JPS6260685A - Pressure-sensitive copying paper - Google Patents

Pressure-sensitive copying paper

Info

Publication number
JPS6260685A
JPS6260685A JP60199582A JP19958285A JPS6260685A JP S6260685 A JPS6260685 A JP S6260685A JP 60199582 A JP60199582 A JP 60199582A JP 19958285 A JP19958285 A JP 19958285A JP S6260685 A JPS6260685 A JP S6260685A
Authority
JP
Japan
Prior art keywords
group
subst
unsubst
color
alkyl
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
Application number
JP60199582A
Other languages
Japanese (ja)
Inventor
Mitsutoshi Anzai
光利 安西
Susumu Suzuka
鈴鹿　進
Kazuyuki Wakasugi
若杉　一行
Michihiro Gonda
通博 権田
Katsumasa Yoshikawa
勝正 吉川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hodogaya Chemical Co Ltd
Original Assignee
Hodogaya Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hodogaya Chemical Co Ltd filed Critical Hodogaya Chemical Co Ltd
Priority to JP60199582A priority Critical patent/JPS6260685A/en
Publication of JPS6260685A publication Critical patent/JPS6260685A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Color Printing (AREA)

Abstract

PURPOSE:To provide a pressure-sensitive copying paper having a high color forming speed and capable of producing a developed color image with a high developed color density and favorable light resistance, by providing a color former layer comprising a specified fluoran compound on a base. CONSTITUTION:A color former layer comprising a fluoran compound of general formula [1] is provided on a base. In the formula, each of R1 and R2 is hydrogen, a 1-8C alkyl, cylohexyl, subst. or ubsubst. phenyl or subst. or unsubst. benzyl, R3 is a 1-8C alkyl, cyclohexyl, subst. or unsubst. phenyl or subst. or unsubst. benzyl, R4 is hydrogen, a 1-8C alkyl, cyclohexyl, subst. or unsubst. phenyl or subst. or unsubst. benzyl, R5 is a 1-8C alkyl, cyclohexyl, subst. or unsubst. phenyl or subst. or unsubst. benzyl, R6 is a 1-4C alkyl, nitro, halogen or hydrogen, and n is an integer of 1-8. The fluoran compound of the formula forms a deep dark green or black dye immediately on making contact with an acidic substance, and has excellent color resistance and heat resistance.

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は、感圧複写紙忙関する。さらに詳細には、本発
明は、発色剤として３位にアルコキシアルキル基を有す
る新規なフルオラン化合物を文月した感圧複写紙に関す
る。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to pressure sensitive copying paper. More specifically, the present invention relates to pressure-sensitive copying paper containing a novel fluoran compound having an alkoxyalkyl group at the 3-position as a color former.

