JPS58157779A - Phthalide derivative, its preparation, and recording material using it - Google Patents

Abstract

NEW MATERIAL:A phthalide derivative shown by the formulaI R1 and R3 are H or alkyl; R2 is H, halogen, alkyl, alkoxy, nitro, or (substituted)amino; R4-R9 are H, alkyl, (substituted)aralkyl, or (substituted)aryl; R4 and R5, R6 and R7, and R8 and R9 together with neighboring nitrogen atom respectively may form heterocyclic ring; X1, X2, Y1 and Y2 are H, alkyl, or alkoxyl; Z is O, or methylene, a and b are 1-3 to make a+b>=3; n is 1-4). EXAMPLE:3,3-Bis 1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl phthalide. USE:Useful as a color substance usable as a recording material such as pressure- sensitive, heat-sensitive, electrically heat-sensitive, photosensitive recording sheet, etc. Especially having improved light resistance, forming color images readable by a reader for an optical letter. PROCESS:A phthalic anhydride derivative shown by the formula II is reacted with an ethylene derivative shown by the formula III, to give a compound shown by the formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to phthalide derivatives that are useful as color-forming substances for use in recording materials such as pressure-sensitive recording sheets, heat-sensitive recording sheets, current-carrying heat-sensitive recording sheets, and photosensitive recording sheets. The present invention relates to a novel phthalide derivative that forms a color image readable by an optical character reader, a method for producing the same, and a recording medium using the derivative.

Conventionally, methods have been developed to record information transmitted through energy media such as pressure, heat, electricity, and light by utilizing the color reaction between a colorless or light-colored basic dye and an organic or inorganic electron-accepting substance. Various methods have been proposed for
(8) Pressure-sensitive copying sheets, heat-sensitive recording sheets, electrically conductive heat-sensitive recording sheets, as described on pages 3 to 470 (1976);
A large number of methods have been proposed, including applications to ultrasonic recording sheets, electron beam recording sheets, electrostatic recording sheets, photosensitive recording sheets, and even photosensitive printing materials, type ribbons, ballpoint pen inks, crayons, stamp inks, etc. There is. 'Crystal violet lactone is the most commonly used colorless or light-colored basic dye that develops blue in these recording media. When this dye comes into contact with an electron-accepting substance, it instantly exhibits a clear blue-purple color, but its fastness to sunlight is extremely poor, so the recorded image (color image)
However, it has the disadvantage that it disappears in a short time due to the ultraviolet rays of sunlight. In addition, in recent years, along with the streamlining of office processes, the number of cases in which recorded images on recording media are read and processed using optical character readers has increased significantly, but recorded images obtained with this dye have a light absorption of 700 to 700. Since it is not in the infrared region of 900 nm, it could not be applied to such applications at all.

(9) However, the specific phthalide derivative of the present invention represented by the following general formula (1) [wherein R7 and R3 each represent a hydrogen atom or an alkyl group, and Rz is a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkoxyl group, a nitro group, an amino group or a substituted amino group, and R4, R5゜R6, R7, R# and R9 each represent a hydrogen atom, an alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group or a substituted aryl group. , R<
and R5XRa and R7 and R, and R2 may each form a heterocycle with the adjacent nitrogen atom.

x, x, y/, yz each represent a hydrogen atom, (10) an alkyl group or an alkoxyl group, Z represents an oxygen atom or a methylene group, and a and b are 1 to 3 such that a+b is 3 or more. n represents an integer of 1 to 4. ] is a colorless or light-colored compound that exhibits a high-density, vivid color tone of blue-green or green when it comes into contact with an electron-accepting substance, but recorded images obtained using this substance cannot be exposed to sunlight for long periods of time. It has the excellent property that it stably maintains its initial color tone even when the image is exposed to sunlight, and that it can also be processed with an optical character reader because the recorded image has light absorption in the infrared region of 700 to 900 nm. be.

