JPH06345986A - Monovinylmethane compound and recording material containing the same - Google Patents

Abstract

(57) [Summary] [Structure] A monovinylmethane compound represented by the following general formula (1) and a recording material containing the same as a color former. In the formula, R ¹ and R ² each independently represent a pyrrolidino group, a piperidino group, a morpholino group or a substituted amino group,
³ represents a hydrogen atom, an alkyl group, an alkoxy group, a benzyloxy group, a phenoxy group, a pyrrolidino group, a piperidino group, a morpholino group or a substituted amino group. [Effect] The color development image of the monovinylmethane compound of the present invention is extremely excellent in light resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monovinylmethane compound which develops a blue color by interaction with an electron-accepting color developer and a recording material containing this monovinyl compound as a color former.

[0002]

BACKGROUND OF THE INVENTION Pressure-sensitive recording materials, heat-sensitive recording materials, and photosensitive recording materials are known as recording materials for obtaining a colored image by the interaction between an electron-donating dye and an electron-accepting developer. Electrically conductive recording materials and thermal transfer recording materials are well known. In particular, as a color former for pressure-sensitive and heat-sensitive recording materials, those having various structures have been proposed so far, and representative ones thereof include a fluoran compound and a phthalide compound. Crystal violet lactone (CVL) has long been known as a typical color-forming agent that develops a blue color, and in addition to this, JP-A-53-55223.
The carbazolyl methane compound described in Japanese Patent Publication No. 1993-242242, and further benzoyl leuco methylene blue (BLMB) are known.

However, the former CVL, which is most often used at present, has a good color development sensitivity, but has a poor light resistance of a color image, and the latter carbazolylmethane compound and leucomethylene blue have a light resistance of a color image. Good but
There are problems that the color development speed is slow and that it is difficult to adjust the hue when used in combination with other color formers. In order to improve such a problem, a new color forming agent having good color forming sensitivity and excellent light resistance has been demanded. The present invention has been achieved as a result of research aiming at achieving such a problem, and relates to a monovinylmethane compound of the general formula (1) useful as a color former. The inventor of the present invention has disclosed in
We have reached another type of monovinylmethane compound disclosed in Japanese Patent No. 7280 (Example 2) and confirmed the color development performance of the compound disclosed in this publication. The absorption wavelength is located on the considerably shorter wavelength side as compared with the case of the monovinylmethane compound of the present invention, and the light resistance of the color image is slightly poorer than that of the compound of the present invention.

[0004]

The present invention relates to a monovinylmethane compound represented by the general formula (1) and a recording material containing the compound as a color former.
In the general formula (1), R ¹ and R ² each independently represent a pyrrolidino group, a piperidino group, a morpholino group or a substituted amino group, and R ³ represents a hydrogen atom, an alkyl group, an alkoxy group or benzyl. Oxy group, phenoxy group,
A pyrrolidino group, a piperidino group, a morpholino group or a substituted amino group is shown.

The compounds represented by the general formula (1) include the following. 1,1-bis (4-dimethylaminophenyl) -3-phenyl-2-propene, 1,1-bis (4-diethylaminophenyl) -3-phenyl-2
-Propene, 1,1-bis (4-dipropylaminophenyl) -3-phenyl-2-propene, 1,1-bis (4-dibutylaminophenyl) -3-phenyl-2-
Propene, 1,1-bis (4-dibenzylaminophenyl) -3-phenyl-2-propene, 1,1-bis (4
-Ethylbenzylaminophenyl) -3-phenyl-2
-Propene, 1,1-bis (4-methylphenylaminophenyl) -3-phenyl-2-propene, 1,1-bis (4-phenylpentylaminophenyl) -3-phenyl-2-propene, 1, 1-bis (4-pyrrolidinophenyl) -3-phenyl-2-propene, 1,1-bis (4-piperidinoaminophenyl) -3-phenyl-2
-Propene, 1,1-bis (4-morpholinophenyl)
-3-Phenyl-2-propene, 1,1-bis (4-N
-Methyl-N-p-tolylphenyl) -3-phenyl-
2-propene, 1,1-bis (4-dimethylaminophenyl) -3- (4-dimethylaminophenyl) -2-propene, 1,1-bis (4-diethylaminophenyl)
-3- (4-diethylaminophenyl) -2-propene, 1,1-bis (4-dipropylaminophenyl)-
3- (4-dipropylaminophenyl) -2-propene, 1,1-bis (4-dibutylaminophenyl) -3
-(4-dibutylaminophenyl) -2-propene,
1,1-bis (4-dibenzylaminophenyl) -3-
(4-dibenzylaminophenyl) -2-propene,
1,1-bis (4-methylphenylaminophenyl)-
3- (4-ethylbenzylaminophenyl) -2-propene, 1,1-bis (4-phenylbenzylaminophenyl) -3- (4-phenylmethylaminophenyl)-
2-propene, 1,1-bis (4-pyrrolidinophenyl) -3- (4-pyrrolidinophenyl) -2-propene, 1,1-bis (4-piperidinoaminophenyl)-
3- (4-piperidinophenyl) -2-propene, 1,
1-bis (4-morpholinophenyl) -3- (4-morpholinophenyl) -2-propene, 1,1-bis (4-
N-methyl-Np-tolylphenyl) -3- (4-dimethylaminophenyl) -2-propene.