（従来の技術） 従来、はぼ無色の発色剤、例えばマラカイトグリーンラ
クトン、ベンゾイルロイコメチレンブルー、クリスタル
バイオレットラクトン、ローダミンＢラクタム、２−留
換アばノー６−置換アばノフルオラン、３−メチル−２
，２−スピロ（ベンゾ（ｆ）クロメン）又はこれらの混
合物と、この発色剤と接触して発色する吸着または反応
性化合物（以下、顕色剤と称する）、例えば酸性白土、
活性白土、アタパルガイド、ゼオライト、ベントナイト
、カオリンのような粘土鉱物、コノ−り酸、タンニン酸
、没食子酸、フェノール化合物のような有機酸、フェノ
ールホルムアルデヒド樹脂のような酸性重合体との着色
反応を利用した感圧複写紙は一般によく知られている（
例えば、米国特許第２、５０５．４７０号、２．５０５
．４７１号、２．５０５．４８９号、２．５４　ａ　３
６６号、２．７１２．５０７号、２、７３０．４５６号
、２．７３０．４５７号および５、４１　ａ　２５０号
明細Ｉｆ）。ここで、発色剤および顕色剤を電子論的に
定義すれば、発色剤とは電子を供与して、或いはプロト
ンを受容して発色する物質であり、顕色剤とは電子を受
容するかまたはプロトンを供与する物質である。(Prior Art) Conventionally, colorless coloring agents such as malachite green lactone, benzoylleucomethylene blue, crystal violet lactone, rhodamine B lactam, 2-distillated abanor6-substituted abanofluorane, 3-methyl-2
, 2-spiro (benzo(f)chromene) or a mixture thereof, and an adsorbed or reactive compound (hereinafter referred to as a color developer) that develops a color upon contact with this color former, such as acid clay,
Utilizes coloring reactions with clay minerals such as activated clay, attapulgide, zeolite, bentonite, and kaolin, organic acids such as conolic acid, tannic acid, gallic acid, phenolic compounds, and acidic polymers such as phenol-formaldehyde resins. Pressure-sensitive copying paper is generally well known (
For example, U.S. Patent No. 2,505.470, 2.505
．． No. 471, No. 2.505.489, 2.54 a 3
No. 66, No. 2.712.507, No. 2, 730.456, No. 2.730.457 and No. 5, 41 a 250 If). Here, if we define color formers and color developers electronically, a color former is a substance that donates electrons or accepts protons to develop color, and a color developer is a substance that accepts electrons or accepts protons. Or it is a substance that donates protons.

（発明が解決しようとする問題点） 感圧複写紙の発色剤に要求される条件は、発色速度が大
きいこと、発色濃度が高いこと、発色色素が所望の色相
になること、色素の耐光性及び耐熱性が優れていること
などである。しかしながら、例えば實色に発色する発色
剤としてクリスタルバイオレットラクトン等が知られて
いるが、耐光性が不充分であり、旧記の要件を満足する
発色剤の出現が望まれている。(Problems to be Solved by the Invention) The conditions required for the coloring agent for pressure-sensitive copying paper are that the coloring speed is high, the coloring density is high, the coloring dye has a desired hue, and the dye has light resistance. and excellent heat resistance. However, for example, crystal violet lactone is known as a coloring agent that develops a true color, but its light resistance is insufficient, and there is a desire for a coloring agent that satisfies the requirements set forth above.

本発明の目的は発色速度が速く、発色濃度が高く、かつ
耐光性が良好な発色像を形成する感圧複写紙を提供する
ことにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a pressure-sensitive copying paper that forms a colored image that has a high color development speed, high color density, and good light resistance.

（問題点を解決するための手段） ａ′ｆｆ記目的を達成する本発明は一般式（１）（式中
、Ｒ１１Ｒ２は、それぞれ水素原子、炭素数１〜８のア
ルキル基、シクロヘキシル基、　置換可能なフェニル基
または置換可能なベンジル基を示し、Ｒ３は、炭素数１
〜８のアルキル基、シクロヘキシル基、置換可能なフェ
ニル基、置換可能なベンジル基を示し、Ｒ４は、水素原
子、炭素数１〜８のアルギル基、置換可能なフェニル基
、置換可能なベンジル基を示し、Ｒ５は、炭素数１〜８
のアルキル基、シクロヘキシル基、置換可能なフェニル
基、置換可能なベンジル基を示し、Ｒ＠は、炭素数１〜
４のアルキル基、ニトロ基、ハロゲン原子または水素原
子を示し、ｎは、１〜８の整数を示す。）で表わされる
フルオラン化合物を含む発色剤層を支持体上に有するこ
とを特徴とする感圧複写紙に関する。(Means for Solving the Problems) The present invention, which achieves the object a'ff, is based on the general formula (1) (wherein R11R2 are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, or a substituted Possible phenyl group or substitutable benzyl group, R3 has 1 carbon number
-8 alkyl group, cyclohexyl group, substitutable phenyl group, substitutable benzyl group, and R4 represents a hydrogen atom, an argyl group having 1 to 8 carbon atoms, a substitutable phenyl group, a substitutable benzyl group. and R5 has 1 to 8 carbon atoms.
represents an alkyl group, a cyclohexyl group, a substitutable phenyl group, a substitutable benzyl group, and R@ is a carbon number of 1 to
4 represents an alkyl group, a nitro group, a halogen atom, or a hydrogen atom, and n represents an integer of 1 to 8. The present invention relates to a pressure-sensitive copying paper characterized in that it has a color forming agent layer containing a fluoran compound represented by () on a support.

