ
ジン系、アンサンスロン系、インダンスロン系、フラバ
ンスロン系、ペリノン系、チオインジゴ系等がある。こ
れらの有機色素は任意に単独かつ複数を組み合わせても
良いが、使用する顔料に近い色相を有するものを使用し
たほうが工業的に有利である。Examples of the organic dye residue represented by Q in the general formula (1) include phthalocyanine type, insoluble azo type, azo lake type, anthraquinone type, quinacridone type, dioxazine type, diketopyrrolopyrrole type, anthrapyrimidine type, Ansanthurones, indanthrone, flavanthrone, perinone, thioindigo, etc. Any of these organic dyes may be used alone or in combination, but it is industrially advantageous to use one having a hue close to that of the pigment used.
【００１０】また、一般式（１）におけるＱで表される
複素環残基としては、例えば、チオフェン、フラン、キ
サンテン、ピロール、イミダゾール、イソインドリン、
イソインドリノン、ベンズイミダゾロン、インドール、
キノリン、カルバゾール、アクリジン、アクリドン、ア
ントラキノン等がある。Ｑが複素環残基の場合、一般式
（１）で表される有機色素化合物が無色ないしはほとん
ど着色していないものが得られるため、汎用性の点で望
ましい。Examples of the heterocyclic residue represented by Q in the general formula (1) include thiophene, furan, xanthene, pyrrole, imidazole, isoindoline,
Isoindolinone, benzimidazolone, indole,
Examples include quinoline, carbazole, acridine, acridone, and anthraquinone. When Q is a heterocyclic residue, the organic dye compound represented by the general formula (1) is colorless or hardly colored, which is desirable in terms of versatility.
【００１１】一般式（１）におけるＸは直接結合、−Ｎ
Ｈ−、−ＣＯＮＨ−Ｙ2 −、−ＳＯ 2 ＮＨ−Ｙ2 −、
または−ＣＨ2 ＮＨＣＯＣＨ2 ＮＨ−Ｙ2 −（Ｙ2 ；置
換基を有してもよいアルキレン基またはアリーレン基）
から選ばれる結合基である。X in the general formula (1) is a direct bond, -N
H-, -CONH-Y2-, -SO 2NH-Y2-,
Or -CH2NHCOCH2NH-Y2-(Y2;
(Alkylene group or arylene group which may have a substituent)
Is a bonding group selected from
【００１２】一般式（１）におけるＹ1 は−ＮＨ−また
は−Ｏ−から選ばれる結合基である。Y 1 in the general formula (1) is a bonding group selected from —NH— or —O—.
【００１３】一般式（１）におけるＺは水酸基、アルコ
キシ基または下記一般式（２）から選ばれる結合基であ
り、一般式（２）であることが望ましい。Z in the general formula (1) is a hydroxyl group, an alkoxy group or a bonding group selected from the following general formula (2), and preferably the general formula (2).
【００１４】一般式（２）General formula (2)
【化６】 （Ｙ3 ；−ＮＨ−、または，−Ｏ−）、あるいはｎ＝１
の場合 −ＮＨ−Ｘ−Ｑであってもよい[Chemical 6] (Y 3 ; -NH-, or -O-), or n = 1
In the case of, it may be -NH-X-Q.
【００１５】一般式（１）および（２）におけるＲ1 、
Ｒ2 はそれぞれ独立に置換もしくは無置換のアルキル
基、またはＲ1 とＲ2 とで少なくともヘテロ環を形成し
てもよく、無置換のアルキル基が望ましい。これらのア
ルキル基は最大で炭素数１８までの範囲で分岐していて
も良く、特にメチル基、エチル基、プロピル基、ブチル
基等の低級アルキル基が好ましい。R 1 in the general formulas (1) and (2),
R 2's may each independently be a substituted or unsubstituted alkyl group, or R 1 and R 2 may form at least a heterocycle, and an unsubstituted alkyl group is preferable. These alkyl groups may be branched in a range of up to 18 carbon atoms, and lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group are particularly preferable.
【００１６】一般式（１）および（２）におけるｍは１
〜６の整数、ｎは１〜４の整数である。In the general formulas (1) and (2), m is 1
Is an integer of 6 and n is an integer of 1 to 4.
