JP3107854B2 - Process for producing 3,5-di (α-methylbenzyl) salicylic acid derivative and use of polyvalent metallized product as color developer - Google Patents
Process for producing 3,5-di (α-methylbenzyl) salicylic acid derivative and use of polyvalent metallized product as color developerInfo
- Publication number
- JP3107854B2 JP3107854B2 JP03178311A JP17831191A JP3107854B2 JP 3107854 B2 JP3107854 B2 JP 3107854B2 JP 03178311 A JP03178311 A JP 03178311A JP 17831191 A JP17831191 A JP 17831191A JP 3107854 B2 JP3107854 B2 JP 3107854B2
- Authority
- JP
- Japan
- Prior art keywords
- methylbenzyl
- salicylic acid
- acid derivative
- weight
- developer
- 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.)
- Expired - Fee Related
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
- B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
-
- 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
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Color Printing (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は感圧複写紙または感熱紙
用の顕色剤として有用な3,5−ジ(α−メチルベンジ
ル)サリチル酸誘導体の新規な製造方法およびその多価
金属化物を含有する顕色剤に関する。BACKGROUND OF THE INVENTION The present invention relates to a novel process for producing a 3,5-di (α-methylbenzyl) salicylic acid derivative useful as a color developer for pressure-sensitive copying paper or thermal paper and a polyvalent metal compound thereof. It relates to the developer contained.
【0002】[0002]
【従来の技術】一般に感圧紙および感熱紙用顕色剤とし
てのサリチル酸系化合物は、発色像の鮮明さおよび保存
安定性等が優れている。反面、感圧紙においては無色の
色素を溶解させたカプセルオイルとの相溶性不足に基づ
く発色速度の遅れや、発色画像が水で消失する等耐水性
が不良であり、これらの欠点を補うため、種々の試みが
なされている。例えば、サリチル酸骨格に芳香族置換基
等を導入して、前記欠点を補う方法が提案されている。2. Description of the Related Art In general, salicylic acid compounds as color developers for pressure-sensitive paper and thermal paper are excellent in clarity of a color image and storage stability. On the other hand, in the pressure-sensitive paper, the color development speed is delayed due to lack of compatibility with the capsule oil in which the colorless dye is dissolved, and the water resistance is poor, such as the disappearance of the color image with water. Various attempts have been made. For example, a method has been proposed in which an aromatic substituent or the like is introduced into a salicylic acid skeleton to compensate for the above-mentioned disadvantage.
【0003】(1)3,5−ジ置換サリチル酸の製造法
として対応する各置換フェノールと二酸化炭素からコル
ベーシュミット反応により製造する方法が知られてい
る。例えば特公昭49−10856に開示されている
3,5−ジ(α,α−ジメチルベンジル)サリチル酸は
フェノールとα−メチルスチレンから得られる2,4−
ジ(α,α−ジメチルベンジル)フェノールを原料とし
て製造されている。しかしこの方法は反応工程が長く、
収率が低いという欠点のほかカルボキシル基を導入する
際反応を高温高圧下で行なうため、一般に高価となると
いう難点がある。(1) As a method for producing 3,5-disubstituted salicylic acid, there is known a method for producing from a corresponding substituted phenol and carbon dioxide by a Kolbe-Schmitt reaction. For example, 3,5-di (α, α-dimethylbenzyl) salicylic acid disclosed in JP-B-49-10856 can be obtained from phenol and α-methylstyrene.
It is manufactured using di (α, α-dimethylbenzyl) phenol as a raw material. However, this method requires a long reaction step,
In addition to the drawback that the yield is low, the introduction of a carboxyl group involves a disadvantage that the reaction is generally carried out under high temperature and high pressure, resulting in high cost.
【0004】(2)このような製造コスト上の問題点を
克服する目的で類似のサリチル酸化合物を製造する試み
がなされている。例えば、サリチル酸あるいはサリチル
酸エステルのアルキル化反応がある。(2) There has been an attempt to produce a similar salicylic acid compound for the purpose of overcoming such a problem in production cost. For example, there is an alkylation reaction of salicylic acid or salicylic acid ester.
【0005】サリチル酸1モルに1−フェニルエタノー
ル類を2モル反応させて5−〔α−メチル−4−(α−
メチルベンジル)−ベンジル〕サリチル酸または3,5
−ジ(α−メチルベンジル)サリチル酸との混合物を得
る方法(特開昭61−100493,62−9644
9)が知られている。この方法では置換サリチル酸は種
々の混合物として製造されさらに煩雑な操作によりモノ
置換サリチル酸あるいはジ置換サリチル酸との混合物の
金属塩として分離するため製造上の問題に加え、この混
合物を感圧複写紙用顕色剤として使用した場合顕色シー
トにおける発色性能や保存安定性等の品質にも再現性が
得られにくいという問題がある。[0005] One mole of salicylic acid is reacted with 2 moles of 1-phenylethanol to give 5- [α-methyl-4- (α-
Methylbenzyl) -benzyl] salicylic acid or 3,5
Method for obtaining a mixture with -di (α-methylbenzyl) salicylic acid (Japanese Patent Application Laid-Open No. 61-100493, 62-9644)
9) is known. In this method, the substituted salicylic acid is produced as various mixtures, and is separated as a metal salt of a mixture with the mono-substituted salicylic acid or the di-substituted salicylic acid by a complicated operation. When used as a coloring agent, there is a problem that it is difficult to obtain reproducibility in quality such as color development performance and storage stability of a color developing sheet.
【0006】(3)脂肪族カルボン酸の存在下に、有機
スルホン酸または無機酸を触媒として用いてサリチル酸
にスチレン化合物を反応させジ置換サリチル酸を得る方
法が提案されている(特開平2−91043)。(3) A method of obtaining a di-substituted salicylic acid by reacting a styrene compound with salicylic acid using an organic sulfonic acid or an inorganic acid as a catalyst in the presence of an aliphatic carboxylic acid has been proposed (JP-A-2-91043). ).
【0007】この場合酢酸、プロピオン酸等の脂肪族カ
ルボン酸と硫酸、メタンスルホン酸とを併用して90〜
130℃で反応を行ない、かつ酸の使用量がサリチル酸
に対して50重量%以上で実施されるため、この廃酸の
処理も問題であり、工業的に有利な方法ではない。この
方法では反応生成物は例えば3,5−ジ(α−メチルベ
ンジル)サリチル酸と3−α−メチルベンジル−5−
(1,3−ジフェニルブチル)サリチル酸および3−
(1,3−ジフェニルブチル)−5−α−メチルベンジ
ルサリチル酸の混合物である。このような反応生成物を
感圧紙用顕色剤として使用した場合、(2)と同様の問
題点がある。[0007] In this case, 90-
Since the reaction is carried out at 130 ° C. and the amount of the acid used is 50% by weight or more based on salicylic acid, the treatment of this waste acid is also a problem and is not an industrially advantageous method. In this method, the reaction product is, for example, 3,5-di (α-methylbenzyl) salicylic acid and 3-α-methylbenzyl-5-
(1,3-diphenylbutyl) salicylic acid and 3-
It is a mixture of (1,3-diphenylbutyl) -5-α-methylbenzylsalicylic acid. When such a reaction product is used as a developer for pressure-sensitive paper, there is a problem similar to (2).
【0008】(4)サリチル酸アルキルエステルのアル
キル化反応については例えばサリチル酸メチルに、アル
カンスルホン酸の存在下にスチレンを反応させ、3,5
−ジ(α−メチルベンジル)サリチル酸メチルを得る方
法が知られている(特公昭61−26772)。この方
法ではスチレンを使用するためスチレンの各種重合物や
その他の副生物が生成する。この方法は本発明者らが特
開平1−133780号にて開示したサリチル酸エステ
ル樹脂を製造する方法と類似しており、触媒、サルチル
酸エステルとスチレンのモル比、反応温度等を変えても
樹脂化する副反応を抑制することはできない。(4) For the alkylation reaction of salicylic acid alkyl ester, for example, styrene is reacted with methyl salicylate in the presence of alkanesulfonic acid to give 3,5
A method for obtaining methyl-di (α-methylbenzyl) salicylate is known (JP-B-61-26772). In this method, since styrene is used, various polymers of styrene and other by-products are generated. This method is similar to the method for producing a salicylate resin disclosed by the present inventors in Japanese Patent Application Laid-Open No. 1-133780, and even when the catalyst, the molar ratio of salicylate to styrene, the reaction temperature, etc. are changed, It is not possible to suppress the side reaction to be changed.
【0009】この特公昭61−26772号の実施例4
を追試した後述の比較例1において3,5−ジ(α−メ
チルベンジル)サリチル酸メチルの選択率は43%であ
った。これは、モノ置換体やトリ置換体の生成に加えス
チレンの重合物、さらにはダイマー付加物等が生成する
ためであり、触媒のアルカンスルホン酸の使用量も多く
有利な方法とはいえない。Example 4 of Japanese Patent Publication No. 61-26772
In Comparative Example 1 to be described later, the selectivity of methyl 3,5-di (α-methylbenzyl) salicylate was 43%. This is because a styrene polymer, a dimer adduct, and the like are formed in addition to the formation of the mono-substituted product and the tri-substituted product.