本発明に係る一般式（１）で表わされるフルオラン化合
物は大気中において安定な無色又は僅かに着色している
固体であり、酸性物質と接触すると直ちに濃い暗緑色な
いし黒色系の色素を形成し、この発色した色素は、浸れ
た耐光性および耐熱性を有しているため十分な利用価値
がある。The fluoran compound represented by the general formula (1) according to the present invention is a colorless or slightly colored solid that is stable in the atmosphere, and immediately forms a deep dark green to black pigment when it comes into contact with an acidic substance, This colored pigment has excellent light resistance and heat resistance, so it has sufficient utility value.

本発明に係る上記一般式ＣＩ）で表わされるフルオラン
化合物は次の（１）又は（２の方法で製造される。The fluoran compound represented by the general formula CI) according to the present invention is produced by the following method (1) or (2).

（１）一般式（Ｉｔ） （式中、Ｒは、水素原子、炭素数１〜４の低級アルキル
基またはアセチル基を表わし、Ｒ３、Ｒ４、Ｒ６、ｎは
ｌ１Ｔｌ記定義と同じ意味である。）で表わされるアニ
リン誘導体と一般式〔１〕 （式中、′Ｒ１，鳥及びＲは一般式ＣＩ）で定義したも
のと同じ意味である。）で表わされるベンゾフェノン化
合物とを濃硫酸の存在下、０〜８０℃の湿度で数時間反
応させる。反応後、反応混合物を水中に加え、水酸化ナ
トリウムを加え、ｐＨな８〜１０とし、析出物をろ過に
より採取する。ケーキにトルエンと５〜１０％の水酸化
ナトリウム水淫液を加え、還流下、１〜５時間かきまぜ
、トルエン層を分液し、分取し、水洗後、濃縮し、析出
した結晶をろ過により採取する。結晶を乾燥することに
より僅かに着色している一般式（１）で表わされる３位
にアルコキシアルキル基を有するフルオラン化合物が高
純度、高収率で得られる。必要ならば、トルエン、アセ
トン、酢酸ブチル、ヘキサンなどのような揮発性有機溶
剤から再結晶する。(1) General Formula (It) (In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or an acetyl group, and R3, R4, R6, and n have the same meanings as defined in 11Tl. ) and the general formula [1] (wherein 'R1, bird and R have the same meanings as defined in the general formula CI). ) in the presence of concentrated sulfuric acid at a humidity of 0 to 80°C for several hours. After the reaction, the reaction mixture is added to water, sodium hydroxide is added to adjust the pH to 8-10, and the precipitate is collected by filtration. Add toluene and 5-10% sodium hydroxide solution to the cake, stir under reflux for 1-5 hours, separate the toluene layer, collect it, wash with water, concentrate, and collect the precipitated crystals by filtration. do. By drying the crystals, a slightly colored fluoran compound represented by general formula (1) having an alkoxyalkyl group at the 3-position is obtained with high purity and high yield. If necessary, recrystallize from volatile organic solvents such as toluene, acetone, butyl acetate, hexane, etc.

