JP2014031443A - Method for manufacturing a quinacridone solid-solution and method for manufacturing a quinacridone solid-solution pigment - Google Patents
Method for manufacturing a quinacridone solid-solution and method for manufacturing a quinacridone solid-solution pigment Download PDFInfo
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000006104 solid solution Substances 0.000 title claims abstract description 118
- 239000000049 pigment Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
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- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 47
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 42
- 125000003118 aryl group Chemical group 0.000 claims abstract description 35
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 23
- 150000007513 acids Chemical class 0.000 abstract description 5
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- LASWYZAZWDFPSC-UHFFFAOYSA-N 2,5-bis(2-chloroanilino)terephthalic acid Chemical compound OC(=O)C=1C=C(NC=2C(=CC=CC=2)Cl)C(C(=O)O)=CC=1NC1=CC=CC=C1Cl LASWYZAZWDFPSC-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- -1 quinacridone sulfonates Chemical class 0.000 description 2
- TXWSZJSDZKWQAU-UHFFFAOYSA-N 2,9-dimethyl-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=CC=C(C)C=C2C(=O)C2=C1C=C(C(=O)C=1C(=CC=C(C=1)C)N1)C1=C2 TXWSZJSDZKWQAU-UHFFFAOYSA-N 0.000 description 1
- SJIQTGOBEGYKSI-UHFFFAOYSA-N 2-[(1,3-dioxoisoindol-2-yl)methyl]-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1CC1=CC=C(NC=2C(=CC3=C(C(C4=CC=CC=C4N3)=O)C=2)C2=O)C2=C1 SJIQTGOBEGYKSI-UHFFFAOYSA-N 0.000 description 1
- BFEJTCHFLJECJN-UHFFFAOYSA-N 4,11-Dichloro-5,12-dihydroquino[2,3-b]acridine-7,14-dione Chemical compound N1C2=C(Cl)C=CC=C2C(=O)C2=C1C=C(C(C=1C=CC=C(C=1N1)Cl)=O)C1=C2 BFEJTCHFLJECJN-UHFFFAOYSA-N 0.000 description 1
- KSLLMGLKCVSKFF-UHFFFAOYSA-N 5,12-dihydroquinolino[2,3-b]acridine-6,7,13,14-tetrone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C(=O)C(C(=O)C1=CC=CC=C1N1)=C1C2=O KSLLMGLKCVSKFF-UHFFFAOYSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
本発明は、キナクリドン固溶体の製造方法及びキナクリドン固溶体顔料の製造方法に関する。 The present invention relates to a method for producing a quinacridone solid solution and a method for producing a quinacridone solid solution pigment.
二種以上の異種構造のキナクリドン化合物は、単なる混合物を形成する場合と、固溶体（混晶と呼ばれることがある）を形成する場合があり、前記混合物と固溶体とでは、物理的或いは光学的性質が異なることが多い。 Two or more kinds of quinacridone compounds having different structures may form a simple mixture or a solid solution (sometimes referred to as a mixed crystal). The mixture and the solid solution have physical or optical properties. Often different.
固溶体とは、ある一つの結晶相の格子点にある原子が全く不規則に別種の原子と置換するか、あるいは格子間隙に別種の原子が統計的に分布されるように入り込んだ相、すなわち、ある結晶相に他物質が溶け込んだとみなされる混合相をいう。結晶相としては均一相であって２相の共存でないものに限られる。 A solid solution is a phase in which atoms at a lattice point of one crystal phase are completely irregularly replaced with another type of atom, or another type of atom is statistically distributed in the lattice gap, that is, A mixed phase in which other substances are considered to be dissolved in a crystal phase. The crystal phase is limited to a homogeneous phase and not a coexistence of two phases.
この様な固溶体は、例えば、結晶Ｘ線回折スペクトルを測定した場合には、単なる混合物の場合には、存在していなかったブラッグ角に新たなピークが発現したり、逆に単なる混合物の場合に存在していた特定ブラッグ角のピークが消失することで、その存在を確認することが出来る。 For example, when a crystal X-ray diffraction spectrum is measured, such a solid solution has a new peak at a Bragg angle that did not exist in the case of a simple mixture, or conversely in the case of a simple mixture. The existence of a specific Bragg angle peak that has existed can be confirmed.
この様な固溶体は、有機顔料分野においても多くの報告がなされており、キナクリドン顔料においては、無置換キナクリドンと２，９−ジメチルキナクリドンとの固溶体からなるキナクリドン顔料や、無置換キナクリドンとキナクリドンキノンとの固溶体からなるキナクリドン顔料であるＣ．Ｉ．ピグメントレッド２０６、無置換キナクリドンと４，１１−ジクロロキナクリドンとの固溶体からなるキナクリドン顔料であるＣ．Ｉ．ピグメントレッド２０７等がよく知られている（特許文献１〜２参照。）。 Many reports have been made on such solid solutions in the field of organic pigments. In quinacridone pigments, quinacridone pigments composed of a solid solution of unsubstituted quinacridone and 2,9-dimethylquinacridone, and unsubstituted quinacridone and quinacridone quinone A quinacridone pigment comprising a solid solution of C.I. I. Pigment Red 206, a quinacridone pigment composed of a solid solution of unsubstituted quinacridone and 4,11-dichloroquinacridone. I. Pigment Red 207 and the like are well known (see Patent Documents 1 and 2).
これらキナクリドン固溶体は、具体的には、異なる二種以上の、アリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸をポリリン酸の存在下で環化することで製造することが出来る。 Specifically, these quinacridone solid solutions are produced by cyclizing 2,5-diarylaminoterephthalic acid, which may have two or more different substituents on the aryl group, in the presence of polyphosphoric acid. I can do it.
しかしながら、上記した従来の技術の製造方法で得られたキナクリドン固溶体からの着色物の彩度は、未だ不充分であるのが実情であった。 However, the actual situation is that the color saturation of the quinacridone solid solution obtained by the above-described conventional manufacturing method is still insufficient.
そこで、本発明者らは上記課題を解決すべく、鋭意研究の結果、第１のアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の環化反応と、第２のアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の環化反応とを、異なるポリリン酸濃度で行う様にすることで、上記した欠点が解消されたキナクリドン固溶体が得られることを見い出し、本発明を完成するに至った。 Therefore, in order to solve the above-mentioned problems, the present inventors have conducted extensive research, and as a result, cyclization reaction of 2,5-diarylaminoterephthalic acid which may have a substituent on the first aryl group, By performing the cyclization reaction of 2,5-diarylaminoterephthalic acid, which may have a substituent on the aryl group, at a different polyphosphoric acid concentration, a quinacridone solid solution in which the above-mentioned drawbacks are eliminated can be obtained. As a result, the present invention has been completed.
また、上記で得られたキナクリドン固溶体を顔料化することで、更に高彩度の着色物が得られるキナクリドン固溶体顔料を製造できることを見い出し、本発明を完成するに至った。 Further, the present inventors have found that a quinacridone solid solution pigment capable of producing a colored product with higher chroma can be produced by pigmenting the quinacridone solid solution obtained above, and the present invention has been completed.