【0010】[0010]
【発明が解決しようとする課題】本発明の目的は顕色剤
として発色性能や耐光黄変性能に優れる3,5−ジ(α
−メチルベンジル)サリチル酸誘導体の経済的な製法の
開発およびこれを用いた顕色剤、ならびに特に発色像の
水に対する安定性、低温下での発色性が改良された顕色
剤組成物を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a 3,5-di (α) which is excellent as a color developer and has excellent color-forming performance and light yellowing resistance.
-Development of an economical process for producing a (-methylbenzyl) salicylic acid derivative and a color developing agent using the same, and a color developing composition having improved water stability and especially low temperature color developing properties of a color image. It is in.
【0011】[0011]
【課題を解決するための手段】発明者らは前記目的を達
成するため鋭意検討した結果、サリチル酸エステル類と
α−メチルベンジルハライド類とを酸触媒の存在下で反
応させて、3,5−ジ(α−メチルベンジル)サリチル
酸エステルを生成させ、ついで加水分解して3,5−ジ
(α−メチルベンジル)サリチル酸誘導体を得る方法を
見出した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have reacted salicylic esters with α-methylbenzyl halides in the presence of an acid catalyst to give 3,5- The inventors have found a method of producing a di (α-methylbenzyl) salicylate and then hydrolyzing to obtain a 3,5-di (α-methylbenzyl) salicylate derivative.
【0012】この場合、加水分解するに先立って、反応
生成物を真空蒸留に付して、3,5−ジ(α−メチルベ
ンジル)サリチル酸エステルを分離することにより、純
度99%以上の3,5−ジ(α−メチルベンジル)サリ
チル酸誘導体を得ることができる。In this case, prior to the hydrolysis, the reaction product is subjected to vacuum distillation to separate 3,5-di (α-methylbenzyl) salicylate, whereby 3,3 having a purity of 99% or more is obtained. A 5-di (α-methylbenzyl) salicylic acid derivative can be obtained.
【0013】さらに、前記サリチル酸エステル類とα−
メチルベンジルハライド類とを酸触媒の存在下で反応さ
せ、反応物を加水分解して得られる、3,5−ジ(α−
メチルベンジル)サリチル酸誘導体を60〜90重量%
含む、α−メチルベンジル基置換サリチル酸誘導体組成
物の多価金属化物を顕色剤として用いると、前記目的が
達成されることを見出した。Further, the salicylic esters and α-
Methylbenzyl halides are reacted in the presence of an acid catalyst, and the reaction product is hydrolyzed to obtain 3,5-di (α-
60-90% by weight of methylbenzyl) salicylic acid derivative
It has been found that the above object can be achieved by using a polyvalent metallized product of an α-methylbenzyl group-substituted salicylic acid derivative composition as a color developer.
【0014】すなわちこの発明は、 (1)一般式(I)That is, the present invention provides the following: (1) General formula (I)
【0015】[0015]
【化5】 (式中、R1 は炭素数1〜12のアルキル基、アラルキ
ル基またはシクロアルキル基を示す)で表わされるサリ
チル酸エステル類に、一般式(II)Embedded image (Wherein, R 1 represents an alkyl group, an aralkyl group or a cycloalkyl group having 1 to 12 carbon atoms) represented by the general formula (II)
【0016】[0016]
【化6】 (式中、R2 ,R3 は水素原子または炭素数1〜4のア
ルキル基を示し、Xはハロゲン原子を示す)で表わされ
るα−メチルベンジルハライド類を酸触媒の存在下で反
応させ、生成する3,5−ジ(α−メチルベンジル)サ
リチル酸エステルを加水分解することを特徴とする3,
5−ジ(α−メチルベンジル)サルチル酸誘導体の製造
方法および (2)上記反応の反応生成物を加水分解して得られる、
3,5−ジ(α−メチルベンジル)サリチル酸誘導体を
60〜90重量%含むα−メチルベンジル基置換サリチ
ル酸誘導体組成物の金属化物およびこれを顕色剤として
使用した顕色シートを提供するものである。Embedded image Wherein R 2 and R 3 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom, in the presence of an acid catalyst. Characterized in that the resulting 3,5-di (α-methylbenzyl) salicylate is hydrolyzed.
A method for producing a 5-di (α-methylbenzyl) salicylic acid derivative, and (2) obtained by hydrolyzing a reaction product of the above reaction,
A metallized α-methylbenzyl group-substituted salicylic acid derivative composition containing 60 to 90% by weight of a 3,5-di (α-methylbenzyl) salicylic acid derivative, and a color developing sheet using the same as a color developer. is there.
【0017】この発明で使用するサリチル酸エステル類
としてはサリチル酸メチル、サリチル酸エチル、サリチ
ル酸−n−プロピル、サリチル酸イソプロピル、サリチ
ル酸イソアミル、サリチル酸−tert−オクチル、サ
リチル酸ノニル、サリチル酸ドデシル、サリチル酸シク
ロヘキシル、サリチル酸ベンジル、サリチル酸−α−メ
チルベンジル等が挙げられるがこれに限定されるもので
はない。工業的に好ましくは安価なサリチル酸メチル、
およびサリチル酸エチルである。The salicylates used in the present invention include methyl salicylate, ethyl salicylate, n-propyl salicylate, isopropyl salicylate, isoamyl salicylate, tert-octyl salicylate, nonyl salicylate, dodecyl salicylate, cyclohexyl salicylate, benzyl salicylate, and benzyl salicylate. -Α-methylbenzyl and the like, but are not limited thereto. Industrially preferably inexpensive methyl salicylate,
And ethyl salicylate.
【0018】この発明で使用するα−メチルベンジルハ
ライド類のハロゲンの種類としては、塩素、臭素が挙げ
られるが、好ましくは塩素である。したがってα−メチ
ルベンジルハライド類としてはα−メチルベンジルクロ
ライド、o−メチル−α−メチルベンジルクロライド、
p−メチル−α−メチルベンジルクロライド、m−メチ
ル−α−メチルベンジルクロライド、o−エチル−α−
メチルベンジルクロライド、p−エチル−α−メチルベ
ンジルクロライド、p−イソプロピル−α−メチルベン
ジルクロライド、2,3−ジメチル−α−メチルベンジ
ルクロライド、2,4−ジメチル−α−メチルベンジル
クロライド、2,5−ジメチル−α−メチルベンジルク
ロライド、3,4−ジメチル−α−メチルベンジルクロ
ライド等が挙げられるがこれらに限定されるものではな
い。これらのうち好ましくはα−メチルベンジルクロラ
イド、p−メチル−α−メチルベンジルクロライドが挙
げられる。Examples of the kind of halogen in the α-methylbenzyl halides used in the present invention include chlorine and bromine, but chlorine is preferred. Accordingly, α-methylbenzyl halides include α-methylbenzyl chloride, o-methyl-α-methylbenzyl chloride,
p-methyl-α-methylbenzyl chloride, m-methyl-α-methylbenzyl chloride, o-ethyl-α-
Methylbenzyl chloride, p-ethyl-α-methylbenzyl chloride, p-isopropyl-α-methylbenzyl chloride, 2,3-dimethyl-α-methylbenzyl chloride, 2,4-dimethyl-α-methylbenzyl chloride, 2, Examples include, but are not limited to, 5-dimethyl-α-methylbenzyl chloride, 3,4-dimethyl-α-methylbenzyl chloride, and the like. Of these, α-methylbenzyl chloride and p-methyl-α-methylbenzyl chloride are preferred.
【0019】この発明の製造方法における各種α−メチ
ルベンジルハライド類の使用量は前記一般式(I)に示
すサリチル酸エステル類1モルに対して1.5〜3モル
が好ましい、1.5モル未満あるいは3モルを超えて使
用した場合主目的の前駆体である3,5−ジ(α−メチ
ルベンジル)サリチル酸エステルの生成率が低くなり好
ましくない。The amount of the various α-methylbenzyl halides used in the production method of the present invention is preferably 1.5 to 3 mol, more preferably less than 1.5 mol, per mol of the salicylic acid ester represented by the above general formula (I). Alternatively, the use of more than 3 moles is not preferred because the production rate of 3,5-di (α-methylbenzyl) salicylate, which is the main target precursor, is reduced.
【0020】この反応で使用する酸触媒は、例えば塩化
第二鉄、塩化亜鉛、塩化アルミニウム、塩化第二錫、四
塩化チタン、三弗化ホウ素等のルイス酸形触媒、超強酸
として知られるパーフルオロアルカンスルホン酸類例え
ばトリフルオロメタンスルホン酸、パーフルオロアルカ
ンスルホン酸樹脂としてNafion H(商品名Du
pont社製)が使用できる。このうち、特に好ましい
のは塩化亜鉛である。The acid catalyst used in this reaction is, for example, a Lewis acid type catalyst such as ferric chloride, zinc chloride, aluminum chloride, stannic chloride, titanium tetrachloride, boron trifluoride, etc. Fluoroalkanesulfonic acids such as trifluoromethanesulfonic acid and Nafion H (trade name Du) as perfluoroalkanesulfonic acid resin
Pont) can be used. Among them, zinc chloride is particularly preferred.
【0021】触媒の使用量はサリチル酸エステル類に対
して0.05〜200モル%好ましくは経済性を考慮し
て0.1〜100モル%の範囲である。The amount of the catalyst to be used is in the range of 0.05 to 200 mol%, preferably 0.1 to 100 mol%, based on salicylic acid esters in view of economy.