The phthalide derivative of the present invention represented by the general formula CI) having the excellent properties as described above can be synthesized mainly by the following representative method. That is, by reacting a phthalic anhydride derivative represented by the general formula CIII) and an ethylene derivative represented by the general formula (rV) at 50 to 200°C for several tens of minutes to several hours using a dehydration condensation agent as shown below, the present invention can be obtained. It is possible to synthesize the phthalide (11) derivative represented by the general formula (11) of the invention.

a, h-n represent the above-mentioned meanings. ] Also, as another method, first, the general formula [III
)' Phthalic anhydride derivative represented by -M formula (■]-
A benzoic acid derivative represented by the general formula (V) is synthesized by condensing an ethylene derivative represented by the formula (V) using a Friedelta raft catalyst.

(12) (V.J. [In the formula, R/, R2, Rg, R7, X/, Yt, Z.

a, b, n have the above meanings. ] By reacting the benzoic acid derivative represented by the general formula (V) and the ethylene derivative represented by the general formula (Vl) at 30 to 150°C for several lθ minutes and several hours using a dehydration condensation agent, the general formula of the present invention can be obtained. Phthalide derivatives of the formula (2) can be synthesized.

(13) (wherein Rt, Rz, R3, Rme, Rj, R1, R7
RJ1. Ry, X7, X<, Y/, Y<, Z,
a.

b and n have the above meanings. ] Furthermore, it is also possible to condense the phthalic anhydride derivative represented by the general formula (I The phthalide derivative represented by the general formula (1) of the present invention can be synthesized (14).

Specific examples of the anhydrophthalic derivative #i represented by the general formula (III) include the following compounds.

Phthalic anhydride, 3 (or 4)-chlorophthalic anhydride, 4.5-dichlorophthalic anhydride, 3゜4.5.6
~tetrachlorophthalic anhydride, 3 (or 4)-bromophthalic anhydride, 4,5-dibromophthalic anhydride,
3.4.5.6-titrabromophthalic anhydride, 4-methylphthalic anhydride, 4-methquinphthalic anhydride, 4
-Ethoxyphthalic anhydride, 3 (or 4)-ditrophthalic anhydride, 3 (or 4)-dimethylaminophthalic anhydride, 3 (or 4)-diethylaminophthalic anhydride 1m, 4-N~ethyl- N-benzylaminophthalic anhydride, 4-N-methyl-N-phenylamino, phthalic anhydride, 4-pyrrolidinophthalic anhydride, 4-piperidinophthalic anhydride, etc.

Specific examples of the ethylene derivative represented by the general formula (IV) include the following compound (15).

1.1-bis(4-pyrrolidinophenyl)ethylene, 1
．． 1-bis(4-piperidinophenyl)ethylene, l,
1-bis(4-morpholinophenyl)ethylene, 1.1
-bis(4-hexamethyleneiminophenyl)ethylene, 1.1-bis(2-methyl-4-pyrrolidinophenyl)ethylene, 1゜1-bis(2-methyl-4-piperidinophenyl)ethylene, 1.1-bis(2-methyl-4
-molar nophenyl)ethylene, i,t-bis(2-
Methyl-4-hexamethyleneiminophenyl)ethylene, l, 1-bis(2-methoxy-4-pyrrolidinophenyl)ethylene, 1,1-bis(2-methoxy-4-
piperidinophenyl)ethylene, 1.1-bis(2-methoxy-4-morpholinophenyl)ethylene, 1.1-
Bis(2-methoxy,-4-hexamethyleneiminophenyl)ethylene, 1-(4-pyrrolidinophenyl)-1
-(4-dimethylaminophenyl)ethylene, 1-(4
-piperidinophenyl)-1-(4-dimethylamino(
16) Phenyl)ethylene, 1-(4-morpholinophenyl)
-1-(4-'; methylaminophenyl)ethylene, ■
-(4-hexamethyleneiminophenyl)-1-(4-
dimethylaminophenyl)ethylene, ■-(4-pyrrolidinophenyl)-1-(4-N-ethyl-N-benzylaminophenyl)ethylene, L-(4-piperidinophenyl)-1-(4-N -ethyl-N-benzylaminophenyl)ethylene, 1-(4-morpholinophenyl)=
1- (4-N-ethyl-N-pendylaminophyl)
Ethylene, 1-(4-hexamethyleneiminophenyl)
-1-(4-N-ethyl-N-benzylaminophenyl)ethylene, 1-(4-pyrrolidinophenyl)-1-(
4-N-Methyl-N-P-1-IJ Ruaminophenyl)ethylene, 1-(4-piperidinophenyl)-1-(
4-N-methyl-N-p-tolylaminophenyl)ethylene, ■-(4-morpholinophenyl)-1-(4-N
-methyl-N-p~tolylaminophenyl)ethylene,
1-(4-hexamethyleneiminophenyl) (17) -1-(4-N-methyl-N-p-tolylaminophenyl)ethylene, 1-(4-pyrrolidinophenyl)-1-
(2-Methyl-4-diethylaminophenyl)ethylene, I-(4-pyrrolidinophenyl> -1-(2-methoxy-4-diethylaminophenyl)ethylene, 1.1
-bis(4-pyrrolidinophenyl)-1-propene, 1
, 1-bis(4-piperidinophenyl)-1-propene, 1゜1-bis(4-morpholinophenyl)-1-propene, ■, ■-bis(4-hexamethyleneiminophenyl>-1-propene etc., Specific examples of the ethylene derivative represented by the general formula (Vl) include the following compounds.