【００１７】本願発明の水性樹脂としては、アクリル共
重合体系、スチレン−アクリル酸共重合体系、スチレン
−マレイン酸共重合体系、アルキッド系、エポキシ系、
ポリエステル系、ウレタン系等の水分散樹脂または水溶
性樹脂が挙げられるが、特にアクリル共重合体系の水分
散樹脂または水溶性樹脂が好ましい。As the water-based resin of the present invention, acrylic copolymer system, styrene-acrylic acid copolymer system, styrene-maleic acid copolymer system, alkyd system, epoxy system,
Examples thereof include water-soluble resins or water-soluble resins such as polyester-based and urethane-based resins, and water-soluble resins or water-soluble resins based on acrylic copolymers are particularly preferable.
【００１８】このアクリル共重合体系樹脂は、（メタ）
アクリル酸アルキルエステル５０〜８０重量％、アクリ
ル酸、メタクリル酸、マレイン酸、イタコン酸等のカル
ボン酸含有単量体５〜３０重量％及びその他の単量体０
〜２０重量％を乳化重合または水溶性溶媒中で溶液重合
して得られる、重量平均分子量５０００〜３００００
０、酸価が１〜２００の樹脂である。This acrylic copolymer resin is (meth)
Acrylic acid alkyl ester 50 to 80% by weight, acrylic acid, methacrylic acid, maleic acid, itaconic acid and other carboxylic acid-containing monomers 5 to 30% by weight and other monomers 0
~ 20% by weight obtained by emulsion polymerization or solution polymerization in a water-soluble solvent, weight average molecular weight 5,000 to 30,000
A resin having an acid value of 0 and an acid value of 1 to 200.
【００１９】上記（メタ）アクリル酸アルキルエステル
としては、（メタ）アクリル酸メチル、（メタ）アクリ
ル酸エチル、（メタ）アクリル酸プロピル、（メタ）ア
クリル酸ｎ−ブチル、（メタ）アクリル酸イソプロピ
ル、（メタ）アクリルイソブチル、（メタ）アクリル酸
２−エチルヘキシル、（メタ）アクリル酸ｎ−ヘキシ
ル、（メタ）アクリル酸ラウリル等がある。Examples of the above-mentioned (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isopropyl (meth) acrylate. , (Meth) acrylic isobutyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-hexyl, and (meth) acrylic acid lauryl.
【００２０】上記その他の単量体としては、（メタ）ア
クリル酸２−ヒドロキシエチル、（メタ）アクリル酸２
−ヒドロキシプロピル、アクリルアミド，Ｎ−メチロー
ルアクリルアミド、ジアセトンアクリルアミド、グリシ
ジル（メタ）アクリレート、スチレン、ビニルトルエ
ン、酢酸ビニル、アクリロニトリル、ビニルアルコー
ル、エチレン等がある。The above-mentioned other monomers include 2-hydroxyethyl (meth) acrylate and 2 (meth) acrylic acid.
-Hydroxypropyl, acrylamide, N-methylol acrylamide, diacetone acrylamide, glycidyl (meth) acrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, vinyl alcohol, ethylene and the like.
【００２１】この水性アクリル樹脂の水性媒体は、水の
みであってもよいが、場合によってはエチルアルコー
ル、イソプロピルアルコール、ｎ−プロピルアルコー
ル、ｎ−ブタノール等のアルコール系溶剤や、エチレン
グリコールまたはジエチレングリコールのモノまたはジ
アルキルエーテル等の水混和性有機溶剤を水性媒体中の
５０重量％まで混和させることができる。The aqueous medium of the aqueous acrylic resin may be only water, but in some cases, an alcohol solvent such as ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butanol, ethylene glycol or diethylene glycol. Water-miscible organic solvents such as mono- or dialkyl ethers can be mixed up to 50% by weight in the aqueous medium.