【0022】反応温度は0〜180℃の範囲で、好まし
くは5〜80℃の範囲であり、さらに好ましくは10〜
40℃である。反応時間は通常1〜120時間である。The reaction temperature ranges from 0 to 180 ° C., preferably from 5 to 80 ° C., more preferably from 10 to 180 ° C.
40 ° C. The reaction time is usually 1 to 120 hours.
【0023】サリチル酸エステル類とα−メチルベンジ
ルハライド類の反応は必要により溶剤を使用してもよ
い。この溶剤としては反応に不活性なもの例えば1,2
−ジクロロエタン、1,1,2−トリクロロエタン等の
ハロゲン化炭化水素類、酢酸、プロピオン酸等の有機酸
類が使用できる。これらの溶剤を使用する場合原料に対
して経済性を考慮すれば30(容量/重量)倍以下が望
ましい。In the reaction between salicylic esters and α-methylbenzyl halides, a solvent may be used if necessary. As the solvent, those inert to the reaction, for example, 1,2
Halogenated hydrocarbons such as dichloroethane and 1,1,2-trichloroethane, and organic acids such as acetic acid and propionic acid can be used. When these solvents are used, the ratio is preferably 30 (volume / weight) or less in consideration of the economical efficiency of the raw material.
【0024】この発明でサリチル酸エステル類とα−メ
チルベンジルハライド類とを反応させる一般的な方法は
前記一般式(I)に示すサリチル酸エステル類と前記式
(II)に示すα−メチルベンジルハライド類および触媒
を所定量一括して仕込み、そのまま所定の温度で反応さ
せるか、あるいはサリチル酸エステル類と触媒を装入後
α−メチルベンジルハライド類を滴下しながら反応させ
る。In the present invention, a general method for reacting a salicylic acid ester with an α-methylbenzyl halide is as follows: a salicylic acid ester represented by the aforementioned general formula (I) and an α-methylbenzyl halide represented by the aforementioned formula (II) And a predetermined amount of the catalyst are charged at once and reacted at a predetermined temperature as it is, or after adding the salicylic acid ester and the catalyst, reacting while dropping α-methylbenzyl halides.
【0025】この反応の終点は高速液体クロマトグラフ
ィーにより原料であるサリチル酸エステル類、α−メチ
ルベンジルハライド類の減少を見ながら決定することが
できる。The end point of this reaction can be determined while observing the reduction of salicylic acid esters and α-methylbenzyl halides as raw materials by high performance liquid chromatography.
【0026】加水分解は酸またはアルカリ水溶液による
通常の方法が用いられる。すなわち酸による加水分解で
は、塩酸、硫酸等の鉱酸類、硫酸と酢酸の併用、ベンゼ
ンスルホン酸、p−トルエンスルホン酸、クロロベンゼ
ンスルホン酸、メタンスルホン酸のような有機スルホン
酸類、塩化アルミニウム、塩化亜鉛、塩化第二錫のよう
なルイス酸、さらにはトリフルオロメタンスルホン酸、
Nafion Hのような超強酸類と水により実施され
る。For the hydrolysis, a usual method using an acid or alkali aqueous solution is used. That is, in the hydrolysis with an acid, mineral acids such as hydrochloric acid and sulfuric acid, a combined use of sulfuric acid and acetic acid, organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, chlorobenzenesulfonic acid, and methanesulfonic acid, aluminum chloride, and zinc chloride. , A Lewis acid such as stannic chloride, and even trifluoromethanesulfonic acid,
It is carried out with super strong acids such as Nafion H and water.
【0027】アルカリによる加水分解では苛性ソーダ、
苛性カリウムと水による方法が一般的である。In the hydrolysis with alkali, caustic soda,
The method using caustic potassium and water is common.
【0028】酸またはアルカリと水の割合は任意の割合
で選択できるが、通常1:100〜99:1、好ましく
は5:95〜95:5(重量比)の範囲である。The ratio of acid or alkali to water can be selected at an arbitrary ratio, but is usually in the range of 1: 100 to 99: 1, preferably 5:95 to 95: 5 (weight ratio).
【0029】加水分解における酸またはアルカリの使用
量は、使用原料のサリチル酸エステルに対して任意の割
合で行なえる。通常は酸の強度により0.05〜30倍
モルの範囲で行なう。アルカリの場合は当量以上〜30
倍モルの範囲である。The amount of the acid or alkali used in the hydrolysis can be determined in any ratio with respect to the salicylate used as the raw material. Usually, it is carried out in the range of 0.05 to 30 times mol depending on the strength of the acid. In the case of an alkali, the equivalent is 30 or more.
The range is twice as high.
【0030】反応温度は50〜200℃の範囲、好まし
くは80〜160℃の範囲である。The reaction temperature ranges from 50 to 200 ° C., preferably from 80 to 160 ° C.
【0031】反応時間は1〜50時間の範囲である。The reaction time ranges from 1 to 50 hours.
【0032】反応時間を短縮する目的で四級アンモニウ
ム塩、四級ホスホニウム塩、クラウンエーテル、クリプ
テート、ポリエチレングリコール類等の相間移動触媒を
反応促進剤として加えてもよい。For the purpose of shortening the reaction time, a phase transfer catalyst such as a quaternary ammonium salt, a quaternary phosphonium salt, crown ether, cryptate or polyethylene glycol may be added as a reaction accelerator.
【0033】またこの加水分解反応では、通常有機溶剤
を使用しないで行なうが、有機溶剤を使用してもよい。
この溶剤としてはN−メチルホルムアミド、N,N−ジ
メチルホルムアミド、N,N−ジメチルアセトアミド、
ジメチルスルホキシド、スルホラン、1,3−ジメチル
−2−イミダゾリジノン、N−メチルピロリドン、ヘキ
サメチルホスホトリアミド等の非プロトン性極性溶剤、
エチレングリコール、ポリエチレングリコールジアルキ
ルエーテル、2−メトキシエタノール、2−エトキシエ
タノール等のグリコール類が使用でき、さらにトルエ
ン、キシレン、モノクロロベンゼン、1,2−ジクロロ
エタン、1,1,2−トリクロロエタン等の水と混和し
ない溶剤も使用できる。この溶剤の使用量は、原料に対
し0.5〜10(容量/重量)倍で十分である。The hydrolysis reaction is usually carried out without using an organic solvent, but an organic solvent may be used.
Examples of the solvent include N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide,
Aprotic polar solvents such as dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, and hexamethylphosphotriamide;
Glycols such as ethylene glycol, polyethylene glycol dialkyl ether, 2-methoxyethanol and 2-ethoxyethanol can be used, and water such as toluene, xylene, monochlorobenzene, 1,2-dichloroethane and 1,1,2-trichloroethane can be used. Immiscible solvents can also be used. The amount of the solvent used is sufficient to be 0.5 to 10 (volume / weight) times the amount of the raw material.
【0034】このようにして得られる加水分解物中の反
応生成物の組成は、3,5−ジ(α−メチルベンジル)
サリチル酸誘導体が60〜90重量%、3または5−
(α−メチルベンジル)サリチル酸誘導体(モノ置換サ
リチル酸誘導体と略記する)が0〜40重量%、3,5
−ジ(α−メチルベンジル)サリチル酸誘導体にさらに
はα−メチルベンジル基が反応したサリチル酸化合物
(トリ置換サリチル酸誘導体と略記する)が0〜40重
量%でこれらが全体で95重量%以上を構成し、残余は
芳香族サリチル酸樹脂、α−メチルベンジルハライド類
のオリゴマーである。加水分解はほぼ定量的に行なわれ
るので、加水分解前のエステルの形の各成分の割合もほ
ぼ同様と考えられる。The composition of the reaction product in the hydrolyzate thus obtained is 3,5-di (α-methylbenzyl)
60-90% by weight of salicylic acid derivative, 3 or 5-
0 to 40% by weight of (α-methylbenzyl) salicylic acid derivative (abbreviated as mono-substituted salicylic acid derivative)
0 to 40% by weight of a salicylic acid compound (abbreviated as a tri-substituted salicylic acid derivative) obtained by reacting a di (α-methylbenzyl) salicylic acid derivative with an α-methylbenzyl group, and these constitute 95% by weight or more in total. The remainder is an aromatic salicylic acid resin and oligomers of α-methylbenzyl halides. Since the hydrolysis is performed almost quantitatively, it is considered that the proportion of each component in the form of the ester before hydrolysis is almost the same.
【0035】3,5−ジ(α−メチルベンジル)サリチ
ル酸誘導体を主成分とし、モノおよび/またはトリ置換
サリチル酸誘導体が含まれることもある前記物質を、こ
の発明でα−メチルベンジル置換サリチル酸誘導体組成
物という。According to the present invention, the substance containing a 3,5-di (α-methylbenzyl) salicylic acid derivative as a main component and sometimes containing a mono- and / or tri-substituted salicylic acid derivative is used in the present invention. Things.
【0036】高純度(99%以上)の3,5−ジ(α−
メチルベンジル)サリチル酸誘導体を得るには、前記加
水分解前の反応生成物から3,5−ジ(α−メチルベン
ジル)サリチル酸エステルを真空蒸留によって分離し、
これを加水分解する。High-purity (99% or more) 3,5-di (α-
To obtain a methylbenzyl) salicylic acid derivative, 3,5-di (α-methylbenzyl) salicylate is separated from the reaction product before the hydrolysis by vacuum distillation,
This is hydrolyzed.
