JPH0241368A - Production of beta-type quinacridone pigment - Google Patents
Production of beta-type quinacridone pigmentInfo
- Publication number
- JPH0241368A JPH0241368A JP63191527A JP19152788A JPH0241368A JP H0241368 A JPH0241368 A JP H0241368A JP 63191527 A JP63191527 A JP 63191527A JP 19152788 A JP19152788 A JP 19152788A JP H0241368 A JPH0241368 A JP H0241368A
- Authority
- JP
- Japan
- Prior art keywords
- quinacridone
- alcohol
- pigment
- type
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 46
- 239000000049 pigment Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 19
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 10
- 229940035429 isobutyl alcohol Drugs 0.000 claims abstract description 8
- 208000012641 Pigmentation disease Diseases 0.000 claims abstract description 6
- 230000019612 pigmentation Effects 0.000 claims abstract description 6
- -1 quinacridone phosphate ester Chemical class 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 230000002378 acidificating effect Effects 0.000 description 19
- 229920000137 polyphosphoric acid Polymers 0.000 description 15
- 239000002253 acid Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ZJQZWNLKRBUEKX-UHFFFAOYSA-N 2,5-dianilinoterephthalic acid Chemical compound OC(=O)C=1C=C(NC=2C=CC=CC=2)C(C(=O)O)=CC=1NC1=CC=CC=C1 ZJQZWNLKRBUEKX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は塗料、グラスチックス、印刷インキ等の着色剤
として有用なβ−型キナクリドン顔料の製造法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing β-type quinacridone pigments useful as colorants for paints, glasstics, printing inks, and the like.
（従来の技術）
従来、β−型キナクリドン顔料の製造法としては、例え
ば２．５−ジアニリノテレフタル酸をポリリン酸又は酸
性ポリリン酸メチルエステル等の縮合剤で環化させて得
られるキナクリドンリン酸エステルを大過剰の水を用い
て加水分解して得られるキナクリドン粗結晶をアルカリ
性アルコール中に浸漬し、アルカリ塩のスラリーを形成
させたのち、当該スラリーに水又は希鉱酸を加えて塩を
解離する方法（特公昭３８−１４１１９号公報）、キナ
クリドン粗結晶を塩化アルミニウム、ニトロベンゼン系
の有機溶剤中で加温する方法（米国特許第２８４４４８
５号公報）、及びキナクリドン粗結晶の含水ケーキをア
ルカリ水溶液中、Ｎ、Ｎ−ジメチルホルムアミド、グリ
コールの存在下にオ−トクレープ中で顔料化処理する方
法（英国特詐第９５１４５１号公報）等が開示されてい
る。(Prior Art) Conventionally, as a method for producing β-type quinacridone pigments, for example, quinacridone phosphoric acid obtained by cyclizing 2,5-dianilinoterephthalic acid with a condensing agent such as polyphosphoric acid or acidic polyphosphoric acid methyl ester has been used. Crude quinacridone crystals obtained by hydrolyzing an ester with a large excess of water are immersed in alkaline alcohol to form a slurry of an alkali salt, and then water or dilute mineral acid is added to the slurry to dissociate the salt. (Japanese Patent Publication No. 38-14119), and a method of heating crude quinacridone crystals in aluminum chloride and a nitrobenzene-based organic solvent (US Pat. No. 284448).
5), and a method in which a water-containing cake of crude quinacridone crystals is pigmented in an autoclave in an alkaline aqueous solution in the presence of N,N-dimethylformamide and glycol (British Special Fraud No. 951451). Disclosed.
（発明が解決しようとする課題）
しかし、これら公知の方法では、β−型以外のα−型及
びｒ−型結晶の混入を避けることが極めて困難であυ、
ま念生産コスト的にみても不利であった。(Problem to be Solved by the Invention) However, in these known methods, it is extremely difficult to avoid contamination of α-type and r-type crystals other than β-type υ,
It was also disadvantageous in terms of production costs.