すなわち本発明は、異なる二種以上の、アリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸をポリリン酸の存在下で環化するキナクリドン固溶体の製造方法において、第１のアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の環化反応と、第２のアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の環化反応とを、異なるポリリン酸濃度で行うことを特徴とするキナクリドン固溶体の製造方法を提供する（以下、第一発明ということがある。）。
また本発明は、異なる二種以上の、アリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸をポリリン酸の存在下で環化するキナクリドン固溶体の製造方法において、第１のアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の環化反応と、第２のアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の環化反応とを、異なるポリリン酸濃度で行うことを特徴とするキナクリドン固溶体の製造方法にて得られたキナクリドン固溶体を、更に顔料化する、キナクリドン固溶体顔料組成物の製造方法を提供する（以下、第二発明ということがある。）。
That is, the present invention provides a method for producing a quinacridone solid solution in which 2,5-diarylaminoterephthalic acid, which may have a substituent in two or more different aryl groups, is cyclized in the presence of polyphosphoric acid. Cyclization reaction of 2,5-diarylaminoterephthalic acid optionally having a substituent on the aryl group and 2,5-diarylaminoterephthalic acid optionally having a substituent on the second aryl group A quinacridone solid solution production method is provided in which the cyclization reaction is performed at different polyphosphoric acid concentrations (hereinafter sometimes referred to as the first invention).
Further, the present invention provides a method for producing a quinacridone solid solution in which two or more different 2,5-diarylaminoterephthalic acids, which may have a substituent in the aryl group, are cyclized in the presence of polyphosphoric acid. Cyclization reaction of 2,5-diarylaminoterephthalic acid optionally having a substituent on the aryl group and 2,5-diarylaminoterephthalic acid optionally having a substituent on the second aryl group The quinacridone solid solution obtained by the method for producing a quinacridone solid solution, wherein the quinacridone solid solution is further pigmented, wherein the cyclization reaction of the quinacridone is performed at different polyphosphoric acid concentrations is provided. , Sometimes referred to as the second invention).
本発明のキナクリドン固溶体の製造方法は、第１のアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の環化反応と、第２のアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の環化反応とを、異なるポリリン酸濃度で行う様にするので、得られたキナクリドン固溶体はより高彩度になるという格別顕著な効果を奏する。
また本発明のキナクリドン固溶体顔料組成物の製造方法は、上記製造方法で得られたキナクリドン固溶体を原料として、それを顔料化するので、得られたキナクリドン固溶体顔料組成物は、顔料化前に比べて更に高彩度になるという格別顕著な効果を奏する。
The method for producing a quinacridone solid solution of the present invention has a cyclization reaction of 2,5-diarylaminoterephthalic acid which may have a substituent in the first aryl group, and a substituent in the second aryl group. Since the cyclization reaction of 2,5-diarylaminoterephthalic acid which may be carried out is carried out at different polyphosphoric acid concentrations, the obtained quinacridone solid solution has a particularly remarkable effect of higher saturation.
In addition, the method for producing a quinacridone solid solution pigment composition of the present invention uses the quinacridone solid solution obtained by the above production method as a raw material, which is converted into a pigment, so that the obtained quinacridone solid solution pigment composition is compared with that before pigmentation. Furthermore, it has a particularly remarkable effect of high saturation.
最初に、第一発明におけるキナクリドン固溶体の製造方法について説明する。 Initially, the manufacturing method of the quinacridone solid solution in 1st invention is demonstrated.
第一発明においては、異なる二種以上の、アリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸をポリリン酸の存在下で環化することでキナクリドン固溶体を得る。以下、アリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸を原料と称する場合がある。 In the first invention, a quinacridone solid solution is obtained by cyclizing 2,5-diarylaminoterephthalic acid, which may have a substituent in two or more different aryl groups, in the presence of polyphosphoric acid. Hereinafter, 2,5-diarylaminoterephthalic acid which may have a substituent in the aryl group may be referred to as a raw material.
アリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸とは、アリール基に置換基を有さない（無置換ということがある）２，５−ジアリールアミノテレフタル酸と、アリール基に置換基を有する（置換ということがある）２，５−ジアリールアミノテレフタル酸との総称であり、そこには、例えば２，５−ジアニリノテレフタル酸の様なアリール基に置換基を有さない２，５−ジアリールアミノテレフタル酸や、２，５−ビス−ｏ−クロロアニリノ−テレフタル酸、２，５−ビス−ｏ−メチルアニリノ−テレフタル酸、２，５−ビス−ｏ−メトキシアニリノ−テレフタル酸の様なアリール基に置換基を有する２，５−ジアリールアミノテレフタル酸が含まれる。 The 2,5-diarylaminoterephthalic acid which may have a substituent in the aryl group is 2,5-diarylaminoterephthalic acid which does not have a substituent in the aryl group (sometimes referred to as unsubstituted), It is a general term for 2,5-diarylaminoterephthalic acid having a substituent in the aryl group (sometimes referred to as substitution). For example, an aryl group such as 2,5-dianilinoterephthalic acid has a substituent. 2,5-diarylaminoterephthalic acid, 2,5-bis-o-chloroanilino-terephthalic acid, 2,5-bis-o-methylanilino-terephthalic acid, 2,5-bis-o-methoxyanilino -2,5-diarylaminoterephthalic acid having a substituent on an aryl group such as terephthalic acid is included.
本発明においては、これらのうちから異なる二種以上が任意に選択して用いられる。その組み合わせは、無置換２，５−ジアリールアミノテレフタル酸と、置換２，５−ジアリールアミノテレフタル酸との組み合わせであっても良いし、置換２，５−ジアリールアミノテレフタル酸同士の組み合わせであっても良い。 In the present invention, two or more different ones are arbitrarily selected and used. The combination may be a combination of unsubstituted 2,5-diarylaminoterephthalic acid and substituted 2,5-diarylaminoterephthalic acid, or a combination of substituted 2,5-diarylaminoterephthalic acids. Also good.
キナクリドン固溶体を得るための、異なる二種以上の、アリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の質量比は、目的の色相の固溶体が形成されれば特に制限されるものではないが、例えば、二種のアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸を用いる場合は、通常、一方：他方＝８０：２０〜２０：８０であり、好ましくは６０：４０〜４０：６０である。 In order to obtain a quinacridone solid solution, the mass ratio of two or more different 2,5-diarylaminoterephthalic acids which may have a substituent in the aryl group is particularly limited as long as a solid solution of the desired hue is formed. However, for example, when 2,5-diarylaminoterephthalic acid which may have a substituent in two kinds of aryl groups is used, usually one: the other = 80: 20 to 20:80 Preferably, it is 60: 40-40: 60.
キナクリドン固溶体を得るに当たっては、予め市販されている様な、異なる二種以上のキナクリドン顔料をポリリン酸や濃硫酸に溶解し、水中に投入した後、析出物を濾過、水洗する方法（アシッドスラリー法と呼ばれる）もあるが、廃酸処理や無機塩除去処理が不要である等の点で、本発明の様な、アリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸から、直接的にキナクリドン固溶体を製造する方法が有利である。 In order to obtain a quinacridone solid solution, a method in which two or more different quinacridone pigments, which are commercially available, are dissolved in polyphosphoric acid or concentrated sulfuric acid, poured into water, and the precipitate is filtered and washed with water (acid slurry method). 2,5-diarylaminoterephthalic acid which may have a substituent in the aryl group as in the present invention in that waste acid treatment or inorganic salt removal treatment is unnecessary. From this, a method of producing a quinacridone solid solution directly is advantageous.