【００２２】本願発明の顔料としては例えば、フタロシ
アニン顔料、不溶性アゾ顔料、アゾレーキ顔料、アント
ラキノン顔料、キナクリドン顔料、ジオキサジン顔料、
ジケトピロロピロール顔料、アントラピリジン顔料、ア
ンサンスロン顔料、インダンスロン顔料、フラバンスロ
ン顔料、ペリノン顔料、ペリレン顔料、チオインジゴ顔
料、カーボンブラック、酸化鉄、鉛白、鉛丹、群青、紺
青、酸化コバルト、二酸化チタン、二酸化チタン被覆雲
母、ストロンチウムクロメート、チタニウムイエロー、
チタンブラック、ジンククロメート、鉄黒、モリブデン
レッド、モリブデンホワイト、リトポン、エメラルドグ
リーン、カドミウムイエロー、カドミウムレッド、コバ
ルトブルー等が挙げられる。Examples of the pigment of the present invention include phthalocyanine pigment, insoluble azo pigment, azo lake pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment,
Diketopyrrolopyrrole pigment, anthrapyridine pigment, anthanthrone pigment, indanthrone pigment, flavanthrone pigment, perinone pigment, perylene pigment, thioindigo pigment, carbon black, iron oxide, lead white, red lead, ultramarine blue, dark blue, cobalt oxide , Titanium dioxide, titanium dioxide coated mica, strontium chromate, titanium yellow,
Examples thereof include titanium black, zinc chromate, iron black, molybdenum red, molybdenum white, lithopone, emerald green, cadmium yellow, cadmium red, cobalt blue and the like.
【００２３】本願発明の水性顔料分散体は、下記２段階
の手順を経て得られる。すなわち、第１段階は水性顔料
分散用樹脂を製造する工程、第２段階は顔料を該顔料分
散用樹脂を用いて分散する工程である。The aqueous pigment dispersion of the present invention is obtained by the following two-step procedure. That is, the first step is a step of producing an aqueous pigment dispersion resin, and the second step is a step of dispersing a pigment using the pigment dispersion resin.
【００２４】水性顔料分散用樹脂は、前記の水性アクリ
ル共重合体系樹脂中の酸性官能基であるカルボキシル基
を、一般式（１）で表される有機色素化合物により中和
することによって得られる。The resin for dispersing an aqueous pigment is obtained by neutralizing the carboxyl group which is an acidic functional group in the above-mentioned aqueous acrylic copolymer resin with an organic dye compound represented by the general formula (1).
【００２５】末端に塩基性基を有する有機色素化合物に
よる中和の手順は、まず、均一に中和が行えるように、
この水性アクリル共重合体系樹脂を加温して低粘度化
し、ディスパーで攪拌しながら一般式（１）で表される
有機色素化合物を添加して中和する。添加の方法として
は、一般式（１）で表される有機色素化合物を乾燥した
粉末状で使用してもよいし、水あるいは前記の水混和性
有機溶剤を用いて、固形分３０〜９５％のスラリー状物
として使用するとより効果的である。この時，一般式
（１）で表される有機色素化合物を添加すると系の粘度
が著しく低下し、樹脂のカルボキシル基が中和されたこ
とが確認できる。また，中和後の樹脂が容易に溶解する
ことからも中和されたことが確認できる。有機色素化合
物によるカルボキシル基の中和率は、５０〜１２０％で
あり、好ましくは、７０〜１００％である。５０％より
も低いと樹脂の水溶化が困難であり、１２０％より多く
用いても用いた分の効果が得られない。中和後に水ある
いは前記の水混和性有機溶剤を用いて、作業がしやすい
ような粘度に希釈する。また、その時のＰＨは７．５〜
９である。The procedure of neutralization with an organic dye compound having a basic group at the end is as follows.
This aqueous acrylic copolymer resin is heated to lower the viscosity, and the organic dye compound represented by the general formula (1) is added to the resin for neutralization while stirring with a disper. As a method of addition, the organic dye compound represented by the general formula (1) may be used in a dry powder form, or water or the water-miscible organic solvent may be used to obtain a solid content of 30 to 95%. It is more effective when used as a slurry. At this time, when the organic dye compound represented by the general formula (1) is added, the viscosity of the system is remarkably reduced, and it can be confirmed that the carboxyl groups of the resin are neutralized. Also, it can be confirmed that the resin was neutralized because the resin after the neutralization was easily dissolved. The carboxyl group neutralization rate by the organic dye compound is 50 to 120%, and preferably 70 to 100%. If it is less than 50%, it is difficult to solubilize the resin, and if it is used more than 120%, the effect of the amount used cannot be obtained. After neutralization, water or the water-miscible organic solvent described above is used to dilute the viscosity to make it easy to work. Also, the PH at that time is 7.5.