（課題を解決するための手段）
本発明者等は、上記の如き欠点を解消するため種々研究
した結果、キナクリドンリン酸エステルを、従来の様に
加水分解することなく、直接、低級脂肪族アルコールで
顔料化処理するという筒便な方法により、α−型及びｒ
−型キナクリドンの混入が実質的にない高純度のβ−型
キナクリドン顔料が得られることを見出し、本発明を完
成するに至った。(Means for Solving the Problems) As a result of various studies in order to eliminate the above-mentioned drawbacks, the present inventors have determined that quinacridone phosphate ester can be directly treated with lower aliphatic alcohol without hydrolyzing it as in the past. α-type and r
The present inventors have discovered that it is possible to obtain a highly pure β-type quinacridone pigment substantially free of contamination with -type quinacridone, and have completed the present invention.
即ち、本発明は、キナクリドンリン酸エステルを低級脂
肪族アルコールで顔料化処理することを特徴とするβ−
型キナクリドン顔料の製造法を提供するものである。That is, the present invention provides β-
The present invention provides a method for producing type quinacridone pigments.
本発明で用いるキナクリドンリン酸エステルは、例Ｌｔ
ｄ２．５−ジアニリノテレフタル酸１部（重量部、以下
同じ）に対し、ポリリン酸、酸性ぼりリン酸アルキルエ
ステル等の縮合剤２〜ｌＯ部、好ましくは２゜５〜５部
を用い、１００〜１８０℃、好ましくは１１０〜１５０
℃の温度で、２〜１２時間、好ましくは２．５〜７時間
撹拌しながら、２．５−ジアニリノテレフタル酸を縮合
環化させ、次いで縮合剤に対して３〜１０倍量（重量倍
量、以下同じ。）、好ましくは４〜７倍景の水又は湯中
に当該反応物を注いで晶出させ、ｐ過して得られる。The quinacridone phosphate ester used in the present invention is Example Lt
d2. For 1 part (by weight, the same applies hereinafter) of 5-dianilinoterephthalic acid, 2 to 10 parts of a condensing agent such as polyphosphoric acid or acidic phosphoric acid alkyl ester, preferably 2. ~180°C, preferably 110-150
2,5-dianilinoterephthalic acid is condensed and cyclized at a temperature of (the same applies hereinafter), preferably by pouring the reaction product into water or hot water at a magnification of 4 to 7 times, crystallizing it, and filtering it.
本発明では、例えばこの様にして得られたキナクリドン
リン酸エステルを、従来の様に加水分解することなく、
直接、５〜２０倍量、好ましくは９〜１５倍量の低級脂
肪族アルコール中で２０〜２００℃、好ましくは５０〜
１５０℃の温度で５〜２４時間、好ましくは７〜１６時
間、撹拌しながら顔料化処理することによシ、高純度の
β−型キナクリドン顔料を製造する。In the present invention, for example, the quinacridone phosphate ester obtained in this manner is not hydrolyzed as in the conventional method.
Directly in 5 to 20 times the amount of lower aliphatic alcohol, preferably 9 to 15 times the amount, at 20 to 200°C, preferably 50 to 200°C.
A highly pure β-quinacridone pigment is produced by pigmentation treatment at a temperature of 150° C. for 5 to 24 hours, preferably 7 to 16 hours while stirring.
キナクリドンリン酸エステルを得る際に縮合剤として用
いるポリリン酸及び酸性ポリリン酸アルキルエステル中
の無水リン酸（Ｐ２Ｏ３）含有量は、それぞれ８３〜８
７重量係及重量０〜８５重量−程度のものが一般に好ま
しい。The phosphoric anhydride (P2O3) content in polyphosphoric acid and acidic polyphosphoric acid alkyl ester used as a condensing agent when obtaining quinacridone phosphate ester is 83 to 8, respectively.
7 weight range and 0 to 85 weight range are generally preferred.