キナクリドン固溶体の製造方法では、異なる二種以上の、アリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸をポリリン酸の存在下で環化させるが、本発明では、二種以上の原料の環化反応を、異なるポリリン酸濃度で行う。 In the method for producing a quinacridone solid solution, two or more different 2,5-diarylaminoterephthalic acids, which may have a substituent in the aryl group, are cyclized in the presence of polyphosphoric acid. Cyclization reactions of more than one species are performed at different polyphosphoric acid concentrations.
本発明では、ポリリン酸が用いられる。このポリリン酸は、公知慣用の製造方法で種々の濃度に調整することが出来る。本発明の製造方法においては、例えば、環化反応に必要な濃度のポリリン酸と、それより高濃度のポリリン酸を、それぞれ予め準備しておき、環化反応に必要な一定濃度のポリリン酸の存在下で最初の環化反応後に、その反応系に、前記したより高濃度のポリリン酸を加えるという方法を採用することが出来る。 In the present invention, polyphosphoric acid is used. This polyphosphoric acid can be adjusted to various concentrations by known and commonly used production methods. In the production method of the present invention, for example, a polyphosphoric acid having a concentration necessary for the cyclization reaction and a polyphosphoric acid having a higher concentration are prepared in advance, and the polyphosphoric acid having a certain concentration necessary for the cyclization reaction is prepared in advance. After the first cyclization reaction in the presence, a method of adding a higher concentration of polyphosphoric acid to the reaction system can be employed.
ポリリン酸は、例えば、リン酸水溶液と無水リン酸とを混合することで得ることも出来る。予め大過剰のリン酸に対して、無水リン酸を少なめに加えることで、反応系に、必要な一定量のポリリン酸を生じさせ、このポリリン酸濃度で第一の環化反応を行った後に、更に無水リン酸を反応系に加える様にして第二の環化反応を行う様にすると、第一の環化反応時に比べて、第二の環化反応時における反応系中のポリリン酸濃度を高めることが出来る。予め異なる濃度のポリリン酸を準備しておくのに比べて、上記した方法は、反応系中のポリリン酸濃度を段階的に高めるのに簡便な方法であり、個々の濃度のポリリン酸やその溶液を貯蔵しておく設備も不要であることから好ましい。 Polyphosphoric acid can also be obtained, for example, by mixing an aqueous phosphoric acid solution and anhydrous phosphoric acid. After adding a small amount of phosphoric anhydride to a large excess of phosphoric acid in advance, the required amount of polyphosphoric acid is generated in the reaction system, and after the first cyclization reaction is performed at this polyphosphoric acid concentration Further, when the second cyclization reaction is performed by adding phosphoric anhydride to the reaction system, the concentration of polyphosphoric acid in the reaction system during the second cyclization reaction is higher than that during the first cyclization reaction. Can be increased. Compared to preparing different concentrations of polyphosphoric acid in advance, the above method is a simple method for increasing the concentration of polyphosphoric acid in the reaction system step by step. It is preferable because there is no need for a facility for storing
環化に用いるポリリン酸水溶液は、反応系を極力無水状態とし環化効率を高めるため、出来るだけ高濃度であることが好ましい。含有率８０％以上のポリリン酸を得るには、８０％以上、中でも８０〜９０％の濃度のリン酸水溶液を用いることが好ましい。 The polyphosphoric acid aqueous solution used for cyclization is preferably as high as possible in order to make the reaction system in an anhydrous state as much as possible and increase the cyclization efficiency. In order to obtain polyphosphoric acid having a content rate of 80% or more, it is preferable to use an aqueous phosphoric acid solution having a concentration of 80% or more, particularly 80 to 90%.
本発明においては原料の環化反応の進行に伴い、系内に水が生成し、リン酸水溶液と無水リン酸とを混合してポリリン酸を生成させその濃度を高めようとする場合には、前記水が無水リン酸を消費することになるため、第二の環化反応を行う場合は、特に、当該水との反応とで消費されてしまう無水リン酸を考慮して、生成水のモル数と使用する無水リン酸との当量は、無水リン酸の当量が生成水の当量の１．１〜１．３倍大きくなる様に調整することが好ましい。 In the present invention, with the progress of the cyclization reaction of the raw material, water is generated in the system, and when mixing the phosphoric acid aqueous solution and phosphoric anhydride to produce polyphosphoric acid and increasing its concentration, Since the water consumes phosphoric anhydride, when performing the second cyclization reaction, in particular, considering the anhydrous phosphoric acid consumed in the reaction with the water, the moles of the produced water The number and the equivalent of phosphoric anhydride to be used are preferably adjusted so that the equivalent of phosphoric anhydride is 1.1 to 1.3 times larger than the equivalent of product water.
異なる二種以上の原料の環化を行うに当たっての反応系中のポリリン酸濃度は特に制限されるものではないが、反応率向上及び副生成物の発生抑制の観点から、いずれも、例えば、８５〜９９％の範囲から選択することが好ましい。中でも、段階的にポリリン酸濃度を高めること、具体的には、第１の原料をポリリン酸濃度８２〜８４％で環化した、リン酸を含む環化反応液に、更に無水リン酸を添加して、ポリリン酸濃度を８５〜８７％とし、第２の原料を環化することが、上記した点で好ましい。 The concentration of polyphosphoric acid in the reaction system for cyclization of two or more different raw materials is not particularly limited. From the viewpoint of improving the reaction rate and suppressing the generation of by-products, for example, 85% It is preferable to select from a range of ˜99%. Among them, increasing the concentration of polyphosphoric acid stepwise, specifically, adding phosphoric anhydride further to the cyclization reaction solution containing phosphoric acid obtained by cyclizing the first raw material at a polyphosphoric acid concentration of 82 to 84% In view of the above, it is preferable that the polyphosphoric acid concentration is 85 to 87% and the second raw material is cyclized.
第１の原料として、アリール基にハロゲン原子を有する２，５−ジアリールアミノテレフタル酸を用い、第２の原料として、アリール基に置換基を有さない２，５−ジアリールアミノテレフタル酸をそれぞれ用いて、上記した方法にて環化を行うと、より副生成物が少ないキナクリドン固溶体が得られる。 2,5-diarylaminoterephthalic acid having a halogen atom in the aryl group is used as the first raw material, and 2,5-diarylaminoterephthalic acid having no substituent in the aryl group is used as the second raw material. When cyclization is performed by the above-described method, a quinacridone solid solution with fewer by-products can be obtained.
前記環化に必要なポリリン酸の使用量は、用いるポリリン酸水溶液の濃度によっても異なり、所定反応温度での撹拌が容易な粘度となる使用量であることが、環化を確実に遂行するために好ましい。具体的には、質量基準で、第一の環化に用いる原料、第二の環化に用いる原料を含む原料全量１００部当たり、ポリリン酸（不揮発分）が、２００〜６００部となる様にすることが好ましい。 The amount of polyphosphoric acid necessary for the cyclization varies depending on the concentration of the polyphosphoric acid aqueous solution to be used, and the amount of the polyphosphoric acid required to give a viscosity that can be easily stirred at a predetermined reaction temperature is used to reliably perform cyclization. Is preferable. Specifically, on a mass basis, polyphosphoric acid (nonvolatile content) is 200 to 600 parts per 100 parts of the total amount of raw materials including the raw material used for the first cyclization and the raw material used for the second cyclization. It is preferable to do.