9
【００２６】このようにして塩基性基を有する有機色素
化合物で中和された顔料分散用樹脂溶液を用いて、水性
顔料分散体を得るには、顔料１００重量部を、固形分５
〜１００重量部、好ましくは５〜５０重量部を有するこ
の顔料分散樹脂溶液で分散することが望ましい。固形分
が５重量部よりも少ないと、顔料の濡れが不十分であり
分散が不良となる。また，固形分が１００重量部より多
く用いても、用いた分の効果が得られない。In order to obtain an aqueous pigment dispersion by using the pigment dispersion resin solution thus neutralized with the organic dye compound having a basic group, 100 parts by weight of the pigment is added to the solid content of 5 parts by weight.
It is desirable to disperse with this pigment-dispersed resin solution having ˜100 parts by weight, preferably 5-50 parts by weight. When the solid content is less than 5 parts by weight, wetting of the pigment is insufficient and dispersion becomes poor. Even if the solid content is more than 100 parts by weight, the effect of the used amount cannot be obtained.
【００２７】水性塗料ならびに水性インキの濃縮分散体
として使用する場合には、顔料１００重量部に対し、水
性樹脂の固形分が５〜３００重量部となるように、分散
終了後に必要に応じて水性樹脂溶液を加える。When it is used as a concentrated dispersion of an aqueous paint or an aqueous ink, an aqueous solution is optionally added after the dispersion so that the solid content of the aqueous resin is 5 to 300 parts by weight with respect to 100 parts by weight of the pigment. Add resin solution.
【００２８】水性塗料ならびに水性インキとするにはさ
らに、下記に示す種々の水性樹脂やメラミン等の硬化剤
を加えて、顔料１００重量部に対し、樹脂の固形分が１
００〜７００重量部となるようにするのが好ましい。To prepare water-based paints and water-based inks, various kinds of water-based resins and curing agents such as melamine shown below are further added, and the solid content of the resin is 1 per 100 parts by weight of the pigment.
It is preferable that the amount is 100 to 700 parts by weight.
【００２９】水性塗料・水性インキの濃縮分散体や水性
塗料・水性インキを得るために加えられる希釈水性樹脂
としては、前述の有機色素化合物で中和した顔料分散用
樹脂を使用しても良いし、全量あるいはその一部を有機
色素化合物の替わりに、トリエチルアミン、エタノール
アミン、ジメチルエタノールアミン、ジエタノールアミ
ン、トリエタノールアミン等のアミン化合物で中和した
水性アクリル共重合体系樹脂溶液を使用しても良い。ま
た、アクリル共重合体系以外の水性樹脂、例えばスチレ
ン─アクリル酸共重合体系、スチレン─マレイン酸共重
合体系、アルキド系、エポキシ系、ポリエステル系、ウ
レタン系等の水分散樹脂または水溶性樹脂を用いること
ができる。As the concentrated dispersion of the water-based paint / water-based ink or the diluted water-based resin added to obtain the water-based paint / water-based ink, the above-mentioned pigment-dispersing resin neutralized with the organic dye compound may be used. Instead of the organic dye compound, the whole amount or a part thereof may be an aqueous acrylic copolymer resin solution neutralized with an amine compound such as triethylamine, ethanolamine, dimethylethanolamine, diethanolamine or triethanolamine. Further, an aqueous resin other than the acrylic copolymer system, for example, a styrene-acrylic acid copolymer system, a styrene-maleic acid copolymer system, an alkyd-based, epoxy-based, polyester-based, urethane-based water-dispersed resin or water-soluble resin is used. be able to.
【００３０】本願発明の水性顔料分散体は、希釈前の分
散体、水性塗料・水性インキの濃縮分散体、および水性
塗料・水性インキを含むものである。The aqueous pigment dispersion of the present invention includes a dispersion before dilution, a concentrated dispersion of a water-based paint / water-based ink, and a water-based paint / water-based ink.