上記酸性、ｊ？ ＩＪ ＩＪン酸アルキルエステルは、
例えば無水リン酸とジアルキルエーテルとから調製され
るもので、酸性ポリリン酸メチルエステル、酸性ポリリ
ン酸エチルエステル、酸性−リリン酸ｎ−グロビルエス
テル、酸性ポリリン酸イソプロピルエステル、酸性ポリ
リフ酸ｎ−ブチルエステル、酸性ポリリン酸イソブチル
エステル、酸性ポリリン酸５ｅＣ−ブチルエステル、酸
性ポリリン酸ｔ−ブチルエステル、酸性ポリリン酸ｎ−
アミルエステル、酸性Ｉリン酸アルキルエステル、酸性
ｌリリ７＃ｔ−アミルエステル等が挙げられる。The above acidic, j? IJ IJ acid alkyl ester is
For example, it is prepared from phosphoric anhydride and dialkyl ether, such as acidic polyphosphoric acid methyl ester, acidic polyphosphoric acid ethyl ester, acidic lyphosphoric acid n-globil ester, acidic polyphosphoric acid isopropyl ester, acidic polyphosphoric acid n-butyl ester. , acidic polyphosphoric acid isobutyl ester, acidic polyphosphoric acid 5eC-butyl ester, acidic polyphosphoric acid t-butyl ester, acidic polyphosphoric acid n-
Examples include amyl ester, acidic I phosphoric acid alkyl ester, acidic I 7#t-amyl ester, and the like.
尚隻酸性Ｉリリン酸アルキルエステルとシテは、その入
手のしやすさから酸性ポリリン酸メチルエステルが好ま
しい。It should be noted that acidic polyphosphoric acid alkyl ester and acidic acid polyphosphoric acid methyl ester are preferred because of their ease of availability.
本発明で用いる低級脂肪族アルコールとしては、例、ｔ
ばメチルアルコール、エチルアルコール、ｎ−グロビル
アルコール、イソプロピルアルコール１、ブチルアルコ
ール、イソブチルアルコール、ｓ＠ｃ−ブチルアルコー
ル、ｔ−ブチルアルコール、ｎ−アミルアルコール、イ
ソアミルアルコール、ｔ−アミルアルコール、エチレン
グリコール、ジエチレングリコール等が挙げられ、なか
でもｎ−グロビルアルコール、イソプロピルアルコール
、ｎ−７”チルアルコール、イソブチルアルコール、−
・Ｃ−ブチルアルコール、ｔ−ブチルアルコール、エチ
レングリコール、ジエチレングリコールが好ましく、特
にイソブチルアルコール及びジエチレングリコールが好
ましい。Examples of the lower aliphatic alcohol used in the present invention include t
Methyl alcohol, ethyl alcohol, n-globyl alcohol, isopropyl alcohol 1, butyl alcohol, isobutyl alcohol, s@c-butyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, t-amyl alcohol, ethylene glycol , diethylene glycol, among others, n-globyl alcohol, isopropyl alcohol, n-7'' alcohol, isobutyl alcohol, -
-C-butyl alcohol, t-butyl alcohol, ethylene glycol, and diethylene glycol are preferred, and isobutyl alcohol and diethylene glycol are particularly preferred.
（実施例）
以下に実施例上挙げ、本発明を更に詳細に説明する。尚
、例中の部及び係は重量基準である。(Example) The present invention will be explained in more detail by referring to Examples below. In addition, parts and units in the examples are based on weight.
実施例１
２．５−ジアニリノテレフタル酸１０部を無水すｙ酸（
Ｐ２Ｏ３）含有量８４．２係の？リリン酸３０部中に１
１０〜１２０℃で撹拌しながら加え、１２０〜１３０℃
で更に３時間撹拌しながら縮合環化反応を行なった後、
得られた熱い溶融状態の反応生成物を１８０部の水中へ
注いで晶出させて懸濁水を得、この懸濁水をＦ遇して中
ナクリドンリン酸エステルを単離した。Example 1 10 parts of 2.5-dianilinoterephthalic acid was mixed with sulfuric anhydride (
P2O3) content 84.2? 1 in 30 parts of lyphosphoric acid
Add while stirring at 10-120℃, 120-130℃
After carrying out the condensation cyclization reaction while stirring for an additional 3 hours,
The resulting hot molten reaction product was poured into 180 parts of water for crystallization to obtain a suspension water, and the suspension water was subjected to F treatment to isolate the middle nacridone phosphate.
次いで、このキナクリドンリン酸エステルを乾燥して脱
水した後、当該リン酸エステルに対して１３重量倍のイ
ソブチルアルコールを加工、撹拌下１４０℃で１０時間
加熱して顔料化処理を行い、鮮明な紫色の高純度β−型
キナクリドン顔料を得た。Next, after drying and dehydrating this quinacridone phosphate ester, the phosphoric ester was treated with 13 times the weight of isobutyl alcohol, heated at 140°C for 10 hours with stirring, and pigmented, resulting in a vivid purple color. A highly purified β-type quinacridone pigment was obtained.