The compound of the general formula (1) of the present invention contains another coloring agent such as a fluorane derivative or a phthalide derivative in order to further improve the storability of a colored image or to obtain a colored image of various color tones. Can be used together.

Further, other near-infrared absorbing compounds may be mixed and used within a range that does not impair the performance of the compound of the general formula (1) of the present invention. For example, the following compounds may be mentioned. 3,3-bis [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) vinyl] -4,
5,6,7-Tetrachlorophthalide, 3,3-bis [2
-(4-Pyrrolidinophenyl) -2- (4-methoxyphenyl) vinyl] -4,5,6,7-tetrachlorophthalide, 2-chloro-3-methyl-6- {p- (p'- Phenylaminophenylamino) phenylamino} fluorane, 3,6,6′-tris (dimethylamino) spiro [fluorene-9,3′phthalide], 3- (4-diethylamino-2-methoxyphenyl) -3- {1 (4-chlorophenyl) -1,3, -butadienyl} phthalide,
3,3-bis [4-dimethylaminophenyl-3-yl] -4-azaphthalide, 3,3-bis [4-diethylaminophenyl-3-yl] -4-azaphthalide, 3,3
3-bis [4-dibutylaminophenyl-3-yl]-
4-Azaphthalide, 3,3-bis [4-diamylaminophenyl-3-yl] -4-azaphthalide, 3,3-bis [4-dipentylaminophenyl-3-yl] -4-
Azaphthalide, 3,3-bis [4-ethylbenzylaminophenyl-3-yl] -4-azaphthalide.

In producing a pressure-sensitive recording material using the compound represented by the general formula (1) as a color-developing agent, for example, known methods described in US Pat. Nos. 2,800,458 and 2,800,457 are adopted. can do.

Examples of color developers include clay, bentonite,
Clays such as activated clay and acid clay, metal salts of salicylic acid and salicylic acid derivatives, p-phenylphenol formalin resin, p-octylphenol formalin resin and metal salts thereof are used. Among these, the color density,
From the viewpoint of image stability, metal salts of salicylic acid derivatives are preferable, and examples of salicylic acid derivatives include the following. Salicylic acid, 3-methyl-5-tert-
Butylsalicylic acid, 3,5-tert-butylsalicylic acid, 3-cyclohexylsalicylic acid, 5-cyclohexylsalicylic acid, cresotinic acid, 5-nonylsalicylic acid,
5-cumylsalicylic acid, 3-phenylsalicylic acid, 2,
5-dihydroxysalicylic acid, naphthoic acid, hydroxynaphthoic acid, 3-tert-butyl-5-α-methylbenzyl salicylic acid, 3,5-di (α-methylbenzyl)
Salicylic acid and the like. Examples of the polyvalent metal forming a salt with these include zinc, magnesium, calcium, aluminum, nickel, copper, etc. Of these, zinc, magnesium, calcium and the like are preferable, and zinc is particularly preferable.