（２）一般式（■） バ・ （式中、Ｒ８、Ｒ２、Ｒ１及びＲ６は一般式（１）で定
義したものと同じ意味である。）で表わされる２−アミ
ノ−３−アルコキシアルキル−６−シ置換アミノ−フル
オランと置換又は非置換のベンジルクロライド又は置換
又は非置換のベンジルブロマイドとを揮発性有機不活性
溶媒中で重炭酸ナトリウム等の脱酸剤の存在下に反応さ
せることにより、あるいは置換又は非ｉｐのブロモベン
ゼン又はクロロベンゼンとを揮発性有機不活性溶媒中で
銅粉とヨウ素を触媒とし炭酸カリウムの存在下に反応さ
せることにより、一般式ＣＩ）で表わされる２−置換ア
ミノ−５−アルコキシアルキル−６−ジー置換アミノ−
フルオランが製造される。(2) 2-amino-3-alkoxyalkyl- represented by general formula (■) By reacting a 6-si-substituted amino-fluorane with substituted or unsubstituted benzyl chloride or substituted or unsubstituted benzyl bromide in a volatile organic inert solvent in the presence of an acid scavenger such as sodium bicarbonate, Alternatively, the 2-substituted amino- 5-alkoxyalkyl-6-di-substituted amino-
Fluorane is produced.

本発明の発色剤を製造する（１）の方法において使用さ
れる縮合剤としては、濃硫酸、無水酢酸、リン酸、ポリ
リン酸、オキシ塩化リンおよび塩化亜鉛などがある。製
造上好ましく（、を上記一般式（１）で表わされるベン
ゾフェノン化合物などの溶媒であると同時に縮合剤でも
ある濃硫酸を便用する方法である。Condensing agents used in the method (1) for producing the color former of the present invention include concentrated sulfuric acid, acetic anhydride, phosphoric acid, polyphosphoric acid, phosphorus oxychloride, and zinc chloride. A preferred method for production is to use concentrated sulfuric acid, which is a condensing agent as well as a solvent for the benzophenone compound represented by the above general formula (1).

本発明の感圧複写紙は、上記の発色剤を単独又は混合し
て、あるいは他の発色剤と共に１例えばアルキル化ナフ
タレン、アルキル化ジフェニル、アルキル化ジフェニル
メタン等のジアリールアルカン、アルキル化ターフェニ
ルなどの合成油、木綿油、ヒマシ油などの植物油、動物
油、鉱物油あるいはこれらの混合油等の溶媒に溶解し、
これをバインダー中に分散するか、またはマイクロカプ
セル中だ含有させた後、紙、プラスチックシート、樹脂
コーテツド紙等の支持体に塗布することによｌノ得られ
る。The pressure-sensitive copying paper of the present invention may contain the above-mentioned color formers alone or in combination, or together with other color formers, such as diarylalkane such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, etc. Dissolved in a solvent such as synthetic oil, cotton oil, vegetable oil such as castor oil, animal oil, mineral oil, or a mixture of these oils,
It can be obtained by dispersing it in a binder or containing it in microcapsules, and then applying it to a support such as paper, plastic sheet, resin-coated paper, or the like.

発色剤の便用量は、所望の塗布厚、感圧複写紙の形態、
カプセルの製法、その他の条件により、決定される。発
色剤をカプセル中に封入する際には、米国特許第２．８
００．４５７号および２．８００，４５８号明細書に記
載された親水性コロイドゾルのコアセルベーションを利
用した方法、英国特許第８６４７９７号、１．　ＣＩ　
９１．０７６号明細書に記載された界面重合法等を利用
すればよい。The amount of coloring agent to be applied depends on the desired coating thickness, the form of pressure-sensitive copying paper,
It is determined by the capsule manufacturing method and other conditions. When encapsulating a coloring agent in a capsule, U.S. Patent No. 2.8
00.457 and 2.800,458, British Patent No. 864797, 1. C.I.
The interfacial polymerization method described in No. 91.076 may be used.

