JP2015017200A - Pyrazolone dye - Google Patents
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Abstract
Description
本発明は新規なピラゾロン色素に関する。 The present invention relates to a novel pyrazolone dye.
ピラゾロン色素はこれまでに数多く合成されており、その有用性が確認され、広く用いられている。近年、写真感光材料、感熱転写記録材料、カラートナー、光記録媒体、インクジェットなど、様々な用途に広く適用することが多くなってきた。 Many pyrazolone dyes have been synthesized so far and their usefulness has been confirmed and widely used. In recent years, it has been widely applied to various uses such as photographic photosensitive materials, thermal transfer recording materials, color toners, optical recording media, and ink jets.
また、上記用途に必要とされる性能としては、例えば、色再現上好ましい分光特性を有すること、所望の有機溶媒に可溶であること、分子吸光係数が大きいこと、光や熱に堅牢であること、種々の化学薬品に堅牢であること、合成が容易であること、安全であることなどがある。 In addition, the performance required for the above applications includes, for example, favorable spectral characteristics for color reproduction, solubility in a desired organic solvent, large molecular extinction coefficient, and robustness to light and heat. In addition, it is robust to various chemicals, easy to synthesize, and safe.
一方、これらを改良する目的で、多くのピラゾロン色素が提案されており、例えば、光、熱堅牢性の改善が提案されたが(特許文献1〜4)、溶解性が不十分であったため、更に改良が望まれていた。 On the other hand, many pyrazolone dyes have been proposed for the purpose of improving these, for example, although improvement of light and heat fastness has been proposed (Patent Documents 1 to 4), the solubility was insufficient. Further improvements were desired.
また、溶媒溶解性の改善について提案されているが(特許文献5)、耐熱性に劣るため、熱堅牢性についてさらなる改良が強く望まれている。
本発明の目的は、高い熱堅牢性を有し、かつ高い溶解性を有する新規ピラゾロン色素の提供である。 An object of the present invention is to provide a novel pyrazolone dye having high heat fastness and high solubility.
本発明者らは、鋭意研究を重ねた結果、以下の構成によって上記課題が達成されることを見出した。 As a result of intensive studies, the present inventors have found that the above problems can be achieved by the following configuration.
下記一般式(1)で表されるピラゾロン色素。
一般式(1)
(一般式(1)中R1は分岐アルキル基を、R2は複素環基を表し、R3は炭素数が2以上のアルキル基、アリール基を表す。Xは―O―、―NR4―を表し、R4は水素原子、アルキル基を表す。)
A pyrazolone dye represented by the following general formula (1).
General formula (1)
(In General Formula (1), R1 represents a branched alkyl group, R2 represents a heterocyclic group, R3 represents an alkyl group having 2 or more carbon atoms, or an aryl group. X represents —O— or —NR4—, R4 represents a hydrogen atom or an alkyl group.)
前記一般式(1)で表されるピラゾロン色素が下記一般式(2)で表されるピラゾロン色素であることを特徴とする請求項1に記載のピラゾロン色素。
一般式(2)
General formula (2)
前記一般式(1)及び(2)においてR2又はR12がピリジン環基である事を特徴とする請求項1、2に記載のピラゾロン色素。 The pyrazolone dye according to claim 1 or 2, wherein R2 or R12 in the general formulas (1) and (2) is a pyridine ring group.
本発明によって、新規な高い熱堅牢性と耐光性を有し、かつ優れた色調性を有し、また、高い溶解性を有するピラゾロン色素の提供できた。 According to the present invention, a novel pyrazolone dye having high heat fastness and light fastness, excellent color tone and high solubility can be provided.
以下、本発明について詳細に解説する。 The present invention will be described in detail below.
本発明は、前記一般式(1)で表されることを特徴とする色素である。 The present invention is a dye represented by the general formula (1).
一般式(1)中、R1は分岐アルキル基を表す。 In general formula (1), R1 represents a branched alkyl group.
分岐アルキル基としては、例えば、iso−プロピル基、tert−ブチル基、iso−ブチル基、sec−ブチル基、neo−ペンチル基、tert−アミル基などが挙げられるが、好ましくはiso−プロピル基、tert−ブチル基であり、最も好ましくはtert−ブチル基である。 Examples of the branched alkyl group include an iso-propyl group, a tert-butyl group, an iso-butyl group, a sec-butyl group, a neo-pentyl group, and a tert-amyl group, preferably an iso-propyl group, A tert-butyl group, most preferably a tert-butyl group.