個々の原料は、その置換基の有無、置換基の種類により挙動が異なり、それぞれの環化に最適な反応条件が異なることが予想される。本発明の製造方法では、反応系中のポリリン酸濃度や反応温度を、仕込まれるアリール基に置換基を有していても良い２，５−ジアリールアミノテレフタル酸の種類毎に設定でき、微細レベルでの固溶体の安定形成にも寄与できるという、従来の製造方法に無い技術的効果を有する。 The behavior of each raw material varies depending on the presence or absence of the substituent and the type of the substituent, and it is expected that the optimal reaction conditions for each cyclization will be different. In the production method of the present invention, the concentration of polyphosphoric acid and the reaction temperature in the reaction system can be set for each type of 2,5-diarylaminoterephthalic acid which may have a substituent in the charged aryl group, and at a fine level. It has a technical effect not found in the conventional manufacturing method that it can contribute to the stable formation of a solid solution.
各環化反応は、それぞれの環化が充分に行われる様に行えば良いが、通常、それぞれ、温度８５〜１４０℃において１〜５時間加熱することで脱水環化反応を行うことが出来る。この加熱に当たっては、反応系を撹拌する様にすることが好ましい。また、反応率を高めるために、反応系内の温度を段階的に変化させてもよい。 Each cyclization reaction may be carried out so that the respective cyclizations are sufficiently performed. Usually, the dehydration cyclization reaction can be performed by heating at a temperature of 85 to 140 ° C. for 1 to 5 hours, respectively. In this heating, it is preferable to stir the reaction system. In order to increase the reaction rate, the temperature in the reaction system may be changed stepwise.
特に、アリール基にハロゲン原子を有する２，５−ジアリールアミノテレフタル酸を第１の原料として用い、ポリリン酸濃度８２〜８４％、温度９０〜１２０℃で環化した、リン酸を含む環化反応液に、更に無水リン酸を添加して、ポリリン酸濃度を８５〜８７％とし、アリール基に置換基を有さない２，５−ジアリールアミノテレフタル酸を第２の原料として用い、温度１２０℃を越えて１３０℃で環化する製造方法は、全体的には、高い反応率、短い反応時間及び少ない副生成物が達成できる三拍子揃った、優れたキナクリドン固溶体の製造方法である。 In particular, cyclization reaction including phosphoric acid, which is cyclized with 2,5-diarylaminoterephthalic acid having a halogen atom in the aryl group as a first raw material at a polyphosphoric acid concentration of 82 to 84% and a temperature of 90 to 120 ° C. Further, phosphoric anhydride is added to the solution to make the polyphosphoric acid concentration 85 to 87%, and 2,5-diarylaminoterephthalic acid having no substituent on the aryl group is used as the second raw material, and the temperature is 120 ° C. The production method for cyclization at 130 ° C. over the above is generally an excellent method for producing a solid quinacridone solid solution with a high reaction rate, a short reaction time, and a triple product capable of achieving a small amount of by-products.
得られたキナクリドン固溶体は、次いで結晶化させるのが好ましい。この結晶化には、公知慣用の手法がいずれも採用でき、例えば、キナクリドン固溶体が不要な液媒体と上記した環化反応液とを混合する方法が挙げられる。本発明の各原料から得られるキナクリドン固溶体は、親水性の置換基を有さないことから、前記液媒体として水を用いて、環化反応液の温度を低下させると共に、それを希釈撹拌することで、キナクリドン固溶体の結晶を水中に沈殿させることが出来る。この沈殿を濾過することでキナクリドン固溶体が得られる。 The resulting quinacridone solid solution is then preferably crystallized. For this crystallization, any known and commonly used method can be employed. For example, a method of mixing a liquid medium that does not require a quinacridone solid solution and the above-described cyclization reaction solution can be mentioned. Since the quinacridone solid solution obtained from each raw material of the present invention does not have a hydrophilic substituent, water is used as the liquid medium, and the temperature of the cyclization reaction liquid is lowered and the mixture is diluted and stirred. Thus, quinacridone solid solution crystals can be precipitated in water. A quinacridone solid solution is obtained by filtering the precipitate.
こうして得られたキナクリドン固溶体は、必要に応じて精製や乾燥を行うことが出来る。洗浄としては、例えば水洗、湯洗、アルカリ洗等を採用でき、洗浄回数も例えば１〜５回とすることが出来る。特にアルカリ洗は、反応系内に残留するリン酸を中和するためであり、この目的においては、後述の顔料化処理においてキナクリドン固溶体が液媒体に溶解しない様に、その使用量は少量にすることが好ましい。 The quinacridone solid solution thus obtained can be purified and dried as necessary. As washing, for example, water washing, hot water washing, alkali washing, etc. can be adopted, and the number of washings can be, for example, 1 to 5 times. In particular, the alkaline washing is for neutralizing phosphoric acid remaining in the reaction system. For this purpose, the amount used is small so that the quinacridone solid solution does not dissolve in the liquid medium in the pigmentation treatment described later. It is preferable.
こうして本発明の製造方法で得られたキナクリドン固溶体は、従来の製造方法で得られたキナクリドン固溶体に比べて未反応原料や副生成物の含有率が低減されていることから、より高彩度を呈する。このキナクリドン固溶体は、そのまま必要な各種用途に使用することが出来るが、着色剤としてより高彩度が求められる場合には、それを顔料化して、キナクリドン固溶体顔料とすることが好ましい。 Thus, the quinacridone solid solution obtained by the production method of the present invention exhibits higher chroma because the content of unreacted raw materials and by-products is reduced compared to the quinacridone solid solution obtained by the conventional production method. The quinacridone solid solution can be used as it is for various uses as it is. However, when a higher chroma is required as a colorant, it is preferable to form a pigment to form a quinacridone solid solution pigment.
こうして得られたキナクリドン固溶体は、顔料化することで、キナクリドン固溶体顔料を製造することが出来る（上記第二発明）。第二発明の様に、第一発明に引き続いて顔料化を行う場合には、上記にて洗浄した後、濾過した状態の含水ウエットケーキを（乾燥させず）そのまま顔料化工程に用いることも出来る。こうすることで、キナクリドン固溶体自体の乾燥工程を省略することが出来るだけでなく、乾燥凝集により顔料化に要する手間が増すことが無くなる点でも好ましい。 The quinacridone solid solution thus obtained can be pigmented to produce a quinacridone solid solution pigment (the second invention described above). As in the second invention, when pigmentation is carried out following the first invention, the wet cake in a filtered state after washing as described above can be used as it is in the pigmentation step (without drying). . By doing so, not only can the drying step of the quinacridone solid solution itself be omitted, but it is also preferable in that the labor required for pigmentation does not increase due to dry aggregation.