【0037】このような製造方法は、従来から知られて
いるフェノールから誘導する方法に比べ安価であり、ま
た、サリチル酸エステル類とスチレン類から製造する方
法に比べて高い選択性を持つため工業的に製造する上で
極めて有利である。Such a production method is inexpensive as compared with a conventionally known method derived from phenol, and has a high selectivity as compared with a method produced from salicylic esters and styrenes. This is extremely advantageous in producing the same.
【0038】本発明の方法で原料のサリチル酸エステル
類の代わりにサリチル酸を使用した場合、電子吸引性基
のカルボキシル基があるため、反応性が低くなり、本発
明の場合より高温で反応させなければならず、このよう
な条件下ではジ置換サリチル酸誘導体の選択率は40〜
50%である。When salicylic acid is used in place of salicylic acid esters in the method of the present invention, the reactivity becomes low due to the presence of a carboxyl group of an electron-withdrawing group. However, under such conditions, the selectivity of the di-substituted salicylic acid derivative is 40 to 40.
50%.
【0039】加水分解反応終了後反応液から反応生成物
を得るには反応液を中和後結晶が析出している場合は結
晶として単離する。もし溶剤を使用し溶解状態にある場
合は溶剤を留去するか、あるいはそのまま水に排出し結
晶として取り出すことができる。In order to obtain a reaction product from the reaction solution after the completion of the hydrolysis reaction, the reaction solution is neutralized and, if crystals are precipitated, isolated as crystals. If a solvent is used and it is in a dissolved state, the solvent can be distilled off, or it can be directly discharged into water and taken out as crystals.
【0040】また場合によっては適当な溶剤の再結晶を
行ない結晶を得ることができる。反応の進行や単離品の
純度は高速液体クロマトグラフィーによる分析で決定で
きる。In some cases, recrystallization of an appropriate solvent can be performed to obtain crystals. The progress of the reaction and the purity of the isolated product can be determined by high-performance liquid chromatography analysis.
【0041】次に、3,5−ジ(α−メチルベンジル)
サリチル酸誘導体およびα−メチルベンジル置換サリチ
ル酸誘導体組成物(両者を総称して以下単にサリチル酸
化合物とする。)の多価金属化物の製法について述べ
る。Next, 3,5-di (α-methylbenzyl)
A method for producing a polyvalent metal compound of a salicylic acid derivative and an α-methylbenzyl-substituted salicylic acid derivative composition (both will be simply referred to as a salicylic acid compound hereinafter) will be described.
【0042】多価金属化物はサリチル酸化合物のアルカ
リ金属塩と水溶性多価金属塩とを、水または双方可溶な
溶剤中で反応させて製造する。The polyvalent metal compound is produced by reacting an alkali metal salt of a salicylic acid compound with a water-soluble polyvalent metal salt in water or a solvent in which both are soluble.
【0043】すなわち、サリチル酸化合物中のカルボキ
シル基に対して当量以上のアルカリ金属の水酸化物、炭
酸塩またはアルコキシドを含有するその水溶液、アルコ
ール溶液あるいは水−アルコール溶液中にサリチル酸化
合物を分散させて、0〜100℃の温度条件下に溶解さ
せ、この溶解液に水溶性多価金属塩をそのまま、または
水溶液、アルコール溶液もしくは水−アルコール溶液と
して0〜100℃において添加反応せしめることにより
沈殿としてサリチル酸化合物の多価金属塩を得る。サリ
チル酸化合物中のカルボキシル基に対して約0.5〜1
当量の水溶性多価金属塩を反応させることが望ましい。That is, the salicylic acid compound is dispersed in an aqueous solution, an alcohol solution or a water-alcohol solution containing a hydroxide, carbonate or alkoxide of an alkali metal in an amount equivalent to or more than the carboxyl group in the salicylic acid compound, The salicylic acid compound is dissolved as a precipitate by dissolving under water temperature conditions of 0 to 100 ° C and adding and reacting the water-soluble polyvalent metal salt as it is or as an aqueous solution, alcohol solution or water-alcohol solution at 0 to 100 ° C. To obtain a polyvalent metal salt of About 0.5 to 1 based on the carboxyl group in the salicylic acid compound
It is desirable to react an equivalent amount of a water-soluble polyvalent metal salt.
【0044】本発明で用いる金属化物の金属としては、
リチウム、ナトリウム、カリウム等のアルカリ金属類を
除く金属を包含するが、好ましい多価金属としては、カ
ルシウム、マグネシム、、アルミニウム、銅、亜鉛、ス
ズ、バリウム、コバルトおよびニッケル等が挙げられ
る。これらのうち、亜鉛が特に有効である。The metal of the metal used in the present invention includes
Including metals excluding alkali metals such as lithium, sodium, potassium, etc., preferred polyvalent metals include calcium, magnesium, aluminum, copper, zinc, tin, barium, cobalt, nickel and the like. Of these, zinc is particularly effective.
【0045】以上説明した方法により得られるサリチル
酸化合物の多価金属化物は、顕色剤として優れた特性を
もつものである。該金属化合物を顕色剤として用いるに
は、例えばサンドグラインディングミルのような粉砕機
によって粉砕し、適当な粒度にして用いるとよい。実際
に使用するには、さらに該顕色剤を溶剤に懸濁させる
か、溶解させて所望の形態にして用いればよく、既知の
顕色剤との併用、すなわち活性白土のような無機固体
酸、フェノール−ホルムアルデヒド樹脂のような有機重
合体または他の芳香族カルボン酸金属塩等との併用も可
能であり、さらに亜鉛、マグネシウム、アルミニウム、
鉛、チタン、カルシウム、コバルト、ニッケル、マンガ
ンおよびバリウムからなる群から選ばれた多価金属の酸
化物、水酸化物または炭酸塩の少なくとも1種とを併用
してもよい。The polyvalent metalated salicylic acid compound obtained by the above-described method has excellent properties as a color developer. In order to use the metal compound as a color developer, the metal compound may be pulverized with a pulverizer such as a sand grinding mill to have an appropriate particle size. For actual use, the developer may be further suspended or dissolved in a solvent and used in a desired form, and used in combination with a known developer, that is, an inorganic solid acid such as activated clay. Can be used in combination with an organic polymer such as a phenol-formaldehyde resin or other metal salts of aromatic carboxylic acids, and further, zinc, magnesium, aluminum,
It may be used in combination with at least one of oxides, hydroxides and carbonates of polyvalent metals selected from the group consisting of lead, titanium, calcium, cobalt, nickel, manganese and barium.
【0046】本発明の顕色剤により感圧複写紙用顕色シ
ートを調製する方法としては、(1)該金属化物の水性
懸濁液を用いて水性塗料を調製し紙等の支持体に塗布す
る方法、(2)抄紙時に該金属化物を漉き込む方法、
(3)該金属化物を有機溶剤に溶解または懸濁したもの
を用いて塗料を調製し支持体に塗布する方法等のいずれ
も使用できる。The method for preparing a color developing sheet for pressure-sensitive copying paper using the color developing agent of the present invention is as follows: (1) A water-based coating is prepared by using the aqueous suspension of the metallized product and is applied to a support such as paper. A method of coating, (2) a method of shaping the metallized material during papermaking,
(3) A method in which a coating material is prepared by dissolving or suspending the metalized product in an organic solvent and applied to a support can be used.
【0047】塗工により紙等の支持体上に顕色剤層を形
成するには、顕色剤は適当な粘度、塗工適性を有してい
ることが望ましく、前記のように水性懸濁液としたり、
溶剤に溶解または懸濁させた後さらにカオリン粘土類、
炭酸カルシウム、澱粉、合成または天然ラッテックス等
を配合して適当な粘度、塗工適性に調整し塗料として用
いる。該塗料において顕色剤成分が占める割合は全固型
分中の10〜70%が望ましく、顕色剤の成分の割合が
10%未満では十分な発色性を発揮し得ず、また70%
を超えると顕色シートの紙面特性が低下する。塗料の塗
布量は乾燥重量で0.5g/m2 以上、好ましくは1〜
10g/m2 である。In order to form a color developer layer on a support such as paper by coating, it is desirable that the color developer has appropriate viscosity and coating suitability. Liquid,
After dissolved or suspended in a solvent, kaolin clays,
Calcium carbonate, starch, synthetic or natural latex, etc. are blended to adjust to appropriate viscosity and coating suitability, and used as a paint. The ratio of the developer component in the paint is desirably 10 to 70% of the total solid content. If the ratio of the developer component is less than 10%, sufficient color developability cannot be exhibited.
If it exceeds, the paper surface characteristics of the color developing sheet will deteriorate. The coating amount of the paint is 0.5 g / m 2 or more by dry weight, preferably 1 to
10 g / m 2 .
【0048】[0048]
【実施例】以下、本発明を実施例により詳細に説明す
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.
【0049】各実施例および比較例で得られた生成物を
顕色剤として用いた感圧複写紙顕色シートの作成および
その顕色シートの性能測定法を以下に述べる。性能測定
結果は一括して表1および表2に示した。The preparation of a pressure-sensitive copying paper color development sheet using the products obtained in each of the examples and comparative examples as a color developer and a method for measuring the performance of the color development sheet are described below. The performance measurement results are collectively shown in Tables 1 and 2.
