JP3887506B2 - Aromatic carboxylic acid compounds - Google Patents
Aromatic carboxylic acid compounds Download PDFInfo
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- JP3887506B2 JP3887506B2 JP10977599A JP10977599A JP3887506B2 JP 3887506 B2 JP3887506 B2 JP 3887506B2 JP 10977599 A JP10977599 A JP 10977599A JP 10977599 A JP10977599 A JP 10977599A JP 3887506 B2 JP3887506 B2 JP 3887506B2
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- Prior art keywords
- carboxylic acid
- aromatic carboxylic
- heat
- recording material
- acid compounds
- 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.)
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- 0 C[C@](*)C(CCCC1*c2ccc(C(*)(c3ccc(*C(CCCC(C4)(C(*)CC*)C(O)=O)C4C(O)=O)cc3)c3ccc(C(C)(C)c4ccc(*C(CCC5)C(*)CC5(C*5CCCC5)C(O)=O)cc4)cc3)cc2)(CC1C(O)=O)C(O)=O Chemical compound C[C@](*)C(CCCC1*c2ccc(C(*)(c3ccc(*C(CCCC(C4)(C(*)CC*)C(O)=O)C4C(O)=O)cc3)c3ccc(C(C)(C)c4ccc(*C(CCC5)C(*)CC5(C*5CCCC5)C(O)=O)cc4)cc3)cc2)(CC1C(O)=O)C(O)=O 0.000 description 1
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- Heat Sensitive Colour Forming Recording (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、画像及び地肌部の保存性に優れた顕色剤として有用な新規な芳香族カルボン酸化合物に関する。
【0002】
【従来の技術】
感熱記録材料は、一般に支持体上に電子供与性の無色もしくは淡色の染料前駆体と電子受容性の顕色剤とを主成分とする感熱発色層を設けたもので、熱ヘッド、熱ペン、レーザー光等で加熱することにより、染料前駆体と顕色剤とが瞬時反応し、記録画像が得られるものであり、特公昭43−4160号、特公昭45−14039号公報等に開示されている。
このような感熱記録材料は、比較的簡単な装置で記録が得られ、保守が容易であること、騒音の発生が少ないなどの利点があり、近年、電子計算機、ファクシミリ、券売機、ラベルプリンター、レコーダー等の記録材料として広範囲な分野に利用されている。
しかしながら、このような電子供与性染料前駆体と電子受容性顕色剤を用いた感熱記録材料は、外観がよい、感触がよい、発色濃度が高い等の優れた特性を有している反面、記録画像部が、ポリ塩化ビニルなどのプラスチック等と接触し、プラスチック中に含有される可塑剤や添加剤などにより消色したり、あるいは食品や化粧品等に含有される薬品と接触して、容易に記録画像部が消色または地肌部が発色するなど、記録材料としての保存性が劣るという欠点を有していた。
【0003】
記録画像の高保存安定性を実現するための手段として高信頼性顕色剤の利用が従来から提案されている。例えば、特開昭58−82788号、特開昭60−13852号にはフェノールスルホン化合物が、特開昭62−169681号には置換サリチル酸化合物が提案されているが、これらの化合物を顕色剤として用いた場合、画像部の可塑剤、油等に対する堅牢性の点では不十分である。
【0004】
【発明が解決しようとする課題】
本発明は、画像部の高保存性特に耐油性に優れ、更に地肌部の耐熱性にも優れた画像を与える顕色剤として有用な新規な芳香族カルボン酸化合物を提供することを目的とする。
【0005】
【課題を解決するための手段】
本発明によれば、第一に、下記一般式(I)で表される芳香族カルボン酸化合物が提供される。
【化2】
(式中Xは、炭化数1から16のアルカントリイルを示す。)
【0006】
第二に、前記一般式(I)におけるXが、プロパントリイルであることを特徴とする上記第一の芳香族カルボン酸化合物が提供される。
【0007】
【発明の実施の形態】
以下、本発明をさらに詳細に説明する。
一般式(I)で表される化合物を用いた感熱記録材料が、高耐油性、高耐熱性を有する理由は明らかではないが、概ね次のような要素が寄与しているものと考えられる。
▲1▼電子吸引性基で置換された強い酸である芳香族カルボン酸が顕色能を持つ。