Binders for producing pressure-sensitive recording materials include polyvinyl alcohol, methyl cellulose,
Hydroxyethyl cellulose, carboxymethyl cellulose, gum arabic, gelatin, casein, den powder, polyvinylpyrrolidone, styrene-maleic anhydride copolymer and the like are used. As an organic solvent for dissolving the color former, alkylbenzene-based, alkylnaphthalene-based,
Various kinds of alkyldiphenyl type, diarylethane type, hydrogenated terphenyl type, and chlorinated paraffin type can be used alone or as a mixture, and for microencapsulation, coacervation method, interfacial polymerization method, in-situ method can be used.
The law etc. can be adopted. In addition, if necessary, various antioxidants, ultraviolet absorbers, surfactants, etc. may be used in combination.

In order to manufacture the thermal recording paper, for example, a known method described in Japanese Patent Publication No. 45-14039 can be adopted. As a binder for producing a heat-sensitive recording paper, polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, which is commonly used for heat-sensitive recording paper,
Carboxymethyl cellulose, gum arabic, gelatin, casein, den powder, polyvinylpyrrolidone, styrene-maleic anhydride copolymer and the like can be used.

As the developer in this case, known p-hydroxybenzoic acid methyl ester, p-hydroxybenzoic acid benzyl ester, 2,2-bis (p-hydroxyphenyl) propane (bisphenol A), 3,4 '-
Isopropylidene diphenol, 2,2-bis (p-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxy-3-allylphenyl) propane,
Bis (4-hydroxyphenyl) acetic acid, 1,1-bis (4-hydroxyphenyl) butyl acetate, 4,4′-cyclohexylidene diphenol, 4,4′-thiodiphenol, bis- (4-hydroxy-3) -Methylphenyl) sulfide, bis (4-hydroxy-3-ter
t-butyl-6-methylphenyl) sulfide, 4,
4'-dihydroxydiphenyl sulfone, 4-hydroxy-4'-methyldiphenyl sulfone, 3,4-dihydroxy-4'-methyldiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4,
4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 4,4'-dihydroxy-3,3'-diallyl diphenyl sulfone, dimethyl 4-hydroxyphthalate, bis [2- (4-hydroxyphenylthio) ethyl] Ether, 4,4′-methylenebis (oxyethylenethio) diphenol, 1-benzyl-2-naphthol, 1,1′-methylenedi-2-naphthol, p-hydroxyphenylsalicylamide, 1,3-diphenylthiourea, 1,3-ditolylthiourea, 1,3-dichlorophenylthiourea, etc. can be used alone or in combination.

As the sensitivity improver (sensitizer), paraffin wax, carnauba wax, higher fatty acid ester,
Higher fatty acid amide, dibenzyl oxalate, di-p-methylbenzyl oxalate, di-p-chlorobenzyl oxalate, phthalate ester, terephthalate ester, benzyl 4-benzyloxybenzoate, naphthol benzyl ether, 1,4
-Dialkoxynaphthalene, 1,5-dialkoxynaphthalene, m-terphenyl, p-benzylbiphenyl,
Dibenzylbenzene, 1-hydroxy-2-naphthoic acid ester, 1-phenoxy-2-naphthoxy (1) ethane, 1,2-diphenoxyethane, 1,2-di (3-methylphenoxy) ethane, 1- ( 2-Isopropylphenoxy) -2-naphthoxy (2) ethane, bis (p-methoxyphenoxyethyl) ether, 2-hydroxy-
3-naphthoic acid ester, 4,4′-dialkoxydiphenyl sulfone, benzamide, diphenylamine, benzenesulfonamide, benzenesulfonanilide,
1,4-dibenzyloxybenzene, 1,4-di (vinyloxyethoxy) benzene, 1,3-di (vinyloxyethoxy) benzene, diphenyl carbonate and the like can be mentioned, and these can be used alone or in combination. can do.

In addition to the sensitivity improver, various antioxidants, deterioration inhibitors, ultraviolet absorbers, etc. are added to improve the light resistance and storability of the image, and the thermosensitive recording paper is made of a polymer substance or the like. You can also overcoat. There are methods shown in the following schemes 1 to 3 for synthesizing the compound represented by the general formula (1).