1.1-bis(p-aminophenyl)ethylene, 1,t
-bis(p-methylaminophenyl)ethylene, 1. l
-bis(p-dimethylaminophenyl)ethylene, 1.
1-bis(p-ethylaminophenyl)ethylene, 1.
I-bis[p-diethylaminophenyl)ethylene, 1
．． 1-bis(p(1B)-dimethylaminophenyl)-1-propene, l.

1-bis(p-diethylaminophenyl)-1-propene, 1.1-bis(4-dimethylamino-2-methylphenyl)ethylene, 1.1-bis(4-diethyl7minor-2-methylphenyl)ethylene, 1,1-bis(4-
dimethylamino-2-methoxyphenyl)ethylene, 1
．． 1-bis(4-diethylamino-2-methoxyphenyl)ethylene, 1.1-bis(p-(N-methyl-N-benzyl)aminophenyl)ethylene, 1.1-bis(p
-(N-ethyl-N-benzyl)aminophenyl)ethylene, 1,1-bis(p-(N-ethyl-N-p-chlorobenzyl)minophenyl)ethylene, 1.1-bis1p-(N- methyl-N-phenyl)aminophenyl)
Ethylene, 1,1-bis(p-(N-methyl-N-p-
tolyl)aminophenyl)ethylene, 1,1-bis(p
-(N-methyl-N-p-methoxyphenyl)aminophenyl)ethylene, 1,1-bis[p-(N-ethyl-
N-p-methoxyphenyl)aminophe(19)yl)ethylene, 1,1-bis(4-dimethylamino-
2-methylphenyl)-1-propene, 1゜1-bis(
4-diethylamino-2-methylphenyl)-1-propene, 1,1-bis(4-dimethylamino-2-methoxyphenyl)-1-propene, ■, 1-bis(4-diethylamino-2-methoxyphenyl) -1-Propene etc.

The dehydration condensation agent used in the reaction between the phthalic anhydride derivative and the ethylene derivative in the first method and the reaction between the benzoic acid derivative and the ethylene derivative in the second method is, for example, acetic anhydride, which also serves as a solvent; Lower fatty acid anhydrides such as propionic anhydride, inorganic acids such as phosphorus oxychloride, phosphorus trichloride, sulfuric acid, and polyphosphoric acid are preferably used, but various other free delta raft catalysts may also be used, and these may be used alone or in combination. Two or more types are used in combination.

The thus obtained phthalide derivative represented by the general formula (1) of the present invention is a colorless to light-colored basic dye that exhibits excellent properties as described above, and in particular, it contains (20) an electron-accepting substance (hereinafter referred to as a color developer). It exhibits extremely excellent effects when used in various recording media that utilize the color reaction with (abbreviated).

In such a recording medium, the phthalide derivatives of the present invention may be used alone or in combination, and if necessary, in combination with the following basic dyes.