▲2▼芳香族カルボン酸を1分子中に2つ以上含有することにより分子量が大きくなり、油や可塑剤等の不揮発性溶剤に対する溶解性が低下する。
【0008】
一般式(I)で表される芳香族カルボン酸化合物は全く新規な化合物である。
これらの化合物は、例えば下記に示されるトリメリット酸無水物とアルコール系化合物とのエステル化反応によって合成することができる。この場合、通常はカルボキシル基の置換位置の異なる化合物(異性体)の混合物として得ることができ、これらの混合物(組成物)を感熱記録材料用の顕色剤として用いる場合には、異性体の混合物(組成物)として用いることができる。また、必要に応じて再結晶、クロマト分離操作等による異性体の分離精製を行って単独品として用いることも可能である。
【化3】
【0009】
一般式(I)中のXの具体例としては、炭化数1から16のアルカントリイルが挙げられる。
【0013】
本発明の前記一般式(I)で表される化合物の具体例を列挙すると以下の様な物が挙げられるが、本発明はこれらに限定されるものではない。
【0014】
【表1】
【0015】
【表2】
【0016】
【表3】
【0017】
【実施例】
次に、実施例を挙げて本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。
また、純度は高速液体クロマトグラフィー(以下、HPLCと略す)又は、ゲル浸透クロマトグラフィー(以下、GPCと略す)を用い、融点は示差走査熱量計を用いて測定した。化合物の同定は核磁気共鳴スペクトル(以下、NMRと略す)を測定して行った。
【0018】
実施例1(具体例No.1の化合物の合成)
反応容器にグリセリン23.0g(0.25mol)、無水トリメリット酸171.2g(0.90mol)、トリエチルアミン171.7g(1.70mol)をテトラヒドロフラン(THF)150gとジメチルホルムアミド50gの混合液に懸濁させて仕込み、溶媒還流下約83℃にて3時間反応させた。冷却後、反応混合物に水100mlを滴下し、約30分撹拌させ、希塩酸をpH2以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、微褐色結晶84.5gを得た(収率51%)。この生成物は、6種の構造異性体混合物で、6種合わせた純度は89.8%(HPLC)、融点は151℃、239℃であり、1H−NMR分析は、目的の化合物であることを示していた。そのNMRスペクトルを以下に示す。
δ(ppm)=8.20(6H,t),7.80(3H,t),5.65(1H,s),4.64(4H,m).
【0019】
次に、前記化合物を感熱記録材料として用いた応用例を示す。なお、ここでの部は重量基準である。
【0020】
応用例1
下記組成よりなる混合物を磁性ボールミルで分散し〔A液〕〜〔E液〕を調製する。
次に、下記組成の混合物をディスパーにで撹拌分散してE液を調製した。
次に、〔A液〕〜〔E液〕を用いて感熱発色層塗布液とアンダーコート塗布液を下記の混合比で調製した。
(感熱発色層塗布液)
〔A液〕:〔B液〕:〔C液〕:〔D液〕=1:4:4:0.5
(アンダーコート塗布液)
〔E液〕:〔C液〕=2:1
〈各層の塗工〉
市販の上質紙(坪量60g/m2)の表面に(アンダーコート塗布液)を乾燥重量が3g/m2となるように塗布乾燥して中間コート紙(アンダーコート層塗布済紙)を得た。このアンダーコート層上に感熱発色層塗布液をロイコ塗料の乾燥重量が0.5g/m2となるように塗布乾燥して感熱発色層を設けた。その後、10kg/cm2の圧力でキャレンダー処理して本発明の感熱記録材料を得た。
【0021】
比較例1
応用例1の〔B液〕において、化合物No.1の代わりに、2,2−ビス(4−ヒドロキシフェニル)プロパン(ビスフェノールA)を用いた以外は応用例1と同様にして調製し感熱記録材料を得た。
【0022】
以上のように作成した感熱記録材料について、次に示す試験を行った。その結果を表4に示す。
松下部品(株)製薄膜ヘッドを有するシュミレータ印字実験装置にて、ヘッド電力0.68W/dot、1ライン記録時間10ms/ライン、走査線密度8×3.85dot/mmの条件でパルス幅0.9msで印字を行い、得られた印字画像部に綿実油を塗布した後、40℃、15時間放置後の画像濃度をマクベス濃度計で測定し耐油性を評価した。更に、同様の試験片を80℃及び、100℃の環境下に15時間放置後の地肌濃度をマクベス濃度計で測定し、耐熱性を評価した。
【0023】
【表4】
表4の結果より、本発明の化合物を顕色剤として用いた感熱記録材料は画像の耐油性、地肌の耐熱性に優れていることが明らかである。
【0024】
【発明の効果】
本発明に係る新規な芳香族カルボン酸化合物は新規物質であり、このものは感熱記録材料の顕色剤として有利であり、このものを顕色剤として用いた感熱記録材料は画像の耐油性、地肌の耐熱性に優れたものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel aromatic carboxylic acid compound useful as a color developer excellent in image and background preservation.