[0015]

[Chemical 2]

In Scheme 1, a propenol derivative and a benzene derivative are methanol, ethanol, i-propyl alcohol, ethyl cellosolve, chloroform, tetrachloroethylene, benzene, toluene, chlorobenzene, o.
− Room temperature to 150 ° C in organic solvent such as dichlorobenzene
Tens of minutes to tens of hours, if necessary, formic acid, acetic acid, acetic anhydride, p-toluenesulfonic acid, phosphorus oxychloride, sulfuric acid,
The condensation is performed in the presence of an acid catalyst such as hydrochloric acid or nitric acid.

[0017]

[Chemical 3]

Scheme 2 shows acrolein derivative and benzene derivative as methanol, ethanol, i-propyl alcohol, ethyl cellosolve, chloroform, tetrachloroethylene, benzene, toluene, chlorobenzene, o.
− Room temperature to 150 ° C in organic solvent such as dichlorobenzene
Tens of minutes to tens of hours, if necessary, formic acid, acetic acid, acetic anhydride, p-toluenesulfonic acid, phosphorus oxychloride, sulfuric acid,
The condensation is performed in the presence of an acid catalyst such as hydrochloric acid or nitric acid.

[0019]

[Chemical 4]

In Scheme 3, a benzene derivative and tetramethoxypropane are used without solvent or, if necessary, in an organic solvent such as benzene, toluene, chlorobenzene, tetrahydrofuran, acetonitrile, chloroform and methylene chloride from room temperature to 150 ° C., preferably 60 to 90 ° C. Then, the presence and condensation of an acid catalyst such as phosphorus oxychloride, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid is carried out.

The present invention will be described in detail below with reference to synthesis examples of the compound of the general formula (1) and examples of recording materials using the compound. Synthesis Example 1 1,1-bis (4-pyrrolidinophenyl) of the following formula (2)
Synthesis of 3-phenyl-2-propene

[0022]

[Chemical 5]

To a mixed solution of 40 ml of water and 38.4 g of 62% sulfuric acid, 29.4 g of phenylpyrrolidine and 33 g of trans-cinnamaldehyde are added, and the mixture is heated at 55 ° C. for 3 hours. Subsequently, it was neutralized with 48% caustic soda to obtain 35.5 g of a slightly blue colored crystal. The crystals were recrystallized from butanol to obtain 28.5 g of pale yellow crystals. mp 12
6 to 138 ° C. The coloring hue on TLC of this compound was green, and its λmax was 662 nm.

Synthesis Example 2 Synthesis of 1,1-bis (4-dimethylaminophenyl) -3-phenyl-2-propene of the following formula (3)

[0025]

[Chemical 6]

Ethyl cellosolve 150 cc trans
-Cinnamaldehyde 19.8 g, dimethylaniline 4
Add 0.0 g to dissolve. 98% sulfuric acid 30.0
g and 14.1 g of urea were added, the temperature was raised to 50 ° C., and the reaction was performed for 2.5 hours. Subsequently, it is discharged into water and neutralized with 48% caustic soda. The precipitated tar-like substance is extracted with toluene and concentrated with a rotary evaporator. The remaining tar was dissolved in ethanol for crystallization. The crystals were collected by filtration to obtain the desired product 19.6.
g white crystals were obtained. mp 81-101 ° C. The coloring hue on TLC of this compound is blue green, and its λma
x was 660 nm.

Synthesis Example 3 Synthesis of 1,1-bis (4-dimethylaminophenyl) -3- (4-dimethylaminophenyl) -2-propene of the formula (4)

[0028]

[Chemical 7]

To 30.7 g of phosphorus oxychloride, 4.84 g of dimethylaniline and 3.3 g of 1,1,3,3-tetramethoxypropane were added under cooling. Then, the mixture was reacted at 40 ° C. for 3 hours and at 60 ° C. for 18 hours. After the reaction, the mixture is discharged into 200 ml of ice water and neutralized with 48% caustic soda. The separated tar-like substance was extracted with toluene and concentrated with an evaporator. The residual tar was dissolved in a mixed solution of toluene and ethanol and crystallized to obtain 1.1 g of cream-colored crystals. mp
160.2-163.5 ° C. The coloring hue on TLC of this compound was blue-green, and λmax was 706 nm.