【００３１】実施例１ 中和剤として下記フタロシアニン系の有機色素化合物
（ａ）を用いて、中和率80% とした重量平均分子量2500
0 、酸価60のアクリル樹脂を顔料分散樹脂として使用す
る。このアクリル樹脂溶液（固形分20%)12.5部、C.I.Pi
gment Blue 15:1（フタロシアニン系顔料）10部、イオ
ン交換水20部，及び 3mmφアルミナビーズ150 部を225
mlのガラス容器に入れペイントコンディショナーで３時
間分散させた。中和剤として下記の有機色素化合物
（ａ）の替わりにジメチルエタノールアミンを用いた以
外は、上記顔料分散樹脂と同内容のアクリル樹脂37.5部
とメチル化メラミン樹脂（商品名 サイメル303 三井サ
イアナミッド株式会社製）4.3 部で希釈して水性塗料を
得た。この水性塗料の粘度をＢ型回転粘度計にて測定し
たところＴＩ値（６rpm 粘度/60rpm粘度）1.1 の優れた
流動性が得られた。また、この水性塗料を 4ミルのフィ
ルムアプリケーターでPET フィルム上に展色し140 ℃で
30分間焼き付けたところ優れた皮膜光沢が得られた。光
沢の測定はデジタル変角光沢計により20°グロスを測定
したところ72％であった。Example 1 Using the following phthalocyanine-based organic dye compound (a) as a neutralizing agent, a weight average molecular weight of 2500 was obtained with a neutralization rate of 80%.
An acrylic resin having an acid value of 60 and an acid value of 60 is used as a pigment dispersion resin. 12.5 parts of this acrylic resin solution (solid content 20%), CIPi
gment Blue 15: 1 (phthalocyanine pigment) 10 parts, ion-exchanged water 20 parts, and 3 mmφ alumina beads 150 parts 225
It was put in a glass container of ml and dispersed for 3 hours with a paint conditioner. 37.5 parts of an acrylic resin having the same content as the above pigment dispersion resin and a methylated melamine resin (trade name: Cymel 303 Mitsui Cyanamid Co., Ltd.) except that dimethylethanolamine was used as a neutralizing agent instead of the following organic dye compound (a) The product was diluted with 4.3 parts to obtain a water-based paint. When the viscosity of this water-based paint was measured by a B-type rotary viscometer, excellent fluidity with a TI value (6 rpm viscosity / 60 rpm viscosity) of 1.1 was obtained. Also, this water-based paint was spread on PET film with a 4 mil film applicator, and the temperature was increased to 140 ° C.
After baking for 30 minutes, excellent film gloss was obtained. The measurement of gloss was 72% when 20 ° gloss was measured with a digital variable angle gloss meter.
【００３２】有機色素化合物（ａ）（フタロシアニン
系）Organic dye compound (a) (phthalocyanine type)
【化７】 [Chemical 7]
【００３３】実施例２ 顔料分散樹脂の中和率を120%に変更した以外は、実施例
１と同様に塗料化し、PET フィルム上に展色し焼き付け
たところ、優れた流動性と優れた皮膜光沢が得られ、Ｔ
Ｉ値は1.1 、20°グロスは68％であった。Example 2 A paint was prepared in the same manner as in Example 1 except that the neutralization ratio of the pigment-dispersed resin was changed to 120%, and the mixture was spread on a PET film and baked, resulting in excellent fluidity and excellent film formation. Gloss is obtained, T
The I value was 1.1 and the 20 ° gloss was 68%.
【００３４】実施例３ 顔料分散樹脂を希釈のアクリル樹脂としても使用した以
外は、実施例１と同様に塗料化し、PET フィルム上に展
色し焼き付けたところ、優れた流動性と優れた皮膜光沢
が得られ、ＴＩ値は1.2 、20°グロスは70％であった。Example 3 A paint was prepared in the same manner as in Example 1 except that the pigment-dispersed resin was also used as a dilute acrylic resin, and the mixture was spread on a PET film and baked to find excellent fluidity and excellent film gloss. The TI value was 1.2 and the 20 ° gloss was 70%.
【００３５】実施例４〜１４ 実施例１に準じて種々の顔料に対して、下記有機色素化
合物（ｂ）〜（ｉ）を中和剤として用いた顔料分散用樹
脂を使用したところ、実施例１と同様に優れた皮膜光沢
が得られた。それらの結果を表１及び表２に示す。Examples 4 to 14 Pigment dispersion resins containing the following organic dye compounds (b) to (i) as neutralizing agents were used in accordance with Example 1 for various pigments. As with No. 1, excellent film gloss was obtained. The results are shown in Tables 1 and 2.