【0050】1.顕色シートの作成 後述する実施例2,5〜8で得られたサリチル酸化合物
の金属化物を顕色剤として用い、下記組成にてサンドグ
ラインディングミルで分散させて懸濁液を調製した。1. Preparation of a Developing Sheet A metal suspension of a salicylic acid compound obtained in Examples 2, 5 to 8 described later was used as a developing agent, and was dispersed by a sand grinding mill with the following composition to prepare a suspension.
【0051】 顕色剤 6重量部 ポリビニルアルコール(クラレ#117)10%水溶液 3重量部 水 22.5重量部 次に該懸濁液を用いて下記組成の塗料を調製した。Developer 6 parts by weight Polyvinyl alcohol (Kuraray # 117) 10% aqueous solution 3 parts by weight Water 22.5 parts by weight Next, a coating material having the following composition was prepared using the suspension.
【0052】 懸濁液 10重量部 軽質炭酸カルシウム 10重量部 澱粉 0.8重量部 合成ゴムラテックス 0.8重量部 水 32.5重量部 これらの塗料を上質紙に乾燥時塗布量が5.0〜5.5
g/m2 となるように塗布乾燥し、顕色シートを得た。Suspension 10 parts by weight Light calcium carbonate 10 parts by weight Starch 0.8 parts by weight Synthetic rubber latex 0.8 parts by weight Water 32.5 parts by weight The amount of these paints applied to high quality paper when dried is 5.0. ~ 5.5
g / m 2 and dried to obtain a color developing sheet.
【0053】2.発色速度および濃度(5℃、60%R
Hおよび20℃、65%RHの恒温恒湿室内で実施) クリスタルバイオレットラクトン(CVL)をおもな感
圧色素とする市販の青発色用上紙(十條製紙製NW−4
0T)を用い、水性塗料を塗布した顕色シート(下用
紙)との両塗布面を対向させて重ね合わせ、電子タイプ
ライターで打圧発色させる。2. Coloring speed and density (5 ° C, 60% R
H and 20 ° C., 65% RH in a constant-temperature and constant-humidity chamber) Commercially available blue-colored paper using crystal violet lactone (CVL) as the main pressure-sensitive dye (NJ-4 manufactured by Jujo Paper)
0T), the coated surface and the developing sheet (lower paper) coated with the water-based paint are superposed on each other, and the color is applied with an electronic typewriter.
【0054】打刻1分30秒後、および24時間後の2
点について測色しY値で表示する。1 minute and 30 seconds after embossing and 2 hours after 24 hours
The points are measured and displayed as Y values.
【0055】3.発色像の耐光堅牢度 2の方法で発色させた顕色シートをカーボンアークフェ
ードメーター(スガ試験機製)に、2時間(および4時
間)暴露し照射後の反射率をΣ−80色差計を用いて測
定しY値で表示した。3. Lightfastness of Colored Image The developed sheet developed by the method of 2 was exposed to a carbon arc fade meter (manufactured by Suga Test Instruments) for 2 hours (and 4 hours), and the reflectance after irradiation was measured using a Σ-80 color difference meter. And measured and indicated by Y value.
【0056】Y値が低く、かつ試験前値との差が小さい
ほど光による褪色が少なく好ましい。The lower the Y value and the smaller the difference from the pre-test value, the less the discoloration due to light, and thus the more preferable.
【0057】4.耐可塑剤性 ジオクチルフタレート(DOP)を芯物質とする平均粒
子径5.0μのメラミン・ホルムアルデヒド樹脂膜マイ
クロカプセルを調製し、少量の液状澱粉系バインダーを
加えて塗液とし、エアナイフコーターで上質紙上に乾燥
塗布量が5g/m2 となるよう塗布乾燥させDOPマイ
クロカプセル塗布紙とする。該DOPマイクロカプセル
塗布紙と2で発色させた顕色シートの発色面を対向させ
たのち100kg/cmの線圧を有するスーパーカレン
ダーロールを通過させ、発色面にDOPを均一に浸透さ
せる。4. Plasticizer resistance A melamine / formaldehyde resin film microcapsule having an average particle diameter of 5.0 μm using dioctyl phthalate (DOP) as a core substance is prepared, and a small amount of a liquid starch-based binder is added to form a coating liquid, which is then coated on a high-quality paper with an air knife coater. The coated DOP microcapsule is coated and dried so that the dry coating amount is 5 g / m 2 . After making the color-developing surface of the color-developing sheet colored with the DOP microcapsule-coated paper 2 face, the DOP microcapsule is passed through a super calender roll having a linear pressure of 100 kg / cm to uniformly penetrate the color-developing surface.
【0058】1時間後の反射率をΣ−80色差計を用い
て測定しY値で表示する。Y値が低くかつ試験前値との
差が小さいほど発色像の可塑剤耐性が良好であることを
意味する。The reflectance after one hour is measured using a Σ-80 color difference meter, and is displayed as a Y value. The lower the Y value and the smaller the difference from the value before the test, the better the plasticizer resistance of the color image.
【0059】5.発色像の耐水性 2の方法で発色させた顕色シートを水中に2時間浸漬
し、発色像の濃度変化を肉眼で観察した。5. Water resistance of the color-developed image The color-developed sheet developed by the method of 2 was immersed in water for 2 hours, and the density change of the color-developed image was visually observed.
【0060】6.顕色シートの黄変性 (6−1)NOxによる黄変 JIS L−1055〔染色物および染料の酸化窒素ガ
ス堅牢度試験方法〕に基づき、顕色シートをNaNO2
(亜硝酸ナトリウム)とH3 PO4 (リン酸)との反応
により発生するNOxガス雰囲気の密閉容器中に1時間
保存して、黄変の程度を調べる。6. Yellowing of Developed Sheet (6-1) Yellowing by NO x Based on JIS L-1055 [Testing method for nitrogen oxide gas fastness of dyed materials and dyes], the developed sheet was made of NaNO 2
(Sodium nitrite) and H 3 PO 4 (phosphoric acid) are stored for 1 hour in a closed container in an atmosphere of NO x gas generated by the reaction, and the degree of yellowing is examined.
【0061】保存終了後、1時間目にΣ−80色差計を
用いWB値で表示する。WB値が大きく、かつNOxガ
スに曝されていないシート(表2には未試験シートと表
示)のWB値との差が小さいほどNOx雰囲気下での黄
変性が少ないことを意味する。At the end of the first hour after storage, the data is displayed as a WB value using a Σ-80 color difference meter. WB value is large and NO (Table 2 displays untested sheet) sheet which is not exposed to x gas means that yellowing in NO x atmosphere smaller the difference between the WB value of is small.
【0062】(6−2)光による黄変 顕色シートをカーボンアークフェードメーター(スガ試
験機製)に4時間照射し、照射後Σ−80色差計を用い
WB値で表示する。WB値が大きく、かつ未照射シート
(表1には未試験シートと表示)のWB値との差が小さ
いほど光照射による黄変性が小さいことを意味する。(6-2) Yellowing due to light The developed sheet is irradiated with a carbon arc fade meter (manufactured by Suga Test Instruments) for 4 hours, and after irradiation, the sheet is indicated by WB value using a Σ-80 color difference meter. The smaller the difference between the WB value and the WB value of the unirradiated sheet (indicated as an untested sheet in Table 1), the smaller the yellowing due to light irradiation.
【0063】実施例−1 152.2g(1モル)のサリチル酸メチル、281.
2g(2モル)の1−クロロエチルベンゼンおよび3g
のトリフルオロメタンスルホン酸をフラスコに仕込んで
室温(20℃)で5日間反応させた。Example-1 152.2 g (1 mol) of methyl salicylate, 281.
2 g (2 mol) of 1-chloroethylbenzene and 3 g
Of trifluoromethanesulfonic acid was charged into a flask and reacted at room temperature (20 ° C.) for 5 days.
【0064】反応終了後トルエン1500mlを装入し
溶解させ、次いで水100mlを加え、60〜70℃で
0.5時間攪拌を行ない、液が有機層と水層(下層)の
2層に分離するまで静置し下層の水層を除いた後、有機
層より溶媒を留去した。残留物の高速液体クロマトグラ
フィー(HLC)による測定の結果、モノ置換サリチル
酸メチル3%、ジ置換サリチル酸メチル89.5%、ト
リ置換サリチル酸メチル7.5%であった。次いで1〜
3mmHgで真空蒸留を行ない、213〜218℃の留
分を採取し3,5−ジ(α−メチルベンジル)サリチル
酸メチル291g(収率81%)を得た。After the completion of the reaction, 1500 ml of toluene is charged and dissolved, then 100 ml of water is added, and the mixture is stirred at 60 to 70 ° C. for 0.5 hour to separate the liquid into an organic layer and an aqueous layer (lower layer). After standing still to remove the lower aqueous layer, the solvent was distilled off from the organic layer. As a result of measurement of the residue by high performance liquid chromatography (HLC), it was found that monosubstituted methyl salicylate was 3%, disubstituted methyl salicylate was 89.5%, and trisubstituted methyl salicylate was 7.5%. Then 1 ~
Vacuum distillation was performed at 3 mmHg, and a fraction at 213 to 218 ° C was collected to obtain 291 g (yield 81%) of methyl 3,5-di (α-methylbenzyl) salicylate.