本発明圧係る感圧複写紙に適用できる顕色剤の具体例を
示すと、クレー類（例えば、酸性白土、活性白土、アタ
パルジャイト、カオリン等）、フェノール樹脂、芳香族
カルボン酸の多価金属塩等をあげることができる。フェ
ノール樹脂とは、具体的Ｋ　ハ、フェノール−アルデヒ
ド重合体（いわゆるノボラック型）及びフェノールアセ
チレン重合体である。芳香族カルボン酸の多価金属塩は
、例えば、米国特許へ８６４，１４６号、同３．９８！
１．２９２号、同４９３４，０７０号、同へ９８３．２
９２号、特願昭５５−２５１５８号明細書等に記載され
ている。Specific examples of color developers that can be applied to the pressure-sensitive copying paper of the present invention include clays (for example, acid clay, activated clay, attapulgite, kaolin, etc.), phenolic resins, and polyvalent metal salts of aromatic carboxylic acids. etc. can be given. Phenolic resins include specifically K, phenol-aldehyde polymers (so-called novolac type), and phenolacetylene polymers. Polyvalent metal salts of aromatic carboxylic acids are disclosed in, for example, US Pat. No. 864,146, 3.98!
No. 1.292, No. 4934,070, No. 983.2
No. 92, Japanese Patent Application No. 55-25158, etc.

上記芳香族カルボン酸の多価金属塩における芳香族のカ
ルボン酸はカルボキシ基に対し、オルト又はパラ位に水
酸基を有するものが有用であり、中でもサリチル酸誘導
体が好ましく、水酸基に対し、オルト又はパラ位の少（
とも一方に、アルキル基、アリール基、アラルキル基等
の置換基を有し置換基の炭素原子数の総和が８以上であ
るものが特に好ましい。上記の多価金属塩の中、亜鉛塩
が特に好ましい。The aromatic carboxylic acid in the polyvalent metal salt of an aromatic carboxylic acid is preferably one having a hydroxyl group at the ortho or para position with respect to the carboxy group, and salicylic acid derivatives are particularly preferred; Small amount (
Particularly preferred are those having a substituent such as an alkyl group, an aryl group, an aralkyl group, etc., and the total number of carbon atoms of the substituents is 8 or more. Among the polyvalent metal salts mentioned above, zinc salts are particularly preferred.

次に本発明に係る３位にアルコキシアルキル基を有する
フルオラン化合物の代表的な製造例を次に示す。Next, a typical production example of a fluoran compound having an alkoxyalkyl group at the 3-position according to the present invention will be shown below.

製造例１ ２−アニリノ−３−エトキシエチル−６−Ｎ、Ｎ−ジエ
チルアミノ−フルオラン（化合物／ｆＬ１）９５％硫酸
１５０？中に２−ヒドロキシ−４−Ｎ、Ｎ−ジエチルア
ミノ−２′−カルボキシ−ベンゾフェノン１５Ｆを加え
約２０℃の温度で完全に溶解すせてから、２−エトキシ
エチル−４−メトキシ−ジフェニルアミン１０ｆを加え
ｓ　　１０〜２０℃の温度で１０時間反応させた。反応
後、反応混合物を氷水１を中に加え、つづいて１０％水
酸化ナトリウム水溶液を加えｓ　ｐＨを７−８とし、析
出物をろ過により採取した。ケーキにトルエン３００ｍ
と１０％水酸化ナトリウム水溶液１５〇−を加え、環流
下２時間かきまぜた後、トルエン層を分液、水洗後濃縮
乾固し、メタノールを加え固化させた。この固化物を乾
燥し、淡桃色の２−アニリノ−３−エトキシエチル−６
−Ｎ、Ｎ−ジエチルアミノーフルオクン１１ｆが得られ
た。このものの融点は１５０．５〜１５２．５℃であっ
た。また、このものの９５％酢酸中でのλｍａｘ及び分
子吸光係数は４４９　ｎｍ（１，９４Ｘ　１０’　）並
に５９５　ｎｍ（１，７３Ｘ１０　　）であった。この
ものをトルエンに溶かした溶液は無色であり、シリカゲ
ルによって速やかに発色し赤黒色を呈する。Production Example 1 2-anilino-3-ethoxyethyl-6-N,N-diethylamino-fluoran (compound/fL1) 95% sulfuric acid 150? Add 15F of 2-hydroxy-4-N,N-diethylamino-2'-carboxy-benzophenone and dissolve completely at a temperature of about 20°C, then add 10F of 2-ethoxyethyl-4-methoxy-diphenylamine. s The reaction was carried out at a temperature of 10 to 20°C for 10 hours. After the reaction, 1 portion of ice water was added to the reaction mixture, followed by 10% aqueous sodium hydroxide solution to adjust the pH to 7-8, and the precipitate was collected by filtration. 300m of toluene in the cake
After adding 150% of a 10% aqueous sodium hydroxide solution and stirring under reflux for 2 hours, the toluene layer was separated, washed with water, concentrated to dryness, and methanol was added to solidify. This solidified product was dried and a pale pink 2-anilino-3-ethoxyethyl-6
-N,N-diethylaminofluorocne 11f was obtained. The melting point of this product was 150.5-152.5°C. Further, the λmax and molecular extinction coefficient of this product in 95% acetic acid were 449 nm (1,94X 10') and 595 nm (1,73X10). A solution prepared by dissolving this product in toluene is colorless, and the silica gel quickly develops the color, giving it a reddish-black color.