3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(p-dibenzylaminophenyl)-3-(1,2-dimethylindol-3-yl)-7-azaphthalide , 3-(4-diethylamine-
2-ethoxyphenyl”)-3-(1-ethyl-2-methylindol-3-yl)-7-azaphthalide, 3.
Triarylmethane lactones such as 3-bis(l-ethyl-2-methylindol-3-yl)phthalide, 3-
Diethyl 7minor 6-methylfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-(N
-Ethyl-N-p-tolylamino)-7-methylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-((21) N-cyclohexyl-N-methyltolylamino)- 6-methyl-7-anilinofluorane, 3-(N-ethyl-N-p
-) fluorans such as lylamino)-6-methyl-7-anilinofluoran, 3-diethylamino-7-0-chloroanilinofluoran, di-β-naphthospiropyran, 3-methyl-di-β-naphtho Spiropyrans such as spiropyran, 4.4'-bis-dimethylaminobenzhydryl benzyl ether, diphenylmethanes such as 4.4'-bis-dimethylaminophenyl-p-+-luenesulfinic acid ester, 3.7-bis (dimethylamino)
Azines such as -10-benzoylphenothiazine and 3.7-bis(diethylamino)-10-benzoylphenoxazine; triaryls such as N-butyl-3-[bis(4-(N-methylanilino)phenyl)methyl]carbazole; such as methane.

As mentioned above, the phthalide derivative of the present invention exhibits extremely excellent effects when used in various recording materials that utilize a color reaction with a color developer.

(22) The color developer used here is appropriately selected depending on the type of recording medium, but it is possible to use a pressure-sensitive method that brings the phthalide derivative into contact with the color developer through the medium of pressure, heat, or electrical energy. A substance that acts as a Brønsted or Lewis acid is preferably used in recording bodies such as recording bodies, heat-sensitive recording bodies, electrically conductive heat-sensitive recording bodies, ultrasonic recording bodies, electrostatic recording bodies, type ribbons, ballpoint pen inks, and crayons. Specifically, for example, inorganic color developers such as acid clay, activated clay, attapulgide, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin, and talc, Scheler's acid, maleic acid, tartaric acid, and citric acid. acids, aliphatic carboxylic acids such as succinic acid and stearic acid, benzoic acid, paratertiary butylbenzoic acid, phthalic acid, gallic acid, salicylic acid, 3-
Isopropylsalicylic acid, 3-phenylsalicylic acid,
3-cyclohexylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-3-(α,α-dimethylben(2
3) Aromatic carboxylic acids such as zyl)salicylic acid, 3,5-di(α-methylbenzyl)salicylic acid, 2-hydroxy-1-benzyl-3-naphthoic acid, 4,4'-isopropylidenediphenol, 4° 4'-isopropylidene bis(2-chlorophenol), 4.4'-isopropylidene bis(2°6-dibromophenol), 4.4'-
Isopropylidene bis(2,6-dichlorophenol)
, 4.4'-isopropylidene bis(2-methylphenol), 4.4'-isopropylidene bis(2,6-dimethylphenol), 4.4'-isopropylidene bis(2-tert-butylphenol), 4.4'-Secondary-butylidene diphenol, 4.4'-cyclohexylidene bisphenol, 4.4'-cyclohexylidene bis(2-methylphenol), 4-tert-butylphenol, 4-phenylphenol, 4- Hydroxy diphenoxide, α-naphthol, β-naphthol, methyl-4-hydroxybenzoate, benzyl-4
-Hydroxybenzoate, 2.2'(24) Monothiobis(4,6-dichlorophenol), 4-tertiaryoctylcatechol, 2.2'-methylenebis(
4-chlorophenol), 2,2'-methylenebis(4
-methyl-6-tert-butylphenol), 2.2
Organic color developers such as phenolic compounds such as '-dihydroxydiphenyl, phenolic resins such as para-phenylphenol-formalin resin, and para-butylphenol-acetylene resin. Salts with polyvalent metals such as calcium, titanium, manganese, tin, and nickel, and hydrohalic acids such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, boric acid, silicic acid, phosphoric acid, sulfuric acid, nitric acid, and peroxide. Chloric acid, aluminum, zinc, nickel, tin, titanium,
Examples include inorganic acids such as halides such as boron.

In addition, in the case of electron beam recording materials and photosensitive recording materials, hydrogen halides such as hydrogen chloride, hydrogen bromide, hydrogen iodide, carboxylic acids, sulfonic acids, phenols, etc. are generated by electron beams or light. Carbon bromide, (25) organic halogen compounds such as α, α, α-tribromoacetophenone, hexa-chloroethane, iodoform, 2-tribromomethylhyricine, trichloromethylsulfonylbenzene, 0-quinonediazide-based compounds, optical Fr1
Phenol esters of carboxylic acids or sulfonic acids that cause es rearrangement are preferably used.