第二発明の様に、キナクリドン固溶体を顔料化することで、キナクリドン固溶体顔料を製造することが出来るが、この際の顔料化には公知慣用の手法をいずれも採用できる。具体的には、上記したキナクリドン固溶体を水溶性無機塩と水溶性有機溶媒と共に混練摩砕し水洗する方法（いわゆるソルベントソルトミリング法）や、上記したキナクリドン固溶体をそれに対して大過剰の、キナクリドン固溶体を溶解しない液媒体中で加熱する方法（いわゆるソルベント法）等がある。 As in the second invention, a quinacridone solid solution pigment can be produced by pigmenting the quinacridone solid solution, and any known and commonly used method can be employed for pigmentation. Specifically, the above-described quinacridone solid solution is kneaded and ground together with a water-soluble inorganic salt and a water-soluble organic solvent and washed with water (so-called solvent salt milling method), or the quinacridone solid solution described above is in a large excess with respect to the quinacridone solid solution. There is a method of heating in a liquid medium that does not dissolve (so-called solvent method).
ソルベントソルトミリング法としては、例えば、キナクリドン固溶体を、塩化ナトリウムや硫酸ナトリウムの様な水溶性無機塩と、ジエチレングリコール、トリエチレングリコールの様な水溶性有機溶媒と共に、加熱しながら混練摩砕し水洗する方法が挙げられる。 As a solvent salt milling method, for example, a quinacridone solid solution is kneaded, ground and washed with water together with a water-soluble inorganic salt such as sodium chloride or sodium sulfate and a water-soluble organic solvent such as diethylene glycol or triethylene glycol. A method is mentioned.
しかしながら、第二発明における顔料化方法としては、機械的エネルギー消費を抑制できるばかりでなく、洗浄のための大量の水も不要で水溶性無機塩による設備腐食等の心配も少ないことから、ソルベントソルトミリング法に比べて、ソルベント法の方を採用することが好ましい。 However, as a pigmentation method in the second invention, not only can the mechanical energy consumption be suppressed, but also a large amount of water for washing is unnecessary, and there is little concern about equipment corrosion due to water-soluble inorganic salts. It is preferable to adopt the solvent method compared to the milling method.
ソルベント法を行う場合の液媒体は、キナクリドン固溶体を溶解しないものを選択して用いる。この液媒体としては、キナクリドン固溶体の結晶制御をより安定的に行うために、水可溶性有機溶媒を必須成分として含む液媒体を用いるのが好ましい。 As the liquid medium for performing the solvent method, a liquid medium that does not dissolve the quinacridone solid solution is selected and used. As this liquid medium, in order to more stably control the crystal of the quinacridone solid solution, it is preferable to use a liquid medium containing a water-soluble organic solvent as an essential component.
本発明に用いられる水可溶性有機溶媒としては、例えば、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチルピロリドン、エタノール、プロパノール、ブタノール、エチレングリコールのようなものが挙げられるが、製造時の加熱温度や価格並びに安全性を考慮すると、Ｎ−メチルピロリドンやブタノールの使用がとくに好ましい。 Examples of the water-soluble organic solvent used in the present invention include dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, ethanol, propanol, butanol, ethylene glycol, and the like. In consideration of safety, use of N-methylpyrrolidone or butanol is particularly preferable.
水可溶性有機溶媒の量は、特に限定されないが、キナクリドン固溶体の質量を基準にして、０．１ないし２０質量倍相当量の範囲、もしくはそれ以上多くてもよいが、単に溶剤回収コストがかさむのみである。従って、好ましい水可溶性有機溶媒の量は、０．１〜１０質量倍相当量が最も好ましい。 The amount of the water-soluble organic solvent is not particularly limited, but may be in the range equivalent to 0.1 to 20 times the mass or more based on the mass of the quinacridone solid solution, but it simply increases the solvent recovery cost. It is. Therefore, the preferable amount of the water-soluble organic solvent is most preferably 0.1 to 10 times by mass.
水可溶性有機溶媒を必須成分として含む液媒体のなかでも、水と水可溶性有機溶媒とを含む液媒体を用いるのが特に好ましい。この場合、水と水可溶性有機溶媒とを含む液媒体中の含水率は、１５〜９５質量％となる様にする。こうすることで、キナクリドン固溶体の溶解を防止出来る。 Among liquid media containing a water-soluble organic solvent as an essential component, it is particularly preferable to use a liquid medium containing water and a water-soluble organic solvent. In this case, the water content in the liquid medium containing water and the water-soluble organic solvent is set to 15 to 95% by mass. By doing so, dissolution of the quinacridone solid solution can be prevented.
一方、液媒体全体の量は、特に限定されないが、キナクリドン固溶体の重量を基準にして、大過剰、なかでも５ないし１５質量倍相当量の範囲が好ましい。 On the other hand, the amount of the entire liquid medium is not particularly limited, but is preferably in a large excess, particularly in the range of 5 to 15 times by mass based on the weight of the quinacridone solid solution.
本発明の製造方法での液媒体の加熱温度は、用いる水可溶性有機溶媒の種類によって変化することもあるが、５０〜１６０℃の任意の温度が採用でき、中でも１００〜１４０℃の温度において行なうのが好ましい。加熱する時間も特に限定されるものではないが、より均一な粒子径の顔料を得るためには、通常は２〜１０時間である。 Although the heating temperature of the liquid medium in the production method of the present invention may vary depending on the type of the water-soluble organic solvent to be used, any temperature of 50 to 160 ° C. can be adopted, and in particular, the temperature is 100 to 140 ° C. Is preferred. Although the heating time is not particularly limited, it is usually 2 to 10 hours in order to obtain a pigment having a more uniform particle size.
この加熱は、例えばキナクリドン固溶体と液媒体とを必須成分として混合し、上記所定の温度下で攪拌することにより実施することが出来る。この加熱操作は、予め温度や攪拌条件を固定して時間毎にサンプリングを行って、顔料の粉末Ｘ線回折測定やＢＥＴ比表面積を求めておき、実際の製造では、キナクリドン固溶体顔料が意図する粉末Ｘ線回折強度やＢＥＴ比表面積となる時間で終点とする様にする。 This heating can be performed, for example, by mixing a quinacridone solid solution and a liquid medium as essential components and stirring at the predetermined temperature. In this heating operation, the temperature and stirring conditions are fixed in advance and sampling is performed every hour to obtain the powder X-ray diffraction measurement and the BET specific surface area of the pigment. In actual production, the quinacridone solid solution pigment is the intended powder. The end point is determined by the time required for the X-ray diffraction intensity or the BET specific surface area.
キナクリドン固溶体にそれ以外のキナクリドン系顔料誘導体を併用して液媒体中で加熱することにより、場合により起こる急激な結晶成長を抑制緩和し、溶媒中での加熱条件が多少変動しても意図した特性のキナクリドン固溶体顔料が容易に得られる。 By combining a quinacridone solid solution with another quinacridone pigment derivative and heating it in a liquid medium, it suppresses and relieves the sudden crystal growth that occurs in some cases, and the intended characteristics even if the heating conditions in the solvent vary slightly. The quinacridone solid solution pigment can be easily obtained.
本発明において用いられるキナクリドン系顔料誘導体としては、当業界において既知であるキナクリドンスルホン酸、ピラゾリル−メチルキナクリドン、ジメチルアミノプロピルキナクリドンモノスルホンアミド、ジメチルアミノプロピルキナクリドンジスルホンアミドおよび２−フタルイミドメチルキナクリドンが含まれる。なお、キナクリドン固溶体として含水ウエットケーキを用いて顔料化を行う場合には、同様にこれらキナクリドン系顔料誘導体としても含水ウエットケーキを用いるのが好ましい。 The quinacridone pigment derivatives used in the present invention include quinacridone sulfonic acid, pyrazolyl-methylquinacridone, dimethylaminopropylquinacridone monosulfonamide, dimethylaminopropylquinacridone disulfonamide and 2-phthalimidomethylquinacridone known in the art. . In addition, when performing pigmentation using a wet wet cake as a quinacridone solid solution, it is preferable to similarly use a wet wet cake as these quinacridone pigment derivatives.