製造例１に準シて、５位にアルコキシアルキル基を有す
るフルオラン化合物〔化合物／＃６２〜慮１４〕を製造
した。以下に、これら化合物の構造式及びシリカゲル上
での発色色相をまとめて次の表に示す。Fluoran compounds having an alkoxyalkyl group at the 5-position [Compounds/#62 to No. 14] were produced in accordance with Production Example 1. The structural formulas of these compounds and the color hues developed on silica gel are summarized in the following table.

（実施例） 次に本発明を実施例について説明するが、本発明はこれ
によりなんら限定されるものではない。(Example) Next, the present invention will be described with reference to Examples, but the present invention is not limited thereto in any way.

実施例 〔化合物／１６２）で表わされる ２−１ニリノー３−エトΦジエチル−６−Ｎ、Ｎ−ジ−
ｎ−ブチルアミノ−フルオラン、１８（重量部、以下同
様）をアルキル化ナフタレン３０部に溶解させた。この
溶液をゼラチン６部とアラビアゴム４部を溶解した水５
０部中に激しくかきまぜながら加えて乳化し、直径１μ
〜１０μの油滴とした後、水２５０部を加えた。酢酸を
少量ずつ加えてｐＨを約４にしてコ１セルベーションヲ
生起させ、油滴のまわりにゼラチンとアラビアゴムの壁
をつくり、ホルマリンを加えてからｐＨを９にあげ、壁
を硬化した。この様にして得られたマイクロカプセル分
散液を紙に塗布乾燥した。この感圧複写紙は優れた保存
安定性を有していた。Example [Compound/162] 2-1 nilino-3-ethoΦdiethyl-6-N,N-di-
18 parts by weight of n-butylamino-fluorane (the same applies hereinafter) was dissolved in 30 parts of alkylated naphthalene. Add this solution to 5 parts of water containing 6 parts of gelatin and 4 parts of gum arabic.
Add to 0 parts while stirring vigorously to emulsify, and make a diameter of 1 μm.
After forming oil droplets of ~10μ, 250 parts of water was added. Acetic acid was added little by little to bring the pH to about 4 to cause co-cervation, creating a wall of gelatin and gum arabic around the oil droplets, and formalin was added and the pH was raised to 9 to harden the wall. The microcapsule dispersion thus obtained was applied to paper and dried. This pressure-sensitive copying paper had excellent storage stability.

この感圧複写紙について、その特性を評価するために、
クレー紙、レジン紙及び有機酸塩紙に重ねて筆記に相当
する圧力を加えた。なお記録紙は次のとおりである。In order to evaluate the characteristics of this pressure-sensitive copying paper,
Pressure equivalent to writing was applied to clay paper, resin paper, and organic acid salt paper. The recording paper used is as follows.