【0065】次いで得られた3,5−ジ(α−メチルベ
ンジル)サリチル酸メチル90g(0.25モル)と4
0%苛性ソーダ水溶液28.9g(NaOH 0.27
5モル)を500mlのフラスコに装入し95〜105
℃の温度で3時間反応させ加水分解を終えた。その後水
430mlを装入し溶解させ、硫酸で中和し、濾過、水
洗、乾燥して純度99%以上の3,5−ジ(α−メチル
ベンジル)サリチル酸84.7g(収率98%)を得
た。Then, 90 g (0.25 mol) of the obtained methyl 3,5-di (α-methylbenzyl) salicylate and 4
28.9 g of a 0% aqueous sodium hydroxide solution (NaOH 0.27
5 mol) into a 500 ml flask and add 95-105
The reaction was carried out at a temperature of ° C. for 3 hours to complete the hydrolysis. Thereafter, 430 ml of water was charged and dissolved, neutralized with sulfuric acid, filtered, washed with water, and dried to obtain 84.7 g (yield 98%) of 3,5-di (α-methylbenzyl) salicylic acid having a purity of 99% or more. Obtained.
【0066】融点147〜150℃Melting point: 147 to 150 ° C.
【0067】[0067]
【表1】 H−N R(DMS −d6) 1.6(m,6H),4.1(m,1H),4.6
(m,1H) 7.1〜7.3(m,1H),7.65(m,1H) 9.4(Br,1H),10.5(s,1H) MS:m/z=346(M+) なお、HLCによる測定結果を図1に示した。[Table 1] H-NR (DMS-d6) 1.6 (m, 6H), 4.1 (m, 1H), 4.6
(M, 1H) 7.1-7.3 (m, 1H), 7.65 (m, 1H) 9.4 (Br, 1H), 10.5 (s, 1H) MS: m / z = 346 (M + ) The measurement results by HLC are shown in FIG.
【0068】測定条件は次の通りである。The measurement conditions are as follows.
【0069】機種 : LIQIOD CHOROMATOGRAPH
LC-3A(島津) カラム : YMC−Pack AM−312 移動層 : アセトニトリル/MeOH/水/トリ
フロロ酢酸 =725ml/100ml/175ml/0.5g 流速 : 1ml/min. 検出器 : SPD−2A(UV−254nm) 波形処理 : 機種 島津クロマトパック C−R3
A 実施例−2 実施例−1で得られた3,5−ジ(α−メチルベンジ
ル)サリチル酸69.2g(0.2モル)を95%苛性
ソーダ8.8g(0.21モル)を水500gに溶解さ
せたアルカリ水溶液に装入し溶解させた。この水溶液
を、予め7水和物の硫酸亜鉛31.6gを水300ml
に溶解させた水溶液中に1時間かけて滴下し、1時間熟
成した後濾過、水洗、乾燥して3,5−ジ(α−メチル
ベンジル)サリチル酸亜鉛塩70g得た。Model: LIQIOD CHOROMATOGRAPH
LC-3A (Shimadzu) Column: YMC-Pack AM-312 Moving layer: acetonitrile / MeOH / water / trifluoroacetic acid = 725 ml / 100 ml / 175 ml / 0.5 g Flow rate: 1 ml / min. Detector: SPD-2A (UV-254nm) Waveform processing: Model Shimadzu Chromatopack C-R3
A Example-2 69.2 g (0.2 mol) of 3,5-di (α-methylbenzyl) salicylic acid obtained in Example-1 was added to 8.8 g (0.21 mol) of 95% caustic soda and 500 g of water. And dissolved in an alkaline aqueous solution dissolved therein. This aqueous solution was previously mixed with 31.6 g of zinc sulfate of heptahydrate in 300 ml of water.
The solution was added dropwise over 1 hour to the aqueous solution dissolved in the above, aged for 1 hour, filtered, washed with water and dried to obtain 70 g of zinc 3,5-di (α-methylbenzyl) salicylate.
【0070】実施例−3 190.3g(1.25モル)のサリチル酸メチルおよ
び予め塩化亜鉛5gを濃塩酸2gに溶解させて調製した
酸触媒をフラスコに仕込んだ後、35℃に昇温し、同温
度で1−クロロエチルベンゼン404.3g(2.87
モル)を2時間かけて滴下する。滴下終了後同温度で2
0時間熟成した。その後トルエン750mlを装入し溶
解させ、次いで水150mlを加え60〜70℃で0.
5時間攪拌を行ない、液が有機層と水層(下層)の2層
に分離するまで静置し下層の水層を除いた後、有機層よ
り溶媒を留去した。残留物のHLCによる測定の結果、
モノ置換サリチル酸メチル2.9%、ジ置換サリチル酸
メチル80%、トリ置換サリチル酸メチル11.2%で
あった。次いで1〜3mmHgで真空蒸留を行ない、2
13〜218℃の留分を採取し、3,5−ジ(α−メチ
ルベンジル)サリチル酸メチル338g(収率75%)
を得た。その後実施例−1と同様に40%苛性ソーダ水
溶液により加水分解を行ない、純度99%の3,5−ジ
(α−メチルベンジル)サリチル酸318g(収率98
%)を得た。Example 3 An acid catalyst prepared by dissolving 190.3 g (1.25 mol) of methyl salicylate and 5 g of zinc chloride in 2 g of concentrated hydrochloric acid was charged into a flask, and then heated to 35 ° C. At the same temperature, 404.3 g (2.87) of 1-chloroethylbenzene
Mol) is added dropwise over 2 hours. After dropping, at the same temperature 2
Aged for 0 hours. Thereafter, 750 ml of toluene was charged and dissolved, and then 150 ml of water was added and the mixture was dissolved at 60 to 70 ° C. and dissolved in 0.1 ml.
After stirring for 5 hours, the solution was allowed to stand until the liquid was separated into two layers, an organic layer and an aqueous layer (lower layer). After removing the lower aqueous layer, the solvent was distilled off from the organic layer. As a result of measurement of the residue by HLC,
2.9% of mono-substituted methyl salicylate, 80% of di-substituted methyl salicylate and 11.2% of tri-substituted methyl salicylate. Then, vacuum distillation is performed at 1-3 mmHg, and 2
A fraction at 13 to 218 ° C. is collected, and 338 g of methyl 3,5-di (α-methylbenzyl) salicylate (75% yield)
I got Thereafter, hydrolysis was carried out using a 40% aqueous solution of sodium hydroxide in the same manner as in Example 1 to give 318 g of 3,5-di (α-methylbenzyl) salicylic acid having a purity of 99% (yield 98%).
%).
【0071】実施例−4 16.6g(0.1モル)のサリチル酸エチル、33.
8g(0.24モル)の1−クロロエチルベンゼンおよ
び0.3gのトリフルオロメタンスルホン酸をフラスコ
に仕込み、20℃で30時間反応させた。反応終了後ト
ルエン150mlを装入し溶解させ、次いで水50ml
を加え60〜70℃で0.5時間攪拌を行ない、液が有
機層と水層の2層に分離するまで静置し下層の水層を除
いた後、実施例−1と同様に有機層より溶媒を留去し
た。残留物のHLCによる測定の結果、サリチル酸エチ
ル6%、モノ置換サリチル酸エチル4.5%、ジ置換サ
リチル酸エチル76.8%、トリ置換サリチル酸エチル
12.7%であった。次いで真空蒸留により3,5−ジ
(α−メチルベンジル)サリチル酸エチル26.2g
(収率70%)を得、その後40%苛性ソーダにより加
水分解を行ない、純度99%の3,5−ジ(α−メチル
ベンジル)サリチル酸23.7g(収率98%)を得
た。Example 4 16.6 g (0.1 mol) of ethyl salicylate;
8 g (0.24 mol) of 1-chloroethylbenzene and 0.3 g of trifluoromethanesulfonic acid were charged into a flask and reacted at 20 ° C. for 30 hours. After completion of the reaction, 150 ml of toluene is charged and dissolved, and then 50 ml of water is added.
And stirred at 60 to 70 ° C. for 0.5 hour. The solution was allowed to stand until the liquid was separated into two layers, an organic layer and an aqueous layer. After removing the lower aqueous layer, the organic layer was removed in the same manner as in Example-1. The solvent was distilled off. As a result of measurement of the residue by HLC, ethyl salicylate was 6%, mono-substituted ethyl salicylate was 4.5%, di-substituted ethyl salicylate was 76.8%, and tri-substituted ethyl salicylate was 12.7%. Then, 26.2 g of ethyl 3,5-di (α-methylbenzyl) salicylate was obtained by vacuum distillation.
(Yield 70%), and then hydrolyzed with 40% sodium hydroxide to obtain 23.7 g (98% yield) of 3,5-di (α-methylbenzyl) salicylic acid with a purity of 99%.