キナクリドン系顔料誘導体は、キナクリドン固溶体の製造工程中に系内に添加することもできるが、その場合にはキナクリドン系顔料誘導体のウエットケーキを乾燥しなければならないこと、強酸中でのキナクリドン系顔料誘導体の化学的安定性などの問題、更には添加量の変更などにおける自由度を考慮すると、キナクリドン固溶体を液媒体中で加熱する前にウエットケーキのまま添加することが好ましい。 The quinacridone pigment derivative can be added into the system during the manufacturing process of the quinacridone solid solution, but in that case, the wet cake of the quinacridone pigment derivative must be dried, the quinacridone pigment derivative in strong acid In view of problems such as chemical stability, and the degree of freedom in changing the addition amount, it is preferable to add the quinacridone solid solution as a wet cake before heating in a liquid medium.
キナクリドン固溶体顔料を製造する際の上記キナクリドン系顔料誘導体の使用量は、適宜選択すれば良いが、好適には、キナクリドン固溶体の質量を基準にして、１〜１０質量％相当量とすると微細で透明性に優れたキナクリドン固溶体顔料が得られやすい。上記のキナクリドン系顔料誘導体の中では、同量使用における結晶成長抑制の効果が大きく、優れた適用性をキナクリドン固溶体顔料に付与できる点で、キナクリドンスルホン酸塩、とりわけアルミニウム金属塩がとくに好ましい。 The amount of the quinacridone pigment derivative used in the production of the quinacridone solid solution pigment may be appropriately selected. Preferably, the amount is preferably 1 to 10% by mass based on the mass of the quinacridone solid solution. It is easy to obtain a quinacridone solid solution pigment having excellent properties. Among the above quinacridone pigment derivatives, quinacridone sulfonates, particularly aluminum metal salts are particularly preferred because they have a large effect of suppressing crystal growth when used in the same amount and can impart excellent applicability to quinacridone solid solution pigments.
また上記加熱を行うに際しては、系内でキナクリドン固溶体及び必要に応じて用いられるキナクリドン系顔料誘導体が溶解しない様に、必要ならば、例えば水酸化ナトリウム、水酸化カリウム等の無機塩基を併用することも出来る。 In addition, when performing the above heating, if necessary, an inorganic base such as sodium hydroxide or potassium hydroxide may be used in combination so that the quinacridone solid solution and the quinacridone pigment derivative used as necessary do not dissolve in the system. You can also.
加熱を中止した後は、通常、このキナクリドン固溶体顔料と液媒体との混合物を濾過し、得られたキナクリドン固溶体顔料を洗浄し、乾燥する。予め水可溶性有機溶媒を系外に除去してから、粗製キナクリドン固溶体顔料と水との混合物について、これらの操作を行うことも出来る。 After stopping the heating, the mixture of the quinacridone solid solution pigment and the liquid medium is usually filtered, and the obtained quinacridone solid solution pigment is washed and dried. These operations can be performed on a mixture of a crude quinacridone solid solution pigment and water after previously removing the water-soluble organic solvent from the system.
尚、この洗浄には、上記キナクリドン固溶体を得る際の方法が採用できる。また乾燥には、熱風乾燥機やスプレードライヤー等を用いることが出来る。 In addition, the method at the time of obtaining the said quinacridone solid solution can be employ | adopted for this washing | cleaning. Moreover, a hot air dryer, a spray dryer, etc. can be used for drying.
こうして得られた本発明のキナクリドン固溶体顔料は、公知慣用の用途、例えば印刷インキ、塗料、熱可塑性樹脂成形品の着色、フォトレジストの着色、静電荷像現像用トナー等の各種用途で使用できる。 The thus obtained quinacridone solid solution pigment of the present invention can be used in various known applications such as printing ink, paint, coloring of thermoplastic resin molded products, coloring of photoresist, toner for developing electrostatic images.
＜実施例＞
以下、実施例、比較例について試験例を用いて本発明を具体的に説明するが、本発明は、これらの実施例に限定されるものではない。なお、以下の例中における「％」は、特に断りのない限り、いずれも質量％である。
<Example>
Hereinafter, although an example and a comparative example explain the present invention concretely using a test example, the present invention is not limited to these examples. In the following examples, “%” is mass% unless otherwise specified.
＜キナクリドン固溶体の製造方法＞
攪拌装置付の反応容器に、８５％リン酸２９８部、無水リン酸３８４部を加えて２０分間攪拌し、リン酸を含む、ポリリン酸６８２部を得た。
ここに、純度９８％の２，５−ジ（o-クロロアニリノ）テレフタル酸８６部を１時間攪拌しながら加えた。この時点の反応系中のポリリン酸濃度は、８３％であった。この原料混合物を１１０℃で１時間撹拌することで環化を行って、第１の原料の環化反応液を得た。
次いで、上記環化反応液に対して、無水リン酸１８２部加えた。この時点の反応系中のポリリン酸濃度は、８６％であった。そこに純度９８％の２，５−ジアニリノテレフタル酸１３０部を２時間攪拌しながら加え、１２５℃で３時間攪拌を行い、第１及び第２の原料の各環化物であるキナクリドン固溶体を含む環化反応液を得た。
<Method for producing quinacridone solid solution>
In a reaction vessel equipped with a stirrer, 298 parts of 85% phosphoric acid and 384 parts of anhydrous phosphoric acid were added and stirred for 20 minutes to obtain 682 parts of polyphosphoric acid containing phosphoric acid.
To this, 86 parts of 98% pure 2,5-di (o-chloroanilino) terephthalic acid was added with stirring for 1 hour. At this time, the concentration of polyphosphoric acid in the reaction system was 83%. The raw material mixture was cyclized by stirring at 110 ° C. for 1 hour to obtain a first raw material cyclization reaction solution.
Next, 182 parts of phosphoric anhydride was added to the cyclization reaction solution. At this time, the polyphosphoric acid concentration in the reaction system was 86%. Thereto, 130 parts of 2,5-dianilinoterephthalic acid with a purity of 98% is added with stirring for 2 hours, stirred at 125 ° C. for 3 hours, and contains a quinacridone solid solution that is each cyclized product of the first and second raw materials. A cyclization reaction solution was obtained.
別の攪拌装置付の容器に２０℃の水８６００部を張り、これの強攪拌下に、第１及び第２の原料の各環化物であるキナクリドン固溶体を含む環化反応液を投入し、３０分間そのまま攪拌し、濾過、水洗してキナクリドン固溶体のウエットケーキ６４０部（固形分３０％）を得た。続いて、別の攪拌装置付の容器に水４６００部を張り、キナクリドン固溶体のウエットケーキを投入し、苛性水溶液を用いてpH１２〜１３に調整。８０℃で１．５時間攪拌し、濾過、水洗しキナクリドン固溶体のアルカリ洗浄ウエットケーキ９５０部（固形分２０％）を得た。 In another vessel with a stirrer, 8600 parts of water at 20 ° C. is put, and under this strong stirring, a cyclization reaction solution containing a quinacridone solid solution, which is each cyclized product of the first and second raw materials, is added, and 30 The mixture was stirred for a minute, filtered and washed with water to obtain 640 parts of a wet cake of quinacridone solid solution (solid content 30%). Subsequently, 4600 parts of water was put in another vessel equipped with a stirrer, a wet cake of quinacridone solid solution was added, and the pH was adjusted to 12 to 13 using a caustic aqueous solution. The mixture was stirred at 80 ° C. for 1.5 hours, filtered and washed with water to obtain 950 parts (20% solid content) of an alkali washed wet cake of quinacridone solid solution.