Various typical recording materials using such a color developer and the phthalide derivative represented by the general formula (1) of the present invention will be explained in more detail below.

Pressure-sensitive recording bodies are disclosed in, for example, U.S. Pat.
No. 505471, No. 2505489, No. 254836
No. 6, No. 2712507, No. 2730456, No. 2
No. 730457, No. 3418250, No. 392402
As described in No. 7 and No. 4010038, there are various types of phthalide derivatives, and the phthalide derivative of the present invention can be used in these various types of pressure-sensitive recording media.

Generally, the phthalide derivatives of the present invention are used alone or in combination,
Furthermore, if necessary, alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, etc. may be added together with basic dyes such as triarylmethane (26) tritons, spiropyrans, fluorans, diphenylmethanes, and azines. synthetic oil,
A dispersion obtained by dissolving this in a solvent such as cotton oil, vegetable oil such as castor oil, animal oil, mineral oil, or a mixture thereof, and dispersing it in a binder, or the above solution can be processed by a coacelation method, an interfacial polymerization method, The present invention can be applied by coating a dispersion of the microcapsules contained in microcapsules by various capsule manufacturing methods such as the 1n-siLu method and dispersed in a binder onto a support such as paper, plastic sheet, or resin-coated paper. A pressure sensitive recording medium is manufactured. Of course, there are the so-called upper sheets in which one side of the support is coated with the above dispersion liquid, and the so-called medium sheets in which one side of the support body is coated with a color developer coating liquid mainly containing a color developer, and the other side is coated with the above dispersion liquid. By applying a coating liquid containing a mixture of the capsules and color developer on the same side of the peripheral sheet and furthermore on the support, or by applying a developer coating liquid on top of the capsule dispersion liquid, As mentioned above, (27) includes various forms such as a so-called stand-alone copying sheet in which a capsule and a color developer coexist. The use of phthalide derivatives varies depending on various conditions such as the desired coating amount, the form of the pressure-sensitive recording medium, the capsule manufacturing method, the composition of the coating liquid including various auxiliaries, and the coating method. You can select it as appropriate. In any case, by using the phthalide derivative represented by the general formula (1) of the present invention as a basic dye for various conventional pressure-sensitive recording materials,
A pressure-sensitive recording material having excellent light resistance and capable of forming a recorded image readable by an optical character reading device can be obtained.

For example, heat-sensitive recording materials are disclosed in Japanese Patent Publication Nos. 44-3680 and 44-3680.
No. 27880, No. 45-14039, No. 48-438
No. 30, No. 49-69, No. 49-70, No. 52-2
As described in No. 0142, etc., there are various forms of the phthalide derivative, and the phthalide derivative of the present invention can be used in these various forms of heat-sensitive recording materials.Moreover, by simply using the phthalide derivative of the present invention as a dye, the phthalide derivative described above can be used. A heat-sensitive recording material exhibiting a recorded image having excellent properties (28) as shown in FIG. Generally, a coating liquid obtained by dispersing the phthalide derivative of the present invention and fine particles of a color developer in a medium in which a binder is dissolved or dispersed is applied to paper, plastic film, synthetic paper, woven fabric sheets, molded articles, etc. The heat-sensitive recording material of the present invention is produced by coating it on a suitable support. The ratio of the basic dye mainly consisting of a phthalide derivative and the color developer used in the recording layer is not particularly limited, but is generally 1 to 50 M parts, preferably 4 to 10 M parts per 1 part by weight of the dye.
Part iii color developer is used.

In addition, inorganic metal compounds such as oxides, hydroxides, and carbonates of polyvalent metals and inorganic pigments are generally used as color developers for the purpose of improving color development, matting the surface of the recording layer, and improving writing properties.
0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight
In addition, various auxiliary agents such as dispersants, ultraviolet absorbers, thermofusible substances, antifoaming agents, fluorescent dyes, and coloring dyes may be used in combination as necessary.

As mentioned above, the heat-sensitive recording material of the present invention generally has a lid (29
) It is produced by coating a support with a coating liquid in which fine particles of a phthalide derivative and a color developer are dispersed. Of course, it is also possible to manufacture by overcoating, or by impregnating or cutting. There are no particular limitations on the preparation method or coating method of the base coating solution, and the coating amount is generally about 2 to 12 g/n (dry weight).