【0072】実施例−5 76.1g(0.5モル)のサリチル酸メチル、1.5
gの塩化第二スズ(SnCl2 )および154.6g
(1.1モル)の1−クロロエチルベンゼンをフラスコ
に仕込み、20〜25℃で5時間反応させた。その後7
0℃に昇温して温水200mlを装入し、さらに95〜
98℃に昇温し15%苛性ソーダ170gを2時間かけ
て滴下し、次いで98〜100℃で5時間熟成し加水分
解を終了した。加水分解物のHLCによる測定結果は、
サリチル酸2%、モノ置換サリチル酸13%、ジ置換サ
ルチル酸67%、トリ置換サリチル酸17%、他1%で
あった。その後水700mlを加えて希釈し、硫酸によ
りpH9に調節し、30℃で43%硫酸亜鉛水溶液18
0gを1時間かけて滴下し、1時間熟成し濾過、水洗、
乾燥してα−メチルベンジル置換サリチル酸組成物の亜
鉛塩200gを得た。 実施例−6 76.1g(0.5モル)のサリチル酸メチル、1gの
塩化アンチモン(SbCl5 )および147.6g
(1.05モル)の1−クロロエチルベンゼンをフラス
コに仕込み30〜35℃で8時間反応させた。その後7
0℃に昇温して温水200mlを装入しさらに95〜9
8℃に昇温し15%苛性ソーダ水溶液170gを2時間
かけて滴下し、次いで98〜100℃で5時間熟成し加
水分解を終了した。加水分解物のHLCによる測定結果
は、モノ置換サリチル酸12%、ジ置換サルチル酸68
%、トリ置換サリチル酸18%、他2%であった。その
後水700mlを加えて希釈し、硫酸によりpH9に調
節し、30℃で43%硫酸亜鉛水溶液180gを1時間
かけて滴下し、1時間熟成し濾過、水洗、乾燥してα−
メチルベンジル置換サリチル酸の亜鉛塩200gを得
た。Example-5 76.1 g (0.5 mol) of methyl salicylate, 1.5
g stannic chloride (SnCl 2 ) and 154.6 g
(1.1 mol) of 1-chloroethylbenzene was charged into a flask and reacted at 20 to 25 ° C. for 5 hours. Then 7
The temperature was raised to 0 ° C., and 200 ml of warm water was charged.
The temperature was raised to 98 ° C, 170 g of 15% caustic soda was added dropwise over 2 hours, and the mixture was aged at 98 to 100 ° C for 5 hours to complete the hydrolysis. The measurement result of the hydrolyzate by HLC is as follows:
Salicylic acid 2%, mono-substituted salicylic acid 13%, di-substituted salicylic acid 67%, tri-substituted salicylic acid 17%, and 1%. Thereafter, 700 ml of water was added to dilute the mixture, and the pH was adjusted to 9 with sulfuric acid.
0 g was dropped over 1 hour, aged for 1 hour, filtered, washed with water,
After drying, 200 g of a zinc salt of the α-methylbenzyl-substituted salicylic acid composition was obtained. Example -6 methyl salicylate 76.1 g (0.5 mol), 1 g of antimony chloride (SbCl 5) and 147.6g
(1.05 mol) of 1-chloroethylbenzene was charged into a flask and reacted at 30 to 35 ° C. for 8 hours. Then 7
The temperature was raised to 0 ° C, 200 ml of warm water was charged, and 95 to 9
The temperature was raised to 8 ° C., 170 g of a 15% aqueous solution of caustic soda was added dropwise over 2 hours, and the mixture was aged at 98 to 100 ° C. for 5 hours to complete the hydrolysis. The results of the HLC measurement of the hydrolyzate were as follows: monosubstituted salicylic acid 12%, disubstituted salicylic acid 68
%, Trisubstituted salicylic acid 18%, and other 2%. Thereafter, 700 ml of water was added to dilute the mixture, the pH was adjusted to 9 with sulfuric acid, 180 g of a 43% aqueous zinc sulfate solution was added dropwise at 30 ° C. over 1 hour, the mixture was aged for 1 hour, filtered, washed with water, and dried to obtain α-.
200 g of a zinc salt of methylbenzyl-substituted salicylic acid was obtained.
【0073】実施例−7 76.1g(0.5モル)のサリチル酸メチルおよび予
め塩化亜鉛2gを濃塩酸0.8gに溶解させ調製した酸
をフラスコに仕込んだ後35℃に昇温し、同温度で1−
クロロエチルベンゼン161.7g(1.15モル)を
2時間かけて滴下する。滴下終了後同温度で20時間反
応させた。その後70℃に昇温して温水200mlを装
入しさらに95〜98℃に昇温し15%苛性ソーダ水溶
液170gを2時間かけて滴下し、次いで98〜100
℃で5時間熟成し加水分解を終了した。加水分解物のH
LCによる測定結果は、モノ置換サリチル酸7%、ジ置
換サリチル酸80%、トリ置換サリチル酸13%であっ
た。その後水700mlを加えて希釈し、硫酸によりp
H9に調節し、30℃で43%硫酸亜鉛水溶液180g
を1時間かけて滴下し、1時間熟成し濾過、水洗、乾燥
してα−メチルベンジル置換サリチル酸の亜鉛塩200
gを得た。Example -7 76.1 g (0.5 mol) of methyl salicylate and an acid previously prepared by dissolving 2 g of zinc chloride in 0.8 g of concentrated hydrochloric acid were charged into a flask, and then heated to 35 ° C. 1- at temperature
Chloroethylbenzene 161.7 g (1.15 mol) is added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 20 hours. Thereafter, the temperature was raised to 70 ° C., 200 ml of warm water was charged, the temperature was further raised to 95 to 98 ° C., and 170 g of a 15% aqueous solution of caustic soda was added dropwise over 2 hours.
The hydrolysis was completed by aging at 5 ° C. for 5 hours. H of the hydrolyzate
As a result of measurement by LC, monosubstituted salicylic acid was 7%, disubstituted salicylic acid was 80%, and trisubstituted salicylic acid was 13%. Thereafter, 700 ml of water was added to dilute the mixture, and p
Adjusted to H9, 180 g of 43% aqueous zinc sulfate solution at 30 ° C
Was dropped over 1 hour, aged for 1 hour, filtered, washed with water and dried to obtain a zinc salt of α-methylbenzyl-substituted salicylic acid 200.
g was obtained.
【0074】実施例−8 76.1g(0.5モル)のサリチル酸メチル1.5g
のトリフルオロメタンスルホン酸、および154.6g
(1.1モル)の1−クロロエチルベンゼンをフラスコ
に仕込み20〜25℃で5日間反応させた。その後70
℃に昇温して温水200mlを装入しさらに95〜98
℃に昇温し15%苛性ソーダ水溶液170gを2時間か
けて滴下し、次いで98〜100℃で5時間熟成し加水
分解を終了した。加水分解物のHLCによる測定結果
は、ジ置換サリチル酸88%、トリ置換サリチル酸11
%、他1%であった(図2)。この図において、RT
8.427は3,5−(α−メチルベンジル)サルチル
酸である。その後水700mlを加えて希釈し、硫酸に
よりpH9に調節し、30℃で43%硫酸亜鉛水溶液1
80gを1時間かけて滴下し、1時間熟成し濾過、水
洗、乾燥して3,5−ジ(α−メチルベンジル)サリチ
ル酸の亜鉛塩200gを得た。Example-8 1.5 g of 76.1 g (0.5 mol) of methyl salicylate
Trifluoromethanesulfonic acid, and 154.6 g
(1.1 mol) of 1-chloroethylbenzene was charged into a flask and reacted at 20 to 25 ° C. for 5 days. Then 70
The temperature was raised to 200 ° C., and 200 ml of warm water was charged.
The temperature was raised to 70 ° C., 170 g of a 15% aqueous sodium hydroxide solution was added dropwise over 2 hours, and the mixture was aged at 98 to 100 ° C. for 5 hours to complete the hydrolysis. The result of measurement of the hydrolyzate by HLC was as follows: di-substituted salicylic acid 88%, tri-substituted salicylic acid 11
% And other 1% (FIG. 2). In this figure, RT
8.427 is 3,5- (α-methylbenzyl) salicylic acid. Thereafter, 700 ml of water was added to dilute the mixture, and the pH was adjusted to 9 with sulfuric acid.
80 g was added dropwise over 1 hour, aged for 1 hour, filtered, washed with water and dried to obtain 200 g of zinc salt of 3,5-di (α-methylbenzyl) salicylic acid.
【0075】比較例−1 76.1(0.5モル)のサリチル酸メチルおよび10
gのメタンスルホン酸をフラスコに仕込み60〜65℃
に温度を保ちながらスチレン140g(1.346モ
ル)を14時間かけて滴下する。滴下終了後、30分間
同温度にて熟成し得られた反応液を実施例−1と同様に
40%苛性ソーダ水溶液により加水分解を行なった。次
いで硫酸で中和し3,5−ジ(α−メチルベンジル)サ
リチル酸を含有する油状生成物を得た。Comparative Example 1 76.1 (0.5 mol) of methyl salicylate and 10
g of methanesulfonic acid into a flask at 60 to 65 ° C.
While maintaining the temperature at 140 g, styrene (140 g, 1.346 mol) is added dropwise over 14 hours. After completion of the dropwise addition, the reaction solution obtained by aging at the same temperature for 30 minutes was hydrolyzed with a 40% aqueous sodium hydroxide solution in the same manner as in Example-1. Then neutralized with sulfuric acid to obtain an oily product containing 3,5-di (α-methylbenzyl) salicylic acid.
【0076】HLCによる分析の結果は3,5−ジ(α
−メチルベンジル)サリチル酸の含有率は43.3%で
あった。これを図3に示す。図中RT8.437が3,
5−ジ(α−メチルベンジル)サリチル酸である。The result of the analysis by HLC was 3,5-di (α
The content of (-methylbenzyl) salicylic acid was 43.3%. This is shown in FIG. In the figure, RT8.437 is 3,
5-di (α-methylbenzyl) salicylic acid.