クレー紙 酸性白土２０部、ヘキサメタリン酸ソーダ０．２部、水
８０部をホモジナイザーで５分間分散し、さらに、５０
％スチレンブタジェンラテックス５部を加えて、クレー
分散液とした。Disperse 20 parts of clay paper acid clay, 0.2 parts of sodium hexametaphosphate, and 80 parts of water using a homogenizer for 5 minutes, and then
% styrene butadiene latex was added to form a clay dispersion.

この分散液を上質紙上に乾燥固形分量５　ｆ／ｒ？とな
るように塗布し、クレー紙を得た。This dispersion was coated on high-quality paper with a dry solid content of 5 f/r? This was applied to obtain clay paper.

レジン紙 ｐ−フェニルフェノールホルマリン１８合物２０部、炭
酸カルシウム１００部、２％ポリビニルアルコール水溶
液６００部をボールミルで分散し、フェノール樹脂分散
液を得た。20 parts of resin paper p-phenylphenol formalin 18 compound, 100 parts of calcium carbonate, and 600 parts of a 2% polyvinyl alcohol aqueous solution were dispersed in a ball mill to obtain a phenol resin dispersion.

この分散液を上質紙上に乾燥固形分子ｉ　５　ｆ／ｒｒ
？となるように塗布し、レジン紙を得た。This dispersion was dried on high-quality paper with solid molecules i 5 f/rr.
? A resin paper was obtained.

有′ａ酸塩紙 餌記レジン紙の製造において、ｐ−フェニルフェノール
ホルマリン縮合物の代すＩＣ，３，５−α−メチル−ベ
ンジルサリチル酸亜鉛を便用して同様に行い、有機酸塩
紙を得た。In the production of organic acid salt paper and resin paper, the same procedure was carried out using IC, 3,5-α-methyl-benzylsalicylic acid zinc instead of p-phenylphenol formalin condensate, and organic acid salt paper was prepared. I got it.

〔化合物２〕を発色剤とする複写紙は各記録紙と重ねて
圧力を加えると、瞬間的に、茶黒色ないし黒色の印像が
得られた。この印像のフレッシュ濃度は１．０５と高く
、耐光値は７８％と優れており、かつ耐熱性にも優れて
いた。When the copying paper containing [Compound 2] as a coloring agent was stacked with each recording paper and pressure was applied, a brownish-black to black image was instantly obtained. This printed image had a high fresh density of 1.05, an excellent light fastness value of 78%, and excellent heat resistance.

フレッシュ濃度１発色剤をトルエンに２％溶解し、クレ
ー紙上に塗布した直後の濃度をマグベス反射濃度計（フ
ィルター、ラツテン＋１０６）により測定した値である
。Fresh Density 1 The color former was dissolved at 2% in toluene, and the density was measured immediately after coating on clay paper using a Magbeth reflection densitometer (filter, Latten+106).

耐光値藤フェード、オ、メーター３時間、照射後の発色
濃度を測定し、次式忙より求めた値である。Lightfastness value The color density was measured after irradiation with a meter for 3 hours, and the value was determined from the following formula.

前記実施例で発色剤として使用したフルオラン〔化合物
４２）の代りに製造例１で得られた〔化合物溝１〕並び
に第１表に示す〔化合物／Ｖ１３〜８〕を使用して実施
例と同様にして感圧複写紙を製造した。これら感圧複写
紙のクレー紙上、レジン紙上及び有機酸塩紙上の発色色
相及びクレー紙上のフレッシュ濃度、耐光値を測定し、
次の表に示した。In place of the fluoran [compound 42] used as the coloring agent in the above example, [compound groove 1] obtained in Production Example 1 and [compounds/V13 to 8] shown in Table 1 were used, but the same as in the example was used. A pressure-sensitive copying paper was produced. The color hue of these pressure-sensitive copying papers on clay paper, resin paper, and organic acid salt paper, as well as fresh density and light fastness on clay paper, were measured.
Shown in the table below.