Example 1; Production Example of Pressure Sensitive Recording Material 10.0 parts of the compound of Synthesis Example 3 (parts represent parts by weight)
MC-113 (Kureha Chemical Industry Co., Ltd., alkylnaphthalene-based pressure-sensitive copying paper solvent) was dissolved in 90 parts, and 24 parts of gelatin and 24 parts of gum arabic were dissolved in 400 parts of water to adjust the pH to 7. Add the liquid. After emulsifying with a homogenizer and adding 1000 parts of warm water and stirring at 50 ° C for 30 minutes, about 1 part of 10% caustic soda solution was added and further stirred at 50 ° C for 30 minutes. Then add dilute acetic acid gradually to add PH
The mixture was adjusted to 4.5, stirred at 50 ° C. for about 1 hour, cooled to 0 to 5 ° C., and further stirred for 30 minutes. Next, 35 parts of a 4% glutaraldehyde aqueous solution was gradually added to cure the capsule, the pH was adjusted to 6 with an aqueous caustic soda solution, and the mixture was stirred at room temperature for several hours to complete encapsulation. This capsule liquid was uniformly applied to paper with a wire bar and dried to obtain a coated paper (upper paper). This was superposed on a paper (lower paper) coated with Shilton clay as a color developer, and when the writing pressure of a ballpoint pen or the impact of a typewriter was applied, a dark blue-green image slowly appeared on the lower paper.

Comparative Example 1 A pressure-sensitive copying paper was obtained by the same operation as in Example 1 except that crystal violet lactone was used instead of the compound of Synthesis Example 1. The color image was blue.

A light fastness test was conducted on each of the colored images from Example 1 to Comparative Example 2 described above, and the change in image density was measured by Macbeth-RD514 (manufactured by Macbeth). The results are shown in Table 1 below, and the compounds of the present invention show good light resistance.

[0034]

[Table 1]

Example 2 Production Example of Thermosensitive Recording Material 1) Preparation of Coloring Agent Dispersion Liquid (A) 1,1-Bis (4-dimethylaminophenyl) -3- (4-dimethylaminophenyl) -2 -Proene (compound of Synthesis Example 3) 5 parts Kaolin 15 parts 10% polyvinyl alcohol aqueous solution 100 parts water 85 parts Paint shaker (manufactured by Toyo Seiki Co., Ltd.)
It was pulverized until the average particle size of the color former became 2 microns. 2) Preparation of developer dispersion (B) liquid Bisphenol A 15 parts Zinc stearate 10 parts 10% aqueous polyvinyl alcohol solution 150 parts The above mixture was ground with a paint shaker until the average particle size became 3 microns.

3) Preparation and coating of heat-sensitive coating liquid 10 parts of liquid A and 6.5 parts of liquid B were mixed and stirred to obtain a heat-sensitive coating liquid. The coating amount after drying this coating solution on paper with a wire bar is 8
The heat-sensitive recording paper was obtained by uniformly coating so as to have g / m ² and then drying. This heat-sensitive recording paper was almost colorless with no background fog and developed a deep blue color when printed with a thermal head. This color image was excellent in light resistance and moisture resistance. Also,
The coated surface was also excellent in light resistance, and neither the coloring nor the deterioration of the coloring ability was caused by irradiation with sunlight.

[0037]

The color image of the monovinylmethane compound of the present invention is extremely excellent in light fastness.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B41M 5/30 C09B 11/00 C 7306-4H

Claims (2)

[Claims] 1. A monovinylmethane compound represented by the following general formula (1). [Chemical 1] In the formula, R ¹ and R ² each independently represent a pyrrolidino group, a piperidino group, a morpholino group or a substituted amino group,
³ represents a hydrogen atom, an alkyl group, an alkoxy group, a benzyloxy group, a phenoxy group, a pyrrolidino group, a piperidino group, a morpholino group or a substituted amino group. 2. A recording material containing the monovinylmethane compound according to claim 1 as a color former.