この顔料は、色相が鮮明な紫色であること、及びそのＸ
線回折パターンが第１図に示す様にβ−型キナクリドン
に特有の回折角（２θ）にピークを有し、α−型及びｒ
−型 キナクリドンに特有のピークがほとんど認められ
ないことによシ、α−型及びγ−型キナクリドンの混入
が実質的になく、純度が極めて高いことが確認された。This pigment has a clear purple hue and its
As shown in Figure 1, the line diffraction pattern has a peak at the diffraction angle (2θ) characteristic of β-type quinacridone, and α-type and r
It was confirmed that there was virtually no contamination of α-type and γ-type quinacridone, and the purity was extremely high, since almost no peaks specific to -type quinacridone were observed.
尚、純粋なα−型、β−型、ｒ−型キナクリドｙのＸ線
回折／譬ターンは、下記第１表に示す回折角（２θ）に
特徴あるピークをそれぞれ有する。Incidentally, the X-ray diffraction/transmission of pure α-type, β-type, and r-type quinacride y has characteristic peaks at the diffraction angles (2θ) shown in Table 1 below.
／
比較例１
実施例１と同様の方法で得られたキナクリドンリン酸エ
ステルを大過剰の水を用いて酸が存在しなくなるまで洗
浄することによシ加水分解し、キナクリドン粗結晶（こ
のものは結晶性の、良くないα−型結晶状態である）の
含水ケーキを得た。次いでこの中性のキナクリドン粗結
晶の含水ケーキを乾燥して脱水した後、実施例１と同様
にして顔料化処理を行ないキナクリドン顔料を得た。こ
の顔料は、実施例１で得られた顔料よりも赤味音帯びた
鮮明性に欠ける紫色であり、そのＸ線回折・パターンは
、第２図に示す様に回折角（２θ）が１２．４と１３．
８と２３．８の位置にも明確なピークが認められること
から、多量のα−型及びｒ−型キナクリドンが混入した
β−型キナクリドンであることが確認され念。/ Comparative Example 1 Quinacridone phosphate ester obtained in the same manner as in Example 1 was hydrolyzed by washing with a large excess of water until no acid was present, and quinacridone crude crystals (this one A water-containing cake of crystallinity (in poor α-type crystalline state) was obtained. Next, this neutral water-containing cake of quinacridone crude crystals was dried and dehydrated, and then pigmented in the same manner as in Example 1 to obtain a quinacridone pigment. This pigment has a purple color with a reddish tone and less sharpness than the pigment obtained in Example 1, and its X-ray diffraction pattern has a diffraction angle (2θ) of 12. 4 and 13.
Clear peaks were also observed at positions 8 and 23.8, confirming that it was β-type quinacridone mixed with a large amount of α-type and r-type quinacridone.
比較例２
比較例１と同様にして得たキナクリドン粗結晶の含水ケ
ーーｒｔ−乾燥して脱水した後、当該キナクリドン粗結
晶に対して１３重量倍の３０％メタノ−ル水溶液と２：
！ｉ：ｉｔ倍の４８係水酸化ナトリウム水溶液を加え、
撹拌下１２０℃で７時間加熱した後、３５憾塩酸水溶液
を加えてｐＨを７．５としてキナクリドン顔料を得た。Comparative Example 2 After rt-drying and dehydrating a hydrous cake of quinacridone crude crystals obtained in the same manner as in Comparative Example 1, a 30% methanol aqueous solution of 13 times the weight of the quinacridone crude crystals and 2:
! Add 48% sodium hydroxide aqueous solution i:it times,
After heating at 120° C. for 7 hours with stirring, a 35% hydrochloric acid aqueous solution was added to adjust the pH to 7.5 to obtain a quinacridone pigment.
この顔料は、実施例１で得られた顔料よシも赤味を帯び
た鮮明性に欠ける紫色であり、そのＸ線回折・９ターン
は、第３図に示す様に回折角（２θ）が１３．８と２３
．８の位置にも明確なピークが認められることから、多
量のｒ−型キナクリドンが混入したβ−型キナクリドン
であることが確認された。This pigment has a reddish purple color that lacks clarity compared to the pigment obtained in Example 1, and its X-ray diffraction 9 turns shows that the diffraction angle (2θ) is as shown in Figure 3. 13.8 and 23
．． Since a clear peak was also observed at position 8, it was confirmed that it was β-type quinacridone mixed with a large amount of r-type quinacridone.