Examples of the binder include starches, cellulose, proteins, gum arabic, polyvinyl alcohol, styrene-maleic anhydride M co-M combined salt, styrene-butadiene copolymer emulsion, acetic acid and maleic anhydride copolymer salt, and polyester. Acrylic fJj etc. are selected and used as appropriate = current-carrying heat-sensitive recording material is disclosed in, for example, JP-A-49-113
44, No. 50-48930, etc. Generally, a coating liquid in which a conductive substance, a basic dye mainly composed of the phthalide derivative of the present invention, and a color developer are dispersed together with a binder is applied to a support such as paper, or a conductive substance is coated on the support30). The electrically conductive heat-sensitive recording material of the present invention is produced by forming a four-electroelectric layer and applying a coating liquid containing a dye, a color developer, and a binder thereon. Note that if both the dye and the color developer do not melt in the preferred temperature range of 70 to 120°C, sensitivity to Joule heat can be adjusted by using an appropriate thermofusible substance in combination.

The photosensitive recording material uses the phthalide derivative of the present invention, for example, Japanese Patent Publication No. 38-24188, Japanese Patent Publication No. 45-1゜550, Japanese Patent Publication No. 4
No. 5-13258, between 49-120.

No. 4, No. 49-6212, No. 49-28449, JP-A No. 47-31615, No. 48-32532, No. 4
No. 9-9227, No. 49-135617, No. 50-8
No. 0120, No. 50-873■7, No. 50-1262
It is manufactured by the method described in No. 28, etc. - Other ultrasonic recording bodies (Temple Patent No. 2120922),
Electron beam recording material (Belgium Patent No. 7959986), electrostatic recording material (Special Publication No. 1973-3932), photosensitive printing material (
JP-A No. 48-12104 (31)), stamping material (JP-A No. 47-10766), type ribbon (JP-A No. 49-3713), ballpoint pen ink (
JP 48-83924), Crayon (U.S. Patent No. 3)
769045), the phthalide derivative of the present invention is used instead of the conventional basic dye,
They can be manufactured by the methods described in their respective patents.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto unless it goes beyond the gist of the present invention. Further, parts and % in the examples represent parts by weight and % by weight, respectively, unless otherwise specified.

Example 1 Phthalic anhydride 3.3 g, l! :1.1-bis(4-pyrrolidinophenyl)ethylene 12.8 g to acetic anhydride 25
After 6 reaction route-7, which was added to g and reacted at 80°C for 1 hour,
The reaction product was poured into water, neutralized with ammonia aqueous solution to decompose acetic anhydride, and the resulting precipitate was collected by filtration. The obtained solid was dried and then recrystallized from ethanol to have a melting point of 198.
6.7 g of 3.3-(32)bis[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl]phthalide at ~201°C was obtained as light green crystals. This phthalide derivative developed a blue-green color on silica gel.

Example 2 N except that 6.3 g of 3.4.5.6-tetrachlorophthalic anhydride was used instead of 3.3 g of phthalic anhydride
In the same manner as in Example 1, 3,3-bis[1,■-bis(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6°7-titrachloro having a melting point of 222 to 227°C was prepared. 14.2 g of phthalide was obtained as pale green crystals. This phthalide derivative developed a green color on silica gel.

Example 3 6.3 g of 3.4.5.6-tetrachlorophthalic anhydride was used instead of phthalic anhydride, and 1. l-bis (4
-pyrrolidinophenyl) 1 for 12.8 g of ethylene
．． 1-bis(4-piperidinophenyl)ethylene13.
The procedure was carried out in the same manner as in Example 1, except that 8 g of 3° (33) 3-bis[l,1-bis(4-piperidinophenyl)ethylene-2-yl with a melting point of 213 to 217°C was used. )-4,5,6,7-titrachlorophthalide was obtained as pale green crystals in an amount of 117 g. This phthalide derivative developed a green color on silica gel.

Examples 4 to I9 Using phthalic anhydride derivatives shown in Table 1 in place of phthalic anhydride, 1,1-bis(4-pyrrolidinophenyl)
The various phthalide derivatives shown in Table 1 were obtained in the same manner as in Example 1 except that the ethylene derivatives shown in Table 1 were used instead of ethylene. Table 1 also lists the temples and temples where the obtained phthalide derivatives were colored with silica gel.