＜キナクリドン固溶体顔料の製造方法＞
攪拌装置付の加圧可能な反応容器に、キナクリドン固溶体のアルカリ洗浄ウエットケーキ１７５部、イソブタノール８８部、水１９０部、キナクリドン誘導体１３部(スラリー換算)、固形量換算では１．０５部を仕込み、粉砕メディアの存在無しに、攪拌翼で内容物を１３０℃で７時間攪拌した。その後、室温まで冷却し、濾過、湯洗、乾燥、粉砕し、キナクリドンスルホン酸誘導体を含有するジクロロキナクリドン固溶体顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２０７）３０部を得た。
<Method for producing quinacridone solid solution pigment>
In a pressurizable reaction vessel equipped with a stirrer, 175 parts of an alkali washed wet cake of quinacridone solid solution, 88 parts of isobutanol, 190 parts of water, 13 parts of quinacridone derivative (in terms of slurry), 1.05 parts in terms of solid amount are charged. The contents were stirred with a stirring blade at 130 ° C. for 7 hours without the presence of grinding media. Thereafter, the mixture was cooled to room temperature, filtered, washed with hot water, dried and pulverized to obtain 30 parts of dichloroquinacridone solid solution pigment (CI Pigment Red 207) containing a quinacridonesulfonic acid derivative.
攪拌装置付の加圧可能な反応容器に、実施例１で得たのと同一のキナクリドン固溶体のアルカリ洗浄ウエットケーキ３５０部、イソブタノール１８８部、水４５０部を仕込み、粉砕メディアの存在無しに、攪拌翼で内容物を１３０℃で７時間攪拌した。その後、室温まで冷却し、濾過、湯洗、乾燥、粉砕し、ジクロロキナクリドン顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２０７）６５部を得た。 In a pressurizable reaction vessel equipped with a stirrer, 350 parts of an alkali washed wet cake of the same quinacridone solid solution obtained in Example 1, 188 parts of isobutanol, and 450 parts of water were charged, and without the presence of grinding media, The contents were stirred with a stirring blade at 130 ° C. for 7 hours. Thereafter, the mixture was cooled to room temperature, filtered, washed with hot water, dried and pulverized to obtain 65 parts of dichloroquinacridone pigment (CI Pigment Red 207).
攪拌装置付の加圧可能な反応容器に、実施例１で得たのと同一のキナクリドン固溶体のウエットケーキ２００部、Ｎ−メチルピロリドン３７８部、水８部を仕込み、粉砕メディアの存在無しに、攪拌翼で内容物を１３０℃で８時間攪拌した。その後、室温まで冷却し、濾過、湯洗、乾燥、粉砕し、ジクロロキナクリドン顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２０７）３５部を得た。
In a pressurizable reaction vessel equipped with a stirrer, 200 parts of a wet cake of the same quinacridone solid solution obtained in Example 1, 378 parts of N-methylpyrrolidone and 8 parts of water were charged, and without the presence of grinding media, The contents were stirred with a stirring blade at 130 ° C. for 8 hours. Thereafter, the mixture was cooled to room temperature, filtered, washed with hot water, dried, and pulverized to obtain 35 parts of dichloroquinacridone pigment (CI Pigment Red 207).
〔比較例１〕
＜キナクリドン固溶体の製造方法＞
攪拌装置付の反応容器に、８５％リン酸４１８部、無水リン酸７３４部を加えて２０分間攪拌し、リン酸を含む、ポリリン酸１１５２部を得た。
ここに、純度９８％の２，５−ジ（o-クロロアニリノ）テレフタル酸１１５部を１１０℃で1時間攪拌させながら加え、続いて純度９８％の２，５−ジアニリノテレフタル酸１７３部を１１０℃で２時間攪拌させながら加え、１２５℃で３時間攪拌を行い、第１及び第２の原料の各環化物であるキナクリドン固溶体を含む環化反応液を得た。
[Comparative Example 1]
<Method for producing quinacridone solid solution>
To a reaction vessel equipped with a stirrer, 418 parts of 85% phosphoric acid and 734 parts of anhydrous phosphoric acid were added and stirred for 20 minutes to obtain 1152 parts of polyphosphoric acid containing phosphoric acid.
To this, 115 parts of 98% pure 2,5-di (o-chloroanilino) terephthalic acid was added with stirring at 110 ° C. for 1 hour, and then 173 parts of 98% pure 2,5-dianilinoterephthalic acid was added to 110 parts. The mixture was added while stirring at 2 ° C. for 2 hours, and stirred at 125 ° C. for 3 hours to obtain a cyclization reaction solution containing a quinacridone solid solution, which was each cyclized product of the first and second raw materials.
別の攪拌装置付の容器に２０℃の水１２０００部を張り、これの強攪拌下に、第１及び第２の原料の各環化物であるキナクリドン固溶体を含む環化反応液を投入し、３０分間そのまま攪拌し、濾過、水洗してキナクリドン固溶体のウエットケーキ８６０部（固形分３０％）を得た。続いて、別の攪拌装置付の容器に水４６００部を張り、キナクリドン固溶体のウエットケーキを投入し、苛性水溶液を用いてpH１２〜１３に調整。８０℃で１．５時間攪拌し、濾過、水洗しキナクリドン固溶体のアルカリ洗浄ウエットケーキ１２００部（固形分２０％）を得た。 In another vessel with a stirrer, 12,000 parts of water at 20 ° C. is placed, and under this strong stirring, a cyclization reaction solution containing a quinacridone solid solution, which is each cyclized product of the first and second raw materials, is added, and 30 The mixture was stirred as such, filtered and washed with water to obtain 860 parts of a quinacridone solid solution wet cake (solid content 30%). Subsequently, 4600 parts of water was put in another vessel equipped with a stirrer, a wet cake of quinacridone solid solution was added, and the pH was adjusted to 12 to 13 using a caustic aqueous solution. The mixture was stirred at 80 ° C. for 1.5 hours, filtered and washed with water to obtain 1200 parts (20% solid content) of an alkali washed wet cake of quinacridone solid solution.
〔比較例２〕
＜キナクリドン固溶体顔料の製造方法＞
攪拌装置付の加圧可能な反応容器に、比較例１で得たのと同一のキナクリドン固溶体のウエットケーキ３５０部、イソブタノール８８部、水３５０部を仕込み、粉砕メディアの存在無しに、攪拌翼で内容物を１２５℃で７時間攪拌した。その後、室温まで冷却し、濾過、湯洗、乾燥、粉砕し、ジクロロキナクリドン顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２０７）６５部を得た。
[Comparative Example 2]
<Method for producing quinacridone solid solution pigment>
In a pressurizable reaction vessel equipped with a stirrer, 350 parts of a wet cake of the same quinacridone solid solution obtained in Comparative Example 1, 88 parts of isobutanol, and 350 parts of water were charged. The contents were stirred at 125 ° C. for 7 hours. Thereafter, the mixture was cooled to room temperature, filtered, washed with hot water, dried and pulverized to obtain 65 parts of dichloroquinacridone pigment (CI Pigment Red 207).