【００３６】有機色素化合物（ｂ）（フタロシアニン
系）Organic dye compound (b) (phthalocyanine type)
【化８】 Embedded image
【００３７】有機色素化合物（ｃ）（フタロシアニン
系）Organic dye compound (c) (phthalocyanine type)
【化９】 [Chemical 9]
【００３８】有機色素化合物（ｄ）（キナクリドン系）Organic dye compound (d) (quinacridone type)
【化１０】 [Chemical 10]
【００３９】有機色素化合物（ｅ）（ジオキサジン系）Organic dye compound (e) (dioxazine type)
【化１１】 [Chemical 11]
【００４０】有機色素化合物（ｆ）（アントラキノン
系）Organic dye compound (f) (anthraquinone type)
【化１２】 [Chemical 12]
【００４１】有機色素化合物（ｇ）（ペリレン系）Organic dye compound (g) (perylene type)
【化１３】 [Chemical 13]
【００４２】有機色素化合物（ｈ）（ジアミノアントラ
キノン系）Organic dye compound (h) (diaminoanthraquinone type)
【化１４】 Embedded image
【００４３】有機色素化合物（ｉ）（ベンズイミダゾロ
ン系）Organic dye compound (i) (benzimidazolone type)
【化１５】 [Chemical 15]
【００４４】比較例１〜９ 実施例１〜１４に用いた顔料を、ジメチルエタノールア
ミンで中和したアクリル樹脂で分散し、塗料化、展色し
焼き付けたところ有機色素化合物（ａ）〜（ｉ）を中和
剤として用いたものに比べて流動性・光沢が劣ってい
た。それらの結果を表１及び表２に示す。Comparative Examples 1 to 9 The pigments used in Examples 1 to 14 were dispersed in an acrylic resin neutralized with dimethylethanolamine, made into a paint, developed, and baked to obtain organic dye compounds (a) to (i). ) Was inferior in fluidity and gloss compared to those using as a neutralizing agent. The results are shown in Tables 1 and 2.
【００４５】[0045]
【表１】 [Table 1]
【００４６】[0046]
【表２】 [Table 2]
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Claims (4)
塩基性基を有する有機色素化合物を主成分とする中和剤
で中和されてなることを特徴とする水性顔料分散用樹
脂。 一般式（１） 【化１】 式中、Ｑ；有機色素残基または複素環残基 Ｘ；直接結合、−ＮＨ−、−ＣＯＮＨ−Ｙ2 −、−ＳＯ
2 ＮＨ−Ｙ2 −または−ＣＨ2 ＮＨＣＯＣＨ2 ＮＨ−Ｙ
2 − （Ｙ2 ；置換基を有してもよいアルキレン基またはアリ
ーレン基） Ｙ1 ；−ＮＨ−または−Ｏ− Ｚ；水酸基、アルコキシ基または一般式（２） 一般式（２） 【化２】 （Ｙ3 ；−ＮＨ−，または，−Ｏ−）、あるいはｎ＝１
の場合 −ＮＨ−Ｘ−Ｑであってもよい Ｒ1 、Ｒ2 ；それぞれ独立に置換もしくは無置換のアル
キル基またはＲ1 とＲ2 とで少なくともヘテロ環を形成
してもよい。 ｍ；１〜６の整数 ｎ；１〜４の整数 を表す。1. A water-based pigment dispersion, characterized in that the water-based resin is neutralized with a neutralizing agent whose main component is an organic dye compound having a basic group at the terminal represented by the general formula (1). resin. General formula (1) Wherein, Q; organic pigment residue or heterocyclic residue X; direct bond, -NH -, - CONH-Y 2 -, - SO
2 NH-Y 2 - or -CH 2 NHCOCH 2 NH-Y
2- (Y 2 ; alkylene group or arylene group which may have a substituent) Y 1 ; -NH- or -O-Z; hydroxyl group, alkoxy group or general formula (2) general formula (2) ] (Y 3 ; -NH-, or -O-), or n = 1
In the case of -NH-X-Q may be R < 1 >, R < 2 >; each independently a substituted or unsubstituted alkyl group or R < 1 > and R < 2 > may form at least a heterocycle. m; an integer of 1 to 6 n; an integer of 1 to 4
を特徴とする請求項１記載の水性顔料分散用樹脂。2. The resin for dispersing an aqueous pigment according to claim 1, wherein the aqueous resin is an acrylic copolymer system.