【0077】さらに実施例8と同様に亜塩化物化を試み
たが、ガム状およびブロック状になり、濾過、水洗、乾
燥は困難であった。Further, subchlorination was attempted in the same manner as in Example 8, but it turned into a gum and a block, and it was difficult to filter, wash and dry.
【0078】[0078]
【表2】 [Table 2]
【0079】[0079]
【表3】 [Table 3]
【0080】[0080]
【発明の効果】本発明の製造方法は3,5−ジ(α−メ
チルベンジル)サリチル酸誘導体を、安価な原料と簡単
な操作で得られるため、工業的に好適な方法といえる。The production method of the present invention can be said to be an industrially suitable method because a 3,5-di (α-methylbenzyl) salicylic acid derivative can be obtained with inexpensive raw materials and simple operations.
【0081】さらに本発明の方法で得られる3,5−ジ
(α−メチルベンジル)サリチル酸誘導体を主成分とす
るα−メチルベンジル置換サリチル酸誘導体組成物の多
価金属化物を用いた顕色シートにおいては、低温時の発
色性に優れるため、従来から問題となっていた寒冷地で
の使用に好適である。また、発色像の水に対する消失と
いう問題点も解消されるため、従来使用が制限されてい
た分野で安定して利用できる。Further, in a color developing sheet using a polyvalent metal compound of an α-methylbenzyl-substituted salicylic acid derivative composition containing a 3,5-di (α-methylbenzyl) salicylic acid derivative as a main component obtained by the method of the present invention. Is suitable for use in cold regions, which has conventionally been a problem, because of its excellent color development at low temperatures. Further, since the problem of disappearance of the color image in water is also solved, it can be stably used in the field where the use has been restricted in the past.
【図1】本発明の方法によって単離した3,5−ジ(α
−ジメチルベンジル)サリチル酸のHLCによる分析結
果の一例を示す。FIG. 1. 3,5-Di (α) isolated by the method of the present invention.
An example of the result of HLC analysis of -dimethylbenzyl) salicylic acid is shown.
【図2】本発明の方法により得られたα−メチルベンジ
ル置換サリチル酸誘導体組成物のHLCによる分析結果
の一例を示す。FIG. 2 shows an example of an HLC analysis result of the α-methylbenzyl-substituted salicylic acid derivative composition obtained by the method of the present invention.
【図3】従来の方法で得られた3,5−ジ(α−ジメチ
ルベンジル)サリチル酸含有油状物のHLCによる分析
結果の一例を示す。FIG. 3 shows an example of an HLC analysis result of a 3,5-di (α-dimethylbenzyl) salicylic acid-containing oil obtained by a conventional method.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特公 昭51−25174(JP,B2) (58)調査した分野(Int.Cl.7,DB名) C07C 65/105 B41M 5/155 B41M 5/30 C07C 51/09 CA(STN) REGISTRY(STN)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-B-51-25174 (JP, B2) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 65/105 B41M 5/155 B41M 5 / 30 C07C 51/09 CA (STN) REGISTRY (STN)
Claims (7)
ル基またはシクロアルキル基を示す)で表わされるサリ
チル酸エステル類1モルに対し、一般式(II) 【化2】 (式中、R2 ,R3 は水素原子または炭素数1〜4のア
ルキル基を示し、Xはハロゲン原子を示す)で表わされ
るα−メチルベンジルハライド類1.5〜3モルを酸触
媒の存在下で温度10℃〜40℃の範囲で反応させ、生
成する3,5−ジ(α−メチルベンジル)サリチル酸エ
ステルを加水分解することを特徴とする3,5−ジ(α
−メチルベンジル)サルチル酸誘導体の製造方法。1. A compound of the general formula (I) (Wherein R 1 represents an alkyl group, an aralkyl group or a cycloalkyl group having 1 to 12 carbon atoms) with respect to 1 mol of the salicylic acid ester represented by the general formula (II): (Wherein, R 2 and R 3 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom). 3,5-di (α-methylbenzyl) salicylate produced by reacting at a temperature of 10 ° C. to 40 ° C. in the presence of 3,5-di (α)
-Methylbenzyl) salicylic acid derivative production method.
により3,5−ジ(α−メチルベンジル)サリチル酸エ
ステル類を分離する請求項1記載の製造方法。2. The process according to claim 1, wherein before the hydrolysis, 3,5-di (α-methylbenzyl) salicylate is separated from the reaction solution by vacuum distillation.
ル基またはシクロアルキル基を示す)で表わされるサル
チル酸エステル類1モルに対し、一般式(II) 【化4】 (式中、R2 ,R3 は水素原子または炭素数1〜4のア
ルキル基を示し、Xはハロゲン原子を示す。)で表わさ
れるα−メチルベンジルハライド類1.5〜3モルを酸
触媒の存在下で温度10℃〜40℃の範囲で反応させ、
生成するα−メチルベンジル置換サリチル酸エステル誘
導体を加水分解して得られ、α−メチルベンジル基のモ
ノ置換サリチル酸誘導体が0〜15重量%の範囲、α−
メチルベンジル基のトリ置換サリチル酸誘導体が10〜
20重量%の範囲および3,5−ジ(α−メチルベンジ
ル)サリチル酸誘導体が60〜90重量%の範囲にあ
り、これらα−メチルベンジル置換サリチル酸誘導体が
全体として95重量%以上を構成することを特徴とする
顕色剤用組成物。3. A compound of the general formula (I) (Wherein R 1 represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group or a cycloalkyl group) with respect to 1 mol of the salicylates represented by the general formula (II): (Wherein, R 2 and R 3 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom.) 1.5 to 3 mol of α-methylbenzyl halides represented by the following formula: At a temperature in the range of 10C to 40C in the presence of
The resulting α-methylbenzyl-substituted salicylic acid ester derivative is obtained by hydrolyzing the mono-substituted salicylic acid derivative having an α-methylbenzyl group in the range of 0 to 15 % by weight.
10 to 10 tri-substituted salicylic acid derivatives of methylbenzyl group
20 % by weight and 3,5-di (α-methylbenzyl) salicylic acid derivative in the range of 60 to 90% by weight, and these α-methylbenzyl-substituted salicylic acid derivatives constitute 95% by weight or more as a whole. Characteristic composition for developer.
サリチル酸誘導体を含む組成物を多価金属塩と反応させ
て成るα−メチルベンジル基のモノ置換サリチル酸誘導
体多価金属化物が0〜15重量%の範囲、α−メチルベ
ンジル基のトリ置換サリチル酸誘導体多価金属化物が1
0〜20重量%の範囲および3,5−ジ(α−メチルベ
ンジル)サリチル酸誘導体の多価金属化物が60〜90
重量%の範囲にあり、これらα−メチルベンジル置換サ
リチル酸誘導体の多価金属化物が全体として95重量%
以上を構成することを特徴とする顕色剤用組成物。Claim 3 composition monosubstituted salicylic acid derivative polyvalent metal compound is 0-15 weight α- methylbenzyl made by reacting a polyvalent metal salt containing α- methylbenzyl-substituted salicylic acid derivative according % range, trisubstituted salicylic acid derivative polyvalent metal products of α- methylbenzyl group 1
In the range of 0 to 20 % by weight and 60 to 90% of the polyvalent metal compound of the 3,5-di (α-methylbenzyl) salicylic acid derivative.
% Of the polyvalent metallized product of the α-methylbenzyl-substituted salicylic acid derivative is 95% by weight as a whole.
A composition for a color developer comprising the above.
ジ(α−メチルベンジル)サリチル酸誘導体を多価金属
塩と反応させることを特徴とする3,5−ジ(α−メチ
ルベンジル)サリチル酸誘導体の多価金属化物の製造方
法。5. The method according to claim 2, wherein
A method for producing a polyvalent metalated 3,5-di (α-methylbenzyl) salicylic acid derivative, comprising reacting a di (α-methylbenzyl) salicylic acid derivative with a polyvalent metal salt.
として用いた顕色シート。6. A developer sheet using the developer composition according to claim 3 as a developer.
して用いた顕色シート。7. A color developing sheet using the polyvalent metal compound according to claim 4 as a color developer.
Priority Applications (1)
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---|---|---|---|
JP03178311A JP3107854B2 (en) | 1990-08-06 | 1991-07-18 | Process for producing 3,5-di (α-methylbenzyl) salicylic acid derivative and use of polyvalent metallized product as color developer |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20671190 | 1990-08-06 | ||
JP2-206711 | 1990-08-06 | ||
JP03178311A JP3107854B2 (en) | 1990-08-06 | 1991-07-18 | Process for producing 3,5-di (α-methylbenzyl) salicylic acid derivative and use of polyvalent metallized product as color developer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05998A JPH05998A (en) | 1993-01-08 |
JP3107854B2 true JP3107854B2 (en) | 2000-11-13 |
Family
ID=26498525
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Application Number | Title | Priority Date | Filing Date |
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JP03178311A Expired - Fee Related JP3107854B2 (en) | 1990-08-06 | 1991-07-18 | Process for producing 3,5-di (α-methylbenzyl) salicylic acid derivative and use of polyvalent metallized product as color developer |
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JP (1) | JP3107854B2 (en) |
Families Citing this family (1)
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JPH06104786B2 (en) * | 1991-12-18 | 1994-12-21 | 三洋化成工業株式会社 | Developer, its dispersion and developer sheet |
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1991
- 1991-07-18 JP JP03178311A patent/JP3107854B2/en not_active Expired - Fee Related
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