なお、一般の感圧複写紙に多用されている発色剤である
クリスタルバイオレットラクトン（ＣＶＬ　）及び２−
　Ｎ、Ｎ−ジベンジルアミノ−６−ジエチルアはノフル
オラン（ＤＢＦ）を便用した複写紙を対照例として表示
した。Note that crystal violet lactone (CVL) and 2-
For N,N-dibenzylamino-6-diethyla, a copy paper prepared with nofluorane (DBF) was shown as a control example.

なお、有機酸塩紙上での各化合物の発色々相はレジ／紙
上での対応各化合物の発色々相と同一であったので、表
記を省略した。Note that the color phases of each compound on the organic acid salt paper were the same as the color phases of the corresponding compounds on the register/paper, so the description was omitted.

（発明の効果） 以上の説明から明らかなよ５１ｃ、本発明によれば一般
式ＣＩ）だ示すフルオラン化合物を発色剤として便用す
るととくより発色濃度が高く、耐光性に優れた発色像を
形成する感圧複写紙が得られる。(Effects of the Invention) It is clear from the above explanation that according to the present invention, when the fluoran compound represented by the general formula CI) is used as a coloring agent, a colored image with a higher color density and excellent light resistance is formed. Pressure-sensitive copying paper is obtained.

保土谷化学工業株式会社Hodogaya Chemical Industry Co., Ltd.

Claims (1)

【特許請求の範囲】 １、一般式 ▲数式、化学式、表等があります▼〔 I 〕 （式中、Ｒ＿１、Ｒ＿２は、それぞれ水素原子、炭素数
１〜８のアルキル基、シクロヘキシル基、置換可能なフ
ェニル基または置換可能なベンジル基を示し、Ｒ＿３は
、炭素数１〜８のアルキル基、シクロヘキシル基、置換
可能なフェニル基、置換可能なベンジル基を示し、Ｒ＿
４は、水素原子、炭素数１〜８のアルキル基、置換可能
なフェニル基、置換可能なベンジル基を示し、Ｒ＿５は
、炭素数１〜８のアルキル基、シクロヘキシル基、置換
可能なフェニル基、置換可能なベンジル基を示し、Ｒ＿
６は、炭素数１〜４のアルキル基、ニトロ基、ハロゲン
原子または水素原子を示し、ｎは１〜８の整数を示す。 ）で表わされるフルオラン化合物を含む発色剤層を支持
体上に有することを特徴とする感圧複写紙。[Claims] 1. General formula▲ Numerical formula, chemical formula, table, etc.▼[I] (In the formula, R_1 and R_2 are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, or a substitutable represents a phenyl group or a substitutable benzyl group, R_3 represents an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a substitutable phenyl group, or a substitutable benzyl group;
4 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substitutable phenyl group, a substitutable benzyl group, and R_5 represents an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a substitutable phenyl group, Indicates a substitutable benzyl group, R_
6 represents an alkyl group having 1 to 4 carbon atoms, a nitro group, a halogen atom, or a hydrogen atom, and n represents an integer of 1 to 8. 1. A pressure-sensitive copying paper comprising, on a support, a color forming agent layer containing a fluoran compound represented by:
JP60199582A 1985-09-11 1985-09-11 Pressure-sensitive copying paper Pending JPS6260685A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60199582A JPS6260685A (en) 1985-09-11 1985-09-11 Pressure-sensitive copying paper

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60199582A JPS6260685A (en) 1985-09-11 1985-09-11 Pressure-sensitive copying paper

Publications (1)

Publication Number Publication Date
JPS6260685A true JPS6260685A (en) 1987-03-17

Family

ID=16410242

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60199582A Pending JPS6260685A (en) 1985-09-11 1985-09-11 Pressure-sensitive copying paper

Country Status (1)

Country Link
JP (1) JPS6260685A (en)

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