実施例２
２．５−ジアニリノテレフタル酸１ｏ部’６ ｐ２ｏ、
含有量８６．５１のＩリリン酸３０部中に、１１０〜１
２０℃で撹拌しながら加え、１２０〜１３０℃で更に６
時間撹拌しながら給金環化反応を行なった後、得られた
熱い溶融状態の反応生成物ｔ−１８０部の湯中へ注いで
晶出させて懸濁水を得、この懸濁水を濾過してキナクリ
ドンのリン酸エステルを単離しな。Example 2 2.5-dianilinoterephthalic acid 1o part'6 p2o,
In 30 parts of I lyphosphoric acid with a content of 86.51, 110 to 1
Add with stirring at 20°C, and add at 120-130°C for 6 more hours.
After carrying out the metal cyclization reaction with stirring for a period of time, t-180 parts of the obtained hot molten reaction product was poured into hot water to cause crystallization to obtain a suspension water, and this suspension water was filtered to remove the quinacridone. Do not isolate the phosphate ester.
次いでこのキナクリドンリン酸エステルの含水イースト
に当該リン酸エステルに対して１０重量倍のジエチレン
グリコールを加え、撹拌下１４５℃で８時間加熱して顔
料化処理を行い、鮮明な紫色の高純度β−型中ナクリト
ン顔料を得九。この顔料は、実施例１の場合と同じく、
その色相及びＸ線回折・ヤターンよシ純度の極めて高い
β−型キナクリドン顔料であることが確認された。Next, diethylene glycol was added to the water-containing yeast of the quinacridone phosphate ester in an amount 10 times the weight of the phosphoric ester, and the mixture was heated at 145°C for 8 hours with stirring to form a pigment, resulting in a bright purple high-purity β-form. 9. Obtaining middle-nacritone pigments. As in Example 1, this pigment was
It was confirmed that the pigment was a β-type quinacridone pigment with extremely high purity in terms of hue, X-ray diffraction, and pattern.
実施例３
２．５−ジアニリノテレフタルＭ １０ ｆＲｋ Ｐ２
Ｏ５含有量８２．５１の酸性プリリン酸メチルエステル
３０部中に１１０〜１２０℃で撹拌しながら加え、１２
０〜１３０℃で更に３時間撹拌しながら給金環化反応を
行なっ次後、得られた溶融状態の反応生成物１ｆ：１５
０部の水中へ注いで晶出させて！Ｍ！濁水を得、とのｇ
濁水を濾過してキナクリドンのリン酸エステルを単離し
た。Example 3 2.5-dianilinoterephthal M 10 fRk P2
Added to 30 parts of acidic methyl priphosphoric acid with an O5 content of 82.51 at 110-120°C with stirring, 12
The cyclization reaction was carried out with stirring at 0 to 130°C for an additional 3 hours, and the resulting molten reaction product 1f:15
Pour it into 0 parts of water and let it crystallize! M! get muddy water, and g
The phosphoric acid ester of quinacridone was isolated by filtering the turbid water.
次いでこの中ナクリドンのリン酸エステル金乾燥して脱
水した後、当該リン酸エステルに対して１０重量倍のジ
エチレングリコールを加え、撹拌下５０℃で１４時間加
熱して顔料化処理を行い、鮮明な紫色の純粋なβ−型キ
ナクリド／顔料を得た。この顔料は、実施例１の場合と
同様にして純度の極めて高いβ−型キナクリドン顔料で
あることが確認された。Next, after drying and dehydrating the gold phosphate ester of nacridone, diethylene glycol was added in an amount of 10 times the weight of the phosphate ester, and the mixture was heated at 50°C for 14 hours with stirring to perform a pigment treatment, resulting in a clear purple color. A pure β-quinacrid/pigment was obtained. As in Example 1, this pigment was confirmed to be a β-type quinacridone pigment with extremely high purity.