〔比較例３〕
＜キナクリドン固溶体顔料の製造方法＞
攪拌装置付の加圧可能な反応容器に、比較例１で得たのと同一のキナクリドン固溶体のウエットケーキ２００部、Ｎ−メチルピロリドン３７８部、水８部を仕込み、粉砕メディアの存在無しに、攪拌翼で内容物を１３０℃で８時間攪拌した。その後、室温まで冷却し、濾過、湯洗、乾燥、粉砕し、ジクロロキナクリドン顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２０７）３５部を得た。
[Comparative Example 3]
<Method for producing quinacridone solid solution pigment>
In a pressurizable reaction vessel equipped with a stirrer, 200 parts of a wet cake of the same quinacridone solid solution obtained in Comparative Example 1, 378 parts of N-methylpyrrolidone, and 8 parts of water were charged. The contents were stirred with a stirring blade at 130 ° C. for 8 hours. Thereafter, the mixture was cooled to room temperature, filtered, washed with hot water, dried, and pulverized to obtain 35 parts of dichloroquinacridone pigment (CI Pigment Red 207).
実施例2と比較例2及び実施例3と比較例3で得られた、各キナクリドン固溶体のウエットケーキを乾燥させた粉体とは、前者の粉体の彩度がより高いことは目視から歴然としていた。 The powder obtained by drying the wet cake of each quinacridone solid solution obtained in Example 2 and Comparative Example 2 and Example 3 and Comparative Example 3 clearly shows that the former powder has higher saturation. I was trying.
また、実施例２〜３及び比較例２〜３で得られた各キナクリドン固溶体顔料を用いて、塗料試験を下記の通り実施した。 Moreover, the coating test was implemented as follows using each quinacridone solid solution pigment obtained in Examples 2-3 and Comparative Examples 2-3.
１．ベース塗料の作製
実施例および比較例の顔料４．０ｇ、アクリル樹脂（大日本インキ化学工業株式会社製の「ベッコゾールＪ−５２４−ＩＭ−６０」）１１．２ｇ、メラミン樹脂（スーパーベッカミンＬ−１１７−６０；大日本インキ化学工業（株）製）４．８ｇ、キシレンとブタノールが重量比で３：１であるシンナー２０．０ｇおよび平均直径３ｍｍのガラスビーズ８０ｇを１００ｍｌ仕込む。この混合物をペイントシェーカーで１時間分散した後、アクリル樹脂（大日本インキ化学工業株式会社製の「ベッコゾールＪ−５２４−ＩＭ−６０」）２８．０ｇとメラミン樹脂（スーパーベッカミンＬ−１１７−６０；大日本インキ化学工業（株）製）１２．０ｇを追加し、１０分間混合して、顔料５．０％の塗料を調整した。
1. Preparation of Base Paint 4.0 g of Examples and Comparative Examples, 11.2 g of acrylic resin (“Beckosol J-524-IM-60” manufactured by Dainippon Ink & Chemicals, Inc.), melamine resin (Super Becamine L- 117-60; manufactured by Dainippon Ink & Chemicals, Inc.) 4.8 g, 20.0 g of xylene and butanol having a weight ratio of 3: 1 and 80 g of glass beads having an average diameter of 3 mm are charged in 100 ml. After this mixture was dispersed for 1 hour with a paint shaker, 28.0 g of acrylic resin (“Beckosol J-524-IM-60” manufactured by Dainippon Ink & Chemicals, Inc.) and melamine resin (Super Becamine L-117-60) Dainippon Ink & Chemicals, Inc.) 12.0 g was added and mixed for 10 minutes to prepare a 5.0% pigment paint.
３．展色物の作製と色相評価
（１）ベース塗料を１０ｍｉｌのアプリケーターを用い両面アート紙に展色する。このアート紙を室温において数時間乾燥し、１３０〜１４０℃において１５分間焼付ける。このようにして作製した実施例および比較例の顔料を用いた展色物（以下、原色塗膜と言う）を目視および測色機を用いて色相を比較評価した。
（２）ベース塗料７．５ｇと白塗料１０ｇとを良く混合した後、６ｍｉｌのアプリケーターを用い白アート紙上に展色する。このフィルムを室温において数時間乾燥し、１３０〜１４０℃において１５分間焼付ける。このようにして作製した展色物（以下、淡色塗膜と言う）の色相についても上記と同様に行った。
これらの塗料試験結果を表１に示した。
3. Preparation of color-extracted material and hue evaluation (1) The base paint is developed on double-sided art paper using a 10 mil applicator. The art paper is dried for several hours at room temperature and baked at 130-140 ° C. for 15 minutes. The color development (hereinafter referred to as the primary color coating film) using the pigments of Examples and Comparative Examples produced in this way was compared and evaluated by visual observation and using a colorimeter.
(2) After 7.5 g of the base paint and 10 g of the white paint are mixed well, the color is spread on white art paper using a 6 mil applicator. The film is dried for several hours at room temperature and baked at 130-140 ° C. for 15 minutes. The hue of the developed color product thus produced (hereinafter referred to as a light-colored coating film) was also carried out in the same manner as described above.
The paint test results are shown in Table 1.
本発明の製造方法で得られる、キナクリドン固溶体やキナクリドン固溶体顔料は、いずれも従来のそれらに比べて高彩度を呈することから、着色剤として利用することができる。 The quinacridone solid solution and the quinacridone solid solution pigment obtained by the production method of the present invention exhibit higher chroma than those of the conventional quinacridone solid solution and can be used as a colorant.
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| WO2016208292A1 (en) * | 2015-06-24 | 2016-12-29 | Dic株式会社 | Process for producing quinacridone pigment composition |
| JP7351120B2 (en) | 2019-07-12 | 2023-09-27 | ブラザー工業株式会社 | Water-based ink and ink set for inkjet recording |
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| WO2011124327A1 (en) * | 2010-04-09 | 2011-10-13 | Clariant International Ltd | New magenta quinacridone pigments |
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| US4099980A (en) * | 1975-12-22 | 1978-07-11 | Harmon Colors Corporation | Process for producing gamma quinacridone solid solutions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016208292A1 (en) * | 2015-06-24 | 2016-12-29 | Dic株式会社 | Process for producing quinacridone pigment composition |
| JP6090544B1 (en) * | 2015-06-24 | 2017-03-08 | Dic株式会社 | Process for producing quinacridone pigment composition |
| CN107429077A (en) * | 2015-06-24 | 2017-12-01 | Dic株式会社 | The manufacture method of quinacridone pigment compositions |
| US10040942B2 (en) | 2015-06-24 | 2018-08-07 | Dic Corporation | Process for producing quinacridone pigment composition |
| CN107429077B (en) * | 2015-06-24 | 2019-12-06 | Dic株式会社 | Process for producing quinacridone pigment composition |
| JP7351120B2 (en) | 2019-07-12 | 2023-09-27 | ブラザー工業株式会社 | Water-based ink and ink set for inkjet recording |
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