[0002]
[Prior art]
A heat-sensitive recording material generally comprises a heat-sensitive color-developing layer mainly comprising an electron-donating colorless or light-colored dye precursor and an electron-accepting developer on a support. By heating with a laser beam or the like, the dye precursor and the developer react instantaneously to obtain a recorded image, which is disclosed in Japanese Patent Publication Nos. 43-4160 and 45-14039. Yes.
Such a heat-sensitive recording material has advantages such that recording can be obtained with a relatively simple device, maintenance is easy, and noise generation is low. In recent years, electronic computers, facsimiles, ticket vending machines, label printers, It is used in a wide range of fields as a recording material for recorders.
However, the heat-sensitive recording material using such an electron-donating dye precursor and an electron-accepting developer has excellent properties such as good appearance, good touch, and high color density, The recorded image part is easy to come into contact with plastics such as polyvinyl chloride, and to be erased by plasticizers and additives contained in plastics, or in contact with chemicals contained in foods and cosmetics. In addition, the recording image portion is decolored or the background portion is colored, so that the storage stability as a recording material is inferior.
[0003]
Conventionally, the use of a highly reliable developer as a means for realizing high storage stability of a recorded image has been proposed. For example, JP-A-58-82788 and JP-A-60-13852 propose phenol sulfone compounds and JP-A-62-169681 proposes substituted salicylic acid compounds. When used as, it is insufficient in terms of fastness to the plasticizer, oil and the like in the image area.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel aromatic carboxylic acid compound that is useful as a developer that gives an image excellent in high storage stability of an image area, in particular, oil resistance, and also excellent in heat resistance of a background area. .
[0005]
[Means for Solving the Problems]
According to the present invention, first, an aromatic carboxylic acid compound represented by the following general formula (I) is provided.
[Chemical 2]
(In the formula, X represents an alkanetriyl having 1 to 16 carbon atoms .)
[0006]
Secondly, the first aromatic carboxylic acid compound is provided, wherein X in the general formula (I) is propanetriyl .
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The reason why the heat-sensitive recording material using the compound represented by the general formula (I) has high oil resistance and high heat resistance is not clear, but it is considered that the following factors are generally contributing.
(1) An aromatic carboxylic acid which is a strong acid substituted with an electron-withdrawing group has a color developing ability.
(2) Inclusion of two or more aromatic carboxylic acids in one molecule increases the molecular weight and lowers the solubility in non-volatile solvents such as oils and plasticizers.
[0008]
The aromatic carboxylic acid compound represented by the general formula (I) is a completely new compound.
These compounds can be synthesized, for example, by an esterification reaction of trimellitic anhydride and an alcohol compound shown below. In this case, it can usually be obtained as a mixture of compounds (isomers) having different substitution positions of carboxyl groups. When these mixtures (compositions) are used as color developers for heat-sensitive recording materials, the isomers can be obtained. It can be used as a mixture (composition). Further, if necessary, the isomers can be separated and purified by recrystallization, chromatographic separation operation or the like and used as a single product.
[Chemical 3]
[0009]
Specific examples of X in the general formula (I), alkane Torii Le from carbide having 1 16 Ru mentioned.
[0013]
Specific examples of the compound represented by the general formula (I) of the present invention are listed as follows, but the present invention is not limited thereto.
[0014]
[Table 1]
[0015]
[Table 2]
[0016]
[Table 3]
[0017]
【Example】
EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
The purity was measured using high performance liquid chromatography (hereinafter abbreviated as HPLC) or gel permeation chromatography (hereinafter abbreviated as GPC), and the melting point was measured using a differential scanning calorimeter. The compound was identified by measuring a nuclear magnetic resonance spectrum (hereinafter abbreviated as NMR).