散用樹脂にて分散してなることを特徴とする水性顔料分
散体。3. An aqueous pigment dispersion, comprising a pigment dispersed by the resin for dispersing an aqueous pigment according to claim 1 or 2.
量部からなることを特徴とする請求項３記載の水性顔料
分散体。4. The aqueous pigment dispersion according to claim 3, which comprises 100 parts by weight of the pigment and 5 to 700 parts by weight of the aqueous resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29945794A JP3132314B2 (en) | 1994-06-03 | 1994-12-02 | Method for producing aqueous pigment dispersion |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12231594 | 1994-06-03 | ||
| JP6-122315 | 1994-06-03 | ||
| JP29945794A JP3132314B2 (en) | 1994-06-03 | 1994-12-02 | Method for producing aqueous pigment dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0848890A true JPH0848890A (en) | 1996-02-20 |
| JP3132314B2 JP3132314B2 (en) | 2001-02-05 |
Family
ID=26459463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29945794A Expired - Fee Related JP3132314B2 (en) | 1994-06-03 | 1994-12-02 | Method for producing aqueous pigment dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3132314B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005010604A (en) * | 2003-06-20 | 2005-01-13 | Toyo Ink Mfg Co Ltd | Photosensitive black composition, black matrix substrate obtained by using the same and color filter |
| EP1975702A2 (en) | 2007-03-29 | 2008-10-01 | Fujifilm Corporation | Colored photocurable composition for solid state image pick-up device, color filter and method for production thereof, and solid state image pick-up device |
| US7948585B2 (en) | 2006-02-22 | 2011-05-24 | Fujifilm Corporation | Inkjet ink for color filter, color filter, methods of producing them, and liquid crystal display device using them |
| US8551676B2 (en) | 2007-03-30 | 2013-10-08 | Fujifilm Corporation | Pigment-dispersed composition, curable composition, and color filter and production method thereof |
| US8785087B2 (en) | 2006-12-27 | 2014-07-22 | Fujifilm Corporation | Pigment-dispersed composition, curable composition, color filter and production method thereof |
| JP2015120826A (en) * | 2013-12-24 | 2015-07-02 | 大日精化工業株式会社 | Pigment dispersant, pigment composition and pigment colorant |
-
1994
- 1994-12-02 JP JP29945794A patent/JP3132314B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005010604A (en) * | 2003-06-20 | 2005-01-13 | Toyo Ink Mfg Co Ltd | Photosensitive black composition, black matrix substrate obtained by using the same and color filter |
| JP4601267B2 (en) * | 2003-06-20 | 2010-12-22 | 東洋インキ製造株式会社 | Photosensitive black composition, black matrix substrate and color filter using the same |
| US7948585B2 (en) | 2006-02-22 | 2011-05-24 | Fujifilm Corporation | Inkjet ink for color filter, color filter, methods of producing them, and liquid crystal display device using them |
| US8785087B2 (en) | 2006-12-27 | 2014-07-22 | Fujifilm Corporation | Pigment-dispersed composition, curable composition, color filter and production method thereof |
| EP1975702A2 (en) | 2007-03-29 | 2008-10-01 | Fujifilm Corporation | Colored photocurable composition for solid state image pick-up device, color filter and method for production thereof, and solid state image pick-up device |
| US8163447B2 (en) | 2007-03-29 | 2012-04-24 | Fujifilm Corporation | Colored photocurable composition for solid state image pick-up device, color filter and method for production thereof, and solid state image pick-up device |
| US8551676B2 (en) | 2007-03-30 | 2013-10-08 | Fujifilm Corporation | Pigment-dispersed composition, curable composition, and color filter and production method thereof |
| JP2015120826A (en) * | 2013-12-24 | 2015-07-02 | 大日精化工業株式会社 | Pigment dispersant, pigment composition and pigment colorant |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3132314B2 (en) | 2001-02-05 |
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