R1 が嵩高くなることにより、色素の耐熱性と溶解性が向上する。 When R1 becomes bulky, the heat resistance and solubility of the dye are improved.
一般式(1)及び(2)においてR2又はR12は、複素環基を表す。 In the general formulas (1) and (2), R2 or R12 represents a heterocyclic group.
複素環としては、例えば、ピリジン環、ピラゾール環、イミダゾール環、ピラジン環、ピリミジン環、トリアジン環、チアゾール環、オキサゾール環、キノリン環、ベンゾチアゾール環、ベンゾオキサゾール環等が挙げられる。更に好ましくは、ピリジン環、ピラゾール環、イミダゾール環、ピラジン環、ピリミジン環であるが、最も好ましくはピリジン環である。 Examples of the heterocyclic ring include a pyridine ring, a pyrazole ring, an imidazole ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a thiazole ring, an oxazole ring, a quinoline ring, a benzothiazole ring, and a benzoxazole ring. More preferred are a pyridine ring, pyrazole ring, imidazole ring, pyrazine ring and pyrimidine ring, and most preferred is a pyridine ring.
R2、又はR12が複素環の場合、耐熱性に寄与する。 When R2 or R12 is a heterocyclic ring, it contributes to heat resistance.
一般式(1)及び(2)においてR3又はR13は炭素数が2以上のアルキル基、アリール基を表す。 In the general formulas (1) and (2), R3 or R13 represents an alkyl group or aryl group having 2 or more carbon atoms.
アルキル基としては、例えば、エチル基、プロピル基、iso−プロピル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基等が挙げられ、アリール基としては、例えば、フェニル基、ナフチル基等が挙げられる。 Examples of the alkyl group include an ethyl group, a propyl group, an iso-propyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group, and an aryl group. Examples thereof include a phenyl group and a naphthyl group.
好ましくは、アルキル基である。アルキル基の中でも、更に好ましくはプロピル基、iso−プロピル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基であり、最も好ましいのは炭素数が3から6である。 Preferably, it is an alkyl group. Among the alkyl groups, more preferred are a propyl group, an iso-propyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group, and most preferred is the number of carbon atoms. Is from 3 to 6.
一般式(1)中、Xは―O―、―NR4―を表し、R4は水素原子、アルキル基を表し、好ましくはアルキル基を表す。 In the general formula (1), X represents —O— or —NR 4 —, and R 4 represents a hydrogen atom or an alkyl group, preferably an alkyl group.
アルキル基としては、前記R3又はR13におけるアルキル基と同様の基を挙げることができる。 As an alkyl group, the group similar to the alkyl group in said R3 or R13 can be mentioned.
以下に、前記一般式(1)、(2)で表される本発明のピラゾロン色素の代表的な具体例を挙げるが、本発明はこれに限定されるものではない。 Specific examples of the pyrazolone dyes of the present invention represented by the general formulas (1) and (2) are shown below, but the present invention is not limited thereto.
以下に本色素の代表的な合成例を示すが、これらは特開平10−60296号、同2006−16564号、同2006−63171号公報等、“The Cyanine Dyes and Related Compounds”,F.Hamer,Interscience Publishers,1964に記載された従来公知を参考に合成する事ができる。 Typical examples of the synthesis of the present dye are shown below, but these are described in JP-A-10-60296, 2006-16564, 2006-63171, etc., “The Cyanine Dyes and Related Compounds”, F.C. It can be synthesized with reference to conventionally known methods described in Hamer, Interscience Publishers, 1964.
(実施例1)例示色素2の合成
アセトニトリル30mlに、10.0gの化合物1、5.1gの化合物2を加え、内温45℃で攪拌しながら、無水酢酸2.2gとトリエチルアミン4.4gの混合溶液を滴下した。滴下終了後減圧下でアセトニトリルを取り除いた後、得られた残渣を酢酸エチルに溶かし、水洗、濃縮後、得られた残渣をメタノールと水の混合溶液で洗浄し、乾燥させて、橙色の固体を6.7g得た。 10.0 g of Compound 1 and 5.1 g of Compound 2 were added to 30 ml of acetonitrile, and a mixed solution of 2.2 g of acetic anhydride and 4.4 g of triethylamine was added dropwise with stirring at an internal temperature of 45 ° C. After completion of the dropwise addition, acetonitrile was removed under reduced pressure, and the resulting residue was dissolved in ethyl acetate, washed with water, concentrated, and the obtained residue was washed with a mixed solution of methanol and water and dried to give an orange solid. 6.7 g was obtained.