[0018]
Example 1 (Synthesis of compound of specific example No. 1)
In a reaction vessel, 23.0 g (0.25 mol) of glycerin, 171.2 g (0.90 mol) of trimellitic anhydride and 171.7 g (1.70 mol) of triethylamine were suspended in a mixed solution of 150 g of tetrahydrofuran (THF) and 50 g of dimethylformamide. The mixture was made turbid, and reacted at about 83 ° C. for 3 hours under solvent reflux. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 84.5 g of fine brown crystals (yield 51%). This product is a mixture of 6 kinds of structural isomers, the purity of the 6 kinds combined is 89.8% (HPLC), melting point is 151 ° C., 239 ° C., and 1 H-NMR analysis is the target compound. It showed that. The NMR spectrum is shown below.
δ (ppm) = 8.20 (6H, t), 7.80 (3H, t), 5.65 (1H, s), 4.64 (4H, m).
[0019]
Next, application examples using the compound as a heat-sensitive recording material will be shown. Here, the part is based on weight.
[0020]
Application example 1
A mixture having the following composition is dispersed with a magnetic ball mill to prepare [A liquid] to [E liquid].
Next, a mixture having the following composition was stirred and dispersed in a disper to prepare solution E.
Next, a thermosensitive coloring layer coating solution and an undercoat coating solution were prepared at the following mixing ratio using [A solution] to [E solution].
(Thermosensitive coloring layer coating solution)
[Liquid A]: [Liquid B]: [Liquid C]: [Liquid D] = 1: 4: 4: 0.5
(Undercoat coating solution)
[E liquid]: [C liquid] = 2: 1
<Coating of each layer>
(Undercoat coating solution) is coated on the surface of commercially available high-quality paper (basis weight 60 g / m 2 ) so that the dry weight is 3 g / m 2, and intermediate coated paper (undercoated paper) is obtained It was. On this undercoat layer, a heat-sensitive coloring layer coating solution was applied and dried so that the dry weight of the leuco paint was 0.5 g / m 2 to provide a heat-sensitive coloring layer. Thereafter, a calender treatment was performed at a pressure of 10 kg / cm 2 to obtain the heat-sensitive recording material of the present invention.
[0021]
Comparative Example 1
In Application Example 1 [Liquid B], compound no. A thermosensitive recording material was obtained in the same manner as in Application Example 1 except that 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) was used instead of 1.
[0022]
The following tests were conducted on the heat-sensitive recording material prepared as described above. The results are shown in Table 4.
In a simulator printing experimental apparatus having a thin film head manufactured by Matsushita Parts Co., Ltd., a pulse width of 0. 8 W / dot, a line recording time of 10 ms / line, and a scanning line density of 8 × 3.85 dots / mm. Printing was performed in 9 ms, and cotton seed oil was applied to the obtained printed image portion, and then the image density after being left at 40 ° C. for 15 hours was measured with a Macbeth densitometer to evaluate oil resistance. Furthermore, the background density after leaving the same test piece in the environment of 80 degreeC and 100 degreeC for 15 hours was measured with the Macbeth densitometer, and heat resistance was evaluated.
[0023]
[Table 4]
From the results of Table 4, it is clear that the heat-sensitive recording material using the compound of the present invention as a developer is excellent in the oil resistance of the image and the heat resistance of the background.
[0024]
【The invention's effect】
The novel aromatic carboxylic acid compound according to the present invention is a novel substance, which is advantageous as a developer of a heat-sensitive recording material, and the heat-sensitive recording material using this as a developer is an oil-resistant image. Excellent heat resistance of the background.
Claims (2)
Priority Applications (1)
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JP10977599A JP3887506B2 (en) | 1999-04-16 | 1999-04-16 | Aromatic carboxylic acid compounds |
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JP10977599A JP3887506B2 (en) | 1999-04-16 | 1999-04-16 | Aromatic carboxylic acid compounds |
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JP2000302730A JP2000302730A (en) | 2000-10-31 |
JP3887506B2 true JP3887506B2 (en) | 2007-02-28 |
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JP10977599A Expired - Fee Related JP3887506B2 (en) | 1999-04-16 | 1999-04-16 | Aromatic carboxylic acid compounds |
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