実施例４
２．５−ジアニリノテレフタル酸１ｏ部’６ ｐ、ｏ５
含有ｉ８１．５％の酸性？リリン酸イソグロビルエステ
ル４０部中に１１０〜１２０℃で撹拌しながら加え、１
２０〜１３０℃で更に３時間撹拌しながら給金環化反応
を行なった後、得られた熱い溶融状態の反応生成物を１
８０部の水中へ注いで晶出させて懸濁水を得、この懸濁
水ｔ−濾過してキナクリドンのリン酸エステルを単離し
た。Example 4 2.5-dianilinoterephthalic acid 1o part'6 p, o5
Contains i81.5% acidic? Add to 40 parts of isoglobil lyphosphate at 110-120°C with stirring,
After carrying out the fed cyclization reaction at 20-130°C with stirring for an additional 3 hours, the resulting hot molten reaction product was
The suspension was poured into 80 parts of water for crystallization to obtain a suspension water, and the suspension water was t-filtered to isolate the phosphoric acid ester of quinacridone.
このキナクリドンリン酸エステルの含水ペーストに、当
該リン酸エステルに対して１３重世倍のイソブチルアル
コールを加え、撹拌下１４０℃で１２時間加熱して顔料
化処理を行い、鮮明な紫色の純粋なβ−型キナクリドン
顔料を得た。この顔料は、実施例１の場合と同様にして
純度の極めて高いβ−型キナクリドン顔料であることが
確認された。To this water-containing paste of quinacridone phosphate, 13 times more isobutyl alcohol than the phosphoric ester was added, and the mixture was heated at 140°C for 12 hours with stirring to form a pigment. - type quinacridone pigment was obtained. As in Example 1, this pigment was confirmed to be a β-type quinacridone pigment with extremely high purity.
実施例５〜１３
Ｐ２Ｏ５含有量８４．２’ｌのＩリリン酸及びイソブチ
ルアルコールの代わシに第２表に示す縮合剤及び低級脂
肪族アルコールを用いた以外には実施例１と同様にして
β−型キナクリドン顔料を得た。Examples 5 to 13 β - type quinacridone pigment was obtained.
実施例５，７，８．１２及び１３で得た顔料は、い、ず
れも鮮明な紫色の純度の極めて高いβ−型キナクリドン
顔料であることが確認された。It was confirmed that the pigments obtained in Examples 5, 7, 8, 12, and 13 were all β-type quinacridone pigments with a clear purple color and extremely high purity.
しかしながら、実施例６，９．１０及び１１で得た顔料
には若干であるがα−壓及びｒ−型キナクリドン顔料の
混入がみとめられたため、顔料化処理条件（撹拌下１４
０℃で１０時間加熱）を実施例６及び１１では撹拌下１
６０℃で１０時間加熱に、また実施例９及びＩＯでは撹
拌下１８０℃で１２時間加熱に変更した以外は実施例１
と同様にして再びβ−型キナクリドン顔料を得た。この
顔料は鮮明な紫色の純度の極めて高いβ−型キナクリド
ン顔料であることが確認された。However, since the pigments obtained in Examples 6, 9, 10, and 11 were found to contain a small amount of α-type and r-type quinacridone pigments, the pigmentation treatment conditions (14 hours under stirring) were observed.
(heated at 0°C for 10 hours) under stirring in Examples 6 and 11.
Example 1 except that heating was performed at 60°C for 10 hours, and in Example 9 and IO, heating was performed at 180°C for 12 hours with stirring.
A β-type quinacridone pigment was again obtained in the same manner as above. This pigment was confirmed to be a β-type quinacridone pigment with a clear purple color and extremely high purity.
（発明の効果）
本発明の製造法では従来知られている諸方法に比べて、
より簡便に純度の極めて高いβ−型キナクリドン顔料を
得ることができる。(Effects of the invention) Compared to conventionally known methods, the manufacturing method of the present invention has the following advantages:
A β-type quinacridone pigment with extremely high purity can be obtained more easily.