得られた固体の1H−NMRは以下の通りであり、例示色素2であることが確認された。収率は75%であった。得られた色素の酢酸エチル溶液中の吸収極大は456nmであった。 1H-NMR of the obtained solid was as follows and was confirmed to be Exemplified Dye 2. The yield was 75%. The absorption maximum of the obtained dye in the ethyl acetate solution was 456 nm.
1H−NMR(400MHz、重水素ジクロロメタン、δ(ppm)):0.98(t,3H),1.45(m,2H),1.51(s,9H),1.87(m,2H),4.01(t,2H),7.02(t,1H),7.13(d,1H),7.24〜7.35(m,3H),7.43(d,1H),7.71(t,1H),8.12(d,1H),8.20(d,1H),8.55(d,1H) 1H-NMR (400 MHz, deuterium dichloromethane, δ (ppm)): 0.98 (t, 3H), 1.45 (m, 2H), 1.51 (s, 9H), 1.87 (m, 2H) ), 4.01 (t, 2H), 7.02 (t, 1H), 7.13 (d, 1H), 7.24-7.35 (m, 3H), 7.43 (d, 1H) 7.71 (t, 1 H), 8.12 (d, 1 H), 8.20 (d, 1 H), 8.55 (d, 1 H)
(実施例2)例示色素44の中間体(化合物3)の合成
(実施例3)例示色素44の合成
例示色素2と同様の操作によって例示色素4、例示色素20、および例示色素27を得た。それぞれの結果を下の表1に示す。 Exemplified dye 4, Exemplified dye 20, and Exemplified dye 27 were obtained by the same operation as Exemplified dye 2. Each result is shown in Table 1 below.
(実施例4)
本発明のピラゾロン色素をトルエンとM E K の1 : 1 混合溶液に溶解させ、得られた着色溶液を1 5 0 μ m の厚さを有する合成紙(ユポFPG−150:王子油化社製)
上に、それぞれウェット膜厚60μmで塗布・乾燥し、塗布試料を作製した。それぞれの溶液の色素濃度を調整することにより、濃度が1
となる塗布試料を作製し、これら塗布試料について下記性能を評価した。
Example 4
The pyrazolone dye of the present invention is dissolved in a 1: 1 mixed solution of toluene and M EK, and the resulting colored solution is a synthetic paper having a thickness of 150 μm (Yupo FPG-150: manufactured by Oji Oil Chemical Co., Ltd.). )
A coated sample was prepared by applying and drying each with a wet film thickness of 60 μm. By adjusting the dye concentration of each solution, the concentration is 1
The following coating samples were prepared, and the following performance was evaluated for these coating samples.
《溶解性》
色素をトルエンとM E K の1 : 1 混合溶液に3 質量% 濃度になる様に溶解させ、その溶解性を目視評価で以下の評価基準に基づいて4 段階評価した。
<< Solubility >>
The dye was dissolved in a 1: 1 mixed solution of toluene and M EK so as to have a concentration of 3% by mass, and the solubility was evaluated by visual evaluation based on the following evaluation criteria.
◎ : 直ちに完溶
○ : 室温で一晩振とうすることで完全に溶解している
△ : 加温することで完全に溶解している
× : 溶け残りが存在している
○ 以上であることが望ましい。
◎: Completely dissolved immediately ○: Completely dissolved by shaking overnight at room temperature △: Completely dissolved by heating ×: Undissolved residue present ○ More than or equal to desirable.
《耐光性》
キセノンフェードメーターにて1 2 0 時間曝射した後の試料について、未曝射試料の可視領域の極大吸収波長における反射スペクトル濃度からの、低下率を評価した。
《Light resistance》
About the sample after 120 hours exposure with a xenon fade meter, the rate of decrease from the reflection spectrum concentration at the maximum absorption wavelength in the visible region of the unexposed sample was evaluated.
耐光性( % ) = ( 曝射試料の極大吸収波長濃度/ 未曝射試料の極大吸収波長濃度) × 10 0 に従って求め、以下の評価基準に基づいて4
段階評価した。
Light resistance (%) = (Maximum absorption wavelength concentration of exposed sample / Maximum absorption wavelength concentration of unexposed sample) × 10 0, 4 based on the following evaluation criteria
Graded.