(34) Manual Vt Amendment (Method) July 26, 1980 Patent Application No. 39965 2, Title of Invention: Phthalide derivative, method for producing the same, and recording material using the derivative 3, Person making the amendment 4. Agent residence (〒660) 11-1, Jokoji Motomachi, Amagasaki City
Within Kanzaki Paper Co., Ltd.

Claims (1)

[Claims] [1] A phthalide derivative represented by the following general formula (1) [
In the formula, Rt and RJ each represent a hydrogen atom or an alkyl group, and R2 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, a nitro group, an amino group, or a substituted group.
Represents an amino group, R(, Rt, R6, Rr, Re, R
? (1) each represents a hydrogen atom, an alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, or a substituted aryl group, and Rt and Rs, R6 and R7, and R8 and R9 each represent an adjacent nitrogen atom and a heterocyclic ring. may be formed. X,,X
To. y, , Y each represent a hydrogen atom, an alkyl group or an alkoxyl group, Z represents an oxygen atom or a methylene group, a, b are integers from 1 to 3 such that a+b is 3 or more, and n is an integer from 1 to 4. ] (2) The phthalide derivative is represented by the following general formula [■] (Derivative according to claim 11). (2) [In the formula, R/ represents a hydrogen atom or an alkyl group, and R2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, a nitro group, an amino group or a substituted amino group, R,
, R7 each represent a hydrogen atom, an alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, or a substituted aryl group, and R6 and R? may form a heterocycle with each adjacent nitrogen atom. X/. YI represents a hydrogen atom, an alkyl group or an alkoxyl group, Z represents an oxygen atom or a methylene group, and a, b
, a+b is 3 or more. n represents an integer of 1 to 4, and n represents an integer of 1 to 4. ] (3) A phthalic anhydride derivative represented by the following general formula CI [l] and (3) [wherein Rz is a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, a nitro group, an amino group or a substituted amine group] , and n represents an integer from 1 to 4. [In the formula, R/ represents a hydrogen atom or an alkyl group, R6,
R7 is a hydrogen atom, an alkyl group, an aralkyl group,
Represents a substituted aralkyl group, aryl group or substituted aryl group, R (and R7 may each form a heterocycle with an adjacent nitrogen atom. represents an oxygen atom or a methylene group, and a and b represent integers of 1 to 3 such that a+b is 3 or more.] (4) Method for producing a phthalide derivative represented by the following general formula (II). a. b and n represent the above-mentioned meanings.] (4) A recording material characterized by containing at least one type of phthalide derivative represented by the following general formula (+3. [In the formula, R/ and Ra each represent a hydrogen atom or represents an alkyl group, R2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, a nitro group, an amino group, or a substituted amino group, R<, R, 9゜R6, R7, R, p, R9
each represents a hydrogen atom, an alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, or a substituted aryl group,
R< and Rs, Ra and R2, and R and R2 may each form a heterocycle with an adjacent nitrogen atom. X/, Xz, YI, and Y2 each represent a hydrogen atom, an alkyl group, or an alkoxyl group, Z represents an oxygen atom or a methylene group, and a and b are 1 such that a is 3 or more.
n represents an integer of 1 to 4. (5) The recording medium according to claim (4), wherein the phthalide derivative is a derivative represented by the following general formula (II). (6) [In the formula, Ry represents a hydrogen atom or an alkyl group, and Rz Represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, a nitro group, an amino group or a substituted amino group, R,
, R7 each represent a hydrogen atom, an alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, or a substituted aral group, and R6 and R7 may each form a heterocycle with the adjacent nitrogen atom. xl. Y represents a hydrogen atom, an alkyl group or a 7' lucoxyl group, Z represents an oxygen atom or a methylene group, and a, b
is an integer from 1 to 3 such that a+b is 3 or more, and n is 1
(7) represents an integer of ~4. (6) The recording medium according to claim (4) or (5), wherein the recording body is a recording body for pressure-sensitive copying sheets. (7) The recording material according to claim (4) or (5), wherein the recording material is a recording material for a heat-sensitive recording sheet.