Ｗｃ１図は実施例１で得た純度の極めて高いβ−型キナ
クリｒ７顔料のＸ線回折／？ターフ、第２図は比較例１
で得たα−型及びｒ−型キナクリドン顔料の混入したβ
−型キナクリドン顔料のＸ線回折ツタ−７、及び第３図
は比較例２で得たｒ−ｍキナクリドン顔料の混入したβ
−型キナクリドン顔料のＸ線回折ａ４ターンである。
代理人 弁理士 高 橋 勝 利
（２θ）
第
図
回
折
角
（２θ）
第
図
回
折
角
（２θ）Wc1 diagram shows the X-ray diffraction/? of the extremely pure β-type quinacrylic r7 pigment obtained in Example 1. Turf, Figure 2 is Comparative Example 1
β mixed with α-type and r-type quinacridone pigments obtained in
- type quinacridone pigment X-ray diffraction pattern 7 and Figure 3 show the β-type quinacridone pigment mixed with the rm quinacridone pigment obtained in Comparative Example 2.
- type quinacridone pigment X-ray diffraction a4 turn. Agent Patent Attorney Katsutoshi Takahashi (2θ) Fig. Diffraction angle (2θ) Fig. Diffraction angle (2θ)
Claims (1)
ルで顔料化処理することを特徴とするβ−型キナクリド
ン顔料の製造法。 ２、低級脂肪族アルコールがｎ−プロピルアルコール、
イソプロピルアルコール、ｎ−ブチルアルコール、イソ
ブチルアルコール、ｔ−ブチルアルコール、エチレング
リコール及びジエチレングリコールから選ばれる１種以
上の脂肪族アルコールである請求項１記載の製造法。 ３、低級脂肪族アルコールがイソブチルアルコール及び
／又はジエチレングリコールである請求項１記載の製造
法。 ４、顔料化処理が、キナクリドンリン酸エステルを、そ
の５〜２０重量倍量の低級脂肪族アルコール中２０〜２
００℃で５〜２４時間撹拌することである請求項１記載
の製造法。[Scope of Claims] 1. A method for producing a β-type quinacridone pigment, which comprises treating quinacridone phosphate ester with a lower aliphatic alcohol to form a pigment. 2. The lower aliphatic alcohol is n-propyl alcohol,
2. The method according to claim 1, wherein the aliphatic alcohol is one or more aliphatic alcohols selected from isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, and diethylene glycol. 3. The production method according to claim 1, wherein the lower aliphatic alcohol is isobutyl alcohol and/or diethylene glycol. 4. Pigmentation treatment involves adding quinacridone phosphate ester to 20 to 20% of lower aliphatic alcohol in an amount of 5 to 20 times its weight.
The method according to claim 1, wherein the stirring is carried out at 00°C for 5 to 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63191527A JPH0241368A (en) | 1988-07-29 | 1988-07-29 | Production of beta-type quinacridone pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63191527A JPH0241368A (en) | 1988-07-29 | 1988-07-29 | Production of beta-type quinacridone pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0241368A true JPH0241368A (en) | 1990-02-09 |
Family
ID=16276149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63191527A Pending JPH0241368A (en) | 1988-07-29 | 1988-07-29 | Production of beta-type quinacridone pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0241368A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0874025A2 (en) * | 1997-04-25 | 1998-10-28 | Ciba SC Holding AG | Beta quinacridone pigment |
| JP2007197630A (en) * | 2006-01-30 | 2007-08-09 | Dainippon Ink & Chem Inc | Method for producing dichloroquinacridone pigment |
| JP2009280819A (en) * | 2008-05-24 | 2009-12-03 | Lanxess Deutschland Gmbh | Fluorine-containing chinacridone in color filter for lcd |
-
1988
- 1988-07-29 JP JP63191527A patent/JPH0241368A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0874025A2 (en) * | 1997-04-25 | 1998-10-28 | Ciba SC Holding AG | Beta quinacridone pigment |
| EP0874025B1 (en) * | 1997-04-25 | 2005-06-08 | Ciba SC Holding AG | Beta quinacridone pigment |
| JP2007197630A (en) * | 2006-01-30 | 2007-08-09 | Dainippon Ink & Chem Inc | Method for producing dichloroquinacridone pigment |
| JP4696937B2 (en) * | 2006-01-30 | 2011-06-08 | Ｄｉｃ株式会社 | Method for producing dichloroquinacridone pigment |
| JP2009280819A (en) * | 2008-05-24 | 2009-12-03 | Lanxess Deutschland Gmbh | Fluorine-containing chinacridone in color filter for lcd |
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