◎ : 耐光性が9 5 % 以上
○ : 耐光性が9 0 % 以上、9 5 % 未満
△ : 耐光性が8 0 % 以上、9 0 % 未満
× : 耐光性が8 0 % 未満
○ 以上であれば実用上問題ない。
◎: Light resistance is 95% or more ○: Light resistance is 90% or more and less than 95% △: Light resistance is 80% or more and less than 90% ×: Light resistance is less than 80% ○ or more There is no practical problem.
《耐熱性》
77℃、10%RH以下の条件下7日間保存し、保存開始前後の濃度比からの、低下率を評価した。
"Heat-resistant"
It was stored for 7 days under conditions of 77 ° C. and 10% RH or less, and the rate of decrease from the concentration ratio before and after the start of storage was evaluated.
耐熱性(%)= (保存後の濃度/ 保存開始前の濃度)× 100に従って求め、以下の標準基準に基づいて4段階評価した。 Heat resistance (%) = (concentration after storage / concentration before storage start) × 100, and evaluated based on the following standard criteria.
◎ : 耐熱性が9 5 % 以上
○ : 耐熱性が8 0 % 以上、9 5 % 未満
△ : 耐熱性が6 0 % 以上、8 0 % 未満
× : 耐熱性が6 0 % 未満
○ 以上であれば実用上問題ない。
◎: Heat resistance is 95% or more ○: Heat resistance is 80% or more and less than 95% △: Heat resistance is 60% or more and less than 80% ×: Heat resistance is less than 60% ○ or more There is no practical problem.
《色調》
各塗布試料についての色調の評価は、イエローとして目視評価を行い、下記のように4段階評価を行った。
《Color tone》
The color tone of each coated sample was visually evaluated as yellow, and evaluated in four stages as follows.
◎ : 際だって鮮やかな色
○ : 鮮やかな色
△ : くすんだ色
× : 汚い色
○ 以上であることが望ましい。
◎: Remarkably vivid color ○: Vivid color △: Dull color ×: Dirty color ○ It is desirable that it is more than the above.
比較色素
表2が示す通り、比較例と比較して本発明の色素は溶解性、耐光性、色調に優れることが分かった。特にピラゾロン部位の5位にtert−ブチル等の分岐アルキル基が存在する場合や、ベンゾオキサゾール、又はイミダゾール部位のN位の置換基を炭素数が2以上であれば溶解性や耐光性、耐熱性に優れ、また、ピラゾロンのN置換部位を複素環にした場合、色調に優れた色素が得られた。そして、これらを組み合わせた場合、特に溶解性、耐光性、耐熱性、色調に優れることが分かった。
Claims (3)
一般式(1)
(一般式(1)中R1は分岐アルキル基を、R2は複素環基を表し、R3は炭素数が2以上のアルキル基、アリール基を表す。Xは―O―、―NR4―を表し、R4は水素原子、アルキル基を表す。)
A pyrazolone dye represented by the following general formula (1).
General formula (1)
(In General Formula (1), R1 represents a branched alkyl group, R2 represents a heterocyclic group, R3 represents an alkyl group having 2 or more carbon atoms, or an aryl group. X represents —O— or —NR4—, R4 represents a hydrogen atom or an alkyl group.)
一般式(2)
General formula (2)
The pyrazolone dye according to claim 1 or 2, wherein R2 or R12 in the general formulas (1) and (2) is a pyridine ring group.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09123620A (en) * | 1995-10-27 | 1997-05-13 | Konica Corp | Thermal transfer recording material and method |
JP2005119280A (en) * | 2003-09-25 | 2005-05-12 | Konica Minolta Photo Imaging Inc | Heat transfer recording material |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09123620A (en) * | 1995-10-27 | 1997-05-13 | Konica Corp | Thermal transfer recording material and method |
JP2005119280A (en) * | 2003-09-25 | 2005-05-12 | Konica Minolta Photo Imaging Inc | Heat transfer recording material |
Non-Patent Citations (2)
Title |
---|
HADACEK VON J., SPISY, vol. 462, JPN6017005608, 1965, pages 161-174 * |
MONATSHEFTE FUR CHEMIE, vol. 99, JPN6017005609, 1968, pages 2365-2368 * |
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